JP6447216B2 - Release film and method for producing molded product - Google Patents

Description

  The present invention relates to a release film and a method for producing a molded product.

  The release film is generally used when a molded product is manufactured or a laminate in which different materials are bonded is manufactured. The release film is, for example, a coverlay film (hereinafter also referred to as “CL film”) via an adhesive with respect to a flexible film (hereinafter also referred to as “circuit exposure film”) from which a circuit is exposed. It is used when a flexible printed circuit board (hereinafter also referred to as “FPC”) is manufactured by bonding with a hot press. Specifically, the release film is used for the purpose of protecting the surface of the molded product or laminate when producing the molded product or the laminate. Therefore, it has been conventionally required for the release film to improve two characteristics described below. The characteristic of the mold release film requested | required first is the ease of peeling of the said mold release film after manufacturing a molded article or the said laminated body, ie, mold release property. The second required property of the release film is the adhesiveness of the release film to the surface of the molded product or the laminate, that is, the followability. Conventionally, various studies have been made to improve characteristics such as releasability and followability in such a release film.

  Examples of techniques that focus on improving the releasability of the release film and techniques that focus on improving followability include the following.

  Patent Document 1 discloses a release film having a polyester layer in which irregularities that satisfy a specific condition are formed on the surface.

JP 2009-90665 A

  FPC is known as a member having excellent bending resistance used for movable wiring. In recent years, the technical level required for downsizing and weight reduction of electronic devices has been increased, and further improvement in flex resistance has been demanded for FPC. Accordingly, the required technical level of various properties of the release film tends to be higher. In view of such circumstances, the present inventor has found that conventional release films have the following problems.

  When the present inventor made an FPC using a conventional release film, the concavo-convex shape formed on the surface of the release film was transferred to the FPC, so that the oozing of the adhesive during hot pressing increased. As a result, it has been found that there may be a disadvantage that the bending resistance of the FPC is lowered. Then, when this inventor earnestly examined the cause which the above-mentioned inconvenience produced, it discovered that controlling the rigidity of a release film was effective as a design guideline. However, when the rigidity of the release film is controlled, the above-mentioned problem of lowering the bending resistance of the FPC can be solved, but there is a new problem that voids are generated in the adhesive. It was discovered.

  Therefore, the present invention uses a release film that has an excellent balance of releasability and followability, and that can be used to produce a molded product that has excellent bending resistance while suppressing the generation of voids, and the above release film. A method for producing a molded product is provided.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor may use a thermoplastic resin material containing a specific amount of organic resin particles of a specific size as a resin material for forming a release surface. The present invention was completed by obtaining the knowledge that it was effective as a design guideline.

According to the present invention, a release film having a release layer containing a thermoplastic resin material on at least one surface,
The thermoplastic resin material includes a thermoplastic resin and organic resin particles,
The average particle diameter d50 of the organic resin particles is 4 μm or more and 20 μm or less,
For the organic resin particles, in the particle size distribution measured by sieving using a JIS standard sieve, the ratio of small particles of less than 3 μm to the whole organic resin particles is 0.1% or less,
A release film containing the organic resin particles in an amount of 0.5 wt% to 10 wt% with respect to the total amount of the release layer is provided.

Furthermore, according to the present invention, the step of disposing the release film on the object such that the release layer of the release film is on the object side;
A step of performing a heat press on the object on which the release film is disposed;
Including
In the step of disposing the release film, a method for producing a molded product is provided in which a surface of the object on which the release film is disposed is formed of a material containing a thermosetting resin.

  According to the present invention, a release film that has an excellent balance of releasability and followability and that can be used to produce a molded product with excellent bending resistance while suppressing generation of voids, and the above release film are used. A method for producing a molded product can be provided.

<Release film>
The release film in the present embodiment is a release film having a release layer containing a thermoplastic resin material on at least one surface, wherein the thermoplastic resin material comprises a thermoplastic resin and organic resin particles. The organic resin particles have an average particle diameter d50 of 4 μm or more and 20 μm or less, and the organic resin particles are employed in an amount of 0.5 wt% or more and 10 wt% or less with respect to the total amount of the release layer. It is. By doing so, it is possible to realize a release film that is excellent in the balance between releasability and followability, and that can be used to produce a molded product having excellent bending resistance while suppressing generation of voids.

