WO2021112238A1 - 電磁波シールド膜付き半導体装置の製造方法及び端子保護用テープ - Google Patents
電磁波シールド膜付き半導体装置の製造方法及び端子保護用テープ Download PDFInfo
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- WO2021112238A1 WO2021112238A1 PCT/JP2020/045307 JP2020045307W WO2021112238A1 WO 2021112238 A1 WO2021112238 A1 WO 2021112238A1 JP 2020045307 W JP2020045307 W JP 2020045307W WO 2021112238 A1 WO2021112238 A1 WO 2021112238A1
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- semiconductor device
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
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- H10P54/00—
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- H10P72/7402—
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Definitions
- the present invention relates to a method for manufacturing a semiconductor device with an electromagnetic wave shielding film and a tape for protecting terminals.
- the present application claims priority based on Japanese Patent Application No. 2019-22146 filed in Japan on December 6, 2019, the contents of which are incorporated herein by reference.
- connection pad portion is made of eutectic solder, high temperature solder, gold, etc.
- a convex electrode hereinafter, referred to as a “terminal” in the present specification
- a mounting method is adopted in which those terminals are brought into face-to-face contact with the corresponding terminal portions on the chip mounting substrate and melted / diffused.
- Patent Document 1 In response to such measures against heat and noise, for example, as disclosed in Patent Document 1, a method of coating an electronic component module with a conductive material to form an electromagnetic wave shielding film is adopted.
- the conductive resin applied to the top surface and the side surface of the individualized electronic component module is heated and cured to form an electromagnetic wave shielding film.
- a conductive resin is applied to an external terminal electrode provided on the back surface of an assembly substrate in a state of being embedded in an adhesive sheet. Since the masking portion is provided at a predetermined position on the adhesive sheet, it is possible to prevent the external terminal electrode and the electromagnetic wave shielding film from being electrically short-circuited. On the other hand, providing a masking portion at a predetermined position on the pressure-sensitive adhesive sheet is complicated in terms of process.
- an electrode surface provided with an electrode of an unshielded electronic component is attached to an adhesive layer of a film for manufacturing an electronic component having a base layer and an adhesive layer provided on one surface side thereof.
- a method for manufacturing an electronic component to be provided is disclosed.
- the present invention relates to a method for manufacturing a semiconductor device with an electromagnetic wave shield film, which can be easily peeled off from the terminal protection tape in a step of peeling the semiconductor device with a terminal on which an electromagnetic wave shield film is formed, and has high manufacturing efficiency.
- An object of the present invention is to provide a terminal protection tape used in a manufacturing method.
- the present invention provides the following method for manufacturing a semiconductor device with an electromagnetic wave shielding film and a terminal protection tape used in the manufacturing method.
- a step of embedding terminals of a semiconductor device with terminals in the viscoelastic layer of a terminal protection tape having a viscoelastic layer A step of forming an electromagnetic wave shielding film on an exposed surface of the terminal-equipped semiconductor device that is not embedded in the viscoelastic layer of the terminal protection tape, and A step of peeling the terminal-equipped semiconductor device on which the electromagnetic wave shielding film is formed from the terminal protection tape by stretching the terminal protection tape.
- a method for manufacturing a semiconductor device with an electromagnetic wave shielding film including.
- a method for manufacturing a semiconductor device with an electromagnetic wave shielding film including.
- the stretched amount of the terminal protection tape in the step of peeling the terminal-attached semiconductor device on which the electromagnetic wave shield film is formed from the terminal protection tape is 1.0 mm or more, [1] or [2].
- the adhesive strength of the terminal protection tape to the terminal-equipped semiconductor device is 6.5 N / 25 mm after the step of burying the terminals of the terminal-equipped semiconductor device and before the step of forming the electromagnetic wave shield film.
- the ratio of the thickness d1 of the viscoelastic layer to the terminal height h0 of the terminal-equipped semiconductor device or the terminal-equipped semiconductor device assembly satisfies 1.2 ⁇ d1 / h0 ⁇ 5.0 [1].
- the method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to any one of [5].
- a method for manufacturing a semiconductor device with an electromagnetic wave shield film which can be easily peeled off and has high manufacturing efficiency, and the above. It becomes possible to provide a terminal protection tape used in a manufacturing method.
- the method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to the first embodiment of the present invention includes a step of embedding the terminals of the semiconductor device with terminals in the viscoelastic layer of the terminal protection tape having a viscoelastic layer, and the terminal protection.
- the step of peeling the semiconductor device from the terminal protection tape is included.
- the method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to a second embodiment of the present invention includes a step of embedding terminals of a semiconductor device assembly with terminals in the viscoelastic layer of a terminal protection tape having a viscoelastic layer, and the above-mentioned.
- the process of dicing the terminal-equipped semiconductor device assembly to make the terminal-equipped semiconductor device assembly into a terminal-equipped semiconductor device in which terminals are embedded in the viscoelastic layer of the terminal protection tape, and the terminal protection tape The step of forming an electromagnetic wave shielding film on the exposed surface of the terminal-equipped semiconductor device not embedded in the viscoelastic layer, and the terminal-attached semiconductor device on which the electromagnetic wave shielding film is formed by stretching the terminal protection tape.
- the step of peeling from the terminal protection tape is included.
- each step of the terminal protection tape used in the method for manufacturing the semiconductor device with the electromagnetic wave shielding film of the first embodiment and the second embodiment of the present invention and the method for manufacturing the semiconductor device with the electromagnetic wave shielding film of the present invention will be described. A detailed explanation will be given.
- FIG. 1 is a cross-sectional view schematically showing an embodiment of the terminal protection tape of the present invention.
- the main part may be enlarged and shown, and the dimensional ratio of each component is the same as the actual one. Is not always the case.
- the terminal protection tape 1 shown in FIG. 1 is a terminal protection tape 1 used in a step of forming an electromagnetic wave shield film on a semiconductor device with terminals, and has a viscoelastic layer 12.
- the viscoelastic layer 12 preferably includes the embedding layer 13 and the pressure-sensitive adhesive layer 14, and more preferably comprises the embedding layer 13 and the pressure-sensitive adhesive layer 14.
- the terminal protection tape of the present embodiment may include a release film 21 on the outermost layer of the viscoelastic layer 12 on the side of the embedded layer 13, and the adhesive layer 14 of the viscoelastic layer 12 may be provided.
- the release film 20 may be provided on the outermost layer on the side of the surface.
- the terminal protection tape of the present embodiment is not limited to the one shown in FIG. 1, and a part of the configuration of the tape shown in FIG. 1 has been changed, deleted or added within the range not impairing the effect of the present invention. It may be a thing.
- both release films 20 and 21 are peeled off, placed on a support, and a semiconductor device with terminals is pressed from above with the terminal side facing down. It can be used in a step of embedding a terminal in the viscoelastic layer 12 and further forming an electromagnetic wave shield film on the terminal.
- the terminal protection tape of the present embodiment may have a structure in which the adhesive layer 14, the embedding layer 13, and the base material 11 are provided in this order.
- the release film 20 may be provided on the outermost layer of the viscoelastic layer 12 on the side of the pressure-sensitive adhesive layer 14.
- the release film 20 is peeled off, and the semiconductor device with terminals is pressed against the viscoelastic layer 12 on the base material 11 as a support with the terminals side down. It can be used in a step of burying a terminal in the viscoelastic layer 12 and further forming an electromagnetic wave shield film on the terminal.
- the terminal protection tape of the present embodiment has a structure in which the adhesive layer 14, the embedding layer 13, and the base material 11 are provided in this order, and is sticky.
- the release film 20 may be provided on the outermost surface layer of the elastic layer 12 on the side of the adhesive layer 14, and the second base material 11 is attached to the support on the side opposite to the adhesive layer 12.
- a pressure-sensitive adhesive layer 15 (that is, a bonded pressure-sensitive adhesive layer) may be provided, or a double-sided tape having a release film 22 on the outermost layer on the side of the second pressure-sensitive adhesive layer 15 may be used.
- the terminal protection tape 3 shown in FIG. 3 is obtained by peeling the release film 22 and fixing it to the support 30 as shown in FIG. 4, and further peeling the release film 20 to attach the terminals to the viscoelastic layer 12.
- the attached semiconductor device can be used in a step of pressing the terminal side down, embedding the terminal in the viscoelastic layer 12, and further forming an electromagnetic wave shield film from above.
- the breaking elongation of the terminal protection tape is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more.
- the breaking elongation of the terminal protection tape is at least the above lower limit value, the terminal protection tape can be sufficiently stretched, and the terminal-equipped semiconductor device on which the electromagnetic wave shielding film is formed is peeled off from the terminal protection tape.
- the peelability in the above is improved.
- the breaking elongation of the terminal protection tape may be less than 45%.
- the breaking elongation of the terminal protection tape is, for example, preferably 10% or more and less than 45%, more preferably 15% or more and less than 45%, and further preferably 20% or more and less than 45%.
- the breaking elongation of the terminal protection tape can be measured by the method described in Examples described later.
- the breaking stress of the terminal protection tape is preferably 5 MPa or more, more preferably 10 MPa or more, and even more preferably 15 MPa or more. When the breaking stress of the terminal protection tape is at least the above lower limit value, the terminal protection tape can be uniformly stretched when it is stretched.
- the breaking stress of the terminal protection tape may be less than 30 MPa.
- the breaking stress of the terminal protection tape is, for example, preferably 5 MPa or more and less than 30 MPa, more preferably 10 MPa or more and less than 30 MPa, and further preferably 15 MPa or more and less than 30 MPa.
- the breaking stress of the terminal protection tape can be measured by the method described in Examples described later.
- the viscoelastic layer is used to protect the terminal forming surface (in other words, the circuit surface) of the semiconductor device with terminals and the terminals provided on the terminal forming surface. Used.
- the viscoelastic layer preferably has an embedded layer and an adhesive layer.
- the thickness of the viscoelastic layer is preferably 1 to 1000 ⁇ m, more preferably 5 to 800 ⁇ m, and even more preferably 10 to 600 ⁇ m.
- the thickness of the viscoelastic layer is at least the above lower limit value, even a terminal electrode such as a solder ball, which tends to float, can be embedded.
- the thickness of the viscoelastic layer is not more than the upper limit value, it is possible to prevent the terminal protection tape from becoming excessively thick.
- the "thickness of the viscoelastic layer” means the thickness of the entire viscoelastic layer, and the thickness of the viscoelastic layer composed of a plurality of layers of the embedded layer and the adhesive layer is the thickness of the embedded layer and the adhesive layer.
- the thickness of each layer can be measured by, for example, a constant pressure thickness measuring device (model number: "PG-02J") manufactured by Teclock Co., Ltd. in accordance with JIS K6783, Z1702, and Z1709.
- PG-02J constant pressure thickness measuring device
- the terminal forming surface of the terminal-equipped semiconductor device When the terminal forming surface of the terminal-equipped semiconductor device is brought into close contact with the viscoelastic layer 12, it is preferable that the terminal forming surface of the terminal-equipped semiconductor device is directly brought into close contact with the adhesive layer 14 in the viscoelastic layer 12. At this time, it is preferable that the pressure-sensitive adhesive layer 14 is set harder than the embedded layer 13 in order to prevent adhesive residue on the terminal forming surface and the terminals.
- the terminals of the terminal-equipped semiconductor device and the outermost layer of the viscoelastic layer 12 (for example, an adhesive layer) It is preferable that the adhesion with is not more than a certain level.
- the adhesion between the terminals of the semiconductor device with terminals and the outermost layer of the viscoelastic layer 12 can be quantitatively evaluated by, for example, the following method.
- the diameter of the substantially circular shadow derived from the bubbles is preferably 0.30 mm or more, more preferably 0.32 mm or more, and further preferably 0.34 mm or more.
- the diameter of the substantially circular shadow derived from the bubbles is equal to or greater than the lower limit, the adhesion between the terminal of the semiconductor device with a terminal and the outermost layer of the viscoelastic layer 12 does not become too high, and an electromagnetic wave shielding film is formed.
- the peelability in the process of peeling the terminal-equipped semiconductor device from the terminal protection tape is improved. Since the diameter of the substantially circular shadow derived from the bubbles appears outside the terminal having a diameter of 0.25 mm, it is naturally larger than 0.25 mm.
- the maximum diameter of the shadow can be adopted.
- the upper limit of the diameter of the substantially circular shadow derived from the bubbles is not particularly limited as long as the effect of the present invention is shown, but may be, for example, 1.00 mm or less.
- the diameter of the substantially circular shadow derived from the bubbles is, for example, preferably 0.30 mm or more and 0.95 mm or less, more preferably 0.32 mm or more and 0.90 mm or less, and 0.34 mm or more and 0. It is more preferably 85 mm or less.
- the diameter of the substantially circular shadow derived from the bubbles can be measured by the method described in Examples described later.
- the pressure-sensitive adhesive layer constituting the viscoelastic layer may be referred to as a "first pressure-sensitive adhesive layer" to distinguish it from the second pressure-sensitive adhesive layer for bonding to a support, which will be described later.
- the first pressure-sensitive adhesive layer is in the form of a sheet or a film and contains a pressure-sensitive adhesive.
- sheet-like or film-like means a thin film-like material having small in-plane thickness variation and flexibility.
- the pressure-sensitive adhesive examples include an acrylic resin (a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group), a urethane-based resin (a pressure-sensitive adhesive made of a resin having a urethane bond), and a rubber-based resin (a resin having a rubber structure).
- acrylic resin a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group
- a urethane-based resin a pressure-sensitive adhesive made of a resin having a urethane bond
- a rubber-based resin a resin having a rubber structure
- silicone resin silicone resin
- epoxy resin an epoxy resin having epoxy group
- polyvinyl ether adhesive resin such as polycarbonate, etc.
- a based resin is preferable.
- the "adhesive resin” is a concept including both a resin having adhesiveness and a resin having adhesiveness.
- a resin having adhesiveness for example, not only the resin itself has adhesiveness but also the resin itself has adhesiveness. It also includes a resin that exhibits adhesiveness when used in combination with other components such as additives, and a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.
- the first pressure-sensitive adhesive layer may be only one layer (single layer), or may be a plurality of layers of two or more layers, and when there are a plurality of layers, the plurality of layers may be the same as or different from each other, and the plurality of layers may be used.
- the combination is not particularly limited.
- first pressure-sensitive adhesive layer not only in the case of the first pressure-sensitive adhesive layer, but also in the case of "a plurality of layers may be the same or different from each other", “all layers may be the same or all layers may be the same”. "The layers may be different, and only some of the layers may be the same", and “multiple layers are different from each other” means that "at least one of the constituent materials and thicknesses of each layer is different from each other". It means “different”.
- the thickness of the first pressure-sensitive adhesive layer is preferably 1 to 1000 ⁇ m, more preferably 2 to 100 ⁇ m, and particularly preferably 8 to 20 ⁇ m.
- the "thickness of the first pressure-sensitive adhesive layer” means the thickness of the entire first pressure-sensitive adhesive layer, and for example, the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers is the thickness of the first pressure-sensitive adhesive layer. Means the total thickness of all the layers that make up.
- the first pressure-sensitive adhesive layer may be formed by using an energy ray-curable pressure-sensitive adhesive or may be formed by using a non-energy ray-curable pressure-sensitive adhesive.
- the first pressure-sensitive adhesive layer formed by using the energy ray-curable pressure-sensitive adhesive is preferable because the physical properties before and after curing can be easily adjusted.
- the "energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like as an ultraviolet source.
- the electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
- energy ray curable means a property of being cured by irradiating with energy rays
- non-energy ray curable means a property of not being cured by irradiating with energy rays. ..
- the elastic modulus of the first pressure-sensitive adhesive layer before curing is preferably 0.01 to 0.50 MPa. It is more preferably 02 to 0.40 MPa, and even more preferably 0.03 to 0.35 MPa.
- the elastic modulus of the first pressure-sensitive adhesive layer before curing is within the above range, the retention property of the semiconductor device can be obtained.
- the elastic modulus of the first pressure-sensitive adhesive layer after curing is preferably 1.0 to 50 MPa, preferably 2.0 to 250 MPa. It is more preferably 45 MPa, further preferably 3.0 to 40 MPa.
- the "elastic modulus” refers to an environment of a sample having a diameter of 8 mm and a thickness of 3 mm at 23 ° C.
- the storage elastic modulus measured below by the torsional shear method.
- the curing of the first pressure-sensitive adhesive layer may be performed by any step of the method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to the first and second embodiments described above, but the curing of the semiconductor device with terminals (or the semiconductor device assembly) may be performed. It is preferable to perform this after the step of burying the terminals and before the step of peeling the terminal-equipped semiconductor device on which the electromagnetic wave shielding film is formed from the terminal protection tape.
- the elastic modulus of the first pressure-sensitive adhesive layer is preferably 0.10 to 0.50 MPa, preferably 0.11 to 0.50 MPa. It is more preferably 0.40 MPa, and even more preferably 0.12 to 0.35 MPa.
- the elastic modulus of the first pressure-sensitive adhesive layer is within the above range, the peelability in the step of peeling the terminal-equipped semiconductor device on which the electromagnetic wave shielding film is formed from the terminal protection tape is improved.
- the first pressure-sensitive adhesive layer can be formed by using a first pressure-sensitive adhesive composition containing a pressure-sensitive adhesive.
- the first pressure-sensitive adhesive layer can be formed on a target portion by applying the first pressure-sensitive adhesive composition to the surface to be formed of the first pressure-sensitive adhesive layer and drying it if necessary. Further, by applying the first pressure-sensitive adhesive composition to the release film and drying it as necessary, a first pressure-sensitive adhesive layer having a desired thickness can be formed, and the first pressure-sensitive adhesive layer can be formed at a target portion. Can also be transcribed. A more specific method for forming the first pressure-sensitive adhesive layer will be described in detail later together with a method for forming the other layers.
- room temperature means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C., for example, 25 ° C.
- the coating of the first pressure-sensitive adhesive composition may be carried out by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and the like.
- a known method for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and the like.
- Examples thereof include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
- the drying conditions of the first pressure-sensitive adhesive composition are not particularly limited, but when the first pressure-sensitive adhesive composition contains a solvent described later, it is preferably heat-dried. In this case, for example, 70 to 130 ° C. It is preferable to dry under the condition of 10 seconds to 5 minutes.
- the first pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive that is, the energy ray-curable first pressure-sensitive adhesive composition is, for example, non-existent.
- a first pressure-sensitive adhesive composition containing an energy ray-curable adhesive resin (I-1a) (hereinafter, may be abbreviated as "adhesive resin (I-1a)") and an energy ray-curable compound.
- Object (I-1) Energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter, "adhesive").
- the first pressure-sensitive adhesive composition (I-2) containing (sometimes abbreviated as "sexual resin (I-2a)"); the pressure-sensitive adhesive resin (I-2a), an energy ray-curable low molecular weight compound, and the like.
- the first pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound.
