JP2020152101A - Combination of mold and release film, release film, mold, and method for manufacturing molding - Google Patents

Abstract

To provide a technique for adjusting a surface state of a molding.SOLUTION: There is provided a combination of molds used for curing a thermosetting resin, and a release film arranged between the thermosetting resin and the mold in the curing. The release film includes a base material layer formed of a thermoplastic resin, and a surface layer which is layered on a surface arranged on the side of the thermosetting resin in the curing in two surfaces of the base material layer and is formed of a fluorine resin containing particles. The mold has unevenness formed on a surface in contact with the release film in the curing.SELECTED DRAWING: Figure 1

Description

The present invention relates to a combination of a mold and a mold release film, a mold release film, a mold, and a method for manufacturing a molded product. More specifically, the mold and the mold release film used for transfer molding or compression molding. The present invention relates to a combination with the above, a release film and a mold constituting the combination, and a method for producing a molded product using the combination.

In order to seal the semiconductor with a resin, molding methods such as a transfer molding method and a compression molding method are used. In the molding technique, a mold release film is often used to easily remove the molded body from the mold after the resin has hardened in the mold. So far, various proposals have been made for release films and molds.

For example, Patent Document 1 below describes a coating film formed from a composition containing a fluororesin (A) containing a functional group X and a release component (B), and a layer formed from a non-fluorinated polymer. A release film comprising the above is disclosed.
Further, in Patent Document 2 below, the product to be molded on which the semiconductor chip is mounted is clamped by the first and second dies facing each other, and the product to be molded is sealed by using the resin filled in the mold. A resin-sealing mold for stopping, in which at least one of the first and second molds is filled with the resin in the mold rather than the thickness of the resin in the opposite direction. A resin-sealed mold is disclosed, wherein the first heater is arranged at a position close to the surface of the resin.

Japanese Unexamined Patent Publication No. 2015-742201 Japanese Unexamined Patent Publication No. 2012-256925

It may be required to adjust the surface of the part. For example, the surface of the molded product may be printed by a laser marker, and it may be required to form a surface that enhances the visibility of the printing or the readability by a reading device.

An object of the present invention is to provide a new technique for adjusting the surface of the molded product.

The present inventors have found that a specific mold, a manufacturing method, a mold release film, and a combination of a mold and a mold release film are suitable for surface adjustment of the molded product.

That is, the present invention
A mold used in combination with a release film for curing thermosetting resins.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film.
The mold is provided.
The surface roughness Ra of the surface of the mold can be 1 μm to 4 μm.
The mold hardness of the mold can be 50 HRC or more.
The unevenness may be an unevenness formed by electric discharge machining or shot blasting.
The mold can be used to form a surface having a glossiness of 3 to 50 at an incident angle of 60 ° on a molded product obtained by curing the thermosetting resin.
The release film used in combination with the mold
A substrate layer formed of a thermoplastic resin and
It may include a surface layer formed of a fluorine-based resin containing particles, which is laminated on the surface arranged on the thermosetting resin side in the curing of the two surfaces of the base material layer.
In the curing, the surface shape of the release film caused by the particles can be directly reflected on the surface of the thermosetting resin.

In addition, the present invention
An arrangement process for arranging the release film in the mold used to cure the thermosetting resin, and
After the placement step, a curing step of curing the thermosetting resin in the mold in contact with the release film,
After the curing step, the present invention includes a mold release step of releasing the cured thermosetting resin from the mold to obtain a molded product.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing step, the unevenness is reflected on the surface of the thermosetting resin via the release film.
A method for producing a molded product is also provided.

In addition, the present invention
A mold release film used in combination with a mold for curing thermosetting resins.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing, the unevenness is used to reflect the unevenness on the surface of the thermosetting resin via the release film.
The release film is also provided.
The tensile breaking strength of the release film is 40 MPa to 200 MPa when measured at 175 ° C. according to JIS K7127, and the tensile breaking elongation of the release film is measured at 175 ° C. according to JIS K7127. In addition, it can be 200% to 500%.
The thickness of the release film can be 30 μm to 100 μm.

In addition, the present invention
A combination of a mold and a mold release film used for curing thermosetting resins.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film.
The combination is also provided.

According to the present invention, the surface of the molded product can be adjusted. For example, according to the present invention, the visibility and readability of printing by a laser marker can be improved.
The effect of the present invention is not necessarily limited to the effects described here, and may be any of the effects described in the present specification.

It is a figure for demonstrating an example of the method of using the combination of this invention in transfer molding. It is a schematic diagram of an example of the laminated structure of the release film which constitutes the combination of this invention. It is a figure for demonstrating an example of the use method of the combination of this invention in compression molding. It is a figure for demonstrating the formation of the surface layer on the molded body side. It is a figure which shows the observation result by a laser marker.

Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the embodiments described below show an example of typical embodiments of the present invention, and the present invention is not limited to these embodiments.

1. 1. Combination of mold and release film

The present invention provides a combination of a mold used for curing a thermosetting resin and a release film arranged between the thermosetting resin and the mold in the curing. The release film includes a base material layer formed of a thermoplastic resin and a surface layer laminated on one of the two surfaces of the base material layer, which is arranged on the thermosetting resin side in the curing. The surface layer is formed of a fluororesin containing particles. The mold has irregularities formed on the surface that comes into contact with the release film during the curing.

By using the combination in a molding method such as a transfer molding method and a compression molding method, the surface state of the molded body can be adjusted, and for example, a desired glossiness can be imparted to the surface of the molded body. .. For example, the combination according to the present invention may be used to produce a molded product having a surface having a glossiness of 3 to 50 at an incident angle of 60 °. For example, a combination according to the present invention has a surface (particularly an epoxy resin surface) having a glossiness of 3 to 15, preferably 3 to 10, more preferably 4 to 8, and even more preferably 4 to 6 at an incident angle of 60 °. ) May be used to produce a molded article.
Further, by using the above combination, for example, the visibility or readability of the print or pattern applied to the surface of the molded product can be enhanced. For example, the combination according to the present invention may be used to produce a molded product having a surface (particularly an epoxy resin surface) on which printing by a laser marker is performed. The character height of the print may be, for example, 0.1 mm to 10 mm, preferably 0.2 mm to 5 mm. The character height of the print may be particularly 0.5 mm to 3 mm. By using the combination of the present invention, the visibility or readability of such small characters on the surface of the manufactured molded product can be enhanced.

The mold release film is suitable for reflecting the unevenness of the surface of the mold on the surface of the molded product, and exhibits excellent mold releasability. In particular, the combination of the particles contained in the surface layer and the fluorine-based resin contributes to exhibiting excellent mold releasability and also contributes to the adjustment of the surface state of the molded product.

Hereinafter, an example of how to use the combination will be described first, and then the release film and the mold, which are the components of the combination, will be described in more detail.

1-1. How to use the combination of the present invention

The combination of the present invention may be used, for example, in various molding methods for thermosetting resins. Preferably, the combination of the present invention can be used to form irregularities on the surface of the cured product of the thermosetting resin.
For example, the molding method is, for example, transfer molding or compression molding, and the combinations of the present invention are particularly suitable for use in these molding methods. In particular, the combination of the present invention can be used to adjust the surface condition of the molded products obtained by these molding methods, preferably to form irregularities on the surface of these molded products.
An example of how to use the combination of the present invention in these molding methods will be described below.

(1) Transfer molding

FIG. 1 is a diagram for explaining an example of how to use the combination of the present invention in transfer molding. As shown in FIG. 1A, the release film 11 constituting the combination of the present invention is placed between the upper mold 12 constituting the combination of the present invention and the lower mold 13 on which the substrate 14 is placed. Be placed. For example, a semiconductor element 17 may be mounted on the substrate 14. The upper mold 12 and the lower mold 13 are used for molding the thermosetting resin 15. By the molding, the semiconductor element 17 is sealed with the cured product of the thermosetting resin 15. Although one semiconductor element 17 is shown in FIG. 1, the number of semiconductor elements 17 sealed in one molding is not limited to one, and is preferably a plurality.
The release film 11 has, for example, the laminated structure shown in FIG. In the release film 11, the base material layer 101 and the surface layer 102 are laminated on one surface of the base material layer 101, and the surface layer 103 is laminated on the other surface. The details of the release film 11 will be described below in "1-2. Release film".
The surface layer 102 is laminated on the surface of the base material layer 101 that is arranged on the thermosetting resin side in the transfer molding. That is, the surface layer 102 comes into contact with the thermosetting resin 15 in the transfer molding. The surface layer 102 is formed of a fluorine-based resin containing particles.
The surface layer 103 is laminated on the surface of the two surfaces of the base material layer 101 that is arranged on the upper mold 12 side in the transfer molding. That is, the surface layer 103 contacts the upper mold 12 in the transfer molding.
Unevenness is formed on the surface 16 of the upper mold 12. That is, the surface 16 comes into contact with the release film 11 (particularly its surface layer 103) in the transfer molding.

Next, as shown in FIG. 1 (B), the upper mold 12 is attached to the substrate 14 and the lower side in a state where the release film 11 (particularly the surface layer 103 thereof) is attached to the surface 16 of the upper mold 12. It is brought into contact with the mold 13.