  In the release film according to the present embodiment, the release layer forms at least a surface (hereinafter, also referred to as “release surface”) that contacts the object when the release film is disposed on the object. It is a resin layer.

  Moreover, the said target object surface before arrange | positioning a release film is normally formed of the material containing the thermosetting resin of a semi-hardened state. The release film according to the present embodiment is used by being disposed on the surface of an object formed of a material containing the semi-cured thermosetting resin. And a molded article can be obtained by performing a heat press in the state which has arrange | positioned the said release film on the target object surface.

  According to the knowledge of the present inventor, in the conventional release film, it is considered that the unevenness is formed on the release surface in order to improve the release property. However, when a conventional release film having unevenness on the release surface is used, as described in the problem to be solved by the above invention, there is a disadvantage that the bending resistance of the molded product is lowered. there were.

  The present inventor has found that by controlling the rigidity of the release film, it is possible to suppress the above-described inconvenience, but has found a new problem that voids are generated in the molded product.

  As described above, the release film according to the present embodiment uses a thermoplastic resin material containing a specific amount of organic resin particles having a specific size as the resin material forming the release surface. By doing so, it is possible to apply a press pressure uniformly to the release film during the production of a molded product. Therefore, it is considered that voids can be prevented from occurring in the molded product regardless of whether fine unevenness is formed on the release surface of the release film.

  In the release film according to the present embodiment, the thermoplastic resin material used to form the release layer includes a thermoplastic resin and organic resin particles. And the average particle diameter d50 of the said organic resin particle is 4 micrometers or more and 20 micrometers or less, and content of the said organic resin particle is 0.5 to 10 weight% with respect to the mold release layer whole quantity. However, the average particle diameter d50 is preferably 5 μm or more and 15 μm or less, and the content is 2% by weight or more and 10% by weight or less with respect to the total amount of the release layer. By doing so, it is possible to improve the rigidity of the release film while giving fine unevenness to the release surface. Therefore, it is possible to realize a release film excellent in the balance between releasability and followability, which is effective for producing a molded product having excellent bending resistance while suppressing generation of voids. However, the present inventor can improve the rigidity of the release film when the release layer is formed using a thermoplastic resin and a resin material that simply contains organic resin particles. It has also been found that there is an inconvenience that voids may still occur in the molded product.

  The surface 10-point average roughness (Rz) of the release surface of the release layer is preferably 0.5 μm or more from the viewpoint of obtaining stable release properties while ensuring the strength of the release layer. Is 0.8 μm or more. On the other hand, from the viewpoint of suppressing the transfer of the surface roughness, the surface 10-point average roughness (Rz) of the release surface of the release layer is preferably 5.0 μm or less, more preferably 4 μm. 0.0 μm or less. The surface 10-point average roughness (Rz) can be measured according to JIS-B0601-1994.

  The average spacing (Sm) of the unevenness of the release surface of the release layer is preferably 180 μm or more, more preferably 195 μm or more, from the viewpoint of obtaining stable release properties while ensuring the strength of the release layer. It is. On the other hand, from the viewpoint of suppressing the transfer of the surface roughness, the average interval (Sm) of the unevenness is preferably 450 μm or less, more preferably 345 μm or less. In addition, the average space | interval (Sm) of an unevenness | corrugation can be measured according to JIS-B0601-1994. In addition, the average space | interval (Sm) of the unevenness | corrugation which concerns on this embodiment points out the numerical value of the surface (release surface) which hits the target object side in a release film, when a release film is arrange | positioned at a target object.

