JP2011005780A - Mold release film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mold release film which is excellent in adhesiveness between respective layers, particularly in shape followability to uneven portions, and has high reduction effect for bleeding of an adhesive at a coverlay opening part, and is more inexpensive.SOLUTION: A multilayer structure has an intermediate layer comprising a resin composition containing an ethylene-α-olefin copolymer resin (E) having a melting point of 50-110°C of 80-50 pts.mass, an epoxidized polyolefin resin (F) having a melting point of 50-110°C of 5-20 pts.mass, and a polybutylene terephthalate-based resin (G) having a bending elastic modulus of 600 MPa or less of 15-30 pts.mass with respect to the resin component of 100 pts.mass between two-layer mold release layers comprising a resin composition wherein a mass ratio of polybutylene terephthalate-based resin (A) obtained by copolymerizing a diol compound as a third component to a polymethylpentene resin (B) is 100:20 to 100:5. In the mold release film, the mold release layer:the intermediate layer=1:10 to 1:3, and the total thickness is 20-160 μm.

Description

  The present invention relates to a release film and a method for manufacturing the release film, and the release film is suitable for a hot press process in a manufacturing process of a printed wiring board, a flexible printed board (hereinafter referred to as “FPC”), a multilayer printed wiring board, and the like. It is used for.

  The heat pressing process in the manufacturing process of printed wiring boards, FPCs, multilayer printed wiring boards, etc. is a process of bonding and laminating a copper circuit and a coverlay film having an open connection portion with a thermosetting adhesive. In the process, hydraulic pressure bonding is performed from above and below with a hot plate provided with silicone rubber.

  When performing the hot pressing process, (1) prevention of silicon migration to the circuit board, (2) prevention of adhesive bleeding to the connection part, and (3) prevention of problems occurring in the circuit such as damage to the coverlay. For the purpose of the above, a release film for preventing contact between the heat plate provided with silicone rubber and the circuit and cover lay film is used.

  Today, various types of release films are known, such as silicon-coated release films, mainly fluorine-based release films made of polytetramethylfluoroethylene (PTFE) (Patent Document 1). , Polymethylpentene release film (Patent Document 2), polybutylene terephthalate (PBT) release film (Patent Document 3, Patent Document 4) and the like.

  Patent Document 5 discloses an ethylene-α-olefin copolymer resin, and Patent Document 6 discloses an epoxidized olefin resin.

JP-A-9-187898 (Claims etc.) JP 2006-212954 A (Claims etc.) JP 2007-84760 A (Claims etc.) JP 2007-98816 A (Claims etc.) JP 2000-53789 A (Claims etc.) JP 2007-106843 A (Claims etc.)

  However, with today's high performance of printed wiring boards, FPCs, multilayer printed wiring boards, etc., and with the emergence of disposal treatment problems, the existing known release films are not always satisfactory. I came.

  For example, when a silicon-coated release film is used, silicon on the release film surface may move to the printed wiring board and impair the quality of the printed wiring board, resulting in poor contamination. In addition, the fluorine-based release film as described in Patent Document 1 is excellent in heat resistance and releasability, but is expensive and difficult to burn at the time of waste incineration treatment after use, and toxic gas. There is a disadvantage that it occurs. Furthermore, the polymethylpentene release film described in Patent Document 2 is also excellent in release properties and heat resistance, but is also expensive, and a single layer cannot sufficiently exhibit cushioning properties.

  On the other hand, PBT release films such as those described in Patent Document 3 and Patent Document 4 have fewer factors that impair the quality of the substrate than the above-mentioned silicon coat release films and fluorine release films. Because of its heat resistance and easy disposal, it is expected as a release film material. However, the PBT release film is inferior to the release property compared to the silicon coat release film and the fluorine release film, and the PBT homopolymer has a high rigidity and has a shape followability to the unevenness of the FPC substrate. Inferior. Further, the PBT copolymer is flexible, but has a drawback that it is inferior to the mold release property of the PBT homopolymer and the film is likely to be blocked.

  In particular, when pressing an FPC having a high degree of circuit fineness, if the shape followability is not sufficient, there is a problem that the thermosetting adhesive sometimes protrudes from the opening of the coverlay film during the hot pressing process. Therefore, the shape followability to the uneven | corrugated | grooved part more excellent was calculated | required.

  A release film having a multilayer structure is also conceivable, but such a release film is required to have good adhesion between the respective layers, and further, a low-cost release film is desired.