Next, as shown in FIG. 1C, the thermosetting resin 15 is introduced between the upper mold 12 (particularly the release film 11) and the substrate 14, and then the thermosetting resin 15 is introduced. It is cured by heating.
In the curing, the uneven shape formed on the surface 16 of the upper mold 12 is reflected on the surface of the thermosetting resin 15 via the release film 11, and the surface shape (particularly the surface) of the release film 11 is reflected. The surface shape caused by the particles contained in the layer 102) is reflected on the surface of the thermosetting resin 15. That is, the uneven shape formed on the surface 16 of the upper mold 12 is indirectly reflected on the surface of the thermosetting resin 15, and is included in the surface shape of the release film 11 (particularly in the surface layer 102). The surface shape caused by the particles) is directly reflected on the surface of the thermosetting resin 15. The thermosetting resin 15 is cured in a state where the uneven shape and the surface shape are reflected on the surface of the thermosetting resin 15. That is, the uneven shape and the surface shape are reflected on the surface of the molded product obtained as a result of the curing. Here, the unevenness formed on the surface of the molded product (cured product) may be different from the unevenness of the mold.
As described above, the combination of the present invention makes it possible to adjust the surface state of the molded product.

After curing, the upper mold 12 is separated from the substrate 14 as shown in FIG. 1 (D). The release film 11 is excellent in releasability because it is formed of a fluorine-based resin containing particles in particular. Therefore, in the step of FIG. 1D, the cured resin 15 is smoothly separated from the cured resin 15. If the releasability is not good, the releasable film 19 may stick to the cured resin 15, for example, as shown in FIG. 1 (E).

(2) Compression molding

FIG. 3 is a diagram for explaining an example of how to use the combination of the present invention in compression molding. As shown in FIG. 3 (A), the release film 11 constituting the combination of the present invention is formed by the upper mold 22 and the lower mold 23 on which the substrate 24 on which the plurality of semiconductor elements 27 are mounted is mounted. Placed in between.
In the release film 11, as described in (1) above, the base material layer 101 and the surface layer 102 are laminated on one surface of the base material layer 101, and the surface layer 103 is laminated on the other surface. There is.
The surface layer 102 is laminated on the surface of the base material layer 101 that is arranged on the thermosetting resin side in the compression molding. That is, the surface layer 102 comes into contact with the thermosetting resin 25, which will be described later, in the compression molding.
The surface layer 103 is laminated on the surface of the two surfaces of the base material layer 101 that is arranged on the lower mold 23 side in the compression molding. That is, the surface layer 103 contacts the lower mold 23 in the compression molding.
Unevenness is formed on the surface 26 of the lower mold 23. That is, the surface 26 comes into contact with the release film 11 (particularly its surface layer 103) in the compression molding.

Next, as shown in FIG. 3B, the thermosetting resin 25 is arranged in the recess of the lower mold 23 in a state where the release film 11 is attached to the surface 26 of the lower mold 23. To.

Next, as shown in FIG. 3C, the upper mold 22 is moved to bring the substrate 24 into contact with the thermosetting resin 25. After that, the thermosetting resin 25 is cured by heating.
In the curing, the uneven shape formed on the surface 26 of the lower mold 23 is reflected on the surface of the thermosetting resin 25 via the release film 11, and the surface shape of the release film 11 (particularly, particularly. The surface shape caused by the particles contained in the surface layer 102) is reflected on the surface of the thermosetting resin 25. That is, the uneven shape formed on the surface 26 of the lower mold 23 is indirectly reflected on the surface of the thermosetting resin 25, and is included in the surface shape of the release film 11 (particularly in the surface layer 102). The surface shape caused by the particles) is directly reflected on the surface of the thermosetting resin 25. The thermosetting resin 25 is cured in a state where the uneven shape and the surface shape are reflected on the surface of the thermosetting resin 25. That is, the uneven shape and the surface shape are reflected on the surface of the molded product obtained as a result of the curing. Here, the unevenness formed on the surface of the molded product (cured product) may be different from the unevenness of the mold.
As described above, the combination of the present invention makes it possible to adjust the surface state of the molded product by the combination of the present invention.

After curing, the upper mold 22 is separated from the lower mold 23 as shown in FIG. 3 (D). The release film 11 is particularly excellent in releasability because its surface layer 102 is formed of a fluororesin containing particles. Therefore, in the step of FIG. 3D, the cured resin 25 can be smoothly released from the lower mold 23.

As described above, the combination of the present invention is used for curing a thermosetting resin. In particular, the combination of the present invention can be used to cure a thermosetting resin to obtain a molded product. The thermosetting resin is, for example, an epoxy resin or a silicone resin, preferably an epoxy resin. The combination of the present invention is particularly suitable for adjusting the surface condition of these resins.

The molding temperature in the molding in which the combination of the present invention is used may be appropriately selected depending on the type of the thermosetting resin. The molding temperature may be, for example, 100 ° C. to 250 ° C., preferably 120 ° C. to 200 ° C., and more preferably 150 ° C. to 200 ° C.

1-2. Release film

The release film constituting the combination of the present invention will be described with reference to FIG. As described above, FIG. 2 is a schematic view of an example of the laminated structure of the release film.

The release film 11 shown in FIG. 2 is a surface laminated on the surface of the base material layer 101 and the base material layer 101 which is arranged on the thermosetting resin side (molded body side) in the curing. Includes layer 102 (also referred to herein as the "mold side surface layer"). The base material layer 101 is formed of a thermoplastic resin. The molded body side surface layer 102 is formed of a fluorine-based resin containing particles. The fact that the release film 11 includes the base material layer 101 and the surface layer 102 on the molded body side contributes to enabling the surface adjustment as described in the above "1-1. How to use the combination of the present invention". Further, since the surface layer 102 on the molded body side is formed of a fluororesin containing particles, it is easy to separate from the cured molded body.

The release film 11 is also referred to as a surface layer 103 (also referred to as a “mold side surface layer” in the present specification) which is laminated on the surface arranged on the mold side in the curing of the two surfaces of the base material layer 101. Also includes). The mold side surface layer 103 may be preferably formed of a fluorine-based resin, and more preferably can be formed of a fluorine-based resin containing particles. As a result, the release film 11 is easily separated from the mold after the thermosetting resin is cured.

As described above, the release film 11 has a laminated structure in which the molded body side surface layer 102, the base material layer 101, and the mold side surface layer 103 are laminated in this order. Each layer will be described in more detail below.

[Base material layer]

The base material layer 101 is formed of a thermoplastic resin. The thermoplastic resin may preferably be a resin having a melting point equal to or higher than the molding temperature used in curing the thermosetting resin, and more preferably a melting point higher than the molding temperature. As a result, in the molding, the unevenness of the surface of the mold is easily reflected on the surface of the thermosetting resin via the release film 11.

The thermoplastic resin is preferably a polyester resin. The polyester resin is a polymer having an ester bond in the main chain. The polyester resin can be, for example, a polymer of a polyhydric alcohol and a polybasic acid. The polyester-based resin is a resin containing polyester as a main component, and may contain, for example, 90% by mass or more, preferably 95% by mass or more, preferably 98% by mass or more of polyester with respect to the mass of the resin.
The thermoplastic resin is selected from, for example, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polybutylene naphthalate (PBN), and polycarbonate (PC) resin resin. It may be one or a mixture of two or more. The thermoplastic resin is more preferably a PET resin or a PEN resin, and particularly preferably a PET resin. The PET resin is particularly suitable for reflecting the unevenness of the surface of the mold on the surface of the thermosetting resin in the molding.

The PET resin may be a general-purpose PET resin or an easily molded PET resin. The glass transition temperature of the general-purpose PET resin can be 100 ° C. or higher. In the present specification, the glass transition temperature is the glass transition temperature measured by differential thermal analysis (DTA). The glass transition temperature of the easily molded PET resin is less than 100 ° C., preferably 60 ° C. to 95 ° C., and more preferably 65 ° C. to 90 ° C. The easily molded PET resin is particularly suitable for preventing contamination of the mold or the molded product by the oligomer contained in the PET resin.

As the base material layer formed from the general-purpose PET resin, for example, a film of the Tetron (registered trademark) series can be used, but the present invention is not limited thereto.

The easily molded PET resin may be, for example, a copolymerized polyethylene terephthalate resin. The copolymerized polyethylene terephthalate may be obtained, for example, by reacting terephthalic acid with ethylene glycol and a copolymerization component, or the polymer of the copolymerization component and polyethylene terephthalate may be mixed and melted and then subjected to a distribution reaction. May be obtained by
The copolymerization component may be, for example, an acid component or an alcohol component. The acid components include aromatic dibasic acids (eg isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid, etc.), aliphatic dicarboxylic acids (eg, adipic acid, azelaic acid, sebacic acid, and decandicarboxylic acid, etc.), and alicyclic. Group dicarboxylic acids (eg cyclohexanedicarboxylic acids) can be mentioned. Examples of the alcohol component include aliphatic diols (such as butanediol, hexanediol, neopentyl glycol, and hexanediol) and alicyclic diols (such as cyclohexanedimethanol). As the copolymerization component, one or a combination of two or more of these compounds may be used. The acid component can be isophthalic acid and / or sebacic acid in particular.