  The arithmetic average roughness (Ra) of the release surface of the release layer is preferably 0.08 μm or more, more preferably from the viewpoint of obtaining stable release properties while ensuring the strength of the release layer. It is 0.14 μm or more. On the other hand, from the viewpoint of suppressing the transfer of the surface roughness, the arithmetic average roughness (Ra) is preferably 1 μm or less, and more preferably 0.78 μm or less. In addition, arithmetic mean roughness (Ra) can be measured according to JIS-B0601-1994. In addition, arithmetic mean roughness (Ra) which concerns on this embodiment points out the numerical value of the surface (release surface) which hits the target object side in a release film, when a release film is arrange | positioned at a target object.

  The peel strength of the release surface of the release layer is preferably as low as possible, but is preferably 5 N / 50 mm or less, and more preferably 3 N / 50 mm or less. The peel strength can be measured, for example, by the following method. First, with respect to the circuit exposure film in which the cover lay film is temporarily fixed via an adhesive, the release surface of the release film is opposed to the surface of the circuit exposure film on which the cover lay film is disposed. A test piece is prepared by performing hot pressing for 2 minutes at 195 ° C. and a pressure of 6 MPa. Thereafter, the release film of the obtained test piece is peeled off by applying stress at a rate of about 50 mm / second in the 180 ° direction using a tensile tester, thereby measuring the peel strength of the release surface. In addition, it is preferable to implement the peeling test mentioned above immediately after giving a hot press process.

  The thickness of the release film according to this embodiment is preferably 50 μm or more and 150 μm or less, more preferably 75 μm or more and 150 μm or less, and most preferably 100 μm or more and 150 μm or less. This makes it possible to apply the press pressure to the release film more uniformly during the production of the molded product, regardless of whether fine unevenness is formed on the release surface of the release film. Therefore, the occurrence of voids in the molded product can be further suppressed to a high degree.

  The release layer includes a thermoplastic resin material including a thermoplastic resin and organic resin particles. Examples of the thermoplastic resin include polyalkylene terephthalate resins such as polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polytrimethylene terephthalate resin (PTT), polyhexamethylene terephthalate resin (PHT), and poly-4. -Methyl 1-pentene resin (TPX: hereinafter referred to as polymethylpentene resin), syndiotactic polystyrene resin (SPS), polypropylene resin (PP), and a copolymer resin obtained by copolymerizing other components. These may be used alone or in combination of two or more. Especially, it is preferable to use 1 or more types selected from the group which consists of a polymethylpentene resin, a polybutylene terephthalate resin, a syndiotactic polystyrene resin, and a polypropylene resin from a viewpoint of improving the balance of mold release property and followable | trackability.

  The release layer includes a thermoplastic resin material including a thermoplastic resin and organic resin particles. The organic resin particles are preferably crosslinked organic resin particles. Specific examples of such crosslinked organic resin particles include polystyrene particles, acrylic particles, polyimide particles, polyester particles, silicone particles, polypropylene particles, polyethylene particles, fluororesin particles, and core-shell particles. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the rigidity of the release film, polystyrene particles and acrylic particles are preferable.

  From the viewpoint of reducing voids, the organic resin particles preferably have a ratio of small particles of less than 3 μm to the whole organic resin particles in the particle size distribution measured by sieving using a JIS standard sieve, preferably 0.1% or less. More preferably, it is 0.08% or less.

  The organic resin particles have a particle diameter d90 with a cumulative frequency of 90% measured using a laser diffraction particle size distribution measuring device for the organic resin particles, preferably 3 μm or more and 20 μm or less, more preferably 5 μm or more and 20 μm or less. This makes it possible to apply the press pressure to the release film more uniformly during the production of the molded product, regardless of whether fine unevenness is formed on the release surface of the release film. Therefore, the occurrence of voids in the molded product can be further suppressed to a high degree.

  The thermoplastic resin material according to the present embodiment includes, in addition to thermoplastic resins, antioxidants, slip agents, antiblocking agents, antistatic agents, coloring agents such as dyes and pigments, additives such as stabilizers, fluororesins Further, an impact resistance imparting agent such as silicon rubber, and an inorganic filler such as titanium oxide, calcium carbonate, and talc may be contained.

  The thickness of the release layer is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of improving the embedding property to the molded product. On the other hand, from the viewpoint of obtaining an appropriate strength, the thickness of the release layer is preferably 100 μm or less, more preferably 50 μm or less, and most preferably 30 μm or less.

