TW201119854A - Release film - Google Patents

Abstract

Provided is a release film having a polyesteric elastomer (A) layer disposed at a surface layer, and a polyester (B) layer. The glass transition temperature of the polyesteric elastomer (A) is 0 to 20 DEG C, and the crystallization rate index thereof is 20 to 50 DEG C. The polyester (B) contains a crystalline aromatic polyester (B1) and a 1, 4-cyclohexanedimethanol copolymerized polyethylene terephthalate (B2), and the mass ratio (B1)/ (B2) is in the range of 5/95 to 50/50. The glass transition temperature of the polyester (B) is 40 to 80 DEG C, and the crystalline heat of fusion thereof is 5 to 40J/g.

Description

201119854 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a release film, and more particularly to a release film used in the manufacture of a printed substrate. In particular, it relates to a release film which is useful when a cover film is formed by a thermosetting adhesive on a printed circuit board having a precise pattern and a high temperature heat-pressure adhesive film. [Prior Art] The release film is widely used industrially. In particular, in a manufacturing step of a printed circuit board, a flexible printed circuit board, or a multilayer printed circuit board, when a copper foil laminate or a copper foil is hot-pressed via a prepreg or a heat-resistant film, it can be used to prevent a prepreg. Or the heat resistant film is adhered to the hot plate. Further, in the manufacturing step of the flexible printed circuit board, when the flexible printed circuit board body forming the electrical circuit is thermally pressure-bonded to the cover film by the heat-curing adhesive, it can be used to prevent the cover film from adhering to the hot plate. The release film of the above-mentioned use may, for example, be a fluorine-based film, a polyoxymethylene-coated polyethylene terephthalate film, a polymethylpentene film or a polypropylene film. However, the fluorine-based film which has been used as a release film in the past is excellent in heat resistance, release property, and non-contamination property, but it is expensive in use, and it is difficult to burn after disposal. The problem of producing toxic gases still exists. Further, the polyoxymethylene-coated polyethylene terephthalate film or the polydecylpentene film contains polyfluorene or a low molecular weight in the film composition, and thus moves on a printed circuit board, particularly a substrate. The copper circuit causes pollution, damage and quality. Further, the polypropylene film is inferior in heat resistance and insufficient in release property. Therefore, the softness, the heat resistance, the release property, and the non-contamination property are improved. 3 322 464 201119854 The 离 烬 can be discarded, and is known to contain, for example, a polypropylene resin and a buffer of a vinyl aromatic elastomer. A film of a release layer composed of a crystalline aromatic polyester is laminated on both surfaces of the (cushion) layer (Patent Document 1). Further, a film of polybutylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and poly-ply-like copolymer has been disclosed as a film of a release layer (Patent Document 2). Or such a film as a buffer layer (Patent Document 3). In addition, a laminated cosmetic sheet having excellent heat resistance and moldability has been disclosed as a film in which an amorphous polyester resin and a crystalline polyester resin are blended or laminated (Patent Document 4, Patent Document 5). [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-049504 [Patent Document 2] International Publication No. 5/〇〇285 No. [Patent Document 3] Japanese Patent No. 4099355 [Patent Document 4] Japanese Patent Laid-Open No. 2003- [Patent Document 5] JP-A-2008-162058 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] However, in such a technique, the release property, heat resistance, and flexibility are not sufficiently obtained. When the release property and the heat resistance are emphasized, the softness is sacrificed, and the embedding property of the printed substrate having the fine pattern is poor. In addition, when the softness and steepness are emphasized, the release property is lowered or the slipperiness of the film surface is deteriorated, and the elastic modulus is low, so that the film is stretched or wrinkled during the winding or the cutting, and the comprehensive processing workability is poor. . For example, in the film described in Patent Document 1, the release property and the embedding property are excellent, but the hardness of the buffer layer resin is low, so that heat resistance is insufficient. Therefore, there is a problem that the buffer layer bleeds from the end of the film when the pressure is 4 322464 201119854, or the printed circuit board is contaminated by the movement of the low molecular weight body. In the techniques of Patent Document 2 and Patent Document 3, the soft copolymerized polybutylene terephthalate is used for the purpose of improving the embedding property, and therefore, it is excellent in release property and non-contamination property. However, the use of polybutylene terephthalate in the inner layer or the outer layer has a hardness which is inferior to the polydecylpentene film used in the prior art. In the techniques of Patent Document 4 and Patent Document 5, the amorphous polyester resin is blended in the crystalline polyester resin for the purpose of improving the moldability of the cosmetic sheet. Therefore, the embedding property is excellent. However, since the surface layer resin is not actively crystallized by paying attention to moldability, there is a problem of poor heat resistance or release property at the time of high-temperature hot pressing of the use of the present invention. The present invention solves the aforementioned problems of the prior art, and an object of the invention is to provide a softness, a release property, a heat recovery property, and a non-pollution property, and in particular, a good embedding property for a printed circuit board having a precise pattern, and a sheet A release film that is excellent in workability when being taken up or cut. [Means for Solving the Problem] The present inventors have solved the above problems and, as a result of intensive research, laminated a polyester elastomer having a specific crystallinity and a polyester having a glass transition temperature higher than that. The polyester elastomer of the surface layer is crystallized to impart release property, and the crystallinity of the polyester of the inner layer of the crystalline resin is adjusted to a specific range, and it is found that the embedding property at the time of hot pressing at a high temperature can be achieved. The opposite characteristics of non-exudative properties complete the present invention. Further, in the present invention, the high-temperature hot pressing is a press working using a hot plate heated to 100 ° C or higher. That is, 5 322464 201119854 The gist of the present invention is as follows. (1) A release film having the characteristics of a polyester-based elastomer (A) layer and a polyester (B) layer disposed on the surface layer, and the glass transition temperature of the polyester-based elastomer (A) is 〇 to The catching and crystallization speed index is 20 to 50. (:, Polyacetate (B) contains crystalline aromatic polyester (B1) and 1,4-cyclohexanol dimethanol copolymerized poly(p-dibenzoic acid ethylene diacetate (8)), mass ratio (called / ( B2 In the range of 5/95 to 50/50, the transfer temperature of the poly (8) glass is 4 〇 ι 8 〇 0 (: and the heat of crystallization heat is 5 to 40 J/g. (2). Release as in (1) The film polyester elastomer (A) has a glass transition temperature of 3 to 12 ° C and a crystallization rate of 25 to 48 < 3 (:, a crystalline aromatic polyester (B1) in the polyester (B) and丨, 4-cyclohexane-methanol copolymerized polyethylene terephthalate (B2) mass ratio (Βι ) / ( B2 ) is in the range of 10/90 to 50/50, polyester (B) glass The transfer temperature is 5 〇 to 73 &lt; t and the heat of crystal fusion is 8 to 35 J/g. (3) The release film of (1) or (2), wherein the polyester elastomer (a) is a poly A release film of a polybutylene terephthalate and a polyether. The release film of any one of (1) or (3), wherein the crystalline aromatic poly (B1) is a poly Butylene terephthalate, poly(trimethylene terephthalate), polyethylene terephthalate, isophthalic acid copolymerization Any one or a mixture of two or more of polyethylene terephthalate. The release film of any one of (1) or (4), wherein the structure of the laminated film is 322464 6 201119854 2 or (A) / (B) 2 is a two-layer, two-layer, two-layer (A) / (B) / (A) a. [Embodiment] [Formation for carrying out the invention] The following is a detailed description of the present invention. In the present invention, the green film of the month of the month has a layer of a polyester-based elastomer (A) disposed on the surface layer and a laminated film of the layer of the polyester (8). <Polyester-based elastomer (A)> Polyester The elastomer (A) layer is disposed on the surface layer of the release film to function as a release layer. If the layer of the poly-I-based elastomer (4) is not provided, the release property during hot pressing is lowered, for example, in a laminate using a cover film. In the hot pressing step, the film is easily peeled off, and the film is adhered to the laminate or the hot plate to contaminate it. For example, the 5-lanthanide elastomer (A) may be, for