Film, method for its production and method for manufacturing a semiconductor device using the film

Abstract

Film (1) comprising a substrate (3) and an adhesive layer (5) provided on a surface of the substrate (3), characterized in that the storage elasticity modulus at 180°C of the substrate (3) is from 10 to 100 MPa, the adhesive layer (5) is a reaction-cured product of a composition for an adhesive layer (5) comprising an acrylic polymer with hydroxyl groups and a polyfunctional isocyanate compound, the total equivalent amount of hydroxyl and carboxylic groups in the acrylic polymer is at most 2000 g / mol, in the composition for an adhesive layer (5) M COOH / (M NCO - M OH ) from 0 to 1.0 is and M NCO / (M COOH + M OH ) from 0.4 to 3.5.

Description

TECHNICAL AREA

[0001] The present invention relates to a film suitable as a mold release film for manufacturing a semiconductor device, a method for manufacturing it and a method for manufacturing a semiconductor device using the film. TECHNICAL BACKGROUND

[0002] A semiconductor chip is typically housed (sealed) in a container, called a package, to shield and protect it from the outside air, and mounted on a substrate as a semiconductor device. A curable resin, such as a thermosetting resin like epoxy resin, is used for the packaging. One known method for manufacturing a semiconductor device is injection molding, in which a semiconductor chip or similar component is positioned at a predetermined location within a mold, and a curable resin is poured into the mold and cured.

[0003] In recent years, it has become common practice to expose or uncover a semiconductor chip or a source electrode bonded to a semiconductor chip in order to improve heat dissipation or achieve a thinner design (e.g., patent document 1). A sensor is a typical example of such a semiconductor component.

[0004] In recent years, it has become common to use a semiconductor device with a hollow structure as a CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, or similar device. This involves laminating a sealing or sealing glass over a ribbed component (spacer) on a substrate, to which a semiconductor chip is attached. In the fabrication of such a semiconductor device, it is common practice, after laminating a sealing glass onto the ribbed component, to further seal the circumferential surface of the ribbed component and the sealing glass with a curable resin (e.g., Patent Document 2).

[0005] Such a semiconductor component (hereinafter also referred to as an “exposed component”), in which part of a semiconductor chip or another location (such as a source electrode or a sealing glass) is exposed, can be produced, for example, by applying pressure to a mold on a section of the semiconductor chip or other location to be exposed (hereinafter also referred to as an “exposed section”) and in that state filling and curing with a curable resin.

[0006] However, leakage of the curable resin in the exposed section (the so-called casting seam) is often problematic during the fabrication of an exposed component. This means that the filled curable resin seeps between the mold and the exposed section and cures in such a way that the surface of the exposed section is likely to be thinly covered by the cured product. If the clamping of the mold to the exposed section under high pressure is increased to reduce the leakage, the exposed section is likely to be dented or damaged, potentially leading to breakage of the semiconductor chip or other component. Therefore, it is necessary to maintain weak contact between the exposed section and the mold, which is likely to result in some leakage.If such a leak occurs, it is necessary to take a step to remove the hardened product covering the exposed section, which will decrease productivity.

[0007] As a countermeasure against such leakage, it was proposed to use mold release films, as described below in (1) to (4). (1) one comprising two layers, i.e. a layer (layer A) that provides separability from a molded item and a layer (layer B) that provides heat resistance to heating during molding (Patent document 3). (2) one comprising at least two layers, i.e. a layer (layer A) that provides separability from a semiconductor device and a layer (layer B) that provides heat resistance to heating during the forming process at the time of resin forming of a semiconductor device, wherein layer B is a polyamide resin (Patent Document 4). (3) one which is made from a composite film comprising a substrate film and an auxiliary layer having a pressure elasticity modulus less than that of the substrate film, and is used such that the auxiliary layer faces the surface of a chip to be sealed (Patent document 5). (4) one formed on a substrate plate of a cushion layer with separability with respect to a molding resin and with a compression elasticity modulus of 15 to 300 MPa at 180°C and a thickness of 20 to 70 µm (Patent document 6).

[0008] In the mold release film (1), layer A is made of an acrylic resin, polyisobutylene, a poly(4-methylpentene-1) resin or a syndiotactic polystyrene resin, and layer B is made of a poly(4-methylpentene-1) resin, biaxially stretched polyethylene terephthalate, a soft copolymerized polyethylene terephthalate resin, polyethersulfone or polyimide.

[0009] For the mold release film (2), an acrylic resin or a silicone resin is used for layer A.

[0010] In the mold release film (3), a fluoro resin (polytetrafluoroethylene, etc.) or fluororubber is used for the auxiliary layer, and a polyimide film or an aluminum foil is used for the substrate film.

[0011] In the mold release film (4), silicone rubber is used for the cushioning layer and polyester is used for the substrate plate. DOCUMENTS ON THE STATE OF TECHNOLOGY PATENT DOCUMENTS+ Patent document 1: JP 2009 - 200 338 A Patent document 2: JP 2014 - 225 619 A Patent document 3: JP 2002 - 158 242 A Patent document 4: JP 2004 - 079 567 A Patent document 5: JP 2001 - 250 838 A Patent document 6: JP 2004 - 253 498 A Patent document 7: JP 2005 - 166 904 A: Mold release film for semiconductor molds Patent Document 8: JP 2012 - 167 177 A: Heat-resistant adhesive tape for the manufacture of semiconductor devices and method for the manufacture of semiconductor chips using the same REVELATION OF THE INVENTIONAL PROBLEM

[0012] The aforementioned mold release film (1) or (2) is insufficiently separable from the curable resin after curing (the resin-sealed section). In the case of a sensor, which is a typical exposed component, the shape is complex and the contact area between the mold release film and the resin-sealed section is large; therefore, better separability from the resin-sealed section is desirable (lower adhesion to the resin-sealed section).

[0013] The mold release film (1), (3), or (4) is inadequate with regard to low migration properties. For example, contamination of a semiconductor chip by an exposed component leads to a defect in appearance, such as discoloration. Therefore, a mold release film is required not to contaminate a semiconductor chip. In the case of the mold release film (1), (3), or (4), contamination of components in contact with the semiconductor chip in the layer (auxiliary layer, layer A, cushioning layer) or of decomposition products (e.g., various additives contained in rubber, reactive oligomers resulting from silicone, etc.) is likely to occur during the sealing step due to migration to the semiconductor chip. A similar problem is likely to occur in the case of the source electrode and the sealing glass.In this description, the property by which the materials (impurities) causing the contamination as described above are less likely to migrate to the semiconductor chip, source electrode or sealing glass is also referred to as the “low migration property”.

[0014] Among the mold release films (1) and (2), the one using an acrylic resin for layer A is inadequate in its release properties against a semiconductor chip. Sealing a semiconductor device is usually performed at a high temperature of approximately 180°C. With mold release film (1) or (2) using an acrylic resin for layer A, the adhesion of layer A increases during the sealing process, and during the removal of the mold release film from the exposed area of ​​the semiconductor chip, some or all of layer A adheres to the semiconductor chip, resulting in the problem of so-called adhesive residue. A similar problem is likely to occur in the case of the source electrode or the sealing glass.In this description, as mentioned above, the ease with which the mold release film can be removed during the removal of the mold release film from the exposed section of the semiconductor chip, source electrode or sealing glass is referred to as the "removal property", and a case where removal is easy is referred to as excellent removal property, and a case where removal is difficult is referred to as inadequate removal property.

[0015] As described above, the mold release films (1) to (4) were not those that were able to satisfy both the separation capability against the resin-sealed section and the low migration and peeling properties against the semiconductor chip, the source electrode or the sealing glass during the manufacture of the semiconductor device in which part of the surface of the semiconductor chip, the source electrode or the sealing glass is exposed.

[0016] An object of the present invention is to provide a film which is excellent in its separability from the resin-sealed section and which is excellent in its low migration and detachment properties from the semiconductor chip, the source electrode or the sealing glass and which is thus suitable as a mold release film for the manufacture of a semiconductor device, wherein a part of the surface of a semiconductor chip, a source electrode or a sealing glass is exposed, and a method for its manufacture, as well as a method for manufacturing a semiconductor device using such a film. SOLUTION TO THE PROBLEM

[0017] The present invention provides a film suitable as a mold release film for the manufacture of a semiconductor device, a method for its manufacture and a method for manufacturing a semiconductor device using such a film with the following designs [1] to

[15] . [1] Film comprising a substrate and an adhesive layer provided on a surface of the substrate, characterized in that The storage elasticity modulus of the substrate at 180°C is between 10 and 100 MPa. The adhesive layer is a reaction-cured product of a composition for an adhesive layer, comprising an acrylic polymer with hydroxyl groups and a polyfunctional isocyanate compound. the total equivalent amount of hydroxyl and carboxylic groups in the acrylic polymer is at most 2000 g / mol, in the composition for an adhesive layer, M COOH / (M NCO - MOH ) from 0 to 1.0, and M NCO / (M COOH + M OH ) from 0.4 to 3.5 (where M OH the number of moles M OH of hydroxy groups, derived from the acrylic polymer, is, M COOH the number of moles of carboxyl groups, derived from the acrylic polymer, is and M NCO the number of moles of isocyanate groups, derived from the polyfunctional isocyanate compound). [2] Foil according to [1], wherein the mass mean molecular weight of the acrylic polymer is from 100,000 to 1,200,000. [3] Slide according to [1] or [2], wherein the polyfunctional isocyanate compound has an isocyanurate ring. [4] Foil according to one of [1] to [3], wherein the storage elasticity modulus at 180°C of the adhesive layer is 2 to 20 MPa. [5] Film according to one of [1] to [4], wherein the degree of insolubility of the adhesive layer obtainable from the basis weight W1 (g / m²) by the formula below 2) the adhesive layer and the basis weight W2 (g / m²) 2 ) of the adhesive layer remaining after the film has been subjected to the following dissolution test, is between 40 and 90%: Degree of insolubility(%)=(W2 / W1)×100 <Auflösungstest>

[0018] The film is immersed in methylene chloride at 20 to 25°C and stirred for one day; after stirring, the film is immersed for one day and washed for 10 minutes in further methylene chloride at 20 to 25°C; and after washing, the film is vacuum-dried at 100°C for two hours.

[0019] [6] Film according to one of [1] to [5], wherein the substrate contains an ethylene tetrafluoroethylene copolymer.

[0020] [7] Film according to one of [1] to [6], wherein the thickness of the substrate is from 50 to 100 µm and the thickness of the adhesive layer is from 0.5 to 15 µm.

[0021] [8] Film according to one of [1] to [7], wherein the composition for an adhesive layer further includes an antistatic agent.

[0022] [9] Film according to one of [1] to [7], which has an antistatic layer between the substrate and the adhesive layer.

[0023]

[10] Film according to one of [1] to [9], which is a mold release film to be used in a sealing process for producing a semiconductor device sealed with a sealing resin.

[0024]

[11] Foil according to

[10] , wherein the semiconductor device sealed with a sealing resin is a semiconductor device in which part of the surface of a semiconductor chip, a source electrode or a sealing glass is exposed by the sealing resin.

[0025]

[12] Film according to

[10] or

[11] , which is a mold release film, which is to be used such that when the curable resin has been cured and formed into the sealing resin in a mold in the sealing process, the substrate side surface of the mold release film is in contact with the mold inner surface, and the surface of the adhesive layer of the mold release film is in contact with a part of the surface of a semiconductor chip.

[0026]

[13] Film according to one of [1] to [9], which is a mold release film to be used in the sealing process described below: Sealing process: A sealing process comprising a step of placing the mold release film onto the surface of a mold to be in contact with a curable resin so that its substrate side surface is in contact with the mold surface, and placing it into the mold of a structure with a semiconductor chip and, if required, with a source electrode or a sealing glass. a step to clamp the mold so that the mold is in contact with the surface of the semiconductor chip, source electrode or sealing glass via the mold release film, a step to fill and cure a curable resin into the mold while clamping the mold to form a resin-sealed section, thereby obtaining a sealing body with the structure and the resin-sealed section, wherein part of the surface is exposed by the semiconductor chip, the source electrode, or the sealing glass, and a step to separate the sealing body from the mold.

[0027]

[14] A method for producing the film as defined in [1] to [9], characterized in that it comprises a step for forming an adhesive layer by applying and drying a coating liquid for an adhesive layer, comprising the composition for an adhesive layer and a liquid medium, on a surface of a substrate.

[0028]

[15] A method for manufacturing a semiconductor device comprising a semiconductor chip and a resin-sealed section and, if required, a source electrode or a sealing glass, wherein a part of the surface is exposed by the semiconductor chip, the source electrode or the sealing glass, characterized in that it comprises a step to place the film, as defined in [1] to [9], onto the surface of a mold to be in contact with a curable resin so that its substrate side surface is in contact with the mold surface, and to place it into the mold of a structure with a semiconductor chip and, if required, with a source electrode or a sealing glass, a step to clamp the mold so that the mold is in contact with the surface of the semiconductor chip, electrode or sealing glass via the mold release film, a step to fill and cure a curable resin into the mold while clamping the mold to form a resin-sealed section, thereby obtaining a sealing body with the structure and the resin-sealed section, and wherein part of the surface is exposed by the semiconductor chip, the source electrode or the sealing glass, and a step to separate the sealing body from the mold. ADVANTAGEOUS EFFECTS OF THE INVENTION

[0029] The film of the present invention is excellent in its separability from the resin-sealed section and excellent in its low migration and detachment properties from the semiconductor chip, the source electrode or the sealing glass, and is usable as a mold release film for manufacturing a semiconductor device, wherein part of the surface is exposed by a semiconductor chip, a source electrode or a sealing glass.

