JP7347803B2 - Combination of mold and release film, method for manufacturing release film, mold, and molded object - Google Patents

Description

The present invention relates to a combination of a mold and a release film, a release film, a mold, and a method for manufacturing a molded article, and more specifically to a mold and a release film used for transfer molding or compression molding. , a release film and a mold constituting the combination, and a method for manufacturing a molded article using the combination.

In order to seal semiconductors with resin, molding techniques such as transfer molding and compression molding are used. In the above molding method, a release film is often used to easily remove the molded article from the mold after the resin has hardened within the mold. Until now, various proposals have been made regarding 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 mold release component (B), and a layer formed from a non-fluorinated polymer. Disclosed is a release film characterized by comprising:
Further, Patent Document 2 below discloses that a molded product on which a semiconductor chip is mounted is clamped between first and second molds facing each other, and the molded product is sealed using a resin filled in the mold. a resin-sealing mold for sealing, wherein at least one of the first and second molds has a thickness that is smaller than a thickness of the resin filled in the mold in a direction in which the molds face each other; A resin-sealed mold is disclosed in which a first heater is disposed near the surface of the mold.

Japanese Patent Application Publication No. 2015-74201 JP2012-256925A

It may be necessary to adjust the surface of the molded body. For example, the surface of the molded body may be printed with a laser marker, and it may be required to form a surface that improves the visibility of the printing or the readability of the print by a reading device.

The present invention aims to provide a new technique for adjusting the surface of the molded body.

The present inventors have discovered that a specific mold, manufacturing method, release film, and combination of the mold and release film are suitable for surface conditioning of the molded article.

That is, the present invention
A mold used in combination with a release film for curing a thermosetting resin,
The mold has unevenness formed on a surface that contacts the release film during the curing,
The surface roughness Ra of the surface of the mold is 1 μm to 4 μm ,
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film, and
Used to form a surface having a glossiness of 3 to 50 at an incident angle of 60° on the molded body obtained by curing the thermosetting resin,
The mold is provided.
The surface may be an epoxy resin surface.
The mold may have a mold hardness of 50HRC or more.
The molded body may have a surface printed with a laser marker.
The character height of the printing may be 0.1 mm to 10 mm.
The release film used in combination with the mold,
a base material layer formed from a thermoplastic resin;
The surface layer may include a surface layer formed of a fluororesin containing particles and laminated on the surface of the base material layer that is disposed on the thermosetting resin side during curing.
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.

Moreover, the present invention
a step of arranging a release film in a mold used for curing the thermosetting resin;
After the placement step, a curing step of curing the thermosetting resin in the mold while in contact with the release film;
After the curing step, the cured thermosetting resin is released from the mold to obtain a molded object, and
The mold has unevenness formed on a surface that contacts the release film during the curing,
The surface roughness Ra of the surface of the mold is 1 μm to 4 μm,
The unevenness is an unevenness formed by electrical discharge machining or shot blasting,
In the curing step, the unevenness is reflected on the surface of the thermosetting resin via the release film , and
A surface having a glossiness of 3 to 50 at an incident angle of 60° is formed on the molded body obtained by curing the thermosetting resin.
A method of manufacturing the molded body is also provided.

Moreover, the present invention
A release film used in combination with a mold for curing a thermosetting resin,
The mold has unevenness formed on a surface that contacts the release film during the curing,
The surface roughness Ra of the surface of the mold is 1 μm to 4 μm,
The unevenness is an unevenness formed by electrical discharge machining or shot blasting,
In the curing, it is used to reflect the unevenness on the surface of the thermosetting resin via the release film , and
Used to form a surface having a glossiness of 3 to 50 at an incident angle of 60° on the molded body obtained by curing the thermosetting resin,
The release film is also provided.
The tensile strength at break of the release film is 40 MPa to 200 MPa when measured at 175°C according to JIS K7127, and the tensile elongation at break of the release film is measured at 175°C according to JIS K7127. It can be between 200% and 500%.
The thickness of the release film may be 30 μm to 100 μm.

Moreover, the present invention
A combination of a mold and a release film used for curing a thermosetting resin,
The mold has unevenness formed on a surface that contacts the release film during the curing,
The surface roughness Ra of the surface of the mold is 1 μm to 4 μm ,
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film, and
Used to form a surface having a glossiness of 3 to 50 at an incident angle of 60° on the molded body obtained by curing the thermosetting resin,
Combinations of the above are also provided.

The present invention makes it possible to adjust the surface of a molded body. For example, according to the present invention, visibility and readability of characters printed by a laser marker can be improved.
Note that the effects of the present invention are not necessarily limited to the effects described herein, and may be any of the effects described herein.

It is a figure for explaining an example of the usage method of the combination of this invention in transfer molding. FIG. 2 is a schematic diagram of an example of a laminated structure of release films constituting the combination of the present invention. It is a figure for explaining an example of the usage method of the combination of this invention in compression molding. FIG. 3 is a diagram for explaining the formation of a surface layer on the molded body side. It is a figure which shows the observation result by a laser marker.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail. Note that the embodiments described below are examples of typical embodiments of the present invention, and the present invention is not limited only to these embodiments.

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 disposed between the thermosetting resin and the mold during the curing. The release film includes a base layer made of a thermoplastic resin, and a surface layer laminated on one of the two surfaces of the base layer that is disposed on the thermosetting resin side during curing. The surface layer is formed from a fluororesin containing particles. The mold has irregularities formed on a surface that comes into contact with the release film during the curing.

By using the above combination in a molding method such as a transfer molding method or a compression molding method, the surface condition of the molded object can be adjusted, and for example, a desired gloss can be imparted to the surface of the molded object. . For example, the combination according to the invention may be used to produce molded bodies having a surface with a gloss level of 3 to 50 at an angle of incidence of 60°. For example, the combination according to the invention provides a surface (in particular an epoxy resin surface) whose gloss at an angle of incidence of 60° is from 3 to 15, preferably from 3 to 10, more preferably from 4 to 8, even more preferably from 4 to 6. ) may be used to produce a molded body.
Further, by using the above combination, it is possible to improve the visibility or readability of, for example, printing or patterns on the surface of the molded article. For example, the combination according to the invention may be used to produce molded bodies having a surface (in particular an epoxy resin surface) which is marked with a laser marker. The character height of the printing may be, for example, 0.1 mm to 10 mm, preferably 0.2 mm to 5 mm. In particular, the character height of the printing may be between 0.5 mm and 3 mm. By using the combination according to the invention, it is possible to increase the visibility or readability of such small characters on the surface of the molded bodies produced.