example, a high melting point crystalline segment and low. The block copolymer of the melting point segment is composed of a high-melting-point crystalline segment mainly composed of 纟. Ba savory scented vinegar unit, and the low-melting point segment is composed of aliphatic polyether unit and/or fat. It is composed of a fatty polyester unit. The copolymerization ratio of the high melting point crystalline segment and the low melting point in the polyacetal elastomer (A) is selected in addition to the monomers constituting each segment to satisfy the melting point described later. The glass transition temperature, the crystallization rate index, and the range of the heat of crystal melting are not particularly limited. However, it is preferable that the polyester elastomer (A) contains a low melting point of 5 to 50% by mass. In the elastomer (A), the crystalline aromatic polyester constituting the high-melting crystalline segment is preferably a polyester formed from an aromatic dicarboxylic acid component and an aliphatic diol component. In detail, § 'From the viewpoint of heat resistance or high crystallinity, 322464 7 201119854 points' should be polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-p-butadiene Acid propylene diester (ΡΓΓ). A polyester obtained from an aromatic dicarboxylic acid component or a diol component such as the following may be used as the crystalline aromatic polyester in addition to the above-mentioned PET, PBT, and PTT. Further, such a crystalline aromatic polyester may be copolymerized with any of PET, ΡΒτ, and PTT. The aromatic dicarboxylic acid component may, for example, be adipic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, dipyridyl-4,4,-di A carboxylic acid, a oxyethylidene dicarboxylic acid, a 5-an isophthalic acid, or the like. The monool component is preferably a diol having a molecular weight of 300 or less. Examples thereof include aliphatic diols such as ethylene glycol, propylene glycol, pentanediol, hexanediol, neopentyl glycol, and decanediol; 1,4-cyclohexanedimethanol, tricyclodecane dimethylol, and the like. Alicyclic diol; dimethyl diol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl Propane, bis[4_(2-hydroxy)phenyl]sulfone, anthracene, bis[4_(2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-p-terphenyl, An aromatic diol such as 4,4'-dihydroxy-p-tetraphenyl or the like. These dicarboxylic acid components and diol components may be used in combination of two or more kinds. The crystalline aromatic polyester may be a copolymer of a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional hydroxy acid component, a polyfunctional hydroxy component, or the like in a range of 5 mol% or less. In the polyester elastomer (A), the aliphatic polyfluorene constituting the low melting point segment may, for example, be a poly(ethylene oxide) diol or a poly(ethylene propylene oxide) diol, 322464 8 201119854 Poly(ethylene epoxide diol, poly(epoxy hexanyl) diol, epoxy ethene and ethoxylates, co-polymer of polyoxypropylene propylene glycol a polymer, a copolymer of ethylene oxide and tetrahydrofuran, etc. The aliphatic polyester constituting the low melting point segment may, for example, be poly(ε•caprolactone), polydecanolactone, polyvalerolactone, polyhexamethylene. Butic acid diester, polyethylene adipate, etc. Among these aliphatic polyethers and/or aliphatic polyesters, the elastic properties of the obtained polyester block copolymer are preferably poly(epoxy). Butadiene) diol, poly(ethylene oxide adduct of propylene propylene glycol, poly(ε_caprolactone), polybutylene adipate, polyethylene adipate, etc. It is preferably a poly(butylene oxide) diol. Further, the number average molecular weight of these low melting point segments is preferably about 300 to 6000 in the state of copolymerization. "Polyester elastomer (Α) glass The transfer temperature must be 〇 to 2〇C. If the glass transition temperature is lower than 0〇c, the release property and heat resistance during hot pressing are inferior, and further, the film forming workability is also lowered. If it exceeds 20. (:, buried The glass transition temperature of the polyester elastomer (A) is preferably from 〇 to 15. 〇. The melting point of the polyester elastomer (A) is preferably 2 〇〇〇 c or more. If the melting point is lower than 200 ° C, there is The heat resistance at the time of hot pressing is inferior. The polyester elastomer (A) must be sufficiently crystallized by a casting roll at the time of film formation. Therefore, the crystallization rate index of the poly(S) elastomer (A) must be 20 to 50C. The crystallization rate index is an index indicating the crystallization rate at the time of cooling after melting of the polyester elastomer (A). When the crystallization rate index exceeds 50 ° C, that is, the crystallization rate at the time of cooling after melting is slow. It is difficult to form the heat resistance of the layer s film, and the laminated film is directly heated by the roll to perform the ablation treatment, and the peeling failure from the roll occurs. If the crystallization rate is in the range of 32246 94 201119854, The resin is crystallized by a cooling roll after being melted, and the casting roll can be Temperature or speed regulates the crystallization state of the sheet. The crystallization rate index is preferably 25 to 5 (TC. The polyester elastomer (A) preferably has a heat of crystal fusion of 25 to 45 J/g. Heat resistance at less than 25 J/g. The release property is not sufficient, and if it exceeds μ J/g, the embedding property is liable to lower. The polyester elastomer (A) having the above crystallization characteristics is preferably a composition, for example, polyparaphenylene. The block copolymer of butylene phthalate and polyether == the copolymerization amount of the ether is preferably from 1 to 4% by mass, more preferably from b to 30% by mass. If the polyether is less copolymerized The softening effect is small, and the :3⁄4 Taixi is too low in heat or crystallinity. If it is such a range, it is easy to polymerize the melting point of the Japanese elastomer (4), the glass transition temperature, the crystallization rate index, the heat of crystal melting, and the like. . The polyester elastomer (A) can be produced by a known method. For example, a method in which a dicarboxylic acid, a lower alcohol, a low molecular weight diol, a low-molecular weight diol, and a low-melting point segment are subjected to a vinegar exchange reaction in the presence of a catalyst to obtain a condensation reaction of the obtained reaction product. . Alternatively, a method in which a dicarboxylic acid, an excess amount of a diol, and a low melting point component are subjected to an esterification reaction in the presence of a catalyst to obtain a condensation reaction of the obtained reaction product. Further, for example, a method in which a high-melting-point crystalline segment is prepared in advance and a low-melting-point segment component is added to be randomized by a transesterification reaction can be mentioned. A method of connecting a high-melting-point crystalline segment and a low-melting-point segment to a chain linking agent can be mentioned. Further, when poly(£-hexane vinegar) is used in the low melting point section, a method of adding an ε-caprolactone monomer to a high-melting crystalline segment may be mentioned. It can also be a method of either. 10 322464 201119854 <Polyester (B)&gt; In the release film of the present invention, it is necessary to laminate the above-mentioned polyester-based elastomer (A) layer which functions as a release layer, and as a hot press at a high temperature. The layer of polyester (B) embedded in the layer. In the case of the non-layer (B), when the film is taken up by the roll during the production of the film, wrinkles are generated due to the fragile body of the film, and the film forming workability is remarkably lowered, which is industrially difficult to produce. Further, the embedding property at the time of hot pressing at a high temperature is insufficient. The component constituting the polyester (B) layer must be a crystalline aromatic polyester (B1) and a polyethylene terephthalate (B2) copolymerized with 1,4-cyclohexanedimethanol. The mass ratio (Bl) / (B2) of the crystalline aromatic polyester (B1) constituting the polyester (B) layer to the i, 4 - cyclohexane dimethanol copolymerized polyethylene terephthalate (B2) must be For the range of 5/95 i 5G/5G, it is preferably in the range of 3〇/7〇 to 50/50. If the crystalline aromatic polyester (B1) does not reach the mass of 'B', the crystallinity of the layer (B) is too low, and the heat resistance at high temperature is lowered. = The tendency is to contaminate the parts due to the bleeding of the (B) layer. . If () is more than 50 s%, the crystallinity of the (8) layer is too high, and the embedding property at the time of high-temperature hot stamping tends to be poor. The glass transition temperature of the polyester (B) must be 4 Torr to 8 Torr. When the glass transition temperature is lower than 25 t, the film is softened at room temperature, so that the sheet is wrinkled during winding, and the workability such as cutting property at the time of cutting becomes insufficient. Further, if the glass transition temperature exceeds 8 Gt: the softening of the film becomes insufficient at the time of the clock, so the embedding property is poor. The glass transition temperature of the polyacetic acid (8) is preferably from Μ to °C, particularly preferably from 50 to 70. 〇 322464