  Therefore, the object of the present invention is to provide a release film that is excellent in releasability, uniform moldability, and easy to dispose of after use. An object of the present invention is to provide a release film that has a high effect of reducing bleeding into an adhesive at a cover lay opening and is less expensive.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a release film having a multilayer structure having a release layer using a specific resin component and an intermediate layer therebetween. It has been found that the solution and the object can be achieved, and the present invention has been completed.

That is, the release film of the present invention comprises a polybutylene terephthalate resin (A) copolymerized with a diol compound as a third component and a polymethylpentene resin (B) as main components, and resin (A): resin. Between two release layers composed of a resin composition having a mass ratio of (B) of 100: 20 to 100: 5,
80 to 50 parts by mass of an ethylene-α-olefin copolymer resin (E) having a melting point of 50 to 110 ° C. and an epoxidized polyolefin resin (F) having a melting point of 50 to 110 ° C. with respect to 100 parts by mass of the resin component 5 to 20 parts by mass, and a multilayer structure having an intermediate layer made of a resin composition containing 15 to 30 parts by mass of a polybutylene terephthalate resin (G) having a flexural modulus of 600 MPa or less,
The thickness ratio between the release layer and the intermediate layer is a release layer: intermediate layer = 1: 10 to 1: 3, and the total thickness is 20 to 160 μm.

  Moreover, the release film of this invention consists of a resin composition in which the said release layer contains 50 mass parts or more of said resin (A) and said resin (B) with respect to 100 mass parts of said resin components. Preferably, the release layer is made of a resin composition containing 30 parts by mass or less of polybutylene terephthalate homopolymer (C) with respect to 100 parts by mass of the resin component.

  Furthermore, as for the release film of this invention, the said release layer is 1-10 mass parts of compatibilizers (D) of the said resin (A) and the said resin (B) with respect to 100 mass parts of said resin components. It is preferable to consist of the resin composition containing.

  Furthermore, the release film of the present invention is a linear low density ethylene-α-olefin copolymer resin obtained by polymerizing the ethylene-α-olefin copolymer resin (E) using a metallocene catalyst. Preferably there is.

  The release film of the present invention has a melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg of the ethylene-α-olefin copolymer resin (E) and the epoxidized polyolefin resin (F), It is preferable that it is 2-15 g / 10min.

  Furthermore, in the release film of the present invention, it is preferable that one or both surfaces of the release layer surface are roughened, and when the release layer surface melt-extrusion-molds the resin composition, It is preferable that the roughening process is given by making it contact with the surface-roughened cooling roll. Moreover, it is preferable that the said release layer surface is roughened by the handle | pattern in which uniform unevenness | corrugation is formed over the whole surface.

  The method for producing a release film of the present invention is characterized in that the resin composition for a release film is kneaded and melted, and then molded by coextrusion with a multilayer T-die molding machine.

  Moreover, it is preferable that the manufacturing method of the release film of this invention is made to contact the cooling roll by which the surface roughening was carried out when melt-extruding film shaping | molding of the said resin composition.

  According to the present invention, in a release film that is excellent in releasability, uniform moldability, and easy to dispose of after use, the adhesion between each layer is good, in particular, excellent in shape followability to uneven parts, It is possible to provide a release film that has a high effect of reducing bleeding into the adhesive at the cover lay opening and is less expensive.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The resin composition forming the release layer of the release film of the present invention comprises a polybutylene terephthalate resin (A) (hereinafter referred to as “resin (A)”) obtained by copolymerizing a diol compound as a third component, Methylpentene resin (B) (hereinafter referred to as “resin (B)”) is a main component, and the mass ratio of resin (A): resin (B) is 100: 20 to 100: 5. When the mass ratio of the resin (A): resin (B) is higher than the ratio of the resin (B) than 100: 20, the thickness of the resin (A) and the resin (B) is reduced due to uneven mixing due to the change in dispersibility. And a uniform film formation becomes difficult. On the other hand, when the ratio of the resin (A) is higher than the mass ratio of 100: 5, the mold release property and the shape followability are inferior. Preferably, the resin (A) and the resin (B) are contained in a total of 50 parts by mass or more with respect to 100 parts by mass of the resin component. When this total amount is less than 50 parts by mass, it cannot be said that shape followability is sufficient.