The 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 release properties. In particular, the combination of particles and fluororesin contained in the surface layer contributes to exhibiting excellent mold releasability and to adjusting the surface condition of the molded article.

Below, an example of how to use the above combination will first be explained, and then the release film and the mold, which are the constituent elements of the above combination, will be explained in more detail.

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

The combinations of the invention may be used, for example, in various molding processes for thermosetting resins. Preferably, the combination of the present invention can be used to form irregularities on the surface of the cured thermosetting resin.
For example, the molding techniques are, for example, transfer molding or compression molding, and the combination of the invention is 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 molded bodies obtained in these molding methods, preferably to form irregularities on the surfaces of these molded bodies.
Examples of how to use the combination of the invention in these molding methods are 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. 1(A), a release film 11 constituting the combination of the present invention is placed between an upper mold 12 and a lower mold 13 on which a substrate 14 is placed, which constitutes the combination of the present invention. 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 to mold the thermosetting resin 15. By this 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, but is preferably plural.
The release film 11 has a laminated structure shown in FIG. 2, for example. The release film 11 includes a base layer 101, a surface layer 102 laminated on one side of the base layer 101, and a surface layer 103 laminated on the other side. The details of the release film 11 will be explained in "1-2. Release Film" below.
The surface layer 102 is laminated on one of the two surfaces of the base material layer 101, which is disposed on the thermosetting resin side in the transfer molding. That is, the surface layer 102 comes into contact with the thermosetting resin 15 during the transfer molding. The surface layer 102 is made of a fluororesin containing particles.
Of the two surfaces of the base material layer 101, the surface layer 103 is laminated on the surface disposed on the upper mold 12 side in the transfer molding. That is, the surface layer 103 contacts the upper mold 12 during the transfer molding.
The surface 16 of the upper mold 12 is formed with projections and depressions. That is, the surface 16 comes into contact with the release film 11 (particularly the surface layer 103 thereof) during the transfer molding.

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

Next, as shown in FIG. 1(C), a 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 Hardened 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 mold release film 11, and the surface shape of the mold release film 11 (especially the surface 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 the surface shape of the release film 11 (particularly the surface shape included in the surface layer 102) is reflected indirectly on the surface of the thermosetting resin 15. The surface shape caused by the particles is directly reflected on the surface of the thermosetting resin 15. The thermosetting resin 15 is cured with the uneven shape and the surface shape 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 body (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 condition of the molded article.

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

(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 attached to an upper mold 22 and a lower mold 23 to which a substrate 24 on which a plurality of semiconductor elements 27 are mounted is attached. placed between.
As explained in (1) above, the release film 11 includes a base layer 101, a surface layer 102 laminated on one side of the base layer 101, and a surface layer 103 laminated on the other side. There is.
The surface layer 102 is laminated on one of the two surfaces of the base material layer 101 that is disposed 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, during the compression molding.
Of the two surfaces of the base material layer 101, the surface layer 103 is laminated on the surface disposed on the lower mold 23 side in the compression molding. That is, the surface layer 103 contacts the lower mold 23 during the compression molding.
The surface 26 of the lower mold 23 is formed with projections and depressions. That is, the surface 26 contacts the release film 11 (particularly the surface layer 103 thereof) during the compression molding.

Next, as shown in FIG. 3(B), the thermosetting resin 25 is placed in the recess of the lower mold 23 with the release film 11 stuck to the surface 26 of the lower mold 23. Ru.

Next, as shown in FIG. 3C, the upper mold 22 is moved to bring the substrate 24 into contact with the thermosetting resin 25. Thereafter, the thermosetting resin 25 is cured by heating.
During 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 (especially The surface shape resulting from 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 the surface shape of the release film 11 (especially the surface layer 102) is (the surface shape caused by the particles) is directly reflected on the surface of the thermosetting resin 25. The thermosetting resin 25 is cured with the uneven shape and the surface shape 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 body (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 condition of the molded article.

After curing, the upper mold 22 is separated from the lower mold 23 as shown in FIG. 3(D). The release film 11 has excellent mold releasability, especially because its surface layer 102 is made of a fluororesin containing particles. Therefore, in the step of FIG. 3(D), it is possible to smoothly release the cured resin 25 from the lower mold 23.

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

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

1-2. release film

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

The release film 11 shown in FIG. 2 has a base material layer 101 and a surface that is laminated on the surface of the base material layer 101 that is disposed on the thermosetting resin side (molded object side) during the curing. It includes a layer 102 (also referred to herein as a "molded object side surface layer"). The base material layer 101 is made of thermoplastic resin. The molded body side surface layer 102 is formed from a fluororesin 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. Method of using the combination of the present invention". Further, since the molded body side surface layer 102 is formed from a fluororesin containing particles, it is easily separated from the cured molded body.

The release film 11 includes a surface layer 103 (also referred to as a "mold side surface layer" in this specification) that is laminated on the surface of the base layer 101 that will be placed on the mold side during curing. ) is also included. The mold side surface layer 103 may be preferably formed from a fluororesin, more preferably formed from a fluororesin containing particles. This makes it easier for the release film 11 to separate 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 explained in more detail below.

[Base material layer]

The base material layer 101 is made of thermoplastic resin. The thermoplastic resin may preferably be a resin having a melting point higher than the molding temperature employed in curing the thermosetting resin, more preferably higher than the molding temperature. Thereby, in the molding, the irregularities on the surface of the mold are easily reflected on the surface of the thermosetting resin via the mold release film 11.

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

The PET resin may be a general-purpose PET resin or an easily moldable PET resin. The glass transition temperature of general-purpose PET resin may be 100° C. or higher. Within this specification, glass transition temperature is the glass transition temperature measured by differential thermal analysis (DTA). The glass transition temperature of the easily moldable PET resin may be less than 100°C, preferably 60°C to 95°C, more preferably 65°C to 90°C. Easily moldable PET resin is particularly suitable for preventing contamination of molds or molded objects by oligomers contained in PET resin.

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

The easily moldable PET resin may be, for example, a copolymerized polyethylene terephthalate resin. Copolymerized polyethylene terephthalate may be obtained, for example, by reacting terephthalic acid, ethylene glycol, and a copolymer component, or by mixing and melting the copolymer component polymer and polyethylene terephthalate, and then performing a partition reaction. It 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 (such as isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid), aliphatic dicarboxylic acids (such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid), and alicyclic acids. Mention may be made, for example, of the group dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of the alcohol component include aliphatic diols (eg, butanediol, hexanediol, neopentyl glycol, hexanediol, etc.) and alicyclic diols (eg, cyclohexanedimethanol, etc.). As the copolymerization component, one or a combination of two or more of these compounds may be used. The acid component can in particular be isophthalic acid and/or sebacic acid.