II 201119854 The crystallization of calcined vinegar (B) must be 5 to 4 〇 j/g. If it is within this range, the (8) layer can fully exert the function of the support layer of the (4) layer, and f can have both heat resistance and burying property at high temperature and heat. If the heat of crystal fusion is less than 5 J/g ', the crystallinity is too low, so the heat resistance at the time of high temperature heat is poor, and when it is =, the (8) layer is oozing out from the end of the film. In addition, when the heat of the crystal is more than 40 J/g, the softening of the film at the time of the hot house is not filled, so the burial property is poor. The crystallization heat transfer amount of the poly (g) is preferably from (7) to 35 J/g ', particularly preferably from 15 to 3 Å; /§. <Crystalline Aromatic Polyester (Bl)&gt; Crystalline Aromatic «(3)) From the viewpoint of heat resistance or high crystallinity, for example, PET, PBT, PTT, and copolymers thereof with isophthalic acid and the like are mentioned. Or a mixture of two or more of these. The bright point of the crystalline aromatic polyester (B1) is preferably 200 ° C or higher. If the melting point is below 200. (: There may be a case where the heat resistance at the time of hot pressing is inferior. When the isophthalic acid is used to form a poly(p-phenylene) group, it is preferable to select a bright point as the above-mentioned range. The ratio of copolymerization is sufficient. Specifically, the ratio of the isophthalic acid component 'isophthalic acid' is preferably 20 mol% to T, particularly preferably 10 mol% or less. If it exceeds 20 mol%, the melting point and crystallinity of the _(8) layer are lowered, so that heat resistance at high temperature and hot pressing tends to be inferior. The crystalline aromatic polyester (B1) may be copolymerized in a range which does not impair the melting point and crystallinity of the (8) layer. The copolymerization component is not particularly limited, and examples of the acid component include isophthalic acid, phthalic acid, 2,6-naphthalene di(tetra), 5·sodium phthalate, oxalic acid, 322464 12 201119854 Diacid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid 'maleic anhydride, maleic acid, fumaric acid, itaconic acid, tumconic acid, mesaconic acid, cyclohexane Acidic acid such as dibasic acid, 4-pyruvic acid, hexanyl vinegar or lactic acid. Further, the 'alcohol component' may, for example, be ethylene glycol, diethylene glycol, 1,3-propanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, triethylene glycol or polyethylene glycol. , an ethylene oxide adduct of polypropylene glycol, polytetramethylene glycol, bisphenol A or bisphenol S, and the like. Further, a trifunctional compound such as trimellitic acid, trimesic acid, pyromellitic acid, trihydroxydecylpropane, glycerin or pentaerythritol can be used in a small amount. These copolymerizable components may be used in combination of two or more kinds. When two or more kinds of these crystalline aromatic polyesters are used in combination, the mixing ratio is considered to be the crystallinity of the (B1) resin, and may be appropriately selected. The crystalline aromatic polyester (B1) can be produced by a known method. For example, a method in which a lower alcohol diester of a monocarboxylic acid and an excessive amount of a low molecular weight diol are subjected to an exchange reaction in the presence of a catalyst to obtain a condensation reaction of the obtained reaction product. Alternatively, for example, a method in which a dicarboxylic acid and an excess amount of a diol are subjected to a transesterification reaction in the presence of a catalyst to obtain a condensation reaction of the obtained reaction product. ^Polymerized polyester contains a monomer or oligomer, a by-product B or tetrahydrogen, etc., so if it is directly used for hot pressing, it causes such a problem that it moves to the substrate. Therefore, it is preferred to use a raw material which is solid-phase polymerized at a temperature of 2 〇〇 ° C or more under reduced pressure or emotional body. 322464 13 201119854 <1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate (B2)&gt; 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate (hereinafter, The abbreviation "CHDM-PET" is a PET copolymer in which one part of ethylene glycol is substituted with cyclohexane dimethanol. In order to increase the degree of amorphization of the polyester (B) layer and to satisfy the embedding property at the time of hot pressing, the 1,4-cyclohexanedimethanol component is contained in an amount of 1% by mole or more, preferably 12%, based on the total diol component. Mole% or more, more preferably 15 mol% or more. Further, if the 14-cyclohexanedi-p-ol component is too much, the film tends to have a lack of heat resistance, and the upper limit is preferably 5 〇 mol%, more preferably 45 mol% or less, and most preferably 4 〇 mol% or less. Specific examples of such CHDM-PET include, for example, Eastman.