  The resin (A) that can be used in the present invention is a polycondensation of a dicarboxylic acid component mainly composed of terephthalic acid or an ester-forming derivative thereof and a diol component mainly composed of 1,4-butanediol or an ester-forming derivative thereof. A copolyester obtained by copolymerizing a polyester mainly composed of PBT repeating units with a diol compound as a third component.

  As the third component diol compound, alkylene glycol can be suitably used. For example, diol compounds such as ethylene glycol, propylene glycol, hexamethylene glycol, polyethylene glycol, polytetramethylene glycol, bisphenol A, and ethoxylated bisphenol A can be used. Among them, polytetramethylene glycol is particularly preferable.

  Resin (A) that can be used in the present invention is a polybutylene terephthalate homopolymer contrast, crystallinity, and rigidity imparted with flexibility by copolymerizing a diol as a third component, Such a resin (A) can be obtained on the market as, for example, a Novaduran (registered trademark) series manufactured by Mitsubishi Engineering Plastics Co., Ltd.

  In addition, the resin (B) that can be used in the present invention is not particularly limited with respect to its molecular weight, crystallinity, etc., but a low-rigidity resin is selected because it does not reduce the shape followability of the release film. It is preferable to do. Such a resin (B) can be obtained on the market as, for example, a TPX (registered trademark) series manufactured by Mitsui Chemicals, Inc.

  In the resin composition for a release film of the present invention, only the resin (A) and the resin (B) can be used as the base material as the resin component, but the amount of the diol compound as the third component of the resin (A) is As the amount increases, the melt flow rate of the resin (A) increases, and the moldability to the release film is somewhat inferior. Therefore, in consideration of the moldability of the release film, the polybutylene terephthalate homopolymer (C) (hereinafter referred to as “homopolymer (C)”) having a flexural modulus of about 2400 MPa as a single unit is used in combination. Can also be improved.

  Such homopolymer (C) is preferably blended at 30 parts by mass or less with respect to 100 parts by mass of the resin component. If the blending amount exceeds 30 parts by mass, shape followability is inferior, and bleeding of the adhesive tends to occur.

  Since the resin (A) used in the present invention has a high polarity, while the resin (B) is a low polarity resin, a compatibilizing agent is used to maintain the dispersibility of the resin (A) and the resin (B). May be added. The compatibilizing agent is not particularly limited, but is preferably a nonpolar polypropylene (PP) portion and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid having polarity. Mention may be made of modified low molecular weight polypropylene. Such a low molecular weight polypropylene resin can be obtained on the market as, for example, the Yumex (registered trademark) series manufactured by Sanyo Chemical Industries.

  It is preferable that the compounding quantity of a compatibilizing agent is 1-10 mass parts with respect to 100 mass parts of resin components. When this amount exceeds 10 parts by mass, the surface state of the film changes due to a change in dispersibility, the releasability is lowered, and the heat resistance necessary for the release film may be lowered. On the other hand, if this amount is less than 1 part by mass, the effect of improving dispersibility by adding a compatibilizer cannot be obtained.

  In producing the release layer of the release film of the present invention, since the resin (A) and the resin (B) are inherently insoluble, in addition to the use of a compatibilizing agent, they are uniformly dispersed and homogenized. In order to form a thin film, it is preferable to form the film using an extruder having a mixing zone or a T-die type extruder having a dull image type single screw extruder. The molding temperature is preferably 230 to 260 ° C. in consideration of the melting points of polybutylene terephthalate resin and polymethylpentene resin, and the die temperature is particularly preferably 250 to 260 ° C. At this time, as the resin composition to be used, a dry blend using a blend mixer can be suitably used.

  The resin component contained in the resin composition forming the intermediate layer of the present invention is easy to obtain, has a good balance with cost, and has excellent moldability as well as excellent shape followability. Therefore, a resin excellent in flexibility during heating is desirable. In addition, for the fluidity of the resin, before the adhesive at the cover lay opening protrudes, it is necessary to form the concavo-convex portion quickly, a certain degree of high fluidity is required, and It is desirable that there is no problem in film formation by co-pressing with the release layer. Further, from the viewpoint of film formation by co-pressing, it is desirable that a certain degree of adhesive force can be maintained with the release layer.

