WO2018173682A1

WO2018173682A1 - Release film for molding and molding method

Info

Publication number: WO2018173682A1
Application number: PCT/JP2018/007855
Authority: WO
Inventors: 惇松本; 白石　史広; 研太佐々木
Original assignee: 住友ベークライト株式会社
Priority date: 2017-03-24
Filing date: 2018-03-01
Publication date: 2018-09-27
Also published as: JPWO2018173682A1; JP2019073022A; TW201841734A; JP6493628B2

Abstract

The present invention pertains to a release film (10) for molding, which is used for molding a first resin composition with a mold, and which has a laminate structure obtained by laminating a release layer comprising a third resin composition on a base material layer comprising a second resin composition, wherein: the release layer (2) and the base material layer (1) are directly joined; the laminate structure has the release layer (2) in the outermost layer thereof; and the release layer (2) is formed by crosslinking a copolymer of a specific structure and a curing agent.

Description

Release film for molding and molding method

The present invention relates to a mold release film and a mold forming method.

Various technologies have been developed as mold release films. For example, Patent Document 1 discloses that a sealing material and a molding machine are used in molding a protective film for a circuit unit or a semiconductor sealing material or a light-emitting diode sealing material when an electronic board such as a flexible printed wiring board is manufactured. There is described a release film that is used as a mold release film for sandwiching between a mold and a mold to release the sealing material and the mold. According to Patent Document 1, the release film includes a coating film formed from a composition containing a fluororesin containing a specific functional group and a release component, and a layer formed from a non-fluorinated polymer. It is described that it has excellent releasability.

Japanese Patent Laid-Open No. 2015-074201

The inventors of the present invention have studied the molding of a resin composition containing an epoxy resin using a conventional mold release film. As a result, when the mold release film described in Patent Document 1 is used, it is formed from a coating film formed from a composition containing a fluororesin containing a specific functional group and a release component, and a non-fluorinated polymer. It was found that the formed layer peeled off.
In addition, in this specification, mold forming means shape | molding using a metal mold | die.

When the above-described coating film and layer are peeled off, the resin composition to be molded comes into contact with a member that does not have the mold release property of the mold release film, and the mold release property is lowered. was there. Moreover, the mold release film has a smooth surface and transfers the mirror surface to the resin composition to be molded, but the smooth surface is damaged by peeling. As a result, the surface of the resin composition to be molded is transferred with scratches derived from peeling, and the moldability is lowered.
In view of the above, an object of the present invention is to provide a mold release film having excellent mold release properties and moldability.

In addition, the present inventors performed mold molding for sealing an electronic element with a first resin composition using a conventional mold release film, and then formed a molded product of the first resin composition. We examined the legibility of electronic devices with printed characters. As a result, it has been found that the readability of characters printed on the electronic device is low.
Here, the present inventors examined the surface structure of the molded product of the first resin composition in order to improve the readability of characters on the surface of the electronic device. As a result, it has been found that the readability of the printed characters is improved when the surface structure of the molded product of the first resin composition is not smooth but has an embossed pattern such as a matte tone.

The present inventors examined a method for imparting an embossed pattern to a molded product of the first resin composition. As a result, the mold release film has a laminated structure in which the release layer is laminated on the base material layer, and the base material layer has unevenness on the surface on which the release layer is laminated. Thus, it was found that an embossed pattern derived from the unevenness of the base material layer can be imparted to the molded product of the first resin composition.
Here, in the molding, the mold release film is interposed between the first resin composition and the mold, and the mold release layer of the mold release film is adhered to the first resin composition. I went there.

Here, the present inventors examined the thickness of the release layer in order to improve the readability of printed characters. As a result, when the thickness of the release layer is large, the unevenness of the base material layer is embedded in the release layer, and an embossed pattern sufficient to improve readability cannot be imparted to the molded product of the first resin composition. It has been found.
On the other hand, when reducing the thickness of the release layer, for example, the release layer cannot be appropriately formed on the convex and concave portions of the base material layer, and the first resin composition and the release film for molding are released. It has been found that there is an inconvenience that the performance decreases.
In view of the above, an object of the present invention is to provide a mold release film that can express the readability of characters printed on a molded product and the release property in a well-balanced manner.

Moreover, the present inventors examined using the mold release film for molding of a resin composition containing an epoxy resin. As a result, it has been found that the conventional mold release film is difficult to peel off the resin composition and the mold release film when the molded resin composition is released. Further, it has been found that the mold release film melts during molding, and may be in a state of being joined to the resin composition.
Then, an object of this invention is to improve mold moldability, such as mold release property and heat resistance of the mold release film.

This inventor examined the method of improving the adhesive force of a base material layer and a mold release layer, in order to suppress peeling with the base material layer and mold release layer of a mold release film. As a result, a specific surface modification is performed on the base material layer, and a base layer and a release layer are laminated on the base material layer by laminating a specific copolymer and a curing agent. It has been found that peeling of the mold layer can be suppressed.
As a result, the present inventors have found that a mold release film excellent in mold release and moldability can be realized, and have completed the present invention.

In addition, the present inventor examined the raw material components constituting the release layer and the thickness of the release layer in order to express the readability of the characters printed on the molded product and the release property in a well-balanced manner. As a result, by forming the release layer with a silicone compound or a fluorine compound, the release layer is uniformly formed over the entire mold release film, and the release layer is also formed on the uneven portions of the base material layer. It was found that it can be formed. Moreover, it discovered that the embossed pattern could be provided with respect to a molded article without embedding the unevenness | corrugation of a base material layer by making thickness of a mold release layer into an appropriate numerical range.
As a result, the present inventor has found that a mold release film for molding that can express the readability of the characters printed on the molded product and the mold release property in a well-balanced manner, and has completed the present invention.

In addition, the present inventors considered arranging a release layer formed of a specific fluorine compound as the outermost layer of the mold release film in order to prevent melting of the mold release film. Thereby, the mold release film was not melted and joined to the resin composition, and the heat resistance of the mold release film could be improved. However, the desired releasability could not be obtained simply by forming the release layer of the mold release film with a specific fluorine compound.

In order to improve the releasability, the present inventors examined the contact angle of the release layer with respect to a specific solvent. As a result, it has been found that when the contact angle of hexadecane with respect to the release layer is within a specific numerical range, excellent release properties are exhibited.
As described above, the present inventor has found that a mold release film having excellent heat resistance and releasability can be realized, and has completed the present invention.

According to the present invention,
A mold release film used for molding the first resin composition,
The release layer constituted by the third resin composition has a laminated structure laminated on the base material layer constituted by the second resin composition,
The release layer and the base material layer are directly bonded,
The outermost layer of the laminated structure has the release layer,
The mold release layer is provided with a mold release film formed by crosslinking a copolymer represented by the following general formula (1) and a curing agent.

(In general formula (1),
l and m respectively represent the molar content of A and B in the copolymer;
l + m = 1,
A contains a fluorocarbon group;
B is a structural unit represented by the following formula (B1). )

(In the general formula (B1),
R ¹ is a group containing a functional group that reacts with the curing agent. )

Moreover, according to the present invention,
A mold release film is interposed between the first resin composition and the mold, and a mold release layer is brought into intimate contact with the first resin composition to perform molding, whereby the first resin composition is formed. A mold release film for molding used to give an embossed pattern to a molded product,
Having a laminated structure in which the release layer constituted by the third resin composition is laminated on the base material layer constituted by the second resin composition;
The third resin composition includes a silicone compound or a fluorine compound,
The base material layer has irregularities on the surface on which the release layer is laminated,
A mold release film for molding is provided in which the release layer has a thickness of 15 μm or less.

Moreover, according to the present invention,
A mold release film used for molding the first resin composition,
The mold release film has a release layer as the outermost layer,
The release layer is composed of a third resin composition,
The third resin composition includes a fluorine compound,
The fluorine compound includes a fluorocarbon group,
There is provided a release film for molding, wherein the contact angle of hexadecane with respect to the surface of the release layer is 20 ° or more and 77 ° or less.

Moreover, according to the present invention,
A mold forming method using the mold release film,
An arrangement step of arranging the mold release film in a mold;
And a introducing step of introducing the first resin composition into a molding space formed by the mold release film.

ADVANTAGE OF THE INVENTION According to this invention, the mold release film and mold molding method which are excellent in mold release property and moldability are provided.
Moreover, according to this invention, the mold release film and mold forming method which express the readability of the character printed on the molding, and mold release property with sufficient balance are provided.
Moreover, according to this invention, the mold forming method using the mold release film excellent in heat resistance and mold release property and this mold release film can be provided.

The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.

It is sectional drawing which shows an example of the mold release film which concerns on 1st Embodiment. It is sectional drawing which shows an example of the mold release film which concerns on 2nd Embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. In all the drawings, the same symbols are attached to the same components, and the description thereof is omitted.

(First embodiment)
The outline | summary of the mold release film of 1st Embodiment is demonstrated.
The mold release film of the first embodiment is a mold release film used for molding the first resin composition, and the release layer constituted by the third resin composition is It has a laminated structure laminated on a base material layer constituted by the second resin composition, the release layer and the base material layer are directly bonded, and the outermost layer of the laminated structure is The release layer is formed by cross-linking a copolymer having a specific structure and a curing agent.

As a method for using the mold release film of the first embodiment, for example, a first resin composition and a mold to be molded are prepared, and molding is performed between the first resin composition and the mold. There is a method in which a mold release film is interposed and a mold release layer described later is brought into close contact with the first resin composition to perform molding. Thereby, it can suppress that the molten 1st resin composition adheres to a metal mold | die etc. and contaminates a metal mold | die at the time of mold forming. In addition, the first resin composition can be accurately formed into a desired shape.

The inventors of the present invention studied the molding of a first resin composition containing an epoxy resin using a conventional mold release film. As a result, it has been found that when a mold is formed using a conventional mold release film, the release layer and the base material layer are peeled off. Although the detailed mechanism is not clear, it is speculated that the cause of peeling is that the adhesion between the release layer and the base material layer is low, and that a high load is applied at a high temperature during molding.

However, when peeling of the release layer and the base material layer occurs, the melted first resin composition comes into contact with a part other than the release layer, for example, the base material layer. When the melted first resin composition comes into contact with the base material layer, the first resin composition and the base material layer are fused, and the first resin composition is separated from the mold release film. There was an inconvenience that it was lost, that is, the releasability was lowered.
In addition, when the release layer and the base material layer are peeled off, the shape of the molding space formed by the mold release film changes from the desired shape. Molding is performed by introducing the first resin composition into the molding space. Therefore, there is a problem that the shape of the molded first resin composition deviates from the desired shape, that is, the moldability is lowered.

The present inventors examined a method for improving the adhesion of the mold release film in order to suppress the peeling of the base layer and the release layer of the mold release film. As a result, first, the base layer is subjected to specific surface modification described later, and then the specific copolymer and the curing agent are applied and crosslinked on the base layer. It has been found that forming the layer is important for directly bonding the base material layer and the release layer and improving the adhesion. Thereby, when using the mold release film, it can suppress that peeling arises in a base material layer and a mold release layer. Therefore, the mold release film according to the first embodiment can suppress the above-described deterioration of the mold release property and moldability.

Hereinafter, the configuration of the mold release film according to the first embodiment will be described in more detail.

FIG. 1 is an example of a mold release film 10 according to the first embodiment. The mold release film according to the first embodiment has a laminated structure in which the release layer 2 is laminated on the base material layer 1.
First, the base material layer 1 and the release layer 2 will be described.

<Base material layer 1>
First, the base material layer 1 will be described. The base material layer 1 is a film composed of the second resin composition.
As a surface shape of the base material layer 1, it is preferable that it is a smooth film, for example. Thereby, when the 3rd resin composition which forms the mold release layer 2 on the base material layer 1 is apply | coated and bridge | crosslinked and the mold release layer 2 is formed, the mold release layer 2 can be made smooth. it can. Thereby, when shape | molding the 1st resin composition molded, it becomes possible to make the surface which the mold release layer 2 and the 1st resin composition contact into a mirror surface. The 1st resin composition shape | molded using the mold release film 10 can be used in order to seal electronic members, such as an electronic element, for example. That is, the mold release film 10 according to the first embodiment can be suitably used for sealing an electronic member such as an electronic composition while having a smooth surface, for example.

The lower limit of the thickness of the base material layer 1 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, further preferably 25 μm or more, and more preferably 50 μm or more. Particularly preferred. Thereby, the rigidity of the base material layer 1 can be appropriately improved as long as the followability of the mold release film 10 is not impaired. Therefore, it is possible to suppress the generation of wrinkles and the like during molding and improve the moldability.
The upper limit value of the thickness of the base material layer 1 is, for example, 100 μm or less, preferably 95 μm or less, more preferably 75 μm or less, and further preferably 55 mm or less. Thereby, it can suppress that the rigidity of the mold release film becomes large too much, and can also follow a fine mold shape. Therefore, moldability can be improved.

The base material layer 1 may be, for example, an unstretched film or a stretched film depending on the production method.
As the base material layer 1, for example, a stretched film is preferable. Thereby, the molecular chain of the thermoplastic resin contained in the second resin composition can be oriented. Therefore, it is possible to suppress physical deformation such as wrinkles when the mold release film 10 follows the mold. Therefore, it is possible to suppress unnecessary scratches from being transferred to the first resin composition and improve moldability.

The second resin composition includes, for example, a thermoplastic resin. In addition to the thermoplastic resin composition, the second resin composition is, for example, an inorganic filler, an antioxidant, a slip agent, an antiblocking agent, an antistatic agent, a colorant, a hydrolysis stabilizer, and an antioxidant. An agent, a lubricant, and a crystal nucleating agent may be further included.
Hereinafter, the detail of a representative component is demonstrated about the content component of a 2nd resin composition.

(Thermoplastic resin)
Specific examples of the thermoplastic resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexanedimethylene terephthalate, polyethylene isophthalate, terephthalic acid-isophthalic acid-ethylene glycol copolymer, terephthalic acid-ethylene glycol- Polyester resin such as 1,4-cyclohexanedimethanol copolymer; Polyamide resin such as nylon 6 and nylon 66; Polyvinyl resin such as polyvinyl chloride; Polyolefin resin such as polypropylene and poly (4-methyl-1-pentene); Examples thereof include polystyrene resins such as polystyrene resin having an tactic structure; and cellulose resins such as triacetyl cellulose resin. As a thermoplastic resin, it can use 1 type or in combination of 2 or more types among the said specific examples.
As a thermoplastic resin, it is preferable that it is a polyester resin among the said specific examples, for example. As the polyester resin, for example, among the above specific examples, polyethylene terephthalate or polybutylene terephthalate is preferable, and polyethylene terephthalate is more preferable. Thereby, the functional group which reacts with the hardening | curing agent formed in the surface of the base material layer 1 by the surface modification mentioned later can be formed, and the base material layer 1 and the release layer 2 can now be couple | bonded directly suitably.

(Inorganic filler)
The inorganic filler is not limited, and specifically, carbon black; silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite, etc. Silicates; metal oxides such as iron oxide, titanium oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; carbides such as silicon carbide; silicon nitride and nitriding Examples thereof include nitrides such as boron.

(Antioxidant)
As the antioxidant, for example, one or more selected from phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants can be used.
Examples of phenolic antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5.5] undecane,
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl ( 3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) Lopionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine 2,2′-methylenebis (4-methyl-6-tert-butyl-6-butylphenol), 2, -2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis ( 4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-) t-butylphenol), 2,2′-ethylidenebis (4-s-butyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl- 3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3 , 5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] methane, 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis (1,1- Dimethyl-2-hydroxyethyl) -2,4-8,10-tetraoxaspiro [5.5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tri Ethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-methyl -6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (6- (1-methylcyclohexyl) -4-methylphenol), 4, 4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis (2- (3-tert-butyl-4-hydroxy-5-methylphenol) Nylpropionyloxy) 1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4 , 4′-bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, 4,4′-thiobis (6-t-butyl-2-methylphenol), 2,5-di-t- Butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-dimethyl -6- (1-methylcyclohexyl, styrene phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol, and the like.
Phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), tetrakis (2 , 4-Di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6 -Dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, Tris (mixed mono and di-nonylphenyl phosphite), bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methoxycal Bonylethyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite, and the like.
Examples of thioether antioxidants include dilauryl-3,3′-thiodipropionate, bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-tert-butylphenyl) sulfide , Distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate, and the like.

(Coloring agent)
The colorant is not limited, and specific examples include carbon black, bengara, titanium oxide and the like. As a coloring agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Slip agent)
Specific examples of the slip agent include amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, and hebenic acid. As a slip agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Anti-blocking agent)
Specific examples of the anti-blocking agent include fine silica, fine aluminum oxide, fine clay, fine silicone resin, liquid silicone resin, fine tetrafluoroethylene resin, fine acrylic resin, and fine methacrylic resin. As an antiblocking agent, it can use 1 type or in combination of 2 or more types among the said specific examples.

(Antistatic agent)
The antistatic agent is not limited, and specifically, inorganic antistatic agents such as zinc oxide, titanium oxide, and carbon black; N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, alkyl sulfonate, and the like Organic antistatic agents and the like. As the antistatic agent, one or two or more of the above specific examples can be used in combination.

(Hydrolysis stabilizer)
It does not limit as a hydrolysis stabilizer, Specifically, the compound etc. which contain a carbodiimide group are mentioned.
Specific examples of the compound containing a carbodiimide group include monocarbodiimide compounds such as dicyclohexylcarbodiimide and bis-2,6-diisopropylphenylcarbodiimide; poly (4,4'-dicyclohexylmethanecarbodiimide), poly (N, N'- Examples of the hydrolysis stabilizer include di-2,6-diisopropylphenylcarbodiimide) and polycarbodiimide compounds such as poly (1,3,5-triisopropylphenylene-2,4-carbodiimide). One or a combination of two or more can be used.
Specific examples of commercially available carbodiimide compounds include B2756 manufactured by Tokyo Chemical Industry; Carbodilite LA-1 manufactured by Nisshinbo Chemical; Stabaxol P, Stabaxol P400, and Stabaxol I manufactured by Rhein Chemie.

(lubricant)
The lubricant is not limited, and specific examples include paraffin wax, microcrystalline wax, polyethylene wax, long chain fatty acids such as montanic acid and montanic acid ester, and esters thereof. As the lubricant, one or two or more of the above specific examples can be used in combination.

(Crystal nucleating agent)
The crystal nucleating agent is not limited. Specifically, fatty acid esters such as stearic acid monoglyceride and behenic acid monoglyceride; hydroxy fatty acid esters such as 12-hydroxystearic acid triglyceride; hydroxy fatty acids such as 12-hydroxystearic acid monoethanolamide Monoamide; Aliphatic bisamides such as ethylene bislauric acid amide, ethylene biscapric acid amide, ethylene biscaprylic acid amide; Hydroxy fatty acid bisamides such as ethylene bis 12-hydroxystearic acid amide, hexamethylene bis 12-hydroxystearic acid amide; -Hydroxy fatty acid metal salts such as calcium hydroxystearate. As the crystal nucleating agent, one or more of the above specific examples can be used in combination.