As the base material layer formed from easily moldable PET resin, a commercially available material may be used. For example, Teflex (trademark) FT, Teflex (trademark) FT3, and Teflex (trademark) FW2 (all manufactured by Teijin Film Solutions Ltd.) can be used as the base material layer formed from easily moldable PET resin. can. Furthermore, Emblet CTK-38 (manufactured by Unitika Co., Ltd.) may be used as the base material layer formed from easily moldable PET resin. Furthermore, CH285J (manufactured by Nanya Plastics Co., Ltd.) may be used as the base material layer.
The base material layer formed from the easily moldable PET resin may be manufactured, 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 base layer has a planar orientation coefficient of preferably 0.06 to 0.16, more preferably 0.07 to 0.16, as described in any of these publications. It may be one obtained by biaxially stretching an easily moldable PET resin so that the particle diameter is 0.15.

The tensile breaking strength of the base layer is preferably 40 MPa to 200 MPa, more preferably 40 MPa to 120 MPa, even more preferably 40 MPa to 110 MPa, particularly when measured at 175° C. according to JIS K7127. Preferably, it may be 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%, even more preferably 300% to 300%, when measured at 175°C according to JIS K7127. It can be 400%.

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

[Surface layer on molded body side]

The molded body side surface layer 102 is formed from a fluororesin containing particles. According to a preferred embodiment of the invention, the fluororesin does not contain chlorine. By not containing chlorine, the durability and/or antifouling properties of the layer are improved. The fluororesin may be, for example, a cured product of a fluororesin composition containing a fluoropolymer containing a reactive functional group and a curing agent.
The fluororesin preferably contains a tetrafluoroethylene resin, and more preferably contains a tetrafluoroethylene resin as a main component. In this specification, the tetrafluoroethylene resin refers to a component obtained by a curing reaction between a reactive functional group-containing tetrafluoroethylene polymer and a curing agent, which will be described below. "Tetrafluoroethylene resin is the main component" means that the fluorocarbon resin consists only of tetrafluoroethylene resin, or the amount of tetrafluoroethylene resin among the components contained in the fluorocarbon resin. means the most. For example, the content 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 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 fluororesin.

The reactive functional group-containing fluoropolymer contained in the fluororesin composition may be a fluoropolymer 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. These groups allow the reaction for obtaining the cured product to proceed favorably.
Among these reactive functional groups, hydroxyl groups are particularly suitable for the reaction to obtain the cured product. That is, the reactive functional group-containing fluoropolymer is preferably a hydroxyl group-containing fluoropolymer, more preferably a hydroxyl group-containing tetrafluoroethylene polymer.

The fluorine-containing units of the reactive functional group-containing fluoropolymer are preferably fluorine-containing units based on perfluoroolefins. The fluorine-containing units based on the perfluoroolefins are more preferably tetrafluoroethylene (tetrafluoroethylene, hereinafter also referred to as "TFE"), hexafluoropropylene (HFP), and perfluoro(alkyl vinyl ether). (PAVE) may be based on one, two, or three selected from (PAVE). Preferably, among the fluorine-containing units based on the perfluoroolefins, the fluorine-containing units based on TFE are the largest.

The hydroxyl value of the reactive functional group-containing fluoropolymer (especially the hydroxyl value of the hydroxyl group-containing fluoropolymer) is preferably 10 mgKOH/g to 300 mgKOH/g, 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. Furthermore, the fact that the hydroxyl value of the reactive functional group-containing fluoropolymer is less than or equal to the upper limit of the numerical range mentioned above contributes to making the cured product of the resin composition suitable for multiple moldings. sell. The hydroxyl value is obtained by measuring by a method based on JIS K 0070.

The acid value of the reactive functional group-containing fluoropolymer (especially 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 mg KOH/g.

The reactive functional group of the reactive functional group-containing fluoropolymer can be obtained by copolymerizing the monomer having the reactive functional group with a fluorine-containing monomer (particularly the above-mentioned perfluoroolefin). may be introduced. That is, the reactive functional group-containing fluoropolymer may include a polymerized unit based on a reactive functional group-containing monomer and a polymerized unit based on a fluorine-containing monomer (particularly the above-mentioned perfluoroolefin).

When the reactive functional group is a hydroxyl group, the monomer having the reactive functional group may preferably be 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, Examples include 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether, and examples of hydroxyl group-containing allyl ethers include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. can. Alternatively, the monomer having reactive functional groups may be a hydroxyalkyl ester of (meth)acrylic acid, such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. As the monomer having the 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 /or 2-hydroxyethyl vinyl ether.

When the reactive functional group is a carboxyl group, the monomer having the reactive functional group may preferably be 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, amino vinyl ether or allylamine.
When the reactive functional group is a silyl group, the monomer having the reactive functional group may preferably be a silicone vinyl monomer.

The fluorine-containing monomer is preferably a perfluoroolefin. As perfluoroolefins, mention may be made, for example, of 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 include polymerized units based on a fluorine-free vinyl monomer in addition to the polymerized units based on the reactive functional group-containing monomer and the polymerized units based on the fluorine-containing monomer. The fluorine-free vinyl monomer can be, for example, one or a combination of two or more selected from the group consisting of carboxylic acid vinyl esters, alkyl vinyl ethers, and non-fluorinated olefins.
Examples of carboxylic acid vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, vinyl benzoate, and vinyl para-t-butylbenzoate.
As alkyl vinyl ethers, mention may be made, for example, of methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.
Examples of non-fluorinated olefins include ethylene, propylene, n-butene, and isobutene.
In addition, the reactive functional group-containing fluoropolymer includes, in addition to a polymer unit based on a reactive functional group-containing monomer and a polymer unit based on a fluorine-containing monomer that is a perfluoroolefin, for example, vinylidene fluoride (VdF), chloro It may also contain polymerized units based on fluoromonomers other than perfluoroolefins, such as trifluoroethylene (CTFE), vinyl fluoride (VF), and fluorovinylether.