  The copolymer resin (E) (hereinafter referred to as “resin (E)”), which is the main component ethylene-α-olefin of the intermediate layer resin, has sufficient elasticity and heating in order to obtain a high unevenness formability. It is necessary to have the flexibility of time, and the melting point is 50 to 110 ° C. When the melting point is higher than the above range, the uneven shape forming property is not sufficient, and when the melting point is lower than the above range, the film is significantly deformed due to melting of the resin and cannot be used.

  Further, regarding the fluidity during heating of the resin (E), it is possible to achieve both of the above-mentioned rapid shapeability to the concavo-convex portion and fluidity that does not hinder the film formation by co-pressing with the release layer. Therefore, a resin having a melt flow rate (hereinafter referred to as MFR) at 190 ° C. under a load of 2.16 kg of 2 to 15 g / 10 min, more preferably 5 to 12 g / 10 min is desirable. When MFR is lower than the above range, the fluidity at the time of hot pressing is low, and the effect of reducing the bleeding into the FPC adhesive is not sufficient. When the MFR is higher than the above range, the fluidity of the intermediate layer is relatively high during film formation by co-pressing, so that the film formation stability is lowered, which causes uneven appearance and occurrence of surging during extrusion. .

  Examples of the resin (E) include linear low density ethylene-α-olefin copolymer resins polymerized using a metallocene catalyst. For example, Evole manufactured by Mitsui Chemicals, Japan Polyethylene Co., Ltd. Available in the market as a kernel series.

  In the case of the resin (E) alone, the release layer and the intermediate layer are not adhesive, and peeling may occur between the release layer and the intermediate layer during handling or hot pressing. In order to impart adhesiveness, an epoxidized polyolefin resin (F) (hereinafter referred to as “resin (F)”) is added. Details of the composition of the epoxidized polyolefin resin (F) are described in JP-A No. 2007-106843.

  The resin (F) is desirably a material that is highly compatible with the resin (E) that is the main component of the intermediate layer and that does not deteriorate the function and film forming property of the intermediate layer by blending with the resin (E). The type of polyolefin used as the base is not particularly limited, but polyethylene having high compatibility with the resin (E) is most suitable. The melting point of the resin (F) is 50 to 110 ° C., and the MFR is 2 to 15 g / 10 min. More preferably, it is 5 to 12 g / 10 min, and it is desirable to be similar to the resin (E). Such resin (F) is commercially available as, for example, Bond First Series manufactured by Sumitomo Chemical Co., Ltd.

  By blending the resin (E) and the resin (F) in the intermediate layer, it is possible to obtain a high uneven shapeability, but it prevents delamination between the film release layer and the intermediate layer, Since a certain amount of the resin (F) is added to maintain the adhesiveness, an increase in raw material cost is inevitable compared to the case of the resin (E) alone. Therefore, in order to maintain the adhesion between the release layer and the intermediate layer and reduce the amount of the resin (F) added, the polybutylene terephthalate resin (G) (hereinafter referred to as “below”) having a flexural modulus of 600 MPa or less. It is important to add resin (G) ”. By adding the resin (G), good adhesion between the release layer and the intermediate layer can be realized at a low cost without affecting the uneven shape forming property and the film forming property. As this resin (G), it can obtain on the market, for example as NOVADURAN series made by Mitsubishi Engineering Plastics Co., Ltd.

  The resin component is obtained by dry blending or melt blending. The resin component (E) is 80 to 50 parts by mass, the resin (F) is 5 to 20 parts by mass, and the resin (G) is 15 to 30 parts by mass with respect to 100 parts by mass of the resin component. It is preferable that (E) is in the range of 70 to 60 parts by mass, the resin (F) is in the range of 10 to 15 parts by mass, and the resin (G) is in the range of 20 to 25 parts by mass.

  When the relative ratio of the resin (E) is higher than the above range, the interlayer strength of the release layer / intermediate layer of the film is not sufficient, and peeling between the release layer / intermediate layer and film disassembly occur. In addition, when the relative ratio of resin (E) is lower than the said range, it is the same as that of the case where the relative ratio of resin (F) described below is high, and the case where the relative ratio of resin (G) is high.

  In addition, when the relative ratio of the resin (F) is higher than the above range, the cost of the raw material for production increases. On the other hand, when the relative ratio of the resin (F) is lower than the above range, the release layer / intermediate layer of the film The interlayer strength of the film is not sufficient, and peeling between the release layer / intermediate layer and film disassembly occur. Furthermore, since the resin (F) has a function as a compatibilizing agent for the resin (E) and the resin (G) at the same time as imparting adhesiveness to the film release layer, an extruder having a high kneading ability is used. When not used, the dispersibility of the resin (E) and the resin (G) decreases.