  The intrinsic viscosity of the resin constituting the release layer of the release film is preferably 0.3 dl / g or more, more preferably 0.5 dl / g or more, from the viewpoint of improving the film formability. . On the other hand, the intrinsic viscosity of the resin constituting the release layer is preferably 2.5 dl / g or less, more preferably 2.0 dl / g or less, from the viewpoint of reducing the load during the production of the release film. Yes, most preferably 1.5 dl / g or less.

  The acid value of the resin constituting the release layer of the release film is preferably 1 or more, more preferably 3 or more, from the viewpoint of improving the balance between peelability and followability. On the other hand, the acid value of the resin constituting the release layer is preferably 40 or less, more preferably 30 or less, and most preferably 25 or less, from the viewpoints of heat resistance and film formability. In addition, the acid value in this embodiment points out the value according to JISK0070 (1992 formula).

  The release film in the present embodiment may have a release layer containing a thermoplastic resin material on at least one surface, but the release layer and another layer different from the release layer are provided. It is preferable to form a multilayer structure including the same. Specifically, the release film may have a release layer containing a thermoplastic resin material on both sides of the release film depending on the application. Moreover, the release film may further have a cushion layer in contact with the release layer. The release film may have a three-layer structure in which a release layer, a cushion layer, and a sub-release layer are laminated in this order. By including such a sub-release layer, when it is hot-pressed with a press, the release property from the hot plate is improved, and the productivity in the production of a molded body and a laminate can be improved. The plurality of release layers may be formed from the same material or may be formed from different materials as long as the material includes a thermoplastic resin material. Further, the plurality of release layers may have different thicknesses.

  The surface 10-point average roughness (Rz) of the release surface of the sub-release layer is preferably 0.5 μm or more from the viewpoint of obtaining stable release properties while ensuring the strength of the sub-release layer. More preferably, it is 0.8 μm or more. On the other hand, from the viewpoint of suppressing the transfer of the surface roughness, the surface 10-point average roughness (Rz) of the release surface of the sub-release layer is preferably 5.0 μm or less, more preferably, 4.0 μm or less. The surface 10-point average roughness (Rz) can be measured according to JIS-B0601-1994. Moreover, the said surface 10-point average roughness (Rz) points out the numerical value of the surface (release surface) on the opposite side to the target object side in a release film, when a release film is arrange | positioned at a target object.

  The cushion layer imparts cushioning properties to the entire release film by using a resin having flexibility. As a result, when the release film is used, heat and pressure from the press hot plate are easily transmitted to the adherend, and the adhesion and followability between the release film and the adherend are further improved. it can.

  As a resin material for forming the cushion layer, an α-olefin polymer such as polyethylene and polypropylene, an α-olefin copolymer having ethylene, propylene, butene, pentene, hexene, methylpentene and the like as a polymer component, Engineering plastics resins such as polyethersulfone and polyphenylene sulfide are listed. These may be used alone or in combination. Of these, α-olefin copolymers are preferred. Examples of the α-olefin copolymer include a copolymer of an α-olefin such as ethylene and a (meth) acrylic acid ester, a copolymer of ethylene and vinyl acetate, and a copolymer of ethylene and (meth) acrylic acid. Examples thereof include polymers and partially ion cross-linked products thereof. Furthermore, from the viewpoint of obtaining a good cushion function, an α-olefin- (meth) acrylic acid ester copolymer such as ethylene alone, or polybutylene terephthalate and 1,4 cyclohexanedimethanol copolymer polyethylene terephthalate And a mixture of an α-olefin polymer and an α-olefin- (meth) acrylate copolymer such as ethylene. For example, a mixture of ethylene and ethylene-methyl methacrylate copolymer (EMMA), a mixture of polypropylene (PP) and ethylene-methyl methacrylate copolymer (EMMA), polybutylene terephthalate (PBT), polypropylene (PP) and ethylene -A mixture with a methyl methacrylate copolymer (EMMA) is more preferable.

