CN109153155B - Mold release film - Google Patents
Mold release film Download PDFInfo
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- CN109153155B CN109153155B CN201780031301.2A CN201780031301A CN109153155B CN 109153155 B CN109153155 B CN 109153155B CN 201780031301 A CN201780031301 A CN 201780031301A CN 109153155 B CN109153155 B CN 109153155B
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- meth
- acrylate
- release film
- release layer
- filler
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/68—Release sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2398/00—Unspecified macromolecular compounds
- B32B2398/10—Thermosetting resins
Abstract
A release film comprising a base material and a release layer provided on the base material and containing a resin component and a filler, wherein the filler has a volume average particle diameter A (μm) and 1m per the release layer2Mass B (g/m) of2) The ratio (A/B) is less than or equal to 1.
Description
Technical Field
The present invention relates to a release film.
Background
The semiconductor chip is generally sealed with a resin for the purpose of shielding and protecting from the outside air, and is mounted on a substrate in a state of a molded product called a package. The molded product is generally molded as a package molded product of chips connected by a runner as a flow path of a sealing resin. In this case, the releasability of the molded article from the mold is obtained by the structure of the mold used for molding the molded article, the addition of a release agent to the sealing resin, and the like.
On the other hand, due to demands for miniaturization, multi-pin packaging, and the like, there are increasing demands for packaging such as a Ball Grid Array (BGA) system, a Quad Flat no-lead (QFN) system, a Wafer Level Chip Size Package (WL-CSP) system, and the like. In the QFN system, a resin mold release film is used to secure a gap (standoff) and prevent burrs from being generated at a terminal portion due to a sealing material, and in the BGA system and the WL-CSP system, a mold release property of a package from a mold is improved (for example, see patent document 1). A molding method using such a release film is referred to as "film-assisted molding".
In the fields of the BGA method and WL-CSP method, a molding method is being changed from the conventional transfer molding method to the compression molding method for the purpose of increasing the size and efficiency of 1 shot (shot).
In addition, the following processes have also been studied, namely: regardless of these molding methods, a functional sheet having another function is mounted on a mold release film in advance, and molding is performed in a molding step so that the functional sheet is disposed on a semiconductor package (see, for example, patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2002-158242
Patent document 2: japanese laid-open patent publication No. 2007-287937
Patent document 3: WO2013/183671 publication
Disclosure of Invention
Problems to be solved by the invention
In the methods described in patent documents 2 and 3, the functional sheet can be collectively disposed on the semiconductor package in the step of molding the semiconductor package. On the other hand, in actual processes, it is desirable that the release film satisfies the performance of retaining the functional sheet without peeling from the release layer in the processes up to the molding process and the performance of releasing the functional sheet satisfactorily in the molding process.
At present, a release film widely used in a compression molding method is not imparted with a property of retaining a functional sheet. Therefore, in order to mold a functional sheet on a semiconductor package in a molding step using this release film, it is necessary to provide the functional sheet after disposing the release film in a mold. However, the step of providing a functional sheet on a release film disposed in a heated mold having a complicated shape is difficult to automate, and there is a problem that the operation efficiency and safety are poor in manual operation.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a mold release film having excellent performance in which the performance of a functional sheet is maintained until a molding step and the performance of releasing the functional sheet in the molding step is excellent.
Means for solving the problems
The method for solving the above problem includes the following embodiments.
< 1 > A mold release film comprising a base material and a mold release layer provided on the base material and containing a resin component and a filler, wherein the filler has a volume average particle diameter A (μm) and 1m per the mold release layer2Mass B (g/m) of2) The ratio (A/B) is less than or equal to 1.
< 2 > the mold release film according to < 1 >, wherein the filler has a volume average particle diameter A of 1 to 50 μm.
< 3 > the release film according to < 1 > or < 2 >, the above release layer being present every 1m2Has a mass B of 0.1g/m2～100g/m2。
< 4 > the release film according to any one of < 1 > to < 3 >, wherein the resin component contains a thermosetting resin.
< 5 > the mold release film according to any one of < 1 > to < 4 >, further comprising a crosslinking agent, wherein the content of the crosslinking agent is 1 to 10 parts by mass based on 100 parts by mass of the resin component.
< 6 > the release film according to any one of < 1 > to < 5 >, wherein the substrate contains at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate.
Effects of the invention
According to the present invention, a release film having excellent performance of retaining a functional sheet until a molding step and releasing the functional sheet in the molding step can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of a release film holding a functional sheet.
Fig. 2 is a view schematically showing a cross section of the apparatus in the case of molding by transfer molding using a release film.
Fig. 3 is a view schematically showing a cross section of the apparatus in the case of molding by transfer molding using a release film.
Fig. 4 is a view schematically showing a cross section of the apparatus in the case of molding by transfer molding using a release film.
Detailed Description
Hereinafter, embodiments for carrying out the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps) are not essential unless otherwise explicitly stated. The same applies to values and ranges, and the invention is not limited thereto.
In the present specification, the term "step" includes a step that is independent of other steps, and includes a step that can be achieved as long as the purpose of the step is achieved, even when the step is not clearly distinguished from other steps.
In the present specification, a numerical range expressed by "to" includes numerical values before and after "to" as a minimum value and a maximum value, respectively.
In the numerical ranges recited in the present specification, the upper limit or the lower limit recited in one numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.
In the present specification, the content or content of each component in the composition refers to the total content or content of a plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.
In the present specification, the particle diameter of each component in the composition refers to a value of a mixture of a plurality of particles present in the composition, when the plurality of particles corresponding to each component are present in the composition, unless otherwise specified.
In the present specification, the term "layer" or "film" includes a case where the layer or the film is formed only in a part of a region except a case where the layer or the film is formed in the whole region when the region is observed.
In the present specification, the term "stacked" means that layers are stacked, and two or more layers may be bonded to each other, or two or more layers may be attached and detached.