Chemical company "PETG 6763" and so on. The polyester elastomer (A), the crystalline aromatic polyester (5), and the CHDM-PET (B2) can be added with a heat stabilizer, an antistatic agent, a crystal nucleating agent, and the like in a non-destructive and practical range. Among them, it is preferred to contain a heat stabilizer. The heat stabilizer is preferably a 5-valent or/and trivalent scaly compound or a chelating compound. The release film of the present invention is preferably a polyester elastomer (A) layer having a thickness of 5 to 5 Å. When the thickness of the poly-I-based elastomer (4) layer is less than 5 when the resin is extruded, the flow between the layers (A) of the layer (A) is balanced and the flow marks are easily generated, which makes it difficult to form a film. If the excess is not enough. The thickness of the layer of the vinegar-based elastomer U) is more preferably from 1 〇 to 3 〇. Here, the thickness of the layer (A) is two layers of three layers, and the thickness of the layer (1) is two layers or more. a 322464 14 201119854 The release film of the present invention is preferably a polyester (B) layer having a thickness of 15 to 160 // m. If the thickness of the polyester (B) layer is less than 15/zm, the soft (A) layer at room temperature is relatively thicker, and since the body of the film becomes weak, the film is easily wrinkled when being wound up, or when hot pressed The softness is insufficient, resulting in a decrease in embedding. When it exceeds 160 #m, when the resin at the time of film production is extruded, the flow balance between the (A) layer and the (B) layer is deteriorated, flow marks are likely to occur, and film formation tends to be difficult. The thickness of the polyester (B) layer is more preferably from 20 to 100 / im. The release film of the present invention preferably has a thickness of from 30/zm to 200/m. When the thickness of the whole is less than 30/m, the strength and rigidity of the sheet are liable to be lowered, and the handling is difficult to change. Further, when it exceeds 200 # m, the traceability of the surface pattern of the printed substrate at the time of hot pressing is liable to be lowered, and it is not suitable for the production of a printed circuit board having a fine pattern. The thickness of the whole is preferably from 30/zm to 150#m, and most preferably from 40 #m to 100/z m. The preferred structure of the release film of the present invention may be, for example, two or three layers of (A)/(B)/(A) of the polyester elastomer (A) and the polyester (B), or Two types of two layers of A)/(B). However, the layer (A) is not limited to this, and the layer (A) may have other layers if it is disposed on the surface layer. The preferred thickness composition of the two types of three layers of (A) / (B) / (A) is 1/2/1 to 1/5/1. In this range, the layer (B) can sufficiently function as a support layer of the layer (A), and can have heat resistance and embedding property at the time of hot pressing at a high temperature. Next, a method of producing the release film of the present invention will be described. In the production of the release film of the present invention, a method of forming a film by a co-extrusion T-die method is preferred. According to this method, it is easy to adjust the thickness of each layer, or to make 15 322464 201119854 (A) layer the desired crystallization state. In the production of the release film of the present invention, it is necessary to provide a crystallization step for the purpose of imparting specific heat characteristics to the film and improving heat resistance and release property. The crystallization method may, for example, be a heating crystallization or an alignment crystallization. However, since dimensional stability at high temperatures is necessary in the application of hot pressing, there is no substantial alignment, and it is preferable to heat crystallization. The method of heating and crystallization is preferably a method of crystallization from the T die and cooling at the same time as cooling, and is preferable in terms of the simplicity of the control step or the film quality. When crystallizing at the same time as cooling, the crystallization rate is considered and the temperature of the casting rolls must be appropriately set. The temperature is preferably 50 to i0 (rc, more preferably 5 to 8 ° C.) in order to adjust the release property and embedding property, and the polyester which becomes the release layer must be used. The elastic body (A) is disposed on the side of the casting roll. The heat shrinkage rate of the release film of the present invention is preferably 2% or less in the MD direction, more preferably 丨 5% or less. For the following, it is more preferably 5%. If it is such a heat shrinkage rate, even if it is in contact with the hot plate during hot pressing, the stomach record becomes wrinkled, and the heat resistance and dimensional stability when manufacturing the printed substrate are good. In the release film of the present invention, the surface state of the polyester-based elastomer layer disposed on the surface layer can be smooth depending on the application, and the slip property and the pressure-resistant property can be imparted for workability. χ, the air is removed by hot pressing as the =, and a moderate embossing pattern can be provided on at least one side of the film. For this embossing process, a surface-processed casting roll can be used. It is excellent in embedding property, heat resistance, release property, and non-contamination property when it is hot pressed at high temperature, and can be disposed of safely and easily. 322464 16 201119854 The release film of the present invention is a hot-pressed copper foil laminate via a prepreg or a heat-resistant film in a manufacturing process such as a printed circuit board, a flexible printed circuit board, or a multilayer printed circuit board. In the case of a copper foil, it can be suitably used as a release film which is adhered to a hot plate, a printed circuit board, a flexible printed circuit board, a multilayer printed circuit board, etc. Further, in the manufacture of a flexible printed circuit board. In the step, when the cover film is adhered by a thermosetting adhesive by hot press forming, it may be suitably used as a release film for preventing adhesion between the cover film and the hot press plate or adhesion between the cover films. Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to the following examples. (Α) Polyester elastomer