As the base material layer formed from the easily molded PET resin, a commercially available one may be used. For example, Teflex (trademark) FT, Teflex (trademark) FT3, and Teflex (trademark) FW2 (all manufactured by Teijin Film Solutions Co., Ltd.) can be used as the base material layer formed from the easily molded PET resin. it can. Further, as a base material layer formed of an easily molded PET resin, Emblet CTK-38 (manufactured by Unitika Ltd.) may be used. Further, CH285J (manufactured by Nan Ya Plastics) may be used as the base material layer.
The base material layer formed from the easily molded PET resin may be produced, for example, by the method described in JP-A-2-305827, JP-A-3-86729, or JP-A-3-110124. .. According to one preferred embodiment of the present invention, the substrate layer preferably has a plane orientation coefficient of 0.06 to 0.16, more preferably 0.07 to 0.07, as described in any of these publications. The easily molded PET resin may be biaxially stretched so as to have a value of 0.15.

The tensile breaking strength of the base material layer is preferably 40 MPa to 200 MPa, more preferably 40 MPa to 120 MPa, still more preferably 40 MPa to 110 MPa, especially when measured at 175 ° C. according to JIS K7127. It can be preferably 45 MPa to 100 MPa.
The tensile elongation at break of the base material layer is preferably 200% to 500%, more preferably 250% to 450%, and even more preferably 300% to 300% when measured at 175 ° C. according to JIS K7127. It can be 400%.

The thickness of the base material layer can be, for example, 10 μm to 80 μm, preferably 15 μm to 75 μm, more preferably 20 μm to 70 μm, and particularly preferably 30 μm to 60 μm. The thickness is suitable for reflecting the uneven shape of the mold surface on the surface of the molded product.

[Surface layer on the molded body side]

The molded body side surface layer 102 is formed of a fluorine-based resin containing particles. According to a preferred embodiment of the present invention, the fluororesin does not contain chlorine. By not containing chlorine, the durability and / or antifouling property of the layer is improved. The fluorine-based resin can be, for example, a cured product of a fluorine-based resin composition containing a reactive functional group-containing fluorine-based polymer and a curing agent.
The fluorine-based resin preferably contains a tetrafluoroethylene-based resin, and more preferably contains a tetrafluoroethylene-based resin as a main component. In the present specification, the tetrafluoroethylene resin refers to a component obtained by a curing reaction between a reactive functional group-containing tetrafluoroethylene polymer described below and a curing agent. The fact that the tetrafluoroethylene resin is the main component means that the fluororesin consists only of the tetrafluoroethylene resin, or the amount of the tetrafluoroethylene resin among the components contained in the fluororesin. Means that is the most. For example, the content ratio of the tetrafluoroethylene resin in the fluororesin is, for example, 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more, based on the total mass of the fluororesin. Particularly preferably, it may be 85% by mass or more. The content ratio may be, for example, 99% by mass or less, particularly 98% by mass or less, and more particularly 97% by mass or less, based on the total mass of the fluorine-based resin.

The reactive functional group-containing fluorine-based polymer contained in the fluorine-based resin composition may be a fluorine-based polymer that can be cured by the curing agent. The reactive functional group and the curing agent may be appropriately selected by those skilled in the art.
The reactive functional group may be, for example, a hydroxyl group, a carboxyl group, a group represented by −COOCO−, an amino group, or a silyl group, and is preferably a hydroxyl group. With these groups, the reaction for obtaining the cured product proceeds well.
Of these reactive functional groups, the hydroxyl group is particularly suitable for the reaction for obtaining the cured product. That is, the reactive functional group-containing fluorine-based polymer may be preferably a hydroxyl group-containing fluorine-based polymer, and more preferably a hydroxyl group-containing tetrafluoroethylene-based polymer.

The fluorine-containing unit of the reactive functional group-containing fluorine-based polymer is preferably a fluorine-containing unit based on a perfluoroolefin. Fluorine-containing units based on the perfluoroolefin are more preferably tetrafluoroethylene (ethylene tetrafluoroethylene, also referred to as "TFE" in the present specification), hexafluoropropylene (HFP), and perfluoro (alkyl vinyl ether). It may be based on one, two, or three selected from (PAVE). Preferably, among the fluorine-containing units based on the perfluoroolefin, the fluorine-containing unit based on TFE is the most.

The hydroxyl value of the reactive functional group-containing fluoropolymer (particularly, the hydroxyl value of the hydroxyl group-containing fluoropolymer) is preferably 10 mgKOH / g to 300 mgKOH / g, and more preferably 10 mgKOH / g to 200 mgKOH / g. And even more preferably 10 mgKOH / g to 150 mgKOH / g. When the hydroxyl value of the reactive functional group-containing fluoropolymer is at least the lower limit of the above numerical range, the curability of the resin composition can be improved. Further, the fact that the hydroxyl value of the reactive functional group-containing fluoropolymer is not more than the upper limit of the above numerical range contributes to making the cured product of the resin composition suitable for molding a plurality of times. sell. The hydroxyl value is obtained by measuring by a method conforming to JIS K 0070.

The acid value of the reactive functional group-containing fluoropolymer (particularly the acid value of the hydroxyl group-containing fluoropolymer) is preferably 0.5 mgKOH / g to 100 mgKOH / g, more preferably 0.5 mgKOH / g. It can be ~ 50 mgKOH / g.

The reactive functional group of the reactive functional group-containing fluoropolymer is obtained by copolymerizing a monomer having the reactive functional group with a fluorine-containing monomer (particularly, the perfluoroolefin). May be introduced in. That is, the reactive functional group-containing fluoropolymer may contain a polymerization unit based on the reactive functional group-containing monomer and a polymerization unit based on the fluorine-containing monomer (particularly the perfluoroolefin).

When the reactive functional group is a hydroxyl group, the monomer having the reactive functional group can be preferably a hydroxyl group-containing vinyl ether or a hydroxyl group-containing allyl ether. Examples of the hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, and the like. 5-Hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether can be mentioned, and examples of the hydroxyl group-containing hydroxyl group-containing allyl ether include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. it can. Alternatively, the monomer having the reactive functional group may be a hydroxyalkyl ester of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. As the monomer having a reactive functional group, one or a combination of two or more of these compounds may be used. When the reactive functional group is a hydroxyl group, the monomer having the reactive functional group is more preferably a hydroxyl group-containing vinyl ether, particularly preferably 4-hydroxybutyl vinyl ether and, from the viewpoint of curability of the resin composition. / Or it can be 2-hydroxyethyl vinyl ether.

When the reactive functional group is a carboxyl group, the monomer having the reactive functional group may be preferably an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or an acid anhydride of an unsaturated carboxylic acid.
When the reactive functional group is an amino group, the monomer having the reactive functional group may be, for example, aminovinyl ether or allylamine.
When the reactive functional group is a silyl group, the monomer having the reactive functional group can be preferably a silicone-based vinyl monomer.

The fluorine-containing monomer is preferably a perfluoroolefin. Examples of perfluoroolefins include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and perfluoro (alkyl vinyl ether) (PAVE). Preferably, the fluorine-containing monomer comprises TFE.

Preferably, the reactive functional group-containing fluoropolymer may contain a polymerization unit based on a fluorine-free vinyl monomer in addition to a polymerization unit based on the reactive functional group-containing monomer and a polymerization unit based on the fluorine-containing monomer. The fluorine-free vinyl monomer may be one or a combination of two or more selected from the group consisting of, for example, carboxylic acid vinyl esters, alkyl vinyl ethers, and non-fluorinated olefins.
Examples of vinyl carboxylic acid esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl laurate, vinyl stearate, vinyl cyclohexyl carboxylate, vinyl benzoate, etc. And para-t-butyl benzoate vinyl can be mentioned.
Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.
Examples of the non-fluorinated olefin include ethylene, propylene, n-butene and isobutene.
Further, the reactive functional group-containing fluoropolymer is, for example, vinylidene fluoride (VdF), chloro, in addition to the polymerization unit based on the reactive functional group-containing monomer and the polymerization unit based on the fluorine-containing monomer which is a perfluoroolefin. It may contain polymerization units based on fluoromonomers other than perfluoroolefins, such as trifluoroethylene (CTFE), vinyl fluoride (VF), and fluorovinyl ether.

The reactive functional group-containing fluoropolymer is, for example, TFE / non-fluorinated olefin / hydroxybutyl vinyl ether-based copolymer, TFE / carboxylic acid vinyl ester / hydroxybutyl vinyl ether-based copolymer, or TFE / alkyl vinyl ether /. It can be a hydroxybutyl vinyl ether-based copolymer.
More specifically, the reactive functional group-containing fluoropolymer is TFE / isobutylene / hydroxybutyl vinyl ether-based copolymer, TFE / vinyl versatic acid / hydroxybutyl vinyl ether-based copolymer, or TFE / VdF / hydroxy. It can be a butyl vinyl ether-based copolymer. The reactive functional group-containing fluoropolymer may be particularly preferably a TFE / isobutylene / hydroxybutyl vinyl ether-based copolymer or a TFE / vinyl versatic acid / hydroxybutyl vinyl ether-based copolymer.
As the reactive functional group-containing fluorine-based polymer, for example, a product of the Zeffle GK series can be used.