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

The curing agent contained in the fluororesin composition may be appropriately selected by those skilled in the art depending on the type of reactive functional group contained in the reactive functional group-containing fluoropolymer.
When the reactive functional group is a hydroxyl group, the curing agent is preferably one or a combination of two or more selected from isocyanate curing agents, melamine resins, silicate compounds, and isocyanate group-containing silane compounds.
When the reactive functional group is a carboxyl group, the curing agent may be one or a combination of two or more selected from amino curing agents and epoxy curing agents.
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 curing agent, and an acid anhydride curing agent.
The content of the curing agent in the fluororesin composition is, for example, 15 parts by mass to 50 parts by mass, preferably 20 parts by mass to 40 parts by mass, based on 100 parts by mass of the reactive functional group-containing fluoropolymer. parts, more preferably 23 parts to 35 parts by weight. 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 chromatography (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 a hexamethylene diisocyanate (HDI)-based polyisocyanate.
The content of the HDI polyisocyanate in the fluororesin composition is, for example, 15 parts by mass to 50 parts by mass, preferably 20 parts by mass to 100 parts by mass of the reactive functional group-containing fluoropolymer. It may be 40 parts by weight, more preferably 23 parts to 35 parts by weight. These numerical ranges also apply to the content of the HDI polyisocyanate in the cured product of the fluororesin composition.

As the HDI-based polyisocyanate, one or a combination of two or more selected from, for example, isocyanurate-type polyisocyanates, adduct-type polyisocyanates, and biuret-type polyisocyanates can be used. In the present invention, the isocyanate-based curing agent is preferably 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, more preferably 25 parts by mass to 35 parts by mass, based on 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 pyrolysis gas chromatography (Py-GC/MS) method.

The fluororesin forming the surface layer on the molded body side contains particles, preferably particles having an average particle size of 1 μm to 10 μm, more preferably 2 μm to 9 μm, as measured according to a laser diffraction particle size analysis method. The average particle diameter is a volume-weighted volume average diameter, 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 article, and the releasability of the release film can be improved. Further, when the average particle diameter 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 article. Furthermore, if the average particle diameter of the particles is higher than the upper limit of the numerical range, the releasability may deteriorate or the particles may fall off from the fluororesin. Furthermore, if the average particle diameter of the particles is higher than the upper limit of the numerical range, for example, streaks may occur when the fluororesin is applied to the base layer, making it difficult to produce a release film. .

The particles are preferably inorganic or organic particles. Examples of inorganic particles include silicon dioxide (especially 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. Examples of organic particles include crosslinked polymer particles and calcium oxalate. In the present invention, the particles are preferably inorganic particles, more preferably silicon dioxide particles, even more preferably amorphous silicon dioxide. Amorphous silicon dioxide can be sol-gel type silica. As the amorphous silicon dioxide, for example, amorphous silicon dioxide of the Cycilia series can be used.

The content of the particles in the fluororesin composition is, for example, 1 part by mass to 30 parts by mass, preferably 2 parts by mass to 25 parts by mass, based on 100 parts by mass of the reactive functional group-containing fluoropolymer. , more preferably 3 parts by weight to 20 parts by weight. These numerical ranges also apply to the content of the particles in the cured product of the fluororesin composition. Having the content within the above numerical range contributes to the surface shape resulting from the particles being reflected in the molded article, and/or contributes to improving the releasability of the release film.
According to one preferred embodiment of the present invention, the content of the particles in the fluororesin composition is, for example, 1 part by mass to 17 parts by mass based on 100 parts by mass of the reactive functional group-containing fluoropolymer. , preferably from 2 parts by weight to 16 parts by weight, particularly preferably from 3 parts by weight to 10 parts by weight. 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 is possible to improve the visibility or readability when printing or patterning is performed on the surface of the molded article using a laser marker.
The content of the particles may be determined 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. As solvents, mention may be made, for example, of 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 include a release promoter. Examples of the release accelerator include amino-modified methylpolysiloxane, epoxy-modified methylpolysiloxane, carboxy-modified methylpolysiloxane, and carbinol-modified methylpolysiloxane. Preferably, the mold release promoter is an amino-modified methylpolysiloxane.
The release accelerator is, for example, 0.01 parts by mass to 3 parts by mass, preferably 0.05 parts by mass to 2 parts by mass, more preferably 0 parts by mass, based on 100 parts by mass of the reactive functional group-containing fluoropolymer. .1 part by weight to 1 part by weight. 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 may be, for example, 1 μm to 10 μm, preferably 2 to 9 μm, and more preferably 3 μm to 8 μm.

The fluororesin 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, homo mixers, 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 fluororesin composition is obtained by coating the fluororesin composition on the surface of the base layer and heating it at, for example, 100°C to 200°C, preferably 120°C to 180°C, for 10 seconds to 240 seconds. , preferably by heating for 30 seconds to 120 seconds. The cured product forms the surface layer. The amount of the fluororesin composition applied may be appropriately determined by those skilled in the art depending on the thickness of the surface layer to be formed.

The shape of the surface layer on the molded body side will be explained with reference to FIG. 4. The fluororesin composition forming the surface layer on the molded body side is applied onto the base material layer. Immediately after application, as shown in FIG. 4(a), 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 evaporates, resulting in the state shown in FIG. 4(b), and the shape resulting from the particles appears. Ultimately, the cured product of the composition has a surface state as shown in FIG. 4(c), that is, an uneven shape due to the particles appears. As shown in the schematic diagram of FIG. 4(d), the release film has a molded body side surface layer 402 having irregularities caused by particles on a base material layer 401. As described above, the release film constituting the combination of the present invention has a molded body side surface layer in which irregularities caused by particles are formed.

[Mold side surface layer]

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

Regarding the reactive functional group-containing fluoropolymer contained in the fluororesin composition, all the explanations regarding the reactive functional group-containing fluoropolymer contained in the molded body side surface layer 102 described above apply, A description of the reactive functional group-containing fluoropolymer will be omitted.

Regarding the curing agent contained in the fluororesin composition, the above explanation regarding the type and content of the curing agent contained in the molded body side surface layer 102 also applies. Explanation regarding the combination will be omitted.

The fluororesin forming the mold side surface layer contains particles, preferably particles having an average particle size of 1 μm to 10 μm, more preferably 2 μm to 9 μm, as measured according to a laser diffraction particle size analysis method. . The average particle diameter is a volume-weighted volume average diameter, and is measured according to JIS Z8825. By including the particles, the releasability of the release film can be improved. Furthermore, if the average particle diameter of the particles is higher than the upper limit of the numerical range, the releasability may deteriorate or the particles may fall off from the fluororesin. Furthermore, if the average particle diameter of the particles is higher than the upper limit of the numerical range, for example, streaks may occur when the fluororesin is applied to the base layer, making it difficult to produce a release film. .