<Release layer 2>
Next, the release layer 2 will be described.
The release layer 2 is a thin film composed of the third resin composition. The third resin composition includes a copolymer represented by the following general formula (1) and a curing agent. The third resin composition is formed as a thin film by crosslinking the copolymer represented by the following general formula (1) and the curing agent. That is, the release layer 2 is formed by crosslinking a copolymer represented by the following general formula (1) and a curing agent.

The upper limit value of the thickness of the release layer 2 is, for example, preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, further preferably 5 μm or less, and further preferably 2 μm or less. It is particularly preferable that Thereby, it can suppress that a film crack arises in the mold release layer 2, and can exhibit favorable followable | trackability with respect to a metal mold | die. Therefore, it is possible to suppress transfer of scratches to the first resin composition to be molded, and to improve moldability.
Moreover, the lower limit of the thickness of the release layer is not limited. The lower limit of the thickness of the release layer is, for example, 0.1 μm or more, preferably 0.2 μm or more, more preferably 0.3 μm or more, and further preferably 0.4 μm or more. preferable. Thereby, possibility that a defect will arise in a mold release layer is reduced, and mold release property can be expressed suitably.
In the first embodiment, the thickness of the release layer 2 is the dry thickness of the release layer 2, that is, the release layer 2 is produced by crosslinking the third resin composition, and the solvent is volatilized. It is the thickness after.

Hereinafter, the copolymer contained in the third resin composition and the curing agent will be described in detail.

(Copolymer)
The copolymer is represented by the general formula (1).
The copolymer represented by the general formula (1) can improve the releasability by including the structural unit of A, for example, and can form the release layer 2 by including the structural unit of B. . Specifically, the release layer 2 which is a thin film can be produced by reacting R ¹ which is a group contained in B with a curing agent to form a crosslinked structure. As will be described later, by interposing a functional group present on the surface of the surface-modified base material layer 1 in the reaction for forming this crosslinked structure, the adhesion strength between the base material layer 1 and the release layer 2 is improved. It is important to do.

In the copolymer represented by the general formula (1), the arrangement of the structural units A and B is not limited. Specific examples of the arrangement of the copolymer represented by the general formula (1) include a random copolymer, an alternating copolymer, a block copolymer, and a periodic copolymer. As an arrangement of the copolymer represented by the general formula (1), among the above specific examples, for example, an alternating copolymer is preferable. Thereby, the structural unit of A and B can be disperse | distributed uniformly, and the adhesiveness of the mold release layer 2 and the base material layer 1 and the mold release property of the mold release layer 2 can be improved. Further, it is advantageous in that the structural unit of A can be uniformly dispersed so that the release layer 2 can be prevented from being deteriorated over time by ultraviolet rays, oxygen, and the like.

In the above general formula (1), the structural unit of A contains a fluorocarbon group. Here, the fluorocarbon group refers to a group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. Such a fluorocarbon group has a bond of a carbon atom and a fluorine atom. Since the fluorocarbon group has a low polarizability, the surface free energy of the release layer 2 having the fluorocarbon group is reduced, and excellent release properties are exhibited even for the first resin composition containing an epoxy resin.

Specific examples of the structure of A include a structural unit in which tetrafluoroethylene, trifluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene is cleaved, and the like. An example of the cleaved structural unit will be described. For example, the structural unit trifluoroethylene _CF 2 = CHF is cleaved _is a -CF 2 -CHF-. Further, as in the structural unit of the general formula (A2) described later, a group obtained by cleaving a structural unit in which a group composed of a hydrogen atom of trifluoroethylene is substituted with another group may be used. Here, specific examples of the structural unit in which a group composed of a hydrogen atom of trifluoroethylene is substituted with another group include chlorotrifluoroethylene.
The structure of A includes tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-vinylidene fluoride copolymer. It may be a structural unit derived from a copolymer of trifluoroethylene such as a copolymer of tetrafluoroethylene such as chlorotrifluoroethylene-ethylene copolymer.
Moreover, as a structure of A, you may combine 1 type, or 2 or more types of structural units among the said specific examples.

A includes, for example, a structural unit represented by the following formula (A1), and more preferably includes a structural unit represented by the following general formula (A2). Thereby, surface free energy can be made small and mold release property can be improved.

(In the above formula (A1), n is an integer of 1 or more.)

(In the general formula (A2), R ^A is selected from the group consisting of a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, and a bromine atom. A group formed by a seed or two or more atoms, and n is an integer of 1 or more.)

In the above formula (A1) and general formula (A2), n is an integer of 1 or more. For example, n may be 1.
In the general formula (A2), R ^A is one selected from the group consisting of a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, and a bromine atom. Or a group formed by two or more atoms.
The plurality of ^RA contained in the copolymer may have, for example, the same structure or different structures.

In the structural unit of A, the carbon sequence can be, for example, linear, branched or cyclic. Among these, linear is preferable. Thereby, mold release property can be improved.

In the above general formula (1), the structural unit of B is a structural unit represented by the following general formula (B1).

In the general formula (B1), R ¹ is a group containing a functional group which reacts with the curing agent to be described later.
Here, specific examples of the functional group that reacts with the curing agent include a hydroxyl group, a carboxyl group, and an amino group. As a functional group which reacts with a hardening | curing agent, 1 type (s) or 2 or more types can be included among the said specific examples. The amino group is preferably a primary amino group or a secondary amino group.

In the general formula (B1), R ¹ is not limited as long as it includes a functional group that reacts with the above-described curing agent.
Specific examples of the atoms constituting R ¹ include a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a fluorine atom, and a chlorine atom.
The R ^1, for example, preferably contains a silicon atom. Further, when a silicon atom is contained, for example, a silicone bond —Si—O— may be provided. The silicone bond is considered to exhibit releasability with respect to the first resin composition. Therefore, in addition to the structure that reacts with the curing agent, a structure that further improves the releasability can be introduced into the structural unit of B, and the releasability of the release layer 2 can be improved.

Specifically, R ¹ may be a hydroxyl group, a carboxyl group, or an amino group itself.
In addition, as R ¹ , for example, a hydrogen atom of a monovalent organic group may be substituted with a hydroxyl group, a carboxyl group, or an amino group. In addition, the monovalence of the monovalent organic group means the valence. Specific examples of such a monovalent organic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups; allyl group, pentenyl group, vinyl group and other alkenyl groups; ethynyl group and other alkynyl groups; methylidene group and ethylidene group and the like Alkylidene groups; aryl groups such as tolyl, xylyl, phenyl, naphthyl and anthracenyl groups; aralkyl groups such as benzyl and phenethyl groups; cycloalkyl groups such as adamantyl, cyclopentyl, cyclohexyl and cyclooctyl An alkaryl group such as a tolyl group or a xylyl group;

As a commercial product of a copolymer represented by the above general formula (1), A containing the structural unit of the above general formula (A2) and B containing the structural unit of the above general formula (B1), Lumiflon manufactured by Asahi Glass Co., Ltd. And Obligato PS306R manufactured by AGC Co-Tech. Obligato manufactured by AGC Co-Tech Co. further contains a bifunctional or higher isocyanate compound as a curing agent.
As other commercially available products including a copolymer in which A contains a structural unit of the above formula (A2) and B contains a structural unit of the above general formula (B1), specifically, Obligato SS0057 manufactured by AGC Co., Ltd. Obligato SS0061, Obligato PS291U-H, Obligato SS0051, Obligato PS309R, Obligato PW501U, and the like. These commercial products further contain a bifunctional or higher functional isocyanate compound as a curing agent in the same manner as Obligato PS306R manufactured by AGC Co-Tech.

(Curing agent)
The curing agent included in the third resin composition includes, for example, an isocyanate compound. This isocyanate compound is a bifunctional or higher functional isocyanate compound. That is, the isocyanate compound contains two or more cyanate groups in its structural unit. In the first embodiment, the cyanate group represents —N═C═O. Thereby, the mold release film 10 concerning 1st Embodiment can couple | bond the base material layer 1 and the release layer 2 suitably directly.

Specific examples of the isocyanate compound described above include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, Examples include hexamethylene diisocyanate and n-pentane-1,4-diisocyanate.

(solvent)
The release layer 2 is produced by dissolving the third resin composition in a solvent and coating it. That is, the third resin composition may further contain a solvent.
The solvent is not limited, and for example, any one or more of diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate, xylene, ethylbenzene, and the like can be used as the solvent.

(Other ingredients)
The third resin composition may further contain other components as long as the release property of the release layer is not lowered.
Other components include, but are not limited to, antistatic agents such as N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, alkyl sulfonate, and inorganic fillers such as titanium oxide, calcium carbonate, talc, silicon dioxide Materials: Organic fillers such as organosilicone powder, polyethylene powder, and polyacryl powder; leveling agents such as fluorine-based nonionic surfactants.

<Method for Producing Mold Release Film 10>
Next, the manufacturing method of the mold release film 10 is demonstrated.
The manufacturing method of the mold release film 10 according to the first embodiment includes, for example, a preparation step (S1) for preparing the base material layer 1 and a surface modification for performing the surface modification treatment of the base material layer 1 first. Step (S2) and the surface-modified base material layer 1 are coated with the third resin composition prepared in the varnish, and the third resin composition is subjected to a crosslinking reaction to produce a release layer 2 Coating step (S3) to be performed.
Moreover, as a manufacturing method of the mold release film 10, you may include the winding process (S4) which uses the mold release film 10 as a wound body after a coating process (S3), for example.

(Preparation process (S1))
First, in the preparation step (S1), the base material layer 1 is prepared.
In 1st Embodiment, the method of manufacturing the base material layer 1 will not be limited if it is a method of producing the film comprised by a 2nd resin composition, According to the component which a 2nd resin composition contains. A known method can be used. It does not limit as a method of manufacturing the base material layer 1, Specifically, the inflation extrusion method, the T-die extrusion method, etc. are mentioned.

(Surface modification step (S2))
In the surface modification step, the surface modification treatment of the base material layer 1 is performed.
The surface modification treatment is not limited as long as it is a method of forming a functional group that reacts with the above-described curing agent on the surface of the base material layer 1. Specific examples of the surface modification treatment include corona discharge treatment.
As conditions for the corona discharge treatment, for example, using a batch corona treatment machine (for example, CORONA GENERATOR CT-0212 manufactured by Kasuga Denki Co., Ltd.), the output is 0.1 kW or more and 2 kW or less, and the conveyance speed is 0.1 m / min. It is preferable that the discharge gap be 0.1 to 20 mm and not more than 40 m / min.

As a result of studying a method for improving the adhesion between the base material layer 1 and the release layer 2, the present inventor performed a surface modification process (S2) for performing a surface modification treatment on the base material layer 1, and then immediately after the third step. It was found that it is important to perform the coating step (S3) for coating the resin composition. Although the detailed mechanism is not clear, when the surface modification step is performed and left for a long time, the functional group that reacts with the curing agent formed on the surface of the base material layer 1 reacts with, for example, oxygen in the atmosphere. It is presumed that it does not have reactivity capable of reacting with the curing agent.
Here, as an interval which performs a surface modification process (S2) and a coating process (S3), it is preferred that it is 10 minutes or more and 2 weeks or less, for example. In addition, when the interval which performs a surface modification process (S2) and a coating process (S3) is 24 hours or more, it is preferable that the film of the base material layer 1 is preserve | saved so that air may not be touched. Thereby, it can suppress that the functional group which reacts with the hardening | curing agent formed in the surface of the base material layer 1 is deactivated because the base material layer 1 and air contact. Therefore, a crosslinking reaction can be suitably caused between the curing agent in the third resin composition and the surface of the base material layer 1. Therefore, the copolymer represented by the general formula (1) in the third resin composition and the surface of the base material layer 1 are cross-linked through the curing agent in the third resin composition. Can do. In the first embodiment, the cross-linking reaction between the surface of the base material layer 1 and the second resin composition, and the base material layer 1 and the release layer 2 being bonded is referred to as direct bonding. . Thus, when the base material layer 1 and the mold release layer 2 are couple | bonding directly, the base material layer 1 and the mold release layer 2 do not peel by the load added at the time of shaping | molding, such as a heat | fever and stress. That is, when the base material layer 1 and the release layer 2 are directly bonded, the release layer 2 does not peel from the base material layer 1, which is convenient from the viewpoint of release properties and moldability.
In addition, the mold release film that is not directly bonded is pasted on the surface of the release layer 2 with, for example, an adhesive tape for packing use such as a gum tape (for example, Karariyan PP cut E manufactured by Denki Kagaku Kogyo Co., Ltd.) Next, the release layer 2 can be peeled from the base material layer 1 by peeling off the tape, and the release layer 2 can be transferred to the tape.

(Coating process (S3))
In the coating step (S3), the third resin composition prepared in the varnish is applied onto the surface-modified base material layer 1, the third resin composition is subjected to a crosslinking reaction, and the release layer 2 Is made.

Specific examples of the method for coating the varnish of the third resin composition include a gravure roll coating method, a doctor blade coating method, a dip coating method, a spray coating method, and a bar coater coating method. As a method for applying the varnish of the third resin composition, it is preferable to use any one of the gravure roll coating method, the bar coater coating method, and the spray coating method among the above specific examples. Thereby, the uniform release layer 2 can be produced. Therefore, the mold release film 10 can exhibit the release property evenly on the entire surface on which the release layer 2 is formed.

As a condition for causing the third resin composition to undergo a crosslinking reaction, for example, if the temperature is 25 ° C., the release reaction 2 can be formed by allowing the crosslinking reaction to proceed sufficiently by standing for one week. It is also possible to promote the crosslinking reaction by heating. For example, when the temperature is 120 ° C., the release reaction 2 can be formed by sufficiently proceeding the crosslinking reaction by heating for 20 minutes. Therefore, the temperature and time conditions can be appropriately set under the conditions of a temperature of 25 ° C. or more and 120 ° C. or less and a period of 20 minutes or more and 1 week or less.

(Winding process (S4))
In the winding step (S4), the mold release film 10 is used as a wound body.
Here, the shape of the wound body is not limited, and may be, for example, a roll shape, that is, a cylindrical shape, or a rectangular shape obtained by laminating a single-wafer mold release film 10 for molding. . When the wound body according to the first embodiment is wound into a cylindrical shape, the release layer 2 on the inner diameter side of the mold release film 10 and the base material layer 1 on the outer diameter side are used. However, even if they are in direct contact, the release layer 2 is not peeled off. Therefore, it is convenient in that the release property of the mold release film 10 is not impaired.

<Release film 10 for molding>
Next, the mold release film 10 according to the first embodiment will be described.
The mold release film 10 has a laminated structure in which a release layer is laminated on a base material layer. And the mold release film 10 has the release layer 2 in the outermost layer.
The mold release film 10 is used so that the release layer 2 disposed in the outermost layer is in contact with the first resin composition when used for molding the first resin composition.

The lamination structure of the mold release film 10 is not limited as long as the release layer has a lamination structure laminated on the base material layer.
The mold release film 10 may include two or more base material layers 1 or may include two or more release layers 2.
Specifically, the laminate structure of the mold release film 10 according to the first embodiment may be a laminate structure in which a release layer and a base material layer are laminated in this order. The material layer and the second base material layer may be laminated in this order, and the release layer, the first base material layer, the second base material layer, and the third base material layer are laminated in this order. The laminated structure may be a laminated structure in which the first release layer, the base material layer, and the second release layer are laminated in this order, and the first release layer, the first base material layer, Examples include a laminated structure in which the second base material layer and the second release layer are laminated in this order.

The upper limit of the thickness of the mold release film 10 is, for example, preferably 200 μm or less, more preferably 150 μm or less, even more preferably 100 μm or less, and even more preferably 65 μm or less. . Thereby, the rigidity of the mold release film 10 can be appropriately controlled. Therefore, the followability to the fine structure of the mold can be improved and the moldability can be improved.
The lower limit of the thickness of the mold release film 10 is, for example, preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, and more preferably 35 μm or more. Particularly preferred. Thereby, it can suppress that the mold release film 10 deform | transforms unnecessarily, and a wrinkle etc. arise. Therefore, it can suppress that the wrinkles of the mold release film 10 are transferred to the first resin composition to be molded, and the moldability can be improved.

<Application>
The release film for molding according to the first embodiment is used for molding the first resin composition.
As a molding method, for example, the first resin composition is introduced into the molding step where the mold release film is placed in the mold (S1), and then into the molding space formed by the mold release film. Introducing step (S2).

(Arrangement process (S1))
In the placing step, the mold release film is placed in the mold.
The position where the mold release film is disposed is not limited. For example, in the introduction process described later, the mold release film is placed in the mold so that the first resin composition does not contact the mold. It arranges in the molding space which forms. Thereby, the mold release film forms the molding space of the mold release film inside the molding space formed by the mold. In addition, although the whole mold surface may be covered with a mold release film, the mold may be appropriately exposed depending on the molding method, such as when a mold extrusion pin is present. Therefore, the molding space of the mold release film may be formed not only by the mold release film but also by the mold and the mold release film.
The position where the base layer and the release layer of the mold release film are arranged is not limited, but the first resin composition is introduced into the molding space of the mold release film in the introduction process described later. Therefore, it is preferable that the release layer forms a molding space for the mold release film. That is, it is preferable that the release layer included in the outermost layer of the mold release film forms a molding space of the mold release film. For example, when the mold release film has a laminated structure in which a release layer and a base material layer are laminated in this order, a release layer forming space is formed, and the base material layer is disposed so as to be in contact with the mold. Is preferred.

Although there is no limitation on the method of disposing the mold release film, it is preferable to prevent the first resin composition from overflowing outside the molding space of the mold release film in the introduction step described later. . Therefore, it is preferable that the mold release film covers the exposed surface of the mold in the molding space formed by the mold and further causes the mold release film to follow the mold forming space. That is, the mold release film needs to have appropriate rigidity to follow the shape of the molding space of the mold.
As a method of causing the mold release film to follow the molding space of the mold, for example, there is a method of providing a hole for sucking gas in the cavity of the mold and sucking air from the hole.

In the arranging step, an electronic member such as an electronic element may be arranged in the cavity of the mold before or after the mold release film is arranged in the mold.
Although it does not limit as an electronic element, For example, a semiconductor element is preferable. Examples of the semiconductor element include, but are not limited to, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.

(Introduction step (S2))
In the introducing step, the first resin composition is introduced into a molding space formed by the mold release film.
The method for introducing the first resin composition is not limited, but for example, a method for introducing a liquid first resin composition, a method for introducing a granular first resin composition, Examples thereof include a method of introducing the sheet-like first resin composition. Specifically, introduction of the liquid first resin composition by injection molding, introduction of the granular first resin composition by compression molding, and the like can be performed by a conventionally known method.
Next, by curing the first resin composition, the electronic device can be molded with the first resin composition to produce an electronic device. That is, the 1st resin composition containing an electronic element can be shape | molded in the shape substantially the same as the shaping | molding space which the mold release film forms.

An electronic device is obtained by molding the electronic element with the first resin composition. The electronic device is not limited, but for example, a semiconductor device obtained by molding a semiconductor element is preferable.
The types of semiconductor devices are not limited, but include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), and QFN (Quad Flat Non-). Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Frame BGA), FCBGA (Flip Chip BW), MAPBGA (Molded Array B) BGA), FOWLP (Fan Out Wafer Level Pac kage).