In the present specification, "(meth) acryloyl group" means at least one of an acryloyl group and a methacryloyl group, "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid, and "(meth) acrylate" means at least one of acrylate and methacrylate.
< mold release film >
The release film of the present embodiment includes a base material, and a release layer provided on the base material and containing a resin component and a filler, wherein the volume average particle diameter a (μm) of the filler and 1m per the release layer2Mass B (g/m) of2) The ratio (A/B) is less than or equal to 1.
The release film of the present embodiment is excellent in the performance of retaining the functional sheet until the molding step and the performance of releasing the functional sheet in the molding step. Therefore, the method can be suitably used for a method of disposing the functional sheet on the surface of the semiconductor package in, for example, a molding process of the semiconductor package.
The reason why the release film of the present embodiment is excellent in the performance of retaining the functional sheet until the molding step and the performance of releasing the functional sheet in the molding step is not necessarily clear, but is presumably due to appropriate tackiness imparted by the resin component contained in the release layer and appropriate surface irregularities imparted by the filler contained in the release layer.
From the viewpoint of maintaining the performance of the functional sheet, the volume average particle diameter a (μm) of the filler contained in the release layer and 1m per release layer2Mass B (g/m) of2) The ratio of (A) to (B) is preferably 1.0 or less, more preferably 0.7 or less, and still more preferably 0.5 or less.
The lower limit of A/B is not particularly limited. For example, when the pressure at the time of molding is to be increased or when the processed surface of the outermost surface of the semiconductor package is to be roughened depending on the type and application of the semiconductor package, the value of a/B is preferably large from the viewpoint of imparting high mold release performance to the mold release film or roughening the surface. For example, it is preferably 0.3 or more, more preferably 0.5 or more.
[ Release layer ]
The releasing layer contains a resin component and a filler, and the volume average particle diameter A (μm) of the filler and 1m per the releasing layer2Mass B (g/m) of2) The ratio (A/B) is less than or equal to 1.
In the present embodiment, the volume average particle diameter a (μm) of the filler is a value measured by a light diffraction/scattering method, and is defined as a particle diameter (D50) when the cumulative particle diameter from the smaller diameter side in the volume-based particle size distribution is 50%.
Every 1m of the release layer2Mass B (g/m) of2) The range (b) is not particularly limited and may be selected in consideration of the relationship with the average particle diameter of the filler. For example, it is preferably 0.1g/m2～100g/m2More preferably 1g/m2～50g/m2。
If the release layer is present every 1m2Has a mass B of 0.1g/m or more2The releasing layer contains a sufficient amount of resin component, and can sufficiently obtain flexibility and extensibility required in the molding step, and the releasing layer can be inhibited from separating from the base materialTendency to peel or fall off. Further, flexibility is sufficiently obtained, and the holding ability of the functional sheet tends to be well maintained.
If the release layer is present every 1m2Has a mass B of less than or equal to 100g/m2Then, the following phenomenon tends to be suppressed: the release layer becomes too thick, and the flatness of the release film is impaired by thermal shrinkage stress at the time of thermal curing. In addition, the following phenomena tend to be suppressed: the release layer becomes too soft, and the functional sheet to be mounted is embedded in the release layer and cannot be accurately disposed on the surface of the package.
In the present embodiment, the thickness of the release layer is determined for each 1m2Mass B (g/m) of2) The method of (3) is not particularly limited. For example, the area may be 100cm2The mass (g) of the release layer is determined from the mass (g) of the release film cut out in the above-described manner (for example, 10 cm. times.10 cm), and the mass (g) of the base material from which the release layer has been removed using an organic solvent or the like, and the obtained value is multiplied by 100 to convert the value into a value per 1m2The mass (g) of the release layer (2) was determined.
The thickness of the release layer is not particularly limited. For example, it is preferably 0.1 μm to 100. mu.m. If the thickness of the release layer is 0.1 μm or more, the resin component can sufficiently hold the filler, and therefore, there is a tendency that troubles such as the filler falling off and mixing into the package during molding are not easily caused, and the semiconductor package can be stably produced. If the thickness of the releasing layer is less than or equal to 100 μm, the raw material for the releasing layer can be saved, which is preferable from the viewpoint of production cost.
In the present embodiment, the thickness of the release layer is a number average value of values obtained by measuring 5 points at arbitrary positions. The thickness of the release layer can be measured using a general micrometer, for example.
The release layer may have irregularities on the outer surface (the surface opposite to the substrate side surface) depending on the application. When the release layer has irregularities on the outer surface, the release layer preferably has an arithmetic average roughness (Ra) of 0.5 to 5 μm on the outer surface (the surface opposite to the substrate side surface) from the viewpoint of uniformity of the outer appearance of the package surface. Further, the ten-point average roughness (Rz) of the outer surface is preferably 5 μm to 50 μm.
The arithmetic average roughness (Ra) and the ten-point average roughness (Rz) of the outer surface of the release layer in the present embodiment may be, for example: the surface roughness measurement apparatus (for example, Minsaka institute, model SE-3500) was used to measure the diameter of the tip of the stylus: 2 μm, transfer speed: 0.5mm/s and scanning distance: the measurement was carried out under the condition of 8mm, and the measurement result was analyzed by the method specified in JIS B0601(2013) or ISO 4287(1997) to obtain a value.
The outer surface of the release layer preferably has a tack force (タック force) of 1.0gf or more at 25 ℃. When the viscosity at 25 ℃ of the outer surface is 1.0gf or more, the performance of holding the functional sheet until the molding step tends to be more excellent.
The outer surface of the release layer preferably has a viscosity of 20.0gf or less at 170 ℃. When the external surface has a viscosity of 20.0gf or less at 170 ℃, the release performance of the functional sheet tends to be more excellent in the molding step.