The particles are preferably inorganic or organic particles. Examples of inorganic particles include silicon dioxide (especially 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. Examples of organic particles include crosslinked polymer particles and calcium oxalate. In the present invention, the particles are preferably inorganic particles, more preferably silicon dioxide particles, even more preferably amorphous silicon dioxide. Amorphous silicon dioxide can be sol-gel type silica. As the amorphous silicon dioxide, for example, 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, based on 100 parts by mass of the reactive functional group-containing fluoropolymer. , more preferably 10 parts by weight to 20 parts by weight. These numerical ranges also apply to the content of the particles in the cured product of the fluororesin composition. The content falling within the numerical range contributes to improving the releasability of the release film.
The content of the particles may be determined 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. As solvents, mention may be made, for example, of 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 include a release promoter. Examples of the release accelerator include amino-modified methylpolysiloxane, epoxy-modified methylpolysiloxane, carboxy-modified methylpolysiloxane, and carbinol-modified methylpolysiloxane. Preferably, the mold release promoter is an amino-modified methylpolysiloxane.
The release accelerator is, for example, 0.01 parts by mass to 3 parts by mass, preferably 0.05 parts by mass to 2 parts by mass, more preferably 0 parts by mass, based on 100 parts by mass of the reactive functional group-containing fluoropolymer. .1 part by weight to 1 part by weight. 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 promoter.

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

As for the method for manufacturing the fluororesin composition, all the explanations regarding the method for manufacturing the fluororesin composition used to form the molded object side surface layer 102 apply, so the description of the method will be omitted.

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

[Features 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, even more preferably 40 MPa, when measured at 175° C. according to JIS K7127. -110 MPa, particularly preferably 45 MPa - 100 MPa, and the tensile elongation at break of the release film is 200% - 500%, more preferably 250 MPa when measured at 175°C according to JIS K7127. % to 450%, and even more preferably 300% to 400%.
It is suitable for the surface shape adjustment by the combination of the present invention that the tensile strength at break and the tensile elongation at break of the release film are within the above numerical ranges.

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

The thickness of the release film may 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 product.

The release film may be used for one molding, or may be used for multiple moldings. The release film may be used for molding, for example, two or more times, preferably four or more times, more preferably five or more times, more preferably six or more times, even more preferably eight or more times. The release film may be molded, for example, from 2 to 20 times, preferably from 4 to 15 times, more preferably from 5 to 15 times, more preferably from 6 to 15 times, even more preferably from 8 to 12 times. can be used for. The release film maintains its performance through multiple demolding cycles and is resistant to tearing. Therefore, the release film can be used for multiple moldings. Thereby, molding costs can be reduced.
In addition, polyester resins (especially PET resins) contain oligomers, and the oligomers are used in molds and/or Or it may contaminate the molded article. However, in the release film, even when the thermoplastic resin forming the base layer is a polyester resin, contamination of the mold and/or the molded body during molding is unlikely to occur. The mold release film is unlikely to cause contamination of the mold and/or molded product even when the same film is repeatedly used for multiple moldings. The low contamination property is thought to be due to the surface layer made of a fluororesin.

[Manufacturing method of release film]
The method for producing the release film includes a coating step of applying a fluororesin composition to two surfaces of the base layer, and a curing step of curing the fluororesin composition after the coating step.
Since the contents described above apply to the base material layer and the fluororesin composition used in the coating process, a description thereof will be omitted.
Said application step may be carried out as appropriate by a person skilled in the art to achieve the desired layer thickness. For example, the fluororesin composition can be applied to the two 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 surfaces. Apparatus for coating by these methods may be appropriately selected by those skilled in the art.
The curing step includes 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 fluororesin composition is cured by the heating.

1-3. Mold

In the mold constituting the combination of the present invention, irregularities are formed on the mold surface with which the release film contacts during curing of the thermosetting resin. The unevenness is reflected on the surface of the thermosetting resin via the release film. In this way, the irregularities are 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 with which the release film contacts during the molding. For example, the unevenness may be provided only in a region of the mold surface that covers a surface portion of the molded object that requires surface adjustment. This makes it possible to reduce the area of the mold surface where irregularities are formed, thereby reducing 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 during the molding.

The surface roughness Ra of the surface of the mold that comes into contact with the release film during curing is preferably 1 μm to 4 μm, more preferably 1.2 μm to 3.8 μm, and particularly preferably 1.4 μm. ~3.6 μm. When the surface of the mold having the unevenness has a surface roughness within the above 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, surface adjustment may not be possible. Furthermore, 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. Furthermore, if the surface roughness is too large, the surface roughness of the mold becomes uneven, which may adversely affect the appearance of the molded product.
In this specification, surface roughness Ra is measured according to JIS B0601.

The unevenness on the mold surface may be formed by a method known in the art, such as electrical discharge machining (EDM) or shot blasting, and preferably by electrical discharge machining (EDM). Electric discharge machining is suitable for forming a surface having a surface roughness Ra within the above numerical range. The electrical discharge machining is particularly suitable for imparting surface roughness to metal surfaces, such as those mentioned above. The electric discharge machining may be performed by a method and apparatus known in the art, and by setting the electric discharge machining apparatus so that desired unevenness is formed and performing the electric discharge machining process, the unevenness is formed in the 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 material of the mold may be selected, for example, from 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 50HRC or more, more preferably 55HRC 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 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 may be plated with hard chrome, for example.

2. release film

The present invention also provides a release film that is used in combination with a mold for curing thermosetting resins. The release film is a release film that constitutes the combination of the present invention described in "1. Combination of mold and release film" above, 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 curing of a thermosetting resin in combination with the mold described in "1. Combination of mold and release film" above, the cured product of the thermosetting resin can be cured. The surface condition of the molded product can be adjusted. The mold release film of the present invention is suitable for reflecting the unevenness of the surface of the mold onto the molded product.
Furthermore, the release film of the present invention has excellent release properties. Although the part of the mold surface that comes into contact with the mold release film during curing is uneven, the mold release film smoothly leaves the mold.

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 that constitutes the combination of the present invention described in the above "1. Combination of mold and release film", and all of the above description also applies to the mold of the present invention.