(A-l) HYTREL 5557 : Toray Dupont, Tm 208 °C, Tg _20°C

(A-2) HYTREL 6347 : Toray Dupont, Tm 221 °C &gt; Tg 3°C

(A-3) HYTREL 7247 : manufactured by Toray Dupont, Tm 221 °C ' Tg 12 ° C

(A-4) HYTREL 6347M : Toray Dupont, Tm 215 °C &gt; Tg 3 °C

Tm means melting point and Tg means glass transition temperature. The following is the same. Any of the above four polyester-based elastic systems is a block copolymer of polybutylene terephthalate and polyether. (B1) crystalline aromatic polyester 322464 17 201119854

(B1-1) Polybutylene terephthalate: "Novaduran 50IOCS" manufactured by Mitsubishi Engineering Plastics Co., Ltd., Tm 223 ° C, Tg 34 ° C (B1-2 ) Polybutylene terephthalate; Shell "Corterra 9200" manufactured by Chemical Japan, Tm 223°C, Tg 52〇C

(Bl-3) Polyethylene terephthalate; "NEH-2050" manufactured by Ester Co., Ltd., Tm 255 ° C, Tg: 80 ° C

(Bl-4) stearic acid 4 mol% copolymerized polyethylene terephthalate, Tm 246 ° C, Tg: 75 ° C (B2) CHDM-PET • "PETG 6763" manufactured by Eastman Chemical Co., Ltd. , Tg 80〇C (C) other