  Moreover, when the relative ratio of resin (G) is higher than the said range, the flexibility at the time of heating of a film will fall, uneven | corrugated shapeability will fall, and also the compatibility effect of resin (F) will become insufficient, and it is favorable A film is not obtained. On the other hand, when the relative ratio of the resin (G) is lower than the above range, the interlayer strength of the release layer / intermediate layer of the film is not sufficient, and peeling between the release layer / intermediate layer and film disassembly occur.

  The ratio of the thickness of the release layer and the intermediate layer is release layer: intermediate layer = 1: 10 to 1: 3, preferably release layer: intermediate layer = 1: 6 to 1: 4. . Release layer: intermediate layer = 1: 10 If the intermediate layer is thicker, there is a risk that the releasability will be lowered due to thinning of the release layer. Further, when the intermediate layer is thinner than the release layer: intermediate layer = 1: 3, the shape followability is not sufficient.

  The total thickness of the release film to which the present invention is applied is 20 to 160 μm, preferably 30 to 130 μm. When the film is less than 20 μm, it is difficult to form the film itself because it is a thin layer, and furthermore, since the total thickness is thin, it is difficult to form each layer. Furthermore, when roughening is performed by contact with an embossing roll, the release layer may be destroyed. On the other hand, when it exceeds 160 μm, the film thickness increases, so that the rigidity becomes high and the shape followability becomes insufficient.

  The release film of the present invention has a multilayer structure having the intermediate layer between two release layers, the release property is imparted by the release layer, and the shape followability is imparted by the intermediate layer. If it has the said mold release layer and intermediate | middle layer, unless the effect of this invention is impaired, you may have a layer which consists of another resin composition.

One or both surfaces of the release layer surface of the release film used in the present invention can be subjected to a surface roughening treatment to such an extent that the object of the present invention is not hindered. By performing the surface roughening treatment, it is possible to prevent the occurrence of unevenness and wrinkles due to thermal shrinkage when the release film is used in a hot press. When performing the surface roughening treatment, the three-dimensional center plane average roughness SR _a of the release layer surface is preferably be such that 0.3 to 10 [mu] m, further, to ensure that the 0.5~5μm Is preferred. If the average roughness of the three-dimensional center plane is less than 0.3 μm, the air in the space between the unevenness due to the heat shrinkage of the release film and the circuit part is difficult to escape, so the effect of suppressing folding wrinkles can be obtained well. Disappear. On the other hand, when the thickness exceeds 10 μm, the degree of unevenness of the release surface becomes excessively large, which may lead to variations in pressure during hot pressing and bleeding of the adhesive.

  The dynamic friction coefficient μd between the release layer of the film and the circuit portion that is the release surface is preferably 0.30 or less. When the dynamic friction coefficient exceeds this value, the slipperiness decreases, so that the release film may not easily move in the surface direction.

  The shape and pattern of the surface unevenness is not particularly limited, but a pattern in which uniform unevenness is formed over the entire surface within a range in which a suitable value of the three-dimensional center plane average roughness is obtained is preferable. For example, a matte tone is preferable. In the case of a pattern with little surface roughening such as a glossy tone, there is a possibility that the effect of reducing the wrinkle cannot be obtained. Irregular uneven patterns and patterns are not suitable because the pressure on the circuit portion becomes non-uniform during pressurization.

  As the film surface roughening method, it is desirable to use a conventionally known method as long as the surface state of the release layer suitable for the present invention can be realized. Among them, since there is no increase in the number of steps, a surface roughening method by contact with an embossing roll is preferable when extruding a molten resin using a T-die type extruder. For the roughening process, a surface-cooled cooling roll is preferable.

  The resin composition constituting the release film of the present invention includes a heat stabilizer, an antioxidant, an anti-aging agent, a rust preventive, a copper anti-damage stabilizer, and an antistatic agent within the range not impairing the object of the present invention. Needless to say, various known additives such as additives can be blended. These may be used individually by 1 type, or may be used in combination of 2 or more type.