  The cushion layer may further contain a rubber component. Examples of the rubber component include thermoplastic elastomer materials such as styrene-based thermoplastic elastomers such as styrene-butadiene copolymer and styrene-isoprene copolymer, olefin-based thermoplastic elastomers, amide-based elastomers, and polyester-based elastomers, and natural rubber. And rubber materials such as isoprene rubber, chloroprene rubber and silicon rubber.

  For the cushion layer, antioxidants, slip agents, anti-blocking agents, antistatic agents, coloring agents such as dyes and pigments, additives such as stabilizers, impact resistance imparting agents such as fluororesin and silicon rubber, titanium oxide Inorganic fillers such as calcium carbonate and talc may be included.

  In addition, as a method of forming a cushion layer, well-known methods, such as an air cooling or a water cooling inflation extrusion method and a T-die extrusion method, are mentioned, for example.

  The thickness of the cushion layer is preferably 10 μm or more and 100 μm or less, more preferably 20 μm or more and 90 μm or less, and most preferably 30 μm or more and 70 μm or less. When the thickness of the cushion layer is equal to or more than the above lower limit value, it is possible to suppress a decrease in the cushioning property of the release film. When the thickness of the cushion layer is equal to or less than the above upper limit value, it is possible to suppress a decrease in releasability.

  Further, the release film may have a configuration of four or more layers such as four layers and five layers having an adhesive layer, a gas barrier layer, and the like. In this case, the adhesive layer and the gas barrier layer are not particularly limited, and known ones can be used.

<Method for producing release film>
The release film in the present embodiment can be produced using a known method such as a co-extrusion method, an extrusion lamination method, a dry lamination method, or an inflation method. In addition, when the release film has a multilayer structure, the release layer and the cushion layer may be manufactured separately and then joined by a laminator or the like, but the air-cooled or water-cooled coextrusion inflation method, coextrusion T It is preferable to form a film by a die method. Among these, a method of forming a film by a coextrusion T-die method is particularly preferable because it is excellent in controlling the thickness of each layer. Further, the release layer and the cushion layer may be joined as they are, or may be joined via an adhesive layer.

<Method of manufacturing molded product>
Next, the manufacturing method of the molded product of this embodiment is demonstrated.
The manufacturing method of the molded product of this embodiment uses the release film mentioned above. And the manufacturing method of the molded article of this embodiment may be used when producing a flexible printed circuit board, for example. In this case, in order to protect the circuit formed on the flexible film, the release film is interposed between the coverlay and the pressing machine when the coverlay film is heated and pressed against the circuit. To use.
Specifically, the release film is used, for example, in a cover lay press laminating process which is one of the manufacturing processes of a flexible printed wiring board. More specifically, the release film is disposed so as to wrap the coverlay film so that the coverlay film adheres to the concavo-convex portion of the circuit pattern when the coverlay film is adhered to the circuit exposed film. At the same time, it is heated and pressurized by a press. At this time, in order to improve cushioning properties, paper, rubber, fluororesin sheet, glass paper, or the like, or a combination of these may be inserted between the release film and the press machine and then heated and pressed.