[0030] According to the method for producing a film of the present invention, it is possible to produce a film which is excellent in its separability from the resin-sealed section and excellent in its low migration and detachment properties from the semiconductor chip, the source electrode or the sealing glass, and which can be used as a mold release film for producing a semiconductor device, part of the surface of which is exposed to a semiconductor chip, a source electrode or a sealing glass. BRIEF DESCRIPTION OF THE DRAWINGS Fig. Figure 1 is a schematic cross-sectional view showing a first embodiment of the film of the present invention. Fig. Figure 2 is a schematic cross-sectional view showing an example of a semiconductor device to be produced by the method for manufacturing a semiconductor device of the present invention. Fig.Figure 3 is a schematic cross-sectional view showing another example of a semiconductor device to be produced by the method for producing a semiconductor device of the present invention. Fig. Figure 4 is a cross-sectional view showing a step (1) in the first embodiment of the method for manufacturing a semiconductor device of the present invention. Fig. Figure 5 is a cross-sectional view showing step (2) in the first embodiment of the method for manufacturing a semiconductor device of the present invention. Fig. Figure 6 is a cross-sectional view showing step (3) in the first embodiment of the method for manufacturing a semiconductor device of the present invention. Fig.Figure 7 is a cross-sectional view showing step (5) in the first embodiment of the method for manufacturing a semiconductor device of the present invention. DESCRIPTION OF EXECUTION FORMS

[0031] In this description, the meanings of the following terms are as follows.

[0032] The term "units" in a resin refers to the structural units (monomer units) that make up the resin. These monomer-based units can sometimes be called "monomeric units."

[0033] An "acrylic polymer" is a polymer containing units based on a (meth)acrylate. These (meth)acrylate-based units within the acrylic polymer can be of one type, two types, or more. The acrylic polymer may also contain other units distinct from those based on a (meth)acrylate.

[0034] A "(meth)acrylate" is a general term for both an acrylate and a methacrylate. A "(meth)acrylic acid" is a general term for both acrylic acid and methacrylic acid.

[0035] The "total equivalent amount of hydroxyl and carboxyl groups" in an acrylic polymer containing hydroxyl groups refers to the total molar mass of hydroxyl and carboxyl groups in the acrylic polymer. In the following, the total equivalent amount is also referred to as the "crosslinkable functional group equivalent amount".

[0036] A "side group" refers to a group (lateral group) bound to the main chain of the resin (polymer).

[0037] The film of the present invention is one suitable for use as a mold release film, sealed with a sealing resin in a sealing process for manufacturing a semiconductor device. Hereinafter, the film to be used in this application is referred to as a "mold release film".

[0038] The mold release film of the present invention is particularly suitable as a mold release film for use in a sealing process for manufacturing a semiconductor device, wherein a portion of the surface of a semiconductor chip, a source electrode, or a sealing glass is exposed or uncovered by a sealing resin. However, its use is not limited to this, and it can also be used in a sealing process for manufacturing other resin-sealed semiconductor devices.

[0039] The mold release film of the present invention can be used such that, during the curing of a curable resin in a mold for forming a sealing resin in the sealing process, the substrate-side surface of the mold release film is in contact with the inner surface of the mold, and the surface of the adhesive layer of the mold release film is in contact with a portion of the surface of the semiconductor chip. Thus, the sealing resin is not formed on the semiconductor chip surface that is in contact with the adhesive layer of the mold release film, and the surface is an exposed surface. Likewise, in a case where the mold release film of the present invention is to be used in a sealing process for producing a semiconductor device, a portion of the surface of which is exposed to the sealing resin by a source electrode or a sealing glass of a semiconductor chip, or...The surface of the adhesive layer of the mold release film of the present invention is brought into contact with a part of the surface of the source electrode or the sealing glass to prevent contact between the surface and the curable resin, wherein the surface of the source electrode or the sealing glass in contact with the surface of the adhesive layer of the mold release film can be formed to form an exposed surface.

[0040] A sealing process for manufacturing a semiconductor device in which part of the surface of a semiconductor chip, source electrode or sealing glass is exposed to the sealing resin can be described as a sealing process consisting of a combination of the steps below, although the sealing process is not limited to them.

[0041] Sealing process: A sealing process comprising a step of placing the mold release film onto the surface of a mold to be in contact with a curable resin such that its substrate side surface is in contact with the mold surface, and placing in the mold a structure with a semiconductor chip and, if required, with a source electrode or a sealing glass; a step of clamping the mold so that the mold is in contact with the surface of the semiconductor chip, the source electrode, or the sealing glass via the mold release film; a step of filling and curing a curable resin into the mold while clamping the mold to form a resin-sealed section, thereby obtaining a sealing body with the structure and the resin-sealed section and wherein part of the surface of the semiconductor chip, the source electrode, or the sealing glass is exposed; and a step of separating the sealing body from the mold.

[0042] Now, with reference to a mold release film to be used as an example in the above sealing process, the details of the mold release film of the present invention will be described.

[0043] The mold release film of the present invention is arranged, for example, during the formation of a resin-sealed section of an exposed component to cover the surface (hereinafter also referred to as the "cavity surface"), to form a cavity of a mold which has a cavity (space) of a mold corresponding to the shape of the resin-sealed section, and is arranged between the formed resin-sealed section and the mold cavity surface, thereby facilitating the separation of the resulting sealed body from the mold. Furthermore, during the formation of the resin-sealed section, it will be in close contact with a portion of the surface of the semiconductor chip, the source electrode, or the sealing glass to prevent the penetration of the curable resin into that portion.The section of the surface of the semiconductor chip, source electrode or sealing glass with which the mold release film is in close contact will be an exposed section on the outer surface (surface in contact with the atmosphere) of the exposed component. [Mold release film in first embodiment]

[0044] Fig. Figure 1 is a schematic cross-sectional view showing a first embodiment of the mold release film of the present invention.

[0045] The mold release film 1 in the first embodiment comprises a substrate 3 and an adhesive layer 5, provided on one side of the substrate 3.

[0046] The adhesive layer 5 is in contact with a curable resin and a semiconductor device during the formation of a resin-sealed section. That is, during the manufacture of a semiconductor package, the mold release film 1 is positioned such that its surface 1a faces the semiconductor chip (adhesive layer 5) and is in contact with the semiconductor chip, a source electrode, or a sealing glass, and with the curable resin during the formation of a resin-sealed section. At the same time, its surface 1b is in close contact with the cavity surface of the mold (substrate 3). Upon curing, the curable resin in this state forms a resin-sealed section corresponding to the shape of the mold cavity.Furthermore, the curable resin will not penetrate between the surface in contact with surface 1a, the semiconductor chip, the source electrode or the sealing glass and the cavity surface, and the surface will be an exposed section. (substrate)

[0047] Substrate 3 has a storage elasticity modulus at 180°C (hereinafter also referred to as a "storage elasticity modulus (180°C)") of 10 to 100 MPa, particularly preferably of 10 to 80 MPa.

[0048] 180°C is a common molding temperature during the sealing of a semiconductor device.

[0049] In the case of a sensor as a typical exposed component, the shape is complex, and the shape of the cavity used in its manufacture will also be complex. If the storage elastic modulus (180°C) is at most the upper limit in the aforementioned range, the mold release film will exhibit appropriate elongation under high-temperature conditions. Even if the cavity surface has a complex shape, as described above, the mold release film will undoubtedly be in close contact with the cavity surface, thus forming a resin-sealed section with high accuracy.

[0050] If the storage elasticity modulus (180°C) is at least the lower limit in the aforementioned range, the mold release film will exhibit suitable strength under high-temperature conditions. Furthermore, during the application of the mold release film to cover the cavity surface of the mold, and during vacuum drawing, tearing or pinhole formation will be less likely. Additionally, uniform tension will be exerted on the mold release film, reducing the likelihood of wrinkle formation and the likelihood of visual defects resulting from the transfer of wrinkles from the mold release film to the surface of the resin-sealed section.

[0051] The storage elastic modulus (180°C) is measured according to ISO 6721-4, 1994 (JIS K7244-4, 1999). The frequency is set to 10 Hz, the static force to 0.98 N, and the dynamic displacement to 0.035%. By increasing the temperature by 20°C at a rate of 2°C / min, the storage elastic modulus, measured at 180°C, is determined to be the storage elastic modulus (180°C).

[0052] The storage elastic modulus (180°C) can be adjusted by, for example, the material (including its composition) that constitutes substrate 3, etc. For instance, in a case where substrate 3 consists of a thermoplastic resin, the storage elastic modulus (180°C) can be adjusted by modifying the crystallinity of the thermoplastic resin. Specifically, the lower the crystallinity of the thermoplastic resin, the lower the storage elastic modulus (180°C). The crystallinity of the thermoplastic resin can be adjusted by a known method. For example, in the case of an ethylene-tetrafluoroethylene copolymer (ETFE), it can be adjusted by the ratio of units based on tetrafluoroethylene and ethylene, or by the type or content of units based on other monomers different from tetrafluoroethylene and ethylene, etc.

[0053] From the standpoint of excellent separability of the mold release film from the mold after sealing, substrate 3 is preferred if it contains a resin with mold release properties.

[0054] A mold-separable resin is one such that a layer consisting solely of the resin exhibits mold-separability. Preferably, the mold-separable resin has a storage elasticity modulus (at 180°C) of a layer consisting solely of that resin within the aforementioned range. Such a resin could be, for example, a fluoropolymer, polymethylpentene, syndiotactic polystyrene, polycycloolefin, silicone rubber, polyester elastomer, polybutylene terephthalate, non-stretched nylon, etc. Other important properties include mold release, heat resistance at a temperature (e.g., 180°C) of the mold during sealing, strength to withstand the flow or pressure of the curing resin, elongation at high temperatures, etc.A fluorinated resin, polymethylpentene, syndiotactic polystyrene, polycycloolefin, or the like is preferred, and from the standpoint of excellent mold release properties, a fluorinated resin is particularly preferred. These resins may be used individually or in combination with two or more of them.

[0055] Substrate 3, one made only from a fluorinated resin, is preferred.

[0056] From the standpoint of excellent mold release properties and heat resistance, a fluoroolefin polymer is preferred as a fluorinated resin. A fluoroolefin polymer is a polymer with units based on a fluoroolefin. The fluoroolefin polymer may also contain other units that differ from those based on a fluoroolefin.

[0057] The fluoroolefin can be, for example, tetrafluoroethylene (hereinafter also referred to as "TFE"), vinyl fluoride, vinylidene fluoride, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, etc. One of the fluoroolefins can be used individually, or two or more of them can be used in combination.

[0058] The fluoroolefin polymer can be, for example, ETFE, a tetrafluoroethylene hexafluoropropylene copolymer (FEP), a tetrafluoroethylene perfluoro(alkyl vinyl ether) copolymer (PFA), a tetrafluoroethylene hexafluoropropylene vinylidene fluoride copolymer (THV), etc. One of the fluoroolefin polymers can be used individually, or two or more of them can be used in combination.

[0059] From the standpoint of high elongation at high temperatures, ETFE is particularly favored as a fluoroolefin polymer. ETFE is a copolymer with TFE units and ethylene units (hereinafter also referred to as "E units").

[0060] ETFE is preferably a polymer containing TFE units, E units, and units based on a third monomer other than TFE and ethylene. The crystallinity of ETFE, as well as the storage elastic modulus (180°C) and other strength properties of substrate 3, can be easily adjusted by the type or content of units based on the third monomer. For example, the inclusion of units based on the third monomer (especially a monomer with fluorine atoms) improves tensile strength and elongation at high temperatures (especially around 180°C).

[0061] The third monomer can be a monomer with fluorine atoms and a monomer without fluorine atoms.

[0062] The following monomers (a1) to (a5) can be mentioned as the monomer containing fluorine atoms. Monomer (a1): a fluoroolefin with 2 or 3 carbon atoms. Monomer (a2): a fluoroalkylethylene, represented by X(CF2) n CY=CH2 (where X and Y are each independently a hydrogen atom or a fluorine atom and n is an integer from 2 to 8). Monomer (a3): a fluorovinyl ether. Monomer (a4): a functional group-containing fluorovinyl ether. Monomer (a5): a fluorinated monomer with an aliphatic ring structure.

[0063] The monomer (a1) can be, for example, a fluoroethylene (trifluoroethylene, vinylidene fluoride, vinyl fluoride, chlorotrifluoroethylene, etc.), a fluoropropylene (hexafluoropropylene (hereinafter also referred to as "HFP"), 2-hydropentafluoropropylene, etc.), etc.

[0064] The monomer (a2) is preferably a monomer where n is from 2 to 6, and a monomer where n is 2 to 4 is particularly preferred. Furthermore, a monomer where X is a fluorine atom and Y is a hydrogen atom, i.e., a (perfluoroalkyl)ethylene, is particularly preferred.