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

4. Method for manufacturing molded bodies

The present invention provides a method for manufacturing a molded article. The manufacturing method includes a step of arranging a release film in a mold used for curing the thermosetting resin, and after the arranging step, placing the thermosetting resin in the mold. The method includes a curing step of curing the resin in contact with a mold film, and a mold release step of releasing the cured thermosetting resin from the mold after the curing step to obtain a molded body.

The mold and the release film used in the manufacturing method of the present invention are the mold and release film that constitute the combination of the present invention described in "1. Combination of mold and release film" above. , all of the above descriptions also apply to the manufacturing method of the present invention. The method for producing the molded body may be, for example, a transfer molding method or a compression molding method, but is not limited thereto.

In the placement step, the release film is placed within the mold. The release film is arranged such that the surface layer on the molded body side of the release film contacts the thermosetting resin and the surface layer on the mold side contacts the surface of the mold on which the unevenness is formed. It may be placed within the mold. For example, in the arrangement step, the release film is arranged so as to be in the state shown in FIG. 1(A) or FIG. 3(A) explained in “1-1. It can be done.

After the placement step, the release film may be attached to the surface of the mold on which the unevenness is formed, for example, by suction. Prior to the pasting, the release film may be softened by heating.

In the curing step, the thermosetting resin is cured within the mold.
For example, in transfer molding, a closed space may be formed prior to curing to prevent the thermosetting resin from leaking out of the mold. For example, as shown in FIG. 1(B), a closed space is formed by closing the upper mold and the lower mold. Then, as shown in FIG. 1(C), 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 may be introduced into the mold prior to curing. For example, as shown in FIG. 3(B), a thermosetting resin can be introduced into the depression 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) is reflected indirectly. The surface shape caused by the contained particles is directly reflected on the surface of the thermosetting resin. The thermosetting resin is cured while 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 body is adjusted.

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

The manufacturing method of the present invention may further include, after the mold release step, a printing step of printing with a laser marker on the surface of the molded article whose surface condition has been adjusted as described above. The manufacturing method according to the present invention can improve the visibility or readability of markings printed with a laser marker. The character height of the printing may be, for example, 0.1 mm to 10 mm, preferably 0.2 mm to 5 mm. In particular, the character height of the printing may be between 0.5 mm and 3 mm. The surface of the molded article obtained by the manufacturing method according to the present invention can improve the visibility or readability of such small characters.

Through the above steps, a molded article with an adjusted surface condition can be obtained.

Hereinafter, the present invention will be explained in more detail based on Examples. It should be noted that the examples described below are only representative examples of the present invention, and the scope of the present invention is not limited only to these examples.

Example 1: Example of surface conditioning of molded body

(1) Manufacture of release film

Two types of release films were manufactured as described below.

(1-1) Production of release film

As a base material layer, a film (Tetron G2CW, Teijin Ltd., thickness 38 μm) made of a general-purpose polyethylene terephthalate resin was prepared.
Next, two types of fluororesin compositions (hereinafter referred to as a first fluororesin composition and a second fluororesin composition) were prepared to be applied to the film. The first fluororesin composition is for forming a mold side surface layer. The second fluororesin composition is for forming a surface layer on the molded body side.
The first fluororesin composition was composed of 100 parts by mass of a composition containing a hydroxyl group-containing tetrafluoroethylene polymer (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass was a hydroxyl group-containing tetrafluoroethylene polymer). ), 11.47 parts by mass of amorphous silicon dioxide (Silysia 380, Fuji Silysia Chemical Co., Ltd.), 10 parts by mass of isocyanurate type polyisocyanate (curing agent, Sumidur N3300, Sumitomo Bayer Urethane Co., Ltd.), adduct type polyisocyanate It was prepared by mixing and stirring 7.79 parts by mass (curing agent, 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. The average particle diameter (the volume average diameter) of the amorphous silicon dioxide is measured using a particle size analyzer (SALD-2200, Shimadzu Corporation) according to the laser diffraction particle size analysis method. , 8.8 μm.
The second fluororesin composition was prepared by adding 0.31 parts by mass of amino-modified methylpolysiloxane (release accelerator, Shin-Etsu Chemical Co., Ltd.) to the first fluororesin composition and the amount of ethyl acetate. The composition was the same as the first fluororesin composition except that the amount of MEK was changed to 44.81 parts by mass and the amount of MEK was changed to 89.63 parts by mass.

The first fluororesin composition was applied to one side of the film, and the second fluororesin composition was applied to the other side 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 to form a release film (hereinafter referred to as "Release Film 1") in which fluorine-based resin layers are laminated on both sides of a general-purpose PET resin film. ) 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 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 5.5±0.5 μm.

The cured product (mold side surface layer) of the first fluororesin composition contains 17.65 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene polymer. , contained 15.39 parts by mass of the isocyanurate type polyisocyanate, and 11.98 parts by mass of the adduct type polyisocyanate.

The cured product of the second fluororesin composition (surface layer on the molded body side) contains 17.65 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene 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 amino-modified methylpolysiloxane.

(1-2) Production of release film

A release film (hereinafter referred to as "release film 2) was produced.
That is, the second fluororesin composition contains 100 parts by mass of a composition containing a hydroxyl group-containing tetrafluoroethylene polymer (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing tetrafluoroethylene polymer). ), 3.42 parts by mass of amorphous silicon dioxide (Silysia 430, Fuji Silysia Chemical Co., Ltd.), 10 parts by mass of isocyanurate type polyisocyanate (curing agent, Sumidur N3300, Sumitomo Bayer Urethane Co., Ltd.), adduct type 7.79 parts by mass of polyisocyanate (curing agent, 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. (Mold release accelerator, Shin-Etsu Chemical Co., Ltd.) was prepared by mixing and stirring. The average particle diameter (the volume average diameter) of the amorphous silicon dioxide is measured using a particle size analyzer (SALD-2200, Shimadzu Corporation) according to the laser diffraction particle size analysis method. , 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 fluororesin composition contains 17.65 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene polymer. , contained 15.39 parts by mass of the isocyanurate type polyisocyanate, and 11.98 parts by mass of the adduct type polyisocyanate.

The cured product of the second fluororesin composition (surface layer on the molded body side) contains 5.26 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene 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 amino-modified methylpolysiloxane.

(2) Manufacture of molds

Four molds were manufactured. These four molds are all molds for transfer molding consisting of a combination of an upper mold and a lower mold, and have the same shape except for the unevenness provided on the cavity surface of the upper mold. I had it. The unevenness was provided at a position corresponding to the surface 16 of the upper mold 12 in FIG. 1(A). All of the above-mentioned irregularities were formed by electric discharge machining.