• Polydecylpentene: "DX 845" manufactured by Mitsui Chemicals Co., Ltd., Tm 233 °C 'Tg 20 °C Various measurement methods and evaluations are shown below. The sample was centrifuged at a speed of 20 using a differential scanning calorimeter ("Pyrisl DSC" manufactured by Perkin Elmer Co., Ltd.). (: / / The temperature was raised to 260 ° C, and the glass transition temperature (Tg), the melting point (Tm), and the heat of crystal melting were measured. Further, after maintaining at 260 ° C for 3 minutes, the temperature was 20. (: / minute cooling, measurement of crystals The peak temperature (Tc) of the peak is the crystallization rate index when the melting point and the temperature of the crystallization peak are lowered. The sample in the measurement of the melting point (Tm), the glass transition temperature (Tg), and the crystallization rate index is The raw material resin is once melted and then quenched to obtain an amorphized sample. The heat of crystal melting of the layer (A) is a polyester elastomer (A) alone resin 'thickness, extrusion speed, casting roll temperature and lamination 18 322464 201119854 A single-layer film sample was prepared by the same method as the condition, and was measured using this. Even in the heat of crystal melting of the (B) layer, the crystalline aromatic polyester (B1) and CHDM-PET were similarly obtained. (B2) The resin to be blended was produced by the same production conditions as those of the laminated film, and was measured using the same. &lt;Film forming workability&gt; After the film end portion obtained by cutting was evaluated based on the following criteria The roll take-up and 〇 are qualified (good). There is no problem with the take-up of the roll. △: A little wrinkle when the roll is taken up. X: There is no wrinkle when the roll is taken up, it is difficult to take up &lt; heat resistance, non-exudation of the intermediate layer, embedding property, release property&gt; Both sides of the thick 25 # m polyimine film ("Kapton 100V" manufactured by Dupont Co., Ltd.) of 20#m epoxy-based adhesive ("AS-60" manufactured by Toagosei Co., Ltd.) were coated on both sides. A copper foil having a thickness of 35 #m was used to produce a three-layer copper foil laminate, and a thickness of 25/zm epoxy-based adhesive ("AS-60" manufactured by Toagosei Co., Ltd.) was applied to one surface thereof. A zm polyimide film ("Kapton 100V" manufactured by Dupont Co., Ltd.) was used as a cover film, and further, a release film for testing was stuck on both sides thereof. At this time, a polyester elastomer (A) which is a release film was used. The surface was placed on the inner side. Thereafter, the surface was heat-pressed at a temperature of 180 ° C and a pressure of 3 MPa for 5 minutes. After hot pressing, the film was quickly taken out from the hot press device and allowed to cool, and then the release film was peeled off. According to the following criteria, the evaluation of the heat, the non-exudation, the embedding, and the release property of the intermediate layer is carried out. The above is judged as qualified (good). The cover film is a true round hole with a diameter of 5 mm, which is used for the evaluation of the exudation of the adhesive. 19 322464 201119854 (Heat resistance) 〇: The film does not show wrinkles after hot pressing. △: After hot pressing The film can be slightly wrinkled. X: Significant wrinkles can be seen in the film after hot pressing. (Intermediate layer non-exudative) 〇: No seepage of the intermediate layer polymer is observed from the end of the film after hot pressing. : The exudation of the interlayer polymer can be seen from the end of the film after hot pressing. X: The exudation of the interlayer polymer can be clearly seen from the end of the film after hot pressing, which can be seen in the laminate or the hot plate. The polymer is attached. (Embedded property) The exudation length of the adhesive in the pore portion of the coating film was observed under a microscope, and evaluated based on the following criteria. ◎: The exudation length of the adhesive is 50 #m or less. 渗: The exudation length of the adhesive is more than 50#m, 70/zm or less. △: The exudation length of the adhesive is more than 70 # m, 100 # m or less X: Adhesive The bleed length is more than 100 # m (release property) ◎: detachment without resistance 〇: slightly impedance, but peeling off without affecting the laminate △: impedance, but the laminate is peeled without deformation X: strong impedance, Deformation accompanying the laminate at the time of peeling &lt;Contamination&quot;&gt; Using a thermal debonding GC-MS, the gas generated from the film was heated at 180 ° C for 10 minutes using a non-polar capillary to separate the detected peaks Total 20 322464 201119854 The amount of hexane in the area is normalized by the film weight as the amount of outgassing. The amount of outgassing should be a small amount, and it is judged to be qualified below 400 ppm ‘(good). &lt;Heat Shrinkage Ratio&gt; The heat shrinkage ratio in the film MD direction and the TD direction was measured in the following order. The sample film was cut into 10 mm x 150 mm, and five test pieces on which two lines were placed were prepared at intervals of 100 mm. The obtained test piece was heat-treated in an oven at 170 ° C for 30 minutes under no load, and the test piece was taken out and returned to room temperature to measure the distance between the lines. The heat shrinkage rate was determined according to the following formula, and the five average values were used as the heat shrinkage ratio of each sample film. 0 Heat shrinkage ratio (%) = (LL,) / Ax 1000 L: Distance between the lines before heat treatment (mm) , L': distance between the marked lines after heat treatment (mm). [Example 1] A pair of independent extruders were supplied with A-2 as the (A) layer resin, and B1-1 and B2 were supplied to have a mass ratio of 40/60 as the (B) layer resin, and the resin of either layer. They are all melt-kneaded at 260 °C. After the respective melts are combined into the three layers of A/B/A before reaching the exit of the T-die, ★ are extruded from the exit of the T-die, and are cooled by a casting roll adjusted to 80 ° C, and cooled. A laminated film having a layer thickness of A/B/A = 20/60/20 (#m) was obtained. The sealing time of the casting is 4 seconds. [Examples 2 to 12, Comparative Examples 1 to 5] Compared with Example 1, the layers of the layers (A) and (B) were used. 21 322464 201119854

The type of the resin, the B layer (5)) (the ratio of the blending ratio, the thickness of the layer is changed to a table... X