[0065] The following compounds can be mentioned as specific examples of the monomer (a2). CF3CF2CH=CH2 CF3CF2CF2CF2CH=CH2 ((Perfluorobutyl)ethylene, hereinafter referred to as “PFBE”) CF3CF2CF2CF2CF=CH2, CF2HCF2CF2CF=CH2, CF2HCF2CF2CF2CF=CH2 etc.

[0066] The following compounds can be mentioned as specific examples of the monomers (a3). Among those listed below is a monomer that is a diene, and a monomer that can be cyclopolymerizable. CF2=CFOCF3 CF2=CFOCF2CF3, CF2=CF(CF2)2CF3 (Perfluoro(propyl vinyl ether, hereinafter referred to as “PPVE”), CF2=CFOCF2CF(CF3)O(CF2)2CF3, CF2=CFO(CF2)30(CF2)2CF3, CF2=CFO(CF2CF(CF3)O)2(CF2)2CF3, CF2=CFOCF2CF(CF3)O(CF2)2CF3, CF2=CFOCF2CF=CF2, CF2=CFO(CF2)2CF=CF2 etc.

[0067] The following compounds can be mentioned as specific examples of the monomer (a4). CF2=CFO(CF2)3CO2CH3, CF2=CFOCF2CF(CF3)O(CF2)3CO2CH3, CF2=CFOCF2CF(CF3)O(CF2)2SO2F etc.

[0068] Specific examples of the monomer (a5) include, for example, perfluoro(2,2-dimethyl-1,3-dioxol), 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxol, perfluoro(2-methylene-4-methyl-1,3-dioxolane), etc.

[0069] The following monomers (b1) to (b4) can be mentioned as monomers without a fluorine atom. Monomer (b1): an olefin, Monomer (b2): a vinyl ester, Monomer (b3): ​​a vinyl ether, Monomer (b4): an unsaturated acid anhydride. Specific examples of the monomer (b1) could be, for example, propylene, isobutene, etc. Specific examples of the monomer (b2) include vinyl acetate, etc. Specific examples of the monomer (b3) include ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, etc. Specific examples of the monomer (b4) include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc.

[0070] The third monomer can be a single type, or two or more types can be used in combination.

[0071] From the standpoint that the crystallinity can be easily adjusted, and the tensile strength and elongation at high temperature (especially around 180°C) are excellent due to the inclusion of units based on a third monomer (especially a monomer with fluorine atoms), the monomer (a2), HFP, PPVE, or vinyl acetate is preferred; HFP, PPVE, CF3CF2CH=CH2, or PFBE is preferred; and PFBE is particularly preferred. That is to say, as ETFE, a copolymer with units based on TFE, units based on E, and units based on PFBE is particularly preferred.

[0072] In ETFE, the molar ratio of TFE units to E units (TFE units / E units) is preferably from 80 / 20 to 40 / 60, more preferably from 70 / 30 to 45 / 55, and particularly preferably from 65 / 35 to 50 / 50. When the TFE units / E units ratio is within the aforementioned range, the heat resistance and mechanical strength of the ETFE will be excellent.

[0073] The ratio of units based on the third monomer in ETFE is preferably from 0.01 to 20 mol%, more preferably from 0.10 to 15 mol%, and most preferably from 0.20 to 10 mol%, to the sum (100 mol%) of all units comprising ETFE. If the ratio of units based on the third monomer is within the aforementioned range, the heat resistance and mechanical strength of ETFE will be excellent.

[0074] In a case where the units, based on the third monomer, contain PFBE units, the ratio of PFBE units is preferably 0.5 to 4.0 mol%, more preferably 0.7 to 3.6 mol%, and particularly preferably 1.0 to 3.6 mol%, to the sum (100 mol%) of all units constituting ETFE. If the ratio of PFBE units is in the aforementioned range, the tensile modulus of elasticity at 180°C of the mold release film can be adjusted within the aforementioned range. Furthermore, the tensile strength and elongation at high temperature (especially around 180°C) will be improved.

[0075] The melt flow rate (MFR) of ETFE is preferably from 2 to 40 g / 10 min, more preferably from 5 to 30 g / 10 min, and particularly preferably from 10 to 20 g / 10 min. MFR is an index of molecular weight, and the higher the MFR, the lower the molecular weight will generally be. If the MFR of ETFE is in the aforementioned range, the formability of ETFE will be improved, and the mechanical strength of the mold release film will be excellent.

[0076] MFR of ETFE is a value measured under a load of 49 N at 297°C according to ASTM D3159.

[0077] Substrate 3 can be made only from a moldable resin or it can contain, in addition to a moldable resin, components that are different from the moldable resin.

[0078] Other components such as lubricant, antioxidant, antistatic agent, plasticizer, mold release agent, etc., may include, for example, a lubricant, an antioxidant, an antistatic agent, a plasticizer, a mold release agent, etc.

[0079] Substrate 3 should preferably not contain any other components with a view to not contaminating the mold.

[0080] The surface of substrate 3, in contact with the mold during the formation of a resin-sealed section (i.e., the substrate 3 side surface 1b of the mold release liner 1), can be smooth or it can have irregularities formed on it. From the standpoint of excellent release from the mold, it is preferable to have irregularities formed on it.

[0081] The surface shape, when irregularities are formed, can be one in which a multitude of protrusions and / or depressions are statistically distributed, or a multitude of protrusions and / or depressions are regularly arranged. The shapes and sizes of the multitude of protrusions and / or depressions can be the same or different.

[0082] The protrusions can be elongated ridges extending across the surface of the mold release film, or scattered projections on the surface, and the depressions can be elongated grooves extending across the surface of the mold release film, or scattered holes on the surface.

[0083] The shape of the mold ridges or grooves can be, for example, linear, curved, or bent. A multitude of mold ridges or grooves can be present on the mold release film surface, running parallel to the mold strips. The cross-sectional shape of the mold ridges or grooves can be perpendicular to the longitudinal direction in one direction, for example, a polygonal shape such as triangular (V-shaped), semicircular, etc.

[0084] The shape of the protrusions or holes can be, for example, a polygonal pyramidal shape, such as a triangular pyramidal shape, a square pyramidal shape, a hexagonal pyramidal shape, etc., a conical shape, a hemispherical shape, a polyhedral shape, other various irregular shapes, etc.

[0085] The arithmetic mean roughness Ra of surface 1b is preferably from 0.2 to 2.5 µm, particularly preferably from 0.2 to 2.0 µm. If the arithmetic mean roughness Ra of surface 1b is at least the lower limit in the aforementioned range, the release from the mold will be better. Furthermore, surface 1b and the mold will be less likely to cause blockage, and wrinkles due to blockage will be less likely to form. If the arithmetic mean roughness Ra of surface 1b is at most the upper limit in the aforementioned range, pinholes will be less likely to form in the mold release film.

[0086] The arithmetic mean roughness Ra is a value measured according to JIS B0601:2013 (ISO 4287:1997, Amd.1:2009). The standard length Ir (cut-off value λc) for a roughness curve is 0.8 mm.

[0087] The thickness of the substrate 3 is preferably from 50 to 100 µm, particularly preferably from 50 to 75 µm. If the thickness of the substrate 3 is at most the upper limit in the aforementioned range, the mold release film 1 can be easily deformed and thus exhibits excellent mold traceability. If the thickness of the substrate 3 is at least the lower limit in the aforementioned range, handling the mold release film 1 (e.g., roll-to-roll processing) will be easy, and creases will be less likely to form during the application of the mold release film 1 to cover the cavity of a mold during its extraction. (adhesive layer)

[0088] The adhesive layer 5 is a reaction-cured product consisting of a composition for an adhesive layer comprising a hydroxyl-containing acrylic polymer and a polyfunctional isocyanate compound. The hydroxyl-containing acrylic polymer reacts with a polyfunctional isocyanate compound, cross-links, and cures to form the reaction-cured product.

[0089] The composition for an adhesive layer may further optionally contain components different from the acrylic polymer and the polyfunctional isocyanate compound (excluding a liquid medium) in an area that does not impair the effects of the present invention. <Hydroxygruppe-enthaltendes Acrylpolymer>

[0090] Hydroxy groups in the hydroxy group-containing acrylic polymer are crosslinkable functional groups, reactive with isocyanate groups of the polyfunctional isocyanate compound.

[0091] The hydroxy value of the hydroxy group-containing acrylic polymer is preferably from 1 to 100 mgKOH / g, particularly preferably from 29 to 100 mgKOH / g.

[0092] The hydroxy value is measured by the method specified in JIS K0070; 1992.

[0093] The hydroxy-group-containing acrylic polymer may or may not contain carboxyl groups. Like the hydroxy groups, the carboxyl groups are crosslinkable functional groups, reactive with isocyanate groups of the polyfunctional isocyanate compound.

[0094] The acidity of the hydroxy group-containing acrylic polymer is preferably from 0 to 100 mgKOH / g, particularly preferably from 0 to 30 mgKOH / g.

[0095] The acid value, like the hydroxy value, is measured by the method specified in JIS K0070; 1992.

[0096] The crosslinkable functional group equivalent amount of the hydroxy group-containing acrylic polymer (the total equivalent amount of hydroxy groups and carboxyl groups) is at most 2,000 g / mol, preferably from 500 to 2,000 g / mol, particularly preferably from 1,000 to 2,000 g / mol.

[0097] The crosslinkable functional group equivalent (FGE) corresponds to the molecular weight between crosslinking sites and is a physical property value that determines the elastic modulus after crosslinking (the elastic modulus of the reaction-cured product). If the crosslinkable FGE is at most the upper limit in the aforementioned range, the elastic modulus of the reaction-cured product will be sufficiently high, and the separability of the adhesive layer 5 from the resin-sealed section and the peelability from the semiconductor chip, source electrode, or sealing glass will be excellent. Furthermore, the low migration property will be excellent.

[0098] In the hydroxy-containing acrylic polymer, hydroxy groups can be present in side chains, at the ends of the main chain, or in both. For ease of adjusting the hydroxy group content, they are preferably present at least in the side chains.

[0099] A copolymer containing a hydroxyl group, wherein hydroxyl groups are present in side groups, is preferred in the form of the unit (c1) and the unit (c2) below.

[0100] Unit (c1): a (meth)acrylate unit with a hydroxyl group.

[0101] Unit (c2): a unit that is different from unit (c1).

[0102] The unit (c1) could, for example, be the following unit. -(CH2-CR 1 (COO-R 2 -OH))-

[0103] In unit (c1) R 1a hydrogen atom or a methyl group, R 2 is a C 2-10 Alkylene group or a C 3-10 cycloalkylene group or -R 3 -OCO-R 5 -COO-R 4 -. R 3 and R 4 are each independently a C 2-10 Alkylene group, and R 5 is a phenylene group.

[0104] R 1 is preferably a hydrogen atom.

[0105] The alkylene groups for R 2 , R 3 and R 4 They can be linear or branched.

[0106] Specific examples of a monomer as a unit (c1) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, etc. One of these can be used individually, or two or more of them can be used in combination.

[0107] From the standpoint of excellent reactivity of the hydroxy group, unit (c1) is one in which R 2 a C 2-10 An alkylene group is preferred. That is, a hydroxyalkyl(meth)acrylate unit with a C 2-10 The hydroxyalkyl group is preferred.

[0108] The ratio of units (c1) to the sum (100 mol%) of all units constituting the hydroxyl-containing acrylic polymer is preferably from 3 to 30 mol%, more preferably from 3 to 20 mol%. If the ratio of units (c1) is at least the lower limit in the aforementioned range, the crosslinking density due to the polyfunctional isocyanate compound will be sufficiently high, and the separability of the adhesive layer 5 from the resin-sealed section and the peelability from the semiconductor chip, source electrode, or sealing glass will be improved. If the ratio of units (c1) is at most the upper limit in the aforementioned range, the adhesion to the semiconductor chip, source electrode, or sealing glass will be improved.

[0109] Unit (c2) is not particularly limited as long as it can be copolymerized with a monomer that constitutes unit (c1). Unit (c2) may contain a carboxyl group, but preferably does not contain a reactive group (e.g., an amino group) capable of reacting with an isocyanate group other than a carboxyl group.

[0110] A monomer comprising unit (c2) can be, for example, a (meth)acrylate without a hydroxyl group, (meth)acrylic acid, acrylonitriles, or a macromer with an unsaturated double bond. The macromer with an unsaturated double bond can be, for example, a macromer with a polyoxyalkylene chain, such as a (meth)acrylate of a polyethylene glycol monoalkyl ether.

[0111] Das (Meth)acrylat ohne Hydroxygruppe kann zum Beispiel ein Alkyl(meth)acrylat, Cyclohexyl(meth)acrylat, Phenyl(meth)acrylat, Toluyl(meth)acrylat, Benzyl(meth)acrylat, 2-Methoxyethyl(meth)acrylat, 3-Methoxybutyl(meth)acrylat, Glycidyl(meth)acrylat, 2-Aminoethyl(meth)acrylat, 3-(Methacryloyloxypropyl)trimethoxysilan, Trifluormethylmethyl(meth)acrylat, 2-Trifluormethylethyl(meth)acrylat, 2-Perfluorethylethyl(meth)acrylat, 2-Perfluorethyl-2-perfluorbutylethyl(meth)acrylat, 2-Perfluorethyl(meth)acrylat, Perfluormethyl(meth)acrylat, Diperfluormethylmethyl(meth)acrylat, 2-Perfluormethyl-2-perfluorethylmethyl(meth)acrylat, 2-Perfluorhexylethyl(meth)acrylat, 2-Perfluor-decylethyl(meth)acrylat, 2-Perfluor-hexadecylethyl(meth)acrylat usw. sein.