The mold forming method using the mold forming release film according to the first embodiment is not limited as long as it includes the arranging step (S1) and the introducing step (S2).
Specific molding methods include a transfer molding method or a compression molding method (compression molding method).

A specific procedure of the transfer molding method will be described. However, the transfer molding method according to the first embodiment is not limited to the following example.
First, the mold release film is made to follow the upper mold in the mold while evacuating the mold. Next, an electronic element or a substrate on which the electronic element is mounted is placed and fixed on the lower mold. Next, after tightening the upper mold and the lower mold, the first resin composition in a fluid state is injected into the mold, and then the first resin composition is cured. Thereafter, by opening the upper mold and the lower mold, the molded product and the mold release film are released.
In addition, when applying the mold release film which concerns on 1st Embodiment to the transfer mold shaping | molding method mentioned above, it is preferable that the shape of the 1st resin composition to be used is a tablet shape.

Next, a specific compression molding method (compression molding method) procedure will be described below. However, the compression molding method (compression molding method) according to the first embodiment is not limited to the following example.
First, the mold release film is made to follow the upper mold in the mold while evacuating the mold. Next, an electronic element or a substrate on which the electronic element is mounted is placed and fixed on the lower mold. Next, under reduced pressure, the lower mold removes the weighed first resin composition by a resin material supply mechanism such as a shutter that constitutes the bottom surface of the resin material supply container while reducing the distance between the upper mold and the lower mold. Supply into the lower mold cavity. As a result, the first resin composition is heated to a predetermined temperature in the lower mold cavity and becomes fluidized. Next, by bonding the upper mold and the lower mold of the mold, the first resin composition in a fluid state is pressed against the molding object fixed to the upper mold, The first resin composition is cured while maintaining the state where the lower mold is bonded. Thereafter, by opening the upper mold and the lower mold, the molded product and the mold release film are released.
In addition, when the mold release film according to the first embodiment is applied to the compression molding method (compression molding method) described above, the shape of the first resin composition to be used is a tablet shape, a granular shape, a sealed shape. It is preferably processed into a granular shape or a sheet shape.

The lower limit of the molding temperature may be, for example, 120 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, 160 ° C. or higher, or 175 ° C. or higher. In addition, even when the mold release film according to the first embodiment is molded with the lower limit value or more, suitable moldability can be exhibited.
When the first resin composition contains an epoxy resin, the molding temperature is set to be equal to or higher than the lower limit, for example. If it was the conventional mold release film for mold forming, there existed a problem that the base material layer 1 and the release layer 2 will peel in mold shaping in the high temperature beyond the said lower limit. This is presumably because the molecular motion at the interface between the base material layer 1 and the release layer 2 becomes active at high temperatures, and the adhesion between the base material layer 1 and the release layer 2 cannot be maintained. On the other hand, in the mold release film 10 according to the first embodiment, since the base layer 1 and the release layer 2 are directly bonded, the base layer 1 and the release layer 2 are not peeled off. There is no inconvenience.
Moreover, the upper limit of the molding temperature may be, for example, 240 ° C. or lower, 200 ° C. or lower, or 185 ° C. or lower.

<First resin composition>
The first resin composition according to the first embodiment is not limited. For example, a thermoplastic resin composition or a thermosetting resin composition can be used. The release film for molding according to the first embodiment is suitably used for molding a first resin composition containing an epoxy resin. This is because the molding temperature of the first resin composition containing the epoxy resin is, for example, 175 ° C. or higher, but the moldability is not degraded even when the base material layer 1 and the release layer 2 are peeled off even at a high temperature of 175 ° C. or higher. It is because it can maintain.

Examples of the thermosetting resin composition include an epoxy resin, a curing agent, and an inorganic filler.

(Epoxy resin)
As the epoxy resin, it is possible to use monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule regardless of the molecular weight and molecular structure. Specific examples of such an epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4 , 4 '-(1,3-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Bisphenol type epoxy resins such as Z type epoxy resin (4,4'-cyclohexyldiene bisphenol type epoxy resin); phenol novolak type epoxy resin, brominated phenol novolak type epoxy resin, cresol novolak type epoxy resin, Novolak type epoxy resins such as laphenol group ethane type novolak type epoxy resins and novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure; biphenyl type epoxy resins; aralkyl type epoxies such as xylylene type epoxy resins and biphenyl aralkyl type epoxy resins Resin: Naphthalene skeleton such as naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalene diol type epoxy resin, bifunctional or tetrafunctional epoxy type naphthalene resin, binaphthyl type epoxy resin, naphthalene aralkyl type epoxy resin Epoxy resin; anthracene epoxy resin; phenoxy epoxy resin; dicyclopentadiene epoxy resin; norbornene epoxy resin; adamantane epoxy resin Fluorene type epoxy resin, phosphorus-containing epoxy resin, cycloaliphatic epoxy resin, aliphatic chain epoxy resin, bisphenol A novolac type epoxy resin, bixylenol type epoxy resin, triphenolmethane type epoxy resin, trihydroxyphenylmethane type epoxy resin Heterocyclic epoxy resins such as tetraphenylolethane type epoxy resin and triglycidyl isocyanurate; N, N, N ′, N′-tetraglycidylmetaxylenediamine, N, N, N ′, N′-tetraglycidylbis Glycidylamines such as aminomethylcyclohexane and N, N-diglycidylaniline, copolymers of glycidyl (meth) acrylate and compounds having an ethylenically unsaturated double bond, epoxy resins having a butadiene structure, bisphenol diglycid It can include ether compound, diglycidyl ethers of naphthalene diol, the one or more selected from glycidyl ethers of phenols.

(Curing agent)
Specific examples of the curing agent include three types, for example, a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent.

Specific examples of the polyaddition type curing agent used as the curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), and diaminodiphenylmethane (DDM). In addition to aromatic polyamines such as m-phenylenediamine (MPDA) and diaminodiphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY) and organic acid dihydrazide; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride Acid anhydrides including alicyclic acid anhydrides such as (MTHPA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenone tetracarboxylic acid (BTDA); Type Examples include phenolic resin-based curing agents such as diol resins, polyvinylphenols, and aralkyl-type phenolic resins; polymercaptan compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and carboxylic acid-containing polyester resins. . As a polyaddition type hardening | curing agent, the 1 type (s) or 2 or more types selected from the said specific example can be included.

Specific examples of the catalyst-type curing agent used as the curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); Examples include imidazole compounds such as methylimidazole and 2-ethyl-4-methylimidazole (EMI24); Lewis acids such as BF3 complex. As a catalyst type hardening | curing agent, the 1 type (s) or 2 or more types selected from the said specific example can be included.

Specific examples of the condensation type curing agent used as the curing agent include a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine resin such as a methylol group-containing melamine resin. As the condensation type curing agent, one type or two or more types selected from the above specific examples can be included.

Among the curing agents, it is preferable to include a phenol resin curing agent.
As the phenol resin-based curing agent, monomers, oligomers, and polymers in general having two or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and molecular structure are not limited.
Specific examples of the phenol resin-based curing agent used as the curing agent include novolak type phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol novolak, and phenol-biphenyl novolak resin; polyvinyl phenol; triphenylmethane type phenol resin, and the like. Polyfunctional phenolic resin; modified phenolic resin such as terpene modified phenolic resin, dicyclopentadiene modified phenolic resin; phenol aralkyl resin having phenylene skeleton and / or biphenylene skeleton, naphthol aralkyl resin having phenylene and / or biphenylene skeleton, etc. Phenol aralkyl type phenol resin; Bisphenol compounds such as bisphenol A, bisphenol F, and the like. As a phenol resin hardening | curing agent, the 1 type (s) or 2 or more types selected from the said specific example can be included.

(Inorganic filler)
Examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, and secondary agglomerated silica; alumina; titanium white; aluminum hydroxide; talc; clay; mica; glass fiber and the like.

In the thermosetting resin composition, one or two of various additives such as a curing accelerator, a coupling agent, a mold release agent, a flame retardant, an ion scavenger, a colorant, and a low stress agent, as necessary. You may mix the above.
Hereinafter, representative components will be described.

(Curing accelerator)
The thermosetting resin composition may further contain a curing accelerator. This hardening accelerator should just be what accelerates | stimulates hardening reaction with an epoxy group and a hardening | curing agent.
Specific examples of the curing accelerator include diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine; 2 -Imidazole compounds such as methylimidazole; Organic phosphines such as triphenylphosphine and methyldiphenylphosphine; Tetraphenylphosphonium / tetraphenylborate, Tetraphenylphosphonium / tetrabenzoic acid borate, Tetraphenylphosphonium / tetranaphthoic acid borate, Tetraphenyl Tetra-substituted phosphonium / tetra-substituted borates such as phosphonium / tetranaphthoyloxyborate and tetraphenylphosphonium / tetranaphthyloxyborate; Triphenylphosphine and the like. As a hardening accelerator, it can use 1 type or in combination of 2 or more types among the said specific examples.

(Coupling agent)
The thermosetting resin composition may further contain a coupling agent.
Specific examples of coupling agents include epoxy silane coupling agents, cationic silane coupling agents, amino silane coupling agents, γ-glycidoxypropyl trimethoxy silane coupling agents, and γ-aminopropyl triethoxy silane cups. Silane coupling agents such as ring agents, γ-mercaptopropyltrimethoxysilane coupling agents, N-phenyl-γ-aminopropyltrimethoxysilane coupling agents, mercaptosilane coupling agents, titanate coupling agents and silicone oil types A coupling agent etc. are mentioned. As a coupling agent, it can use 1 type or in combination of 2 or more types among the said specific examples.

(Release agent)
The thermosetting resin composition may further contain a release agent.
Specific examples of the release agent include natural waxes such as carbana wax; synthetic waxes such as montanic acid ester; higher fatty acids or metal salts thereof; paraffin; polyethylene oxide and the like. As a mold release agent, it can use 1 type or in combination of 2 or more types among the said specific examples.

(Flame retardants)
The thermosetting resin composition may further contain a flame retardant.
Specific examples of the flame retardant include magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. As the flame retardant, one or more of the above specific examples can be used.

(Coloring agent)
The thermosetting resin composition may further contain a colorant.
Specific examples of the colorant include carbon black, bengara, and titanium oxide. As a coloring agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Ion scavenger)
The thermosetting resin composition may further contain an ion scavenger.
Specific examples of the ion scavenger include hydrotalcite; zeolite; hydrous oxide of an element selected from magnesium, aluminum, bismuth, titanium, and zirconium. As the ion scavenger, one or two or more of the above specific examples can be used.

(Low stress agent)
The thermosetting resin composition may further contain a low stress agent.
Specific examples of the low stress agent include polybutadiene compounds, acrylonitrile butadiene copolymer compounds, silicone compounds such as silicone oil and silicone rubber. As the low stress agent, one or more of the above specific examples can be used in combination.

(Second Embodiment)
Hereinafter, although the mold release film for molding according to the second embodiment will be described, the difference from the above-described first embodiment will be mainly described. Matters not described can be the same as in the first embodiment.

The outline | summary of the mold release film of 2nd Embodiment is demonstrated.
In the mold release film of the second embodiment, a mold release film is interposed between the first resin composition and the mold, and a release layer described later is adhered to the first resin composition. A mold release film for molding that is used to give an embossed pattern to the molded product of the first resin composition by performing mold molding, and is constituted by the second resin composition It has a laminated structure in which the release layer constituted by the third resin composition is laminated on the base material layer, and the third resin composition contains a silicone compound or a fluorine compound, and The base material layer has irregularities on the surface on which the release layer is laminated, and the thickness of the release layer is 15 μm or less.

In recent years, with the miniaturization of electronic devices, it has been required to reduce the characters printed on the electronic devices. The inventor performs mold molding for sealing an electronic element with the first resin composition using a conventional mold release film, and then prints characters on the molding of the first resin composition. We examined the legibility of the electronic devices. As a result, it has been found that the readability of characters printed on the electronic device is low. The reason for the low readability is not clear, but is presumed as follows.
The release layer of the conventional mold release film has a smooth surface. Accordingly, when molding is performed with the release layer in close contact with the first resin composition, the surface of the first molded product becomes a mirror surface, and specular reflection occurs on the surface. In this case, the printed portion is glossy, and it is assumed that the detector or the human body cannot recognize the elements that identify the printed portion and the non-printed portion, such as contrast of light and darkness, color difference, and focus. . As mentioned above, it is estimated that the readability of the printed character is low in the molded object and electronic device which were created using the conventional mold release film.
Here, specific examples of the electronic device include a semiconductor device. Specific examples of the characters printed on the electronic device include information indicating manufacturing information such as a lot, information indicating the position of the electronic device in an automated manufacturing process, and the like. As a result, when the readability of the characters is low, there are inconveniences in terms of management of the electronic device and automation of the manufacturing process of the electronic device. In addition, it is not limited as a character, Specifically, language symbols such as hiragana, katakana, alphabet, etc .; polygon, sphere, indefinite shape, linear, striped pattern, barcode, matrix type two-dimensional code, stack type two-dimensional Non-linguistic symbols such as codes; numerals such as Arabic numerals and Greek numerals; designs such as logo marks and schematic diagrams.

The inventor studied the surface structure of the molded product of the first resin composition in order to improve the readability of characters on the surface of the electronic device. As a result, it has been found that the readability of the printed characters is improved when the surface structure of the molded product of the first resin composition is not smooth but has an embossed pattern such as a matte tone. The detailed mechanism is not clear, but the reason is presumed as follows. First, as a premise, the reflected light is the sum of regular reflection light and irregular reflection light. Here, by forming an appropriate embossed pattern on the surface of the molded product of the first resin composition, the intensity of specular reflection light is reduced compared to the case where the surface of the molded product is smooth, and irregularly reflected light. It is estimated that the strength of As a result, it is considered that the gloss caused by the regular reflection light is less likely to occur in the print portion. From the above, it is presumed that the readability of printed characters is improved when the surface structure of the molded product of the first resin composition is an embossed pattern such as a matte tone.
Therefore, the present inventor examined the thickness of the release layer in order to improve the readability of the printed characters. As a result, when the thickness of the release layer is large, the release layer embeds unevenness of the base material layer, and an embossed pattern suitable for improving readability is imparted to the molded product of the first resin composition. It turned out not to be possible.
On the other hand, when reducing the thickness of the release layer, for example, the release layer cannot be appropriately formed on the convex and concave portions of the base material layer, and the first resin composition and the release film for molding are released. It has been found that there is an inconvenience that the performance decreases.
From the above, the readability of the characters printed on the molded product and the releasability were in a trade-off relationship depending on the thickness of the release layer.

The present inventor has studied the raw material components constituting the release layer in order to express the readability of the characters printed on the molded product and the release property in a balanced manner. As a result, it has been found that a release layer can be formed thinly and uniformly on the entire mold release film by forming the release layer with a silicone compound or a fluorine compound. Thereby, it discovered that the embossed pattern derived from the unevenness | corrugation of a base material layer could be provided with respect to a molded object, without embedding the unevenness | corrugation of a base material layer.
In addition, as a result of the inventor's study on the release property of a mold release film, when a silicone compound or a fluorine compound is used, sufficient release properties can be exhibited even when the release layer is thin. I found.
From the above, the mold release film according to the second embodiment can realize a mold release film that expresses the readability of the characters printed on the molded product and the mold release property in a well-balanced manner.

Hereinafter, the configuration of the mold release film according to the second embodiment will be described in more detail.

FIG. 2 is an example of a mold release film 10 according to the second embodiment. The mold release film according to the second embodiment has a laminated structure in which a release layer 2 is laminated on a base material layer 1.
First, the base material layer 1 and the release layer 2 will be described.

<Base material layer 1>
First, the base material layer 1 according to the second embodiment will be described. The base material layer 1 is a film composed of the second resin composition.
At least one surface of the base material layer 1 is a surface having irregularities. The mold release film 10 according to the second embodiment has a laminated structure in which a release layer is laminated on the surface of the base material layer 1 having the unevenness. Thereby, the embossed pattern originating in the unevenness | corrugation of the base material layer 1 can be provided to the molded product of the 1st resin composition.
In addition, the said description does not limit that the both surfaces of the base material layer 1 are a surface provided with an unevenness | corrugation. The mold release film 10 according to the second embodiment has, for example, unevenness on both surfaces of the base material layer 1 and lamination of the release layer 2 on both surfaces of the base material layer 1 according to the shape of the mold. A laminated structure may be provided.

The shape of the unevenness of the base material layer 1 is not limited, and can be set according to the embossed pattern transferred to the molded product of the first resin composition. Specifically, the shape of the unevenness and the shape of the embossed pattern are matte tone; mesh tone; fabric tone; stone tone such as cleaved surface of granite; skin tone; wood tone such as conduit groove, annual ring, myelin Tile-like; brick-like; pear-like. Of the above specific examples, the uneven shape and the embossed pattern shape are preferably matte, for example. Moreover, it is more preferable that it is a sand mat tone formed by sand blasting among the mat tones. Thereby, it is considered that the light flux of the regular reflection light can be reduced and the light flux of the irregular reflection light can be increased. Therefore, the readability of printing can be improved. Moreover, the mold release part which is a space | gap can be formed between the embossed shape of the mold release film 10 and the molding of the 1st resin composition in the case of mold release. Thereby, it is possible to release the entire close contact portion of the mold release film 10 and the molded product of the first resin composition starting from the release portion which is a void. Therefore, the releasability can be improved.

About the surface provided with the unevenness | corrugation of the base material layer 1, as a lower limit of arithmetic mean roughness Ra, it is preferable that it is 0.10 micrometer or more, for example, it is more preferable that it is 0.30 micrometer or more, It is 0.40 micrometer or more. More preferably, it is more preferably 0.50 μm or more, and still more preferably 0.65 μm or more. By being more than the said lower limit, the whole roughness of the base material layer 1 can be enlarged appropriately. Thereby, even when forming a release layer, an appropriate embossed pattern can be provided to the molded product of the first resin composition via the release layer. Therefore, the readability of characters can be improved.
Moreover, about the surface provided with the unevenness | corrugation of the base material layer 1, as upper limit of arithmetic mean roughness Ra, 1.0 micrometer or less may be sufficient, 0.90 micrometer or less may be sufficient, and 0.80 micrometer or less may be sufficient. Thereby, it can suppress that an unevenness | corrugation becomes large too much in the whole base material layer 1. FIG. Thereby, it can suppress that an embossing shape bites into the 1st resin composition too much, and a mold release layer falls.
In the second embodiment, the arithmetic average roughness Ra can be measured in accordance with, for example, JIS B 0601-2013.

The lower limit of the 10-point average surface roughness Rz of the surface of the base material layer 1 having irregularities is, for example, preferably 1.0 μm or more, more preferably 2.0 μm or more, and 3.0 μm. More preferably, it is more preferably 4.0 μm or more, and even more preferably 4.5 μm or more. Thereby, the local roughness of the base material layer 1 can be enlarged appropriately. Thereby, even when forming a release layer, an appropriate embossed pattern can be provided to the molded product of the first resin composition via the release layer. Therefore, the readability of characters can be improved.
Further, when Rz is equal to or more than the above lower limit value, the releasability can be improved. Although the detailed mechanism is not clear, it is presumed that the shape of the interface between the release layer and the molded product of the first resin composition can be made easier to peel.
Moreover, as an upper limit of 10-point average surface roughness Rz about the surface provided with the unevenness | corrugation of the base material layer 1, it may be 10.0 micrometers or less, may be 8.0 micrometers or less, and may be 6.0 micrometers or less, for example. Good. Thereby, it can suppress that an unevenness | corrugation becomes large too much from the local viewpoint about the base material layer 1. FIG. Thereby, it can suppress that an embossing shape bites into the 1st resin composition too much, and a mold release layer falls.
In the second embodiment, the 10-point average surface roughness Rz can be measured according to, for example, JIS B 0601-1994.