- the adhesive resin (I-1a) is preferably an acrylic resin.
- the acrylic resin include acrylic polymers having at least a structural unit derived from (meth) acrylic acid alkyl ester.
- the structural unit of the acrylic resin may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferable. More specifically, as the (meth) acrylic acid alkyl ester, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, (meth) acrylic acid.
- n-butyl isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Undecyl acrylate, dodecyl (meth) acrylate (also called lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also called myristyl (meth)
- (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”.
- (meth) acrylate is a concept that includes both “acrylate” and “methacrylate”, and is a "(meth) acryloyl group”. Is a concept that includes both an "acryloyl group” and a “methacryloyl group”.
- the acrylic polymer has a structural unit derived from a (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group.
- the alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms, from the viewpoint of further improving the adhesive strength of the first pressure-sensitive adhesive layer.
- the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.
- the acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester.
- the functional group-containing monomer may be, for example, acrylic when the functional group reacts with a cross-linking agent described later to become a starting point of cross-linking, or when the functional group reacts with a functional group in an unsaturated group-containing compound. Examples thereof include those capable of introducing an unsaturated group into the side chain of the system polymer.
- Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
- hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth).
- Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-acrylic acids such as vinyl alcohol and allyl alcohol.
- Saturated alcohol that is, unsaturated alcohol having no (meth) acryloyl skeleton
- 2-hydroxyethyl (meth) acrylate being preferred
- 2-hydroxyethyl acrylate being more preferred.
- Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, and citracon.
- Ethylene unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like. Be done.
- a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.
- the functional group-containing monomer constituting the acrylic polymer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 3 to 32% by mass, based on the total amount of the structural units. It is particularly preferably 5 to 30% by mass.
- the acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer.
- the other monomer is not particularly limited as long as it can be copolymerized with a (meth) acrylic acid alkyl ester or the like.
- Examples of the other monomer include styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.
- the other monomer constituting the acrylic polymer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the acrylic polymer can be used as the above-mentioned non-energy ray-curable adhesive resin (I-1a).
- a product obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group) has the above-mentioned energy ray-curable adhesiveness. It can be used as a resin (I-2a).
- "energy ray polymerizable" means the property of polymerizing by irradiating with energy rays.
- the pressure-sensitive adhesive resin (I-1a) contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.
- the content of the pressure-sensitive resin (I-1a) is 5 to 99% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-1). It is preferably, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.
- Examples of the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
- examples of the monomer include trimethylpropantri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4.
- Multivalent (meth) acrylates such as -butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) Acrylate and the like can be mentioned.
- the energy ray-curable compounds examples include oligomers obtained by polymerizing the monomers exemplified above.
- the energy ray-curable compound has a relatively large molecular weight, and urethane (meth) acrylate and urethane (meth) acrylate oligomer are preferable in that the storage elastic modulus of the first pressure-sensitive adhesive layer is unlikely to be lowered.
- oligomer means a substance having a weight average molecular weight or formula weight of 5,000 or less (excluding monomers).
- the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrary. You can choose.
- the content of the energy ray-curable compound is 1 to 95% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-1). Is preferable, 5 to 90% by mass is more preferable, and 10 to 85% by mass is particularly preferable.
- the first pressure-sensitive adhesive composition is used.
- the product (I-1) preferably further contains a cross-linking agent.
- the cross-linking agent for example, reacts with the functional group to cross-link the adhesive resins (I-1a) with each other.
- the cross-linking agent include tolylene diisocyanate such as tolylen-2,6-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); ethylene glycol.
- Epoxy-based cross-linking agents such as glycidyl ether, N, N'-(cyclohexane-1,3-diylbismethylene) bis (glycidylamine); hexa [1- (2-methyl) -aziridinyl) ]
- Aziridine-based cross-linking agent such as trifoosphatriazine (cross-linking agent having an aziridinyl group); metal chelate-based cross-linking agent such as aluminum chelate (cross-linking agent having a metal chelate structure); isocyanurate-based cross-linking agent (having an isocyanurate skeleton) Cross-linking agent) and the like.
- the cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoints of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesive force of the first pressure-sensitive adhesive layer and being easily available.
- the cross-linking agent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). , 0.1 to 20 parts by mass is more preferable, and 1 to 10 parts by mass is particularly preferable.
- the first pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator.
- the first pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.
- photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone and 2-hydroxy.
- benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone and 2-hydroxy.
- Acetphenone compounds such as -2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine
- Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide
- sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide
- ⁇ -ketol compounds such as 1-hydroxycyclohexylphenylketone
- Azo compounds such as azobisisobutyronitrile
- titanosen compounds such as titanosen
- thioxanthone compounds such as thioxanthone
- peroxide compounds diketone compounds such as diacetyl; benzyl, dibenzyl, benzophenone, 2,4-diethylthioxanthone,
- the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..
- the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound. , 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
- the first pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
- the other additives include antioxidants, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers.
- Known additives such as reaction retarders and cross-linking accelerators (catalysts).
- the reaction delaying agent is used in the first pressure-sensitive adhesive composition (I-1) during storage due to the action of the catalyst mixed in the first pressure-sensitive adhesive composition (I-1). It suppresses the progress of the cross-linking reaction.
- the other additives contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected. ..
- the content of other additives is not particularly limited and may be appropriately selected according to the type thereof.
- the first pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the first pressure-sensitive adhesive composition (I-1) contains a solvent, the coating suitability on the surface to be coated is improved.
- the solvent is preferably an organic solvent
- examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane, n-hexane and the like.
- ketones such as methyl ethyl ketone and acetone
- esters such as ethyl acetate (carboxylic acid esters)
- ethers such as
- the solvent used in the production of the pressure-sensitive adhesive resin (I-1a) is used as it is in the first pressure-sensitive adhesive composition (I-1) without being removed from the pressure-sensitive adhesive resin (I-1a).
- the same or different type of solvent as that used in the production of the adhesive resin (I-1a) may be added separately during the production of the first pressure-sensitive adhesive composition (I-1).
- the solvent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited and may be appropriately adjusted.
- the first pressure-sensitive adhesive composition (I-2) has an energy ray-curable adhesiveness in which an unsaturated group is introduced into the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). Contains resin (I-2a).
- the adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.
- the unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group.
- a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group.
- It is a compound having a group.
- the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (also referred to as an ethenyl group), an allyl group (also referred to as a 2-propenyl group), and the like, and a (meth) acryloyl group. Is preferable.
- Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of reacting with a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of reacting with a carboxy group or an epoxy group. And so on.
- the unsaturated group-containing compound examples include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate, and (meth) acryloyloxyethyl isocyanate is preferable, and 2-methacryloyl is preferable.
- Oxyethyl isocyanate is particularly preferred.
- the isocyanate compound can react with the hydroxyl groups in the adhesive resin (I-1a), and when the total hydroxyl groups in the adhesive resin (I-1a) are 100 mol, the amount of the isocyanate compound used is 10. It is preferably ⁇ 150 mol, more preferably 20 to 140 mol, and even more preferably 30 to 130 mol.
- the pressure-sensitive adhesive resin (I-2a) contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.
- the content of the pressure-sensitive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-2). It is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 10 to 90% by mass.
- the product (I-2) may further contain a cross-linking agent.
- Examples of the cross-linking agent in the first pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the first pressure-sensitive adhesive composition (I-1).
- the cross-linking agent contained in the first pressure-sensitive adhesive composition (I-2) may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof can be arbitrarily selected.
- the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). , 0.1 to 20 parts by mass is more preferable, and 1 to 10 parts by mass is particularly preferable.
- the first pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator.
- the first pressure-sensitive adhesive composition (I-2) containing the photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.
- Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiators in the first pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, and when two or more types, the combination and ratio thereof can be arbitrarily selected. ..
- the content of the photopolymerization initiator is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). Is preferable, 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.
- the first pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
- Examples of the other additive in the first pressure-sensitive adhesive composition (I-2) include the same as the other additives in the first pressure-sensitive adhesive composition (I-1).
- the other additives contained in the first pressure-sensitive adhesive composition (I-2) may be only one kind, two or more kinds, and when there are two or more kinds, their combinations and ratios can be arbitrarily selected. ..
- the content of other additives is not particularly limited and may be appropriately selected according to the type thereof.
- the first pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the first pressure-sensitive adhesive composition (I-1).
- Examples of the solvent in the first pressure-sensitive adhesive composition (I-2) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
- the solvent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited and may be appropriately adjusted.
- the first pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low-molecular-weight compound.
- the content of the pressure-sensitive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the first pressure-sensitive adhesive composition (I-3). It is preferably, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.
- Examples of the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. , The same as the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) can be mentioned.
- the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof are It can be selected arbitrarily.
- the content of the energy ray-curable low molecular weight compound is 0.01 to 300 mass by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a).
- the amount is preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.
- the first pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator.
- the first pressure-sensitive adhesive composition (I-3) containing the photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.
- Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators in the first pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and when two or more types, the combination and ratio thereof can be arbitrarily selected. ..
- the content of the photopolymerization initiator is 100 parts by mass with respect to the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable low molecular weight compound. It is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
- the first pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
- Examples of the other additive include the same as the other additive in the first pressure-sensitive adhesive composition (I-1).
- the other additives contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected. ..
- the content of other additives is not particularly limited and may be appropriately selected according to the type thereof.
- the first pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the first pressure-sensitive adhesive composition (I-1).
- Examples of the solvent in the first pressure-sensitive adhesive composition (I-3) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
- the solvent contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and when two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited and may be appropriately adjusted.
- first pressure-sensitive adhesive compositions other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) Up to this point, the first pressure-sensitive adhesive composition (I-1), the first pressure-sensitive adhesive composition (I-2), and the first pressure-sensitive adhesive composition (I-3) have been mainly described, but the components contained therein.
- the general first pressure-sensitive adhesive compositions other than these three types of first pressure-sensitive adhesive compositions in the present embodiment, "first pressure-sensitive adhesive compositions (I-1) to (I-)" are described as. It can also be used in the same manner with the first pressure-sensitive adhesive composition other than 3).
- the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) in addition to the energy ray-curable first pressure-sensitive adhesive composition, a non-energy ray-curable first pressure-sensitive adhesive composition is used.
- Adhesive compositions are also mentioned.
- the non-energy ray-curable first pressure-sensitive adhesive composition include an acrylic resin (resin having a (meth) acryloyl group), a urethane resin (resin having a urethane bond), and a rubber resin (having a rubber structure). Resin), silicone resin (resin having siloxane bond), epoxy resin (resin having epoxy group), polyvinyl ether, those containing adhesive resin such as polycarbonate, and those containing acrylic resin. Is preferable.
- the first pressure-sensitive adhesive compositions other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, and the content thereof is the above-mentioned content. The same can be applied to the case of the first pressure-sensitive adhesive composition (I-1) and the like.
- the first pressure-sensitive adhesive composition such as the first pressure-sensitive adhesive compositions (I-1) to (I-3) is a first pressure-sensitive adhesive containing the pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive. It is obtained by blending each component for constituting the composition. The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time. When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or diluting any of the compounding components other than the solvent in advance. You may use it by mixing the solvent with these compounding components without leaving.
- the method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
- the temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
- the composition of the first pressure-sensitive adhesive layer in the present embodiment is the composition obtained by removing the solvent from the above-mentioned first pressure-sensitive adhesive layer composition.
- the content ratio of the adhesive resin (I-1a) to the adhesive resin (I-1a) is preferably 50 to 99% by mass, more preferably 55 to 95% by mass, and even more preferably 60 to 90% by mass.
- the content ratio of the adhesive resin (I-1a) to the total mass of the first pressure-sensitive adhesive layer (I-1) may be 25 to 80% by mass, which is 30. It may be up to 75% by mass, or 35 to 70% by mass.
- the content ratio of the energy ray-curable compound with respect to the total mass of the first pressure-sensitive adhesive layer (I-1) is preferably 1 to 50% by mass, more preferably 2 to 48% by mass, and 5 It is more preferably to 45% by mass.
- the content ratio of the cross-linking agent to the total mass of the first pressure-sensitive adhesive layer (I-1) is preferably 0.1 to 10% by mass.
- the content ratio of the photopolymerization initiator to the total mass of the first pressure-sensitive adhesive layer (I-1) is 0.5 to 18.0 mass. %, More preferably 0.7 to 17.5% by mass, and even more preferably 1.0 to 15.0% by mass.
- the "content ratio" in the present specification means the content ratio of the monomer itself when the target is a monomer, or the content ratio of a constituent unit derived from the monomer when the monomer is polymerized.
- the content ratio of the adhesive resin (I-2a) to the adhesive resin (I-2a) is preferably 70.0 to 99.0% by mass, more preferably 72.5 to 97.5% by mass, and 75.0 to 95% by mass. It is more preferably 0.0% by mass.
- the first pressure-sensitive adhesive layer (I-2) contains a cross-linking agent
- the content ratio of the cross-linking agent to the total mass of the first pressure-sensitive adhesive layer (I-2) is 0.1 to 3.0% by mass. It is preferably 0.2 to 2.5% by mass, more preferably 0.3 to 2.0% by mass.
- the content ratio of the photopolymerization initiator to the total mass of the first pressure-sensitive adhesive layer (I-2) is 0.5 to 18.0 mass. %, More preferably 0.7 to 17.5% by mass, and even more preferably 1.0 to 17.0% by mass.
- the content ratio of the adhesive resin (I-2a) to the adhesive resin (I-2a) is preferably 50 to 99% by mass, more preferably 55 to 95% by mass, and even more preferably 60 to 90% by mass.
- the content ratio of the energy ray-curable low molecular weight compound with respect to the total mass of the first pressure-sensitive adhesive layer (I-3) is preferably 1 to 50% by mass, more preferably 2 to 48% by mass. It is more preferably 5 to 45% by mass.
- the content ratio of the cross-linking agent to the total mass of the first pressure-sensitive adhesive layer (I-3) is preferably 0.1 to 10% by mass. , 0.2 to 9% by mass, more preferably 0.3 to 8% by mass.
- the content ratio of the photopolymerization initiator to the total mass of the first pressure-sensitive adhesive layer (I-3) is 0.5 to 18.0 mass. %, More preferably 0.7 to 17.5% by mass, and even more preferably 1.0 to 17.0% by mass.
- the first pressure-sensitive adhesive layer (I-2) contains a pressure-sensitive adhesive resin (1-2a) and a cross-linking agent.
- the adhesive resin (1-2a) contains an isocyanate group and an energy ray-polymerizable unsaturated group in an acrylic polymer having a structural unit derived from a (meth) acrylic acid alkyl ester and a unit derived from a hydroxyl group-containing monomer. It is preferably an acrylic polymer obtained by reacting an unsaturated group-containing compound having an unsaturated group.
- the compound exemplified in the first pressure-sensitive adhesive composition (I-1) can be used, and it is particularly preferable to use trilen-2.6-diisocyanate.
- the photopolymerization initiator the compounds exemplified in the first pressure-sensitive adhesive composition (I-1) can be used, and it is particularly preferable to use 1-hydroxycyclohexylphenyl ketone.
- the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester to the total mass of the adhesive resin (1-2a) is preferably 50 to 99% by mass, more preferably 60 to 98% by mass. , 70-97% by mass, more preferably.
- the content ratio of the unit derived from the hydroxyl group-containing monomer to the total mass of the adhesive resin (1-2a) is preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass. It is more preferably 2.0 to 10% by mass.
- the (meth) acrylic acid alkyl ester in the adhesive resin (1-2a) preferably has an alkyl group having 1 to 12 carbon atoms, and more preferably 1 to 4 carbon atoms.
- the adhesive resin (1-2a) preferably has a structural unit derived from two or more kinds of (meth) acrylic acid alkyl esters, and is a structural unit derived from methyl (meth) acrylate and n-butyl (meth) acrylic acid. It is more preferable to have a structural unit derived from methyl methacrylate and n-butyl acrylate.
- the hydroxyl group-containing monomer in the adhesive resin (1-2a) those exemplified in the above-mentioned adhesive resin (I-1a) can be used, and it is particularly preferable to use 2-hydroxyethyl acrylate. ..
- the unsaturated group-containing compound having an isocyanate group and an energy ray-polymerizable unsaturated group the compound exemplified in the first pressure-sensitive adhesive composition (I-2) can be used, and 2-methacryloyloxyethyl isocyanate is used. It is particularly preferable to do so.
- the amount of the unsaturated group-containing compound having an isocyanate group and an energy ray-polymerizable unsaturated group is preferably 20 to 80 mol, more preferably 25 to 75 mol. It is preferable, and 30 to 70 mol is more preferable.
- the embedded layer is a layer among viscoelastic layers that embeds and protects the terminals of a semiconductor device with terminals.
- the embedded layer is in the form of a sheet or a film, and the constituent material thereof is not particularly limited as long as the above conditions are satisfied.
- the purpose is to prevent the viscoelastic layer from being deformed by reflecting the shape of the terminals existing on the semiconductor surface on the viscoelastic layer covering the terminal forming surface of the semiconductor device with terminals to be protected.
- preferable constituent materials of the embedded layer include urethane (meth) acrylate, acrylic resin and the like from the viewpoint of further improving the stickability of the embedded layer.
- the embedded layer may be only one layer (single layer), or may be a plurality of layers of two or more layers, and when there are a plurality of layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is particularly suitable. Not limited.
- the thickness of the embedded layer can be appropriately adjusted according to the height of the terminals on the terminal forming surface of the terminal-equipped semiconductor device to be protected so that the thickness of the viscoelastic layer falls within the above-mentioned preferable range, but is relatively It is preferably 50 to 600 ⁇ m, more preferably 70 to 550 ⁇ m, and even more preferably 80 to 500 ⁇ m, from the viewpoint that the influence of a terminal having a high height can be easily absorbed.
- the thickness of the embedded layer is at least the above lower limit value, a viscoelastic layer having higher terminal protection performance can be formed. Further, when the thickness of the embedded layer is not more than the upper limit value, the productivity and the winding suitability in the roll shape are improved.
- the "thickness of the embedded layer” means the thickness of the entire embedded layer, and for example, the thickness of the embedded layer composed of a plurality of layers is the total thickness of all the layers constituting the embedded layer. means.
- the embedded layer preferably has a soft property suitable for embedding terminals, and is preferably softer than the first adhesive layer.
- the embedded layer may be formed by using an energy ray-curable constituent material or may be formed by using a non-energy ray-curable constituent material.
- An embedded layer formed using an energy ray-curable constituent material is preferable because its physical properties before and after curing can be easily adjusted.
- the elastic modulus of the embedded layer before curing is preferably 0.01 to 1.0 MPa, preferably 0.02 to 0.9 MPa. It is more preferably 0.03 to 0.8 MPa. When the elastic modulus of the embedded layer before curing is within the above range, the retention of the semiconductor device can be obtained.