The adhesive force (gf) of the outer surface of the release layer in the present embodiment may be a value measured by measuring a front load of 10gf, a front load time of 1 second, and a rise rate at the time of measurement of 600mm/min using, for example, a viscosity tester (manufactured by Rhesca corporation) and a probe having a diameter of 5 mm.
The content of the filler in the release layer is not particularly limited. For example, it is preferably 1.0 to 50.0 mass% of the total mass of the release layer. If the content of the filler is 1.0 mass% or more of the total mass of the release layer, the surface of the molded semiconductor package tends to be finished to have a uniform appearance without unevenness by the surface roughness of the release layer. If the content of the filler is less than or equal to 50.0 mass% of the total mass of the release layer, the resin component can sufficiently hold the filler component, and therefore, a defect that the filler component falls off and is mixed into the package during molding tends to be less likely to occur, and the semiconductor package can be stably produced.
The release layer may contain other components such as a solvent, an anchor improving agent, a crosslinking accelerator, an antistatic agent, and a colorant, in addition to the resin component and the filler, as required.
(resin component)
The kind of the resin component contained in the releasing layer is not particularly limited. For example, the resin may be a resin (thermosetting resin) having a property of undergoing a crosslinking reaction by heating and curing. Examples of the resin that can be used as the resin component include acrylic resins, olefin resins, styrene resins, acrylonitrile resins, silicone resins, epoxy resins, cyanate resins, maleimide resins, allylnadimide resins, phenol resins, urea resins, melamine resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, resorcinol-formaldehyde resins, xylene resins, furan resins, polyurethane resins, ketone resins, triallyl cyanurate resins, isocyanate resins, tris (2-hydroxyethyl) isocyanurate-containing resins, triallyl trimellitate-containing resins, thermosetting resins synthesized from cyclopentadiene, thermosetting resins obtained by trimerization of aromatic dicyandiamide, and the like. The resin component contained in the release layer may be only one kind or two or more kinds.
The releasing layer preferably contains at least one selected from the group consisting of acrylic resins, olefin resins, styrene resins, and acrylonitrile resins as a resin component from the viewpoint of releasability from the semiconductor package.
Examples of the acrylic resin include homopolymers or copolymers containing at least a (meth) acrylic monomer in a polymerization component. Specific examples thereof include poly (meth) acrylic acid and poly (meth) acrylate.
As the (meth) acrylic monomer constituting the acrylic resin, there can be mentioned: (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, cyclopentyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-fluoroethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like.
Examples of the monomer other than the (meth) acrylic monomer constituting the acrylic resin include styrene, α -methylstyrene, cyclohexylmaleimide, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, and the like.
The olefin resin may be a homopolymer of an olefin monomer or an olefin monomer, or a copolymer containing an olefin monomer or an olefin monomer as a polymerization component. Specific examples thereof include polyolefins such as polyethylene, polypropylene and polymethylpentene.
Examples of the styrene resin include homopolymers of styrene or styrene derivatives, and copolymers containing styrene or styrene derivatives as a polymerization component. As the styrene derivative, there can be mentioned: alkyl-substituted styrenes having an alkyl chain such as α -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 2-ethylstyrene, 3-ethylstyrene and 4-ethylstyrene, halogen-substituted styrenes such as 2-chlorostyrene, 3-chlorostyrene and 4-chlorostyrene, fluorine-substituted styrenes such as 4-fluorostyrene and 2, 5-difluorostyrene, and vinylnaphthalene.
Examples of the acrylonitrile resin include homopolymers of (meth) acrylonitrile monomers and copolymers containing (meth) acrylonitrile monomers as a polymerization component.
In the case of using a thermosetting resin as the resin component, a crosslinking agent may be used. In the case of using a crosslinking agent, the content of the crosslinking agent with respect to 100 parts by mass of the thermosetting resin is not particularly limited. For example, the content of the crosslinking agent may be 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the thermosetting resin.
The kind of the crosslinking agent is not particularly limited, and may be selected according to the kind of the thermosetting resin, a desired curing speed, and the like. For example, when an acrylic resin is used as the thermosetting resin, it can be selected from known crosslinking agents such as isocyanate compounds, melamine compounds, and epoxy compounds.
[ Filler ]
The volume average particle diameter of the filler is set so long as the volume average particle diameter A (. mu.m) and the volume average particle diameter of the release layer per 1m are satisfied2Mass B (g/m) of2) The condition that the ratio (A/B) is 1 or less is not particularly limited. For example, it is preferably 1 μm to 50 μm.
When the volume average particle diameter of the filler is 1 μm or more, there is a tendency that sufficient unevenness can be formed on the outer surface of the release layer, and the uniformity of the appearance of the surface of the molded semiconductor package is improved, and flow marks of the sealing material can be suppressed. If the volume average particle diameter of the filler is 50 μm or less, the thickness of the releasing layer required for suppressing the falling-off of the filler from the releasing layer tends to be suppressed.
The upper limit of the volume average particle diameter of the filler is preferably 50 μm, and more preferably 20 μm, from the viewpoint of the appearance of the surface of the semiconductor package. The lower limit of the volume average particle diameter of the filler is preferably 1 μm from the viewpoint of adjusting the surface roughness of the molded semiconductor package.
The shape of the filler contained in the releasing layer is not particularly limited. Examples thereof include spherical, elliptical and irregular shapes.
The filler is not particularly limited as long as it can maintain its form in a state of being contained in the release layer (i.e., is hardly dissolved in an organic solvent used for forming the release layer, a resin component contained in the release layer, or the like), and may be a filler composed of an organic substance, a filler composed of an inorganic substance, or a filler composed of both an organic substance and an inorganic substance. The filler contained in the releasing layer may be only one kind, or two or more kinds.
Examples of the inorganic material to be used as a filler material include: metals such as silver, gold, and copper, and silica, alumina, titania, and iron oxide. The inorganic substance may or may not have conductivity.