Moreover, you may use the release film of this embodiment with the following method.
First, the mold release surface in the mold release layer of the mold release film according to the present embodiment is arranged on the surface of an object formed of a material containing a thermosetting resin. And it press-processes in the metal mold | die with respect to the target object which has arrange | positioned the release film. Here, the thermosetting resin described above may be in a semi-cured state or a cured state. However, when the thermosetting resin is in a semi-cured state, the effect of the release film becomes more remarkable. In particular, when the thermosetting resin is a resin composition containing an epoxy resin, the epoxy resin is preferably in an intermediate stage of the curing reaction, that is, in a B-stage state.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Hereinafter, examples of the reference form will be added.
1. A release film having a release layer containing a thermoplastic resin material on at least one surface,
The thermoplastic resin material includes a thermoplastic resin and organic resin particles,
The average particle diameter d50 of the organic resin particles is 4 μm or more and 20 μm or less,
A release film containing the organic resin particles in an amount of 0.5% by weight to 10% by weight with respect to the total amount of the release layer.
2. In the release film, the surface roughness of the release surface of the release layer is 0.5 μm or more and 5.0 μm or less in terms of 10-point surface average roughness Rz. A release film as described in 1.
3. 1. The thickness of the release film is 50 μm or more and 150 μm or less. Or 2. A release film as described in 1.
4). The organic resin particles are crosslinked organic resin particles; To 3. A release film according to any one of the above.
5). The organic resin particles are one or more particles selected from the group consisting of polystyrene particles, acrylic particles, polyimide particles, polyester particles, silicone particles, polypropylene particles, polyethylene particles, fluororesin particles, and core-shell particles. Including, To 4. A release film according to any one of the above.
6). About the said organic resin particle, the ratio of the small particle of less than 3 micrometers with respect to the whole said organic resin particle in the particle size distribution measured by sieving using a JIS standard sieve is 0.1% or less. To 5. A release film according to any one of the above.
7). Regarding the organic resin particles, the particle diameter d90 at which the cumulative frequency measured using a laser diffraction particle size distribution measuring device is 90% is 3 μm or more and 20 μm or less. To 6. A release film according to any one of the above.
8). The thermoplastic resin is one or more selected from the group consisting of poly-4-methyl 1-pentene resin, polybutylene terephthalate resin, syndiotactic polystyrene resin and polypropylene resin. To 7. A release film according to any one of the above.
9. 1. It has a three-layer structure in which the release layer, cushion layer, and sub-release layer are laminated in this order. To 8. A release film according to any one of the above.
10. 8. The surface roughness of the release surface of the sub-release layer in the release film is 0.5 μm or more and 5 μm or less in terms of the surface 10-point average roughness Rz. A release film as described in 1.
11. 1. The surface of the release layer is used by being superimposed on the surface of a molding formed of a material containing a thermosetting resin in a semi-cured state. To 10. A release film according to any one of the above.
12 10. The thermosetting resin includes an epoxy resin. A release film as described in 1.
13. 1. To 12. A step of disposing the release film on the object such that the release layer of the release film according to any of the above is on the object side;
A step of performing a heat press on the object on which the release film is disposed;
Including
In the step of disposing the release film, the surface of the object on which the release film is disposed is formed of a material containing a thermosetting resin.
14 12. The molded product is a flexible printed circuit board; The manufacturing method of the molded article as described in 2.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.

<Example 1>
Using a resin material consisting of polymethylpentene resin (TPX (registered trademark)) (manufactured by Mitsui Chemicals, TPX DX820) and acrylic beads (manufactured by Sekisui Plastics Co., Ltd., SSX-110), TPX is produced by extrusion T-die method. A release layer was obtained by forming a film. Here, the average particle diameter d50 of the acrylic beads used for the production of the release layer was 10.2 μm, and the particle diameter d90 was 15 μm. Further, the resin material used for the production of the release layer was prepared by blending with the TPX so that the content of the acrylic beads with respect to the total amount of the release layer was 5% by weight.
Cushion layer (compounding ratio: TPX: polypropylene: ethylene) composed of the release layer, TPX, polypropylene (manufactured by Sun Aroma, PB270A), and modified polyethylene (ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., WH102)). -Methyl methacrylate copolymer: = 50: 30: 20) and a sub-release layer composed of TPX were laminated in this order by an extrusion T-die method to produce a release film consisting of three layers.
The thickness of each layer of the obtained release film was 30 μm for the release layer and the second release layer, and 40 μm for the cushion layer.

<Example 2>
Using a resin material blended with polymethylpentene resin (TPX (registered trademark)) (manufactured by Mitsui Chemicals, TPX DX820) such that the content of acrylic beads with respect to the total amount of the release layer is 2% by weight, the release layer is formed. A release film was obtained in the same manner as in Example 1 except that the produced point and the thickness of the release layer were 25 μm.

