Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/50—Working by transmitting the laser beam through or within the workpiece
  • B23K26/53—Working by transmitting the laser beam through or within the workpiece for modifying or reforming the material inside the workpiece, e.g. for producing break initiation cracks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
  • B23K26/04—Automatically aligning, aiming or focusing the laser beam, e.g. using the back-scattered light
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/36—Removing material
  • B23K26/38—Removing material by boring or cutting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
  • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
  • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
  • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
  • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
  • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
  • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
  • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
  • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
  • H01L2221/68336—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding involving stretching of the auxiliary support post dicing
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
  • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
  • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
  • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
  • H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer

Definitions

• the present invention relates to a method for manufacturing a work piece with a first protective film.
• a work such as bumps, pillars, etc.
• protruding electrodes For example, by using a so-called face-down method, a projecting electrode in a workpiece (for example, a semiconductor chip that is a divided semiconductor wafer) is used as a corresponding terminal portion on the substrate.
• the flip-chip mounting method has been adopted, which is face-to-face, contact, and fusion/diffusion bonding.
• a curable resin film is attached to the surface of the projecting electrode and the circuit surface of the work in order to protect the circuit surface of the work and the projecting electrode, and the film is cured. Then, a protective film may be formed on these surfaces.
• the surface of the projecting electrode and the circuit surface of the work or the workpiece are sometimes referred to as “projecting electrode forming surface”.
• the curable resin film is attached to the projecting electrode forming surface of the work in a state of being softened by heating.
• the upper portion including the crown portion of the projecting electrode penetrates the curable resin film and projects from the curable resin film.
• the curable resin film spreads between the protruding electrodes so as to cover the protruding electrodes of the work and adheres closely to the circuit surface, as well as the surface of the protruding electrodes, especially the surface near the circuit surface. And the protruding electrode is embedded.
• the curable resin film is further cured to cover the circuit surface of the work and the surface of the portion in the vicinity of the circuit surface of the projecting electrode to form a protective film that protects these areas.
• the semiconductor chip used in this mounting method is, for example, a semiconductor wafer having projecting electrodes formed on the circuit surface, the surface opposite to the circuit surface is ground, It is obtained by dicing and dividing.
• a curable resin film is attached to the protruding electrode forming surface for the purpose of protecting the circuit surface of the semiconductor wafer and the protruding electrodes, and the film is cured to form the protruding electrodes.
• the semiconductor wafer is divided into semiconductor chips, and finally, the semiconductor chip having the protective film on the protruding electrode formation surface (in this specification, "with protective film” Sometimes referred to as “semiconductor chip”) (see Patent Document 1).
• Such a work product having a protective film on the protruding electrode formation surface (in the present specification, it may be referred to as a "work product with a protection film”) is further prepared on a substrate. It becomes a package by being mounted on, and the target device is constructed by using this package. When the semiconductor chip with the protective film is mounted on the substrate, the semiconductor package thus obtained is used to configure the target semiconductor device.
• Patent Document 1 Japanese Patent No. 5 5 1 5 8 1 1
• an object of the present invention is to provide a novel manufacturing method for manufacturing a workpiece by dividing a workpiece having a protective film on the surface where the protruding electrodes are formed by dividing the workpiece.
• the present invention is a method for manufacturing a work piece with a first protective film, comprising: a work piece; and a first protective film formed on a surface of the work piece having a protruding electrode. Then, a step of attaching a thermosetting resin film to the surface of the workpiece having the protruding electrodes, a step of thermally curing the thermosetting resin film after attachment to form a first protective film, A step of forming a modified layer inside the work by irradiating a laser beam from the side provided with the first protective film through the first protective film; The work after the quality layer is formed is expanded together with the first protective film in a direction parallel to the circuit surface of the work, thereby dividing the work at the portion of the modified layer to form a work product.
• the present invention provides a method for manufacturing a work piece having a first protective film, the method including:
• the work in the step of obtaining the work piece with a workpiece, the work is divided at a site of the modified layer, and the first protective film is cut. Good.