When a filler composed of an inorganic substance is used, an inorganic ion exchanger may be used in combination. As the inorganic ion exchanger, the following are effective: it was confirmed that ions (Na) extracted in the aqueous solution were captured when the release layer film was extracted in hot water+、K+Cl-, F-, RCOO-, Br-, etc., and R is alkyl, aryl, etc.). Examples of such an inorganic ion exchanger include: natural minerals such as naturally occurring zeolite, acid clay, dolomite, hydrotalcite, and synthetic zeolite.
Examples of the organic substance to be used as a filler material include acrylic resins, imide resins, amide imide resins, olefin resins, styrene resins, carbonate resins, silicone resins, and ABS resins. These resins are preferably in a state of being cured by a crosslinking reaction.
Among the above fillers, a filler containing an acrylic resin in a state of being cured by a crosslinking reaction (hereinafter, also referred to as a crosslinking-type acrylic resin) is preferable because it is excellent in dispersibility in a resin component and characteristics such as a shape, a particle diameter, and heat resistance of the filler can be easily adjusted by selecting a kind of a monomer to be a polymerization component.
The crosslinking acrylic resin is preferably a (meth) acrylic copolymer obtained by copolymerizing a (meth) acrylic monomer not containing a functional group such as butyl (meth) acrylate, ethyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate with a (meth) acrylic monomer having a functional group such as (meth) acrylic acid, hydroxyethyl (meth) methacrylate, meth) acrylamide, or (meth) acrylonitrile, or other monomers.
Examples of the (meth) acrylic monomer to be a polymerization component of the crosslinking-type acrylic resin include (1) a (meth) acrylic monomer having a chain alkyl group, (2) a (meth) acrylic monomer having an alicyclic skeleton, (3) a polyfunctional (meth) acrylic monomer, and (4) a (meth) acrylic monomer having a functional group. Hereinafter, each (meth) acrylic acid monomer will be described.
(1) (meth) acrylic acid monomer having chain alkyl group
Examples of the (meth) acrylic monomer having a chain hydrocarbon group include (meth) acrylates having a chain hydrocarbon group in an ester portion (hereinafter, the (meth) acrylate may be referred to as a (meth) acrylate).
Examples of the (meth) acrylate having a chain hydrocarbon group include (meth) acrylates having a chain hydrocarbon group having 1 to 20 carbon atoms. If the number of carbon atoms of the hydrocarbon group is 20 or less, the elastic modulus tends to be low. The number of carbon atoms is preferably 2 to 18 from the viewpoint of solubility of the acrylic polymer, and more preferably 4 to 18 from the viewpoint of heat resistance in the molding step. The chain hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms.
The chain hydrocarbon group may be linear or branched, and when it is branched, it preferably does not contain a tertiary carbon atom. Since the composition does not contain a tertiary carbon atom, the composition is less likely to suffer from mass reduction due to thermal decomposition at low temperatures, and is advantageous in terms of heat resistance.
Specific examples of the (meth) acrylate having a chain-like hydrocarbon group having 1 to 20 carbon atoms include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, 1-dodecyl (meth) acrylate, isostearyl (meth) acrylate, and the like.
(2) (meth) acrylic monomer having alicyclic skeleton
As the (meth) acrylic monomer having an alicyclic skeleton, a (meth) acrylate having an alicyclic skeleton can be mentioned. Examples of the alicyclic skeleton include a cycloalkane skeleton, a bicycloalkane skeleton, a norbornyl skeleton, and an isobornyl skeleton. Among them, from the viewpoint of improving transparency, a bicycloalkane skeleton and a norbornyl skeleton are preferable.
Specific examples of the (meth) acrylic monomer having an alicyclic skeleton include: cyclopentyl (meth) acrylate, (cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl methyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fenchyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [ 5.2.1.0.2,6]Decyl-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)2,6]Decyl-4-methyl ester, cyclodecyl (meth) acrylate, and the like.
From the viewpoint of heat resistance, preferred are cyclopentyl acrylate, cyclohexyl acrylate, isobornyl acrylate, norbornyl methyl acrylate, and tricyclo [5.2.1.0 ] acrylate2,6]Decyl-8-yl ester, acrylic acid tricyclo [5.2.1.02,6]Decyl-4-methyl ester, adamantyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, norbornyl methyl methacrylate, isobornyl methacrylate, bornyl methacrylate, menthyl methacrylate, fenchyl methacrylate, adamantyl methacrylate, dimethyladamantyl methacrylate, tricyclo [5.2.1.0 ] methacrylate2,6]Decyl-8-yl ester, tricyclo [5.2.1.0 ] methacrylate2,6]Decyl-4-methyl ester, cyclodecyl methacrylate, methylAcrylic acid phenyl norbornyl ester and the like.
Further, cyclopentyl acrylate, cyclohexyl acrylate, isobornyl acrylate, norbornyl methyl acrylate, tricyclo [5.2.1.0 ] acrylate are more preferable from the viewpoint of high heat resistance2,6]Decyl-8-yl ester, acrylic acid tricyclo [5.2.1.02,6]Deca-4-methyl ester, adamantyl acrylate, and the like.
(3) Multifunctional (meth) acrylic monomers
The polyfunctional (meth) acrylic monomer is not particularly limited as long as it has two or more (meth) acryloyl groups. As the polyfunctional (meth) acrylic monomer, there can be mentioned: (meth) acrylic monomer having two or more (meth) acryloyl groups and alicyclic skeleton, (meth) acrylic monomer having two or more (meth) acryloyl groups and aliphatic skeleton, and (meth) acryloyl group and di
A (meth) acrylic monomer having an alkylene glycol skeleton, a (meth) acrylic monomer having two or more (meth) acryloyl groups, and a functional group which the (meth) acrylic monomer having a functional group (4) described later can have, and the like.