- the elastic modulus of the embedded layer after curing is preferably 1.0 to 100 MPa, more preferably 2.0 to 95 MPa. It is preferably 3.0 to 90 MPa, more preferably 3.0 to 90 MPa. When the elastic modulus of the embedded layer after curing is within the above range, the retention of the semiconductor device can be obtained.
- the embedded layer is the embedded layer (I) formed by using the embedded layer forming composition (I) containing the acrylic resin described later, the curing of the embedded layer (I) is performed in the first and second above-mentioned.
- any step of the method for manufacturing a semiconductor device with an electromagnetic wave shielding film of the second embodiment may be performed, but the electromagnetic wave shielding film is formed after the step of embedding the terminals of the semiconductor device with terminals (or the semiconductor device assembly). It is preferable to perform this before the step of peeling the terminal-equipped semiconductor device from the terminal protection tape.
- the embedded layer is the embedded layer (II) formed by using the embedded layer forming composition (II) containing the urethane (meth) acrylate described later
- the curing of the embedded layer (II) is the above-mentioned first. It may be carried out in any step of the method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to the second embodiment, but it is preferably carried out before the step of embedding the terminals of the semiconductor device with terminals (or the semiconductor device assembly).
- the embedded layer can be formed by using an embedded layer forming composition containing the constituent material.
- an embedded layer can be formed at a target site by applying a composition for forming an embedded layer to a surface to be formed of an embedded layer, drying the composition as necessary, and curing the surface by irradiating with energy rays. Further, by applying the composition for forming an embedded layer to the release film, drying it if necessary, and curing it by irradiation with energy rays, an embedded layer having a desired thickness can be formed, and the desired portion can be formed. The embedded layer can also be transferred. A more specific method for forming the embedded layer will be described in detail later together with other methods for forming the layer.
- the ratio of the contents of the components that do not vaporize at room temperature in the composition for forming the embedded layer is usually the same as the ratio of the contents of the components of the embedded layer.
- the composition for forming an embedded layer may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and the like.
- a known method for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and the like.
- Examples thereof include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
- the drying conditions of the composition for forming the embedded layer are not particularly limited, but the composition for forming the embedded layer is preferably heat-dried when it contains a solvent described later, and in this case, for example, 70 to 130 ° C. It is preferable to dry under the condition of 10 seconds to 5 minutes.
- the composition for forming an embedded layer has energy ray curability, it is preferably cured by irradiation with energy rays.
- composition for forming an embedded layer examples include a composition for forming an embedded layer (I) containing an acrylic resin, a composition for forming an embedded layer containing urethane (meth) acrylate (II), and the like.
- the composition for forming an embedded layer (I) contains an acrylic resin.
- the composition (I) for forming an embedded layer includes, among the above-mentioned first pressure-sensitive adhesive compositions (I-1), a pressure-sensitive adhesive resin (I-1a) which is an acrylic resin, an energy ray-curable compound, and the like.
- the first pressure-sensitive adhesive composition (I-2) which contains the above, an energy ray-curable pressure-sensitive adhesive in which an unsaturated group is introduced into the side chain of the pressure-sensitive adhesive resin (I-1a) which is an acrylic resin.
- a composition containing the sex resin (I-2a) can be used as the composition for forming an embedded layer (I).
- the adhesive resin (I-1a) and the energy ray-curable compound used in the embedded layer forming composition (I) are the adhesive resin (I-1a) used in the above-mentioned first adhesive composition (I-1). And the description of the energy ray curable compound is the same.
- the adhesive resin (I-2a) used in the embedded layer forming composition (I) is the same as the description of the adhesive resin (I-2a) used in the first adhesive composition (I-2) described above. ..
- the composition for forming an embedded layer (I) preferably further contains a cross-linking agent.
- the cross-linking agent used in the embedded layer forming composition (I) is the same as the description of the cross-linking agent used in the first pressure-sensitive adhesive composition (I-1) and the first pressure-sensitive adhesive composition (I-2) described above. ..
- the composition for forming an embedded layer (I) may further contain a photopolymerization initiator and other additives.
- the photopolymerization initiator and other additives used in the embedded layer forming composition (I) are the light used in the first pressure-sensitive adhesive composition (I-1) and the first pressure-sensitive adhesive composition (I-2) described above.
- the description is the same as for the polymerization initiator and other additives.
- the composition for forming an embedded layer (I) may contain a solvent.
- the solvent used in the embedded layer forming composition (I) is the same as the description of the solvent used in the first pressure-sensitive adhesive composition (I-1) and the first pressure-sensitive adhesive composition (I-2) described above.
- the embedded layer has a soft property suitable for embedding terminals.
- the embedded layer can be designed as Further, by adjusting the content of the cross-linking agent in the composition for forming the embedded layer (I), the embedded layer can be designed to have a soft property suitable for embedding terminals.
- the composition of the embedded layer in the present embodiment is the above-mentioned composition for forming an embedded layer (I) from which the solvent has been removed.
- the composition (I) for forming an embedded layer is the above-mentioned first pressure-sensitive adhesive composition (I-1), which is an acrylic resin, a pressure-sensitive resin (I-1a), an energy ray-curable compound, and the like.
- the content ratio of the adhesive resin (I-1a), which is an acrylic resin, to the total mass of the embedded layer (I) in the embedded layer (I) in the case of the composition containing the above is 50 to 99% by mass. Is more preferable, 55 to 95% by mass is more preferable, and 60 to 90% by mass is further preferable.
- the content ratio of the adhesive resin (I-1a), which is an acrylic resin, to the total mass of the embedded layer (I) may be 45 to 90% by mass, and 50 to 85% by mass. May be%.
- the content ratio of the energy ray-curable compound with respect to the total mass of the embedded layer (I) is preferably 0.5 to 50% by mass, and more preferably 5 to 45% by mass.
- the content ratio of the cross-linking agent to the total mass of the embedded layer (I) is preferably 0.1 to 10% by mass, preferably 0.2 to 9% by mass. More preferably, it is more preferably 0.3 to 8% by mass.
- the content ratio of the photopolymerization initiator to the total mass of the embedded layer (I) is preferably 0.5 to 18.0% by mass, preferably 0.7. It is more preferably to 17.5% by mass, and even more preferably 1.0 to 17.0% by mass.
- the composition for forming an embedded layer (I) contains an energy ray-curable adhesive resin (1-2a) in which an unsaturated group is introduced into the side chain of the adhesive resin (I-1a) which is an acrylic resin.
- the content ratio of the energy ray-curable adhesive resin (1-2a) in which an unsaturated group is introduced into the side chain with respect to the total mass of the embedded layer in the embedded layer (I) is 10 to 70. It is preferably by mass, more preferably 15 to 65% by mass, and even more preferably 20 to 60% by mass.
- the content ratio of the cross-linking agent to the total mass of the embedded layer (I) is preferably 0.1 to 10% by mass, preferably 0.2 to 9% by mass.
- the embedded layer (I) contains a photopolymerization initiator
- the content ratio of the photopolymerization initiator to the total mass of the embedded layer (I) is preferably 0.5 to 18.0% by mass, preferably 0.7. It is more preferably to 17.5% by mass, and even more preferably 1.0 to 17.0% by mass.
- the embedded layer (I) of the present embodiment may further contain the adhesive resin (I-1a) which is the acrylic resin.
- the content ratio of the adhesive resin (I-1a), which is an acrylic resin, to the total mass of the embedded layer (I) is preferably 20.0 to 60.0% by mass, and 22.5 to 57.
- the embedded layer (I) of the present embodiment further contains the adhesive resin (I-1a) which is the acrylic resin, the adhesive resin with respect to 100 parts by mass of the adhesive resin (1-2a).
- the content of (1-1a) is preferably 70.0 to 99.0 parts by mass, more preferably 72.5 to 97.5 parts by mass, and 75.0 to 95.0 parts by mass. Is more preferable.
- the composition of the curable adhesive resin (1-2a) includes the adhesive resin (I-1a), which is an acrylic resin used in the above-mentioned first pressure-sensitive adhesive composition (I-1), and an energy ray-curable compound. , The same as the description of the energy ray-curable adhesive resin (1-2a) in which an unsaturated group is introduced into the side chain of the adhesive resin (I-1a) may be used.
- the embedded layer (I) containing the adhesive resin (1-2a), the adhesive resin (1-1a), the cross-linking agent, and the photopolymerization initiator is preferable.
- the adhesive resin (1-1a) is preferably an acrylic polymer having a structural unit derived from a (meth) acrylic acid alkyl ester and a unit derived from a carboxy group-containing monomer.
- the adhesive resin (1-2a) has an isocyanate group and an energy ray-polymerizable unsaturated group in an acrylic polymer having a structural unit derived from a (meth) acrylic acid alkyl ester and a unit derived from a hydroxyl group-containing monomer.
- the cross-linking agent the compound exemplified in the above-mentioned first pressure-sensitive adhesive composition (I-1) can be used, and trilen-2,6-diisocyanate, N, N'-(cyclohexane-1,3-diyl) can be used. It is particularly preferred to use bismethylene) bis (glycidylamine).
- the cross-linking agent the compound exemplified in the above-mentioned first pressure-sensitive adhesive composition (I-1) can be used, and it is particularly preferable to use 1-hydroxycyclohexylphenyl ketone.
- the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester to the total mass of the adhesive resin (1-1a) is preferably 75 to 99% by mass, more preferably 80 to 98% by mass. , 85-97% by mass, more preferably.
- the content ratio of the constituent unit of the carboxy group-containing monomer to the total mass of the adhesive resin (1-1a) is preferably 1.0 to 30% by mass, more preferably 2.0 to 25% by mass. , 3.0 to 20% by mass, more preferably 5.0 to 15% by mass.
- the (meth) acrylic acid alkyl ester in the adhesive resin (1-1a) preferably has an alkyl group having 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
- the adhesive resin (1-1a) is preferably an acrylic acid alkyl ester.
- the (meth) acrylic acid alkyl ester is particularly preferably n-butyl acrylate.
- the carboxy-containing monomer in the adhesive resin (1-1a) include ethylenically unsaturated monocarboxylic acid, ethylenically unsaturated dicarboxylic acid, and anhydride of ethylenically unsaturated dicarboxylic acid, and among them, ethylenically unsaturated. Saturated monocarboxylic acids are preferred, (meth) acrylic acids are more preferred, and acrylic acids are particularly preferred.
- the weight average molecular weight of the adhesive resin (1-1a) of the present embodiment is preferably 100,000 to 800,000, more preferably 150,000 to 700,000, and more preferably 200,000 to 600,000. It is more preferably 000.
- the "weight average molecular weight” is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
- the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester to the total mass of the adhesive resin (1-2a) is preferably 1.0 to 95% by mass, preferably 2.0 to 90% by mass. More preferably, it is more preferably 3.0 to 85% by mass.
- the content ratio of the unit derived from the hydroxyl group-containing monomer to the total mass of the adhesive resin (1-2a) is preferably 1.0 to 50% by mass, more preferably 2.0 to 45% by mass. It is more preferably 3.0 to 40% by mass.
- the (meth) acrylic acid alkyl ester in the adhesive resin (1-2a) preferably has an alkyl group having 1 to 12 carbon atoms, and more preferably 1 to 4 carbon atoms.
- the adhesive resin (1-2a) preferably has a structural unit derived from two or more kinds of (meth) acrylic acid alkyl esters, and is a structural unit derived from methyl (meth) acrylate and n-butyl (meth) acrylic acid. It is more preferable to have a structural unit derived from methyl methacrylate and n-butyl acrylate.
- the hydroxyl group-containing monomer in the adhesive resin (1-2a) those exemplified in the first pressure-sensitive adhesive composition (I-1) described later can be used, and 2-hydroxyethyl acrylate is used. Is particularly preferable.
- the unsaturated group-containing compound having an isocyanate group and an energy ray-polymerizable unsaturated group the compound exemplified in the first pressure-sensitive adhesive composition (I-2) described later can be used, and 2-methacryloyloxyethyl It is particularly preferred to use isocyanates.
- the amount of the unsaturated group-containing compound having an isocyanate group and an energy ray-polymerizable unsaturated group is preferably 20 to 200 mol, more preferably 30 to 190 mol. It is preferable, and 30 to 180 mol is more preferable.
- the weight average molecular weight of the adhesive resin (1-2a) of the present embodiment is preferably 50,000 to 1,000,000, more preferably 60,000 to 900,000, and 70,000. It is more preferably ⁇ 800,000.
- composition for forming an embedded layer (II) contains urethane (meth) acrylate.
- Urethane (meth) acrylate is a compound having at least a (meth) acryloyl group and a urethane bond in one molecule, and has energy ray polymerization property.
- Urethane (meth) acrylate may be monofunctional (having only one (meth) acryloyl group in one molecule) or bifunctional or more ((meth) acryloyl group in one molecule). , That is, a polyfunctional one, but it is preferable to use at least a monofunctional one.
- the compound or resin having at least a (meth) acryloyl group and urethane bond in one molecule is a compound or resin. It is excluded from the urethane (meth) acrylate in the embedded layer forming composition (II).
- the urethane (meth) acrylate contained in the composition for forming an embedded layer includes, for example, a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound with a polyvalent isocyanate compound, and further having a hydroxyl group and (meth). ) Examples thereof include those obtained by reacting a (meth) acrylic compound having an acryloyl group.
- the "terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.
- the urethane (meth) acrylate contained in the composition for forming an embedded layer (II) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule.
- one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.
- polyol compound examples include alkylene diols, polyether-type polyols, polyester-type polyols, polycarbonate-type polyols, and the like.
- the polyol compound may be any of a bifunctional diol, a trifunctional triol, a tetrafunctional or higher functional polyol, etc., but the diol is preferable in terms of easy availability, excellent versatility, reactivity and the like. ..
- the polyether-type polyol is not particularly limited, but is preferably a polyether-type diol, and examples of the polyether-type diol include a compound represented by the following formula (1). ..
- n represents the number of repeating units of the group represented by the equation "-RO-", and is not particularly limited as long as it is an integer of 2 or more. Among them, n is preferably 10 to 250, more preferably 25 to 205, and particularly preferably 40 to 185.
- R is not particularly limited as long as it is a divalent hydrocarbon group, but is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, and an ethylene group. It is more preferably a propylene group or a tetramethylene group, and particularly preferably a propylene group or a tetramethylene group.
- the compound represented by the above formula (1) is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol, and more preferably polypropylene glycol or polytetramethylene glycol.
- a terminal isocyanate urethane prepolymer having an ether bond portion represented by the following formula (1a) can be obtained as the terminal isocyanate urethane prepolymer. ..
- the urethane (meth) acrylate can form a urethane (meth) acrylate having the ether bond portion, that is, a structural unit derived from the polyether type diol. It becomes a urethane (meth) acrylate having.
- the polyester-type polyol is not particularly limited, and examples thereof include a polyester-type polyol obtained by carrying out an esterification reaction using a polybasic acid or a derivative thereof.
- the term "derivative” means a compound in which one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified.
- the "group” includes not only an atomic group formed by bonding a plurality of atoms but also one atom.
- polybasic acid and its derivative examples include a polybasic acid and its derivative which are usually used as a raw material for producing polyester.
- polybasic acid examples include saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid, aromatic polybasic acid and the like, and dimer acid corresponding to any of these may be used.
- saturated aliphatic dibasic acid examples include saturated aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. ..
- unsaturated aliphatic dibasic acid examples include unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid.
- aromatic polybasic acid include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid; aromatic tribasic acids such as trimellitic acid; pyromellitic acid and the like. Aromatic tetrabasic acid and the like.
- Examples of the derivative of the polybasic acid include the above-mentioned saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid and acid anhydride of aromatic polybasic acid, hydrogenated dimer acid and the like.
- polybasic acid or a derivative thereof one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..
- the polybasic acid is preferably an aromatic polybasic acid in that it is suitable for forming an embedded layer having an appropriate hardness.
- a known catalyst may be used if necessary.
- the catalyst include tin compounds such as dibutyltin oxide and stannous octylate; alkoxytitanium such as tetrabutyl titanate and tetrapropyl titanate.
- the polycarbonate-type polyol is not particularly limited, and examples thereof include those obtained by reacting a glycol similar to the compound represented by the above formula (1) with an alkylene carbonate.
- a glycol similar to the compound represented by the above formula (1) with an alkylene carbonate.
- the glycol and the alkylene carbonate one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected. ..
- the number average molecular weight calculated from the hydroxyl value of the polyol compound is preferably 1000 to 10000, more preferably 2000 to 9000, and particularly preferably 3000 to 7000.
- the number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated from the following formula.
- the polyol compound is preferably a polyether-type polyol, and more preferably a polyether-type diol.
- the polyisocyanate compound to be reacted with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.
- the polyisocyanate compound one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.
- polyvalent isocyanate compound examples include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornan diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and dicyclohexylmethane-2.
- chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate
- isophorone diisocyanate norbornan diisocyanate
- dicyclohexylmethane-4,4'-diisocyanate dicyclohexylmethane-2.
- the multivalent isocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate or xylylene diisocyanate from the viewpoint of handleability.
- the (meth) acrylic compound to be reacted with the terminal isocyanate urethane prepolymer is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth) acryloyl group in one molecule. ..
- the (meth) acrylic compound one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.
- Examples of the (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxycyclooctyl (meth) acrylate Hydroxyl-containing (meth) acrylic acid esters such as hydroxy-3-phenyloxypropyl, pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; N-methylol (meth) acrylamide, etc.
- Hydroxy group-containing (meth) acrylamide examples thereof include a reactant obtained by reacting vinyl alcohol, vinylphenol or bisphenol A diglycidyl ether with (meth) acrylic acid.
- the (meth) acrylic compound is preferably a hydroxyl group-containing (meth) acrylic acid ester, more preferably a hydroxyl group-containing (meth) acrylic acid alkyl ester, and (meth) acrylic acid 2-. Hydroxyethyl is particularly preferred.
- the reaction between the terminal isocyanate urethane prepolymer and the (meth) acrylic compound may be carried out using a solvent, a catalyst or the like, if necessary.
- the conditions for reacting the terminal isocyanate urethane prepolymer with the (meth) acrylic compound may be appropriately adjusted.
- the reaction temperature is preferably 60 to 100 ° C.
- the reaction time is 1 to 1 to 1. It is preferably 4 hours.
- the urethane (meth) acrylate may be any of an oligomer, a polymer, and a mixture of the oligomer and the polymer, but is preferably an oligomer.
- the weight average molecular weight of the urethane (meth) acrylate is preferably 1000 to 100,000, more preferably 3000 to 80000, and particularly preferably 5000 to 65000.
- the weight average molecular weight is 1000 or more, in the polymer of urethane (meth) acrylate and the polymerizable monomer described later, due to the intermolecular force between the structures derived from urethane (meth) acrylate, the embedded layer The hardness can be easily optimized.
- the composition for forming an embedded layer (II) may contain a polymerizable monomer in addition to the urethane (meth) acrylate from the viewpoint of further improving the film-forming property.