Comparative Examples 1 to 5 were carried out at 2:2 &lt; to 7, Example 10, _ ', C, and the examples 8 to 9 were melted at 280 ° C and exited from the T die exit. The resin to be extruded is adhered to a washing roll which has been adjusted to the temperature shown in Table 3. The other conditions were the same as those of the implementers, and two types of three-layer laminated films having a structure of A/B/A were obtained. The adhesion time of the casting rolls was 4 seconds. [Embodiment 13] t pairs of two independent extruders, respectively, are supplied with A-2 as a (4) layer tree. B1-1 and B2 have a mass ratio of 4 〇 / 6 作为 as (b) layer - 状 状 Μ 叱 26 叱 叱 。 。 Make each of the (4) stratified A/B layer 2 before the exit to the T die = 'Exit from the ^ head exit, close to the wash that has been adjusted to 8〇〇c~==2 to the layer A laminate film with a thickness of 趟Q (#m). The adhesion time of the roller was 4 seconds. [Examples 14 to 15 and Comparative Example 6] The type of the tree scorpion, the blending ratio of the layer B, and the layer thickness of each layer of the (4) layer and the (B) layer were changed to, for example, the same as in the embodiment 13'. '3 records. Then, it was made 26 (the TC melted and was ejected from the τ die outlet, and was also adjusted to the temperature shown in Tables 2 to 3. The conditions of the pot were the same as in Example i, and it was obtained. Two kinds of two-layer laminated films were formed. The adhesion time of the washing rolls was 4 seconds. [Comparative Examples 7 to 10] The resin shown in Table 3 was supplied to the extruder, and the mixture was condensed at 26 〇t and 322464. 22 201119854 = Cooling was carried out with a pound-washing roller adhered to the temperature shown in Table 4 to obtain a single-layer film having the thickness shown in Table 3. In the case of Lin, it was measured in seconds. The films produced in Examples 7 to 1 () are evaluated as non-bleeding of the single layer and the second layer. The layer ratio, various characteristics, and properties of the samples 1 to 15 'Comparative Examples i to 1' will be obtained. The results of the evaluation are shown in Tables i to 3. The B blend ratio shows the mass ratio. In each table, 322464 23 201119854 Example 12 A/B/A 10/50/10 A-2 40/60 S a CO § CO 00 CM 00 in 〇〇〇〇〇S I__I -0.3 Example 11 A/B/A 50/100/50 A-2 B1-1 40/60 ga CO 3 K CNJ CM CO CNJ oo ιο 〇〇〇0 ◎ 〇C 5 Example 10 A/B/A 5/20 /5 A-2 B1-1 40/60 sa CO ? R CNJ CO CM c〇m 〇〇〇0 0 I 实施 Example 9 A/B/A 20/60/20 A-2 B1-4 40/60 § δ CO 5 240 s σ&gt; in 〇0 〇◎ 〇§ I is -0.7 Example 8 A/B/A 20/60/20 A-2 B1-3 40/60 § § CO 9 s 250 CO CO P 〇〇〇〇◎ S 1.8 ! -0.7 Example 7 A/B/A 20/60/20 A-2 B1-2 40/60 ga CO o S csi in CSi 00 CO 〇〇〇〇〇160 m -0.5 Example 6 A/B/A 20/60/20 A-2 B1-1 10/90 ga CO s CO 00 〇〇〇 ◎ 〇〇q -0.4 Example 5 A/B/A 20/60/20 A -2 B1-1 50/50 ga CO K ass 〇〇〇〇◎ 2 σ Example 4 A/B/A 20/60/20 A-4 B1-1 40/60 g 刁ossa CO CSi CO in 〇〇 〇〇◎ 〇α7 CNJ Example 3 A/B/A 20/60/20 A-3 B1-1 40/60 gn SJ CM wear 3 aa CO in 〇〇〇〇 ◎ 〇 0) g Example 2 A/ B/A 20/60/20 A-2 B1-1 40/60 8 a CO KS CO CM 00 to 0 〇〇 ◎ ◎ 0.8 实施 Example 1 A/B/A 20/60/20 A-2 B1- 1 40/60 § a CO OT K a CO CM CO LO 0 〇〇〇〇S ί 15 CO layer layer thickness (/im) A layer resin crystalline aromatic polyester ( Bl) B layer &amp; mass ratio (B1) / (B2) j casting roll temperature (°c) Tm (°C) Tg (°c) crystallization rate index (°c) Tm (°C) Tg (° C) Film-forming workability Heat-resistant intermediate layer Non-exudative Buried release pollution (released ppm) f MD direction heat shrinkage rate 00 1 TD direction heat shrinkage rate (X) QQ resin B oa Performance evaluation 24 322464 201119854 [Table 2] Example 13 Example 14 Example 15 Layer Composition A/BA/BA/B Layer Thickness (//m) 30/70 10/40 20/60 A layer resin A-2 A-3 A- 4 B layer crystalline aromatic polyester (B1) BH B1-1 B1-1 Resin B layer blending mass ratio (B1) / (B2) 40 / 60 40 / 60 40 / 60 casting roll temperature (°C) 80 80 60 Tm(°C) 221 223 215 A layer Tg(°C) 3 12 3 Crystallization speed index rc) 48 46 25 ZlHm(J/g) 37 43 38 Tm(°C) 221 221 221 B layer ZlHm(« J/g) 28 28 28 Tg(°C) 58 58 58 Film-making workability, heat-treating, intermediate layer, non-exudation, 〇〇〇 performance, embedding ◎ 〇 ◎ Evaluation of release 〇 ◎ ◎ Contaminant (released gas ppm) 160 110 140 MD direction heat shrinkage rate (%) 1.7 1.4 1.2 TD Thermal contraction rate (9〇0.2 0.4 0.1 25 322464 201119854 [e&lt;&gt;] Comparative Example 10 &lt; g B1-l/B2=40/60 I g CM S in CO csj I 〇X ◎ X 180 T- C'i Ό.5 Comparative Example 9 &lt; 8 T - Ο I g 233 in CO II 〇〇〇 ◎ - 1400 ! 0.8 5 Comparative Example 8 &lt; S Β1-1 II § n Si § !〇II i 〇〇1 X ◎ S * - 0.6 5 Comparative Example 7 8 Α-2 II § δ CO IIIX l &lt;\ &lt; I &lt; 〇§ 0.8 Comparative Example 6 A/B 30/70 Α-1 B1-1 40/60 § 200 CO CNi GO CM s &lt; X ϊ &lt; 〇◎ X 〇T-2_3 -0.7 Comparative Example 5 A/B/A 20/60/20 5 B1-1 40/60 § 200 o 00 csi a 00 CM S &lt X l &lt; 〇 ◎ X 〇 1.8 -0.3 Comparative Example 4 A/B/A 20/60/20 Α-2 B1-1 60/40 s δ CO S 〇s 〇〇〇X 1 &lt; 〇0.9 5 Comparative Example 3 A/B/A 20/60/20 Α-2 i 0/100 § 222 CO !? 3 I 〇g 〇&lt;1 X ◎ 〇S Ί— 2.4 〇. Comparative Example 2 A/B/A 20/60/20 Α-2 B1-1 100/0 § τ— CM OJ CO CO s OJ ΙΛ 荛〇〇〇X 〇§ 0.8 〇Comparative example 1 A/B/A ! 20/60/20 Β1- 1 I 5 100/0 § 223 Ο g CM CO CM I 〇〇〇X 1 &l t;1 ◎ 〇T— 5 layer composition|layer thickness (jum) | Α layer resin crystalline aromatic polyester (Bl) B layer compounding mass ratio (B1)/(B2) I casting roll temperature (°c) Tm (°C) Tg(°C) I Crystallization speed index rc) ZlHm (J/g) Tm(°C) Tg(°C) Film-forming work-resistant heat-resistant intermediate layer non-exudative embedding release resistance Contaminant (exhaust gas ppm) MD direction heat shrinkage rate (3⁄4), TD direction heat shrinkage rate (9〇CQ resin CO performance evaluation 26 322464 201119854 ^ Real palladium examples 1 to 15 of the sheet system various characteristics are specified in the present invention _Inner's is completely full ^ as the required performance of the release type. In particular, since it is excellent in release property and embedding property at the time of high-temperature hot pressing, it is possible to cope with a printed circuit board having the precision of Fig. 3L, and has a small amount of outgassing and excellent stain resistance. In Comparative Example 1, the release layer was polybutylene terephthalate and the intermediate layer was a polyester elastomer. Therefore, although the release property is good, the glass transition temperature and the crystal heat dissipation are high, so the embedding property is poor. - Comparative Example 2 is a release layer of a polyester elastomer and an intermediate layer of polybutylene terephthalate. Therefore, the crystal melting heat is high and the embedding property is poor. In Comparative Example 3, since the intermediate layer did not contain the crystalline aromatic polyester, the intermediate layer was in an amorphous state. Therefore, although the embedding property is good, the heat resistance is poor, and the bleed out of the polymer derived from the intermediate layer is remarkable. In Comparative Example 4, the content of the crystalline aromatic polyester in the intermediate layer was too large, and the crystallinity of the intermediate layer was too high, so that the embedding property was poor. In Comparative Examples 5 and 6, the glass transition temperature of the release layer was too low, so that the embedding property was good, but the heat resistance or the release property was poor, and the film was broken during the filming. In Comparative Example 7, the polyester-based elastomer single layer did not have the polyester layer of the intermediate layer. Therefore, the film body was weak, the film forming workability was poor, and the flexibility at the time of hot pressing was insufficient, so that the embedding property was also insufficient. Comparative Example 8 is a single layer of polybutylene terephthalate, and since the crystallinity is too high, the release property or heat resistance is good, but the embedding property is poor. Comparative Example 9 is a film composed of polymethyl decene which is widely used as a release film, but 'the outgassing generation is as large as about 1 〇 322 464 27 201119854 times of the film of the present invention, which is poor in pollution resistance. . The comparative example ίο does not have a release layer composed of a polyester elastomer. Therefore, although the embedding property at the time of hot pressing is excellent, the crystallinity of the film is low, so heat resistance or release property is inferior. [Simple description of the diagram] None. [Main component symbol description] None. 322464 28