The curing agent contained in the fluorine-based resin composition may be appropriately selected by a person skilled in the art according to the type of the reactive functional group contained in the reactive functional group-containing fluorine-based polymer.
When the reactive functional group is a hydroxyl group, the curing agent may be preferably one or a combination of two or more selected from an isocyanate-based curing agent, a melamine resin, a silicate compound, and an isocyanate group-containing silane compound.
When the reactive functional group is a carboxyl group, the curing agent may be preferably one or a combination of two or more selected from an amino-based curing agent and an epoxy-based curing agent.
When the reactive functional group is an amino group, the curing agent may be one or a combination of two or more selected from a carbonyl group-containing curing agent, an epoxy-based curing agent, and an acid anhydride-based curing agent.
The content of the curing agent in the fluorine-based resin composition is, for example, 15 parts by mass to 50 parts by mass, preferably 20 parts by mass to 40 parts by mass with respect to 100 parts by mass of the reactive functional group-containing fluorine-based polymer. Parts, more preferably 23 parts by mass to 35 parts by mass. These numerical ranges also apply to the content of the curing agent in the cured product of the fluororesin composition.
The content of the curing agent may be measured by a pyrolysis gas chromatograph (Py-GC / MS) method.

In one embodiment of the present invention, the reactive functional group contained in the reactive functional group-containing fluoropolymer may be a hydroxyl group and the curing agent may be an isocyanate-based curing agent. In this embodiment, the isocyanate-based curing agent is preferably hexamethylene diisocyanate (HDI) -based polyisocyanate.
The content of the HDI-based polyisocyanate in the fluorine-based resin composition is, for example, 15 parts by mass to 50 parts by mass, preferably 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the reactive functional group-containing fluorine-based polymer. It can be 40 parts by mass, more preferably 23 parts by mass to 35 parts by mass. These numerical ranges also apply to the content of the HDI-based polyisocyanate in the cured product of the fluororesin composition.

As the HDI-based polyisocyanate, for example, one or a combination of two or more selected from isocyanurate type polyisocyanate, adduct type polyisocyanate, and biuret type polyisocyanate can be used. In the present invention, the isocyanate-based curing agent may preferably be an isocyanurate-type polyisocyanate and / or an adduct-type polyisocyanate, and more preferably a combination of an isocyanurate-type polyisocyanate and an adduct-type polyisocyanate.
When a combination of isocyanurate-type polyisocyanate and adduct-type polyisocyanate is used as the curing agent, the mass ratio of the two is, for example, 10: 6 to 10:10, preferably 10: 7 to 10: 9. The total amount of both is, for example, 15 parts by mass to 50 parts by mass, preferably 20 parts by mass to 40 parts by mass, and more preferably 25 parts by mass to 35 parts by mass with respect to 100 parts by mass of the reactive functional group-containing fluoropolymer. It can be parts by mass.
The content ratio of these curing agents may be determined by a pyrolysis gas chromatograph (Py-GC / MS) method.

The fluororesin forming the surface layer on the molded body side contains particles, and preferably contains particles having an average particle size of 1 μm to 10 μm, more preferably 2 μm to 9 μm, measured according to a laser diffraction type particle size analysis measurement method. The average particle size is a volume average diameter weighted by volume and is measured according to JIS Z8825. By including the particles, the shape caused by the particles can be reflected on the surface of the molded product, and the releasability of the release film can be enhanced. Further, when the average particle size of the particles is smaller than the lower limit of the numerical range, the surface shape caused by the particles may not be reflected on the surface of the molded product. Further, when the average particle size of the particles is higher than the upper limit of the numerical range, the releasability may be lowered or the particles may fall off from the fluororesin. Further, when the average particle size of the particles is higher than the upper limit of the numerical range, for example, when the fluorine-based resin is applied to the base material layer, streaks may occur, which may make it difficult to manufacture a release film. ..

The particles are preferably inorganic particles or organic particles. Inorganic particles include, for example, silicon dioxide (particularly amorphous silicon dioxide), calcium carbonate, magnesium carbonate, calcium phosphate, kaolin, talc, aluminum oxide, titanium oxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, And molybdenum sulfide can be mentioned. Examples of the organic particles include crosslinked polymer particles and calcium oxalate. In the present invention, the particles are preferably inorganic particles, more preferably silicon dioxide particles, and even more preferably amorphous silicon dioxide. Amorphous silicon dioxide can be sol-gel type silica. As the amorphous silicon dioxide, for example, the amorphous silicon dioxide of the Cycilia series can be used.

The content of the particles in the fluorine-based resin composition is, for example, 1 part by mass to 30 parts by mass, preferably 2 parts by mass to 25 parts by mass with respect to 100 parts by mass of the reactive functional group-containing fluorine-based polymer. , More preferably 3 parts by mass to 20 parts by mass. These numerical ranges also apply to the content of the particles in the cured product of the fluororesin composition. When the content is within the above numerical range, it contributes to the surface shape caused by the particles being reflected in the molded product and / or to the improvement of the releasability of the releasable film.
According to one preferred embodiment of the present invention, the content of the particles in the fluorine-based resin composition is, for example, 1 part by mass to 17 parts by mass with respect to 100 parts by mass of the reactive functional group-containing fluorine-based polymer. It can be preferably 2 parts by mass to 16 parts by mass, and particularly preferably 3 parts by mass to 10 parts by mass. These numerical ranges also apply to the content of the particles in the cured product of the fluororesin composition. When the content is within the above numerical range, the visibility or readability when the surface of the molded product is printed or patterned with a laser marker can be improved.
The content of the particles may be measured by thermogravimetric analysis (TGA).

The fluororesin composition may contain a solvent. The type of solvent may be appropriately selected by those skilled in the art. Examples of the solvent include butyl acetate, ethyl acetate, and methyl ethyl ketone (also referred to as MEK). For example, a mixture of these three types can be used as the solvent. This mixture is suitable for preparing the fluororesin composition.

The fluororesin composition may contain a mold release accelerator. Examples of the release accelerator include amino-modified methylpolysiloxane, epoxy-modified methylpolysiloxane, carboxy-modified methylpolysiloxane, and carbinol-modified methylpolysiloxane. Preferably, the release accelerator is an amino-modified methylpolysiloxane.
The release accelerator is, for example, 0.01 part by mass to 3 parts by mass, preferably 0.05 part by mass to 2 parts by mass, and more preferably 0, based on 100 parts by mass of the reactive functional group-containing fluorine-based polymer. It can be 1 part by mass to 1 part by mass. These numerical ranges also apply to the content of the release accelerator in the cured product of the fluororesin composition.

The thickness of the surface layer on the molded body side can be, for example, 1 μm to 10 μm, preferably 2 to 9 μm, and more preferably 3 μm to 8 μm.

The fluorine-based resin composition can be produced by mixing and stirring the components described above by means known to those skilled in the art. Mixers such as high speed mixers, homomixers, and paint shakers can be used for the mixing and stirring. For the mixing and stirring, a dissolver such as an edge turbine type high-speed dissolver may be used.
The cured product of the fluorine-based resin composition is prepared by applying the fluorine-based resin composition to the surface of the base material layer, for example, at 100 ° C. to 200 ° C., preferably 120 ° C. to 180 ° C., for example, 10 seconds to 240 seconds. It is preferably obtained by heating for 30 seconds to 120 seconds. The cured product forms the surface layer. The amount of the fluororesin composition to be applied may be appropriately set by those skilled in the art according to the thickness of the surface layer to be formed.

The shape of the surface layer on the molded body side will be described with reference to FIG. The fluorine-based resin composition forming the surface layer on the molded body side is applied onto the base material layer. Immediately after the application, as shown in FIG. 4A, the resin composition is in a liquid state, and particles are present in the composition. By heating the resin composition as described above, the solvent in the composition is volatilized, and the state shown in FIG. 4B is obtained, and the shape caused by the particles appears. Finally, the cured product of the composition has a surface condition as shown in FIG. 4 (c), that is, an uneven shape due to particles appears. As shown in the schematic view of FIG. 4D, the release film has a molded body side surface layer 402 having irregularities due to particles on the base material layer 401. As described above, the release film constituting the combination of the present invention has a molded body side surface layer on which irregularities due to particles are formed.

[Mold side surface layer]

The mold side surface layer 103 may also be formed of a fluorine-based resin containing particles. According to a preferred embodiment of the present invention, the fluororesin does not contain chlorine. The fluorine-based resin preferably contains a tetrafluoroethylene-based resin, and more preferably contains a tetrafluoroethylene-based resin as a main component. The fluorine-based resin can be, for example, a cured product of a fluorine-based resin composition containing a reactive functional group-containing fluorine-based polymer and a curing agent.

With respect to the reactive functional group-containing fluoropolymer contained in the fluororesin composition, all the descriptions of the reactive functional group-containing fluoropolymer contained in the surface layer 102 on the molded body side described above apply. The description of the reactive functional group-containing fluoropolymer will be omitted.

As for the curing agent contained in the fluororesin composition, the description about the type and content of the curing agent contained in the surface layer 102 on the molded body side described above applies, so that the reactive functional group-containing fluorine-based weight The description of coalescence is omitted.

The fluorine-based resin forming the mold-side surface layer contains particles, and preferably contains particles having an average particle size of 1 μm to 10 μm, more preferably 2 μm to 9 μm, measured according to a laser diffraction particle size analysis measurement method. .. The average particle size is a volume average diameter weighted by volume and is measured according to JIS Z8825. By including the particles, the releasability of the release film can be enhanced. Further, when the average particle size of the particles is higher than the upper limit of the numerical range, the releasability may be lowered or the particles may fall off from the fluororesin. Further, when the average particle size of the particles is higher than the upper limit of the numerical range, for example, when the fluorine-based resin is applied to the base material layer, streaks may occur, which may make it difficult to manufacture a release film. ..