• the thermosetting resin film contains a thermosetting component other than an acrylic resin having an epoxy group, and the thermosetting resin In the resin film, the ratio of the content of the thermosetting component to the total mass of the thermosetting resin film is 40% by mass or more, and the thickness of the thermosetting resin is one layer.
• Wavelength of a resin film or a laminated film having a total thickness of 200, which is constituted by laminating two or more layers of the thermosetting resin film having a thickness of less than 200, The light transmittance of the door may be 50% or more.
• thermosetting ⁇ 2020/175428 4 (: 170? 2020/007341
• the resin film contains two or more kinds of thermosetting components other than the acrylic resin having an epoxy group, and in the thermosetting resin film, with respect to the total mass of the thermosetting resin film,
• the proportion of the total content of the thermosetting components is 40% by mass or more, and the thermosetting components contained in the thermosetting resin film have the following formulas for each type:
• thermosetting component [Equivalent of functional group involved in thermosetting reaction of thermosetting component (9 / 69)] X [Content of thermosetting component of thermosetting resin film (part by mass)] / [Thermosetting resin Total content of all thermosetting components of the film (parts by mass)]
• the total value of the X values in all of the above-mentioned thermosetting components contained in the thermosetting resin film is calculated, the total value is not more than 40 09/ ⁇ . May be.
• a novel manufacturing method for manufacturing a workpiece by dividing a workpiece provided with a protective film on the protruding electrode forming surface by dividing the workpiece.
• FIG. 1 is a cross-sectional view schematically showing an example of a state in which a curable resin film is used to form a first protective film on a surface on which a protruding electrode is formed, in an embodiment of the present invention.
• FIG. 2 is a cross-sectional view schematically showing an example of a first protective film forming sheet used in an embodiment of the present invention.
• FIG. 3 is a cross-sectional view schematically showing another example of the first protective film forming sheet used in the embodiment of the present invention.
• FIG. 4 is a sectional view schematically showing still another example of the first protective film forming sheet used in the embodiment of the present invention.
• FIG. 58 An enlarged cross-sectional view for schematically explaining the manufacturing method of the first work piece with a protective film in the case of using the sheet for forming the first protective film in the embodiment of the present invention. Is.
• FIG. 58 In an embodiment of the present invention, a method for manufacturing a work piece with a first protective film, in which a sheet for forming a first protective film is used, is enlarged for schematically explaining. ⁇ 2020/175428 5 ⁇ (: 170? 2020 /007341
• FIG. 1 A first figure.
• FIG. 5(:] an enlarged cross-sectional view for schematically explaining the method for manufacturing the first work piece with a protective film in the case of using the first protective film forming sheet. It is a figure.
• FIG. 68 An enlarged cross-sectional view for schematically explaining the manufacturing method of the first work piece with a protective film in the case of using the sheet for forming the first protective film in the embodiment of the present invention. Is.
• FIG. 68 is an enlarged cross-sectional view for schematically explaining the method for manufacturing the first workpiece with the protective film in the case of using the sheet for forming the first protective film in the embodiment of the present invention. is there.
• a method for manufacturing a work piece with a first protective film includes a work piece and a surface having a projecting electrode of the work piece (in the present specification, " (Hereinafter, also referred to as “protruding electrode formation surface”), a method for manufacturing a work piece with a first protective film, comprising: That is, a step of adhering a thermosetting resin film to the protruding electrode forming surface) (may be abbreviated as “adhesion step” in the present specification), and thermosetting the thermosetting resin film after adhering.
• thermosetting resin film alone, or by using the first protective film forming sheet comprising the thermosetting resin film, ⁇ 2020/175428 6 ⁇ (: 170? 2020/007341
• a work piece with the first protective film can be manufactured.
• examples of the work include a semiconductor wafer and the like.
• workpieces include semiconductor chips, which are divided semiconductor wafers, and the like.
• the machining of the work includes, for example, division.
• Examples of the protruding electrodes include bumps and pillars.
• the projecting electrode is provided on the connection pad of the work and is made of eutectic solder, high temperature solder, gold or copper.
• thermosetting resin film and the first protective film forming sheet which are suitable for use in the present embodiment, will be described in detail.