- the polymerizable monomer is preferably a compound having energy ray polymerizable property, having a weight average molecular weight of less than 1000, and having at least one (meth) acryloyl group in one molecule.
- Examples of the polymerizable monomer include a (meth) acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has 1 to 30 carbon atoms and is chain-like; a hydroxyl group, an amide group, an amino group, an epoxy group, or the like.
- Functional group-containing (meth) acrylic compound having a functional group of; (meth) acrylic acid ester having an aliphatic cyclic group; (meth) acrylic acid ester having an aromatic hydrocarbon group; having a heterocyclic group ( Meta) Acrylic acid ester; a compound having a vinyl group; a compound having an allyl group and the like can be mentioned.
- Examples of the (meth) acrylic acid alkyl ester having a chain alkyl group having 1 to 30 carbon atoms include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and n-propyl (meth) acrylic acid.
- Examples of the functional group-containing (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylate.
- Hydroxyl-containing (meth) acrylic acid esters such as 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (Meta) acrylamides such as N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc.
- (meth) acrylic acid ester having an amino group hereinafter, may be referred to as "amino group-containing (meth) acrylic acid ester”
- one hydrogen atom of the amino group is replaced with a group other than the hydrogen atom.
- a (meth) acrylic acid ester having a mono-substituted amino group hereinafter, may be referred to as "mono-substituted amino group-containing (meth) acrylic acid ester”
- the two hydrogen atoms of the amino group are other than hydrogen atoms.
- a (meth) acrylic acid ester having a disubstituted amino group substituted with a group (hereinafter, may be referred to as "disubstituted amino group-containing (meth) acrylic acid ester”); glycidyl (meth) acrylate, (meth). ) (Meta) acrylic acid ester having an epoxy group such as methyl glycidyl acrylate (hereinafter, may be referred to as "epoxy group-containing (meth) acrylic acid ester"), etc., and 2-hydroxy (meth) acrylic acid. Butyl is preferred, and 2-hydroxypropyl acrylate is more preferred.
- amino group-containing (meth) acrylic acid ester means a compound in which one or more hydrogen atoms of the (meth) acrylic acid ester are substituted with an amino group (-NH 2). ..
- the "mono-substituted amino group-containing (meth) acrylic acid ester” means a compound in which one or more hydrogen atoms of the (meth) acrylic acid ester are substituted with a mono-substituted amino group.
- disubstituted amino group-containing (meth) acrylic acid ester means a compound in which one or more hydrogen atoms of the (meth) acrylic acid ester are substituted with a disubstituted amino group.
- Examples of the group other than the hydrogen atom (that is, the substituent) in which the hydrogen atom is substituted in the "mono-substituted amino group" and the "di-substituted amino group” include an alkyl group and the like.
- Examples of the (meth) acrylic acid ester having an aliphatic cyclic group include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include dicyclopentenyloxyethyl, cyclohexyl (meth) acrylate, and adamantyl (meth) acrylate. Isobornyl (meth) acrylate is preferable, and isobornyl acrylate is more preferable.
- Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenylhydroxypropyl (meth) acrylate, benzyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Can be mentioned.
- the heterocyclic group in the (meth) acrylic acid ester having a heterocyclic group may be either an aromatic heterocyclic group or an aliphatic heterocyclic group.
- Examples of the (meth) acrylic acid ester having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and (meth) acryloyl morpholine.
- Examples of the compound having a vinyl group include styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone, N-vinylcaprolactam and the like.
- Examples of the compound having an allyl group include allyl glycidyl ether and the like.
- the polymerizable monomer preferably has a relatively bulky group from the viewpoint of good compatibility with the urethane (meth) acrylate, and such a monomer has an aliphatic cyclic group (meth).
- Acrylate ester, (meth) acrylic acid ester having an aromatic hydrocarbon group, (meth) acrylic acid ester having a heterocyclic group, and (meth) acrylic acid ester having an aliphatic cyclic group are more suitable. preferable.
- the polymerizable monomer contained in the embedded layer forming composition (II) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the polymerizable monomer is preferably 10 to 99% by mass, more preferably 15 to 95% by mass, and 20 to 90% by mass. Is more preferable, and 25 to 80% by mass is particularly preferable.
- the composition for forming an embedded layer (II) may contain a photopolymerization initiator in addition to the urethane (meth) acrylate and the polymerizable monomer.
- the composition for forming an embedded layer (II) containing a photopolymerization initiator sufficiently promotes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.
- Examples of the photopolymerization initiator in the embedded layer forming composition (II) include the same photopolymerization initiator in the first pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the embedded layer forming composition (II) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the photopolymerization initiator is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total content of the urethane (meth) acrylate and the polymerizable monomer. It is preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
- the composition for forming an embedded layer (II) may contain a resin component other than the urethane (meth) acrylate as long as the effects of the present invention are not impaired.
- the type of the resin component and the content thereof in the composition for forming an embedded layer (II) may be appropriately selected depending on the intended purpose, and are not particularly limited.
- the composition for forming an embedded layer (II) may contain other additives that do not correspond to any of the above-mentioned components as long as the effects of the present invention are not impaired.
- the other additives include cross-linking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes) and the like.
- Additives can be mentioned.
- examples of the chain transfer agent include thiol compounds having at least one thiol group (mercapto group) in one molecule.
- thiol compound examples include nonyl mercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, triazinedithiol, triazinetrithiol, 1,2,3-propanetrithiol, and the like.
- the other additives contained in the composition for forming an embedded layer (II) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.
- the content of other additives is not particularly limited and may be appropriately selected according to the type thereof.
- composition for forming an embedded layer (II) may contain a solvent. Since the composition for forming the embedded layer (II) contains a solvent, the suitability for coating on the surface to be coated is improved.
- the composition of the embedded layer (II) in the present embodiment is the above-mentioned composition for forming an embedded layer (II) from which the solvent has been removed.
- the content ratio of urethane (meth) acrylate with respect to the total mass of the embedded layer (II) is preferably 20.0 to 60.0% by mass, more preferably 22.5 to 57.5% by mass. It is more preferably 25.0 to 55.0% by mass.
- the content ratio of the polymerizable monomer to the total mass of the embedded layer (II) is preferably 40.0 to 80.0% by mass, and 42.5 to 77.
- the polymerizable monomer preferably contains either one or both of isobornyl acrylate and 2-hydroxypropyl acrylate.
- the content ratio of the cross-linking agent to the total mass of the embedded layer (II) is preferably 0.1 to 5.0% by mass, preferably 0.2 to 4.5. It is more preferably mass%, and even more preferably 0.3 to 4.0 mass%.
- the content ratio of the photopolymerization initiator with respect to the total mass of the embedded layer (II) is preferably 0.1 to 10.0% by mass, preferably 0.2. It is more preferably about 9.0% by mass, and even more preferably 0.3 to 8.0% by mass.
- the photopolymerization initiator preferably contains 2-hydroxy-2-methyl-1-phenyl-propane-1-one.
- the content ratio of the thiol compound with respect to the total mass of the embedded layer (II) is preferably 0.5 to 10.0% by mass, and 0.6 to 9.0. It is more preferably mass%, and even more preferably 0.7 to 8.0 mass%.
- the thiol compound preferably contains pentaerythritol tetrakis (3-mercaptobutyrate).
- the composition for forming an embedded layer such as the composition for forming an embedded layer (I) and (II) can be obtained by blending each component for forming the composition.
- the order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
- a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or diluting any of the compounding components other than the solvent in advance. You may use it by mixing the solvent with these compounding components without leaving.
- the method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
- the temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
- the base material is in the form of a sheet or a film, and examples of the constituent materials thereof include various resins.
- the resin include polyethylene such as low density polyethylene (also referred to as LDPE), linear low density polyethylene (also referred to as LLDPE), and high density polyethylene (also referred to as HDPE); polypropylene, polybutene, polybutadiene, and polymethyl.
- Polyethylene other than polyethylene such as penten and norbornene resin; ethylene-vinyl acetate copolymer (also referred to as EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- Ethylene-based copolymers such as norbornene copolymers (ie, copolymers obtained using ethylene as the monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (ie, vinyl chloride as the monomer) Resin obtained using); Polyethylene; Polycycloolefin; Polyethylene terephthalate (also referred to as PET), polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, all constituents.
- EVA ethylene-vinyl acetate copolymer
- ethylene- (meth) acrylic acid copolymer ethylene
- Polyethylene such as total aromatic polyester having an aromatic cyclic group as a unit; a copolymer of two or more kinds of the polyester; poly (meth) acrylic acid ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; Examples thereof include polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; polyether ketone and the like.
- the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.
- the resin for example, a crosslinked resin in which one or more of the resins exemplified above are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.
- the resin constituting the base material may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
- the base material may be only one layer (single layer), may be a plurality of layers of two or more layers, and when there are a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of these multiple layers is particularly suitable. Not limited.
- the thickness of the base material is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, further preferably 15 to 300 ⁇ m, and particularly preferably 20 to 150 ⁇ m.
- the "thickness of the base material” means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.
- the base material has a high thickness accuracy, that is, a base material in which the variation in thickness is suppressed regardless of the part.
- a material that can be used to construct a base material having such a high accuracy of thickness for example, polyethylene, a polyolefin other than polyethylene, polyethylene terephthalate, and an ethylene-vinyl acetate copolymer ( EVA) and the like.
- the base material contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). You may.
- the Young's modulus of the base material is preferably 100 to 2000 MPa, more preferably 150 to 1500 MPa, and even more preferably 200 to 1000 MPa.
- the Young's modulus of the base material is at least the lower limit of the above range, dimensional stability can be ensured when the electromagnetic wave shielding film is formed.
- the Young's modulus of the base material is not more than the upper limit of the above range, the stretchability of the terminal protection tape is improved.
- the Young's modulus of the base material can be measured by the method described in Examples described later.
- the elongation at break of the base material is preferably 50 to 2000%, more preferably 70 to 1600%, and even more preferably 90 to 1200%.
- the elongation at break of the base material can be measured by the method described in Examples described later.
- the breaking stress of the base material is preferably 10 to 300 MPa, more preferably 20 to 250 MPa, and even more preferably 30 to 200 MPa.
- a method of grasping and stretching the outer peripheral portion of the terminal protection tape by using the gripping member or the like described in ⁇ Stretching method 1 of the terminal protection tape> described later (biaxial stretching). )
- ⁇ Stretching method of terminal protection tape 2> can be stretched by the method using the ring frame.
- the breaking stress of the base material can be measured by the method described in Examples described later.
- the base material may be transparent, opaque, colored depending on the purpose, or another layer may be vapor-deposited.
- the base material is preferably one that allows energy rays to pass through.
- the base material can be produced by a known method.
- a base material containing a resin can be produced by molding a resin composition containing the resin.
- the release film may be one known in the art.
- the preferred release film is, for example, one in which at least one surface of a resin film such as polyethylene terephthalate is peeled by a silicone treatment or the like; at least one surface of the film is a release surface made of polyolefin. And so on.
- the thickness of the release film is preferably the same as the thickness of the base material.
- the second pressure-sensitive adhesive layer (that is, the bonded pressure-sensitive adhesive layer) is a pressure-sensitive adhesive layer for bonding the terminal protection tape of the present embodiment to the support.
- the second pressure-sensitive adhesive layer may be one known in the art, and can be appropriately selected from those described in the above-mentioned first pressure-sensitive adhesive layer according to the support.
- the second pressure-sensitive adhesive composition for forming the second pressure-sensitive adhesive layer is the same as the first pressure-sensitive adhesive composition, and the method for producing the second pressure-sensitive adhesive composition is also the production of the first pressure-sensitive adhesive composition. Similar to the method.
- the terminal protection tape can be manufactured by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship.
- the method of forming each layer is as described above.
- the embedded layer is laminated by applying the above-mentioned composition for forming an embedded layer on the peeled surface of the release film and drying it if necessary.
- the first pressure-sensitive adhesive layer is laminated by applying the above-mentioned first pressure-sensitive adhesive composition on the peel-processed surface of another release film and drying it if necessary.
- the terminal protection tape in which the embedding layer and the first pressure-sensitive adhesive layer are laminated on the base material in this order in the thickness direction can be produced by the method shown below. For example, by peeling off the release film on the side of the embedding layer of the terminal protection tape in which the release film, the embedding layer, the first adhesive layer, and the release film are laminated in this order, and sticking this to the base material. , A terminal protection tape in which an embedded layer, a first pressure-sensitive adhesive layer, and a release film are laminated in this order can be obtained. The release film may be removed when the terminal protection tape is used.
- the method for manufacturing a semiconductor device with an electromagnetic wave shielding film includes a step of embedding the terminals of the semiconductor device with terminals in the viscoelastic layer of the terminal protection tape having a viscoelastic layer, and the terminal protection.
- the step of peeling the semiconductor device from the terminal protection tape is included.
- FIG. 5 shows a method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to the present embodiment, in which a terminal protection tape 3 having an adhesive layer 14, an embedded layer 13, and a base material 11 in this order is shown. It is sectional drawing which shows typically the manufacturing method of the semiconductor device with an electromagnetic wave shielding film fixed to the support 30 as shown in 4.
- the semiconductor device 65 with terminals is placed on the viscoelastic layer 12 of the terminal protection tape, and the terminal 91 side, that is, the terminal forming surface 63a of the circuit board 63 is below.
- the terminal 91 is embedded in the viscoelastic layer 12 by pressing the terminal 91.
- the viscoelastic layer 12 is brought into contact with the terminal 91 of the terminal-equipped semiconductor device 65, and the terminal-equipped semiconductor device 65 is pressed against the terminal protection tape.
- the outermost surface of the viscoelastic layer 12 on the side of the adhesive layer 14 is sequentially crimped to the surface of the terminal 91 and the terminal forming surface 63a of the circuit board 63.
- the viscoelastic layer 12 is softened, spreads between the terminals 91 so as to cover the terminals 91, adheres to the terminal forming surface 63a, and is in close contact with the surface of the terminals 91, particularly the terminals.
- the terminal 91 is embedded by covering the surface of the portion near the forming surface 63a.
- a known method of crimping and attaching various sheets to an object can be applied, and examples thereof include a method using a laminate roller and a vacuum laminator.
- the pressure at which the semiconductor device 65 with terminals is crimped onto the terminal protection tape is not particularly limited, but is preferably 0.1 to 1.5 MPa, more preferably 0.3 to 1.3 MPa. ..
- the heating temperature is preferably 30 to 70 ° C, more preferably 35 to 65 ° C, and particularly preferably 40 to 60 ° C. Further, it is preferable to attach the first adhesive layer 14 of the viscoelastic layer 12 to the terminal forming surface 63a.
- the elastic modulus of the embedded layer 13 is preferably 0.05 to 20 MPa, preferably 0.07 to 18 MPa. More preferably, it is 0.09 to 16 MPa. When the elastic modulus is within the above range, it becomes easy to embed the semiconductor device with terminals in the terminal protection tape.
- a conductive resin 101 is applied to the exposed surface of the semiconductor device 65 with terminals that is not embedded in the viscoelastic layer 12 of the terminal protection tape (FIG. 5 (c)), and further thermoset to form a conductive material.
- the electromagnetic wave shield film 10 is formed (FIG. 5 (d)).
- a method of forming the electromagnetic wave shielding film 10 by coating with a conductive material a method such as sputtering, ion plating, or spray coating can also be used.
- the adhesive strength of the terminal protection tape 3 to the terminal-equipped semiconductor device 65 after the step of embedding the terminal-equipped semiconductor device 65 and before the step of forming the electromagnetic wave shield film is 1.0 to 6.5 N / 25 mm. It is preferably 1.1 to 6.0 N / 25 mm, more preferably 1.2 to 5.5 N / 25 mm, and even more preferably 1.2 to 5.5 N / 25 mm.
- the adhesive strength is within the above range, the peelability in the step of peeling the terminal-equipped semiconductor device on which the electromagnetic wave shielding film is formed from the terminal protection tape is improved.
- the method for measuring the adhesive strength will be described in detail in Examples.
- the bonding area between the terminal-equipped semiconductor device on which the electromagnetic wave shield film is formed and the viscoelastic layer 12 is reduced, and the terminal-equipped semiconductor device on which the electromagnetic wave shield film is formed is terminal-protected. It is peeled off from the tape 3 (FIG. 5 (e)).
- the push-up height u1 in picking is preferably higher than the height h1 of the terminal 91, and is preferably 2.0 ⁇ u1 / h1 ⁇ 10.
- the "terminal height” means the height of the terminal at the highest position from the terminal forming surface.
- the stretched amount of the terminal protection tape in stretching is preferably 1.0 mm or more, more preferably 2.0 mm or more, and further preferably 3.0 mm or more.
- the stretching amount is equal to or greater than the lower limit, the bonding area between the terminal-equipped semiconductor device on which the electromagnetic wave shield film is formed and the viscoelastic layer 12 becomes sufficiently small, and the terminal-equipped semiconductor device on which the electromagnetic wave shield film is formed becomes available. It becomes easy to peel off from the terminal protection tape 3.
- the upper limit of the stretching amount is not particularly limited as long as it shows the effect of the present invention, but may be, for example, 20.0 mm or less.
- the stretching amount is, for example, preferably 1.0 mm or more and 19.0 mm or less, more preferably 2.0 mm or more and 18.0 mm or less, and further preferably 3.0 mm or more and 17.0 mm or less.
- the "stretched amount” means "the length of the terminal protection tape in the stretching direction after stretching"-"the length of the terminal protecting tape in the stretching direction before stretching".
- the semiconductor device 65 with terminals to be shielded by electromagnetic waves may be a semiconductor device 65 with terminals manufactured individually, and is individualized by a dicing method.
- the semiconductor device 65 with terminals may be used.
- a semiconductor device 65 with terminals which is separated into individual pieces and whose individual electronic components 61 and 62 are sealed with a sealing resin 64, is used with a terminal protection tape 3.
- the method of electromagnetic wave shielding has been shown.
- the terminal-equipped semiconductor device 65 is electromagnetically shielded from the terminal-equipped semiconductor device assembly 6 before being separated by using the terminal protection tape 2. You can also.
- Another method of manufacturing a semiconductor device with an electromagnetic wave shielding film according to another embodiment of the present invention includes a step of embedding terminals of a semiconductor device assembly with terminals in the viscoelastic layer of a terminal protection tape having a viscoelastic layer, and the above-mentioned.
- the process of dicing the terminal-equipped semiconductor device assembly to make the terminal-equipped semiconductor device assembly into a terminal-equipped semiconductor device in which terminals are embedded in the viscoelastic layer of the terminal protection tape, and the terminal protection tape The step of forming an electromagnetic wave shielding film on the exposed surface of the terminal-equipped semiconductor device not embedded in the viscoelastic layer, and the terminal-attached semiconductor device on which the electromagnetic wave shielding film is formed by stretching the terminal protection tape. The step of peeling from the terminal protection tape is included.