[0112] The alkyl(meth)acrylate is preferably a compound with 1 to 12 carbon atoms in the alkyl group, such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, etc.

[0113] Unit (c2) preferably contains at least one alkyl(meth)acrylate unit.

[0114] The ratio of alkyl(meth)acrylate units to the sum (100 mol%) of all units constituting the hydroxyl-containing acrylic polymer is preferably from 70 to 97 mol%, particularly preferably from 60 to 97 mol%. If the ratio of alkyl(meth)acrylate units is at least the lower limit in the aforementioned range, a glass transition point or mechanical properties derived from the structure of the alkyl(meth)acrylate will be exhibited, and the adhesive layer 5 will be excellent in mechanical strength and adhesion properties. If the ratio of alkyl(meth)acrylate units is at most the upper limit in the aforementioned range, the hydroxyl group content will be sufficient, increasing the crosslinking density, and achieving the predetermined modulus of elasticity.

[0115] The mean molecular weight (Mw) of the hydroxyl-containing acrylic polymer is preferably from 100,000 to 1,200,000, more preferably from 200,000 to 1,000,000, and particularly preferably from 200,000 to 700,000. If the mean molecular weight is at least the lower limit in the above range, the separability from the resin-sealed section and the peelability from the semiconductor chip, the source electrode, or the sealing glass will be better. If the mean molecular weight is at most the upper limit in the above range, the adhesion to the semiconductor chip, the source electrode, or the sealing glass will be better.

[0116] The mass mean molecular weight of a hydroxy group-containing acrylic polymer is a value calculated as polystyrene, obtainable by measurement by gel permeation chromatography, using a calibration curve prepared using a standard polystyrene sample with a known molecular weight.

[0117] The glass transition temperature (Tg) of the hydroxy group-containing acrylic polymer is preferably at most 20°C, particularly preferably at most 0°C. If Tg is at least the lower limit in the above range, even if the temperature becomes low, the adhesive layer will exhibit sufficient flexibility and it will be easy to remove the substrate 3.

[0118] The lower limit of Tg is not particularly limited, but in the molecular weight range mentioned above it is preferably at least -60°C.

[0119] In this description, Tg represents the midpoint glass transition temperature, measured by a dynamic differential scanning calorimetry (DSC) method. <Polyfunktionelle Isocyanat-Verbindung>

[0120] A polyfunctional isocyanate compound is a compound with at least two isocyanate groups, preferably a compound with 3 to 10 isocyanate groups.

[0121] The polyfunctional isocyanate compound can be, for example, hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), tolide diisocyanate (TODI), isophorone diisocyanate (IPDI), xylene diisocyanate (XDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, etc. Furthermore, an isocyanurate (trimer) or biuret of such a polyfunctional isocyanate compound, or an adduct of such a polyfunctional isocyanate compound and a polyol compound, can also be mentioned.

[0122] The polyfunctional isocyanate compound preferably has an isocyanurate ring, since the reaction-cured product (adhesive layer) exhibits a high modulus of elasticity due to the planarity of the ring structure.

[0123] The polyfunctional isocyanate compound with an isocyanurate ring can be, for example, an isocyanurate of HDI (isocyanurate type HDI), an isocyanurate of TDI (isocyanurate type TDI), an isocyanurate of MDI (isocyanurate type MDI), etc. <Andere Komponenten>

[0124] Other components that may be included, if required by the composition of an adhesive layer, could be, for example, a crosslinking catalyst (e.g., an amine, a metal compound, an acid, etc.), a reinforcing filler, a coloring dye, a pigment, an antistatic agent, etc.

[0125] The crosslinking catalyst can be any substance that acts as a catalyst for the reaction (urethanization reaction) of the hydroxy-group-containing acrylic copolymer with a crosslinking agent, in the case of using a polyfunctional isocyanate compound as the crosslinking agent. A standard urethanization reaction catalyst can be used. For example, an amine-type compound, such as a tertiary amine, etc., or an organometallic compound, such as an organotin compound, an organolead compound, an organozinc compound, etc., can be used. The tertiary amine could be, for example, a trialkylamine, an N,N,N',N'-tetraalkyldiamine, an N,N-dialkylamino alcohol, triethylenediamine, a morpholine derivative, a piperazine derivative, etc. The organotin compound can be, for example, a dialkyltin oxide, a fatty acid salt of a dialkyltin, a tin(II) fatty acid salt, etc.

[0126] An organotin compound is preferred as the crosslinking catalyst, and dioctyltin oxide, dioctyltin dilaurate, dibutyltin laurate, or dibutyltin dilaurate is particularly preferred. Alternatively, a dialkylacetylacetone-tin complex catalyst can be used, which is synthesized by reacting a dialkyltin ester and acetylacetone in a solvent and which has a structure in which two acetylacetone molecules are coordinated for one atom by a dialkyltin.

[0127] The amount of crosslinking catalyst to be used is preferably from 0.01 to 0.5 parts by mass to 100 parts by mass of the hydroxy group-containing acrylic polymer.

[0128] The antistatic agent can be, for example, an ionic liquid, a conductive polymer, a metal ion conductive salt, a conductive metal oxide, etc.

[0129] A conductive polymer is a polymer in which electrons move and diffuse along the polymer skeleton (polymer backbone). Examples of conductive polymers include polyaniline-type polymers, polyacetylene-type polymers, polyparaphenylene-type polymers, polypyrrole-type polymers, polythiophene-type polymers, polyvinylcarbazole-type polymers, and so on.

[0130] The metal ion conductive salt can be, for example, a lithium salt compound, etc.

[0131] The conductive metal oxide can be, for example, tin oxide, tin-doped indium oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, zinc antimonate, antimony oxide, etc.

[0132] The content of the antistatic agent in the composition for an adhesive layer is suitably adjusted depending on the desired surface resistance of the adhesive layer 5.

[0133] In the composition for an adhesive layer, the respective levels of the hydroxy group-containing acrylic polymer and the polyfunctional isocyanate compound are adjusted depending on the respective amounts of hydroxy groups, carboxyl groups and isocyanate groups, so that M COOH / (M NCO - M OH ) would be from 0 to 1.0, and M NCO / (M COOH + M OH ) would be from 0.4 to 3.5.

[0134] M COOH / (M NCO - M OH ) is preferably from 0 to 1.0, particularly preferably from 0 to 0.5.

[0135] M NCO / (M COOH + M OH ) is preferably from 0.4 to 4.0, particularly preferably from 0.4 to 3.0.

[0136] Here is M OH the number of moles M OH of hydroxy groups, derived from the hydroxy group-containing acrylic polymer, M COOHis the number of moles of carboxyl groups, derived from the hydroxy group-containing acrylic polymer, and M NCO is the number of moles of isocyanate groups, derived from the polyfunctional isocyanate compound.

[0137] M COOH / (M NCO - M OH ) is a ratio of the number of moles of carboxyl groups to the number of moles of isocyanate groups that do not react with hydroxyl groups among the isocyanate groups of the polyfunctional isocyanate compound contained in the composition for an adhesive layer. That is, the smaller the M COOH / (M NCO - M OHThe higher the concentration, the fewer free carboxyl groups there are, with the remaining material in adhesive layer 5 becoming the reaction-cured product of the composition for an adhesive layer. If free carboxyl groups are present in adhesive layer 5, they will likely react with a curable resin, e.g., an epoxy resin, and removal is generally difficult. If M COOH / (M NCO - M OH ) at most 1.0, free carboxyl groups in the adhesive layer 5 will be sufficiently low and the separability against the resin-sealed section will be excellent.

[0138] M NCO / (M COOH + M OH) is a ratio of the number of moles of isocyanate groups in the polyfunctional isocyanate compound to the total number of moles of hydroxyl and carboxyl groups (i.e., crosslinkable functional groups) in the hydroxyl-containing acrylic polymer included in the composition for an adhesive layer. If M NCO / (M COOH + M OH ) at least the lower limit in the aforementioned range, the crosslinking density, and thus the elastic modulus, of the reaction-cured product will be sufficiently high, and the separability of the adhesive layer 5 from the resin-sealed section, and the peelability of the adhesive layer 5 from the semiconductor chip, the source electrode, or the sealing glass will be excellent. If M NCO / (M COOH + M OHSince the elastic modulus of the adhesive layer 5 is at most the upper limit in the aforementioned range, it will not be too high, and the adhesion to the semiconductor chip, source electrode, or sealing glass will be excellent. Furthermore, the amount of polyfunctional isocyanate compound remaining unreacted in the adhesive layer 5 will be small, and the low migration property towards the semiconductor chip, source electrode, or sealing glass will be excellent.

[0139] The total content of the hydroxy-group-containing acrylic polymer and the polyfunctional isocyanate compound in the composition for an adhesive layer is preferably at least 50% by weight of the total amount of the composition for an adhesive layer. The adhesive layer 5 is a layer formed from the composition for an adhesive layer and can be formed by reacting the hydroxy-group-containing acrylic polymer and the polyfunctional isocyanate compound.

[0140] As a method for forming the adhesive layer 5 from the standpoint that the materials contained in the composition for an adhesive layer are uniformly mixed so that a uniform adhesive layer is obtained, and it is possible to obtain an adhesive layer of any desired thickness or width, a method is preferred in which the composition for an adhesive layer and a liquid medium are pre-mixed and the coating liquid for an adhesive layer obtained thereby is applied to a surface of the substrate 3, followed by drying. Such a method will be described in more detail later.

[0141] The storage elastic modulus (180°C) of the adhesive layer 5 is preferably from 2 to 20 MPa. If the storage elastic modulus (180°C) of the adhesive layer 5 is at least the lower limit in the aforementioned range, the separability from the resin-sealed section and the peelability from the semiconductor chip, the source electrode, or the sealing glass will be improved. If the storage elastic modulus (180°C) of the adhesive layer 5 is at most the upper limit in the aforementioned range, the adhesion to the semiconductor chip, the source electrode, or the sealing glass will be improved, and the effectiveness in preventing leakage of the curable resin at the exposed section will be improved.

[0142] The storage elasticity modulus (180°C) of the adhesive layer 5 can be increased by M COOH / (M NCO - M OH ), M NCO / (M COOH + M OH), the type of polyfunctional isocyanate compound, the mixing ratio of the hydroxy group-containing acrylic polymer and the polyfunctional isocyanate compound, etc., can be adjusted.

[0143] The degree of insolubility of the adhesive layer 5 is preferably from 40 to 90%, particularly preferably from 50 to 90%. The degree of insolubility of the adhesive layer 5 is an index of the crosslinking density of the hydroxyl-containing acrylic polymer. The higher the crosslinking density of the hydroxyl-containing acrylic polymer, the higher the degree of insolubility will generally be. If the degree of insolubility is at least the lower limit in the aforementioned range, the separability from the resin-sealed section and the peelability from the semiconductor chip, the source electrode, or the sealing glass will be improved. If the degree of insolubility is at most the upper limit in the aforementioned range, the adhesion to the semiconductor chip, the source electrode, or the sealing glass will be improved.

[0144] The degree of insolubility of the adhesive layer 5 is calculated from the basis weight W1 (g / m²) using the following formula. 2) the adhesive layer 5 and the basis weight W2 (g / m²) 2 ) of the adhesive layer 5 available, which remains after the mold release film 1 has been placed underneath and undergoes the following dissolution test: Degree of insolubility(%)=(W2 / W1)×100 <Auflösungstest>

[0145] The mold release film is immersed in methylene chloride at 20–25°C and stirred for one day. After stirring, the mold release film is immersed again for one day and washed for 10 minutes in further methylene chloride at 20–25°C. After washing, the mold release film is vacuum-dried at 100°C for two hours.

[0146] The degree of insolubility of the adhesive layer 5 can be determined by M NCO / (M COOH + M OH ), the type of polyfunctional isocyanate compound, the temperature during the reaction of the hydroxy group-containing acrylic polymer and the polyfunctional isocyanate compound, etc., can be set.

[0147] The surface resistance of the adhesive layer 5 is preferably at most 10 10 Ω / □, preferred 10 9 Ω / □. If the surface resistance is at most 10 10 If Ω / □ is, it is possible to effectively prevent breakage of a semiconductor chip due to discharge during detachment.

[0148] The surface of the adhesive layer 5 in contact with a curable resin during the formation of a resin-sealed section, i.e., the surface 1a of the adhesive layer 5 side of the mold release film 1, may be smooth or may have irregularities formed on it.

[0149] The arithmetic mean roughness Ra of surface 1a is preferably from 0.05 to 2.5 µm, more preferably from 0.05 to 2.0 µm, and particularly preferably from 0.05 to 0.5 µm. If the arithmetic mean roughness Ra of surface 1a is at least the lower limit in the aforementioned range, the resin flow marks (flow marks) on the formed resin-sealed section will be uniform. If the arithmetic mean roughness Ra of surface 1a is at most the upper limit in the aforementioned range, the adhesion between surface 1a and the semiconductor device or an associated component will be excellent. Furthermore, the visibility of markings applied to the resin-sealed section after its formation will be improved.