• the first protective film is formed on the surface of the work by sticking it on the surface having the protruding electrodes (that is, the surface on which the protruding electrodes are formed) and thermally curing it.
• the thermosetting resin film contains a thermosetting component other than an acrylic resin having an epoxy group, in the thermosetting resin film. With respect to the total mass of the resin film, the ratio of the content of the thermosetting component,
• thermosetting resin film having a thickness of 200 40% by mass or more and one layer of the thermosetting resin film having a thickness of 200, or two or more layers of the thermosetting resin film having a thickness of less than 200.
• the sheet for forming a first protective film in the present embodiment includes a first support sheet, and the thermosetting resin film on one surface of the first support sheet.
• the “thermosetting resin film” may be referred to as a “thermosetting resin layer”.
• the first protective film forming sheet is made of the thermosetting resin film (thermosetting resin). ⁇ 2020/175428 7 ⁇ (: 170? 2020/007341
• thermosetting resin film After attachment has increased fluidity due to heating, and the upper portion including the crown of the protruding electrode penetrates the thermosetting resin film and projects from the thermosetting resin film. Further, the thermosetting resin film spreads between the protruding electrodes so as to cover the protruding electrodes, adheres to the circuit surface, and covers the surface of the protruding electrodes, particularly the surface of the portion near the circuit surface, Embed the protruding electrodes.
• thermosetting resin film in this state is further cured by heating to finally form the first protective film, and protects the above-mentioned circuit surface and the protruding electrode in a state in which they are in close contact with each other.
• the thermosetting resin film of the present embodiment by using the thermosetting resin film of the present embodiment, the circuit surface of the work and the portion of the protruding electrode near the circuit surface, that is, the base portion are sufficiently protected by the first protective film.
• the work after the first protective film-forming sheet is attached is, for example, if necessary, after the surface opposite to the circuit surface is ground, the first support sheet is removed, and then the heat treatment is performed.
• the heating of the curable resin film embeds the protruding electrodes and forms the first protective film.
• the work is divided (that is, the work is divided into individual pieces) and the first protective film is cut, and the first protective film obtained by the cutting is provided on the protruding electrode formation surface.
• a semiconductor device is manufactured using a work product (which may be referred to as a “first work product with a protective film” in the present specification). These steps will be described in detail later.
• curable resin film means “curable resin film before curing”, and mere “curable resin layer”.
• the description means “a curable resin layer before curing”.
• thermosetting resin film means “thermosetting resin film before curing”
• first protective film means a cured product of the thermosetting resin film.
• thermosetting resin film is suitable for applying a method different from the conventional one as a method of dividing (in other words, dividing into pieces) a work into work pieces.
• the “method different from the conventional method” is a method described later. ⁇ 2020/175 428 8 ⁇ (: 170? 2020 /007341
• a modified layer is formed inside the work by irradiating the work with the first protective film formed of the thermosetting resin film on the projecting electrode forming surface with laser light. .. Then, a force is applied to the work after the modified layer is formed. More specifically, in the present embodiment, the work is expanded in the direction parallel to the circuit surface. As a result, the work is divided at the portion of the modified layer. At this time, by applying a force also to the first protective film, more specifically, by expanding the first protective film in a direction parallel to the sticking surface to the work, the first protective film is simultaneously expanded. It may be possible to disconnect. At this time, the first protective film is cut along the dividing points of the work.
• the workpiece workpiece with the first protective film which includes the workpiece workpiece and the first protective film after cutting formed on the projecting electrode forming surface of the workpiece workpiece. can get.
• the first protective film cannot be cut at the same time when the work is divided, the first protective film is further cut after the work is divided. As a result, the same work piece with the first protective film as described above can be obtained.
• a method of dividing a work that involves the formation of such a modified layer is called stealth dicing (registered trademark), and the work is irradiated with laser light to scrape the work at the irradiation site while removing the work. It is essentially completely different from laser dicing, which is the process of cutting the wafer from its surface.
• thermosetting component that defines the above-mentioned content ratio is a component that exhibits a curing reaction when heated.
• acrylic resin having an epoxy group is not included in this thermosetting component.