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

The main material of these four molds was all SUS440C. Furthermore, all of these four molds had a hardness of HRC55 or higher, and their surfaces were plated with hard chrome.

(3) Manufacture of molded bodies

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 employed in the molding. In the molding, the molding temperature employed to cure the thermosetting resin was 175°C. The glossiness of the surface of each of the molded bodies obtained by the molding at an incident angle of 60° was measured using a glossmeter (PG-IIM, Nippon Denshoku Kogyo 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 gloss level 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 condition of the molded product through the release film 1.
Similarly, when the release film 2 was used, the gloss level 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 condition of the molded product via the mold release film 2.

Further, when comparing the four results using mold 1, even with the same mold, the glossiness of the surface of the molded article differs depending on the difference in the release film. Release films 1 and 2 differ in the composition of the surface layer on the molded body side, particularly in the content ratio of particles in the surface layer. These results show that the shape of the surface layer of the release film, particularly the shape caused by particles in the surface layer, is reflected in the surface condition of the molded article.

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

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

Furthermore, in the molding, all of the release films were smoothly separated from the molded product. Therefore, it can be seen that the release film constituting the combination of the present invention can be smoothly separated from the molded product having an uneven surface after the molded product is molded.

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

(1) Manufacture of release film

Three types of release films were manufactured as described below.

(1-1) Production of release film

As a base material layer, a film (CH285J, Nan-ya Plastics Co., Ltd., thickness 50 μm) made of easily moldable polyethylene terephthalate resin was prepared.
Next, two types of fluororesin compositions (hereinafter referred to as a first fluororesin composition and a second fluororesin composition) were prepared to be applied to the film. The first fluororesin composition is for forming a mold side surface layer. The second fluororesin composition is for forming a surface layer on the molded body side.
The first fluororesin composition was composed of 100 parts by mass of a composition containing a hydroxyl group-containing tetrafluoroethylene polymer (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass was a hydroxyl group-containing tetrafluoroethylene polymer). ), 11.47 parts by mass of amorphous silicon dioxide (Silysia 380, Fuji Silysia Chemical Co., Ltd.), 10 parts by mass of isocyanurate type polyisocyanate (curing agent, Sumidur N3300, Sumitomo Bayer Urethane Co., Ltd.), adduct type polyisocyanate It was prepared by mixing and stirring 7.79 parts by mass (curing agent, 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. The average particle diameter (the volume average diameter) of the amorphous silicon dioxide is measured using a particle size analyzer (SALD-2200, Shimadzu Corporation) according to the laser diffraction particle size analysis method. , 8.8 μm.
The second fluororesin composition was prepared by adding 0.31 parts by mass of amino-modified methylpolysiloxane (release accelerator, Shin-Etsu Chemical Co., Ltd.) to the first fluororesin composition and the amount of ethyl acetate. The composition was the same as the first fluororesin composition except that the amount of MEK was changed to 44.81 parts by mass and the amount of MEK was changed to 89.63 parts by mass.

The first fluororesin composition was applied to one side of the film, and the second fluororesin composition was applied to the other side of the film. These coatings were performed using a kiss-reverse coating device. After the application, these compositions are cured by heating at 150° C. for 60 seconds to form a release film (hereinafter referred to as "Release Film 3") in which fluorine-based resin layers are laminated on both sides of a general-purpose PET resin film. ) 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 mold side surface layer had a thickness of 5.5±0.5 μm, and the molded body side surface layer had a thickness of 5.5±0.5 μm.

The cured product (mold side surface layer) of the first fluororesin composition contains 17.65 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene polymer. , contained 15.39 parts by mass of the isocyanurate type polyisocyanate, and 11.98 parts by mass of the adduct type polyisocyanate.

The cured product of the second fluororesin composition (surface layer on the molded body side) contains 17.65 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene 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 amino-modified methylpolysiloxane.

(1-2) Production of release film

A release film (hereinafter referred to as , "Release Film 4") was manufactured.
That is, the second fluororesin composition contains 100 parts by mass of a composition containing a hydroxyl group-containing tetrafluoroethylene polymer (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing tetrafluoroethylene polymer). ), 9.71 parts by mass of amorphous silicon dioxide (Silysia 380, Fuji Silysia Chemical Co., Ltd.), 10 parts by mass of isocyanurate type polyisocyanate (curing agent, Sumidur N3300, Sumitomo Bayer Urethane Co., Ltd.), adduct type 7.79 parts by mass of polyisocyanate (curing agent, 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. (Mold release accelerator, Shin-Etsu Chemical 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 mold side surface layer had a thickness of 5.5±0.5 μm, and the molded body side surface layer had a thickness of 5.5±0.5 μm.

The cured product (mold side surface layer) of the first fluororesin composition contains 17.65 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene polymer. , contained 15.39 parts by mass of the isocyanurate type polyisocyanate, and 11.97 parts by mass of the adduct type polyisocyanate.

The cured product of the second fluororesin composition (surface layer on the molded body side) contains 14.94 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene 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 amino-modified methylpolysiloxane.

(1-3) Production of release film

A release film (hereinafter referred to as , referred to as "Release Film 5") was manufactured.
That is, the second fluororesin composition contains 100 parts by mass of a composition containing a hydroxyl group-containing tetrafluoroethylene polymer (Zeffle GK570, Daikin Industries, Ltd., of which 65% by mass is a hydroxyl group-containing tetrafluoroethylene polymer). ), 3.42 parts by mass of amorphous silicon dioxide (Sycilia 380, Fuji Silysia Chemical Co., Ltd.), 10 parts by mass of isocyanurate-type polyisocyanate (curing agent, Sumidur N3300, Sumitomo Bayer Urethane Co., Ltd.), adduct-type polyisocyanate 7.79 parts by mass of isocyanate (curing agent, 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 ( A mold release accelerator (Shin-Etsu Chemical Co., Ltd.) was mixed and stirred.

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 mold side surface layer had a thickness of 5.5±0.5 μm, and the molded body side surface layer had a thickness of 3.5±0.5 μm.

The cured product (mold side surface layer) of the first fluororesin composition contains 17.65 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene polymer. , contained 15.39 parts by mass of the isocyanurate type polyisocyanate, and 11.98 parts by mass of the adduct type polyisocyanate.

The cured product of the second fluororesin composition (surface layer on the molded body side) contains 5.26 parts by mass of the amorphous silicon dioxide based on 100 parts by mass of the hydroxyl group-containing tetrafluoroethylene 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 amino-modified methylpolysiloxane.