The lower limit of the thickness of the base material layer 1 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, further preferably 25 μm or more, and preferably 30 μm or more. Particularly preferred. Thereby, the rigidity of the base material layer 1 can be appropriately improved as long as the followability of the mold release film 10 is not impaired. Therefore, the mold release film 10 can be prevented from being wrinkled, and a desired embossed pattern can be imparted to the molded product of the first resin composition.
The upper limit value of the thickness of the base material layer 1 is, for example, 100 μm or less, preferably 95 μm or less, more preferably 75 μm or less, and further preferably 55 mm or less. In the fine electronic device, the mold also has fine irregularities, and the mold shape of the mold release film 10 is required for the mold shape. Convenient in that the thickness of the base material layer 1 is less than or equal to the above upper limit value, so that the mold release film 10 can be prevented from becoming too rigid and follow the fine irregularities of the mold. Is good.

As a 2nd resin composition which concerns on 2nd Embodiment, the thing similar to 1st Embodiment can be used.
In addition, as a thermoplastic resin, it is preferable that it is a polyester resin among the said specific examples, for example. As the polyester resin, for example, among the above specific examples, polyethylene terephthalate or polybutylene terephthalate is preferable, and polyethylene terephthalate is more preferable. Thereby, heat resistance and intensity | strength can be provided also to the fine unevenness | corrugation of a base material layer. Therefore, in molding, even if the mold release film 10 is exposed to high temperature and pressure, the unevenness of the base material layer 1 is prevented from collapsing, and desired for the molded product of the first resin composition. The embossed pattern can be provided.

<Release layer 2>
Next, the release layer 2 according to the second embodiment will be described.
The release layer 2 is a thin film composed of the third resin composition. The release layer 2 is formed on the surface having the unevenness of the base material layer 1 described above. Therefore, the mold release film has an emboss shape reflecting the unevenness of the base material layer on the surface provided with the release layer.
Although it explains in full detail in the manufacturing method of the mold release film 10, the manufacturing method of the mold release layer 2 coats the 3rd resin composition prepared in the varnish on the base material layer 1, for example. A method of cross-linking the third resin composition can be used.

The upper limit value of the thickness of the release layer 2 is 15 μm or less, for example, preferably 10 μm or less, more preferably 7 μm or less, further preferably 5 μm or less, and preferably 3 μm or less. More preferably, it is particularly preferably 0.6 μm or less. Thereby, the mold release layer 2 can be formed without embedding the unevenness | corrugation of the base material layer 1 mentioned above. That is, the mold release film 10 can have an embossed shape. Therefore, at the time of molding, an embossed pattern can be suitably imparted to the molded product of the first resin composition, and the readability of printing can be improved.
The lower limit value of the thickness of the release layer 2 is, for example, 0.1 μm or more, preferably 0.2 μm or more, more preferably 0.3 μm or more, and 0.4 μm or more. More preferably. Thereby, it can suppress that the mold release layer 2 is not formed in the uneven | corrugated convex part of the base material layer 1. FIG. Therefore, the mold release film 10 can exhibit a release property suitably.
In the second embodiment, the thickness of the release layer 2 is the dry thickness of the release layer 2, that is, the release layer 2 is produced by crosslinking the third resin composition, and the solvent is volatilized. It is the thickness after.

The third resin composition includes, for example, a silicone compound or a fluorine compound and a curing agent. Thereby, the release layer 2 is formed by crosslinking the silicone compound or the fluorine compound with the curing agent. That is, the release layer 2 is formed by crosslinking a silicone compound or a fluorine compound and a curing agent.
Here, the third resin composition preferably includes, for example, a fluorine compound. Thereby, mold release property can be improved more. In addition, even when the thickness is reduced, it is convenient from the viewpoint that the release layer 2 can be formed uniformly.
Hereinafter, each component included in the third resin composition will be described in detail.

(Fluorine compound)
As the fluorine compound according to the second embodiment, the copolymer represented by the general formula (1) described in the first embodiment can be used.

(Silicone compound)
Specific examples of the silicone compound include those containing polydialkylsiloxane. Such a silicone compound may be used in combination with a fluoropolyether. As polydialkylsiloxane, what is represented by the following general formula (SI1) is mentioned, for example. Moreover, as a fluoro polyether, what is represented by the following general formula (SI2) is mentioned, for example.

(In the general formula (SI1), a plurality of R ^s each independently represents an organic group having 1 to 30 carbon atoms. At least one R ^S is a functional group that reacts with at least one curing agent. A and b are each independently an integer of 1 or more.)

(In the general formula (SI2), a plurality of R ^s each independently represents an organic group having 1 to 30 carbon atoms. At least one R ^S is a functional group that reacts with at least one curing agent. D, e, and f are each independently an integer of 1 or more.)

In the polydialkylsiloxane and fluoropolyether represented by the general formulas (SI1) and (SI2), at least one R ^s includes a functional group that reacts with at least one curing agent.
Here, specific examples of the functional group that reacts with the curing agent include a hydroxyl group, a carboxyl group, and an amino group. As a functional group which reacts with a hardening | curing agent, 1 type (s) or 2 or more types can be included among the said specific examples. The amino group is preferably a primary amino group or a secondary amino group.

In the above general formulas (SI1) and (SI2), R ^s specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -Alkyl groups such as butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl; alkenyl such as allyl, pentenyl, vinyl; alkynyl such as ethynyl; methylidene Group, alkylidene group such as ethylidene group; aryl group such as tolyl group, xylyl group, phenyl group, naphthyl group and anthracenyl group; aralkyl group such as benzyl group and phenethyl group; adamantyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group A cycloalkyl group such as: tolyl group, xylyl group, etc. Examples include a ryl group.
Further, R ^s with a functional group which reacts with the curing agent may be used after replacing a hydrogen atom in the above embodiment, a functional group which reacts with the curing agent.

(Curing agent)
As a hardening | curing agent which concerns on 2nd Embodiment, the thing similar to the hardening | curing agent of 1st Embodiment can be used.

(solvent)
The release layer 2 is produced, for example, by dissolving the third resin composition in a solvent and coating it. That is, the third resin composition may further contain a solvent.
As a solvent which concerns on 2nd Embodiment, the thing similar to the solvent of 1st Embodiment mentioned above can be used.

(Other ingredients)
In addition, the 3rd resin composition may contain another component in the range which can solve a subject.
As other components according to the second embodiment, the same antistatic agent, inorganic filler, organic filler, leveling agent and the like as in the first embodiment described above can be used.

<Method for Producing Mold Release Film 10>
Next, the manufacturing method of the mold release film 10 is demonstrated.
In the method for producing the mold release film 10 according to the second embodiment, for example, first, a film composed of the second resin composition is prepared, and irregularities are imparted to the film to form the base material layer 1. A base material preparation step (S1), a coating step (S3) for applying the third resin composition prepared on the varnish, causing the third resin composition to undergo a crosslinking reaction, and preparing the release layer 2; ,including.
In addition, as a manufacturing method of the mold release film 10, for example, after the base material preparation step (S1), and before the coating step (S3), the surface modification for performing the surface modification treatment of the base material layer 1 is performed. A quality step (S2) may be included. Moreover, as a manufacturing method of the mold release film 10, you may include the winding process (S4) which uses the mold release film 10 as a wound body after a coating process (S3), for example.

(Substrate preparation step (S1))
First, in a base material preparation process (S1), the film comprised by the 2nd resin composition is prepared, an unevenness | corrugation is provided to this film, and it is set as the base material layer 1. FIG.
In 2nd Embodiment, the method of manufacturing the film comprised with a 2nd resin composition is not limited, A well-known method can be used according to the component which a 2nd resin composition contains. Specific examples of the method for producing a film composed of the second resin composition include an inflation extrusion method and a T-die extrusion method.

Subsequently, in a base material preparation process (S1), an unevenness | corrugation is provided to the film comprised with a 2nd resin composition.
The method for imparting irregularities to the base material layer 1 is not limited, and a conventionally known method for forming irregularities on the film can be employed. Specifically, as a method for imparting unevenness to the base material layer 1, a method of transferring the unevenness of the embossing roll during or after the manufacture of the base material layer 1, or a sandblasting method or Examples thereof include a method of scraping the surface of the base material layer 1 using an etching method. As a method for imparting irregularities to the base material layer 1, it is preferable to use, for example, a sandblast method among the above specific examples. Thereby, the embossed shape of the mold release film 10 can be made less bite into the first resin composition, and can be made suitable for improving the release property.
In addition, as the base material layer 1, you may use the commercial item which provided the unevenness | corrugation using the sandblast method, for example.

(Surface modification step (S2))
You may perform the surface modification process which performs the surface modification process of the base material layer 1 after a base material preparation process and before a coating process. In the surface modification step, the surface modification treatment of the base material layer 1 is performed. Thereby, it is estimated that a crosslinking reaction can be caused by the curing agent in the third resin composition and the surface of the base material layer 1. Therefore, the adhesive force of the base material layer 1 and the release layer 2 can be improved, and it is possible to suppress the inconvenience that the base material layer 1 and the release layer 2 are peeled off during molding.
As the surface modification treatment, a treatment for forming a functional group that reacts with the above-described curing agent on the surface of the base material layer 1 can be performed. Specific examples of the surface modification treatment include corona discharge treatment.
As conditions for the corona discharge treatment, for example, using a batch corona treatment machine (for example, CORONA GENERATOR CT-0212 manufactured by Kasuga Denki Co., Ltd.), the output is 0.1 kW or more and 2 kW or less, and the conveyance speed is 0.1 m / min. It is preferable that the discharge gap be 0.1 to 20 mm and not more than 40 m / min.
Here, as an interval which performs a surface modification process (S2) and a coating process (S3), it is preferred that it is 10 minutes or more and 2 weeks or less, for example. In addition, when corona discharge is performed as the surface modification treatment, when the interval for performing the surface modification step (S2) and the coating step (S3) is 24 hours or more, the film of the base material layer 1 is exposed to air. It is preferable to store it so that it does not exist. Thereby, it can suppress that the functional group which reacts with the hardening | curing agent formed in the surface of the base material layer 1 is deactivated because the base material layer 1 and air contact. Therefore, a crosslinking reaction can be suitably caused by the curing agent in the third resin composition and the surface of the base material layer 1, and the release layer 2 and the base material layer 1 can be appropriately adhered. Therefore, even if the uneven | corrugated shape of the base material layer 1 exists, suitable releasability can be expressed.

(Coating process (S3))
In a coating process (S3), the 3rd resin composition prepared to the varnish is applied on the base material layer 1, a 3rd resin composition is made to cross-link, and the mold release layer 2 is produced.
The method and conditions of the coating process can be the same as in the coating process (S3) of the first embodiment described above.

(Winding process (S4))
In the winding step (S4), the mold release film 10 is used as a wound body.
Here, the shape of the wound body is not limited, and may be, for example, a cylindrical shape or a rectangular shape. When the wound body according to the second embodiment is wound into a columnar shape, the release layer 2 on the inner diameter side of the mold release film 10 and the base material layer 1 on the outer diameter side are used. However, even if it contacts directly, the embossed shape of the mold release film 10 derived from the unevenness of the base material layer 1 is not impaired. Therefore, it is convenient in that the release property of the mold release film 10 is not impaired.

<Release film 10 for molding>
Next, the mold release film 10 according to the second embodiment will be described.
The mold release film 10 has a laminated structure in which a release layer constituted by a third resin composition is laminated on a base material layer constituted by a second resin composition. Thereby, the mold release film 10 according to the second embodiment has an emboss shape derived from the unevenness of the base material layer 1.
In addition, the mold release film 10 has the release layer 2 in the outermost layer. Thereby, when performing mold shaping | molding, the mold release layer 2 can be closely_contact | adhered to 1st resin composition, and mold shaping | molding can be performed.

The laminate structure of the mold release film 10 is not limited as long as it has a laminate structure in which the release layer 2 is laminated on the base material layer 1. In addition, the unevenness | corrugation of the base material layer 1 is reflected in the release layer 2 appropriately, and from a viewpoint of forming a desired emboss shape in the mold release film 10, between the base material layer 1 and the release layer 2 is provided. For example, it is preferable not to include an adhesive layer.
In addition, the laminated structure of the mold release film 10 according to the second embodiment can be the same as that of the first embodiment.

For the surface having the embossed shape of the mold release film 10, the upper limit of the glossiness, which is the reflectance of light at an incident angle of 60 °, is preferably 23 or less, and more preferably 20 or less. It is preferably 17 or less, more preferably 15 or less, and even more preferably 12 or less. Thereby, the intensity | strength of specular reflection light can be reduced and the intensity | strength of irregular reflection light can be improved with the embossing pattern of the molding of the 1st resin composition.
Here, this inventor examined the method of controlling the glossiness of the surface provided with the embossed shape of the mold release film 10. As a result, the mold release film according to the second embodiment includes the arithmetic average roughness Ra and the 10-point average surface roughness Rz of the surface having the unevenness of the base material layer 1, and the release layer 2 constituting the release layer 2. It was found that the glossiness can be controlled to the upper limit value or less by appropriately controlling the blending components of the resin composition 3 and the thickness of the release layer 2. Thereby, the embossed pattern suitable for improving the readability of printing can be transferred to the molded product of the first resin composition.
Moreover, about the surface provided with the embossed shape of the mold release film 10, the lower limit of the glossiness, which is the reflectance of light at an incident angle of 60 °, may be 1 or more, for example, or 2 or more.
In the second embodiment, the gloss level can be measured in accordance with JIS Z 8741. A specific method for measuring glossiness will be described. As a premise, on the surface having a refractive index of 1.567, the intensity of light having a reflectance of 10% is assumed to have a glossiness of 100 and the intensity of light having a reflectance of 0% is assumed to be 0 when the incident angle is 60 °. To do. Accordingly, a value of 1/100 of the intensity of light having a reflectance of 10% corresponds to a gloss level of 1. Here, the intensity | strength of the light of the surface provided with the embossed pattern of the mold release film 10 is measured using the reflectometer of the geometric condition of incident angle 60 degrees. Then, the glossiness can be calculated by dividing the obtained light intensity by 1/100 of the light intensity having the reflectance of 10%.

The upper limit of the total thickness of the mold release film 10 is, for example, preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and 65 μm or less. Particularly preferred. Thereby, the rigidity of the mold release film 10 can be appropriately improved as long as the followability to the mold is not impaired. Therefore, the mold release film 10 does not invade the desired molding space, which is advantageous in that a desired embossed pattern can be imparted to the molded product of the first resin composition.
Further, the lower limit of the total thickness of the mold release film 10 is, for example, preferably 10 μm or more, more preferably 20 μm or more, further preferably 30 μm or more, and 35 μm or more. It is particularly preferable. Thereby, it can suppress that the mold release film 10 deform | transforms unnecessarily, and a wrinkle etc. arise. Therefore, a desired embossed pattern can be imparted to the molded product of the first resin composition.

<Application>
The mold release film according to the second embodiment is used for molding the first resin composition.
The molding method according to the second embodiment and the obtained electronic device can be the same as those in the first embodiment described above.
In the arrangement step (S1), for example, when the mold release film has a laminated structure in which a release layer and a base material layer are laminated in this order, a release layer forming space is formed, and the base material layer is formed. Is preferably arranged so as to be in contact with the mold. Thereby, the mold release film for molding is interposed between the first resin composition and the mold, the mold release layer is brought into close contact with the first resin composition, and the first resin is molded. An embossed pattern can be imparted to the molded product of the composition.

The lower limit of the molding temperature may be, for example, 120 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, 160 ° C. or higher, or 175 ° C. or higher. When the first resin composition contains an epoxy resin, the molding temperature is set to be equal to or higher than the lower limit, for example. In the case of a conventional mold release film for molding, there is an inconvenience that the molding at a high temperature equal to or higher than the lower limit value is insufficient in heat resistance and the embossed shape collapses. However, in the mold release film according to the second embodiment, the second resin composition and the third resin composition constituting the base layer 1 and the release layer 2 are selected according to the selection of the raw material components described above. It is convenient in that the embossed shape does not collapse even when molding at a high temperature equal to or higher than the lower limit. Thereby, an embossed pattern can be suitably given with respect to the molding of the 1st resin composition. Therefore, the readability of printing can be improved.
The mold release film according to the second embodiment is advantageous in that the base material layer 1 and the release layer 2 do not peel off even when used for high temperature and high pressure mold forming. Although the detailed mechanism is not clear, since the release layer 2 bites into the fine irregularities of the base material layer 1 and acts as an anchor effect, the adhesion between the base material layer 1 and the release layer 2 is high. It is guessed.
Moreover, the upper limit of the molding temperature may be, for example, 240 ° C. or lower, 200 ° C. or lower, or 185 ° C. or lower.

<First resin composition>
The first resin composition according to the second embodiment is not limited. For example, a thermoplastic resin composition or a thermosetting resin composition can be used. The mold release film according to the second embodiment is suitably used for molding a first resin composition containing an epoxy resin. This is because the molding temperature of the first resin composition containing the epoxy resin is, for example, 175 ° C. or higher, but the unevenness of the base material layer 1 does not collapse even at a high temperature of 175 ° C. or higher.
As a thermosetting resin composition, the thing similar to 1st Embodiment mentioned above can be used.

(Third embodiment)
Hereinafter, the mold release film for molding according to the third embodiment will be described. The description will focus on differences from the first embodiment described above. Matters not described can be the same as in the first embodiment.

The mold release film in the third embodiment is a mold release film used for the molding of the first resin composition, and the mold release film has a release layer as the outermost layer. The release layer is composed of a third resin composition, the third resin composition contains a fluorine compound, the fluorine compound contains a fluorocarbon group, and the surface of the release layer There is provided a mold release film in which the contact angle of hexadecane is 20 ° or more and 77 ° or less.

The present inventors examined the heat resistance of a mold release film when molding a first resin composition containing an epoxy resin. As a result, it has been found that the conventional mold release film melts and may be joined to the first resin composition. This is presumably because the mold temperature of the first resin composition containing the epoxy resin is high, for example, 175 ° C. or higher, and the conventional mold release film cannot withstand the high temperature. It was.

The present inventors considered arranging a release layer formed of a specific fluorine compound in the outermost layer of the mold release film in order to prevent melting of the mold release film. Thereby, the heat resistance of the mold release film could be improved. The detailed mechanism is not clear, but the reason is presumed as follows. The specific fluorine compound includes a fluorocarbon group. A fluorocarbon group refers to a group in which some or all of the hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms. Such a fluorocarbon group has a bond of a carbon atom and a fluorine atom. The bond between carbon and fluorine atoms requires more thermal energy for the molecular motion of the bond, such as vibration and rotation, than the bond between carbon atoms, the bond between carbon and hydrogen atoms, and the bond between carbon and oxygen atoms. It is guessed. Therefore, it is considered that the movement of the molecular chain due to heat is limited and the heat resistance is improved.