Examples of the polyfunctional (meth) acrylic monomer include: cyclohexane-1, 4-dimethanol di (meth) acrylate, cyclohexane-1, 3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate (e.g., KAYARAD R-684, tricyclodecane dimethylol diacrylate, manufactured by Nippon Kabushiki Kaisha), tricyclodecane dimethanol di (meth) acrylate (e.g., A-DCP, tricyclodecane dimethanol diacrylate, manufactured by Newzhongmura chemical Co., Ltd.), Dicidol (meth) acrylate
Alkanediol di (meth) acrylate (e.g., KAYARAD R-604, manufactured by Nippon Kagaku K.K.)
Alkylene glycol diacrylateEtc.), neopentyl glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethylene oxide-modified 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (poly) ethylene oxide-modified neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide-modified bisphenol a type di (meth) acrylate (preferably polyethylene oxide-modified bisphenol a type di (meth) acrylate, more preferably ethylene oxide-modified bisphenol a type di (meth) acrylate of 5 to 15 moles), and (poly) ethylene oxide-modified phosphoric acid di (meth) acrylate.
(4) (meth) acrylic monomer having functional group
The (meth) acrylic monomer having a functional group includes a (meth) acrylic monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, an amide group, and an epoxy group in a molecule.
As the (meth) acrylic monomer having a carboxyl group as a functional group, there can be mentioned: (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, and the like.
Examples of the (meth) acrylic monomer having a hydroxyl group as a functional group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and N-methylol (meth) acrylamide.
Examples of the (meth) acrylic monomer having an acid anhydride group as a functional group include trimellitic anhydride (meth) acryloyloxyethyl ester and cyclohexanetricarboxylic anhydride (meth) acryloyloxyethyl ester.
Examples of the (meth) acrylic monomer having an amino group as a functional group include diethylaminoethyl (meth) acrylate, 2,6, 6-tetramethylpiperidine (meth) acrylate, and (meth) acrylamide.
Examples of the (meth) acrylic monomer having an amide group as a functional group include N- (meth) acryloyl glycinamide and the like.
As the (meth) acrylic monomer having an epoxy group as a functional group, there can be mentioned: glycidyl (meth) acrylate, glycidyl a-ethyl (meth) acrylate, glycidyl a-n-propyl (meth) acrylate, 2- (2, 3-glycidoxy) ethyl (meth) acrylate, 3- (2, 3-glycidoxy) propyl (meth) acrylate, 4- (2, 3-glycidoxy) butyl (meth) acrylate, 5- (2, 3-glycidoxy) pentyl (meth) acrylate, 6- (2, 3-glycidoxy) hexyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 4, 5-epoxypentyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 6-ethyl (meth) acrylate, 7-epoxyheptyl ester, 3-methyl-3, 4-epoxybutyl (meth) acrylate, 4-methyl-4, 5-epoxypentyl (meth) acrylate, 5-methyl-5, 6-epoxyhexyl (meth) acrylate, (. beta. -methylglycidyl (meth) acrylate, -. beta. -methylglycidyl alpha-ethyl (meth) acrylate, (. 3-methyl-3, 4-epoxybutyl (meth) acrylate, (. 4-methyl-4, 5-epoxypentyl (meth) acrylate, 5-methyl-5, 6-epoxyhexyl (meth) acrylate, and the like.
Among the functional group-containing (meth) acrylic monomers, an acrylic resin obtained by polymerizing a functional group-containing (meth) acrylic monomer (preferably glycidyl methacrylate) having an epoxy group is preferable from the viewpoint of improving the stain-proofing property of the release film because it is excellent in air-tightness.
(other monomers)
The crosslinking acrylic resin may contain a monomer (other monomer) other than the above (meth) acrylic monomer as a polymerization component. Examples of the other monomer include a (meth) acrylic monomer containing a benzene ring or a heterocyclic ring, an aromatic vinyl compound, a vinyl cyanide compound, an unsaturated dicarboxylic anhydride, and an N-substituted maleimide.
Examples of the (meth) acrylic monomer containing a benzene ring or a heterocycle include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, naphthyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.
Examples of the aromatic vinyl compound include 4-vinylpyridine, 2-vinylpyridine, α -methylstyrene, α -ethylstyrene, α -fluorostyrene, α -chlorostyrene, α -bromostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, methoxystyrene, (o-, m-, p-) hydroxystyrene, styrene and the like.
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride.
Examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and N-phenylmaleimide.
(crosslinking agent)
The kind of the crosslinking agent used for causing the crosslinking reaction of the crosslinkable acrylic resin is not particularly limited. Examples of the crosslinking agent include known crosslinking agents such as isocyanate compounds, melamine compounds and epoxy compounds. In order to form a slowly expanding network structure in the crosslinking acrylic resin, a polyfunctional crosslinking agent is preferably used. In the present specification, "polyfunctional" means 3 or more functional groups.
[ base Material ]
The kind of the base material is not particularly limited. The base material preferably has heat resistance to such an extent that the base material can withstand heating of the mold for a predetermined time during molding and flexibility that can sufficiently follow the structure of the mold. As the substrate having such characteristics, a substrate containing a heat-resistant resin is exemplified. When the base material contains a resin, the number of the resins may be only one or two or more.
In view of molding the sealing material at a high temperature (usually, about 100 to 200 ℃), it is desirable that the base material has heat resistance to such a degree that the base material can withstand a predetermined time period. In addition, in order to suppress the generation of wrinkles, cracks, and the like in the release film of the sealing resin that flows when the release film is attached to the mold and during molding, it is important to select the release film in consideration of the elastic modulus, the elongation, and the like at high temperatures.
The base material preferably contains polyester as a resin from the viewpoint of heat resistance and modulus of elasticity at high temperature. Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, resins containing two or more of the polymerization components of these polyesters as polymerization components, and resins obtained by modifying these polyesters. Among them, at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate is preferably contained.