- a method of manufacturing the semiconductor device with an electromagnetic wave shielding film of the present embodiment will be described with reference to FIG.
- FIG. 6 shows a method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to the present embodiment, in which a terminal protection tape 3 having an adhesive layer 14, an embedded layer 13, and a base material 11 in this order is shown. It is sectional drawing which shows typically the manufacturing method of the semiconductor device with an electromagnetic wave shielding film fixed to the support 30 as shown in 4.
- the semiconductor device assembly 6 with terminals connected to the viscoelastic layer 12 of the terminal protection tape by the circuit board 63 is attached to the terminal 91 side, that is, the circuit.
- the terminal 91 is embedded in the viscoelastic layer 12 by pressing the substrate 63 with the terminal forming surface 63a facing down, as in the cases of FIGS. 5A and 5B.
- the terminals 91 are embedded in the viscoelastic layer 12 of the terminal protection tape as in the cases of FIGS. 5A and 5B. ..
- the viscoelastic layer 12 can be softened and the viscoelastic layer 12 can be brought into close contact with the terminal forming surface 63a of the circuit board 63.
- the pressure at which the semiconductor device assembly 6 with terminals is crimped onto the terminal protection tape is not particularly limited, but is preferably 0.1 to 1.5 MPa, preferably 0.3 to 1.3 MPa. More preferred.
- the heating temperature is preferably 30 to 70 ° C, more preferably 35 to 65 ° C, and particularly preferably 40 to 60 ° C. Further, it is preferable to attach the first adhesive layer 14 of the viscoelastic layer 12 to the terminal forming surface 63a.
- the terminal protection tape of the present invention used in the step of forming the electromagnetic wave shield film also serves as a dicing tape for the terminal-equipped semiconductor device assembly 6.
- the dicing tape is used in the method for manufacturing the semiconductor device with an electromagnetic wave shielding film shown in FIG. 5 when the semiconductor device 65 with a terminal to be the target of the electromagnetic wave shielding is the semiconductor device 65 with a terminal separated by the dicing method. It is necessary to pick up the above semiconductor device with terminals and replace it with the terminal protection tape (FIG. 5 (a)). However, in the method of manufacturing the semiconductor device with electromagnetic wave shielding film shown in FIG. 6, the dicing tape is used. The work of replacing the terminal-equipped semiconductor device 65 with the terminal protection tape can be omitted.
- the conductive resin 101 is applied to the exposed surface of the semiconductor device 65 with terminals that is not embedded in the viscoelastic layer 12 of the terminal protection tape (FIG. 6 (d)). At this time, if the conductive resin 101 is not sufficiently separated at the boundary portion of each terminal-equipped semiconductor device 65 of the terminal-equipped semiconductor device assembly 6, the terminal protection tape may be stretched using an expanding device or the like. Good. Individual terminal-equipped semiconductor devices 65 can be individualized with the conductive resin 101 coated on each side surface of the individualized terminal-equipped semiconductor device 65. Further, the conductive resin 101 applied to the top surface and the side surface of the fragmented semiconductor device 65 with terminals is heated and cured to be not embedded in the viscoelastic layer 12 of the terminal protection tape.
- An electromagnetic wave shielding film 10 made of a conductive material is formed on the exposed surface of 65 (FIG. 6 (e)).
- the electromagnetic wave shielding film 10 may be formed by directly sputtering the conductive material onto the semiconductor device 65 with terminals (FIG. 6 (c)) (FIG. 6 (e)).
- the bonding area between the terminal-equipped semiconductor device on which the electromagnetic wave shield film is formed and the viscoelastic layer 12 is reduced, and the terminal-equipped semiconductor device on which the electromagnetic wave shield film is formed is terminal-protected. It is peeled off from the tape 3 (FIG. 6 (f)). When peeling, it is preferable to perform picking by pushing upward with a pin or the like from the base material 11 side of the terminal protection tape 3.
- the semiconductor device 65 with terminals coated with the electromagnetic wave shield film 10 can be taken out (FIG. 6 (g)). ..
- the embedded layer 13 and the adhesive layer 14 are energy ray-curable, before the step of embedding the terminals of the semiconductor assembly with terminals in the viscoelastic layer 12 of the terminal protection tape, or It is preferable to perform curing after the step of embedding the terminals of the semiconductor device assembly with terminals in the viscoelastic layer 12 of the end terminal protection tape and before dicing.
- a step of stretching the terminal protection tape 3 during the steps of the above-mentioned manufacturing method 1 of the semiconductor device with the electromagnetic wave shielding film and the manufacturing method 2 of the semiconductor device with the electromagnetic wave shielding film (FIGS. 5 (e) and 6 (f)).
- the method for stretching the terminal protection tape 3 in) is not particularly limited, and examples thereof include the following two methods.
- the method of stretching the terminal protection tape of the present embodiment is a method of grasping and stretching the outer peripheral portion of the terminal protection tape using a gripping member or the like.
- the terminal protection tape is preferably stretched by at least biaxial stretching.
- the terminal protection tape is stretched by applying tension in four directions of, for example, the + X-axis direction, the ⁇ X-axis direction, the + Y-axis direction, and the ⁇ Y-axis direction in the X-axis and the Y-axis orthogonal to each other.
- Biaxial stretching as described above can be performed, for example, by using a separation device that applies tension in the X-axis direction and the Y-axis direction.
- the X-axis and the Y-axis are orthogonal to each other, one of the directions parallel to the X-axis is the + X-axis direction, the direction opposite to the + X-axis direction is the -X-axis direction, and the direction parallel to the Y-axis.
- One of them is defined as the + Y-axis direction
- the direction opposite to the + Y-axis direction is defined as the ⁇ Y-axis direction.
- the separating device applies tension to the terminal protection tape in four directions of + X-axis direction, ⁇ X-axis direction, + Y-axis direction, and ⁇ Y-axis direction, and a plurality of holding means in each of the four directions. And, it is preferable to provide a plurality of tension applying means corresponding to them.
- the number of holding means and tension applying means in each direction depends on the size of the terminal protection tape, but may be, for example, 3 or more and 10 or less.
- the method of stretching the terminal protection tape of the present embodiment is a method of fixing the outer peripheral portion of the terminal protection tape with a fixing jig and pressing an expander to stretch the terminal protection tape.
- An example of the method of stretching the terminal protection tape of the present embodiment will be described with reference to FIG. 7.
- the viscoelastic layer 12 is attached to the ring frame 17 via the third pressure-sensitive adhesive layer 16.
- the third pressure-sensitive adhesive layer may be known in the art, and can be appropriately selected from those described in the above-mentioned first pressure-sensitive adhesive layer and second pressure-sensitive adhesive layer according to the material of the ring frame 17. ..
- the third pressure-sensitive adhesive composition for forming the third pressure-sensitive adhesive layer is the same as the first pressure-sensitive adhesive composition and the second pressure-sensitive adhesive composition, and the method for producing the third pressure-sensitive adhesive composition is also the same as the first pressure-sensitive adhesive composition. 1
- the method for producing the pressure-sensitive adhesive composition and the second method for producing the pressure-sensitive adhesive composition are the same. In this way, the terminal protection tape whose outer peripheral portion is fixed by the ring frame is pressed against the cylindrical expander 18 from the base material 11 side and pushed upward to stretch the terminal protection tape.
- the height h0 of the terminal 91 is preferably lower than the thickness d1 of the viscoelastic layer 12, and preferably 1.2 ⁇ d1 / h0 ⁇ 5.0.
- the height of the terminal 91 is preferably 20 to 300 ⁇ m, more preferably 30 to 270 ⁇ m, and particularly preferably 40 to 240 ⁇ m.
- the function of the terminal 91 can be further improved.
- the height of the terminal 91 is not more than the upper limit value, the effect of suppressing the remaining of the viscoelastic layer 12 on the upper part of the terminal 91 becomes higher.
- the "terminal height” means the height of the terminal at the highest position from the terminal forming surface.
- the height h0 of the terminals 91 can be the average of them.
- the height of the terminal can be measured by, for example, a non-contact three-dimensional optical interference type surface roughness meter (manufactured by Japan Veeco, trade name: Wyko NT1100).
- the width of the terminal 91 is not particularly limited, but is preferably 170 to 350 ⁇ m, more preferably 200 to 320 ⁇ m, and particularly preferably 230 to 290 ⁇ m.
- the width of the terminal 91 is equal to or larger than the lower limit value, the function of the terminal 91 can be further improved. Further, when the width of the terminal 91 is not more than the upper limit value, the effect of suppressing the remaining of the viscoelastic layer 12 on the upper part of the terminal 91 becomes higher.
- the "terminal width” is obtained by connecting two different points on the terminal surface with a straight line when the terminal is viewed in a plan view from a direction perpendicular to the terminal forming surface. It means the maximum value of the line segment.
- the terminal width means the maximum diameter (terminal diameter) of the terminal when the terminal is viewed in a plan view.
- the distance between adjacent terminals 91 (that is, the pitch between terminals) is not particularly limited, but is preferably 250 to 800 ⁇ m, more preferably 300 to 600 ⁇ m, and particularly preferably 350 to 500 ⁇ m.
- the distance is equal to or greater than the lower limit value, the embedding property of the terminal 91 can be further improved.
- the distance is not more than the upper limit value, the effect of suppressing the remaining of the viscoelastic layer 12 on the upper part of the terminal 91 becomes higher.
- the "distance between adjacent terminals" means the minimum value of the distance between the surfaces of adjacent terminals.
- ⁇ Measurement method of physical properties Young's modulus of the base material, amount of air bubbles when terminals are embedded in the viscoelastic layer of the terminal protection tape, adhesive strength of the terminal protection tape to the semiconductor device with terminals, elastic modulus of the first adhesive layer and the embedded layer , The breaking stress of the base material and the terminal protection tape, and the breaking elongation of the base material and the terminal protection tape were measured by the following methods.
- the tensile elastic modulus of the base material at 23 ° C. was measured according to JIS K7161: 2014 and used as Young's modulus.
- the width of the base material at the time of measurement was 15 mm, the distance between the gripping tools was 10 mm, and the tensile speed was 50 mm / min.
- a terminal having a diameter of 0.25 mm was embedded in a viscoelastic layer of a terminal protection tape.
- the diameter of the circular void formed from the base material side to the outside of the terminal was measured using a digital optical microscope (manufactured by KEYENCE, product name "VHX-1000"). The measurement was performed when peeling after irradiation with ultraviolet rays in ⁇ evaluation of peelability> described later. That is, when the terminal protection tape was stretched at the time of peeling, the above measurement was performed on the stretched terminal protection tape.
- the measurement was performed as follows according to JIS Z0237: 2009.
- the terminal protection tape is cut to a width of 25 mm and a length of 250 mm, the release sheet is peeled off, and the exposed adhesive layer is placed on a semiconductor device as an adherend with a 2 kg rubber roller in an environment of 23 ° C. and 50% RH. It was affixed using and left in the same environment for 24 hours.
- the base material or the terminal protection tape was cut out as a sample having a width of 10 mm and a length of 75 mm.
- the above sample is set in a tensile tester (manufactured by Orientec, product name "Tencilon") so that the sample measurement site has a width of 10 mm and a length of 25 mm (extension direction), and is placed in an environment of 23 ° C. and 50% RH. It was stretched at a tensile speed of 200 mm / min using the tensile tester. The sample was stretched until it broke, and the elongation at break (%) and the stress at rupture (MPa) were measured.
- HEA 2-Hydroxyethyl acrylate
- BA n-butyl acrylate
- MMA Methyl methacrylate
- AAc Acrylic acid
- a resin solution (adhesive base, solid) to which 2-methacryloyloxyethyl isocyanate (about 50 mol% with respect to HEA) was added to an acrylic copolymer consisting of 74 parts by mass of BA, 20 parts by mass of MMA, and 6 parts by mass of HEA. 35% by mass) was prepared.
- 1-hydroxycyclohexylphenylketone (manufactured by BASF, product name "Irgacure 184", solid content concentration 100%) as a photopolymerization initiator, 3 parts by mass, and trilen as a cross-linking agent, based on 100 parts by mass of this pressure-sensitive adhesive base material.
- the pressure-sensitive adhesive layer forming composition A was applied to the peeled surface of the peeled film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 ⁇ m) in which one side of the polyethylene terephthalate film was peeled by silicone treatment. By heating and drying at 100 ° C. for 1 minute, the pressure-sensitive adhesive layer A having a thickness of 10 ⁇ m and 20 ⁇ m, respectively, was produced.
- the elastic modulus of the pressure-sensitive adhesive layer A before the energy ray curing was 0.05 MPa, and the elastic modulus after curing was 24 MPa.
- composition B for Forming Embedded Layer 40 parts by mass of single-purpose urethane acrylate, 45 parts by mass of isobornyl acrylate (IBXA), 15 parts by mass of 2-hydroxypropyl acrylate (HPA), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd., product name) "Karens MT PE1", secondary tetrafunctional thiol-containing compound, solid content concentration 100% by mass) 3.5 parts by mass, cross-linking agent 1.8 parts by mass, and 2-hydroxy-2- as a photopolymerization initiator
- a composition B for forming an embedded layer was prepared by blending 1.0 part by mass of methyl-1-phenyl-propane-1-one (manufactured by BASF, product name "DaroCure 1173", solid content concentration 100% by mass). ..
- Base material A polyethylene film having a thickness of 80 ⁇ m was used as the base material A.
- the Young's modulus of the base material A was 340 MPa, the elongation at break was 950%, and the stress at break was 45 MPa.
- Example 1 The composition A for forming an embedded layer is applied to the peeled surface of a release film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 ⁇ m) in which one side of a polyethylene terephthalate film is peeled by silicone treatment, and at 100 ° C. After heating and drying for 1 minute, a release film (Lintec's "SP-PET382150", thickness 38 ⁇ m) in which one side of a polyethylene terephthalate film was peeled off by a silicone treatment on the composition A for forming an embedded layer was peeled off. The treated surface was laminated to produce an embedded layer having a thickness of 50 ⁇ m.
- SP-PET38131 manufactured by Lintec Corporation, thickness 38 ⁇ m
- the surfaces from which the laminated release film of the embedded layer was peeled off were pasted together to prepare an embedded layer having a thickness of 100 ⁇ m.
- the embedded layers were laminated and laminated to prepare an embedded layer A having a thickness of 300 ⁇ m.
- the elastic modulus of the embedded layer A before the energy ray curing was 0.06 MPa, and the elastic modulus after the curing was 65 MPa.
- An embedded layer A having a thickness of 300 ⁇ m was bonded to the pressure-sensitive adhesive layer A having a thickness of 10 ⁇ m.
- the release film on the side of the embedded layer A is peeled off and bonded to the easy-adhesion-treated side of the base material A, and the terminal protection tape in the form of the base material 11 / embedded layer 13 / adhesive layer 14 shown in FIG. 1 was manufactured.
- the configuration and physical characteristics of the terminal protection tape 1 are shown in Tables 1 and 2 (the same applies hereinafter). The peelability was evaluated using the terminal protection tape 1.
- Table 3 shows the peeling conditions and the evaluation results.
- Example 2 The terminal protection tape 2 was manufactured in the same manner as in the production example except that the pressure-sensitive adhesive layer A having a thickness of 20 ⁇ m was used instead of the pressure-sensitive adhesive layer A having a thickness of 10 ⁇ m. The peelability was evaluated using the terminal protection tape 2. Table 3 shows the peeling conditions and the evaluation results.
- composition A for forming an embedded layer is applied by a fountain die method to a peeling film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 ⁇ m) in which one side of a polyethylene terephthalate film is peeled by silicone treatment. Obtained a coating film. A semi-cured layer was formed by irradiating ultraviolet rays from the coating film side.
- SP-PET38131 manufactured by Lintec Corporation, thickness 38 ⁇ m
- a belt conveyor type ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., product name "ECS-401GGX”) is used as the ultraviolet irradiation device, and a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd., product name "H04") is used as the ultraviolet source.
- -L41 "was used, and the irradiation conditions were an illuminance of 112 mW / cm 2 with a light wavelength of 365 nm and a light amount of 117 mJ / cm 2 (measured by the product name" UVPF-A1 "manufactured by Eye Graphics Co., Ltd.).
- the base material A is laminated on the formed semi-cured layer, and further irradiated with ultraviolet rays (using the above-mentioned ultraviolet irradiation device and ultraviolet source, illuminance 271 mW / cm 2 and light intensity 1,200 mJ / cm 2 ). Then, the composition B for forming an embedded layer was completely cured to form an embedded layer B having a thickness of 300 ⁇ m on the base material A, and a laminate of the base material A and the embedded layer B was obtained.
- the release film is peeled off, and the pressure-sensitive adhesive layer A having a thickness of 10 ⁇ m is attached to the surface of the embedded layer B opposite to the base material A, and the form of the base material 11 / embedded layer 13 / pressure-sensitive adhesive layer 14 shown in FIG.
- the terminal protection tape 3 of the above was manufactured.
- the peelability was evaluated using the terminal protection tape 3. Table 3 shows the peeling conditions and the evaluation results.
- the method for manufacturing the semiconductor device with an electromagnetic wave shield film of the present invention can be easily peeled off in the step of peeling the semiconductor device with terminals on which the electromagnetic wave shield film is formed from the terminal protection tape. , It was confirmed that the manufacturing efficiency is improved.
- the semiconductor device with terminals can be electromagnetically shielded, and the semiconductor device with an electromagnetic wave shielding film can be manufactured.