Hereinafter, the present invention will be described based on examples.
Example 1
80 parts by mass of PBT copolymer obtained by copolymerizing polytetramethylene glycol as a third component as a release layer material (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trademark registration: Novaduran 5505S, hereinafter referred to as “resin (A)”) 20 parts by mass of PBT homopolymer (Mitsubishi Engineering Plastics Co., Ltd., trademark registration: Novaduran 5026, hereinafter referred to as “resin (C)”), polymethylpentene (Mitsui Chemicals Co., Ltd., trademark registration: Using 10 parts by mass of TPX MX002 (hereinafter referred to as “resin (B)”), these were dry blended with a blend mixer. In addition, about the PBT resin of resin (A) and resin (C), what was previously dried at 120 degreeC with the hot air dryer for 8 hours was used.

As an intermediate layer material, a linear low density ethylene-α-olefin copolymer polymerized using a metallocene catalyst (manufactured by Nippon Polyethylene Co., Ltd., trademark registration: Kernel KC570S (d = 0.906 g / cm ³⁾ , Melting point: 102 ° C., MFR = 10.5), hereinafter referred to as “resin (E)”) 70 parts by mass, epoxidized polyolefin resin (manufactured by Sumitomo Chemical Co., Ltd., trademark registration: Bond Fast 7M (d = 0.960 g) / Cm ³ , melting point 52 ° C., MFR = 7), hereinafter referred to as “resin (F)”) 10 parts by mass, and polybutylene terephthalate resin having a flexural modulus of 600 MPa or less (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) Trademark registration: 20 parts by weight of Nova Duran 5510S melting point 219 ° C. (hereinafter referred to as “resin (G)”) It was blended. Resin (G) used was dried in advance with a hot air dryer at 120 ° C. for 8 hours.

  The resin composition dry-blended as described above was kneaded and melted with a dull mage type three-layer single-screw extruder, and then co-extruded from a T die, and the ratio of the thicknesses of the layers was determined as release layer: intermediate layer: release A three-layer film having a layer = 1: 4: 1 and a total thickness of 120 μm was produced.

(Example 2)
As release layer material, 80 parts by mass of resin (A), 20 parts by mass of resin (C), 10 parts by mass of resin (B), and low molecular weight polypropylene (Sanyo Chemical Industries Co., Ltd.) ), Registered trademark: Umex 1001, hereinafter referred to as “Compatibilizer (D)”) 5 parts by mass, and these were dry blended with a blend mixer. In addition, about the PBT resin of resin (A) and resin (C), what was previously dried at 120 degreeC with the hot air dryer for 8 hours was used. As an intermediate layer material, 70 parts by mass of resin (E), 10 parts by mass of resin (F), and 20 parts by mass of resin (G) were used, and these were dry blended with a blend mixer. Resin (G) used was dried in advance with a hot air dryer at 120 ° C. for 8 hours.

  The resin composition dry-blended as described above is kneaded and melted with a dalmage type three-layer single-screw extruder, and then co-extruded from a T-die, and the ratio of the thicknesses of each layer is a release layer: intermediate layer: release layer = 1: 4: 1 A three-layer film having a total thickness of 120 μm was produced.

(Example 3)
The thickness of each layer is the same as in Example 1 except that 60 parts by mass of resin (E), 15 parts by mass of resin (F), and 25 parts by mass of resin (G) used for the intermediate layer material are used. A ratio of release layer: intermediate layer: release layer = 1: 4: 1, and a three-layer film having a total thickness of 120 μm was produced.

(Example 4)
The thickness of each layer is the same as in Example 2 except that 60 parts by mass of the resin (E) used for the intermediate layer material, 15 parts by mass of the resin (F), and 25 parts by mass of the resin (G) are used. A ratio of release layer: intermediate layer: release layer = 1: 4: 1, and a three-layer film having a total thickness of 120 μm was produced.

(Example 5)
The thickness ratio of each layer is the same as that in Example 1 except that a matte embossing roll is brought into contact with the molten resin immediately after extrusion and both surfaces are roughened. A three-layer film having a mold layer = 1: 4: 1 and a total thickness of 120 μm was produced.

(Example 6)
The thickness ratio of each layer is the same as in Example 2 except that a matte embossing roll is brought into contact with the molten resin immediately after extrusion and the both surfaces are roughened. A three-layer film having a mold layer = 1: 4: 1 and a total thickness of 120 μm was produced.

(Comparative Example 1)
The release layer material of Example 1 was used and dry blended in the same manner as in Example 1 to produce a 120 μm single layer film.