Next, the present inventors examined the mold release properties of the mold release film when the first resin composition containing the epoxy resin was molded. As a result, it has been found that simply forming the release layer with a specific fluorine compound does not improve the releasability to the required level. Therefore, the present inventors examined the contact angle of the release layer with respect to a specific solvent, that is, the wettability of the release layer in order to improve the release property. As a result, it has been found that when the contact angle of hexadecane with respect to the release layer is within a specific numerical range, excellent release properties are exhibited. Although the detailed mechanism is not clear, the reason is presumed as follows.
First, the epoxy resin has a glycidyl group exhibiting polarity. When the contact angle of the release layer with respect to hexadecane is not more than a specific numerical range, it is possible to suppress the affinity with the glycidyl group from becoming too high. The epoxy resin has a nonpolar skeleton. When the contact angle of the release layer with respect to hexadecane is not less than a specific numerical range, it is possible to suppress the affinity for the nonpolar skeleton from becoming too high. Therefore, when the contact angle of the release layer with respect to hexadecane is within a specific numerical range, it is estimated that the affinity between the release layer and the epoxy resin can be prevented from becoming too high, and the release property can be improved. The
From the above, it is presumed that the mold release film according to the third embodiment is excellent in heat resistance and mold release and can improve the moldability.

Hereinafter, the configuration of the mold release film according to the third embodiment will be described in more detail.

<Release layer>
First, the release layer will be described.
The mold release film in the third embodiment has a release layer as at least the outermost layer. The release layer is a film composed of the third resin composition.

<Third resin composition>
The 3rd resin composition which forms a mold release layer is demonstrated.
The third resin composition contains at least a fluorine compound.
The fluorine compound only needs to contain a fluorocarbon group. Specifically as a fluorine compound, what is shown to following General formula (2) is preferable.

(In the above general formula (2),
X is a group containing a fluorocarbon group.
Y is a group having at least one polar functional group at the terminal, and the polar functional group is selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a hydroxy group, a silanol group, and an alkoxysilane group. Species or two or more. )

As a result of studying that the contact angle with respect to hexadecane is in a specific numerical range, the present inventor has found that it is effective for controlling the contact angle that the fluorine compound has a polar functional group at the terminal. The detailed mechanism is not clear, but the reason is presumed as follows.
The molecular chain of the fluorine compound has a low cohesive force between the molecular chains due to the influence of the interaction between fluorine atoms. However, when the fluorine compound has a polar functional group at the terminal, it is presumed that the polar functional groups are bonded to each other. Thereby, the fluorine compound which has a polar functional group at the terminal has high cohesive force of a molecular chain compared with the thing which does not have a polar functional group at the terminal. Therefore, it is considered that the density of fluorine atoms in the release layer can be improved, and the contact angle with respect to hexadecane can be made within a specific numerical range.
Moreover, the strength of the release layer is improved by improving the cohesion of the molecular chain of the fluorine compound. Thereby, it can prevent that uneven | corrugated shapes, such as a sink mark, arise in a mold release layer. When a mold release film having such a release layer is used for molding, there is no problem in that the uneven shape is not transferred. Accordingly, the mold release film of the third embodiment can improve moldability.

Y in the general formula (2) is a group having at least one polar functional group at the terminal.
Specific examples of the polar functional group include a carboxyl group, a sulfonic acid group, an amino group, a hydroxy group, a silanol group, and an alkoxysilane group. As a polar functional group, it can use 1 type or in combination of 2 or more types among the said specific examples.
Of the above specific examples, the polar functional group preferably includes a silanol group or an alkoxysilane group having 1 to 10 carbon atoms. Thereby, the molecular chains of a fluorine compound can couple | bond together suitably. Therefore, it can suppress that a polar group remains in a fluorine compound and mold release property with an epoxy resin falls.
As the fluorine compound containing a silanol group or an alkoxysilane group having 1 to 10 carbon atoms, for example, a compound represented by the following general formula (3) is preferable. In the following general formula (3), when A is a hydroxy group, the fluorine compound contains a silanol group. In the following general formula (3), when A is an alkoxy group, the fluorine compound contains an alkoxysilane group.

(In the general formula (3), X is the same as in the general formula (2).
A plurality of A's are groups formed by one or more atoms independently selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. . A may be the same as or different from each other. At least one of A is a hydroxy group or an alkoxy group having 1 to 10 carbon atoms. )

In the general formula (3), a plurality of A are each independently one or more selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. It is a group formed by the atoms.

In the general formula (3), at least one of the plurality of A is a hydroxy group or an alkoxy group having 1 to 10 carbon atoms, preferably a hydroxy group or an alkoxy group having 1 to 7 carbon atoms. Further, a hydroxy group or an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.

In the general formula (3), a plurality of A may be the same as or different from each other.
It is sufficient that at least one of A is a hydroxy group or an alkoxy group having 1 to 10 carbon atoms, and two or more of A are preferably a hydroxy group or an alkoxy group having 1 to 10 carbon atoms. It is more preferable that three of them are a hydroxy group or an alkoxy group having 1 to 10 carbon atoms. Thereby, when the primer layer or base material layer to be described later is present, the A containing the polar functional group and the primer layer or the base material layer form a bond, thereby releasing on the primer layer or the base material layer. A layer can be formed stably.
In the general formula (3), when two or more of A are a hydroxy group or an alkoxy group having 1 to 10 carbon atoms, A reacts between the molecular chains of the fluorine compound, and the molecular chain represents A. Thus, a release layer having a uniform and high density of fluorine atoms can be formed. Therefore, it can suppress that the defect of the molecular chain which forms a mold release layer arises, and can further improve mold release property.

In the general formula (3), as A other than the hydroxy group or the alkoxy group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Alkyl groups such as isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl; alkenyl such as allyl, pentenyl, vinyl Alkynyl group such as ethynyl group; alkylidene group such as methylidene group and ethylidene group; aryl group such as tolyl group, xylyl group, phenyl group, naphthyl group and anthracenyl group; aralkyl group such as benzyl group and phenethyl group; adamantyl group; Cycloal such as cyclopentyl, cyclohexyl and cyclooctyl Le group; tolyl group, and alkaryl groups, such as xylyl group.

In the above general formulas (2) and (3), X is a monovalent group containing a fluorocarbon group. In the third embodiment, the fluorocarbon group refers to a functional group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. A monovalent group indicates a valence. That is, X indicates that there is one hand that bonds with another atom.

X preferably includes, for example, a structural unit represented by the following formula (X1). Thereby, the fluorine atom density of a mold release layer can be improved.

(In the above formula (X1), n is an integer of 2 or more.)

X preferably includes, for example, an ether bond, that is, a carbon atom-oxygen atom-carbon atom bond. Thereby, it is estimated that the mobility of the part of X in the general formulas (2) and (3) is increased. Therefore, the flexibility of the release layer is improved, and even if deformation is applied by molding or the like, it is difficult for defects to occur in the release layer. From the above, the moldability can be improved.

Specific examples of the structure of X include tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-vinylidene fluoride. Mention may be made of structural units derived from tetrafluoroethylene such as copolymers and chlorotrifluoroethylene-ethylene copolymers. As the structure of X, among the above specific examples, one type or two or more types of structural units may be combined.

The carbon sequence of X can be, for example, linear, branched or cyclic. Among these, linear is preferable. Thereby, the density of the fluorine atom of a fluorine compound can be improved.

Specific examples of commercially available fluorine compounds represented by the above general formula (2) and containing the structural unit of (X1) include FG-5084SH or 6050 manufactured by Fluoro Technology Co., Ltd., Flease 85 manufactured by Neos Co., Ltd. CYTOP CTX-809A manufactured by AGC Seimi Chemical Co., RB-5910EX-III manufactured by Neos, and the like. As a fluorine compound, it is preferable to use 1 type or in combination of 2 or more types among the said specific examples. Thereby, mold release property can be improved.

The third resin composition may further contain other components as long as the release property of the release layer is not lowered.
Other components include, but are not limited to, antistatic agents such as N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, alkyl sulfonate, and inorganic fillers such as titanium oxide, calcium carbonate, talc, silicon dioxide Materials: Organic fillers such as organosilicone powder, polyethylene powder, and polyacryl powder; leveling agents such as fluorine-based nonionic surfactants.

<Manufacturing method of release layer>
In 3rd Embodiment, the method to manufacture a release layer is not limited, A conventionally well-known method can be used according to a 3rd resin composition. Specifically, it is preferable to use a method of applying and drying the third resin composition prepared on the varnish with a solvent. Examples of the coating method include a gravure roll coating method, a doctor blade coating method, a dip coating method, a spray coating method, a bar coater coating method, and a direct coating method using paper.
As a method for producing the release layer, for example, a third resin composition is directly applied to a base material layer to be described later, and the third resin composition is dried to form a release film for molding. It is preferable to obtain. Thereby, a release layer and a mold release film can be produced with high dimensional accuracy.
The conditions for drying the coated third resin composition are not limited as long as volatile components such as a solvent can be dried. Specifically, the drying temperature condition can be 25 ° C. or more and 150 ° C. or less.

From the viewpoint of suppressing the affinity between the release layer and the first resin composition from becoming too high and improving the release property of the release film for molding, the lower limit of the contact angle of hexadecane to the surface of the release layer The value is 20 ° or more at 25 ° C., preferably 30 ° or more, and preferably 50 ° or more.
From the same viewpoint, the upper limit of the contact angle of hexadecane with respect to the surface of the release layer is 75 ° or less and preferably 70 ° or less at 25 ° C.
The method for measuring the contact angle of hexadecane is not limited. For example, a commercially available contact angle meter such as DROPMASTER-501 manufactured by Kyowa Interface Science Co., Ltd. is used. The contact angle after 7 seconds can be measured by a liquid suitable method.

The upper limit value of the contact angle of water with respect to the surface of the release layer is preferably, for example, 118 ° or less, more preferably 113 ° or less, and further preferably 110 ° or less at 25 ° C. More preferably, it is 109 ° or less. Thereby, it can suppress that the affinity of the nonpolar group of a 1st resin composition and a release layer becomes high too much. Therefore, the releasability can be improved.
Further, the lower limit value of the contact angle of water with the surface of the release layer is preferably 100 ° or more, and more preferably 105 ° or more at 25 ° C. Thereby, when mold-molding the 1st resin composition containing an epoxy resin, it can suppress that affinity with polar groups, such as a glycidyl group of an epoxy resin, and a mold release layer becomes high too much. Therefore, the releasability can be improved.
The method for measuring the water contact angle is not limited. For example, a commercially available contact angle meter such as DROPMASTER-501 manufactured by Kyowa Interface Science Co., Ltd. is used. The contact angle 7 seconds after 2 μL of water is deposited can be measured by a liquid appropriate method.

The upper limit value of the thickness of the release layer is, for example, 80 μm or less, 55 μm or less, 40 μm or less, or 30 μm or less. Thereby, it can be set as the mold release film formed by the single mold release layer, and can follow favorable followability with respect to a metal mold | die.
The release layer may be thinned when it is applied to a substrate. When thinning, the upper limit of the thickness of the release layer is, for example, preferably 5 μm or less, more preferably 2 μm or less, further preferably 1 μm or less, and 0.5 μm or less. Is more preferably 0.1 μm or less. Thereby, as above-mentioned, the molecule | numerator of a fluorine compound can be arranged suitably, and the contact angle of hexadecane can be controlled within the said numerical range.
Moreover, the lower limit of the thickness of the release layer is not particularly limited. For example, it is 0.0001 μm or more, preferably 0.0005 μm or more, more preferably 0.001 μm or more, and further preferably 0.005 μm or more. Thereby, possibility that a defect will arise in a mold release layer is reduced and it can control that mold release nature to the 1st resin composition falls.

As a result of studying a method for setting the contact angle of hexadecane on the surface of the release layer to the above specific numerical range, the present inventors have found that it is effective to apply the above-described fluorine compound to 5 μm or less. . Although the detailed mechanism is not clear, it is presumed that the molecular chain of the fluorine compound can be suitably aligned by coating the fluorine compound so as to be 5 μm or less.

<Base material layer>
The mold release film according to the third embodiment may include a base material layer in addition to the release layer described above. That is, the mold release film may have a laminated structure in which a release layer and a base material layer are laminated. Thereby, appropriate rigidity can be provided to the mold release film. Therefore, it is possible to suppress the occurrence of deformation such as wrinkles in the mold release film.
Here, the base material layer is a film composed of the second resin composition.

<Second resin composition>
The second resin composition includes, for example, a thermoplastic resin.
Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyethylene isophthalate; polyamide resins such as nylon 6 and nylon 66; polyvinyl resins such as polyvinyl chloride; polypropylene, poly ( Polyolefin resins such as 4-methyl-1-pentene); polystyrene resins such as polystyrene resins having a syndiotactic structure; thermoplastic elastomers such as styrene elastomers, polyester elastomers, polyamide elastomers, polyolefin elastomers, urethane elastomers Etc. As a thermoplastic resin, it can use 1 type or in combination of 2 or more types among the said specific examples.
As the thermoplastic resin contained in the second resin composition, among the above specific examples, it is preferable to use a polyester resin. Among the above specific examples, the polyester resin is preferably polyethylene terephthalate or polybutylene terephthalate, and more preferably polyethylene terephthalate. Thereby, mold release property can be improved. Although the detailed mechanism is not clear about this reason, it estimates as follows. First, it is presumed that a slight carboxyl group residue exists on the surface of the base material layer. Thereby, it is thought that the polar functional group of the fluorine compound that forms the release layer and the residue of the carboxyl group on the surface of the base material layer form a bond. Therefore, the release layer can be uniformly formed on the surface of the base material layer, and the occurrence of defects in the release layer is suppressed. As described above, releasability can be improved.
Furthermore, when polyethylene terephthalate is used as the thermoplastic resin, excellent release properties can be realized. Polyethylene terephthalate has high heat resistance and excellent strength at high temperatures. Thereby, even if heat and a load are applied to the mold release film, it is possible to suppress deformation with a large strain rate. Thereby, it can suppress that a release layer tracks a base material layer and is destroyed. Therefore, excellent releasability can be realized.

The second resin composition may further contain other components as necessary.
Other components include, but are not limited to, antioxidants, slip agents, antiblocking agents, antistatic agents, coloring agents such as dyes and pigments; additives such as stabilizers, impact resistance such as fluororesins and silicone rubber Giving agents; inorganic fillers such as titanium oxide, calcium carbonate, talc and the like.

<Manufacturing method of base material layer>
In 3rd Embodiment, the method of manufacturing a base material layer is not limited, A conventionally well-known method can be used according to the kind of 2nd resin composition. The film containing the second resin composition as the base material layer may be an unstretched film or a film stretched in a uniaxial direction or a biaxial direction. Among these, it is preferable to use a film stretched in a uniaxial direction or a biaxial direction. Thereby, the molecular chain of the 2nd resin composition contained in a base material layer can be oriented. Thereby, intensity | strength and heat resistance can be improved and it can suppress that deformation | transformation, such as a wrinkle, arises in the mold release film.

The surface of the base material layer may be modified by surface treatment, for example. Specific examples of the surface treatment include corona treatment and plasma treatment. As the surface treatment, the corona treatment is preferable among the above specific examples. The surface of the base material layer can be modified by corona treatment. Specifically, as the surface modification, polar functional groups such as hydroxy groups and carboxyl groups can be formed on the surface of the substrate layer subjected to corona treatment. Therefore, when a release layer or a primer layer described later is formed on the surface of the base material layer, the release layer or the primer layer can be formed more uniformly. Therefore, it can suppress that the defect of the molecular chain which forms a mold release layer or a primer layer arises, and can suppress that a mold release property falls.
Moreover, the adhesive strength of the base material layer surface, a mold release layer, or a primer layer can be improved by performing the said surface treatment. Thereby, it can suppress that the laminated structure of the mold release film for mold formation separates during mold forming. Therefore, moldability can be improved. Further, since the adhesion strength is improved, for example, when the mold release film is transported, even if the mold release film is deformed, there is no problem in that it is possible to suppress the separation of the laminated structure. .
In addition, the surface shape of the base material layer may be a smooth mirror surface shape or an uneven shape as long as it does not affect the releasability.

In addition, as a result of the study by the present inventors, when the base layer is present, the contact angle with respect to hexadecane of the release layer and the contact angle with water within the specific numerical range described above are specified as follows. It has been found that it is preferable to subject the substrate layer to a corona treatment of conditions. Although the detailed mechanism is not clear, it is estimated that the terminal polar functional group of the above-mentioned fluorine compound forms a bond with the polar functional group on the surface of the base material layer. Thereby, the molecular chain of a fluorine compound arranges appropriately. Therefore, it is considered that the contact angle can be in a specific numerical range.
Here, as a condition of corona treatment when the contact angle is within the above-mentioned numerical range, for example, a batch corona treatment machine (for example, CORONA GENERATOR CT-0212 manufactured by Kasuga Electric Co., Ltd.) is used, and the output is It is preferably performed at 0.1 kW or more and 2.0 kW or less, a conveyance speed of 0.1 m / min or more and 40 m / min or less, and a discharge gap of 0.1 mm or more and 20 mm or less.

The lower limit value of the thickness of the base material layer according to the third embodiment is, for example, 10 μm or more, preferably 15 μm or more, and more preferably 20 μm or more. Thereby, it can prevent that the rigidity of the mold release film becomes too small. Accordingly, it is possible to prevent wrinkles from being generated on the mold release film at the time of molding and releasing, and transferring the shape of the wrinkles to the surface of the first resin composition to be molded.
Further, the upper limit value of the thickness of the base material layer is, for example, 150 μm or less, preferably 100 μm or less, more preferably 75 μm or less, and further preferably 50 μm or less. Thereby, it can prevent that the rigidity of the mold release film for molding becomes large too much. Accordingly, it is possible to improve the followability of the mold release film to the mold without forming wrinkles during molding and mold release.

The lower limit value of the melting point of the base material layer according to the third embodiment is, for example, preferably 160 ° C. or higher, more preferably 200 ° C. or higher, further preferably 220 ° C. or higher, and 225 ° C. or higher. More preferably, it is 230 degreeC or more. Thereby, even when a base material layer touches a metal mold | die, melting | fusing of the mold release film can be suppressed. Therefore, the heat resistance of the mold release film can be improved.
Moreover, the upper limit of melting | fusing point of a base material layer is not limited, For example, it can be 300 degrees C or less. Thereby, the base material layer can exhibit appropriate rigidity even at the time of molding. Therefore, deformation such as wrinkles can be suppressed in the mold release film, and moldability can be improved.

<Primer layer>
The laminated structure of the mold release film according to the third embodiment may further include a primer layer in addition to the release layer and the base material layer described above. Here, the laminated structure of the mold release film may have a primer layer between the release layer and the base material layer. Thereby, the adhesiveness of a mold release layer and a base material layer can be improved, and also the mold release property of the mold release film can be stably expressed.