The particles are preferably inorganic particles or organic particles. Inorganic particles include, for example, silicon dioxide (particularly amorphous silicon dioxide), calcium carbonate, magnesium carbonate, calcium phosphate, kaolin, talc, aluminum oxide, titanium oxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, And molybdenum sulfide can be mentioned. Examples of the organic particles include crosslinked polymer particles and calcium oxalate. In the present invention, the particles are preferably inorganic particles, more preferably silicon dioxide particles, and even more preferably amorphous silicon dioxide. Amorphous silicon dioxide can be sol-gel type silica. As the amorphous silicon dioxide, for example, the amorphous silicon dioxide of the Cycilia series can be used.

The content of the particles in the fluororesin composition is, for example, 3 parts by mass to 30 parts by mass, preferably 5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the reactive functional group-containing fluorine-based polymer. , More preferably 10 parts by mass to 20 parts by mass. These numerical ranges also apply to the content of the particles in the cured product of the fluororesin composition. When the content is within the above numerical range, it contributes to the improvement of the releasability of the releasable film.
The content of the particles may be measured by thermogravimetric analysis (TGA).

The fluororesin composition may contain a solvent. The type of solvent may be appropriately selected by those skilled in the art. Examples of the solvent include butyl acetate, ethyl acetate, and methyl ethyl ketone (also referred to as MEK). For example, a mixture of these three types can be used as the solvent. This mixture is suitable for preparing the fluororesin composition.

The fluororesin composition may contain a mold release accelerator. Examples of the release accelerator include amino-modified methylpolysiloxane, epoxy-modified methylpolysiloxane, carboxy-modified methylpolysiloxane, and carbinol-modified methylpolysiloxane. Preferably, the release accelerator is an amino-modified methylpolysiloxane.
The release accelerator is, for example, 0.01 part by mass to 3 parts by mass, preferably 0.05 part by mass to 2 parts by mass, and more preferably 0, based on 100 parts by mass of the reactive functional group-containing fluorine-based polymer. It can be 1 part by mass to 1 part by mass. These numerical ranges also apply to the content of the release accelerator in the cured product of the fluororesin composition.
Preferably, the fluororesin composition used to form the mold side surface layer does not contain a mold release accelerator.

The thickness of the mold-side surface layer can be, for example, 1 μm to 10 μm, preferably 2 to 9 μm, and more preferably 3 μm to 8 μm.

Since all the descriptions of the method for producing the fluorine-based resin composition used for forming the surface layer 102 on the molded body side apply to the method for producing the fluorine-based resin composition, the description of the production method will be omitted.

In one preferred embodiment of the present technology, the molded product side surface layer is formed from the reactive functional group-containing fluorine-based polymer (particularly, a hydroxyl group-containing tetrafluoroethylene-based polymer), the curing agent, the particles, and the separation. It is formed from a cured product of a fluororesin composition containing a mold accelerator. Further, the surface layer on the mold side is a curing of a fluorine-based resin composition containing the reactive functional group-containing fluorine-based polymer (particularly, a hydroxyl group-containing tetrafluoroethylene-based polymer), the curing agent, and the particles. It is made of things.
More preferably, the molded product side surface layer is formed from a cured product of a fluororesin composition containing a hydroxyl group-containing tetrafluoroethylene-based polymer, HDI-based polyisocyanate, silicon dioxide particles, and amino-modified methylpolysiloxane. There is. The mold-side surface layer is formed from a cured product of a fluorine-based resin composition containing a hydroxyl group-containing tetrafluoroethylene-based polymer, HDI-based polyisocyanate, and silicon dioxide particles.
The fact that the release film has such two surface layers makes it possible to adjust the surface state of the molded body by the combination of the present invention and / or improves the releasability of the release film. Especially contributes.

[Characteristics of release film]

According to a preferred embodiment of the present invention, the tensile breaking strength of the release film is 40 MPa to 200 MPa, more preferably 40 MPa to 120 MPa, still more preferably 40 MPa when measured at 175 ° C. according to JIS K7127. It is ~ 110 MPa, particularly preferably 45 MPa ~ 100 MPa, and the tensile elongation at break of the release film is 200% to 500%, more preferably 250 when measured at 175 ° C. according to JIS K7127. It can be% to 450%, and even more preferably 300% to 400%.
It is suitable for adjusting the surface shape by the combination of the present invention that the tensile breaking strength and the tensile breaking elongation of the release film are within the above numerical ranges.

_{(O 2)} gas permeability of the release film, when measured at 175 ° C. according to JIS K7126-1, for example ^{5000~50000cc / m 2 · 24hr · atm} , particularly 5000~30000cc / ^{m 2} · 24 hr or · an atm, more particularly can be a less ^{5000~20000cc / m 2 · 24hr · atm} . The release film has such low gas permeability. Therefore, by performing molding using the release film, mold contamination by the gas generated from the resin is suppressed.

The thickness of the release film can be, for example, 30 μm to 100 μm, preferably 35 μm to 90 μm, and more preferably 40 μm to 80 μm. When the thickness of the release film is within the above numerical range, the uneven shape of the mold surface is easily reflected in the molded body.

The release film may be used for one molding, or may be used for a plurality of moldings. The release film can be used for molding, for example, 2 times or more, preferably 4 times or more, more preferably 5 times or more, more preferably 6 times or more, and even more preferably 8 times or more. The release film is molded, for example, 2 to 20 times, preferably 4 to 15 times, more preferably 5 to 15 times, more preferably 6 to 15 times, and even more preferably 8 to 12 times. Can be used for. The release film maintains its performance through multiple release and is not easily torn. Therefore, the release film can be used for a plurality of moldings. As a result, the molding cost can be reduced.
Further, the polyester resin (particularly PET resin) contains an oligomer, and the oligomer can be used in molding (particularly when a release film containing the resin is repeatedly used in a plurality of moldings) in a mold and /. Or it can contaminate the molded product. However, in the release film, even when the thermoplastic resin forming the base material layer is a polyester resin, contamination of the mold and / or the molded product during molding is unlikely to occur. The release film is less likely to contaminate the mold and / or the molded product even when the film is repeatedly used for molding a plurality of times. The low pollution property is considered to be due to the surface layer formed of the fluororesin in particular.

[Manufacturing method of release film]
The method for producing the release film includes a coating step of applying the fluorine-based resin composition to the two surfaces of the base material layer, and a curing step of curing the fluorine-based resin composition after the coating step.
Since the contents described above apply to the base material layer and the fluorine-based resin composition used in the coating step, the description thereof will be omitted.
The coating step may be appropriately performed by those skilled in the art so as to achieve a desired layer thickness. For example, the fluorine-based resin composition has two of the base material layers by a gravure roll method, a reverse roll method, an offset gravure method, a kiss coating method, a reverse kiss coating method, a wire bar coating method, a spray coating method, or an impregnation method. Can be applied to the surface. A device for performing coating by these methods may be appropriately selected by those skilled in the art.
The curing step comprises heating the fluororesin composition at, for example, 100 ° C. to 200 ° C., preferably 120 ° C. to 180 ° C., for example, 10 seconds to 240 seconds, preferably 30 seconds to 120 seconds. The heating cures the fluororesin composition.

1-3. Mold

In the mold constituting the combination of the present invention, irregularities are formed on the surface of the mold with which the release film comes into contact during the curing of the thermosetting resin. The unevenness is reflected on the surface of the thermosetting resin via the release film. As described above, the unevenness is indirectly reflected on the surface of the thermosetting resin. Therefore, the unevenness formed on the surface of the cured product of the thermosetting resin may be different from the unevenness of the mold.

According to one embodiment of the present invention, the unevenness may be provided on a part of the mold surface that the release film comes into contact with in the molding. For example, the unevenness may be provided only in the region of the mold surface that covers the surface portion of the molded product that needs to be surface-adjusted. As a result, it is possible to reduce the area of the mold surface where irregularities are formed, and it is possible to reduce the manufacturing cost of the mold.
According to another embodiment of the present invention, the unevenness may be provided on the entire surface of the mold with which the release film comes into contact in the molding.

The surface roughness Ra of the surface of the mold that comes into contact with the release film during the curing is preferably 1 μm to 4 μm, more preferably 1.2 μm to 3.8 μm, and particularly preferably 1.4 μm. It can be ~ 3.6 μm. When the surface of the mold having the unevenness has a surface roughness within the numerical range, the unevenness is easily reflected on the surface of the cured product of the thermosetting resin via the release film. If the surface roughness is too small, the surface adjustment may not be possible. Further, if the surface roughness is too large, the release film may be difficult to separate from the mold, and / or the release film may be torn during molding. Further, if the surface roughness is too large, the surface roughness of the mold becomes non-uniform, which may adversely affect the appearance of the molded product.
In the present specification, the surface roughness Ra is measured according to JIS B0601.

The unevenness of the mold surface may be formed by a method known in the art such as electric discharge machining (EDM) or shot blasting, but is preferably formed by electric discharge machining (EDM). Electric discharge machining is suitable for forming a surface having a surface roughness Ra within the above numerical range. The electric discharge machining is particularly suitable for imparting surface roughness as described above to a metal surface, for example. The electric discharge machining may be performed by a method and an apparatus known in the art, and by setting the electric discharge machining apparatus so that a desired unevenness is formed and performing the electric discharge machining process, the unevenness is formed into a mold. Can be formed on the surface.