The substrate is preferably in the form of a sheet. Specifically, a substrate obtained by molding a resin into a sheet shape is exemplified. From the viewpoint of the following property to the mold, a resin sheet (film) biaxially stretched is preferable.
The thickness of the base material is not particularly limited. For example, it is preferably 1 μm to 100. mu.m, and more preferably 3 μm to 20 μm. When the thickness of the substrate is 1 μm or more, the release film tends to have excellent handling properties and be less likely to form wrinkles. When the thickness is 100 μm or less, the following property to a mold at the time of molding is excellent, and the occurrence of wrinkles and the like in a molded semiconductor package tends to be suppressed.
In the present embodiment, the thickness of the base material is a number average value of values obtained by measuring 5 points at arbitrary positions. The thickness of the substrate can be measured, for example, using a conventional micrometer.
Since the base material is in contact with the surface of the mold, depending on the material, a larger peeling force may be required to peel the release film from the mold. When the substrate is difficult to be peeled from the mold, it is preferable to adjust the substrate so as to be easily peeled from the mold.
Examples of the method for adjusting the substrate so as to be easily released from the mold include: a method of subjecting the surface of the substrate opposite to the surface on the release layer side (the surface in contact with the mold) to processing for imparting unevenness to the surface, such as pear peel processing, a method of further providing another release layer (the 2 nd release layer) on the substrate, and the like.
When the 2 nd releasing layer is provided on the base material, the material of the 2 nd releasing layer is not particularly limited. For example, the release layer may be formed using the same material as that used for the release layer. The thickness of the 2 nd releasing layer is not particularly limited, but is preferably 0.1 μm to 100. mu.m. The thickness of the 2 nd releasing layer is defined in the same manner as the thickness of the releasing layer described above.
[ other Components ]
The release film may have members other than the release layer and the base material as necessary. For example, members such as a releasing layer, an anchor enhancing layer of the 2 nd releasing layer, an antistatic layer, and a colored layer may be provided between the releasing layer and the base material, between the base material and the 2 nd releasing layer, and the like. In addition, a protective layer may be provided to protect the surface of the release film.
< method for producing mold release film >
The method for producing the release film is not particularly limited. For example, a composition for forming a release layer is prepared and applied to one surface of a substrate, and if necessary, volatile components in the composition are removed by drying to form a release layer on the substrate, thereby producing a release film. In this case, the volume average particle diameter a (μm) of the filler contained in the formed release layer and the amount of the filler used can be adjusted by adjusting the amount of the composition to be imparted to the substrate and the amount of the filler used, thereby adjusting the volume average particle diameter a (μm) of the filler contained in the release layer per 1m of the release layer2Mass B (g/m) of2) The ratio (A/B) is set to be less than or equal to 1.
The method for preparing the composition for forming the release layer is not particularly limited. For example, the resin component, the filler and the solvent may be mixed and prepared. From the viewpoint of forming a release layer in which thickness unevenness is suppressed on a base material, an organic solvent capable of dissolving a resin component is preferably used as the solvent. Examples of the organic solvent include toluene, methyl ethyl ketone, and ethyl acetate.
The method of imparting the composition to the substrate is not particularly limited. For example, the coating can be applied by a known coating method such as roll coating, bar coating, and kiss coating. When the composition for forming a release layer is applied to a substrate, the composition is preferably applied so that the thickness of the release layer to be formed is 0.1 to 100 μm.
If necessary, the composition applied to the substrate may be dried to remove volatile components such as a solvent in the composition. The drying method is not particularly limited, and can be carried out by a known method. The drying may be carried out at 50 to 150 ℃ for 0.1 to 60 minutes, for example.
[ method of Using Release film ]
An example of a method of using the release film of the present embodiment will be described below with reference to the drawings. The sizes of the members in the drawings are conceptual sizes, and the relative relationship between the sizes of the members is not limited to this.
Fig. 1 schematically shows a cross section of a release film in a state where a functional sheet is held. In fig. 1, a release film 10 includes a substrate 1 and a release layer 2, and a functional sheet 3 is disposed on the release layer 2.
Fig. 2 schematically shows a cross section of a molding apparatus of transfer molding type in which the release film 10 is supplied and wound out from a roll. In fig. 2, reference numeral 4 denotes a mold, and reference numeral 5 denotes a plunger for injecting a sealing resin into a space in the mold. Reference numeral 6 denotes a support member for semiconductor packaging, and in a BGA type package form or the like, a circuit is often provided inside the support member. Reference numeral 7 denotes a semiconductor chip, and a circuit on the semiconductor chip is generally connected to a circuit in the support member by a wire (not shown) made of metal such as gold or copper.
As shown in fig. 2, the release film 10 is wound from the roll 8A and disposed in the recess of the mold 4. At this time, the functional sheet 3 mounted on the release film 10 is also disposed in the recess of the mold 4. The mold 4 is heated (for example, at about 170 ℃), and is set so that the sealing resin injected in the subsequent step melts.
Fig. 3 schematically shows a state in which the upper and lower molds 4 are brought into contact with each other and the sealing resin 9 is injected into the gap in the mold 4 by using the plunger 5.
Fig. 4 schematically shows a state in which the upper and lower molds 4 are separated after the molding is completed. As shown in fig. 4, the functional sheet 3 mounted on the release film 10 is separated from the release film 10 and disposed on the semiconductor package. The used release film 10 is wound into a roll 8B and collected.
Since the release film of the present embodiment has excellent retention of the functional sheet until the molding step, the functional sheet is not detached from the release film and is disposed in the mold. Further, since the performance of releasing the functional sheet in the molding step is excellent, the functional sheet can be detached from the release sheet and disposed on the semiconductor package when the upper and lower molds are separated after the molding is completed.