[0150] The thickness of the adhesive layer 5 is preferably from 0.5 to 15 µm, particularly preferably from 1 to 10 µm. If the thickness of the adhesive layer 5 is at least the lower limit in the above range, the adhesion to the semiconductor chip, the source electrode, or the sealing glass will be better. If the thickness of the adhesive layer 5 is at most the upper limit in the above range, the separability from the resin-sealed section will be better. (Physical properties of the mold release film)

[0151] The mold release film 1 preferably meets the following conditions i) to iii). i) The peel strength at 180°C of the epoxy resin, obtainable by the following test procedure (hereinafter also referred to as the ‘peel strength (180°C) of the epoxy resin’), is from 0.001 to 0.1 N / cm. ii) The adhesive strength at 180°C, obtainable by the following test procedure (hereinafter also referred to as the ‘adhesion strength (180°C)’) is from 0.005 to 0.1 N / 24 mm. iii) The migration property, obtainable by the following test procedure (AI element peak intensity after pressurization / AI element peak intensity before pressurization) is from 0.6 to 1.

[0152] The release force (180°C) of the epoxy resin in i) is an index of the separability against the resin-sealed section, and the lower the value, the better the separability. The release force (180°C) of the epoxy resin is preferably from 0.001 to 0.05 N / cm.

[0153] The adhesion force (180°C) in ii) is an index of the adhesion force against the semiconductor chip, the source electrode, or the sealing glass. If the adhesion force (180°C) is at least the lower limit specified above, it is possible to sufficiently reduce leakage from a resin to the exposed area on the surface of the semiconductor chip, the source electrode, or the sealing glass. If the adhesion force (180°C) is at most the upper limit specified above, the release property against the semiconductor chip, the source electrode, or the sealing glass will be excellent. The adhesion force (180°C) is preferably from 0.005 to 0.05 N / 24 mm.

[0154] The Al element peak intensity after pressure application / Al element peak intensity before pressure application in iii) is an index for the migration property against the semiconductor device, and the maximum is 1. The closer the value is to 1, the lower the migration property. The lower the migration property, the better the appearance of the exposed section of the surface of the semiconductor chip, source electrode, or sealing glass. For example, discoloration of the semiconductor chip surface after solder flowback is suppressed. <Ablösekraft (180°C) von Epoxid-Harz>

[0155] A square aluminum foil, 100 µm thick and 15 cm × 15 cm, is placed on a square metal plate (SUS304) 3 mm thick and 15 cm × 15 cm in size. A square spacer, 100 mm thick and 15 cm × 15 cm in size, with a rectangular hole 10 cm × 8 cm formed at its center, is placed on the aluminum foil. 2 g of the epoxy resin composition described below are placed near the center of the hole. A square mold release film, 15 cm × 15 cm in size, is then placed on top, with the adhesive-side surface facing the protruding spacer side. and a square second metal plate (SUS304) with a thickness of 3 mm and a size of 15 cm × 15 cm is placed on top to produce a laminated sample.The laminated sample is subjected to pressure under conditions of 180°C, 10 MPa and 5 minutes to harden the epoxy resin composition.

[0156] The laminate of the mold release film, the layer with the hardened epoxy resin composition and the aluminum plate is cut to a width of 25 mm to produce five test sample pieces.

[0157] For each test specimen, the 180-degree release force at 180°C and a speed of 100 mm / min is measured using a tensile tester. The force (N)-gripping distance curve is then used to obtain the mean value (unit N / cm) of the release force from 25 mm to 125 mm at the gripping distance.

[0158] An arithmetic mean of the mean peel forces of the five test samples is obtained and the obtained value is taken as the peel force (180°C) of the epoxy resin.

[0159] Epoxy resin composition: 8 parts by mass of a phenylene skeleton-containing phenolic alkyl type epoxy resin (softening point: 58°C, epoxy equivalent: 277), 2 parts by mass of a bisphenol A type epoxy resin (melting point: 45°C, epoxy equivalent: 172), 2 parts by mass of a phenylene skeleton-containing phenolic alkyl resin (softening point: 65°C, hydroxy equivalent: 165), 2 parts by mass of a phenol novolak resin (softening point: 80°C, hydroxy equivalent: 105), 0.2 parts by mass of a hardening accelerator (triphenylphosphine), 84 parts by mass of an inorganic filler (calcined spherical silicon dioxide with a mean diameter of 16 µm), 0.1 part by mass of carnauba wax, 0.3 parts by mass of soot, 0.2 parts by mass of an adhesive (3-glycidoxypropyltrimethoxysilane).

[0160] The above materials were pulverized and mixed for 5 minutes using a super mixer. <Haftkraft (180°C)>

[0161] According to JIS Z0237; 2009 (ISO29862; 2007) the 180 degree peel adhesion force (N / 24 mm) is measured at 180°C against a stainless steel (SUS) plate and the value obtained is taken as the 180°C adhesion force. <migrations-eigenschaft>

[0162] A cardboard sheet 1 mm thick, a mold release film, an aluminum plate made of A1N30H-H18 according to JIS H4160; 2006 with a thickness of 0.1 mm, and a cardboard sheet 1 mm thick are placed on top of these in this order so that the adhesive layer of the mold release film and the aluminum plate are in contact, and are subjected to pressure for 20 minutes at 180°C and 5 MPa; the mold release film is removed from the aluminum plate; the surface of the aluminum plate in contact with the mold release film before and after pressure application is analyzed by X-ray photoelectron spectroscopy, obtaining the Al element peak intensities before and after pressure application, and the (Al element peak intensity after pressure application / Al element peak intensity before pressure application) is obtained. (Method for producing the mold release film)

[0163] The mold release film 1 can, for example, be produced by a manufacturing process using the method described below.

[0164] Form release film manufacturing process: A process wherein a coating liquid for an adhesive layer, comprising the aforementioned composition for an adhesive layer and a liquid medium, is applied to one side of a substrate 3 and dried to form an adhesive layer 5.

[0165] During drying, the reaction of the hydroxy group-containing acrylic polymer and the polyfunctional isocyanate compound proceeds to form a reaction-cured product, thereby forming the adhesive layer 5.

[0166] Furthermore, heating can be carried out according to the above method to accelerate the hardening of the composition for an adhesive layer.

[0167] Substrate 3 is defined as above. Surface treatment can be applied to the surface of substrate 3, where the coating liquid for an adhesive layer is to be applied, to improve adhesion to the adhesive layer 5. Such surface treatments include corona treatment, plasma treatment, coating with a silane adhesion promoter, coating with an adhesive, etc.

[0168] The coating fluid for an adhesive layer comprises the aforementioned composition for an adhesive layer and a liquid medium. That is, it comprises the hydroxy-group-containing acrylic polymer, the polyfunctional isocyanate compound, and the liquid medium, and may contain other components if required.

[0169] The hydroxy group-containing acrylic polymer, the polyfunctional isocyanate compound, other components, M COOH / (M NCO - M OH ), M NCO / (M COOH + M OH ) in the coating fluid for an adhesive layer are accordingly the same as defined above.

[0170] The liquid medium can be water, an organic solvent, etc. The organic solvent can be, for example, an alcohol compound, an ester compound, etc.

[0171] The solids content concentration in the coating liquid for an adhesive layer is preferably 5 to 30 wt%, particularly preferably 10 to 30 wt%. If the solids content concentration is at least the lower limit in the above range, cissing will be unlikely to occur when applied to substrate 3. If the solids content concentration is at most the upper limit in the above range, the leveling property of the coated surface will be excellent.

[0172] Various well-known wet coating methods can be used as the application method for the coating fluid for an adhesive layer, and examples include engraving coating, nozzle coating, rod coating, etc.

[0173] The drying temperature is preferably between 45 and 100°C. (Beneficial effects)

[0174] In the mold release film 1, the adhesive layer 5 is in contact with the semiconductor chip, the source electrode or the sealing glass and with the curable resin, during the formation of a resin-sealed section, a reaction-cured product of the aforementioned composition for an adhesive layer, wherein the separability against the resin-sealed section and the low migration and peelability against the semiconductor chip, the source electrode or the sealing glass will be excellent.

[0175] Furthermore, in the mold release film 1, the layer is in contact with the exposed section of the semiconductor chip, the source electrode or the sealing glass, during the formation of a resin-sealed section, the adhesive layer 5, whereby it is possible to obtain an exposed component, wherein the mold release film is in close contact with the exposed section and the leakage of the curable resin to the exposed section is reduced.

[0176] Furthermore, the mold release film 1 exhibits the storage elasticity modulus (180°C) of the substrate 3 in the aforementioned area, displaying suitable strength and elongation while conforming to the mold, and thus possessing excellent mold-following properties. For example, even for a mold with a complex shape, such as that used in the production of a semiconductor device with an intricate shape and an exposed section, like a sensor, the mold release film 1 will conform sufficiently, and cracks or pinholes, leakage of the curable resin at the mold side, wrinkling of the mold release film, and associated problems such as defects in the appearance of the resin-sealed section are unlikely to occur.

[0177] In the foregoing, the mold release film of the present invention was described with reference to the first embodiment; however, the present invention is not limited to the aforementioned embodiment. The respective designs in the aforementioned embodiment and their combinations are only exemplary, and various additions, omissions, substitutions, or other modifications of the designs are possible within a scope that does not deviate from the overall concept and intent of the present invention.

[0178] In the first embodiment, an example is shown where the substrate 3 is a single-layer structure, but the substrate 3 can also be a multi-layer structure. The multi-layer structure can, for example, be a structure in which a plurality of layers, each containing a release resin, are laminated. In such a case, the release resin contained in each of the plurality of layers can be the same or different. From the standpoint of morphological properties, tensile strain, manufacturing costs, etc., the substrate 3 is preferably a single-layer structure.

[0179] In the first embodiment, a substrate and an adhesive layer are shown directly laminated, but the mold release film of the present invention can comprise another layer between the substrate and the adhesive layer. Alternatively, it can comprise another layer on the side opposite the adhesive layer side of the substrate.

[0180] Such an additional layer can be, for example, a gas barrier layer, an antistatic layer, a colored layer, etc. A single type of additional layer can be used individually, or two or more types can be used in combination. The thickness of this additional layer is preferably from 0.05 to 3 µm, and more preferably from 0.05 to 2 µm.

[0181] An antistatic layer between the substrate and the adhesive layer is preferred, making it possible to effectively prevent breakage of the semiconductor chip due to discharge during removal.

[0182] The antistatic layer is a layer containing an antistatic agent. The antistatic agent can be the same as mentioned above.

[0183] In the antistatic layer, the antistatic agent is preferably dispersed in a resin binder. The resin binder is preferably one with permanent heat resistance (e.g., 180°C) in the sealing step, and examples include acrylic resin, silicone resin, urethane resin, polyester resin, polyamide resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, chlorotrifluoroethylene-vinyl alcohol copolymer, tetrafluoroethylene-vinyl alcohol copolymer, etc.

[0184] The resin binder can be cross-linked. If the resin binder is cross-linked, the heat resistance is excellent compared to non-cross-linked resins.

[0185] The surface resistance of the antistatic layer is preferably at most 10 10 Ω / □, preferably at most 10 9 Ω / □.

[0186] The mold release film of the present invention is preferably one with a layered structure comprising any of the adhesive layer / substrate, the adhesive layer / antistatic layer / substrate, or the adhesive layer / gas barrier layer / substrate, on the side that is in contact with the curable resin during the formation of a resin-sealed section. Of these, from the standpoint of excellent adhesion between the adhesive layer and the substrate, as in the first embodiment, a two-layer structure of the adhesive layer / substrate is particularly preferred over a single-layer structure. [Semiconductor component]

[0187] A semiconductor device to be produced by the method for producing a semiconductor device of the present invention, as described below, is one comprising a semiconductor chip and a resin-sealed section and may include a source electrode (also referred to as a "source terminal" or "supply terminal") or a sealing glass, if required, wherein a portion of the surface of the semiconductor chip, the source electrode or the sealing glass is exposed.

[0188] The resin-sealed section is designed to be formed from a curable resin. A thermosetting resin, such as an epoxy resin, a silicone resin, etc., is preferred, and an epoxy resin is particularly favored.

[0189] The sealing glass is a glass plate laminated onto a semiconductor chip using a ribbed component (spacer) to seal the semiconductor chip in an airtight cavity. The sealing glass also acts as a light detector in a sensor (semiconductor component), such as a CCD image sensor or a CMOS image sensor.

[0190] The semiconductor device of the present invention can be one with a source electrode or sealing glass, or one without a source electrode or sealing glass.

[0191] In the case of one without a source electrode and without a sealing glass, one of which part of the surface is exposed is a semiconductor chip.

[0192] In the case of a single-source electrode, typically the electrode with part of its surface exposed will be the source electrode, and the semiconductor chip will have its surface covered by the resin-sealed section, the source electrode, and other components, and will not be exposed.

[0193] In the case of one with a sealing glass, typically one of which a portion of the surface is exposed will be the sealing glass, and the semiconductor chip will be sealed by the substrate, the sealing glass, the rib component, and the resin-sealed section and will not be exposed.