- 1,2,3 ... Terminal protection tape 10 ... Electromagnetic shield film, 11 ... Base material, 12 ... Viscoelastic layer, 13 ... Embedded layer, 14 ... Adhesive layer , 15 ... 2nd adhesive layer (bonded adhesive layer), 16 ... 3rd adhesive layer, 17 ... ring frame, 18 ... expander, 30 ... support, 6 ... Semiconductor device assembly with terminals, 60 ... Semiconductor device assembly, 60a ... Terminal forming surface, 61, 62 ... Electronic components, 63 ... Circuit board, 63a ... Terminal forming surface , 64 ... Sealing resin layer, 65 ... Semiconductor device with terminal, 66 ... Semiconductor device with electromagnetic wave shielding film, 91 ... Terminal, 101 ... Conductive resin, 20, 21, 22, ... ⁇ ⁇ Release film
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Abstract
Description
本願は、2019年12月6日に、日本に出願された特願2019-221466号に基づき優先権を主張し、その内容をここに援用する。
前記端子保護用テープの粘弾性層に埋設されていない前記端子付き半導体装置の露出面に電磁波シールド膜を形成する工程と、
前記端子保護用テープを延伸することにより、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程と、
を含む電磁波シールド膜付き半導体装置の製造方法。
[2] 粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置集合体の端子を埋設させる工程と、
前記端子付き半導体装置集合体をダイシングして、前記端子付き半導体装置集合体を、前記端子保護用テープの粘弾性層に端子が埋設された端子付き半導体装置とする工程と、
前記端子保護用テープの粘弾性層に埋設されていない前記端子付き半導体装置の露出面に電磁波シールド膜を形成する工程と、
前記端子保護用テープを延伸することにより、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程と、
を含む電磁波シールド膜付き半導体装置の製造方法。
[3] 電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する前記工程における前記端子保護用テープの延伸量が1.0mm以上である、[1]又は[2]に記載の電磁波シールド膜付き半導体装置の製造方法。
[4] 直径0.25mmの端子を前記端子保護用テープの前記粘弾性層に埋設したときに、前記端子保護用テープの厚さ方向から観察される前記埋設された端子の外側に現れる気泡に由来する略円状の影の直径が0.30mm以上である[1]~[3]のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
[5] 前記端子付き半導体装置の端子を埋設させる前記工程後で、かつ電磁波シールド膜を形成する前記工程前における、前記端子付き半導体装置に対する前記端子保護用テープの粘着力が6.5N/25mm以下である[1]~[4]のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
[6] 前記端子付き半導体装置又は端子付き半導体装置集合体の端子の高さh0に対する前記粘弾性層の厚さd1の割合が、1.2≦d1/h0≦5.0を満たす[1]~[5]のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
[7] 前記粘弾性層が、埋め込み層及び粘着剤層を有する[1]~[6]のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
[8] 粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置又は端子付き半導体装置集合体の端子を埋設させる前記工程における、前記埋め込み層の弾性率が0.05~20MPaである、[7]に記載の電磁波シールド膜付き半導体装置の製造方法。
[9] 前記粘着剤層と、前記埋め込み層と、基材と、をこの順で有する、[7]又は[8]に記載の電磁波シールド膜付き半導体装置の製造方法。
[10] 前記基材のヤング率が100~2000MPaである[9]に記載の電磁波シールド膜付き半導体装置の製造方法。
[11] 前記埋め込み層は、エネルギー線硬化性の構成材料を用いて形成された埋め込み層である、[7]~[10]のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
[12] 前記粘着剤層は、エネルギー線硬化性の粘着剤を用いて形成された粘着剤層である、[7]~[11]のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
[13] [4]~[12]のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法に用いられる端子保護用テープ。
本発明の第一実施形態の電磁波シールド膜付き半導体装置の製造方法は、粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置の端子を埋設させる工程と、前記端子保護用テープの粘弾性層に埋設されていない前記端子付き半導体装置の露出面に電磁波シールド膜を形成する工程と、前記端子保護用テープを延伸することにより、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程と、を含む。
以下、本発明の第一実施形態及び第二実施形態の電磁波シールド膜付き半導体装置の製造方法で使用される端子保護用テープ、及び本発明の電磁波シールド膜付き半導体装置の製造方法の各工程について詳細に説明を行う。
図1は、本発明の端子保護用テープの一実施形態を模式的に示す断面図である。なお、以下の説明で用いる図は、本発明の特徴を分かり易くするために、便宜上、要部となる部分を拡大して示している場合があり、各構成要素の寸法比率等が実際と同じであるとは限らない。
本実施形態の端子保護用テープは、図1に示すものに限定されず、本発明の効果を損なわない範囲内において、図1に示すものにおいて、一部の構成が変更、削除又は追加されたものであってもよい。
図2に示す端子保護用テープ2は、剥離フィルム20を剥離して、支持体としての基材11の上の粘弾性層12に、端子付き半導体装置を、端子の側を下にして押し付けて、粘弾性層12に端子を埋設し、更にその上から電磁波シールド膜を形成する工程に使用することができる。
端子保護用テープの破断伸度は、後述の実施例に記載の方法により測定することができる。
端子保護用テープの破断応力は、後述の実施例に記載の方法により測定することができる。
本実施形態の端子保護用テープにおいて、粘弾性層は、端子付き半導体装置の端子形成面(換言すると回路面)、及びこの端子形成面上に設けられた端子を保護するために用いられる。
粘弾性層は、埋め込み層及び粘着剤層を有することが好ましい。
粘弾性層の厚さが前記下限値以上であることで、はんだボール等の浮きの生じやすい端子電極であっても埋め込むことができる。また、粘弾性層の厚さが前記上限値以下であることで、端子保護用テープが過剰な厚さとなることが抑制される。
ここで、「粘弾性層の厚さ」とは、粘弾性層全体の厚さを意味し、埋め込み層及び粘着剤層の複数層からなる粘弾性層の厚さは、埋め込み層及び粘着剤層の合計の厚さを意味する。
本明細書において、各層の厚みは例えば、JIS K6783、Z1702、Z1709に準拠して、株式会社テクロック製の定圧厚さ測定器(型番:「PG-02J」)によって測定することができる。
気泡に由来する略円状の影の直径は、後述の実施例に記載の方法により測定することができる。
以下、粘弾性層を構成する粘着剤層を、後述の、支持体に貼合するための第2粘着剤層と区別して、「第1粘着剤層」と称することがある。
第1粘着剤層は、シート状又はフィルム状であり、粘着剤を含有する。本明細書において、「シート状又はフィルム状」とは、薄い膜状で、面内の厚さのばらつきが小さく、フレキシブル性を有するものを意味する。
前記粘着剤としては、例えば、アクリル系樹脂((メタ)アクリロイル基を有する樹脂からなる粘着剤)、ウレタン系樹脂(ウレタン結合を有する樹脂からなる粘着剤)、ゴム系樹脂(ゴム構造を有する樹脂からなる粘着剤)、シリコーン系樹脂(シロキサン結合を有する樹脂からなる粘着剤)、エポキシ系樹脂(エポキシ基を有する樹脂からなる粘着剤)、ポリビニルエーテル、ポリカーボネート等の粘着性樹脂が挙げられ、アクリル系樹脂が好ましい。
ここで、「第1粘着剤層の厚さ」とは、第1粘着剤層全体の厚さを意味し、例えば、複数層からなる第1粘着剤層の厚さとは、第1粘着剤層を構成するすべての層の合計の厚さを意味する。
本発明において、「エネルギー線」とは、電磁波又は荷電粒子線の中でエネルギー量子を有するものを意味し、その例として、紫外線、電子線等が挙げられる。
紫外線は、例えば、紫外線源として高圧水銀ランプ、ヒュージョンHランプ又はキセノンランプ等を用いることで照射できる。電子線は、電子線加速器等によって発生させたものを照射できる。
本発明において、「エネルギー線硬化性」とは、エネルギー線を照射することにより硬化する性質を意味し、「非エネルギー線硬化性」とは、エネルギー線を照射しても硬化しない性質を意味する。
第1粘着剤層がエネルギー線硬化性の粘着剤を用いて形成されている場合、硬化後の第1粘着剤層の弾性率は、1.0~50MPaであることが好ましく、2.0~45MPaであることがより好ましく、3.0~40MPaであることがさらに好ましい。硬化後の第1粘着剤層の弾性率が前記範囲内であると、半導体装置の保持性が得られる。
本明細書において「弾性率」は、粘弾性測定装置(例えば、Rheometrics社製、装置名「DYNAMIC ANALYZER RDAII」)を用いて、直径8mm×厚さ3mmサイズのサンプルを、1Hzで23℃の環境下でねじりせん断法により測定される貯蔵弾性率である。
第1粘着剤層の硬化は、上述の第一及び第二実施形態の電磁波シールド膜付き半導体装置の製造方法のどの工程で行ってもよいが、端子付き半導体装置(又は半導体装置集合体)の端子を埋設させる工程後でかつ、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程前に行うことが好ましい。
第1粘着剤層は、粘着剤を含有する第1粘着剤組成物を用いて形成できる。例えば、第1粘着剤層の形成対象面に第1粘着剤組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に第1粘着剤層を形成できる。また、剥離フィルムに第1粘着剤組成物を塗工し、必要に応じて乾燥させることで、目的とする厚さの第1粘着剤層を形成でき、目的とする部位に第1粘着剤層を転写することもできる。第1粘着剤層のより具体的な形成方法は、他の層の形成方法とともに、後ほど詳細に説明する。第1粘着剤組成物中の、常温で気化しない成分同士の含有量の比率は、通常、第1粘着剤層の前記成分同士の含有量の比率と同じとなる。なお、本明細書において、「常温」とは、特に冷やしたり、熱したりしない温度、即ち平常の温度を意味し、15~25℃の温度等が挙げられ、例えば25℃である。
第1粘着剤組成物(I-1)は、上述の様に、非エネルギー線硬化性の粘着性樹脂(I-1a)と、エネルギー線硬化性化合物と、を含有する。
前記粘着性樹脂(I-1a)は、アクリル系樹脂であることが好ましい。
前記アクリル系樹脂としては、例えば、少なくとも(メタ)アクリル酸アルキルエステル由来の構成単位を有するアクリル系重合体が挙げられる。
前記アクリル系樹脂が有する構成単位は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
(メタ)アクリル酸アルキルエステルとして、より具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸tert-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル((メタ)アクリル酸ラウリルともいう。)、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル((メタ)アクリル酸ミリスチルともいう。)、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル((メタ)アクリル酸パルミチルともいう。)、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル((メタ)アクリル酸ステアリルともいう。)、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸イコシル等が挙げられる。
前記官能基含有モノマーとしては、例えば、前記官能基が後述する架橋剤と反応することで架橋の起点となったり、前記官能基が不飽和基含有化合物中の官能基と反応することで、アクリル系重合体の側鎖に不飽和基の導入を可能とするものが挙げられる。
即ち、官能基含有モノマーとしては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー等が挙げられる。
前記他のモノマーは、(メタ)アクリル酸アルキルエステル等と共重合可能なものであれば特に限定されない。
前記他のモノマーとしては、例えば、スチレン、α-メチルスチレン、ビニルトルエン、ギ酸ビニル、酢酸ビニル、アクリロニトリル、アクリルアミド等が挙げられる。
一方、前記アクリル系重合体中の官能基に、エネルギー線重合性不飽和基(エネルギー線重合性基)を有する不飽和基含有化合物を反応させたものは、上述のエネルギー線硬化性の粘着性樹脂(I-2a)として使用できる。
なお、本発明において、「エネルギー線重合性」とは、エネルギー線を照射することにより重合する性質を意味する。
第1粘着剤組成物(I-1)が含有する前記エネルギー線硬化性化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー又はオリゴマーが挙げられる。
エネルギー線硬化性化合物のうち、モノマーとしては、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトール(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,4-ブチレングリコールジ(メタ)アクリレート、1,6-へキサンジオール(メタ)アクリレート等の多価(メタ)アクリレート;ウレタン(メタ)アクリレート;ポリエステル(メタ)アクリレート;ポリエーテル(メタ)アクリレート;エポキシ(メタ)アクリレート等が挙げられる。
エネルギー線硬化性化合物のうち、オリゴマーとしては、例えば、上記で例示したモノマーが重合したオリゴマー等が挙げられる。
エネルギー線硬化性化合物は、分子量が比較的大きく、第1粘着剤層の貯蔵弾性率を低下させにくいという点では、ウレタン(メタ)アクリレート、ウレタン(メタ)アクリレートオリゴマーが好ましい。
本明細書において、「オリゴマー」とは、重量平均分子量又は式量が5,000以下の物質を意味する(但し、モノマーは除く)。
粘着性樹脂(I-1a)として、(メタ)アクリル酸アルキルエステル由来の構成単位以外に、さらに、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、第1粘着剤組成物(I-1)は、さらに架橋剤を含有することが好ましい。
架橋剤としては、例えば、トリレン-2,6-ジイソシアネート等のトリレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、これらジイソシアネートのアダクト体等のイソシアネート系架橋剤(イソシアネート基を有する架橋剤);エチレングリコールグリシジルエーテル、N,N’-(シクロヘキサン-1,3-ジイルビスメチレン)ビス(グリシジルアミン)等のエポキシ系架橋剤(グリシジル基を有する架橋剤);ヘキサ[1-(2-メチル)-アジリジニル]トリフオスファトリアジン等のアジリジン系架橋剤(アジリジニル基を有する架橋剤);アルミニウムキレート等の金属キレート系架橋剤(金属キレート構造を有する架橋剤);イソシアヌレート系架橋剤(イソシアヌル酸骨格を有する架橋剤)等が挙げられる。
粘着剤の凝集力を向上させて第1粘着剤層の粘着力を向上させる点、及び入手が容易である等の点から、架橋剤はイソシアネート系架橋剤であることが好ましい。
第1粘着剤組成物(I-1)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する第1粘着剤組成物(I-1)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。
また、前記光重合開始剤としては、例えば、1-クロロアントラキノン等のキノン化合物;アミン等の光増感剤等を用いることもできる。
第1粘着剤組成物(I-1)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、例えば、帯電防止剤、酸化防止剤、軟化剤(可塑剤)、充填剤(フィラー)、防錆剤、着色剤(顔料、染料)、増感剤、粘着付与剤、反応遅延剤、架橋促進剤(触媒)等の公知の添加剤が挙げられる。
なお、反応遅延剤とは、例えば、第1粘着剤組成物(I-1)中に混入している触媒の作用によって、保存中の第1粘着剤組成物(I-1)において、目的としない架橋反応が進行するのを抑制するものである。反応遅延剤としては、例えば、触媒に対するキレートによってキレート錯体を形成するものが挙げられ、より具体的には、1分子中にカルボニル基(-C(=O)-)を2個以上有するものが挙げられる。
第1粘着剤組成物(I-1)は、溶媒を含有していてもよい。第1粘着剤組成物(I-1)は、溶媒を含有していることで、塗工対象面への塗工適性が向上する。
第1粘着剤組成物(I-2)は、上述の様に、非エネルギー線硬化性の粘着性樹脂(I-1a)の側鎖に不飽和基が導入されたエネルギー線硬化性の粘着性樹脂(I-2a)を含有する。
前記粘着性樹脂(I-2a)は、例えば、粘着性樹脂(I-1a)中の官能基に、エネルギー線重合性不飽和基を有する不飽和基含有化合物を反応させることで得られる。
前記エネルギー線重合性不飽和基としては、例えば、(メタ)アクリロイル基、ビニル基(エテニル基ともいう。)、アリル基(2-プロペニル基ともいう。)等が挙げられ、(メタ)アクリロイル基が好ましい。
粘着性樹脂(I-1a)中の官能基と結合可能な基としては、例えば、水酸基又はアミノ基と反応可能なイソシアネート基及びグリシジル基、並びにカルボキシ基又はエポキシ基と反応可能な水酸基及びアミノ基等が挙げられる。
前記イソシアネート化合物は、粘着性樹脂(I-1a)中の水酸基と反応可能であり、粘着性樹脂(I-1a)中の全水酸基を100molとしたときの、前記イソシアネート化合物の使用量は、10~150molが好ましく、20~140molがより好ましく、30~130molがさらに好ましい。
粘着性樹脂(I-2a)として、例えば、粘着性樹脂(I-1a)におけるものと同様な、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、第1粘着剤組成物(I-2)は、さらに架橋剤を含有していてもよい。
第1粘着剤組成物(I-2)が含有する架橋剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-2)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する第1粘着剤組成物(I-2)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。
第1粘着剤組成物(I-2)が含有する光重合開始剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-2)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
第1粘着剤組成物(I-2)における前記その他の添加剤としては、第1粘着剤組成物(I-1)におけるその他の添加剤と同じものが挙げられる。
第1粘着剤組成物(I-2)が含有するその他の添加剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-2)は、第1粘着剤組成物(I-1)の場合と同様の目的で、溶媒を含有していてもよい。
第1粘着剤組成物(I-2)における前記溶媒としては、第1粘着剤組成物(I-1)における溶媒と同じものが挙げられる。
第1粘着剤組成物(I-2)が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-2)において、溶媒の含有量は特に限定されず、適宜調節すればよい。
第1粘着剤組成物(I-3)は、上述の様に、前記粘着性樹脂(I-2a)と、エネルギー線硬化性低分子化合物と、を含有する。
第1粘着剤組成物(I-3)が含有する前記エネルギー線硬化性低分子化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー及びオリゴマーが挙げられ、第1粘着剤組成物(I-1)が含有するエネルギー線硬化性化合物と同じものが挙げられる。