(Comparative Example 2)
As the resin used for the intermediate layer material, the ratio of the thicknesses of the respective layers is the same as in Example 1 except that 95 parts by mass of the resin (E) and 5 parts by mass of the resin (F) are used. : Intermediate layer: Release layer = 1: 4: 1, and a three-layer film having a total thickness of 120 μm was produced.

(Comparative Example 3)
As the resin used for the intermediate layer material, the ratio of the thicknesses of the respective layers is the same as in Example 1 except that 80 parts by mass of resin (E) and 20 parts by mass of resin (G) are used. : Intermediate layer: Release layer = 1: 4: 1, and a three-layer film having a total thickness of 120 μm was produced.

(Comparative Example 4)
Each layer was the same as in Example 1 except that 55 parts by mass of resin (E), 10 parts by mass of resin (F), and 35 parts by mass of resin (G) were used as the resin used for the intermediate layer material. The ratio of the thickness was release layer: intermediate layer: release layer = 1: 4: 1, and a three-layer film having a total thickness of 120 μm was produced.

(Comparative Example 5)
Each resin was used in the same manner as in Example 1 except that 85 parts by mass of resin (E), 10 parts by mass of resin (F), and 5 parts by mass of resin (G) were used as the resin used for the intermediate layer material. The ratio of the thickness was release layer: intermediate layer: release layer = 1: 4: 1, and a three-layer film having a total thickness of 120 μm was produced.

  As in Example 1, except that 100 parts by mass of the resin (G) was used as the resin for the intermediate layer material, the ratio of the thicknesses of the respective layers was as follows: release layer: intermediate layer: release layer = 1 : 4: 1, and a three-layer film having a total thickness of 120 μm was produced.

(Comparative Example 7)
In the same manner as in Example 1, a three-layer film having a thickness ratio of each layer of release layer: intermediate layer: release layer = 1: 22: 1 and a total thickness of 120 μm was produced.

(Comparative Example 8)
In the same manner as in Example 1, a three-layer film having a thickness ratio of each layer of release layer: intermediate layer: release layer = 55: 10: 55 and a total thickness of 120 μm was produced.

(Comparative Example 9)
In the same manner as in Example 1, a three-layer film having a thickness ratio of each layer of release layer: intermediate layer: release layer = 3.5: 13: 3.5 and a total thickness of 15 μm was produced. .

(Comparative Example 10)
In the same manner as in Example 1, a three-layer film having a thickness ratio of each layer of release layer: intermediate layer: release layer = 1: 2: 1 and a total thickness of 200 μm was produced.

A hole having a diameter of 1.5 mm was formed in the coverlay / adhesive sheet having a total thickness of 35 μm to form an opening. An electrolytic copper foil and the above cover lay / adhesive sheet are laminated to produce an FPC, which is obtained in each of Examples 1 to 6 and Comparative Examples 1 to 10 at 190 ° C., 35 kg / cm ² , and a heating time of 120 s. The release film was hot-pressed, and each release film was evaluated for the following items.

Evaluation items (surface contamination after heat pressing)
The contamination of the coverlay surface after hot pressing was visually evaluated. The case where the surface of the coverlay was not contaminated by the molten resin was evaluated as ◯, and the case where it was contaminated was evaluated as x.

(Adhesive bleeding amount: Adhesive bleeding from cover lay opening)
After the hot pressing step, bleeding of the adhesive at the cover lay opening was observed and evaluated with a microscope. The case where the bleeding of the adhesive was less than 0.05 mm was evaluated as ◯, and the case where the bleeding of the adhesive was 0.05 mm or more was evaluated as x.

(Peelability 1: Ease of peeling)
The peelability of the release film was evaluated by feeling. When peeled by hand, it was evaluated as “Good” when it was peeled off smoothly, and when it was peeled off by hand, the resistance was large and could not be peeled at once.

(Peelability 2: Film tear at the time of peeling / film release / intermediate layer-with or without peeling)
The peelability of the release film was evaluated. At the time of peeling, the film was evaluated as “◯” when the film was not torn and delamination was not generated, and “X” was generated. The obtained results are shown in Tables 3 and 4 below.

  All of the films of Examples 1 to 6 were excellent in releasability, had little thickness unevenness, and did not tear the film during hot pressing, adhesion to a cover lay, or peeling. Further, the shape conformability was excellent, and the standard was satisfied with respect to the amount of adhesive oozing out at the cover lay opening.