[0194] In addition to the semiconductor chip, the source electrode, and the sealing glass, a portion of the surface of a component connected to the semiconductor chip may be exposed in the semiconductor device. This component connected to the semiconductor chip could, for example, be solder points.

[0195] A semiconductor component can be an integrated circuit with integrated semiconductor components, such as a transistor, a diode, etc.; a light-emitting diode with a light-emitting component, etc.

[0196] The component form of the integrated circuit can be, for example, BGA (Ball Grid Array), QFN (Quad Flat Non-leaded package), SON (Small Outline Non-leaded package), etc.

[0197] From a productivity standpoint, a semiconductor component that is preferably manufactured via batch encapsulation and singulation, for example an integrated circuit, where the sealing system is a MAP (Molded Array PackAltern) system or a WL (Wafer Label packAltern) system, can be mentioned as preferable.

[0198] Fig. Figure 2 is a schematic cross-sectional view showing an example of a semiconductor device.

[0199] A semiconductor device 10 of this example has a substrate 11, a semiconductor chip 13, a plurality of points 15 for bonding the semiconductor chip 13 to the substrate 11 and a resin-sealed section 17.

[0200] Substrate 11 can be, for example, a printed circuit board, a circuit board, etc.

[0201] The resin-sealed section 17 seals a void between the main surface (the surface on the substrate 11 side) of the semiconductor chip 13 and the substrate 11, and side surfaces of the semiconductor chip 13, and the rear surface 13a (the surface opposite the substrate 11 side) of the semiconductor chip 13 forms an exposed section.

[0202] Fig. Figure 3 is a schematic cross-sectional view showing another example of a semiconductor device.

[0203] A semiconductor component 50 of this example comprises a substrate 51, a semiconductor chip 53, a resin-sealed section 57, a sealing glass 59 and a ribbed component 61.

[0204] The substrate 51 can be, for example, a printed circuit board, a circuit board, etc.

[0205] The semiconductor chip 53 is bonded to the substrate 51 by a multitude of bond wires 55a and 55b.

[0206] The ribbed component 61 is placed on the substrate 51 to surround the semiconductor chip 53. The height of the ribbed component 61 is greater than the height of the semiconductor chip 53, and the sealing glass 59 is positioned on the ribbed component 61. Thus, a void is formed between the substrate 51, the sealing glass 59, and the ribbed component 61 to seal the semiconductor chip 53.

[0207] The resin-sealed section 57 is in the form of a frame extending upwards from the peripheral section of the substrate 51 and is in contact with the outer peripheral surface of the substrate 51, the outer peripheral surface of the rib component 61 and the outer peripheral surface of the sealing glass 59.

[0208] In the semiconductor device 50, the upper surface (the surface opposite the substrate 51 side) of the sealing glass 59 forms an exposed section. The side surface of the sealing glass 59 is in contact with the resin-sealed section 57.

[0209] In this example, the height of the resin-sealed section 57 is the same as the height of the upper surface of the sealing glass 59, but the height of the resin-sealed section 57 can be greater than the height of the upper surface of the sealing glass 59. In such a case, a portion (peripheral section) of the upper surface of the sealing glass 59 can be in contact with the resin-sealed section 57. Furthermore, in this example, the ribbed component 61 is arranged on the substrate 51, but the ribbed component 61 can be arranged on the semiconductor chip 53. In such a case, the substrate 51 is provided with an inner conductor (upper surface) and an outer conductor (lower surface), electrically connected to each other via perforations, and the inner conductor is connected to the semiconductor chip 53 via bond wires. [Method for manufacturing a semiconductor device]

[0210] The method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device comprising a semiconductor chip and a resin-sealed section formed from a curable resin, and with, if required, a source electrode or a sealing glass, wherein a portion of the surface of the semiconductor chip, the source electrode, or the sealing glass is exposed, comprising a step for placing the mold release film of the present invention onto the surface of a mold to be in contact with a curable resin, so that its substrate side surface is in contact with the mold surface, and placing it in the mold of a structure with a semiconductor chip and with, if required, a source electrode or a sealing glass, a step to clamp the mold so that the mold is in contact with the surface of the semiconductor chip, electrode or sealing glass via the mold release film, a step to fill and cure a curable resin into the mold, while clamping the mold, to form a resin-sealed section, thereby obtaining a sealing body with the structure and the resin-sealed section, and with part of the surface of the semiconductor chip, the source electrode or the sealing glass exposed, and a step to separate the sealing body from the mold.

[0211] For the method of manufacturing a semiconductor device according to the present invention, it is possible to use a known manufacturing method, with the exception of the use of the mold release film of the present invention. For example, a transfer molding method can be used as the molding method for the resin-sealed section, and a known transfer molding device can be used as the equipment to be employed at that time. The manufacturing conditions can also be the same as in the known method for manufacturing a semiconductor device. (First embodiment)

[0212] With reference to Fig. Sections 4 to 7 describe a first embodiment of the method for manufacturing a semiconductor device of the present invention. This embodiment is an example in which, by using the mold release film 1 described above as a mold release film, a semiconductor device 10 is manufactured as described in Fig. 2 shown, is produced by a transfer-forming process.

[0213] The method for manufacturing a semiconductor device of this embodiment comprises the following steps (1) to (6). Step (1): a step to place a mold release film 1 such that the substrate side surface 1b of the mold release film 1 separates the cavity 21 from an upper mold 20 from a mold with the upper mold 20 and the lower mold 30 ( Fig. 4) covers. Step (2): a step to vacuum suction the mold release film 1 to the side of the cavity surface 23 of the upper mold 20 and separate placement on a substrate exchange section 31 of the lower mold 30, a substrate 11 from an array (structure) in which a plurality of semiconductor chips 13 are attached to the substrate 11 surface by points 15 ( Fig. 5) are bonded. Step (3): a step to clamp the upper mold 20 and the lower mold 30 to keep the mold release film 1 in close contact with the back surfaces of the semiconductor chips 13 and to push up a plunger 35 from a resin exchange section 33 of the lower mold 30 to fill a curable resin 40, previously arranged in the resin exchange section 33, into the cavity 21 via a resin introduction section 25 of the upper mold 20 ( Fig. 6). Step (4): a step of curing the curable resin 40, filled into the cavity 21 to form a resin-sealed section 17 to obtain a sealing body 100. Step (5): a step of removing the sealing body 100 from the form ( Fig. 7). Step (6): a step of cutting the sealing body 100 to separate the multitude of semiconductor chips 13 to obtain a multitude of semiconductor components 10.

[0214] In step (1) the mold release film 1 is arranged such that the surface 1b on the substrate 3 side of the mold release film 1 is in contact with the cavity surface 23 of the upper mold 20, i.e. the surface 1a on the adhesive layer 5 side, which faces the opposite side (the void in the cavity 21).

[0215] Step (3) is a so-called mold underfill (MUF) process.

[0216] Clamping in step (3) is performed under a clamping pressure of preferably 0.05 to 2 MPa, particularly preferably 0.2 to 1 MPa per semiconductor chip. If the clamping pressure is at least the lower limit in the foregoing range, even if there is height variation among the plurality of semiconductor chips 13, the mold release film will be in sufficiently close contact with the back surface (the exposed sections) of the respective semiconductor chips 13, thus preventing leakage of the curable resin to the respective back surfaces. If the clamping pressure is at most the upper limit in the foregoing range, breakage of the semiconductor chip 13 during mold clamping will be less likely.

[0217] In the present invention, by using the mold release film described above, it is possible to sufficiently prevent leakage of the curable resin, even under a clamping pressure that is lower than the conventional clamping pressure.

[0218] In step (5), a cured product 19 is attached to the resin-sealed section 17 of the sealing body 100, which has been removed from the mold, using the curable resin 40, cured in the resin introduction section 25. Such a cured product 19 is usually offcut.

[0219] Before or after step (6), if necessary, a layer of printing ink can be formed on the surface of the resin-sealed section 17 by using a printing ink.

[0220] The preceding section described the method for manufacturing a semiconductor device of the present invention with reference to the first embodiment; however, the present invention is not limited to the aforementioned embodiment. The respective designs and their combinations in the preceding embodiment are exemplary and within a scope that does not deviate from the overall concept and intent of the present invention, whereby additions, omissions, substitutions, and other modifications may be made.

[0221] The timing of the resin-sealed section's detachment from the mold release film is not limited, whereas when the resin-sealed section is removed from the mold, it is possible that the resin-sealed section is removed from the mold along with the mold release film, and then the mold release film is detached from the resin-sealed section.

[0222] The spacing between the multiple sealed semiconductor devices can be uniform or non-uniform. From the perspective that the load exerted on each of the multiple semiconductor devices would be uniform (the load being minimized), it is preferable to equalize the spacing between the multiple semiconductor devices.

[0223] The shape is not limited to what is shown in the first embodiment, and a known one can be used.

[0224] The mold release film can be a mold release film of the present invention and is not limited to the mold release film 1.

[0225] The semiconductor device to be produced by the method for manufacturing a semiconductor device according to the present invention is not limited to semiconductor device 10. Depending on the semiconductor device to be produced, step (6) need not be performed. The semiconductor device to be sealed in the resin-sealed section can be one or more. The shape of the resin-sealed section is not limited to that shown in Fig. 2, limited and it can be a shape with a step, a rise, a curved surface, etc.

[0226] For example, a semiconductor device to be manufactured can be one provided with a sealing glass, such as a semiconductor device 50, or it can be one provided with a gate electrode. The semiconductor device 50 can, for example, be manufactured in the same manner as described above, except that the shape of the cavity 21 of the upper mold 20 is changed to a shape corresponding to the resin-sealed section 57; instead of the setup in step (2), a setup is used in which a plurality of semiconductor chips 53 are bonded to the substrate 51 surface by bond wires 55a and 55b accordingly; the sealing glass 59 is provided over the ribbed component 61 and laminated around it; and by clamping in step (3), the mold release film 1 is brought into close contact with the upper surface of the sealing glass 59. EXAMPLES

[0227] The present invention is described in more detail below with reference to examples. However, the present invention is not limited by the following description.

[0228] Examples 1 to 21 below, 1 to 3, 5 to 8, 13, 14, 16 and 18 to 21 are examples of the present invention, and examples 4, 9 to 12, 15 and 17 are comparative examples.

[0229] The evaluation procedures and materials used in each example are shown below. [Evaluation procedure](Thickness)

[0230] The thickness of a substrate (µm) was measured according to ISO 4591; 1992 (JIS K7130; B1 method in 1999, method for measuring thickness by a quantity method, from a sample taken from a plastic film or sheet).

[0231] The thickness of an adhesive layer (µm) was measured using an RX-100 transmission-type infrared film thickness gauge (trade name, manufactured by Kurabo Industries Ltd.). (Arithmetic mean roughness Ra of substrate surface)

[0232] The arithmetic mean roughness Ra (µm) of a substrate surface was measured according to JIS B0601; 2013 (ISO 4287; 1997, Amd.1; 2009). The standard length Ir (cut-off value λc) was set to 0.8 mm and the measurement length to 8 mm. Using a SURFCOM 480A (manufactured by Tokyo Seimitsu Co., Ltd.), Ra was measured at three locations perpendicular to the flow direction during film production and at three locations parallel to it, for a total of six locations. The mean value was then taken as the surface Ra. (Storage elasticity modulus (180°C))

[0233] Using a Solid L-1 dynamic viscoelasticity measuring device (manufactured by Toyo Seiki Co., Ltd.), the storage elastic modulus (180°C) of a substrate according to ISO 6721-4:1994 (JIS K7244-4:1999) was measured. By setting the frequency to 10 Hz, the static force was set to 0.98 N and the dynamic displacement to 0.035%, and by increasing the temperature from 20°C at a rate of 2°C / min, the storage elastic modulus was measured at 180°C.