Examples
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
< examples 1 to 10, comparative examples 1 to 7 >
(preparation of composition for Forming Release layer)
An acrylic resin, a crosslinking agent, and a filler as resin components were mixed with toluene so that the nonvolatile components of the respective materials were in the amounts (parts by mass) shown in table 1 or table 2, to prepare a toluene solution having a solid content of 15 mass%, thereby preparing a composition for forming a release layer.
As the acrylic resin, a 24 mass% toluene solution of a copolymer of acrylic acid ester, ethyl acetate and n-butyl acrylate (trade name "S-43" available from Soken chemical Co., Ltd.) was used.
As the crosslinking agent, a 75 mass% toluene solution of an isocyanate compound (tradename "Coronate L" available from Tosoh corporation) and an adduct of hexamethylene diisocyanate-modified polyisocyanate (tradename "Duranate AE 710-100" available from Asahi Kasei Co., Ltd.) were used.
As the filler, particles of a cross-linking type acrylic resin (trade name "MX-150 (volume average particle diameter: 1.5 μm)", "MX-300 (volume average particle diameter: 3.0 μm)", and "MX-1000 (volume average particle diameter: 10.0 μm)", available from Sokka Chemicals Co., Ltd.) or silica particles (volume average particle diameter: 5.0 μm, trade name "sylospere C-0809" available from FUJI Silysia chemical Co., Ltd.) were used as a copolymer of methacrylic acid ester.
(preparation of Release film)
The prepared composition for forming a release layer was applied to one surface of a substrate at a speed of 0.5 to 3m/min using a roll coater, and in this state, drying was performed at 100 ℃ in a drying furnace having a length of 3m, thereby forming a release layer on the substrate to obtain a release film. At this time, the amount of the polymer is 1m per dried composition2The gap during coating was adjusted so that the coating amount (mass of the release layer) became the value (g) shown in table 1 or table 2.
As the substrate, a biaxially stretched polyethylene terephthalate (PET) film (trade name "FT 3-25" manufactured by DuPont film Co., Ltd.) having a thickness of 25 μm and a biaxially stretched polybutylene terephthalate (PBT) film (manufactured by Kakko Co., Ltd.) were each subjected to corona treatment.
(measurement of the quality of the Release layer)
The release film thus produced was cut into a size of 10cm × 10cm and the mass was measured. Then, the release layer was removed with methyl ethyl ketone, air-dried, and the mass was measured again, and the mass of the release layer was calculated from the difference between the masses before and after. Multiplying the obtained value by 100 to calculate each 1m2Mass (g/m) of the releasing layer of (2)2). The results are shown in table 1 or table 2.
(measurement of adhesive force)
The release film thus produced was set in a tack tester (product name "TAC-II" manufactured by Rhesca) so that a measurement probe was brought into contact with the release layer at the time of measurement. Then, using a probe having a diameter of 5mm, at a probe lowering speed: 120mm/min, measurement front load: 10gf, rising speed at measurement: the viscosity (gf) was measured under the condition of 600 mm/min. The measurement of the viscosity was carried out at a temperature (25 ℃ C.) assumed to be room temperature and a temperature (170 ℃ C.) assumed to be a molding step. The results are shown in table 1 or table 2.
(evaluation of Retention)
In order to evaluate the ability of the release film to hold a functional sheet, the following test was performed
The release film thus produced was cut into a size of 15cm × 30cm, and a 50cm × 100cm dust-free paper was bonded to the release layer of the cut release film using a silicone rubber roll. Then, the sheet was placed on a table with the dust-free paper down in an environment of 25 ℃, the end of the release film was grasped and lifted by 50cm to 100cm in the direction of 90 °, and whether or not the attached dust-free paper was peeled off was observed. The results are shown in table 1 or table 2, where "OK" indicates that the non-dust-laden paper is not peeled off, and "NG" indicates that the paper is peeled off.
(evaluation of surface roughness)
Using a surface roughness measuring apparatus (Seisakusho K.K., model SE-3500), the diameter of the tip of a stylus: 2 μm, transfer speed: 0.5mm/s and scanning distance: the measurement was performed under the condition of 8mm, and the measured results were analyzed by JIS B0601(2013) or ISO 4287(1997), thereby obtaining an arithmetic average roughness (Ra) and a ten-point average roughness (Rz) of the outer surface of the release layer. The results are shown in table 1 or table 2.
< comparative example 8 >
The same evaluation as in example was carried out for an ETFT (Ethylene Tetra Fluoro Ethylene, Ethylene-tetrafluoroethylene) film (product name: "Aflex 50 HK", Asahi glass Co., Ltd.) which is widely used mainly as a mold release film of compression molding system. The results are shown in Table 2. Note that Aflex 50HK had no resin layer (release layer), and therefore the mass measurement of the release layer was not performed.
[ Table 1]
[ Table 2]
As shown in Table 1, the volume average particle diameter A (. mu.m) of the filler and the release layer per 1m thereof were found2Mass B (g/m) of2) An embodiment wherein the ratio (A/B) is less than or equal to 1The release films of examples 1 to 10 had high viscosity at 25 ℃ and were excellent in retention property because no peeling of the dust-free paper was observed in the retention property evaluation test. On the other hand, it is found that the adhesive strength at 170 ℃ is low and the releasability in the molding step is good. It is further understood that even if the surface roughness is changed by adjusting the type and content of the filler contained in the release layer, favorable results are obtained, and thus it is possible to cope with diversification of combinations of the material of the release film and the package while maintaining desired characteristics.
Regarding the volume average particle diameter A (. mu.m) of the filler and each 1m of the releasing layer2Mass B (g/m) of2) The release films of comparative examples 1 to 7, in which the ratio (A/B) exceeds 1, had significantly low tack at 25 ℃ and had poor retention compared to the examples, and the release films were also peeled from the dust-free paper in the evaluation test of retention.