<Fourth resin composition>
The primer layer is composed of a fourth resin composition.
Although a 4th resin composition is not limited, For example, it is preferable that a siloxane compound is included.
Among siloxane compounds, those that form silanol groups by hydrolysis are preferred. Furthermore, when the fluorine compound of the third resin composition contains a silanol group, it is more preferable that the silanol groups of the siloxane compound and the fluorine compound can undergo a dehydration condensation reaction. Thereby, a release layer can be formed more stably. Therefore, it can suppress that a mold release property falls because a defect arises in a mold release layer.

Specific examples of the siloxane compound included in the fourth resin composition include epoxy silane, amino silane, alkyl silane, ureido silane, mercapto silane, vinyl silane, styryl silane, methacryl silane, sulfide silane, and isocyanate silane.
Specific substance names of the siloxane compound include, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane N-6- (aminohexyl) -3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, γ-glycidoxypropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Examples include methoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and vinyltriethoxysilane. The resin composition may contain one of these alone or two or more.

<Manufacturing method of primer layer>
In 3rd Embodiment, the method of manufacturing the thin film containing the 4th resin composition which is a primer layer is not limited, A conventionally well-known method can be used according to a 4th resin composition. Specifically, it is preferable to use a method of applying and drying the fourth resin composition prepared on the varnish with a solvent. Examples of the coating method include a roll coating method, a doctor blade coating method, a dip coating method, a spray coating method, a bar coater coating method, and a direct coating method using paper.
For example, when producing a primer layer, it is preferable to apply a 4th resin composition directly with respect to the base material layer mentioned above, and to dry a 4th resin composition and to obtain a primer layer. Thereby, a primer layer can be produced with high dimensional accuracy.
The thickness of the primer layer is not limited. The lower limit of the thickness of the primer layer is, for example, 0.0005 μm or more, preferably 0.001 μm or more, more preferably 0.005 μm or more, and more preferably 0.01 μm or more. preferable. Thereby, the adhesiveness of a mold release layer and a base material layer can be improved. Therefore, the mold release film having a laminated structure in which the release layer, the primer layer, and the base material layer are laminated in this order can be stably formed.
Moreover, as an upper limit of the thickness of a primer layer, it is preferable that it is 3 micrometers or less, for example, it is preferable that it is 2 micrometers or less, and it is preferable that it is 1 micrometer or less. Thereby, it can suppress that the crack arises on the surface of the mold release film, and also the mold followability of the mold release film can be improved.

<Method for producing mold release film>
The release film for molding in the third embodiment can be prepared by using a conventionally known method according to the laminated structure.
A mold release film having a laminated structure in which a release layer, a primer layer, and a base material layer are laminated in this order is prepared, for example, by preparing the base material layer described above, and a primer layer and a mold release on the base material layer. It can be produced by coating and forming the layers in this order.

The laminated structure of the mold release film has at least an outermost release layer. The laminated structure may include one or more release layers, substrate layers, and primer layers, respectively.
Specifically, the laminated structure is a laminated structure in which a release layer and a base material layer are laminated in this order; a laminated structure in which a release layer, a primer layer, and a base material layer are laminated in this order; A laminated structure in which a mold layer, a base material layer, and a second release layer are laminated in this order; a first release layer, a first primer layer, a base material layer, a second primer layer, a second release layer Examples include a laminated structure in which mold layers are laminated in this order; a laminated structure in which a release layer, a first base material layer, a second base material layer, and a third base material layer are laminated in this order.
Of the above specific examples, the laminated structure is preferably a laminated structure in which a release layer, a primer layer, and a base material layer are laminated in this order. Thereby, mold release property and heat resistance can be improved.
In addition, when a several release layer exists, the same thing may be used for a release layer, and a different thing may be used. Moreover, when a several base material layer exists, the same base material layer may be used and a different thing may be used. In addition, when a plurality of primer layers are present, the same primer layer may be used, or different ones may be used.

The upper limit of the thickness of the mold release film is, for example, 255 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and further preferably 80 μm or less. Thereby, the mold release film can ensure followability to the shape of the mold.
Further, the lower limit of the thickness of the mold release film is, for example, 0.0001 μm or more, preferably 10 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more, More preferably, it is 30 μm or more. Thereby, the mold release film can exhibit mold release property suitably.

<Application>
The release film for molding according to the third embodiment is used for molding the first resin composition.
The molding method according to the third embodiment and the obtained electronic device can be the same as those in the first embodiment described above.

The molding method using the mold release film according to the third embodiment is not limited as long as it includes the placement step (S1) and the introduction step (S2).
Specific molding methods include a transfer molding method or a compression molding method (compression molding method). Among these, the release film for molding according to the third embodiment is suitably used in transfer molding. This is because the mold release film according to the third embodiment has a good balance between heat resistance and followability. Thereby, even if the first resin composition is introduced in transfer molding, the mold release film does not melt or shift and can exhibit good release properties.
The transfer mold molding method and the compression mold molding method can be the same as those in the first embodiment described above.

The mold release film according to the third embodiment can also be suitably used in mold forming at a temperature lower than 175 ° C. The molding temperature of the first resin composition is not limited, and the molding temperature can be set according to the raw material components contained in the first resin composition described later.
The lower limit of the molding temperature may be, for example, 120 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, 160 ° C. or higher, or 175 ° C. or higher. The mold release film for molding according to the third embodiment can exhibit suitable moldability even when it is molded at the lower limit value or more.
Moreover, the upper limit of the molding temperature may be, for example, 240 ° C. or lower, 200 ° C. or lower, and preferably 185 ° C. or lower. Thereby, the fall of the heat resistance of a mold release film and a moldability can be suppressed.

<First resin composition>
The first resin composition according to the third embodiment is not limited. For example, a thermoplastic resin composition or a thermosetting resin composition can be used. The mold release film according to the third embodiment is excellent in heat resistance. Thereby, it can be suitably used, for example, in the molding of a thermosetting resin composition performed at 175 ° C. or higher.
As a thermosetting resin composition, the thing similar to 1st Embodiment mentioned above can be used.

Hereinafter, examples of the reference form will be added.
1. A mold release film used for molding the first resin composition,
The release layer has a laminated structure laminated on the base material layer,
The release layer and the base material layer are directly bonded,
The outermost layer of the laminated structure has the release layer,
The mold release layer is a mold release film formed by crosslinking a copolymer represented by the following general formula (1) and a curing agent.

(In the general formula (B1),
R ¹ is a group containing a functional group that reacts with the curing agent. )
2. 1. A mold release film as described in
A mold release film for molding, in which a surface of the base material layer directly bonded to the release layer is smooth.
3. 1. Or 2. A mold release film as described in
In the general formula (1), A is a mold release film including a structural unit represented by the following formula (A1).

(In the above formula (A1), n is an integer of 1 or more.)
4). 1. To 3. A mold release film for molding according to any one of
The curing agent is a mold release film containing an isocyanate compound.
5). 1. To 4. A mold release film for molding according to any one of
The mold release film for molding, wherein the functional group of R ¹ that reacts with the curing agent includes one or more selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group.
6). 1. To 5. A mold release film for molding according to any one of
The first resin composition includes a thermosetting resin,
The thermosetting resin is a mold release film containing an epoxy resin.
7). 1. To 6. A mold release film for molding according to any one of
The base material layer is composed of a second resin composition,
The second resin composition is a mold release film containing a polyester resin.
8). 1. To 7. A mold release film for molding according to any one of
A mold forming method using the mold forming release film is a mold forming release film, which is a transfer mold forming method or a compression mold forming method.
9. 1. To 8. A mold forming method using the mold release film according to any one of the above,
The mold release film has a mold forming temperature of 120 ° C. or higher and 240 ° C. or lower.
10. 1. To 9. A mold forming method using the mold release film according to any one of the above,
An arrangement step of arranging the mold release film in a mold;
And a step of introducing a first resin composition into a molding space formed by the mold release film.
11. 10. The mold forming method according to claim 1,
The first resin composition is a thermosetting resin composition,
The said thermosetting resin composition is a molding method containing an epoxy resin.

Hereinafter, examples of the reference form will be added.
1. A mold release film is interposed between the first resin composition and the mold, and a mold release layer is brought into intimate contact with the first resin composition to perform molding, whereby the first resin composition is formed. A mold release film for molding used to give an embossed pattern to a molded product,
Having a laminated structure in which a release layer constituted by the third resin composition is laminated on the base material layer constituted by the second resin composition;
The third resin composition includes a silicone compound or a fluorine compound,
The base material layer has irregularities on the surface on which the release layer is laminated,
The mold release film has a thickness of 15 μm or less.
2. 1. A mold release film as described in
The mold release film is a mold release film having an embossed shape on the surface provided with the release layer.
3. 2. A mold release film as described in
A mold having a glossiness of 1 or more and 23 or less, which is a reflectance of light at an incident angle of 60 °, measured according to JIS Z 8741 with respect to the surface having the embossed shape of the mold release film. Mold release film.
4). 1. To 3. A mold release film for molding according to any one of
The third resin composition includes the fluorine compound and a curing agent,
The fluorine compound is a copolymer represented by the following general formula (1),
The mold release layer is a mold release film formed by crosslinking the fluorine compound and the curing agent.

(In general formula (1),
l and m respectively represent the molar content of A and B in the copolymer;
l + m = 1,
A contains a fluorocarbon group;
B is a structural unit represented by the following general formula (B1). )

(In the general formula (B1),
R ¹ is a group containing a functional group that reacts with the curing agent. )
5). 4). A mold release film as described in
In the copolymer represented by the general formula (1), A is a mold release film containing a structural unit represented by the following formula (A1).

(In the above formula (A1), n is an integer of 1 or more.)
6). 4). Or 5. A mold release film as described in
Functional group reactive with the curing agent wherein R ¹ comprises comprises one or a two or more, release film for molding is selected from the group consisting of hydroxyl group, carboxyl group, an amino group.
7). 4). To 6. A mold release film for molding according to any one of
The curing agent is a mold release film containing an isocyanate compound.
8). 1. To 7. A mold release film for molding according to any one of
A mold release film for molding which has an arithmetic average roughness Ra of 0.10 μm or more and 1.0 μm or less on the surface of the base material layer having the unevenness.
9. 1. To 8. A mold release film for molding according to any one of
A mold release film having a 10-point average surface roughness Rz of 1.0 μm or more and 10.0 μm or less on the surface of the base material layer having the unevenness.
10. 1. To 9. A mold release film for molding according to any one of
The first resin composition includes a thermosetting resin,
The release film for molding, wherein the thermosetting resin is an epoxy resin.
11. 1. To 10. A mold release film for molding according to any one of
The second resin composition is a mold release film containing a polyester resin.
12 1. To 11. A mold release film for molding according to any one of
The mold forming method is a mold release film which is a transfer mold forming method or a compression mold forming method.
13. 1. To 12. A mold release film for molding according to any one of
The mold release film has a mold forming temperature of 120 ° C. or higher and 240 ° C. or lower.
14 1. To 13. A mold forming method using the mold release film according to any one of the above,
An arrangement step of arranging the mold release film in a mold;
And a step of introducing a first resin composition into a molding space formed by the mold release film.

Hereinafter, examples of the reference form will be added.
1. A mold release film used for molding the first resin composition,
The mold release film has a release layer as the outermost layer,
The release layer is composed of a second resin composition,
The second resin composition contains a fluorine compound,
The fluorine compound includes a fluorocarbon group,
A release film for molding, wherein the contact angle of hexadecane with respect to the surface of the release layer is 20 ° or more and 77 ° or less.
2. 1. A mold release film as described in
The mold release film has a laminated structure in which the release layer and the base material layer are laminated,
The base material layer is composed of a third resin composition,
The mold release film for molding, wherein the third resin composition contains a thermoplastic resin.
3. 2. A mold release film as described in
A mold release film for molding, wherein the base material layer has a melting point of 160 ° C or higher and 300 ° C or lower.
4). 2. Or 3. A mold release film as described in
The said fluorine compound is a mold release film shown by following General formula (2).

(In the general formula (2), X is a group containing a fluorocarbon group.
Y is a group having at least one polar functional group at the terminal, and the polar functional group is selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a hydroxy group, a silanol group, and an alkoxysilane group. Species or two or more. )
5). 4). A mold release film as described in
The said fluorine compound is a mold release film shown by following General formula (3).

(In the general formula (3), X is the same as X in the general formula (2).
A plurality of A's are groups formed by one or more atoms independently selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. . A may be the same as or different from each other. At least one of A is a hydroxy group or an alkoxy group having 1 to 10 carbon atoms. )
6). 2. To 5. A mold release film according to any one of the above,
The laminated structure has a primer layer between the release layer and the base material layer,
The primer layer is composed of a fourth resin composition,
The fourth resin composition is a mold release film containing a siloxane compound.
7). 1. To 6. A mold release film for molding according to any one of
The first resin composition is a thermosetting resin composition,
The thermosetting resin composition is a mold release film containing an epoxy resin.
8). 1. To 7. A mold release film for molding according to any one of
The mold molding is a mold release film for molding which is a transfer mold molding method or a compression mold molding method.
9. 1. To 8. A mold release film for molding according to any one of
A mold release film having a water contact angle of 100 ° or more and 118 ° or less with respect to the surface of the release layer.
10. 1. To 9. A mold release film for molding according to any one of
A mold release film for molding, wherein the release layer has a thickness of 0.0001 μm or more and 5 μm or less.
11. 1. To 10. A mold forming method using the mold release film according to any one of the above,
An arrangement step of arranging the mold release film in a mold;
And a step of introducing a first resin composition into a molding space formed by the mold release film.
12 11. The mold forming method according to claim 1,
The first resin composition is a thermosetting resin composition,
The thermosetting resin composition is a molding method including an epoxy resin.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above can also be employ | adopted.

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

[Example A]
First, details of the release films for molding of Examples A-1 to A-4 and Comparative Examples A-1 to A-2 will be described in detail.

Example A-1
First, the base material layer 1 was prepared. As the base material layer 1, a stretched polyethylene terephthalate film (E5100, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm was prepared. The base material layer 1 was a film having smooth surfaces.
Subsequently, the base material layer 1 was subjected to a surface modification treatment. As the surface modification treatment, corona discharge treatment was performed. Specifically, the corona discharge treatment was performed using a batch corona treatment machine (CORONA GENERATOR CT-0212 manufactured by Kasuga Electric Co., Ltd.) with an output of 2 kW, a conveyance speed of 40 m / min, and a discharge gap of 20 mm.
The base material layer subjected to the corona discharge treatment was allowed to stand so as not to touch air. After 168 hours of standing, the third resin composition prepared in varnish was applied to the surface of the surface-modified base material layer 1. Here, as a 3rd resin composition, 13 weight part of main ingredients and 1 weight part of hardening | curing agents of Obligato PS306R made from AGC Cortec were dissolved in 28 weight part of methyl ethyl ketone, and used. Here, the main component of Obligato PS306R manufactured by AGC Co., Ltd. is represented by the general formula (1) described in the section of this embodiment, A includes the structural unit of the above formula (A2), and B includes the above general formula. A copolymer containing the structural unit (B1) is included. Moreover, the curing agent of Obligato PS306R manufactured by AGC Co., Ltd. contains a bifunctional isocyanate compound. The third resin composition was applied using a gravure roll coating method. After the coating, the mold of Example A-1 is obtained by sufficiently crosslinking the third resin composition at a temperature of 120 ° C. for 20 minutes to form the release layer 2 on the base material layer 1. A mold release film 10 was obtained. The dry thickness of the release layer 2 was 0.8 μm.
In addition, the mold release film of Example A-1 was prepared by applying an adhesive tape (Caraliyan PP cut E, manufactured by Denki Kagaku Kogyo Co., Ltd.) to the surface of the release layer 2, and then peeling the adhesive tape. The release layer 2 could not be peeled from the base material layer 1.

Example A-2
As the third resin composition, the method described in Example A-1 was used except that 13 parts by weight of the main ingredient of obligato manufactured by AGC Co-Tech and 1 part by weight of the curing agent were dissolved in 42 parts by weight of methyl ethyl ketone. Then, a mold release film of Example A-2 was produced.
The dry thickness of the release layer 2 was 0.4 μm.
In addition, the mold release film of Example A-2 was obtained by applying an adhesive tape (Carariyan PP cut E, manufactured by Denki Kagaku Kogyo Co., Ltd.) to the surface of the release layer 2, and then peeling the adhesive tape. The release layer 2 could not be peeled from the base material layer 1.

Example A-3
Except that a stretched polyethylene terephthalate film (E5100, manufactured by Toyobo Co., Ltd.) having a thickness of 38 μm was prepared as the base material layer, the mold release film of Example A-3 was prepared by the method described in Example A-1. Produced. Here, the base material layer 1 was a film having smooth surfaces.
In addition, the mold release film of Example A-3 was obtained by applying an adhesive tape (Carariyan PP cut E, manufactured by Denki Kagaku Kogyo Co., Ltd.) to the surface of the release layer 2, and then peeling the adhesive tape. The release layer 2 could not be peeled from the base material layer 1.

Example A-4
As a base material layer, a stretched polyethylene terephthalate film (E5100, manufactured by Toyobo Co., Ltd.) having a thickness of 38 μm is prepared. A release film for molding of Example A-4 was prepared by the method described in Example A-1, except that a part was dissolved in 42 parts by weight of methyl ethyl ketone. Here, the base material layer 1 was a film having smooth surfaces.
The dry thickness of the release layer 2 was 0.4 μm.
In addition, the mold release film of Example A-4 was obtained by applying an adhesive tape (Carariyan PP cut E, manufactured by Denki Kagaku Kogyo Co., Ltd.) to the surface of the release layer 2, and then peeling the adhesive tape. The release layer 2 could not be peeled from the base material layer 1.

(Comparative Example A-1)
A mold release film for molding of Comparative Example A-1 was prepared by the method described in Example A-1, except that the surface modification treatment was not performed on the base material layer 1.
In addition, the mold release film of Comparative Example A-1 was obtained by applying an adhesive tape (Carariyan PP cut E, manufactured by Denki Kagaku Kogyo Co., Ltd.) to the surface of the release layer 2, and then peeling the adhesive tape. It was confirmed that the release layer 2 was peeled from the base material layer 1 and the release layer 2 could be transferred to the adhesive tape, and the release layer 2 and the base material layer 1 were not directly bonded. .

(Comparative Example A-2)
For the mold release film produced in Comparative Example A-1, the base material layer 1 was obtained by applying and peeling an adhesive tape (Carariyan PP cut E, manufactured by Denki Kagaku Kogyo Co., Ltd.) on the surface of the release layer 2. The release layer 2 was peeled off, and the release layer 2 was transferred to the adhesive tape. Next, an acrylic adhesive (Primal N580, manufactured by Rohm and Haas Co., Ltd.) is applied to the base material layer 1 at a coating amount of 50 g / m ² , and the release layer 2 transferred to the adhesive tape is adhered and dried. Thus, a release film for molding of Comparative Example A-2 was produced, in which the base material layer 1, the dried acrylic adhesive, and the release layer 2 were laminated in this order. The thickness of the dried acrylic adhesive layer was 0.1 mm.