• thermosetting component examples include the thermosetting component (Mitsumi) described below.
• thermosetting component examples include epoxy thermosetting resins, polyimide resins, unsaturated polyester resins and the like.
• Epoxy thermosetting resin consists of epoxy resin (Min 1) and thermosetting agent (Min 2), and these two components are both subject to the above-mentioned content ratio regulation. ⁇ 2020/175 428 9 ⁇ (: 170? 2020/007341
• acrylic resin having an epoxy group which is not included in the thermosetting component
• acrylic resins in the polymer component (8) described later those having an epoxy group can be mentioned.
• an acrylic resin having a glycidyl group is included in an acrylic resin having an epoxy group.
• thermosetting component contained in the thermosetting resin film may be only one type, or may be two or more types, and in the case of two or more types, a combination thereof.
• the combination and ratio can be arbitrarily selected.
• thermosetting component content (parts by mass )]/[The total mass (parts by mass) of the thermosetting resin film] XI 0) is 40% by mass or more as described above.
• thermosetting resin film contains two or more thermosetting components
• thermosetting component content means the total content of these two or more thermosetting components. It means the amount (part by mass).
• thermosetting resin film does not remain in the upper part including the crown of the projecting electrode when it is attached to the projecting electrode forming surface of the work. It can be suppressed and has appropriate properties as a resin film for forming the first protective film.
• the thermosetting resin film does not remain on the upper portion of the protruding electrode, in other words, the upper portion of the protruding electrode does By protruding through the curable resin film, the finally obtained work piece can be sufficiently electrically coupled to the substrate by the projecting electrodes when the flip chip is mounted. That is, unless the thermosetting resin film is capable of suppressing the remaining on the upper portion of the projecting electrode, the work piece cannot be put to practical use.
• the ratio of the content of the thermosetting component to the total mass of the thermosetting resin film is, for example, 50 mass% or more, 60 mass% or more, 70 mass% ⁇ 2020/175 428 10 ⁇ (: 170? 2020/007341
• the upper limit of the content ratio is not particularly limited.
• the content ratio is preferably 90% by mass or less.
• the ratio of the content can be appropriately adjusted within a range set by arbitrarily combining the lower limit value and the upper limit value.
• the ratio of the content is 40 to 90 mass%, 50 to 90 mass%, 60 to 90 mass%, 70 to 90 mass%, and 80 to 90 mass%. It may be any of 90% by mass.
• the one-layer thermosetting resin film having a thickness of 200 has a light transmittance of 50% or more at a wavelength of 1 3 42 2 as described above.
• the laminated film having a total thickness of 200 which is constituted by laminating two or more layers of the thermosetting resin film having a thickness of less than 200, has a wave length of 1 3 4 2 n.
• the light transmittance is 50% or more as described above.
• laser light having a wavelength of 1 3 4 2 01 is applied.
• the modified layer can be formed by irradiating the work with.
• the laser light may be irradiated to the work from the circuit surface side or the back surface side.
• the laser light is irradiated through the first protective film formed on the circuit surface.
• thermosetting resin film and its cured product eg, the first protective film
• the thermosetting resin film and its cured product have almost or exactly the same transmittance for light of the same wavelength. Therefore, one layer of thermosetting resin film with a thickness of 200,
• the transmittance of the cured product When the transmittance of the cured product is 50% or more, the transmittance of the cured product of light having a wavelength of 1 3 4 2 n is also 50% or more. Similarly, in the case of the laminated film, the transmittance of light having a wavelength of 1 3 4 2 n is 50% or more, and the transmittance of light of a wavelength of 1 3 4 2 n of the cured product is also 50% or more. Becomes That is, the transmittance of such light ⁇ 2020/175 428 1 1 ⁇ (: 170? 2020/007341
• the first protective film formed by using the thermosetting resin film having the same composition as the one satisfying the conditions allows the laser beam having the wavelength of 1 3 4 2 n to be satisfactorily transmitted. Therefore, a work provided with such a first protective film on the circuit surface is suitable for forming a modified layer inside the work by irradiating laser light from the circuit surface side. is there.