  On the other hand, in Comparative Example 1, the amount of adhesive oozing from the cover lay was greater than the reference value during hot pressing. In Comparative Example 2, the amount of adhesive oozing from the cover lay during hot pressing was less than the reference value, but the interlayer strength of the film release layer / intermediate layer was low, and the film delamination during peeling after hot pressing Dismantling by occurred. Further, in Comparative Example 3, since the resin (F) was not added and the interlayer strength of the film release layer / intermediate layer was low, the interlayer strength of the film and dismantling occurred at the time of peeling after hot pressing. Furthermore, in Comparative Example 4, since the ratio of the resin (G) was high and the flexibility at the time of heating was reduced, the amount of adhesive oozing out from the cover lay at the time of hot pressing exceeded the reference value. Furthermore, in Comparative Example 5, since the ratio of the resin (G) is low and the effect of maintaining the interlayer strength of the film release layer / intermediate layer is not sufficient, the film release layer / intermediate layer interlayer at the time of peeling after hot pressing. Peeling and dismantling occurred.

  In Comparative Example 6, since the formability was not sufficient, the amount of adhesive oozing out from the cover lay was greater than the reference value during hot pressing. Moreover, in Comparative Example 7, the release layer was insufficiently formed and the peelability was lowered. In Comparative Example 8, the thickness of the intermediate layer was thin and the shape followability was insufficient, and bleeding from the adhesive from the coverlay occurred during hot pressing. In Comparative Example 9, the total thickness of the film was thin, and it was difficult to produce the film because the film was torn during film formation. In Comparative Example 10, since the release layer was thick, the rigidity was high, and bleeding of the adhesive from the coverlay occurred during hot pressing.

Claims (11)

The main component is a polybutylene terephthalate resin (A) copolymerized with a diol compound as a third component and a polymethylpentene resin (B), and the mass ratio of resin (A): resin (B) is 100: 20. Between two release layers composed of a resin composition of ~ 100: 5,
80 to 50 parts by mass of an ethylene-α-olefin copolymer resin (E) having a melting point of 50 to 110 ° C. and an epoxidized polyolefin resin (F) having a melting point of 50 to 110 ° C. with respect to 100 parts by mass of the resin component 5 to 20 parts by mass, and a multilayer structure having an intermediate layer made of a resin composition containing 15 to 30 parts by mass of a polybutylene terephthalate resin (G) having a flexural modulus of 600 MPa or less,
The release film is characterized in that the ratio of the thickness of the release layer and the intermediate layer is release layer: intermediate layer = 1: 10 to 1: 3, and the total thickness is 20 to 160 μm.   The release film according to claim 1, wherein the release layer is made of a resin composition containing 50 parts by mass or more of the resin (A) and the resin (B) in total with respect to 100 parts by mass of the resin component.   The release film according to claim 1 or 2, wherein the release layer is made of a resin composition containing 30 parts by mass or less of polybutylene terephthalate homopolymer (C) with respect to 100 parts by mass of the resin component.   The said release layer consists of a resin composition which contains 1-10 mass parts of compatibilizers (D) of the said resin (A) and the said resin (B) with respect to 100 mass parts of said resin components. The release film according to any one of 3.   The ethylene-α-olefin copolymer resin (E) is a linear low density ethylene-α-olefin copolymer resin polymerized using a metallocene catalyst. The release film as described in the item.   The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg of the ethylene-α-olefin copolymer resin (E) and the epoxidized polyolefin resin (F) is 2 to 15 g / 10 min. The release film as described in any one of -5.   The release film according to any one of claims 1 to 6, wherein one or both surfaces of the release layer surface are roughened.   8. The release film according to claim 7, wherein the release layer surface is subjected to a roughening process by bringing it into contact with a surface-roughened cooling roll when the resin composition is melt-extruded to form a film.   The release film according to claim 7 or 8, wherein the release layer surface is roughened with a handle on which uniform irregularities are formed over the entire surface.   It is a manufacturing method of the release film as described in any one of Claims 1-9, Comprising: The said resin composition for release films is knead | mixed, it melts, Then, it coextrudes with a multilayer T-die type molding machine. A method for producing a release film, characterized by being molded by   The method for producing a release film according to claim 10, wherein the release layer is roughened by bringing the resin composition into contact with a roughened cooling roll when forming the melt-extruded film.