About each mold-molding release film of each Example and each comparative example, the tablet of the thermosetting resin composition used for evaluation of a moldability and mold release property was produced. Details of the manufacturing method will be described.
The following were used as the raw material of the thermosetting resin composition used for evaluation of moldability and mold release.
・ Epoxy resin 1: Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000)
-Epoxy resin 2: biphenyl type epoxy resin (Mitsubishi Chemical Corporation, YL6677)
Curing agent 1: Biphenylene skeleton-containing phenol aralkyl resin (Nippon Kayaku Co., Ltd., GPH-65)
Curing agent 2: triphenylmethane type phenol resin modified with formaldehyde (Air Water, HE910-20)
Curing accelerator: Triphenylphosphine (Hokuko Chemical Industries, TPP)
・ Inorganic filler: fused spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., FB-950FC)
Colorant: Carbon black (Mitsubishi Chemical Corporation MA-600)
Coupling agent: N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical, KBM-573)
・ Release agent: Carnauba wax (Nikko Fine, Nikko Carnauba)

First, 4.5 parts by weight of the epoxy resin 1, 4.5 parts by weight of the epoxy resin 2, 2.8 parts by weight of the curing agent 1, 2.8 parts by weight of the curing agent 2, and 0% of the curing accelerator described above. 4 parts by weight, 84.2 parts by weight of an inorganic filler, 0.2 parts by weight of a colorant, 0.4 parts by weight of a coupling agent, and 0.2 parts by weight of a release agent were prepared. Next, each raw material component was mixed at room temperature using a mixer, and then roll kneaded while heating with two rolls at 45 ° C. and 90 ° C. to obtain a kneaded product. Next, the kneaded product was cooled and then pulverized to obtain a pulverized product. Next, the pulverized product was tableted to obtain a tablet-shaped thermosetting resin composition.

<Molding>
After setting the mold release film on the transfer mold machine (TOWA, Y-SERIES), the mold release machine's internal space is vacuumed to follow the mold release film. I let you. Next, the tablet of the thermosetting resin composition was disposed at a predetermined position. Thereafter, the mold provided in the molding machine is clamped at a clamping pressure of 300 kg / cm ² , and then the molten thermosetting resin composition is provided in the molding machine at an injection pressure of 80 kg / cm ^2. Poured into the interior space of the mold and molded at 175 ° C. for 2 minutes. After molding, the mold was opened, and the cured product of the thermosetting resin composition was taken out from the mold.

(Formability)
After the molding, the appearance of the mold release film 10 and the appearance of the cured product of the obtained thermosetting resin composition were visually observed, and the moldability was evaluated according to the following criteria. The evaluation results are shown in Table 1 below.
(Double-circle): About the mold release film for shaping | molding after shaping | molding, peeling of the base material layer 1 and the mold release layer 2 was not observed. Moreover, when the surface of the hardened | cured material of the thermosetting resin composition was observed visually, it was finished in the mirror surface and there was no damage | wound by the trace originating from peeling of the mold release film for transcription | transfer.
◯: No peeling of the base material layer 1 and the release layer 2 was observed for the mold release film after molding. Moreover, when the surface of the hardened | cured material of the thermosetting resin composition was observed visually, although there was a fine trace derived from the wrinkle of the mold release film, it was a grade which is satisfactory as a mirror surface. Moreover, there was no peeling of the mold release film, and there were no scratches transferred with traces derived from the peeling.
X: When the surface of the hardened | cured material of the thermosetting resin composition was observed visually, peeling of the base material layer 1 and the mold release layer 2 was observed. Moreover, when the surface of the hardened | cured material of the thermosetting resin composition was observed visually, the trace derived from peeling of the mold release film was transferred, and the desired mirror surface was not obtained.

(Releasability)
In the above mold molding, the mold releasability between the mold forming release film and the thermosetting resin composition when the mold was opened was evaluated according to the following criteria. The evaluation results are shown in Table 1 below.
○: When the mold was opened, the mold release film and the cured product of the thermosetting resin composition were released naturally.
X: When the mold was opened, the mold release film and the cured product of the thermosetting resin composition were not released.

The evaluation results for the above evaluation items are shown in Table 1 below.

As shown in Table 1, the mold release films 10 of Examples A-1 to A-4 have excellent moldability without causing the base material layer 1 and the release layer 2 to peel off by molding. It showed releasability.
On the other hand, in the mold release films 10 of Comparative Examples A-1 and A-2, the base material layer 1 and the release layer 2 were peeled off by molding, and the moldability and mold release properties were as described in Example A- It was confirmed that the film was inferior to the mold release film of 1 to A-4.

[Example B]
Details of the mold release films of Examples B-1 to B-4 and Comparative Examples B-1 to B-2 will be described in detail.

Example B-1
First, the base material layer 1 was prepared. As the base material layer 1, a biaxially stretched polyethylene terephthalate film (made by Kaisei Kogyo Co., Ltd., type A) having a thickness of 50 μm was prepared. Here, the base material layer 1 is obtained by subjecting one surface of a polyethylene terephthalate film to sandblasting. That is, one surface of the base material layer 1 is provided with unevenness, and the other surface is smooth.
Next, a surface modification treatment was performed on the surface of the base material layer 1 having the unevenness. As the surface modification treatment, corona discharge treatment was performed. Specifically, the corona discharge treatment was performed using a batch corona treatment machine (CORONA GENERATOR CT-0212 manufactured by Kasuga Electric Co., Ltd.) with an output of 2 kW, a conveyance speed of 40 m / min, and a discharge gap of 20 mm.
Here, when the arithmetic average roughness Ra of the unevenness of the base material layer 1 was measured in accordance with JIS B 0601-2013, it was 0.62 μm. Further, the 10-point average surface roughness Rz was measured according to JIS B 0601-1994 and found to be 4.97 μm.
The base layer subjected to the corona discharge treatment was allowed to stand so as not to come into contact with air. 168 hours after standing still, the 3rd resin composition prepared to the varnish was applied to the one surface provided with the unevenness | corrugation of the base material layer 1. FIG. Here, as a 3rd resin composition, 13 weight part of main ingredients and 1 weight part of hardening | curing agents of Obligato PS306R made from AGC Cortec were dissolved in 42 weight part of methyl ethyl ketone, and were used. Here, the main component of Obligato PS306R manufactured by AGC Co., Ltd. is represented by the general formula (1) described in the section of this embodiment, A includes the structural unit of the above formula (A2), and B includes the above general formula. A copolymer containing the structural unit (B1) is included. Moreover, the curing agent of Obligato PS306R manufactured by AGC Co., Ltd. contains a bifunctional isocyanate compound. Here, the coating of the third resin composition was performed using a gravure roll coating method. After coating, the coating is dried at a temperature of 100 ° C. for 1 minute, and then subjected to a heat treatment at a temperature of 120 ° C. for 20 minutes to cause the third resin composition to undergo a crosslinking reaction, thereby sufficiently crosslinking the third resin composition. By forming the release layer 2 on the material layer 1, the release film 10 for molding of Example B-1 was obtained. Here, it was visually confirmed that the mold release film 10 has an embossed shape on the surface on which the release layer is formed.
The dry thickness of the release layer 2 was 0.4 μm. Moreover, about the surface provided with the embossed shape of the mold release film 10, the glossiness was 11.0. The glossiness was measured in accordance with JIS Z 8741 with an incident angle of light of 60 °.

Example B-2
Except that a biaxially stretched polyethylene terephthalate film (Kaisei Kogyo Co., Ltd., type AZ) having a thickness of 50 μm was prepared as the base material layer 1, the mold release of Example B-2 was carried out by the method described in Example B-1. A mold film 10 was produced. Here, it was visually confirmed that the mold release film 10 has an embossed shape on the surface on which the release layer is formed.
In addition, the base material layer 1 gives the sand blast process to the single side | surface of a polyethylene terephthalate film. That is, one surface of the base material layer 1 is provided with unevenness, and the other surface is smooth.
The arithmetic mean roughness Ra of the unevenness of the base material layer 1 was measured according to JIS B 0601-2013, and was 0.67 μm. Further, the 10-point average surface roughness Rz was measured according to JIS B 0601-1994, and it was 5.24 μm.
The dry thickness of the release layer 2 was 0.4 μm. Furthermore, the glossiness of the surface having the embossed shape of the mold release film 10 was 10.0. The glossiness was measured in accordance with JIS Z 8741 with an incident angle of light of 60 °.

Example B-3
Except that a biaxially stretched polyethylene terephthalate film (Kaisei Kogyo Co., Ltd., Type D) having a thickness of 50 μm was prepared as the base material layer 1, the mold release of Example B-3 was performed by the method described in Example B-1. A mold film 10 was produced. Here, it was visually confirmed that the mold release film 10 has an embossed shape on the surface on which the release layer is formed.
In addition, the base material layer 1 gives the sand blast process to the single side | surface of a polyethylene terephthalate film. That is, one surface of the base material layer 1 is provided with unevenness, and the other surface is smooth.
The arithmetic mean roughness Ra of the unevenness of the base material layer 1 was measured according to JIS B 0601-2013, and was 0.43 μm. Further, the 10-point average surface roughness Rz was measured according to JIS B 0601-1994 and found to be 4.10 μm.
The dry thickness of the release layer 2 was 0.4 μm. Moreover, about the surface provided with the embossed shape of the mold release film 10, the glossiness was 14.4. The glossiness was measured in accordance with JIS Z 8741 with an incident angle of light of 60 °.

Example B-4
A biaxially stretched polyethylene terephthalate film (made by Kaisei Kogyo Co., Ltd., type AZ) having a thickness of 50 μm is prepared as the base material layer 1, and the third resin composition is 13 wt. Part B and 1 part by weight of a curing agent were dissolved in 28 parts by weight of methyl ethyl ketone, and the coating of the third resin composition was carried out in Example B-1, except that the coating was performed using a bar coater coating method. The mold release film 10 of Example B-4 was produced by the method described. Here, it was visually confirmed that the mold release film 10 has an embossed shape on the surface on which the release layer is formed.
In addition, the base material layer 1 gives the sand blast process to the single side | surface of a polyethylene terephthalate film. That is, one surface of the base material layer 1 is provided with unevenness, and the other surface is smooth.
The arithmetic mean roughness Ra of the unevenness of the base material layer 1 was measured according to JIS B 0601-2013, and was 0.67 μm. Further, the 10-point average surface roughness Rz was measured according to JIS B 0601-1994, and it was 5.24 μm.
The release layer 2 had a dry thickness of 0.8 μm. Moreover, the glossiness of the surface having the embossed shape of the mold release film 10 was 12.7. The glossiness was measured in accordance with JIS Z 8741 with an incident angle of light of 60 °.

(Comparative Example B-1)
As the third resin composition, except that 13 parts by weight of the main ingredient of Obligato PS306R manufactured by AGC Co-Tech and 1 part by weight of the curing agent were dissolved in 42 parts by weight of methyl ethyl ketone and used as described in Example B-1. By the method, a mold release film 10 of Comparative Example B-1 was produced.
The release layer 2 had a dry thickness of 16 μm.

(Comparative Example B-2)
As the base material layer 1, a biaxially stretched polyethylene terephthalate film (made by Kaisei Kogyo Co., Ltd., type A) having a thickness of 50 μm was prepared. Here, the base material layer 1 is obtained by subjecting one surface of a polyethylene terephthalate film to sandblasting. That is, one surface of the base material layer 1 is provided with unevenness, and the other surface is smooth.
Here, when the arithmetic average roughness Ra of the unevenness of the base material layer 1 was measured in accordance with JIS B 0601-2013, it was 0.62 μm. Further, the 10-point average surface roughness Rz was measured according to JIS B 0601-1994 and found to be 4.97 μm.
This base material layer 1 was used as it was as the mold release film 10 of Comparative Example B-2. In the evaluation described later, the molding was performed such that the surface of the base material layer 1 having the unevenness was in close contact with the first resin composition.
Note that when the mold was formed with the mold release film of Comparative Example B-2, the mold could not be released, so the printability test was not performed.

For the mold release films of Examples B-1 to B-4 and Comparative Examples B-1 to B-2, tablets of thermosetting resin compositions used for evaluation of print readability and mold release were prepared. . Details of the manufacturing method will be described.
The following were used as the raw material of the thermosetting resin composition used for evaluation of moldability and mold release.
・ Epoxy resin 1: Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000)
-Epoxy resin 2: biphenyl type epoxy resin (Mitsubishi Chemical Corporation, YL6677)
Curing agent 1: Biphenylene skeleton-containing phenol aralkyl resin (Nippon Kayaku Co., Ltd., GPH-65)
Curing agent 2: triphenylmethane type phenol resin modified with formaldehyde (Air Water, HE910-20)
Curing accelerator: Triphenylphosphine (Hokuko Chemical Industries, TPP)
・ Inorganic filler: fused spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., FB-950FC)
Colorant: Carbon black (Mitsubishi Chemical Corporation MA-600)
Coupling agent: N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical, KBM-573)
・ Release agent: Carnauba wax (Nikko Fine, Nikko Carnauba)

<Molding>
After setting the mold release film on the transfer mold machine (TOWA, Y-SERIES), the mold release machine's internal space is vacuumed to follow the mold release film. I let you. Next, the tablet of the thermosetting resin composition was disposed at a predetermined position. Thereafter, the mold provided in the molding machine is clamped at a clamping pressure of 300 kg / cm ² , and then the molten thermosetting resin composition is provided in the molding machine at an injection pressure of 80 kg / cm ^2. Poured into the interior space of the mold and molded at 175 ° C. for 2 minutes. The molding was performed so that the embossed shape of the release film for molding and the thermosetting resin composition were in close contact with each other. After molding, the mold was opened, and the cured product of the thermosetting resin composition was taken out from the mold.

(Readability of printing)
First, a random 10-character string consisting of 2 mm long and 2 mm wide alphabets and Arabic numerals was printed on the surface onto which the embossed pattern of the cured product of the thermosetting resin composition was transferred. . The cured product of the thermosetting resin composition was black and the printing was white. Next, an area where the character string of 46 mm × 46 mm was printed was photographed with a fixed camera from a distance of 1.0 m to obtain image data. The obtained image data was binarized and a test for reading the character string was performed. This test was performed on 100 cured products of the thermosetting resin composition and evaluated according to the following criteria. The evaluation results are shown in Table 2 below. In Comparative Example B-2, evaluation was not performed because the cured product of the thermosetting resin composition and the mold release film could not be peeled off.
A: All character strings printed on the cured product of the thermosetting resin composition could be recognized. Further, the characters constituting the character string could be suitably identified.
○: Regarding the character string printed on the cured product of the thermosetting resin composition, a part of the symbol forming the character string was sometimes recognized missing due to the gloss, but there was a problem in identifying the symbol. There wasn't.
X: Regarding the cured product of the thermosetting resin composition, there was one or more that could not recognize a character string due to gloss.

(Releasability)
In the above mold molding, the mold releasability between the mold forming release film and the thermosetting resin composition when the mold was opened was evaluated according to the following criteria. The evaluation results are shown in Table 2 below.
○: When the mold was opened, the mold release film and the cured product of the thermosetting resin composition were released naturally.
X: When the mold was opened, the mold release film and the cured product of the thermosetting resin composition were not released.

The evaluation results for the above evaluation items are shown in Table 2 below.

As shown in Table 2, the molded articles using the mold release films 10 of Examples B-1 to B-4 used the mold release films of Comparative Examples B-1 to B-2. Compared with the case, it was excellent in the readability of printing of a molded product.
Further, as shown in Table 2, the mold release films 10 of Examples B-1 to B-4 were superior to the mold release films of Comparative Examples B-1 to B-2. It showed releasability.

[Example C]
Details of the mold release films of Examples C-1 to C-8 and Comparative Examples C-1 to C-5 will be described in detail.

Example C-1
First, a biaxially stretched polyethylene terephthalate film (hereinafter referred to as O-PET film) (Toyobo Co., Ltd., ester film, model number E5100) having a thickness of 38 μm was prepared as a base material layer. The surface of the O-PET film was subjected to corona treatment with an output of 0.26 kW, a conveyance speed of 12 m / min, and a discharge gap of 4 mm.
Next, a primer layer was formed on the surface of the base material layer. Specifically, silane coupling agent 1 (Fluoro Technology Co., Ltd., PC-3B), which is a siloxane compound, was applied to one surface of the base material layer with a bar coater so as to have a coating thickness of 4 μm. Next, the silane coupling agent was dried at 120 ° C. for 10 minutes to form a primer layer. The thickness of the primer layer after drying was 0.03 μm.
Next, a release layer was formed on the surface of the primer layer. Specifically, fluorine compound 1 (manufactured by Fluoro Technology, FG-5084SH) was applied to the primer layer surface with a bar coater so as to have a coating thickness of 4 μm. Next, the fluorine compound 1 was dried at 25 ° C. for 90 minutes. After drying, fluorine compound 1 (manufactured by Fluoro Technology, FG-5084SH) was applied again with a bar coater to a coating thickness of 4 μm. Next, the fluorine compound 1 was dried at 25 ° C. for 90 minutes to form a release layer. The thickness of the release layer was 0.008 μm.
From the above steps, a mold release film was prepared by laminating a base material layer, a primer layer, and a release layer in this order.
In addition, the fluorine compound 1 includes the structural unit represented by (X1) described above. Moreover, the fluorine compound 1 contains an alkoxysilane group at the end of the molecular chain. In the alkoxysilane group, a silicon atom and an alkoxy group having 1 to 10 carbon atoms are bonded to each other. That is, the fluorine compound 1 includes the structural unit represented by the above-described (X1) in the general formula (2) described above, and three of A are alkoxy groups having 1 to 10 carbon atoms.

Example C-2
A mold release film for molding was produced in the same manner as in Example C-1, except that the method for forming the release layer was changed as follows.
Fluorine compound 1 (FG-5084SH, manufactured by Fluoro Technology Co., Ltd.) was applied to the primer layer surface with paper so as to have a coating thickness of 2 μm. Next, the fluorine compound 1 was dried at 25 ° C. for 90 minutes to form a release layer. After drying, the thickness of the release layer was 0.002 μm.
From the above steps, a mold release film was prepared by laminating a base material layer, a primer layer, and a release layer in this order.

Example C-3
A mold release film for molding was produced in the same manner as in Example C-1, except that the method for forming the release layer was changed as follows.
Fluorine compound 1 (FG-5084SH, manufactured by Fluoro Technology Co., Ltd.) was applied to the primer layer surface with paper so as to have a coating thickness of 2 μm. Next, the fluorine compound 1 was dried at 25 ° C. for 90 minutes. After drying, Fluorine Compound 1 (manufactured by Fluoro Technology, FG-5084SH) was applied again with paper to a coating thickness of 2 μm. Subsequently, it dried on 25 degreeC and the conditions for 90 minutes, and shape | molded the mold release layer. After drying, the thickness of the release layer was 0.004 μm.
From the above steps, a mold release film was prepared by laminating a base material layer, a primer layer, and a release layer in this order.

Example C-4
A mold release film for molding was produced in the same manner as in Example C-1, except that the molding method of the mold release layer was changed to 120 ° C. and 10 minutes for the drying condition of the fluorine compound 1. After drying, the thickness of the release layer was 0.008 μm.