The material of the mold may be appropriately selected by those skilled in the art depending on, for example, the type of thermosetting resin and / or the shape of the molded product. The mold material may be selected from, for example, materials commonly used in transfer molding or compression molding. The material of the mold may be, for example, martensitic stainless steel, more specifically SUS404C. The hardness of the mold is preferably 50 HRC or more, and more preferably 55 HRC or more. The mold may be manufactured by a method known in the art, for example by NC cutting.

The mold is preferably surface-treated. The type of the surface treatment may be appropriately selected by those skilled in the art depending on the material of the mold. When the material of the mold is martensitic stainless steel, the mold can be subjected to, for example, hard chrome plating.

2. 2. Release film

The present invention also provides a release film used in combination with a mold for curing a thermosetting resin. The release film is a release film constituting the combination of the present invention described in "1. Combination of mold and release film", and all of the explanations also apply to the release film of the present invention. ..

By using the release film of the present invention in the curing of a thermosetting resin in combination with the mold described in "1. Combination of a mold and a release film" above, a cured product of the thermosetting resin can be obtained. The surface condition of the molded product can be adjusted. The release film of the present invention is suitable for reflecting the unevenness of the surface of the mold on the molded product.
Further, the release film of the present invention is excellent in releasability. The release film is smoothly separated from the mold even though the portion of the mold surface that comes into contact with the release film during the curing is provided with irregularities.

3. 3. Mold

The present invention also provides a mold used in combination with a release film for curing a thermosetting resin. The mold is a mold constituting the combination of the present invention described in "1. Combination of mold and mold release film", and all of the explanations also apply to the mold of the present invention.

By using the mold of the present invention in the curing of a thermosetting resin in combination with the mold release film described in "1. Combination of mold and mold release film", the cured product of the thermosetting resin can be obtained. The surface condition of the molded product can be adjusted.

4. Manufacturing method of molded product

The present invention provides a method for producing a molded product. The manufacturing method includes an arrangement step of arranging a release film in a mold used for curing a thermosetting resin, and a release of the thermosetting resin in the mold after the arrangement step. It includes a curing step of curing in contact with a mold film, and a mold removing step of removing the cured thermosetting resin from the mold after the curing step to obtain a molded product.

The mold and the release film used in the production method of the present invention are the mold and the release film constituting the combination of the present invention described in the above "1. Combination of the mold and the release film". , All of the above description also applies to the manufacturing method of the present invention. The method for producing the molded product may, for example, follow a transfer molding method or a compression molding method, but is not limited thereto.

In the arrangement step, the release film is arranged in the mold. The release film is formed so that the surface layer on the molded body side of the release film is in contact with the thermosetting resin and the surface layer on the mold side is in contact with the surface on which the unevenness of the mold is formed. It can be placed in the mold. For example, the release film is arranged in the arrangement step so as to be in the state shown in FIG. 1 (A) or FIG. 3 (A) described in the above "1-1. How to use the combination of the present invention". Can be done.

After the placement step, the release film can be attached to the surface of the mold on which the irregularities are formed, for example by suction. Prior to the application, the release film may be softened by heating.

In the curing step, the thermosetting resin is cured in the mold.
For example, in transfer molding, a closed space can be formed so that the thermosetting resin does not leak from the mold prior to the curing. For example, as shown in FIG. 1 (B), the upper mold and the lower mold are closed to form a closed space. Then, as shown in FIG. 1C, the thermosetting resin is introduced into the closed space, and the thermosetting resin can be cured by heating.
For example, in compression molding, a thermosetting resin can be introduced into a mold prior to the curing. For example, as shown in FIG. 3B, the thermosetting resin can be introduced into the recess of the lower mold. Then, as shown in FIG. 3C, the upper mold having the semiconductor element mounting substrate is moved toward the lower mold, and these molds are closed. With these molds closed, the thermosetting resin is cured by heating.

In the curing step, the uneven shape formed on the surface of the mold is indirectly reflected on the surface of the thermosetting resin, and the surface shape of the release film (particularly in the surface layer on the molded body side). The surface shape caused by the contained particles) is directly reflected on the surface of the thermosetting resin. The thermosetting resin is cured in a state where the uneven shape and the surface shape are reflected on the surface of the thermosetting resin. That is, the uneven shape and the surface shape are reflected on the surface of the molded product obtained as a result of the curing. In this way, the surface condition of the molded product is adjusted.

In the mold release step, the cured thermosetting resin (molded product) is released from the mold. For example, as shown in FIG. 1 (D) or FIG. 3 (D), the molded product leaves the mold having the surface on which the unevenness is formed.

The manufacturing method of the present invention may further include a printing step of printing with a laser marker on the surface of the molded product whose surface state has been adjusted as described above after the mold release step. By the manufacturing method according to the present invention, the visibility or readability of printing by the laser marker can be improved. The character height of the print may be, for example, 0.1 mm to 10 mm, preferably 0.2 mm to 5 mm. The character height of the print may be particularly 0.5 mm to 3 mm. The surface of the molded product obtained by the manufacturing method according to the present invention can enhance the visibility or readability of such small characters.

By the above steps, a molded product having an adjusted surface condition can be obtained.

Hereinafter, the present invention will be described in more detail based on Examples. The examples described below show examples of typical examples of the present invention, and the scope of the present invention is not limited to these examples.

Example 1: Example of surface adjustment of a molded product

(1) Manufacture of release film

As described below, two types of release films were produced.

(1-1) Manufacture of release film

As a base material layer, a film (Tetron G2CW, Teijin Limited, thickness 38 μm) formed of a general-purpose polyethylene terephthalate resin was prepared.
Next, two types of fluorine-based resin compositions (hereinafter, referred to as a first fluorine-based resin composition and a second fluorine-based resin composition) for coating on the film were prepared. The first fluorine-based resin composition is for forming a surface layer on the mold side. The second fluorine-based resin composition is for forming a surface layer on the molded body side.
The first fluorine-based resin composition is 100 parts by mass (Zefle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing ethylene tetrafluoride polymer) of the hydroxylated-containing ethylene tetrafluoride polymer-containing composition. ), 11.47 parts by mass of amorphous silicon dioxide (Cycilia 380, Fuji Silysia Chemical Ltd.), 10 parts by mass of isocyanurate type polyisocyanate (hardener, Sumijour N3300, Sumitomo Bayer Urethane Co., Ltd.), Adduct type polyisocyanate It was prepared by mixing and stirring 7.79 parts by mass (hardener, duranate AE700-100), 6.18 parts by mass of butyl acetate, 44.62 parts by mass of ethyl acetate, and 89.25 parts by mass of MEK. When the average particle size of the amorphous silicon dioxide (which is the volume average diameter) is measured according to the laser diffraction type particle size analysis measurement method using a particle size analyzer (SALD-2200, Shimadzu Corporation). , 8.8 μm.
As for the second fluororesin composition, 0.31 part by mass of amino-modified methylpolysiloxane (release accelerator, Shin-Etsu Chemical Industry Co., Ltd.) was added to the first fluororesin composition, and the amount of ethyl acetate was added. Is changed to 44.81 parts by mass and the amount of MEK is changed to 89.63 parts by mass, which is the same as that of the first fluororesin composition.

The first fluorine-based resin composition was applied to one surface of the film, and the second fluorine-based resin composition was applied to the other surface of the film. These coatings were performed using a kiss-reverse coating device. After the coating, these compositions are cured by heating at 150 ° C. for 60 seconds, and a release film in which a fluorine-based resin layer is laminated on both sides of a general-purpose PET resin film (hereinafter, “release film 1””. ) Was obtained.

The thickness of the release film 1 was 60 ± 5 μm. The thickness of the base material layer in the release film 1 was 38 μm ± 10%. Of the two surface layers of the release film 1, the thickness of the mold side surface layer was 5.5 ± 0.5 μm, and the thickness of the molded body side surface layer was 5.5 ± 0.5 μm.

The cured product (mold side surface layer) of the first fluorine-based resin composition contains 17.65 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. , The isocyanurate-type polyisocyanate was contained in an amount of 15.39 parts by mass, and the adduct-type polyisocyanate was contained in an amount of 11.98 parts by mass.

The cured product (surface layer on the molded body side) of the second fluororesin composition contains 17.65 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. It contained 15.39 parts by mass of the isocyanurate-type polyisocyanate, 11.98 parts by mass of the adduct-type polyisocyanate, and 0.48 parts by mass of an amino-modified methylpolysiloxane.

(1-2) Manufacture of release film

The release film (hereinafter, "release film") is formed in the same manner as in (1-1) above, except that the composition of the second fluorine-based resin composition described in (1-1) above is changed as follows. 2 ”) was manufactured.
That is, the second fluorine-based resin composition is 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer-containing composition (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing ethylene tetrafluoride polymer. ), Amorphous silicon dioxide 3.42 parts by mass (Cycilia 430, Fuji Silysia Chemical Ltd.), Isocyanurate type polyisocyanate 10 parts by mass (hardener, Sumijour N3300, Sumitomo Bayer Urethane Co., Ltd.), Adduct type 7.79 parts by mass of polyisocyanate (hardener, duranate AE700-100), 1.84 parts by mass of butyl acetate, 41.15 parts by mass of ethyl acetate, 82.30 parts by mass of MEK, and 0.11 parts by mass of amino-modified methylpolysiloxane. (Separation accelerator, Shin-Etsu Chemical Industry Co., Ltd.) was prepared by mixing and stirring. The average particle size of the amorphous silicon dioxide (which is the volume average diameter) is measured according to a laser diffraction type particle size analysis measurement method using a particle size analyzer (SALD-2200, Shimadzu Corporation). It was 4.1 μm.