第1粘着剤組成物(I-3)が含有する前記エネルギー線硬化性低分子化合物は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-3)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する第1粘着剤組成物(I-3)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。
第1粘着剤組成物(I-3)が含有する光重合開始剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-3)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、第1粘着剤組成物(I-1)におけるその他の添加剤と同じものが挙げられる。
第1粘着剤組成物(I-3)が含有するその他の添加剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-3)は、第1粘着剤組成物(I-1)の場合と同様の目的で、溶媒を含有していてもよい。
第1粘着剤組成物(I-3)における前記溶媒としては、第1粘着剤組成物(I-1)における溶媒と同じものが挙げられる。
第1粘着剤組成物(I-3)が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
第1粘着剤組成物(I-3)において、溶媒の含有量は特に限定されず、適宜調節すればよい。
ここまでは、第1粘着剤組成物(I-1)、第1粘着剤組成物(I-2)及び第1粘着剤組成物(I-3)について主に説明したが、これらの含有成分として説明したものは、これら3種の第1粘着剤組成物以外の全般的な第1粘着剤組成物(本実施形態においては、「第1粘着剤組成物(I-1)~(I-3)以外の第1粘着剤組成物」と称する)でも、同様に用いることができる。
非エネルギー線硬化性の第1粘着剤組成物としては、例えば、アクリル系樹脂((メタ)アクリロイル基を有する樹脂)、ウレタン系樹脂(ウレタン結合を有する樹脂)、ゴム系樹脂(ゴム構造を有する樹脂)、シリコーン系樹脂(シロキサン結合を有する樹脂)、エポキシ系樹脂(エポキシ基を有する樹脂)、ポリビニルエーテル、又はポリカーボネート等の粘着性樹脂を含有するものが挙げられ、アクリル系樹脂を含有するものが好ましい。
第1粘着剤組成物(I-1)~(I-3)等の前記第1粘着剤組成物は、前記粘着剤と、必要に応じて前記粘着剤以外の成分等の、第1粘着剤組成物を構成するための各成分を配合することで得られる。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。
本実施形態における、第1粘着剤層の組成は、上述の第1粘着剤層組成物から溶媒を除いたものである。
第1粘着剤層組成物が、前記第1粘着剤組成物(I-1)である場合の第1粘着剤層(I-1)における、第1粘着剤層(I-1)の総質量に対する粘着性樹脂(I-1a)の含有割合は、50~99質量%であることが好ましく、55~95質量%であることがより好ましく、60~90質量%であることがさらに好ましい。また、本発明の別の側面としては、第1粘着剤層(I-1)の総質量に対する粘着性樹脂(I-1a)の含有割合は、25~80質量%であってもよく、30~75質量%であってもよく、35~70質量%であってもよい。また、第1粘着剤層(I-1)の総質量に対するエネルギー線硬化性化合物の含有割合は、1~50質量%であることが好ましく、2~48質量%であることがより好ましく、5~45質量%であることがさらに好ましい。第1粘着剤層(I-1)が架橋剤を含有する場合、第1粘着剤層(I-1)の総質量に対する架橋剤の含有割合は0.1~10質量%であることが好ましく、0.2~9質量%であることがより好ましく、0.3~8質量%であることがさらに好ましい。第1粘着剤層(I-1)が光重合開始剤を含有する場合、第1粘着剤層(I-1)の総質量に対する光重合開始剤の含有割合は0.5~18.0質量%であることが好ましく、0.7~17.5質量%であることがより好ましく、1.0~15.0質量%であることがさらに好ましい。
以下、本明細書において「含有割合」とは、その対象がモノマーの場合、モノマー自体の含有割合、又はモノマーが重合している場合にはモノマー由来の構成単位の含有割合を意味する。
本実施形態の端子保護用テープにおいて、埋め込み層は、粘弾性層のうち端子付き半導体装置の端子を埋め込んで保護する層である。
埋め込み層は、シート状又はフィルム状であり、前記条件の関係を満たす限り、その構成材料は、特に限定されない。
ここで、「埋め込み層の厚さ」とは、埋め込み層全体の厚さを意味し、例えば、複数層からなる埋め込み層の厚さとは、埋め込み層を構成するすべての層の合計の厚さを意味する。
埋め込み層がエネルギー線硬化性の構成材料を用いて形成されている場合、硬化前の埋め込み層の弾性率は、0.01~1.0MPaであることが好ましく、0.02~0.9MPaであることがより好ましく、0.03~0.8MPaであることがさらに好ましい。硬化前の埋め込み層の弾性率が前記範囲内であると、半導体装置の保持性が得られる。
埋め込み層がエネルギー線硬化性の構成材料を用いて形成されている場合、硬化後の埋め込み層の弾性率は、1.0~100MPaであることが好ましく、2.0~95MPaであることがより好ましく、3.0~90MPaであることがさらに好ましい。硬化後の埋め込み層の弾性率が前記範囲内であると、半導体装置の保持性が得られる。
埋め込み層が、後述のアクリル系樹脂を含有する埋め込み層形成用組成物(I)を用いて形成された埋め込み層(I)の場合、埋め込み層(I)の硬化は、上述の第一及び第二実施形態の電磁波シールド膜付き半導体装置の製造方法のどの工程で行ってもよいが、端子付き半導体装置(又は半導体装置集合体)の端子を埋設させる工程後でかつ、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程前に行うことが好ましい。
埋め込み層が、後述のウレタン(メタ)アクリレートを含有する埋め込み層形成用組成物(II)を用いて形成された埋め込み層(II)の場合、埋め込み層(II)の硬化は、上述の第一及び第二実施形態の電磁波シールド膜付き半導体装置の製造方法のどの工程で行ってもよいが、端子付き半導体装置(又は半導体装置集合体)の端子を埋設させる工程前に行うことが好ましい。
埋め込み層は、その構成材料を含有する埋め込み層形成用組成物を用いて形成できる。
例えば、埋め込み層の形成対象面に埋め込み層形成用組成物を塗工し、必要に応じて乾燥させ、エネルギー線の照射によって硬化させることで、目的とする部位に埋め込み層を形成できる。また、剥離フィルムに埋め込み層形成用組成物を塗工し、必要に応じて乾燥させ、エネルギー線の照射によって硬化させることで、目的とする厚さの埋め込み層を形成でき、目的とする部位に埋め込み層を転写することもできる。埋め込み層のより具体的な形成方法は、他の層の形成方法とともに、後ほど詳細に説明する。埋め込み層形成用組成物中の、常温で気化しない成分同士の含有量の比率は、通常、埋め込み層の前記成分同士の含有量の比率と同じとなる。
埋め込み層形成用組成物は、エネルギー線硬化性を有する場合、エネルギー線の照射により硬化させることが好ましい。
埋め込み層形成用組成物(I)は、アクリル系樹脂を含有する。
埋め込み層形成用組成物(I)としては、上述の第1粘着剤組成物(I-1)のうち、アクリル系樹脂である粘着性樹脂(I-1a)と、エネルギー線硬化性化合物と、を含有する組成物、第1粘着剤組成物(I-2)のうち、アクリル系樹脂である粘着性樹脂(I-1a)の側鎖に不飽和基が導入されたエネルギー線硬化性の粘着性樹脂(I-2a)を含有する組成物を、埋め込み層形成用組成物(I)として用いることができる。
埋め込み層形成用組成物(I)において用いる粘着性樹脂(I-2a)は、上述の第1粘着剤組成物(I-2)で用いる粘着性樹脂(I-2a)の説明と同じである。
埋め込み層形成用組成物(I)は、さらに架橋剤を含有することが好ましい。埋め込み層形成用組成物(I)において用いる架橋剤は、上述の第1粘着剤組成物(I-1)、第1粘着剤組成物(I-2)で用いる架橋剤の説明と同じである。
埋め込み層形成用組成物(I)は、さらに光重合開始剤、その他の添加剤を含有していてもよい。埋め込み層形成用組成物(I)において用いる光重合開始剤、その他の添加剤は、上述の第1粘着剤組成物(I-1)、第1粘着剤組成物(I-2)で用いる光重合開始剤、その他の添加剤の説明と同じである。
埋め込み層形成用組成物(I)は、溶媒を含有していてもよい。埋め込み層形成用組成物(I)において用いる溶媒は、上述の第1粘着剤組成物(I-1)、第1粘着剤組成物(I-2)で用いる溶媒の説明と同じである。
また、埋め込み層形成用組成物(I)のうち、架橋剤の含有量を調整することで、埋め込み層が、端子を埋め込むに相応しい、柔らかい性質を有するよう設計することができる。
本実施形態における、埋め込み層の組成は、上述の埋め込み層形成用組成物(I)から溶媒を除いたものである。
埋め込み層形成用組成物(I)が、上述の、第1粘着剤組成物(I-1)のうち、アクリル系樹脂である粘着性樹脂(I-1a)と、エネルギー線硬化性化合物と、を含有する組成物である場合の埋め込み層(I)における、埋め込み層(I)の総質量に対するアクリル系樹脂である粘着性樹脂(I-1a)の含有割合は50~99質量%であることが好ましく、55~95質量%であることがより好ましく、60~90質量%であることがさらに好ましい。本発明の別の側面としては、埋め込み層(I)の総質量に対するアクリル系樹脂である粘着性樹脂(I-1a)の含有割合は45~90質量%であってもよく、50~85質量%であってもよい。また、埋め込み層(I)の総質量に対するエネルギー線硬化性化合物の含有割合は0.5~50質量%であることが好ましく、5~45質量%であることがさらに好ましい。埋め込み層(I)が架橋剤を含有する場合、埋め込み層(I)の総質量に対する架橋剤の含有割合は0.1~10質量%であることが好ましく、0.2~9質量%であることがより好ましく、0.3~8質量%であることがさらに好ましい。埋め込み層(I)が光重合開始剤を含有する場合、埋め込み層(I)の総質量に対する光重合開始剤の含有割合は0.5~18.0質量%であることが好ましく、0.7~17.5質量%であることがより好ましく、1.0~17.0質量%であることがさらに好ましい。
本実施形態の粘着性樹脂(1-1a)の重量平均分子量は、100,000~800,000であることが好ましく、150,000~700,000であることがより好ましく、200,000~600,000であることがさらに好ましい。
なお、本明細書において、「重量平均分子量」とは、特に断りのない限り、ゲル・パーミエーション・クロマトグラフィー(GPC)法により測定されるポリスチレン換算値である。
本実施形態の粘着性樹脂(1-2a)の重量平均分子量は、50,000~1,000,000であることが好ましく、60,000~900,000であることがより好ましく、70,000~800,000であることがさらに好ましい。
埋め込み層形成用組成物(II)は、ウレタン(メタ)アクリレートを含有する。
ウレタン(メタ)アクリレートは、1分子中に少なくとも(メタ)アクリロイル基及びウレタン結合を有する化合物であり、エネルギー線重合性を有する。
ウレタン(メタ)アクリレートは、単官能のもの(1分子中に(メタ)アクリロイル基を1個のみ有するもの)であってもよいし、二官能以上のもの(1分子中に(メタ)アクリロイル基を2個以上有するもの)、即ち多官能のものであってもよいが、少なくとも単官能のものを用いることが好ましい。
なお、上述の粘着性樹脂(1-2a)、エネルギー線硬化性化合物、エネルギー線硬化性低分子化合物の中で、1分子中に少なくとも(メタ)アクリロイル基及びウレタン結合を有する化合物又は樹脂は、埋め込み層形成用組成物(II)におけるウレタン(メタ)アクリレートからは除かれる。
前記ポリオール化合物は、1分子中に水酸基を2個以上有する化合物であれば、特に限定されない。
前記ポリオール化合物は、1種を単独で用いてもよいし、2種以上を併用してもよく、2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。
前記ポリオール化合物は、2官能のジオール、3官能のトリオール、4官能以上のポリオール等のいずれであってもよいが、入手が容易であり、汎用性及び反応性等に優れる点では、ジオールが好ましい。
前記ポリエーテル型ポリオールは、特に限定されないが、ポリエーテル型ジオールであることが好ましく、前記ポリエーテル型ジオールとしては、例えば、下記式(1)で表される化合物が挙げられる。
前記ポリエステル型ポリオールは、特に限定されないが、例えば、多塩基酸又はその誘導体を用いて、エステル化反応を行うことで得られたポリエステル型ポリオール等が挙げられる。なお、本実施形態において「誘導体」とは、特に断りのない限り、元の化合物の1個以上の基がそれ以外の基(置換基)で置換されてなるものを意味する。ここで、「基」とは、複数個の原子が結合してなる原子団だけでなく、1個の原子も包含する。
前記多塩基酸としては、例えば、飽和脂肪族多塩基酸、不飽和脂肪族多塩基酸、芳香族多塩基酸等が挙げられ、これらのいずれかに該当するダイマー酸を用いてもよい。
前記不飽和脂肪族多塩基酸としては、例えば、マレイン酸、フマル酸等の不飽和脂肪族二塩基酸等が挙げられる。
前記芳香族多塩基酸としては、例えば、フタル酸、イソフタル酸、テレフタル酸、2,6-ナフタレンジカルボン酸等の芳香族二塩基酸;トリメリット酸等の芳香族三塩基酸;ピロメリット酸等の芳香族四塩基酸等が挙げられる。
前記触媒としては、例えば、ジブチルスズオキサイド、オクチル酸第一スズ等のスズ化合物;テトラブチルチタネート、テトラプロピルチタネート等のアルコキシチタン等が挙げられる。
ポリカーボネート型ポリオールは、特に限定されないが、例えば、上記(1)式で表される化合物と同様のグリコールと、アルキレンカーボネートと、を反応させて得られたもの等が挙げられる。
ここで、グリコール及びアルキレンカーボネートは、いずれも1種を単独で用いてもよいし、2種以上を併用してもよく、2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。
ポリオール化合物の水酸基価から算出した前記数平均分子量とは、下記式から算出された値である。
[ポリオール化合物の数平均分子量]=[ポリオール化合物の官能基数]×56.11×1000/[ポリオール化合物の水酸基価(単位:mgKOH/g)]
ポリオール化合物と反応させる前記多価イソシアネート化合物は、イソシアネート基を2個以上有するものであれば、特に限定されない。
多価イソシアネート化合物は、1種を単独で用いてもよいし、2種以上を併用してもよく、2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。
これらの中でも、多価イソシアネート化合物は、取り扱い性の点から、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート又はキシリレンジイソシアネートであることが好ましい。
前記末端イソシアネートウレタンプレポリマーと反応させる、前記(メタ)アクリル系化合物は、1分子中に少なくとも水酸基及び(メタ)アクリロイル基を有する化合物であれば、特に限定されない。
前記(メタ)アクリル系化合物は、1種を単独で用いてもよいし、2種以上を併用してもよく、2種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。
これらの中でも、前記(メタ)アクリル系化合物は、水酸基含有(メタ)アクリル酸エステルであることが好ましく、水酸基含有(メタ)アクリル酸アルキルエステルであることがより好ましく、(メタ)アクリル酸2-ヒドロキシエチルであることが特に好ましい。
例えば、前記ウレタン(メタ)アクリレートの重量平均分子量は、1000~100000であることが好ましく、3000~80000であることがより好ましく、5000~65000であることが特に好ましい。前記重量平均分子量が1000以上であることで、ウレタン(メタ)アクリレートと後述する重合性モノマーとの重合物において、ウレタン(メタ)アクリレート由来の構造同士の分子間力に起因して、埋め込み層の硬さの最適化が容易となる。
埋め込み層形成用組成物(II)は、製膜性をより向上させる点から、前記ウレタン(メタ)アクリレート以外に、重合性モノマーを含有していてもよい。
前記重合性モノマーは、エネルギー線重合性を有し、重量平均分子量が1000未満である、1分子中に少なくとも1個の(メタ)アクリロイル基を有する化合物であることが好ましい。
「1置換アミノ基」及び「2置換アミノ基」における、水素原子が置換される水素原子以外の基(即ち、置換基)としては、例えば、アルキル基等が挙げられる。
前記複素環式基を有する(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリロイルモルホリン等が挙げられる。
埋め込み層形成用組成物(II)は、前記ウレタン(メタ)アクリレート及び重合性モノマー以外に、光重合開始剤を含有していてもよい。光重合開始剤を含有する埋め込み層形成用組成物(II)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。
埋め込み層形成用組成物(II)は、本発明の効果を損なわない範囲内において、前記ウレタン(メタ)アクリレート以外の樹脂成分を含有していてもよい。
前記樹脂成分の種類と、その埋め込み層形成用組成物(II)における含有量は、目的に応じて適宜選択すればよく、特に限定されない。
埋め込み層形成用組成物(II)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、例えば、架橋剤、帯電防止剤、酸化防止剤、連鎖移動剤、軟化剤(可塑剤)、充填剤、防錆剤、着色剤(顔料、染料)等の公知の添加剤が挙げられる。
例えば、前記連鎖移動剤としては、1分子中に少なくとも1個のチオール基(メルカプト基)を有するチオール化合物が挙げられる。
埋め込み層形成用組成物(II)は、溶媒を含有していてもよい。埋め込み層形成用組成物(II)は、溶媒を含有していることで、塗工対象面への塗工適性が向上する。
本実施形態における、埋め込み層(II)の組成は、上述の埋め込み層形成用組成物(II)から溶媒を除いたものである。
埋め込み層(II)の総質量に対するウレタン(メタ)アクリレートの含有割合は、20.0~60.0質量%であることが好ましく、22.5~57.5質量%であることがより好ましく、25.0~55.0質量%であることがさらに好ましい。
埋め込み層(II)が重合性モノマーを含む場合、埋め込み層(II)の総質量に対する重合性モノマーの含有割合は、40.0~80.0質量%であることが好ましく、42.5~77.5質量%であることがより好ましく、45.0~75.0質量%であることがさらに好ましい。重合性モノマーとしては、アクリル酸イソボルニル及びアクリル酸2-ヒドロキシプロピルのいずれか一方又は両方を含むことが好ましい。
埋め込み層(II)が架橋剤を含む場合、埋め込み層(II)の総質量に対する架橋剤の含有割合は、0.1~5.0質量%であることが好ましく、0.2~4.5質量%であることがより好ましく、0.3~4.0質量%であることがさらに好ましい。
埋め込み層(II)が光重合開始剤を含む場合、埋め込み層(II)の総質量に対する光重合開始剤の含有割合は、0.1~10.0質量%であることが好ましく、0.2~9.0質量%であることがより好ましく、0.3~8.0質量%であることがさらに好ましい。光重合開始剤としては、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オンを含むことが好ましい。
埋め込み層(II)がチオール化合物を含む場合、埋め込み層(II)の総質量に対するチオール化合物の含有割合は、0.5~10.0質量%であることが好ましく、0.6~9.0質量%であることがより好ましく、0.7~8.0質量%であることがさらに好ましい。チオール化合物としては、ペンタエリスリトールテトラキス(3-メルカプトブチレート)を含むことが好ましい。
埋め込み層形成用組成物(I)、(II)等の埋め込み層形成用組成物は、これを構成するための各成分を配合することで得られる。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。
基材は、シート状又はフィルム状であり、その構成材料としては、例えば、各種樹脂が挙げられる。
前記樹脂としては、例えば、低密度ポリエチレン(LDPEともいう。)、直鎖低密度ポリエチレン(LLDPEともいう。)、高密度ポリエチレン(HDPEともいう。)等のポリエチレン;ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ノルボルネン樹脂等のポリエチレン以外のポリオレフィン;エチレン-酢酸ビニル共重合体(EVAともいう。)、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸エステル共重合体、エチレン-ノルボルネン共重合体等のエチレン系共重合体(すなわち、モノマーとしてエチレンを用いて得られた共重合体);ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂(すなわち、モノマーとして塩化ビニルを用いて得られた樹脂);ポリスチレン;ポリシクロオレフィン;ポリエチレンテレフタレート(PETともいう。)、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン-2,6-ナフタレンジカルボキシレート、すべての構成単位が芳香族環式基を有する全芳香族ポリエステル等のポリエステル;2種以上の前記ポリエステルの共重合体;ポリ(メタ)アクリル酸エステル;ポリウレタン;ポリウレタンアクリレート;ポリイミド;ポリアミド;ポリカーボネート;フッ素樹脂;ポリアセタール;変性ポリフェニレンオキシド;ポリフェニレンスルフィド;ポリスルホン;ポリエーテルケトン等が挙げられる。
また、前記樹脂としては、例えば、前記ポリエステルとそれ以外の樹脂との混合物等のポリマーアロイも挙げられる。前記ポリエステルとそれ以外の樹脂とのポリマーアロイは、ポリエステル以外の樹脂の量が比較的少量であるものが好ましい。