(Example C-5)
First, a biaxially stretched polyethylene terephthalate film (hereinafter referred to as O-PET film) (Toyobo Co., Ltd., ester film, model number E5100) having a thickness of 38 μm was prepared as a base material layer. The surface of the O-PET film was subjected to corona treatment with an output of 0.26 kW, a conveyance speed of 12 m / min, and a discharge gap of 4 mm.
Next, a release layer was formed on the surface of the base material layer. Specifically, the fluorine compound 2 (manufactured by Neos, Fleet 85) was molded on one side of the base material layer with a bar coater so as to have a coating thickness of 12 μm. Next, the fluorine compound 2 was dried at 25 ° C. for 24 hours to form a release layer. After drying, the thickness of the release layer was 0.12 μm.
From the above steps, a mold release film was prepared by laminating the base material layer and the release layer in this order.
In addition, the fluorine compound 2 includes the structural unit represented by (X1) described above. Moreover, the fluorine compound 2 contains a carboxyl group at the end of the molecular chain. That is, the fluorine compound 2 is a compound in which, in the general formula (1) described above, X includes the structural unit represented by (X1) described above, and Y includes a carboxyl group at the terminal.

(Example C-6)
First, a biaxially stretched polyethylene terephthalate film (hereinafter referred to as O-PET film) (Toyobo Co., Ltd., ester film, model number E5100) having a thickness of 38 μm was prepared as a base material layer. The surface of the O-PET film was subjected to corona treatment with an output of 0.26 kW, a conveyance speed of 12 m / min, and a discharge gap of 4 mm.
Next, a release layer was formed on the surface of the base material layer. Specifically, fluorine compound 3 (manufactured by AGC Seimi Chemical Co., Cytop CTX-809A) was applied to one surface of the base material layer with a bar coater so as to have a coating thickness of 12 μm. Next, the fluorine compound 3 was dried at 25 ° C. for 20 minutes. After drying, fluorine compound 3 (AGC Seimi Chemical Co., Cytop CTX-809A) was applied again with a bar coater to a coating thickness of 12 μm. Next, the fluorine compound 3 was dried at 25 ° C. for 20 minutes to form a release layer. The thickness of the release layer was 1.2 μm.
From the above steps, a mold release film was prepared by laminating the base material layer and the release layer in this order.
In addition, the fluorine compound 3 includes the structural unit represented by (X1) described above. Moreover, the fluorine compound 3 contains a carboxyl group at the end of the molecular chain. That is, the fluorine compound 3 is a compound in which, in the general formula (1) described above, X includes the structural unit represented by (X1) described above, and Y includes a carboxyl group at the terminal.

(Example C-7)
First, a biaxially stretched polyethylene terephthalate film (hereinafter referred to as O-PET film) (Toyobo Co., Ltd., ester film, model number E5100) having a thickness of 38 μm was prepared as a base material layer. The surface of the O-PET film was subjected to corona treatment with an output of 0.26 kW, a conveyance speed of 12 m / min, and a discharge gap of 4 mm.
Next, a release layer was formed on the surface of the base material layer. Specifically, fluorine compound 4 (manufactured by Fluoro Technology, 6050) was formed on one side of the base material layer with a bar coater so as to have a coating thickness of 12 μm. Next, the fluorine compound 4 was dried at 80 ° C. for 10 minutes. After drying, the fluorine compound 4 (Fluoro Technology, 6050) was once again molded with a bar coater so as to have a coating thickness of 12 μm. Next, the fluorine compound 4 was dried at 80 ° C. for 10 minutes to form a release layer. The thickness of the release layer was 0.24 μm.
From the above steps, a mold release film was prepared by laminating the base material layer and the release layer in this order.
In addition, the fluorine compound 4 includes the structural unit represented by (X1) described above. Moreover, the fluorine compound 4 contains a sulfonic acid group at the end of the molecular chain. That is, the fluorine compound 4 is a compound in which, in the general formula (1) described above, X includes the structural unit represented by (X1) described above, and Y includes a sulfonic acid group at the terminal.

(Example C-8)
First, as a base material layer, a biaxially stretched polyethylene terephthalate film (hereinafter referred to as O-PET film) (hereinafter referred to as O-PET film) having a thickness of 38 μm subjected to corona discharge treatment on both surfaces was prepared. . The surface of the O-PET film was subjected to corona treatment with an output of 0.26 kW, a conveyance speed of 12 m / min, and a discharge gap of 4 mm.
Next, a release layer was formed on the surface of the base material layer. Specifically, fluorine compound 5 (manufactured by Neos, RB-5910EX-III) was molded on one surface of the release layer with a bar coater so as to have a coating thickness of 12 μm. Next, the fluorine compound 5 was dried at 100 ° C. for 60 minutes to form a release layer. The thickness of the release layer was 0.1 μm.
From the above steps, a mold release film was prepared by laminating the base material layer and the release layer in this order.
In addition, the fluorine compound 5 includes the structural unit represented by (X1) described above. Moreover, the fluorine compound 5 contains an alkoxysilane group at the end of the molecular chain. In the alkoxysilane group, a silicon atom and an alkoxy group having 1 to 10 carbon atoms are bonded to each other. That is, the fluorine compound 5 includes the above-described general formula (2), wherein X includes the structural unit represented by the above-described (X1), and three of A are alkoxy groups having 1 to 10 carbon atoms. is there.

(Comparative Example C-1)
A biaxially stretched polyethylene terephthalate film (hereinafter referred to as O-PET film) (Toyobo Co., Ltd., ester film, model number E5100) having a thickness of 38 μm was prepared as a base material layer.
From the above steps, a mold release film comprising a base material layer was prepared.

(Comparative Example C-2)
Using a polymethylpentene resin (TPX (registered trademark)) (manufactured by Mitsui Chemicals, TPX DX845) as a base material layer, a 50 μm-thick TPX film was produced by an extrusion T-die method.
From the above steps, a mold release film comprising a base material layer was prepared.

(Comparative Example C-3)
A PVDF film having a thickness of 38 μm was prepared by an extrusion T-die method using a vinylidene fluoride homopolymer (Solvay (registered trademark) 9009) as a release layer.
From the above steps, a mold release film comprising a release layer was prepared.

(Comparative Example C-4)
A polytetrafluoroethylene resin film (hereinafter referred to as PTFE) (manufactured by Daikin Industries Yodogawa Hutec, Yodoflon PTFE, 50 μm) was prepared as a release layer.
From the above steps, a mold release film comprising a release layer was prepared.

(Comparative Example C-5)
A biaxially stretched polyethylene terephthalate film (hereinafter referred to as O-PET film) (Toyobo Co., Ltd., ester film, model number E5100) having a thickness of 38 μm was prepared as a base material layer. The surface of the O-PET film was subjected to corona treatment with an output of 0.26 kW, a conveyance speed of 12 m / min, and a discharge gap of 4 mm.
Next, a release layer was formed on the surface of the base material layer subjected to the corona discharge treatment. Specifically, fluorine compound 6 (FS-1010TH, manufactured by Fluoro Technology Co., Ltd.) was applied to one side of the base material layer with a bar coater so as to have a coating thickness of 12 μm. Next, the fluorine compound 6 was dried at 25 ° C. for 90 minutes. After drying, fluorine compound 6 (manufactured by Fluoro Technology, FS-1010TH) was applied again with a bar coater to a coating thickness of 12 μm. After molding, it was dried at 25 ° C. for 90 minutes to form a release layer. After drying, the release layer had a thickness of 3.0 μm.
Through the above steps, a mold release film according to Comparative Example C-5 was produced by laminating the base material layer and the release layer in this order.
In addition, the fluorine compound 6 includes the structural unit represented by (X1) described above. The fluorine compound 6 does not contain a polar functional group at the end of the molecular chain.

The following evaluations were performed for the mold release films for Examples C-1 to C-8 and Comparative Examples C-1 to C-5. The results are shown in Table 3.

(Melting point of base material layer)
Using the suggested scanning calorimetry (DSC, manufactured by Seiko Instruments Inc., DSC 6220) for the base material layers of Examples C-1 to C-8 and Comparative Examples C-1 to C-5, a sample mass of 10 mg, a measurement temperature range The melting point was measured during the temperature rising process under the conditions of 20 ° C. to 280 ° C., temperature rising rate 5 ° C./min, sample container Al pan, nitrogen flow 30 ml / min. The evaluation results are shown in Table 3 below.
Note that the melting point of the PVDF film was evaluated as the melting point of the base material layer of Comparative Example C-3. Further, the melting point of the polytetrafluoroethylene resin film was evaluated as the melting point of the base material layer of Comparative Example C-4.

(Thermosetting resin composition)
A tablet of a thermosetting resin composition used for evaluation of releasability and heat resistance was produced. Details of the manufacturing method will be described.
The following were used as raw materials for the thermosetting resin composition used for evaluation of releasability and heat resistance.
・ Epoxy resin 1: Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000)
-Epoxy resin 2: biphenyl type epoxy resin (Mitsubishi Chemical Corporation, YL6677)
Curing agent 1: Biphenylene skeleton-containing phenol aralkyl resin (Nippon Kayaku Co., Ltd., GPH-65)
Curing agent 2: triphenylmethane type phenol resin modified with formaldehyde (Air Water, HE910-20)
Curing accelerator: Triphenylphosphine (Hokuko Chemical Industries, TPP)
・ Inorganic filler: fused spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., FB-950FC)
Colorant: Carbon black (Mitsubishi Chemical Corporation MA-600)
Coupling agent: N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical, KBM-573)
・ Release agent: Carnauba wax (Nikko Fine, Nikko Carnauba)

First, 4.5 parts by mass of the epoxy resin 1, 4.5 parts by mass of the epoxy resin 2, 2.8 parts by mass of the phenol resin curing agent 1, and 2.8 parts by mass of the phenol resin curing agent 2 described above are cured. 0.4 parts by mass of accelerator, 84.2 parts by mass of inorganic filler, 0.2 parts by mass of colorant, 0.4 parts by mass of silane coupling agent, and 0.2 parts by mass of release agent were prepared. . Next, each raw material component was mixed at room temperature using a mixer, and then roll kneaded while heating with two rolls at 45 ° C. and 90 ° C. to obtain a kneaded product. Next, the kneaded product was cooled and then pulverized to obtain a pulverized product. Next, the pulverized product was tableted to obtain a tablet-shaped thermosetting resin composition.

(Releasability)
After setting the mold release film on a transfer mold machine (TOWA, Y-SERIES), the mold release film is vacuum-evacuated to remove the mold release film. It was made to follow the mold. Next, the tablet of the thermosetting resin composition was placed at a predetermined position of the molding machine. Thereafter, the mold provided in the molding machine is clamped at a clamping pressure of 300 kg / cm ² , and then the molten thermosetting resin composition is provided in the molding machine at an injection pressure of 80 kg / cm ^2. Poured into the inner space of the mold and molded at 175 ° C. for 2 minutes to produce a cured product of the thermosetting resin composition. Subsequently, the mold release property between the mold release film and the cured product of the thermosetting resin composition when the mold was opened was evaluated according to the following criteria.
A: When the mold was opened, the mold release film and the cured product of the thermosetting resin composition spontaneously released. Further, no roughness was visually observed on the surface of the obtained cured product.
○: When the mold was opened, the mold release film and the cured product of the thermosetting resin composition were released. Further, although roughening was visually observed on the surface of the obtained cured product, it was rough with no practical problem.
X: When the mold was opened, the mold release film and the cured product of the thermosetting resin composition were not released.

(Heat-resistant)
After setting a mold release film on a transfer mold machine (TOWA, Y-SERIES), the mold release machine is vacuumed to release the mold release film into the mold. I made it follow. The heat resistance of the release film with respect to the mold at this time was evaluated according to the following criteria.
○: It was confirmed that the release film was following the mold without causing wrinkles or floats.
X: Generation | occurrence | production of a wrinkle, a float, or a tear was confirmed by the release film for shaping | molding. Alternatively, the mold release film was melted or semi-molten and joined to the mold.

(Water contact angle)
Using a contact angle meter (DROPMASTER-501, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle 7 seconds after 2 μL of purified water was deposited on the measurement surface of the release surface of the obtained mold release film. Was measured by the droplet method. The measurement temperature was 25 ° C. The unit is °.

(Hexadecane contact angle)
Using a contact angle meter (Dropmaster-501, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle 7 seconds after 6 μl of hexadecane was deposited on the measurement surface of the release surface of the obtained mold release film. It was measured by the droplet method. The measurement temperature was 25 ° C. The unit is °.

As shown in Table 3, the mold release films of Examples C-1 to C-8 were more easily releasable than the mold release films of Comparative Examples C-1 to C-5. It was confirmed that it was excellent in heat resistance.

This application was filed on June 16, 2017, Japanese Patent Application No. 2017-1119070 filed on June 16, 2017, Japanese Application No. 2017-119072, filed on June 16, 2017, and filed on March 24, 2017. Claiming priority based on Japanese Patent Application No. 2017-59177, the entire disclosure of which is incorporated herein.

Claims

A mold release film used for molding the first resin composition,
The release layer constituted by the third resin composition has a laminated structure laminated on the base material layer constituted by the second resin composition,
The release layer and the base material layer are directly bonded,
The outermost layer of the laminated structure has the release layer,
The mold release layer is a mold release film formed by crosslinking a copolymer represented by the following general formula (1) and a curing agent.

(In general formula (1),
l and m respectively represent the molar content of A and B in the copolymer;
l + m = 1,
A contains a fluorocarbon group;
B is a structural unit represented by the following formula (B1). )

(In the general formula (B1),
R 1 is a group containing a functional group that reacts with the curing agent. )
A mold release film according to claim 1,
A mold release film for molding, in which a surface of the base material layer directly bonded to the release layer is smooth.
The mold release film for molding according to claim 1 or 2,
In the general formula (1), A is a mold release film including a structural unit represented by the following formula (A1).

(In the above formula (A1), n is an integer of 1 or more.)
It is a mold release film for molding according to any one of claims 1 to 3,
The curing agent is a mold release film containing an isocyanate compound.
A mold release film for molding according to any one of claims 1 to 4,
The mold release film for molding, wherein the functional group of R 1 that reacts with the curing agent includes one or more selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group.
A mold release film is interposed between the first resin composition and the mold, and a mold release layer is brought into intimate contact with the first resin composition to perform molding, whereby the first resin composition is formed. A mold release film for molding used to give an embossed pattern to a molded product,
Having a laminated structure in which the release layer constituted by the third resin composition is laminated on the base material layer constituted by the second resin composition;
The third resin composition includes a silicone compound or a fluorine compound,
The base material layer has irregularities on the surface on which the release layer is laminated,
The mold release film has a thickness of 15 μm or less.
It is a mold release film for molding according to claim 6,
The mold release film is a mold release film having an embossed shape on the surface provided with the release layer.
It is a mold release film for molding according to claim 7,
A mold having a glossiness of 1 or more and 23 or less, which is a reflectance of light at an incident angle of 60 °, measured according to JIS Z 8741 with respect to the surface having the embossed shape of the mold release film. Mold release film.
A mold release film for molding according to any one of claims 6 to 8,
The third resin composition includes the fluorine compound and a curing agent,
The fluorine compound is a copolymer represented by the following general formula (1),
The mold release layer is a mold release film formed by crosslinking the fluorine compound and the curing agent.

(In general formula (1),
l and m respectively represent the molar content of A and B in the copolymer;
l + m = 1,
A contains a fluorocarbon group;
B is a structural unit represented by the following general formula (B1). )

(In the general formula (B1),
R 1 is a group containing a functional group that reacts with the curing agent. )
A mold release film according to claim 9, wherein
In the copolymer represented by the general formula (1), A is a mold release film containing a structural unit represented by the following formula (A1).

(In the above formula (A1), n is an integer of 1 or more.)
The mold release film for molding according to claim 9 or 10,
Functional group reactive with the curing agent wherein R 1 comprises comprises one or a two or more, release film for molding is selected from the group consisting of hydroxyl group, carboxyl group, an amino group.
It is a mold release film for molding according to any one of claims 9 to 11,
The curing agent is a mold release film containing an isocyanate compound.
A mold release film for molding according to any one of claims 6 to 12,
A mold release film for molding which has an arithmetic average roughness Ra of 0.10 μm or more and 1.0 μm or less on the surface of the base material layer having the unevenness.
The mold release film for molding according to any one of claims 6 to 13,
A mold release film having a 10-point average surface roughness Rz of 1.0 μm or more and 10.0 μm or less on the surface of the base material layer having the unevenness.
A mold release film used for molding the first resin composition,
The mold release film has a release layer as the outermost layer,
The release layer is composed of a third resin composition,
The third resin composition includes a fluorine compound,
The fluorine compound includes a fluorocarbon group,
A release film for molding, wherein the contact angle of hexadecane with respect to the surface of the release layer is 20 ° or more and 77 ° or less.
The mold release film according to claim 15,
The mold release film has a laminated structure in which the release layer and the base material layer are laminated,
The base material layer is composed of a second resin composition,
The mold release film for molding, wherein the second resin composition contains a thermoplastic resin.
A mold release film for molding according to claim 16,
A mold release film for molding, wherein the base material layer has a melting point of 160 ° C or higher and 300 ° C or lower.
A mold release film for molding according to any one of claims 16 and 17,
The laminated structure has a primer layer between the release layer and the base material layer,
The primer layer is composed of a fourth resin composition,
The fourth resin composition is a mold release film containing a siloxane compound.
The mold release film for molding according to any one of claims 15 to 18,
The said fluorine compound is a mold release film shown by following General formula (2).

(In the general formula (2), X is a group containing a fluorocarbon group.
Y is a group having at least one polar functional group at the terminal, and the polar functional group is selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a hydroxy group, a silanol group, and an alkoxysilane group. Species or two or more. )
A mold release film for molding according to claim 19,
The said fluorine compound is a mold release film shown by following General formula (3).

(In the general formula (3), X is the same as X in the general formula (2).
A plurality of A's are groups formed by one or more atoms independently selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. . A may be the same as or different from each other. At least one of A is a hydroxy group or an alkoxy group having 1 to 10 carbon atoms. )
The mold release film for molding according to any one of claims 15 to 20,
A mold release film having a water contact angle of 100 ° or more and 118 ° or less with respect to the surface of the release layer.
The release film for molding according to any one of claims 15 to 21,
A mold release film for molding, wherein the release layer has a thickness of 0.0001 μm or more and 5 μm or less.
A mold release film for molding according to any one of claims 1 to 22,
The first resin composition includes a thermosetting resin,
The thermosetting resin is a mold release film containing an epoxy resin.
The mold release film for molding according to any one of claims 1 to 14 or claim 16 to 23,
The second resin composition is a mold release film containing a polyester resin.
A mold release film for molding according to any one of claims 1 to 24,
The mold forming method is a mold release film which is a transfer mold forming method or a compression mold forming method.
A mold forming method using the mold release film according to any one of claims 1 to 25,
The mold release film has a mold forming temperature of 120 ° C. or higher and 240 ° C. or lower.
A molding method using the mold release film according to any one of claims 1 to 26,
An arrangement step of arranging the mold release film on the mold;
And an introduction step of introducing the first resin composition into a molding space formed by the mold release film.
The mold forming method according to claim 27,
The first resin composition is a thermosetting resin composition,
The said thermosetting resin composition is a molding method containing an epoxy resin.