<Example 3>
A polymethylpentene resin (TPX (registered trademark)) was prepared so that the content of acrylic beads having an average particle diameter d50 of 19.7 μm and a particle diameter d90 of 27.8 μm was 1.5% by weight based on the total amount of the release layer. (Trademark)) (Mitsui Chemicals, TPX DX820) and a release layer was prepared using a resin material, and the release layer was released in the same manner as in Example 1 except that the thickness of the cushion layer was 60 μm. A film was obtained.

<Example 4>
Using a resin material blended with polymethylpentene resin (TPX (registered trademark)) (manufactured by Mitsui Chemicals, TPX DX820) so that the content of acrylic beads with respect to the total amount of the release layer is 10% by weight, the release layer is formed. A release film was obtained in the same manner as in Example 1 except that the thickness of the cushion layer was 90 μm.

<Comparative Example 1>
A release film was obtained in the same manner as in Example 1 except that acrylic beads having an average particle diameter d50 of 2.8 μm and a particle diameter d90 of 5.1 μm were used.

<Comparative Example 2>
A release layer was prepared using a resin material made of polymethylpentene resin (TPX (registered trademark)) (manufactured by Mitsui Chemicals, TPX DX820), and an embossed shape was imparted by pressure bonding to a metal roll of Rz = 10. Except for this, a release film was obtained in the same manner as in Example 1.

<Comparative Example 3>
A release film was obtained in the same manner as in Example 1 except that a release layer using acrylic beads having an average particle diameter d50 of 28.5 μm and a particle diameter d90 of 40.2 μm was prepared.

  The following evaluation was performed using each release film of an Example and a comparative example. The results are shown in Table 1.

<Evaluation method>
-Particle size distribution of organic resin particles: What weighed 40 g of organic resin particles to 1 mg was used as a sample. Using a JIS standard sieve with a mesh size of 3 μm provided in a low-tap type sieve vibrator (manufactured by Maruhishi Kagaku Seisakusho, Model-SS-100A), these sieves were vibrated over 20 minutes (hammer strike rate: 120 times / minute). The sample was passed through a sieve and classified. Subsequently, the mass of the fine powder which passed the 3 micrometers sieve was measured, and mass ratio with respect to the total sample mass before classification was calculated | required.

-Particle diameter d90 of organic resin particles: Cumulative frequency from results obtained by measuring particles using a laser diffraction particle size distribution measuring apparatus (Malvern, Mastersizer 2000) with water as a solvent and dispersing particles. Was determined to obtain a particle diameter d90 of 90%.

・ 10-point average roughness (Rz)
The surface of the release surface of the release film was measured for the center n = 3 using “Handy Surf E-35B manufactured by Tokyo Seimitsu Co., Ltd.” according to JIS B0601 (1994).

・ Releasability: Adhesive surface of coverlay (CM type) manufactured by Arisawa Manufacturing Co., Ltd. is pasted on the release surface of the release film, heat pressed at 195 ° C x 2 minutes x 6 MPa, and a tensile tester (A & D) The peel force between the release surface and the coverlay adhesive was measured at a speed of about 1000 mm / min in the 180 ° direction using a Force gauge AD-4932A-50N). The measurement was performed immediately after pressing, and the releasability was evaluated based on the following criteria.
○: Peelable ×: Peeling is heavy and film or coverlay breaks

・ Followability Bonding the polyimide surface of the coverlay (CM type) manufactured by Arisawa Manufacturing Co., Ltd. to the release surface of the release film, heat-pressing at 195 ° C. × 2 minutes × 6 MPa, and then releasing the release film. The surface of the coverlay was measured according to the “7.5.7.2 wrinkle” of the JPCA standard.
○: Wrinkle occurrence rate less than 2.0% ×: Wrinkle occurrence rate 2.0% or more

-Presence / absence of voids: First, the copper foils on both sides of the copper-clad laminate for flexible wiring boards were etched to create a 3 cm square opening. Next, a cover lay (CM type) manufactured by Arisawa Manufacturing Co., Ltd. is attached to the opening formed in the copper-clad laminate for flexible wiring boards, and is overlaid so that the release surface of the release film is on the cover lay side. The release film was peeled off after hot pressing at 145 ° C. × 5 minutes × 5 MPa. In the obtained copper-clad laminate for flexible wiring boards, it was evaluated whether or not voids were generated in the adhesive that entered the opening.