[0234] The storage elasticity modulus of an adhesive layer (180°C) was measured in the same way as the storage elasticity modulus of the substrate (180°C) with respect to a test sample produced by the following method. <mess-probe>

[0235] A 12 cm × 12 cm cardboard sheet (1 mm thick) with a 10 cm × 10 cm hole was formed on silicone-coated PET (NS separator A (trade name), manufactured by Nakamoto Packs Co., Ltd.) and covered with adhesive to create a 1 mm high tray. A coating liquid for the adhesive layer was poured onto the inside of the tray and dried at room temperature for 1 day; then further dried in a vacuum dryer at room temperature for 1 day, followed by drying and aging at 40°C for 3 days to produce a 200 µm thick film. This film was used as a measurement sample. (Degree of insolubility of the adhesive layer)

[0236] Calculation of the basis weight of the adhesive layer (W1): In each example, the basis weight (g / m²) is used. 2 ) of the film (the substrate) before the coating liquid for an adhesive layer (hereinafter referred to as "the basis weight before coating") is applied and the basis weight (g / m²) 2 The coating liquid for an adhesive layer is applied to the film, and the adhesive layer is formed (the total basis weight of the film and the adhesive layer, hereinafter referred to as "the basis weight of the film after coating") was measured. From the results, the basis weight W1 (g / m²) was determined. 2 ) of the adhesive layer calculated solely from the formula below. W1=(area weight of the film after coating)−(area weight of the film before coating) Resolution test:

[0237] The mold release film, cut into 10 cm × 10 cm squares, was immersed in methylene chloride at 20 to 25°C and stirred for one day. After stirring for one day, the mold release film was immersed and washed for 10 minutes in a different methylene chloride solution at 20 to 25°C. Following washing, the mold release film was vacuum-dried at 100°C for two hours. Calculation of the degree of insolubility:

[0238] By measuring the mass of the mold release film after vacuum drying in the above dissolution test, the basis weight (g / m²) was determined. 2 ) of the mold release film (hereinafter also referred to as "the basis weight of the film after washing"). From the results of the basis weight W2 (g / m²) 2 The remaining amount of adhesive after the dissolution test was calculated using the formula below. W2=(area weight of the film after washing)−(area weight of the film before coating)

[0239] The degree of insolubility (%) of the obtained W1 and W2 was obtained using the formula below. Degree of insolubility(%)=(W2 / W1)×100 (Surface resistance of adhesive layer)

[0240] The surface resistance (Ω / Ω) was measured according to IEC 60093, using the double-ring electrode method. An R8340 ultra-high resistance meter (manufactured by Advantec) was used as the measuring device, and the measurement was performed at an applied voltage of 500 V for a duration of 1 minute. (Removal power (180°C) of epoxy resin)

[0241] A square aluminum foil, 100 µm thick and 15 cm × 15 cm, was placed on a square metal plate (SUS304) 3 mm thick and 15 cm × 15 cm in size. A square spacer, 100 mm thick and 15 cm × 15 cm in size, with a rectangular hole 10 cm × 8 cm formed at its center, was placed on the aluminum foil. 2 g of the epoxy resin composition described below were placed near the center of the hole. A square mold release film, 15 cm × 15 cm in size, was then placed on top, with its adhesive-side surface facing the protruding spacer side. and a square second metal plate (SUS304) with a thickness of 3 mm and a size of 15 cm × 15 cm was placed on top to produce a laminated sample.

[0242] The laminated sample was subjected to pressure under conditions of 180°C and 10 MPa for 5 minutes to harden the epoxy resin composition.

[0243] The laminate, comprising the mold release film, a layer of the hardened epoxy resin composition and the aluminum foil, was cut to a width of 25 mm to produce five test sample pieces.

[0244] For each sample, the 180-degree release force was measured at 180°C and a speed of 100 mm / min using a tensile tester (RTC-131-A, manufactured by Orientec Co., Ltd.). A mean value (unit: N / cm) of the release force from 25 mm to 125 mm in the gripping distance was obtained from the force (N)-th gripping distance curve.

[0245] An arithmetic mean of the mean peel strengths of the five test samples was obtained and the obtained value was taken as the peel strength (180°C) of the epoxy resin.

[0246] Epoxy resin composition: 8 parts by mass of phenylene skeleton-containing phenolic alkyl type epoxy resin (softening point: 58°C, epoxy equivalent: 277), 2 parts by mass of bisphenol A-type epoxy resin (melting point: 45°C, epoxy equivalent: 172), 2 parts by mass of phenylene skeleton-containing phenolic alkyl resin (softening point: 65°C, hydroxy equivalent: 165), 2 parts by mass of phenol-novolak resin (softening point: 80°C, hydroxy equivalent: 105), 0.2 parts by mass of a hardening accelerator (triphenylphosphine), 84 parts by mass of an inorganic filler (calcined spherical silicon dioxide with a mean diameter of 16 µm), 0.1 part by mass of carnauba wax, 0.3 parts by mass soot, 0.2 parts by mass of an adhesive (3-glycidoxypropyltrimethoxysilane).

[0247] The above components were pulverized and mixed for 5 minutes using a super mixer.

[0248] The glass transition temperature of the hardened product of the epoxy resin composition was 135°C; the storage elasticity modulus at 130°C was 6 GPa; and the storage elasticity modulus at 180°C was 1 GPa. (Adhesive strength (180°C))

[0249] The 180°C release adhesion strength (N / 24 mm) was measured at 180°C for a stainless steel plate according to JIS Z0237; 2009 (ISO29862; 2007). Specifically, a mold release film 24 mm wide and 300 mm long was bonded under pressure to a 50 mm × 125 mm stainless steel plate (SUS304 CP BA (cold rolled, followed by light heat treatment)) with a thickness of 0.1 mm. This was done by reversing a 1 kg hand roller twice at a speed of 10 mm / s at a temperature of 180°C. Regarding the pressure-bonded test sample, the 180-degree peel strength (N / 24 mm) was measured on a hot plate at 180°C using a digital measuring device. The measured value (N / 24 mm) was adopted as the 180-degree peel strength without being converted to N / 10 mm. (Migration property)

[0250] An aluminum plate (5 cm × 10 cm), made of A1 N30H-H18 material according to JIS H4160:2006, and 0.1 mm thick, and washed by immersion in acetone, was placed on a cardboard sheet (5 cm × 10 cm) with a thickness of mm. A mold release film (5 cm × 10 cm) was placed on top, so that its surface was in contact with an exposed section (the adhesive side) of the underside (the aluminum plate side). A cardboard sheet (5 cm × 10 cm) with a thickness of 1 mm was then placed on top (on the surface side, to be in contact with a mold) to create a laminated specimen. The laminated specimen was subjected to pressure in a machine, heated to 180°C, and then subjected to pressure of 5 MPa for 5 minutes.After pressure was applied, the cardboard backing was removed from both sides, and the surface of the aluminum plate before pressure and the surface of the aluminum plate in contact with the mold release film after pressure were analyzed using X-ray photoelectron spectroscopy (XPS). From the analysis results, the ratio of the peak area of ​​aluminum atoms on the surface of the aluminum plate after removal to the peak area of ​​aluminum atoms on the surface before pressure was obtained (Al peak area after pressure / Al peak area before pressure).

[0251] For the XPS, a QuanteraSXM-type X-ray photoelectron spectroscopy system manufactured by ULVAC-PHI, Inc., was used. Monochromatic AlKα radiation at 15 kV and 25 W was used as the X-ray source; the X-ray surface-to-photoelectron detection angle was set to 45 degrees; the photoelectron transmission energy was set to 114 eV; the number of measurements was 10; and the analysis area was set to 0.5 mm × 0.5 mm. The (Al element peak area before pressure / Al element peak area after pressure) was obtained from the average of triple measurements using the peak intensities of Al (1s) detected under the above conditions. (Sealing test)

[0252] The sealing test was performed using a sealing device of the same design as that shown in Fig. 3 (Transmission Form Device G-LINE Manual System, manufactured by APIC YAMADA CORPORATION), executed.

[0253] Ten times ten times ten semiconductor chips, each 1 mm × 1 mm thick and 0.1 mm thick, were mounted on a 50 mm × 50 mm printed circuit board and subjected to a sealing test. The same epoxy resin composition used in the preceding evaluation of the release force of an epoxy resin at 180°C was employed as the curing resin. The mold release film was applied in a roll-to-roll process on 100 mm wide rollers.

[0254] After arranging the printed circuit board with semiconductor chips mounted on it in a lower mold, the mold release film was vacuum-suctioned to an upper mold. The mold was then clamped under the conditions described below, and a curable resin was injected. After applying pressure for 5 minutes, the mold was opened, and the semiconductor device was removed. The separation between the mold release film and the resin-sealed section (the cured product of the curable resin), as well as the appearance of the exposed sections of the semiconductor chip, were visually inspected and evaluated according to the standards described below. Furthermore, the charge voltage of the semiconductor device was measured. <abdicht-bedingungen> Form clamping pressure: 0.5 MPa per semiconductor chip. Transmission pressure: 5 MPa. Molding temperature (sealing temperature): 180°C. <Abgelöster Zustand zwischen der Formtrennfolie und dem Harz-gesiegelten Abschnitt> ◯ (good): correctly replaced. × (bad): not detached correctly, and the circuit board was outside the lower shape. <Aussehen des exponierten Abschnitts des Halbleiterchips> ◯ (good): Resin coverage or transfer of migrating substance from the film is less than two. × (bad): Resin coating or transfer of migrating substance from the film is more than two. <Aufladungs-Spannung des Halbleiter-Bauelements nach Abdichten>

[0255] The charge voltage of the removed semiconductor device was measured at a measuring distance of 10 mm using a non-contact surface potential meter, model 520-1 (manufactured by TREK JAPAN). [Materials used](substrate)

[0256] ETFE film: Fluon (registered trademark) ETFE C-88AXP (manufactured by Asahi Glass Company, Limited) was fed into an extruder equipped with a T-nozzle and drawn between a pressure roller with surface irregularities and a metal roller with a mirror surface to form a film with a thickness of 50 µm. The temperature of the extruder and T-nozzle was 320°C, and the temperature of the pressure roller and metal roller was 100°C. The surface roughness (Ra) of the resulting film was 2.0 µm on the pressure roller side and 0.2 µm on the mirror surface side. The mirror surface was corona-treated so that the wetting stress would be at least 40 mN / m according to ISO 8296:1987 (JIS K6768:1999).

[0257] The storage elasticity modulus (180°C) of the ETFE film was 40 MPa. (Materials for an adhesive layer)<Hydroxygruppe-enthaltendes Acrylpolymer> Acrylic polymer 1: Nissetsu (registered trademark) KP2562 (manufactured by Nippon Carbide Industries Co., Inc.). Acrylic polymer 2: TERPLUS (registered trademark) N3508 (manufactured by Otsuka Chemical Co., Ltd.). Acrylic polymer 3: TEISANRESIN (registered trademark) WS-023 (manufactured by Nagase ChemteX Corporation).

[0258] For each of the acrylic polymers 1 to 3, the molecular weight, hydroxy value, acid value, glass transition temperature Tg and crosslinkable functional group equivalent amount are shown in Table 1. [Table 1] Copolymer composition Amount of solids content (mass %) Mass average molecular weight Hydroxy value (mgKOH / g) Acidity value (mg KOH / g) Tg(°C) Networkable functional groups equivalent quantity (g / mol) Acrylic polymer 1 2-Ethylhexyl acrylate / Hydroxybutyl acrylate = 84 / 16 (mol ratio) 35 200 000 70 0 -25 800 Acrylic polymer 2 Butyl acrylate / 2-Hydroxybutyl acrylate = 98 / 2 (molar ratio) 21 600 000 20 0 -55 2 805 Acrylic polymer 3 Ethyl acrylate / Butyl acrylate / Acrylonitrile / 2-Hydroxyethyl acrylate = 45 / 20 / 28 / 5 / 3 (molar ratio) 30 500 000 13 20 -10 1 700 <Polyfunktionelle Isocyanat-Verbindung>

[0259] Polyfunctional isocyanate compound 1: Nissetsu CK157 (manufactured by Nippon Carbide Industries Co., Inc.), solids content: 100%, hexamethylene diisocyanate of the isocyanurate type, NCO content: 21 wt%.

[0260] Polyfunctional Isocyanate Compound 2: Coronate (registered trademark) HXR (manufactured by Tosoh Corporation), solids content: 100%, hexamethylene diisocyanate of the isocyanurate type, NCO content: 22 wt%.

[0261] Polyfunctional isocyanate compound 3: Coronate L (manufactured by Tosoh Corporation), solids content: 75%, polyisocyanate with 3 mol tolylene diisocyanate (TDI) reacted with one mol trimethylolpropane, NCO content: 13.5 wt%. <Antistatisches Mittel>

[0262] Antistatic agent 1: HTCP-200T (manufactured by Japan Carlit Co., Ltd.), solids content: 8%, a toluene solution of a conductive polythiophene.

[0263] Antistatic agent 2: Sankonol (registered trademark) MEK-50R (manufactured by Sanko Chemical Industry Co., Ltd.), solids content: 50%, lithium bistrifluoromethanesulfonylimide.

[0264] Antistatic agent 3: Sankonol (registered trademark) AD2600-50R (manufactured by Sanko Chemical Industry Co., Ltd.), solids content: 100%, a mixture of polyethylene glycol bis(2-ethylhexoate) and lithium bistrifluoromethanesulfonylimide. (Materials for antistatic layer)

[0265] Antistatic agent-containing material: ARACOAT (registered trademark) AS601D (manufactured by Arakawa Chemical Industries, Ltd.), solids content: 3.4%, conductive polythiophene: 0.4%, acrylic resin: 3.0%.

[0266] Curing agent: ARACOAT (registered trademark) CL910 (manufactured by Arakawa Chemical Industries, Ltd.), solids content: 10%, polyfunctional aziridine compound. [Example 1]

[0267] A coating fluid for an adhesive layer was prepared by mixing 100 parts by mass of acrylic polymer 1, 4 parts by mass of polyfunctional isocyanate compound 1, and ethyl acetate. The amount of ethyl acetate used was such that the solids content of the coating fluid for an adhesive layer would be 25% by mass.