Claims (1)

201119854 - VII. Patent application scope: ι_ A release film characterized by a polyester elastomer (A) layer disposed on the surface layer, and a polyester (B) layer, and a polyester elastomer (A) The glass transition temperature is 〇 to 2 (rc and the crystallization rate is 20 to 50, the polyester (B) contains the crystalline aromatic polyester (B1) and the cyclohexanedimethanol copolymerization pair Ethylene phthalate (B2), mass ratio (B1) / (B2) is in the range of 5/95 to 50/50, and polyester (B) is glass transition temperature of 4 〇 to 8 〇 ° C and crystallization The heat of fusion is 5 to 40 J/g. 2. The release film according to claim 1, wherein the polyg-type elastomer (A) has a glass transition temperature of 3 to 12 and the crystallization rate index The quality of the copolymerization of the crystalline aromatic polyester (B1) in the polyester (B) with iota, 4·cyclohexanone, and the polyethylene terephthalate (Β2) at 25 to 48 ° C The ratio (Bl) / (Β2) is in the range of 10/90 to 50/50, and the polyester (Β) glass transition temperature is 50 to 73. (: and the heat of crystal melting is 8 to 35 J/g. Article 1 or 2 of the patent scope The film-type film, wherein the polyester-based elastomer (A) is a block copolymer of polybutylene terephthalate and a polyether. 4. The release film according to claim 1 or 2, Among them, the crystalline aromatic polyester (B1) is polybutylene terephthalate, poly(p-propylene bis-dicarboxylate), polyethylene terephthalate, and copolymerization of diphenyl phthalate 1 322464 201119854 Any one or a mixture of two or more of polyethylene terephthalate. 5. The release film according to claim 1 or 2, wherein the composition of the laminated film is (A) / (B) / (A) 2 kinds of 3 layers, or (A) / (B) of 2 kinds of 2 layers. 322464 201119854 Fourth, the designated representative map: This case has no schema. (1) The representative representative of the case is: (2) Simple description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 0 322464