Flex resistance (adhesive oozing shape): First, copper foils on both sides of a copper-clad laminate for flexible wiring boards were etched to create a 3 cm square opening. Next, a cover lay (CM type) manufactured by Arisawa Manufacturing Co., Ltd. is attached to the opening formed in the copper-clad laminate for flexible wiring boards, and is overlaid so that the release surface of the release film is on the cover lay side. The release film was peeled off after hot pressing at 145 ° C. × 5 minutes × 5 MPa. In the obtained copper-clad laminate for flexible wiring boards, the oozing shape of the adhesive that entered the opening was observed, and the bending resistance was evaluated based on the following criteria.
○: The shape of the adhesive oozing is flat (flat).
X: The oozing shape of the adhesive has irregularities.

  The release films of Examples 1 to 4 and Comparative Examples 1 to 3 all met the required level in terms of the balance between the release property and the followability. And the molded article produced using the release film of Examples 1-4 was excellent in the bending resistance without a void. On the other hand, the molded product produced using the release film of Comparative Example 1 had voids. Moreover, the molded article produced using the release films of Comparative Examples 2 and 3 did not satisfy the required level in terms of bending resistance.

Claims (13)

A release film having a release layer containing a thermoplastic resin material on at least one surface,
The thermoplastic resin material includes a thermoplastic resin and organic resin particles,
The average particle diameter d50 of the organic resin particles is 4 μm or more and 20 μm or less,
For the organic resin particles, in the particle size distribution measured by sieving using a JIS standard sieve, the ratio of small particles of less than 3 μm to the whole organic resin particles is 0.1% or less,
A release film containing the organic resin particles in an amount of 0.5% by weight to 10% by weight with respect to the total amount of the release layer.   The release film of Claim 1 whose surface roughness of the release surface of the said release layer is 0.5 micrometer or more and 5.0 micrometers or less in the surface 10 point average roughness Rz in the said release film.   The release film of Claim 1 or 2 whose thickness of the said release film is 50 micrometers or more and 150 micrometers or less.   The release film according to any one of claims 1 to 3, wherein the organic resin particles are crosslinked organic resin particles.   The organic resin particles are one or more particles selected from the group consisting of polystyrene particles, acrylic particles, polyimide particles, polyester particles, silicone particles, polypropylene particles, polyethylene particles, fluororesin particles, and core-shell particles. The release film as described in any one of Claims 1 thru | or 4 containing. About the said organic resin particle, the particle diameter d90 from which the cumulative frequency measured using a laser diffraction type particle size distribution measuring apparatus will be 90% is 3 micrometers or more and 20 micrometers or less, It is any one of Claims 1 thru | or 5. Release film. Wherein the thermoplastic resin is a poly 4-methyl 1-pentene resin is polybutylene terephthalate resin, one or more selected from the group consisting of syndiotactic polystyrene resins and polypropylene resins, any one of claims 1 to 6 The release film as described in the item. The release film according to any one of claims 1 to 7 , which has a three-layer structure in which the release layer, the cushion layer, and the sub-release layer are laminated in this order. The surface roughness of the release surface of the at the release film secondary release layer is 0.5μm or more 5μm or less at the surface 10-point average roughness Rz, the release film of claim 8. The release film according to any one of claims 1 to 9 , wherein the release layer is used by superimposing the surface of the release layer on the surface of a molded product formed of a material containing a thermosetting resin in a semi-cured state. The release film according to claim 10 , wherein the thermosetting resin contains an epoxy resin. The step of disposing the release film on the object such that the release layer of the release film according to any one of claims 1 to 11 is on the object side;
A step of performing a heat press on the object on which the release film is disposed;
Including
In the step of disposing the release film, the surface of the object on which the release film is disposed is formed of a material containing a thermosetting resin. The method for producing a molded product according to claim 12 , wherein the molded product is a flexible printed circuit board.