[0268] Corona treatment was applied to the surface of the ETFE film. The coating fluid for an adhesive layer was applied and dried using an engraving applicator to form an adhesive layer 2 µm thick. Coating was carried out using a direct engraving process with a roller with a 150# grid, measuring 100 mm in diameter × 250 mm in width and 40 µm in depth, as the engraving plate. Drying was performed at 100°C for 1 minute by passing the film through a roller-type drying oven at an airflow of 19 m / s. Aging was then carried out at 40°C for 120 hours to obtain a mold release film. [Examples 2 to 17]

[0269] In the same manner as in Example 1, with the exception of changing the type of hydroxy group-containing acrylic polymer and the type or amount of the polyfunctional isocyanate compound, as shown in Tables 2 and 3, a coating liquid for an adhesive layer (solids content: 25 wt%) was prepared and a mold release film was obtained.

[0270] Tables 2 and 3 show the mixing quantity of each of the acrylic polymers 1 to 3 and polyfunctional isocyanate compounds 1 to 3 in relation to the total quantity of the liquid medium. [Example 18]

[0271] An antistatic coating fluid (solids content: 2 wt%) was produced by mixing 100 parts by mass of ARACOAT AS601D, 10 parts by mass of ARACOAT CL910 and 100 parts by mass of methanol.

[0272] The antistatic coating liquid was applied to the surface of the corona-treated ETFE film using an engraving applicator and allowed to dry, forming an antistatic layer 0.1 µm thick. The coating was applied using a direct engraving process with a roller featuring a 150# grid, measuring 100 mm in diameter × 250 mm in width and 40 µm in depth, as the engraving plate. Drying was carried out at 100°C for one minute by passing the film through a roller-type drying oven at an airflow of 19 m / s.

[0273] Then, an adhesive layer was formed on the antistatic layer in the same way as in Example 1 to obtain a mold release film. [Examples 19 to 21]

[0274] In Examples 19 to 21, an antistatic agent was incorporated into the coating fluid for an adhesive layer (solids content: 25 wt%). Specifically, the antistatic agent-containing coating fluid for an adhesive layer was prepared in the same manner as in Example 1, with the exception of changing the type of hydroxyl-containing acrylic polymer, the type of polyfunctional isocyanate compound, and the type or amount of the antistatic agent, as shown in Tables 2 and 3, and a mold release film was obtained.

[0275] The amount of each material used in the coating liquid for an adhesive layer in each example, the number of moles of OH groups, the number of moles of COOH, the number of moles of NCO, M COOH / (M NCO - M OH ), M NCO / (M COOH + M OH The storage elasticity modulus (180°C) of the adhesive layer in the obtained mold release film, the insolubility of the adhesive layer, the surface resistance of the adhesive layer, the release force (180°C) of the epoxy resin, the adhesion force (180°C), the migration property, the state of separation between the mold release film and the resin-sealed section, the appearance of the exposed section of the semiconductor chip, and the charge voltage of the semiconductor device after sealing are shown in Tables 2 and 3. [Table 2] [Table 2] (continued) [Table 3] 12 13 14 15 16 17 18 19 20 21 Hydroxy group-containing acrylic polymer Acrylic polymer 1 - - - - - - 100 100 100 100 Acrylic polymer 2 - - - - - - - - - - Acrylic polymer 3 100 100 100 100 100 100 - - - - Polyfunctional isocyanate compound Polyfunctional isocyanate compound 1 - - - - - - 6 6 6 6 Polyfunctional isocyanate compound 2 - - - 3 10 15 - - - - Polyfunctional isocyanate compound 3 5 13 20 - - - - - - - Antistatic agent Antistatic agent 1 - - - - - - - 70 - - Antistatic agent 2 - - - - - - - - 8 - Antistatic agent 3 - - - - - - - - - 8 M OH (Part of moles in the mixture) 0.007 0,007 0,007 0,007 0.007 0,007 0,044 0,044 0,044 0,044 M COOH (Part of moles in the mixture) 0.011 0,011 0,011 0,011 0,011 0,011 0 0 0 0 M NCO (Part of moles in the mixture) 0.012 0,031 0,048 0,016 0,052 0,079 0,030 0,030 0,030 0,030 M COOH / (M COOH - M OH ) 2.1 0,4 0,3 1,2 0,2 0,1 0 0 0 0 M NCO / (M COOH + M OH ) 0.68 1,78 2,73 0,89 2,97 4,45 0,69 0,69 0,69 0,69 [Table 3] (continued)

[0276] As shown in the preceding results, the release force (at 180°C) of the epoxy resin in the mold release films in Examples 1 to 3, 5 to 8, 13, 14, 16, and 18 to 21 was at most 0.1 N / cm, demonstrating excellent separability against the resin-sealed section. Furthermore, it was at least 0.005 N / cm, indicating that the curable resin was less likely to have seeped in.

[0277] With these mold release films, the adhesive force (180°C) was 0.05 to 0.1 N / 24 mm, demonstrating excellent adhesion to the exposed section of the semiconductor chip and excellent release properties from the exposed section.

[0278] Furthermore, with these mold release films, the migration property was at least 0.6, and it was shown that the migration from the adhesive layer to the exposed section of the semiconductor chip was low.

[0279] In the current sealing test, the detached condition between the mold release film and the resin-sealed section and the evaluation result of the appearance of the exposed section of the semiconductor chip were also good.

[0280] Furthermore, in the case where the mold release films in Examples 18 to 21 were used, wherein the adhesive layer contains an antistatic agent, or an antistatic layer is formed between the substrate and the adhesive layer, the charge voltage of the semiconductor device after sealing was low, and it exhibited excellent antistatic function.

[0281] On the other hand, in the case of the mold release film in Example 4, where M NCO / (M COOH + M OH The adhesive strength (at 180°C) was low, and the appearance of the exposed section of the semiconductor chip was also poor. This was determined because the crosslinking density was too high and the elastic modulus of the adhesive layer was high, resulting in poor adhesion. Consequently, the bond between the exposed section and the adhesive layer was insufficient, and the curable resin penetrated the exposed section.

[0282] In the case of the mold release films in Examples 9 to 11, using acrylic polymer 2 with a crosslinkable functional group equivalent exceeding 2000 g / mol, the release force (180°C) of the epoxy resin was high; the adhesion (180°C) was high, and the migration properties were poor. Furthermore, the separation between the mold release film and the resin-sealed section, and the resulting appearance of the exposed section of the semiconductor chip, were also poor. This is because the high crosslinkable functional group equivalent, the low crosslink density, and therefore the insufficient elastic modulus of the adhesive layer resulted in strong tackiness for the epoxy resin or the exposed section. It is also noted that, due to the low crosslink density, the low molecular weight material contained in the adhesive layer bleed out and contaminated the chip.Furthermore, it was found that when a large amount of a crosslinking agent (polyfunctional isocyanate compound) was incorporated to increase the crosslinking density as in Examples 10 and 11, an unreacted crosslinking agent remained and migrated to the exposed section, contaminating the seal.

[0283] In the case of the mold release film in Example 12, where M COOH / (M NCO - M OH ) 2.1 was and the mold release film in Example 15, where M COOH / (M NCO - M OH ) 1.2, the release force (180°C) of the epoxy resin was high. Furthermore, the condition of the separation between the mold release film and the resin-sealed section was poor. This is because free carboxyl groups remained in the adhesive layer, and the carboxyl and epoxy groups of the curable resin had reacted to form the adhesive or bond.

[0284] In the case of the mold release film in Example 17, where M NCO / (M COOH + M OH When the value was 4.45, the migration property was poor. Furthermore, the appearance of the exposed section of the semiconductor chip was also poor. This was determined because a large amount of crosslinking agent was incorporated to increase the crosslink density, but some of the agent remained unreacted and migrated to the exposed section, contaminating it during sealing.

[0285] The entire disclosure of Japanese patent application no. 2015-022691, filed on February 6, 2015, as contained in the description, claims, drawings and abstract, is hereby incorporated in its entirety by this notice. Reference symbol list 1 mold release film, 3 Substrate, 5 adhesive layers, 10 semiconductor components, 11 Substrate, 13 Semiconductor chip, 15 points, 17 resin-sealed section, 19 hardened product, 20 upper form, 21 cavity, 23 Cavity surface, 25 Resin introduction section, 30 lower form, 31 Substrate exchange unit, 33 Resin exchange unit, 35 stamps, 40 hardenable resin, 50 semiconductor components, 51 substrate, 53 Semiconductor chips, 55a to 55b Bond wire, 57 a resin-sealed section, 59 sealing glasses, 61 rib component, 100 sealing bodies

Claims

[1] Film (1) comprising a substrate (3) and an adhesive layer (5), provided on a surface of the substrate (3), characterized by , that the storage elasticity modulus at 180°C of the substrate (3) is from 10 to 100 MPa, the adhesive layer (5) is a reaction-cured product of a composition for an adhesive layer (5) comprising an acrylic polymer with hydroxyl groups and a polyfunctional isocyanate compound, the total equivalent amount of hydroxyl and carboxylic groups in the acrylic polymer is at most 2000 g / mol, in the composition for an adhesive layer (5) M COOH / (M NCO - M OH ) from 0 to 1.0 is and M NCO / (M COOH + M OH ) from 0.4 to 3.

5. [2] Foil (1) according to claim 1, wherein the mass mean molecular weight of the acrylic polymer is from 100,000 to 1,200,000. [3] Film (1) according to claim 1 or 2, wherein the polyfunctional isocyanate compound has an isocyanurate ring. [4] Film (1) according to one of claims 1 to 3, wherein the storage elasticity modulus at 180°C of the adhesive layer (5) is 2 to 20 MPa. [5] Film (1) according to any one of claims 1 to 4, wherein the degree of insolubility of the adhesive layer (5) obtainable from the basis weight W1 (g / m²) by the following formula 2 ) the adhesive layer (5) and the basis weight W2 (g / m²) 2 ) of the adhesive layer (5) remaining after the film has been subjected to the following dissolution test, is from 40 to 90%: Degree of insolubility(%)=(W2 / W1)×100 [6] Film (1) according to any one of claims 1 to 5, wherein the substrate (3) contains an ethylene tetrafluoroethylene copolymer. [7] Film (1) according to any one of claims 1 to 6, wherein the thickness of the substrate (3) is from 50 to 100 µm and the thickness of the adhesive layer (5) is from 0.5 to 15 µm. [8] Film (1) according to any one of claims 1 to 7, wherein the composition for an adhesive layer (5) further comprises an antistatic agent. [9] Film (1) according to any one of claims 1 to 7, comprising an antistatic layer between the substrate (3) and the adhesive layer (5). [10] Film (1) according to any one of claims 1 to 9, which is a mold release film (1) to be used in a sealing process for producing a semiconductor device (10) sealed with a sealing resin. [11] Foil (1) according to claim 10, wherein the semiconductor device (10) sealed with a sealing resin is a semiconductor device in which part of the surface of a semiconductor chip (13), a source electrode or a sealing glass (59) is exposed by the sealing resin. [12] Film (1) according to claim 10 or 11, which is a mold release film (1) to be used such that when the curable resin (40) has been cured and formed into the sealing resin in a mold in the sealing process, the substrate side surface (1b) of the mold release film (1) is in contact with the mold of the inner surface (23), and the surface (1a) of the adhesive layer (5) of the mold release film (1) is in contact with a part of the surface of a semiconductor chip (13). [13] Film (1) according to any one of claims 1 to 9, which is a mold release film (1) to be used in the sealing process below: Sealing process: A sealing process comprising a step of placing the mold release film (1) onto the surface of a mold (20) to be in contact with a curable resin (40) so that its substrate side surface (1b) is in contact with the mold surface (23), and placing into the mold (30) a structure with a semiconductor chip (13) and, if required, with a source electrode or a sealing glass (59), a step to clamp the form (20, 30) so that the form (20) is in contact with the surface of the semiconductor chip (13), the source electrode or the sealing glass (59) via the form release film (1), a step to fill and harden a curable resin (40) into the mold (20, 30) while clamping the mold to form a resin-sealed section (17) in order to obtain a sealing body (100) with the structure and the resin-sealed section (17) and wherein part of the surface is exposed by the semiconductor chip (13), the source electrode or the sealing glass (59), and a step to separate the sealing body (100) from the mold. [14] Method for producing the film (1) as defined in any one of claims 1 to 9, characterized by , that it comprises a step to form an adhesive layer (5) by applying and drying a coating liquid for an adhesive layer (5), comprising the composition for an adhesive layer (5) and a liquid medium, on a surface of a substrate (3). [15] Method for manufacturing a semiconductor device (10) comprising a semiconductor chip (13) and a resin-sealed section (17), and if required, a source electrode or a sealing glass (59), wherein a part of the surface of the semiconductor chip (13), the source electrode or the sealing glass (59) is exposed, characterized by that it includes a step for placing the film (1), as defined in any one of claims 1 to 9, onto the surface of a mold (20) to be in contact with a curable resin (40) such that its substrate side surface (1b) is in contact with the mold surface (23), and placing it into the mold (30) of a structure with a semiconductor chip (13) and, if required, with a source electrode or a sealing glass (59), a step to clamp the form (20, 30) so that the form (20) is in contact with the surface of the semiconductor chip (13), the electrode or the sealing glass (59) via the form release film (1), a step for filling and curing a curable resin (40) into the mold (20, 30) while clamping the mold (20, 30) to form a resin-sealed section (17) in order to obtain a sealing body (100) with the structure and the resin-sealed section (17), wherein part of the surface of the semiconductor chip (13), the source electrode or the sealing glass (59) is exposed, and a step to separate the sealing body (100) from the form.

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