The thickness of the release film 2 was 60 ± 5 μm. The thickness of the base material layer in the release film 2 was 38 μm ± 10%. Of the two surface layers of the release film 2, the thickness of the surface layer on the mold side was 5.5 ± 0.5 μm, and the thickness of the surface layer on the molded body side was 3.5 ± 0.5 μm.

The cured product (mold side surface layer) of the first fluorine-based resin composition contains 17.65 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. , The isocyanurate-type polyisocyanate was contained in an amount of 15.39 parts by mass, and the adduct-type polyisocyanate was contained in an amount of 11.98 parts by mass.

The cured product (surface layer on the molded body side) of the second fluorine-based resin composition contains 5.26 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. It contained 15.39 parts by mass of the isocyanurate-type polyisocyanate, 11.98 parts by mass of the adduct-type polyisocyanate, and 0.16 parts by mass of an amino-modified methylpolysiloxane.

(2) Mold manufacturing

Four molds were manufactured. All of these four molds are molds for transfer mold molding consisting of a combination of an upper mold and a lower mold, and have the same shape except that the irregularities provided on the cavity surface of the upper mold are different. Had. The unevenness was provided at a position corresponding to the surface 16 of the upper mold 12 of FIG. 1 (A). All of the irregularities were formed by electric discharge machining.

The surface roughness Ra of the uneven region of the four molds was 2.0 μm, 2.5 μm, 3.0 μm, and 3.5 μm, respectively, as measured according to JIS B0601. A mold having a surface having a surface roughness Ra of 2.0 μm is hereinafter referred to as “mold 1”. The molds having a surface roughness Ra of 2.5 μm, 3.0 μm, and 3.5 μm are also referred to as “mold 2”, “mold 3”, and “mold 4”, respectively.

The main material of these four molds was SUS440C. Further, all of these four molds had a hardness of HRC55 or higher, and the surface thereof was hard chrome plated.

(3) Manufacture of molded product

A thermosetting resin (epoxy resin, GE100, Hitachi Chemical Co., Ltd.) was molded using a combination of a release film and a mold as shown in Table 1 below. A transfer pressure of 8.5 MPa or 5.0 MPa was adopted in the molding. The molding temperature adopted for curing the thermosetting resin in the molding was 175 ° C. The glossiness of the surface of each molded product obtained by the molding at an incident angle of 60 ° was measured by a glossiness meter (PG-IIM, Nippon Denshoku Industries Co., Ltd.). The measurement results are also shown in Table 1 below.

As shown in Table 1, when the release film 1 was used, the glossiness decreased as the Ra of the mold increased. From these results, it can be seen that the unevenness of the molds 1 to 4 is reflected in the surface state of the molded product via the release film 1.
Similarly, when the release film 2 was used, the glossiness decreased as the Ra of the mold increased. From this result, it can be seen that the unevenness of the molds 1 to 4 is reflected in the surface state of the molded product via the release film 2.

Further, comparing the four results when the mold 1 is used, even if the mold is the same, the glossiness of the surface of the molded product differs depending on the difference in the release film. The release films 1 and 2 have different compositions of the surface layer on the molded body side, and particularly different in the content ratio of particles in the surface layer. From these results, it can be seen that the shape of the surface layer of the release film, particularly the shape caused by the particles in the surface layer, is reflected in the surface state of the molded product.

From the above results, it can be seen that the surface condition of the molded product can be adjusted by the combination of the mold and the release film according to the present invention. For example, it can be seen that the glossiness of the surface of the molded product can be adjusted by the combination.

In addition, the surface state of all the obtained molded bodies (particularly the state of unevenness on the surface) is different from the unevenness of the surface of the mold used, and the surface state of the surface layer on the molded body side of the release film used. It was also different. From this result, it is considered that both the unevenness of the mold surface and the shape of the surface layer on the molded body side of the release film contribute to the adjustment of the surface state of the molded body (particularly the state of the surface unevenness).

Further, in the molding, all the release films were smoothly separated from the molded body. Therefore, it can be seen that the release film constituting the combination of the present invention can be smoothly separated from the molded product after molding the molded product having irregularities on the surface.

Example 2: Evaluation of the surface of the molded product printed by the laser marker

(1) Manufacture of release film

As described below, three types of release films were produced.

(1-1) Manufacture of release film

As a base material layer, a film (CH285J, Nan Ya Plastics, thickness 50 μm) formed of an easily molded polyethylene terephthalate resin was prepared.
Next, two types of fluorine-based resin compositions (hereinafter, referred to as a first fluorine-based resin composition and a second fluorine-based resin composition) for coating on the film were prepared. The first fluorine-based resin composition is for forming a surface layer on the mold side. The second fluorine-based resin composition is for forming a surface layer on the molded body side.
The first fluorine-based resin composition is 100 parts by mass (Zefle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing ethylene tetrafluoride polymer) of the hydroxylated-containing ethylene tetrafluoride polymer-containing composition. ), 11.47 parts by mass of amorphous silicon dioxide (Cycilia 380, Fuji Silysia Chemical Ltd.), 10 parts by mass of isocyanurate type polyisocyanate (hardener, Sumijour N3300, Sumitomo Bayer Urethane Co., Ltd.), Adduct type polyisocyanate It was prepared by mixing and stirring 7.79 parts by mass (hardener, duranate AE700-100), 6.18 parts by mass of butyl acetate, 44.62 parts by mass of ethyl acetate, and 89.25 parts by mass of MEK. When the average particle size of the amorphous silicon dioxide (which is the volume average diameter) is measured according to the laser diffraction type particle size analysis measurement method using a particle size analyzer (SALD-2200, Shimadzu Corporation). , 8.8 μm.
As for the second fluororesin composition, 0.31 part by mass of amino-modified methylpolysiloxane (release accelerator, Shin-Etsu Chemical Industry Co., Ltd.) was added to the first fluororesin composition, and the amount of ethyl acetate. Is changed to 44.81 parts by mass and the amount of MEK is changed to 89.63 parts by mass, which is the same as that of the first fluororesin composition.

The first fluorine-based resin composition was applied to one surface of the film, and the second fluorine-based resin composition was applied to the other surface of the film. These coatings were performed using a kiss-reverse coating device. After the coating, these compositions are cured by heating at 150 ° C. for 60 seconds, and a release film in which a fluorine-based resin layer is laminated on both sides of a general-purpose PET resin film (hereinafter, “release film 3””. ) Was obtained.

The thickness of the release film 3 was 70 ± 5 μm. The thickness of the base material layer in the release film 3 was 50 μm ± 10%. Of the two surface layers of the release film 3, the thickness of the mold-side surface layer was 5.5 ± 0.5 μm, and the thickness of the molded product-side surface layer was 5.5 ± 0.5 μm.

The cured product (mold side surface layer) of the first fluorine-based resin composition contains 17.65 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. , The isocyanurate-type polyisocyanate was contained in an amount of 15.39 parts by mass, and the adduct-type polyisocyanate was contained in an amount of 11.98 parts by mass.

The cured product (surface layer on the molded body side) of the second fluororesin composition contains 17.65 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. It contained 15.39 parts by mass of the isocyanurate-type polyisocyanate, 11.98 parts by mass of the adduct-type polyisocyanate, and 0.48 parts by mass of an amino-modified methylpolysiloxane.

(1-2) Manufacture of release film

The release film (hereinafter referred to as the release film) is formed in the same manner as the release film 3 described in the above (1-1) except that the composition of the second fluorine-based resin composition described in the above (1-1) is changed as follows. , "Release film 4") was manufactured.
That is, the second fluorine-based resin composition is 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer-containing composition (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing ethylene tetrafluoride polymer. ), Amorphous silicon dioxide 9.71 parts by mass (Cycilia 380, Fuji Silysia Chemical Ltd.), Isocyanurate type polyisocyanate 10 parts by mass (hardener, Sumijour N3300, Sumitomo Bayer Urethane Co., Ltd.), Adduct type 7.79 parts by mass of polyisocyanate (hardener, duranate AE700-100), 5.23 parts by mass of butyl acetate, 44.03 parts by mass of ethyl acetate, 88.07 parts by mass of MEK, and 0.30 parts by mass of amino-modified methylpolysiloxane. (Separation accelerator, Shin-Etsu Chemical Industry Co., Ltd.) was prepared by mixing and stirring.

The thickness of the release film 4 was 60 ± 5 μm. The thickness of the base material layer in the release film 4 was 50 μm ± 10%. Of the two surface layers of the release film 4, the thickness of the mold-side surface layer was 5.5 ± 0.5 μm, and the thickness of the molded product-side surface layer was 5.5 ± 0.5 μm.

The cured product (mold side surface layer) of the first fluorine-based resin composition contains 17.65 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. , The isocyanurate-type polyisocyanate was contained in an amount of 15.39 parts by mass, and the adduct-type polyisocyanate was contained in an amount of 11.97 parts by mass.