また、前記樹脂としては、例えば、ここまでに例示した前記樹脂の1種又は2種以上が架橋した架橋樹脂;ここまでに例示した前記樹脂の1種又は2種以上を用いたアイオノマー等の変性樹脂も挙げられる。
ここで、「基材の厚さ」とは、基材全体の厚さを意味し、例えば、複数層からなる基材の厚さとは、基材を構成するすべての層の合計の厚さを意味する。
基材のヤング率は、後述の実施例に記載の方法により測定することができる。
基材の破断伸度は、後述の実施例に記載の方法により測定することができる。
基材の破断応力は、後述の実施例に記載の方法により測定することができる。
前記粘弾性層がエネルギー線硬化性である場合、基材はエネルギー線を透過させるものが好ましい。
前記剥離フィルムは、本分野で公知のものでよい。
好ましい前記剥離フィルムとしては、例えば、ポリエチレンテレフタレート等の樹脂製フィルムの少なくとも一方の表面が、シリコーン処理等によって剥離処理されたもの;フィルムの少なくとも一方の表面が、ポリオレフィンで構成された剥離面となっているもの等が挙げられる。
剥離フィルムの厚さは、基材の厚さと同様であることが好ましい。
第2粘着剤層(すなわち、貼合粘着剤層)は、本実施形態の端子保護用テープを支持体に貼合するための粘着剤層である。
前記第2粘着剤層は、当該分野で公知のものでよく、上述の第1粘着剤層で説明したものから、支持体に合わせて適宜選択することができる。
第2粘着剤層を形成するための第2粘着剤組成物は、前記第1粘着剤組成物と同様であり、第2粘着剤組成物の製造方法も、前記第1粘着剤組成物の製造方法と同様である。
前記端子保護用テープは、上述の各層を対応する位置関係となるように順次積層することで製造できる。各層の形成方法は、先に説明したとおりである。
例えば、上述の、剥離フィルム、埋め込み層、第1粘着剤層及び剥離フィルムがこの順に積層された端子保護用テープの埋め込み層の側の剥離フィルムを剥離し、これを基材と貼り合わせることで、基材上に埋め込み層、第1粘着剤層及び剥離フィルムがこの順に積層された端子保護用テープを得ることができる。剥離フィルムは、端子保護用テープの使用時に取り除けばよい。
本発明の一の実施形態の電磁波シールド膜付き半導体装置の製造方法は、粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置の端子を埋設させる工程と、前記端子保護用テープの粘弾性層に埋設されていない前記端子付き半導体装置の露出面に電磁波シールド膜を形成する工程と、前記端子保護用テープを延伸することにより、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程と、を含む。以下、図5を参照して本実施形態の電磁波シールド膜付き半導体装置の製造方法を説明する。
このとき、端子付き半導体装置65の端子91に粘弾性層12を接触させて、端子保護用テープに端子付き半導体装置65を押し付ける。これにより、粘弾性層12の粘着剤層14の側の最表面を、端子91の表面及び回路基板63の端子形成面63aに、順次圧着させる。このとき、粘弾性層12を加熱することで、粘弾性層12は軟化し、端子91を覆うようにして端子91間に広がり、端子形成面63aに密着するとともに、端子91の表面、特に端子形成面63aの近傍部位の表面を覆って、端子91を埋設させる。
粘着力が前記範囲内であると、電磁波シールド膜が形成された端子付き半導体装置を端子保護用テープから剥離する工程における剥離性が向上する。前記粘着力の測定方法は、実施例において詳述する。
ピッキングにおける押し上げの高さu1は、端子91の高さh1よりも高いことが好ましく、2.0≦u1/h1≦10であることが好ましい。
なお、本明細書において、「端子の高さ」とは、端子のうち、端子形成面から最も高い位置に存在する部位での高さを意味する。
本明細書において「延伸量」とは、「延伸後の延伸方向の端子保護用テープの長さ」-「延伸前の延伸方向の端子保護用テープの長さ」を意味する。複数の方向から端子保護用テープを延伸するときには、最も延伸量の多い方向における延伸量を採用することができる。
本発明の別の実施形態の電磁波シールド膜付き半導体装置の製造方法は、粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置集合体の端子を埋設させる工程と、前記端子付き半導体装置集合体をダイシングして、前記端子付き半導体装置集合体を、前記端子保護用テープの粘弾性層に端子が埋設された端子付き半導体装置とする工程と、前記端子保護用テープの粘弾性層に埋設されていない前記端子付き半導体装置の露出面に電磁波シールド膜を形成する工程と、前記端子保護用テープを延伸することにより、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程と、を含む。以下、図6を参照して本実施形態の電磁波シールド膜付き半導体装置の製造方法を説明する。
本実施形態の端子保護用テープの延伸方法は、把持部材などを用いて端子保護用テープの外周部を掴んで引き延ばす方法である。
本実施形態においては、端子保護用テープは少なくとも2軸延伸によって延伸されることが好ましい。
この場合、端子保護用テープは、例えば互いに直交するX軸及びY軸における+X軸方向、-X軸方向、+Y軸方向、-Y軸方向の4方向に張力を付与して引き延ばされる。
本実施形態の端子保護用テープの延伸方法は、端子保護用テープの外周部を固定冶具により固定し、エキスパンダを押し当てて、端子保護用テープを引き延ばす方法である。
図7を参照して、本実施形態の端子保護用テープの延伸方法の例を説明する。本実施形態においては、粘弾性層12が第3粘着剤層16を介してリングフレーム17に貼着されている。
前記第3粘着剤層は、当該分野で公知のものでよく、上述の第1粘着剤層、第2粘着剤層で説明したものから、リングフレーム17の材質に合わせて適宜選択することができる。
第3粘着剤層を形成するための第3粘着剤組成物は、前記第1粘着剤組成物、第2粘着剤組成物と同様であり、第3粘着剤組成物の製造方法も、前記第1粘着剤組成物の製造方法、第2と粘着剤組成物の製造方法と同様である。
このようにして、外周部がリングフレームにより固定された端子保護用テープを基材11側から円筒状のエキスパンダ18を押し当て、上方に押し上げることにより、端子保護用テープを引き延ばす。
なお、本明細書において、「端子の高さ」とは、端子のうち、端子形成面から最も高い位置に存在する部位での高さを意味する。端子付き半導体装置集合体及び端子付き半導体装置65が複数の端子91を有する場合、端子91の高さh0はそれらの平均とすることができる。端子の高さは、例えば、非接触型3次元光干渉式表面粗さ計(日本Veeco社製、商品名:Wyko NT1100)によって測定することができる。
なお、本明細書において、「端子の幅」とは、端子形成面に対して垂直な方向から端子を見下ろして平面視したときに、端子表面上の異なる2点間を直線で結んで得られる線分の最大値を意味する。端子が球形、又は半球形であるときは、「端子の幅」とは、端子を見下ろして平面視したときのその端子の最大直径(端子径)をいう。
なお、本明細書において、「隣り合う端子間の距離」とは、隣り合う端子同士の表面間の距離の最小値を意味する。
基材のヤング率、端子保護用テープの粘弾性層に端子を埋設させたときの気泡の量、端子付き半導体装置に対する端子保護用テープの粘着力、第1粘着剤層及び埋め込み層の弾性率、基材及び端子保護用テープの破断応力、及び基材及び端子保護用テープの破断伸度の測定は、以下の方法で測定を行った。
JIS K7161:2014に準拠して、23℃における基材の引張弾性率を測定し、ヤング率とした。基材の測定時の幅を15mm、つかみ具間距離を10mm、引張速度を50mm/minとした。
径0.25mmの端子を端子保護用テープの粘弾性層に埋設した。デジタル光学顕微鏡(KEYENCE社製、製品名「VHX-1000」)を用いて基材側から端子の外側に生じた円形の空隙の直径を測定した。なお、測定は、後述の<剥離性の評価>における、紫外線照射後の剥離を行う際に行った。すなわち、剥離の際に端子保護用テープの延伸を行った場合は、延伸後の端子保護用テープにおいて上記測定を行った。
JIS Z0237:2009に準じて以下の通り測定した。端子保護用テープを幅25mm、長さ250mmに裁断し、剥離シートを剥離し、露出した粘着剤層を、23℃、50%RHの環境下で、被着体として半導体装置に2kgゴムローラーを用いて貼付し、同環境下に24時間放置した。そして、紫外線照射(照度230mW/cm2、光量190mJ/cm2)を行った後、万能型引張試験機(オリエンテック社製、製品名「テンシロンUTM-4-100」)を用いて、剥離角度180°、剥離速度300mm/minで端子保護用テープを上記半導体装置から剥離することにより、その粘着力を測定した。
粘弾性測定装置(Rheometrics社製、装置名「DYNAMIC ANALYZER RDAII」)を用いて、直径8mm×厚さ3mmサイズのサンプルを、1Hzで23℃の環境下でねじりせん断法により測定した。
基材又は端子保護用テープを10mm幅×75mm長のサンプルとして切り出した。サンプル測定部位が10mm幅×25mm長(伸長方向)になるように、上記サンプルを引張試験機(オリエンテック社製、製品名「テンシロン」)にセットし、23℃、50%RHの環境下で当該引張試験機を用いて引張速度200mm/分で伸長させた。上記サンプルが破断するまで伸長させ、破断伸度(%)及び破断応力(MPa)を測定した。
略記しているモノマーの正式名称を、以下に示す。
HEA:アクリル酸2-ヒドロキシエチル
BA:アクリル酸n-ブチル
MMA:メタクリル酸メチル
AAc:アクリル酸
BA74質量部、MMA20質量部及びHEA6質量部からなるアクリル系共重合体に対して、2-メタクリロイルオキシエチルイソシアネート(HEAに対して約50モル%)を付加した樹脂の溶液(粘着剤主剤、固形分35質量%)を調製した。この粘着剤主剤100質量部に対して、光重合開始剤としての1-ヒドロキシシクロヘキシルフェニルケトン(BASF社製,製品名「イルガキュア184」、固形分濃度100%)3質量部、架橋剤としてトリレン-2,6-ジイソシアネート(トーヨーケム株式会社製、製品名「BHS 8515」、固形分濃度:37.5%)を0.5質量部添加し、30分間攪拌を行って粘着剤層形成用組成物Aを調製した。
ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)の剥離処理面に、前記粘着剤層形成用組成物Aを塗工し、100℃で1分加熱乾燥させることにより、厚さがそれぞれ、10μmと、20μmの粘着剤層Aを製造した。
粘着剤層Aのエネルギー線硬化前の弾性率は0.05MPa、硬化後の弾性率は24MPaであった。
BA91質量部、AAc9質量部からなるアクリル系共重合体の溶液(重量平均分子量(Mw)400,000、粘着剤主剤、固形分濃度33.6%、日本カーバイド工業株式会社製、製品名「ニッセツ PE-121」)100質量部と、BA62質量部、MMA10質量部及びHEA28質量部からなるアクリル系共重合体に2-メタクリロイルオキシエチルイソシアネートをHEA100mol%に対して付加率が80mol%となるように付加した樹脂の溶液(重量平均分子量(Mw)100,000、粘着剤主剤、固形分濃度45%、日本合成化学工業株式会社製、製品名「コーポニール UN-2528LM1」)93.5質量部と、光重合開始剤としての1-ヒドロキシシクロヘキシルフェニルケトン(BASF社製,製品名「イルガキュア184」、固形分濃度100%)3質量部と、架橋剤としてトリレン-2,6-ジイソシアネート(トーヨーケム株式会社製、製品名「BHS-8515」、固形分濃度:37.5%)2.5質量部と、架橋剤としてN,N’-(シクロヘキサン-1,3-ジイルビスメチレン)ビス(グリシジルアミン)(三菱ガス化学社製、製品名「TETRAD-C」、固形分濃度:5%)2.5質量部を添加し、30分間撹拌して埋め込み層形成用組成物Aを調製した。
単官ウレタンアクリレート40質量部、イソボルニルアクリレート(IBXA)45質量部、2-ヒドロキシプロピルアクリレート(HPA)15質量部、ペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工株式会社製、製品名「カレンズMT PE1」、第2級4官能のチオール含有化合物、固形分濃度100質量%)3.5質量部、架橋剤1.8質量部、及び光重合開始剤としての2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(BASF社製、製品名「ダロキュア1173」、固形分濃度100質量%)1.0質量部を配合して、埋め込み層形成用組成物Bを調製した。
厚さ80μmのポリエチレンフィルムを基材Aとして用いた。
基材Aのヤング率は、340MPa、破断伸度は950%、破断応力は45MPaであった。
実施例及び比較例の端子保護用テープの剥離性を評価するに当たり、次の端子付き半導体装置を準備した。
・端子付き半導体装置
半導体装置の大きさ:10mm×10mm
端子の高さ:250μm
端子径:250μm
端子間ピッチ:400μm
端子の数:10×10=100個
端子付き半導体装置の端子の側を下にして、端子保護用テープに、プレス圧力(荷重1.1MPa)、プレス時間40s、加熱時間50℃で押し付けラミネートした。その後、常温にて24時間放置後、紫外線照射(照度230mW/cm2、光量190mJ/cm2)を行った後、必要に応じ端子保護用テープを延伸、ピックアップを行い、半導体装置から端子保護用テープを剥離し剥離の可否を評価した。評価結果は、○:剥離可能、×:剥離不能とした。
埋め込み層形成用組成物Aをポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)の剥離処理面に塗工し、100℃で1分加熱乾燥させた後、埋め込み層形成用組成物Aの上にポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム(リンテック社製「SP-PET382150」、厚さ38μm)の剥離処理面をラミネートし、厚さ50μmの埋め込み層を製造した。
前記埋め込み層のラミネートした剥離フィルムを剥がした面どうしを貼合し、厚さ100μmの埋め込み層を作製した。同様にして埋め込み層を貼合して積層し、厚さ300μmの埋め込み層Aを作製した。
埋め込み層Aのエネルギー線硬化前の弾性率は0.06MPa、硬化後の弾性率は65MPaであった。
厚さ10μmの粘着剤層Aに厚さ300μmの埋め込み層Aを貼合した。さらに、埋め込み層Aの側の剥離フィルムを剥離し、基材Aの易接着処理側と貼り合わせ、図2に示す、基材11/埋め込み層13/粘着剤層14の形態の端子保護用テープ1を製造した。端子保護用テープ1の構成及び物性を表1及び2に示す(以下、同様)。
端子保護用テープ1を用いて、剥離性の評価を行った。剥離条件並びに評価結果を表3に示す。
厚さ10μmの粘着剤層Aの代えて厚さ20μmの粘着剤層Aを使用したこと以外は製造例と同様にして、端子保護用テープ2を製造した。
端子保護用テープ2を用いて、剥離性の評価を行った。剥離条件並びに評価結果を表3に示す。
埋め込み層形成用組成物Aをポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)の剥離処理面にファウンテンダイ方式で、塗布して塗膜を得た。
塗膜側から紫外線を照射して半硬化層を形成した。紫外線照射は、紫外線照射装置として、ベルトコンベア式紫外線照射装置(アイグラフィクス株式会社製、製品名「ECS-401GGX」)を用い、紫外線源として高圧水銀ランプ(アイグラフィクス株式会社製、製品名「H04-L41」を使用し、照射条件として光波長365nmの照度112mW/cm2、光量117mJ/cm2(アイグラフィクス株式会社製、製品名「UVPF-A1」にて測定)で行った。
形成した半硬化層の上に、基材Aを積層し、さらに紫外線照射(上記の紫外線照射装置、紫外線源を用い、照射条件として、照度271mW/cm2、光量1,200mJ/cm2)を行い、埋め込み層形成用組成物Bを完全に硬化させて、基材A上に厚さ300μmの埋め込み層Bを形成し、基材Aと埋め込み層Bの積層体を得た。
剥離フィルムを剥がし、埋め込み層Bの基材Aとは反対側の面に厚さ10μmの粘着剤層Aを貼り合わせ、図2に示す、基材11/埋め込み層13/粘着剤層14の形態の端子保護用テープ3を製造した。
端子保護用テープ3を用いて、剥離性の評価を行った。剥離条件並びに評価結果を表3に示す。
端子保護用テープ1を用いて、剥離性の評価を行った。剥離条件並びに評価結果を表3に示す。
Claims (13)
- 粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置の端子を埋設させる工程と、
前記端子保護用テープの粘弾性層に埋設されていない前記端子付き半導体装置の露出面に電磁波シールド膜を形成する工程と、
前記端子保護用テープを延伸することにより、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程と、
を含む電磁波シールド膜付き半導体装置の製造方法。 - 粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置集合体の端子を埋設させる工程と、
前記端子付き半導体装置集合体をダイシングして、前記端子付き半導体装置集合体を、前記端子保護用テープの粘弾性層に端子が埋設された端子付き半導体装置とする工程と、
前記端子保護用テープの粘弾性層に埋設されていない前記端子付き半導体装置の露出面に電磁波シールド膜を形成する工程と、
前記端子保護用テープを延伸することにより、電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する工程と、
を含む電磁波シールド膜付き半導体装置の製造方法。 - 電磁波シールド膜が形成された前記端子付き半導体装置を前記端子保護用テープから剥離する前記工程における前記端子保護用テープの延伸量が1.0mm以上である、請求項1又は2に記載の電磁波シールド膜付き半導体装置の製造方法。
- 直径0.25mmの端子を前記端子保護用テープの前記粘弾性層に埋設したときに、前記端子保護用テープの厚さ方向から観察される前記埋設された端子の外側に現れる気泡に由来する略円状の影の直径が0.30mm以上である請求項1~3のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
- 前記端子付き半導体装置の端子を埋設させる前記工程後で、かつ電磁波シールド膜を形成する前記工程前における、前記端子付き半導体装置に対する前記端子保護用テープの粘着力が6.5N/25mm以下である請求項1~4のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
- 前記端子付き半導体装置又は端子付き半導体装置集合体の端子の高さh0に対する前記粘弾性層の厚さd1の割合が、1.2≦d1/h0≦5.0を満たす請求項1~5のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
- 前記粘弾性層が、埋め込み層及び粘着剤層を有する請求項1~6のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
- 粘弾性層を有する端子保護用テープの前記粘弾性層に、端子付き半導体装置又は端子付き半導体装置集合体の端子を埋設させる前記工程における、前記埋め込み層の弾性率が0.05~20MPaである、請求項7に記載の電磁波シールド膜付き半導体装置の製造方法。
- 前記粘着剤層と、前記埋め込み層と、基材と、をこの順で有する、請求項7又は8に記載の電磁波シールド膜付き半導体装置の製造方法。
- 前記基材のヤング率が100~2000MPaである請求項9に記載の電磁波シールド膜付き半導体装置の製造方法。
- 前記埋め込み層は、エネルギー線硬化性の構成材料を用いて形成された埋め込み層である、請求項7~10のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
- 前記粘着剤層は、エネルギー線硬化性の粘着剤を用いて形成された粘着剤層である、請求項7~11のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法。
- 請求項4~12のいずれか一項に記載の電磁波シールド膜付き半導体装置の製造方法に用いられる端子保護用テープ。
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- 2020-12-04 CN CN202080059202.7A patent/CN114270494B/zh active Active
- 2020-12-04 JP JP2021562753A patent/JP7611168B2/ja active Active
- 2020-12-04 TW TW109142878A patent/TWI880994B/zh active
- 2020-12-04 KR KR1020227002752A patent/KR102858395B1/ko active Active
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Also Published As
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| JPWO2021112238A1 (ja) | 2021-06-10 |
| KR102858395B1 (ko) | 2025-09-12 |
| JP7611168B2 (ja) | 2025-01-09 |
| TWI880994B (zh) | 2025-04-21 |
| KR20220113345A (ko) | 2022-08-12 |
| TW202137303A (zh) | 2021-10-01 |
| CN114270494B (zh) | 2025-10-24 |
| CN114270494A (zh) | 2022-04-01 |
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