The Aflex 50HK used as the release film of comparative example 8 had a low viscosity at 25 ℃ and a low viscosity at 170 ℃, and was excellent in releasability. However, in the evaluation test of the holding property, the dust-free paper was peeled off, and the holding property was inferior to that of the examples.
From the above results, the release film of the present embodiment is excellent in the performance of retaining the functional sheet until the molding step and the performance of releasing the functional sheet in the molding step.
The disclosure of japanese patent application no 2016-. All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.
Claims (6)
1. A release film comprising a base material and a release layer provided on the base material and containing a resin component and a filler, wherein the filler has a volume average particle diameter A and 1m per the release layer2A ratio of A/B of 1 or less, wherein A is in μm and B is in g/m2。
2. The release film according to claim 1, wherein the filler has a volume average particle diameter A of 1 to 50 μm.
3. The release film according to claim 1 or 2, which is the release layer per 1m2Has a mass B of 0.1g/m2～100g/m2。
4. The release film according to claim 1 or 2, the resin component containing a thermosetting resin.
5. The release film according to claim 1 or 2, further comprising a crosslinking agent, wherein the content of the crosslinking agent is 1 to 10 parts by mass with respect to 100 parts by mass of the resin component.
6. The release film according to claim 1 or 2, the base material containing at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016101820 | 2016-05-20 | ||
| JP2016-101820 | 2016-05-20 | ||
| PCT/JP2017/018930 WO2017200102A1 (en) | 2016-05-20 | 2017-05-19 | Mold release film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109153155A CN109153155A (en) | 2019-01-04 |
| CN109153155B true CN109153155B (en) | 2020-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780031301.2A Active CN109153155B (en) | 2016-05-20 | 2017-05-19 | Mold release film |
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| Country | Link |
|---|---|
| JP (1) | JP6414345B2 (en) |
| KR (1) | KR102340703B1 (en) |
| CN (1) | CN109153155B (en) |
| MY (1) | MY188629A (en) |
| SG (1) | SG11201810343TA (en) |
| TW (2) | TW201819141A (en) |
| WO (1) | WO2017200102A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SG11202012850XA (en) | 2018-06-22 | 2021-01-28 | Kobayashi & Co Ltd | Release film and method of manufacturing release film |
| WO2020040240A1 (en) * | 2018-08-24 | 2020-02-27 | 住友ベークライト株式会社 | Release film and method for producing molded article |
| KR20220085765A (en) * | 2019-10-24 | 2022-06-22 | 쇼와덴코머티리얼즈가부시끼가이샤 | Method for manufacturing release film and semiconductor package |
| CN111016017B (en) * | 2019-12-31 | 2021-10-22 | 上海凯陆高分子材料有限公司 | Material for surface treatment of vulcanization mold and preparation method and application thereof |
| TWI724765B (en) | 2020-01-21 | 2021-04-11 | 達興材料股份有限公司 | Laser-debondable composition, laminate thereof, and laser-debonding method |
| WO2022038712A1 (en) * | 2020-08-19 | 2022-02-24 | 昭和電工マテリアルズ株式会社 | Release film and electronic component device manufacturing method |
| JP6870775B1 (en) * | 2020-10-21 | 2021-05-12 | 住友ベークライト株式会社 | Manufacturing method of release film and molded product |
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- 2017-05-19 KR KR1020187036120A patent/KR102340703B1/en active IP Right Grant
- 2017-05-19 TW TW106116589A patent/TW201819141A/en unknown
- 2017-05-19 JP JP2017554553A patent/JP6414345B2/en active Active
- 2017-05-19 WO PCT/JP2017/018930 patent/WO2017200102A1/en active Application Filing
- 2017-05-19 CN CN201780031301.2A patent/CN109153155B/en active Active
- 2017-05-19 SG SG11201810343TA patent/SG11201810343TA/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004200467A (en) * | 2002-12-19 | 2004-07-15 | Hitachi Chem Co Ltd | Release sheet for semiconductor mould |
| JP2004344962A (en) * | 2003-05-26 | 2004-12-09 | Yamauchi Corp | Sheet for hot pressing |
| CN1984776A (en) * | 2004-07-13 | 2007-06-20 | 琳得科株式会社 | Releasing sheet and formed article obtained by using such releasing sheet |
| CN101842236A (en) * | 2007-10-31 | 2010-09-22 | 尤尼吉可株式会社 | Releasing polyester film |
| JP2009143091A (en) * | 2007-12-13 | 2009-07-02 | Teijin Dupont Films Japan Ltd | Mold release film for molding of green sheet and its manufacturing method |
| CN102639634A (en) * | 2009-12-03 | 2012-08-15 | 旭硝子株式会社 | Process for producing fluorocopolymer nanocomposite |
| CN102782075A (en) * | 2010-02-15 | 2012-11-14 | 旭硝子株式会社 | Release agent composition |
| CN104520978A (en) * | 2012-06-08 | 2015-04-15 | 日立化成株式会社 | Method for manufacturing semiconductor device |
| CN104470719A (en) * | 2012-10-19 | 2015-03-25 | 东丽株式会社 | Biaxially oriented polyester film for mold release |
| CN104112693A (en) * | 2013-04-19 | 2014-10-22 | 株式会社巴川制纸所 | Release film for mold forming |
Also Published As
| Publication number | Publication date |
|---|---|
| MY188629A (en) | 2021-12-22 |
| SG11201810343TA (en) | 2018-12-28 |
| WO2017200102A1 (en) | 2017-11-23 |
| TW201819141A (en) | 2018-06-01 |
| JPWO2017200102A1 (en) | 2018-05-31 |
| CN109153155A (en) | 2019-01-04 |
| KR20190008883A (en) | 2019-01-25 |
| TW202237368A (en) | 2022-10-01 |
| KR102340703B1 (en) | 2021-12-16 |
| JP6414345B2 (en) | 2018-10-31 |
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