The cured product (surface layer on the molded body side) of the second fluororesin composition contains 14.94 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. It contained 15.38 parts by mass of the isocyanurate-type polyisocyanate, 11.97 parts by mass of the adduct-type polyisocyanate, and 0.46 parts by mass of an amino-modified methylpolysiloxane.

(1-3) Manufacture of release film

The mold release film (hereinafter , "Release film 5") was manufactured.
That is, the second fluorine-based resin composition is 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer-containing composition (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing ethylene tetrafluoride resin. Yes), Amorphous silicon dioxide 3.42 parts by mass (Cycilia 380, Fuji Silysia Chemical Ltd.), Isocyanurate type polyisocyanate 10 parts by mass (hardener, Sumijour N3300, Sumitomo Bayer Urethane Co., Ltd.), Adduct type poly 7.79 parts by mass of isocyanate (hardener, duranate AE700-100), 1.84 parts by mass of butyl acetate, 41.15 parts by mass of ethyl acetate, 82.30 parts by mass of MEK, and 0.11 parts by mass of amino-modified methylpolysiloxane ( It was prepared by mixing and stirring a release accelerator (Shinetsu Chemical Industry Co., Ltd.).

The thickness of the release film 5 was 60 ± 5 μm. The thickness of the base material layer in the release film 5 was 50 μm ± 10%. Of the two surface layers of the release film 5, the thickness of the mold-side surface layer was 5.5 ± 0.5 μm, and the thickness of the molded product-side surface layer was 3.5 ± 0.5 μm.

The cured product (mold side surface layer) of the first fluorine-based resin composition contains 17.65 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. , The isocyanurate-type polyisocyanate was contained in an amount of 15.39 parts by mass, and the adduct-type polyisocyanate was contained in an amount of 11.98 parts by mass.

The cured product (surface layer on the molded body side) of the second fluorine-based resin composition contains 5.26 parts by mass of the amorphous silicon dioxide with respect to 100 parts by mass of the hydroxyl group-containing ethylene tetrafluoride polymer. It contained 15.39 parts by mass of the isocyanurate-type polyisocyanate, 11.98 parts by mass of the adduct-type polyisocyanate, and 0.16 parts by mass of an amino-modified methylpolysiloxane.

(2) Mold manufacturing

A mold for compression mold (hereinafter referred to as "mold 5") composed of a combination of an upper mold and a lower mold was manufactured. Unevenness was formed on the surface of the lower mold constituting the mold. The unevenness was provided at a position corresponding to the surface 26 of the lower mold 23 of FIG. 3 (A). The unevenness was formed by electric discharge machining. The surface roughness Ra of the region where the unevenness was formed was 1.0 μm when measured according to JIS B0601.

The main material of the mold 5 was SUS440C. Further, the mold 5 had a hardness of HRC55 or higher, and its surface was hard chrome plated.

(3) Manufacture of molded product

A thermosetting resin (epoxy resin, GE100, Hitachi Chemical Co., Ltd.) was molded using any one of the release films 3 to 5 and the mold 5. The molding temperature adopted for curing the thermosetting resin in the molding was 175 ° C. The surface of each molded product obtained by the molding was printed with a laser marker (MD-S9910 type 3D YVO ₄ laser marker, KEYENCE CORPORATION). The printing conditions were as follows:
Character height: 1 mm
Power: 3.6W
Switch frequency: 40KHz
Scan speed: 700 mm / s

The printing on the surface of each molded product was visually observed with a 3D microscope (VR-3200 type 3D microscope, KEYENCE Co., Ltd.).

The observation result by the 3D microscope is shown in FIG. As shown in FIG. 5, the molded body obtained by using the release film 4 has better visibility of characters than the molded body obtained by using the release film 3, and further, the release film is obtained. The visibility of the characters was better in the molded product obtained by using the release film 5 than in the molded product obtained by using 4. Similar observation results were obtained in the case of visual inspection. Based on these results, even when a mold having the same surface unevenness is used, the surface condition of the molded body can be adjusted by using a release film having a different shape of the surface layer on the molded body side of the release film. You can see that you can.

Further, based on the above results, the particle content of the surface layer on the molded body side is preferably 16 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the fluororesin, and is printed by the laser marker. It is considered that the visibility of the characters or patterns can be improved.

The present invention may also adopt the following configuration.
[1]
It is a combination of a mold used for curing a thermosetting resin and a release film arranged between the thermosetting resin and the mold in the curing.
The release film is
A substrate layer formed of a thermoplastic resin and
A surface layer formed of a fluorine-based resin containing particles, which is laminated on the surface arranged on the thermosetting resin side in the curing of the two surfaces of the base material layer, and
Including and
The mold has irregularities formed on the surface that comes into contact with the release film during the curing.
The combination.
[2]
The combination according to [1], wherein the average particle size of the particles is 1 μm to 10 μm when measured according to a laser diffraction type particle size analysis measurement method.
[3]
The combination according to [1] or [2], wherein the surface roughness Ra of the surface of the mold that comes into contact with the release film during the curing is 1 μm to 4 μm.
[4]
The combination according to any one of claims [1] to [3], wherein the fluorine-based resin in the surface layer contains a tetrafluoroethylene-based resin.
[5]
The combination according to any one of [1] to [4], wherein the fluorine-based resin in the surface layer further contains an isocyanate-based curing agent.
[6]
The combination according to any one of [1] to [5], wherein the particles are silicon dioxide.
[7]
The combination according to any one of [1] to [6], wherein the thermoplastic resin of the base material layer is a polyethylene terephthalate resin.
[8]
The combination according to any one of [1] to [7], wherein the thermosetting resin is an epoxy resin.
[9]
The combination according to any one of [1] to [8], which is used for forming irregularities on the surface of a cured product of the thermosetting resin.
[10]
The combination according to [9], wherein the unevenness formed on the surface of the cured product of the thermosetting resin is different from the unevenness of the mold.
[11]
The combination according to any one of [1] to [10], wherein the combination is used for transfer molding or compression molding.
[12]
A mold release film used in combination with a mold for curing thermosetting resins.
The release film is
A substrate layer formed of a thermoplastic resin and
A surface layer formed of a fluorine-based resin containing particles, which is laminated on the surface arranged on the thermosetting resin side in the curing of the two surfaces of the base material layer, and
Including
The mold has irregularities formed on the surface that comes into contact with the release film during the curing.
The release film.
[13]
A mold used in combination with a release film for curing thermosetting resins.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
The release film is
A substrate layer formed of a thermoplastic resin and
A surface layer formed of a fluorine-based resin containing particles, which is laminated on the surface arranged on the thermosetting resin side in the curing of the two surfaces of the base material layer, and
The mold, including.
[14]
An arrangement process for arranging the release film in the mold used to cure the thermosetting resin, and
After the placement step, a curing step of curing the thermosetting resin in the mold in contact with the release film,
After the curing step, the present invention includes a mold release step of releasing the cured thermosetting resin from the mold to obtain a molded product.
The release film is
A substrate layer formed of a thermoplastic resin and
A surface layer formed of a fluorine-based resin containing particles, which is laminated on the surface arranged on the thermosetting resin side in the curing of the two surfaces of the base material layer, and
Including
The mold has irregularities formed on the surface that comes into contact with the release film during the curing.
A method for manufacturing a molded product.

11 Release film 12 Upper mold 13 Lower mold

Claims (12)

A mold used in combination with a release film for curing thermosetting resins.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film.
The mold. The mold according to claim 1, wherein the surface roughness Ra of the surface of the mold is 1 μm to 4 μm. The mold according to claim 1 or 2, wherein the mold hardness of the mold is 50 HRC or more. The mold according to any one of claims 1 to 3, wherein the unevenness is an unevenness formed by electric discharge machining or shot blasting. The invention according to any one of claims 1 to 4, which is used for forming a surface having a glossiness of 3 to 50 at an incident angle of 60 ° on a molded product obtained by curing the thermosetting resin. Mold. The release film used in combination with the mold
A substrate layer formed of a thermoplastic resin and
A surface layer formed of a fluorine-based resin containing particles, which is laminated on the surface arranged on the thermosetting resin side in the curing of the two surfaces of the base material layer, is included.
The mold according to any one of claims 1 to 5. The mold according to any one of claims 1 to 6, wherein in the curing, the surface shape of the release film caused by the particles is directly reflected on the surface of the thermosetting resin. An arrangement process for arranging the release film in the mold used to cure the thermosetting resin, and
After the placement step, a curing step of curing the thermosetting resin in the mold in contact with the release film,
After the curing step, the present invention includes a mold release step of releasing the cured thermosetting resin from the mold to obtain a molded product.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing step, the unevenness is reflected on the surface of the thermosetting resin via the release film.
A method for manufacturing a molded product. A mold release film used in combination with a mold for curing thermosetting resins.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing, it is used to reflect the unevenness on the surface of the thermosetting resin via the release film.
The release film. The tensile breaking strength of the release film is 40 MPa to 200 MPa when measured at 175 ° C. according to JIS K7127, and the tensile breaking elongation of the release film is measured at 175 ° C. according to JIS K7127. The release film according to claim 9, which is 200% to 500%. The release film according to claim 9 or 10, wherein the release film has a thickness of 30 μm to 100 μm. A combination of a mold and a mold release film used for curing thermosetting resins.
The mold has irregularities formed on the surface that comes into contact with the release film during the curing, and the mold has irregularities.
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film.
The combination.