(2) Manufacture of molds

A compression mold (hereinafter referred to as "mold 5") consisting of a combination of an upper mold and a lower mold was manufactured. Irregularities were formed on the surface of the lower mold that constitutes the mold. The unevenness was provided at a position corresponding to the surface 26 of the lower mold 23 in FIG. 3(A). The unevenness was formed by electrical 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. Furthermore, the mold 5 had a hardness of HRC55 or higher, and its surface was plated with hard chrome.

(3) Manufacture of molded bodies

A thermosetting resin (epoxy resin, GE100, Hitachi Chemical Co., Ltd.) was molded using any one of release films 3 to 5 and mold 5. In the molding, the molding temperature employed to cure the thermosetting resin was 175°C. Printing was performed on the surface of each of the molded bodies obtained by the molding using a laser marker (MD-S9910 type three-dimensional YVO ₄ laser marker, Keyence Corporation). The printing conditions were as follows:
Character height: 1mm
Power: 3.6W
Switch frequency: 40KHz
Scan speed: 700mm/s

The printing on the surface of each molded body was observed visually using a 3D microscope (VR-3200 model 3D microscope, Keyence Corporation).

The results of observation using a 3D microscope are shown in FIG. As shown in FIG. 5, the molded product obtained using the release film 4 has better character visibility than the molded product obtained using the release film 3. The molded product obtained using release film 5 had better visibility of characters than the molded product obtained using molded product 4. Similar observation results were obtained in the case of visual observation. Based on these results, even when using molds with the same surface unevenness, it is possible to adjust the surface condition of the molded object by using a release film with a different shape of the surface layer on the molded object side of the mold release film. It turns out that you can do it.

In addition, from the above results, by setting the particle content of the surface layer on the molded body side to preferably 16 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the fluororesin, it is possible to print with a laser marker. It is thought that the visibility of written characters or patterns can be improved.

Note that the present invention can also adopt the following configuration.
[1]
A combination of a mold used for curing a thermosetting resin and a release film disposed between the thermosetting resin and the mold during the curing,
The release film is
a base material layer formed from a thermoplastic resin;
A surface layer formed from a fluororesin containing particles, which is laminated on one of the two surfaces of the base layer that will be placed on the thermosetting resin side during curing;
including, and
The mold has irregularities formed on a surface that contacts the release film during the curing.
The above combination.
[2]
The combination according to [1], wherein the average particle diameter of the particles is 1 μm to 10 μm when measured according to a laser diffraction particle size analysis method.
[3]
The combination according to [1] or [2], wherein the surface of the mold that comes into contact with the release film during the curing has a surface roughness Ra of 1 μm to 4 μm.
[4]
The combination according to any one of claims [1] to [3], wherein the fluororesin of the surface layer includes a tetrafluoroethylene resin.
[5]
The combination according to any one of [1] to [4], wherein the fluororesin of the surface layer further contains an isocyanate 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 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 to form irregularities on the surface of the 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 release film used in combination with a mold for curing a thermosetting resin,
The release film is
a base material layer formed from a thermoplastic resin;
A surface layer formed from a fluororesin containing particles, which is laminated on one of the two surfaces of the base layer that will be placed on the thermosetting resin side during curing;
including;
The mold has irregularities formed on a surface that contacts the release film during the curing.
The release film.
[13]
A mold used in combination with a release film for curing a thermosetting resin,
The mold has irregularities formed on a surface that contacts the release film during the curing, and
The release film is
a base material layer formed from a thermoplastic resin;
A surface layer formed from a fluororesin containing particles, which is laminated on one of the two surfaces of the base layer that will be placed on the thermosetting resin side during curing;
The mold.
[14]
a step of arranging a release film in a mold used for curing the thermosetting resin;
After the placement step, a curing step of curing the thermosetting resin in the mold while in contact with the release film;
After the curing step, the cured thermosetting resin is released from the mold to obtain a molded object, and
The release film is
a base material layer formed from a thermoplastic resin;
A surface layer formed from a fluororesin containing particles, which is laminated on one of the two surfaces of the base layer that will be placed on the thermosetting resin side during curing;
including;
The mold has irregularities formed on a surface that contacts the release film during the curing.
Method for manufacturing a molded object.

11 Release film 12 Upper mold 13 Lower mold

Claims (9)

A mold used in combination with a release film for curing a thermosetting resin,
The mold has unevenness formed on a surface that contacts the release film during the curing,
The surface roughness Ra of the surface of the mold is 1 μm to 4 μm ,
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film, and
Used to form a surface having a glossiness of 3 to 50 at an incident angle of 60° on the molded body obtained by curing the thermosetting resin,
The mold. The mold according to claim 1, wherein the surface is an epoxy resin surface. The mold according to claim 1 or 2, wherein the mold has a mold hardness of 50HRC or more. The mold according to any one of claims 1 to 3, wherein the molded body has a surface printed with a laser marker. The mold according to claim 4, wherein the character height of the printed character is 0.1 mm to 10 mm. The release film used in combination with the mold,
a base material layer formed from a thermoplastic resin;
a surface layer formed from a fluororesin containing particles and laminated on the surface of the base material layer that is disposed on the thermosetting resin side during curing;
The mold according to any one of claims 1 to 5. The mold according to claim 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. a step of arranging a release film in a mold used for curing the thermosetting resin;
After the placement step, a curing step of curing the thermosetting resin in the mold while in contact with the release film;
After the curing step, the cured thermosetting resin is released from the mold to obtain a molded object, and
The mold has unevenness formed on a surface that contacts the release film during the curing,
The surface roughness Ra of the surface of the mold is 1 μm to 4 μm,
The unevenness is an unevenness formed by electrical discharge machining or shot blasting,
In the curing step, the unevenness is reflected on the surface of the thermosetting resin via the release film, and the molded article obtained by curing the thermosetting resin has a gloss at an incident angle of 60°. A surface with a degree of 3 to 50 is formed.
Method for manufacturing a molded object. A combination of a mold and a release film used for curing a thermosetting resin,
The mold has unevenness formed on a surface that contacts the release film during the curing,
The surface roughness Ra of the surface of the mold is 1 μm to 4 μm ,
In the curing, the unevenness is reflected on the surface of the thermosetting resin via the release film, and
Used to form a surface having a glossiness of 3 to 50 at an incident angle of 60° on the molded body obtained by curing the thermosetting resin,
The above combination.