• thermosetting resin film having a thickness of 200 or a laminated film having a total thickness of 200 is The light transmittance may be, for example, 60% or more, 70% or more, 80% or more, and 85% or more.
• the value is not particularly limited, and the higher the value, the better.
• the light transmittance is preferably 95% or less.
• the light transmittance can be appropriately adjusted within a range set by arbitrarily combining the lower limit value and the upper limit value.
• the light transmittance is, for example, 50 to 95%, 60 to 95%, 70 to 95%, 80 to 95%, and 85 to 95%. It may be either.
• thermosetting resin film having a thickness of 200 and a total thickness of 2
• the light transmittance of these (one layer of thermosetting resin film and laminated film) is 1 3 4 2 01 Not only when, but the same as each other.
• the number of layers of the thermosetting resin film having a thickness of less than 200 constituting the laminated film is not particularly limited, but is preferably 2 to 6. With such a number of layers, the laminated film can be produced more easily.
• thermosetting resin film having a thickness of less than 200, which composes the laminated film may have the same thickness, may have different thicknesses, or may have only the same thickness. May be ⁇ 2020/175 428 12 (: 170? 2020/007341
• the thickness is specified to be 200 because the thickness is This is because by using a thermosetting resin film or a laminated film, the transmittance of the light can be measured more accurately and easily, in the present embodiment, one layer of the thermosetting resin film, and two or more layers
• the thickness of each of the thermosetting resin films composed of a plurality of layers is not limited to 200 0 1, as described later.
• the light transmittance is, for example, the types and contents of the components contained in the thermosetting resin film, such as the coloring agent ( ⁇ ) and the filler (mouth) described later, and the thermosetting resin film. It can be adjusted by adjusting the surface condition, etc.
• thermosetting resin film other than acrylate resin having an epoxy group
• thermosetting resin film contains two or more of the thermosetting components
• the following formulas are used for each type of the thermosetting component contained in the thermosetting resin film.
• thermosetting component [Equivalent of functional group involved in thermosetting reaction of thermosetting component (9 / 69)] X [Content of thermosetting component of thermosetting resin film (part by mass)] / [Thermosetting resin Total content of all thermosetting components of the film (parts by mass)]
• the total value of the X values in all types of the thermosetting components contained in the thermosetting resin film is calculated, the total value is, for example, It may be the following.
• thermosetting resin film satisfies such a condition
• the work piece is manufactured.
• the first protective film can also be cut. Therefore, it is not necessary to separately provide a step for cutting the first protective film, and the work piece with the first protective film can be manufactured with high efficiency.
• thermosetting resin film ⁇ 0 2020/175 428 13 ⁇ (: 17 2020 /007341
• thermosetting component for which the X value is calculated is the same as the “thermosetting component” that defines the above-mentioned content ratio in the thermosetting resin film.
• the "functional group involved in the thermosetting reaction of the thermosetting component" for calculating the X value is, for example, in the case of the epoxy resin (Mitsumi 1) described later, an epoxy group, and In the case of the curing agent (Mitsumi 2), it is a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, or a group in which an acid group is dehydrated.
• the functional groups are examples of the functional groups.
• thermosetting resin film contains various kinds of thermosetting components (wherein is an integer of 2 or more). These thermosetting components are 1 ⁇ for each type. Then, the equivalent of the functional group of the thermosetting component IV!] is set to (9/69), and the equivalent of the functional group of the thermosetting component IV! is set to (9/eq). Let the content of thermosetting component IV! ! (3 ! (Parts by mass) be the content of thermosetting component of thermosetting resin film. (Mass part)
• thermosetting component IV for the thermosetting component IV!, the above-mentioned value (hereinafter referred to as “X” value) is calculated by the following formula.
• thermosetting component Also for the above, the above-mentioned value (hereinafter, referred to as “ [3 value]”) is calculated by the following formula.
• thermosetting resin film the total value of the above-mentioned values (X !, Hex) in all types of thermosetting components (IV ! , He 1 ⁇ / ⁇ ) contained in the thermosetting resin film is as follows: ⁇ 2020/175 428 14 ⁇ (: 171? 2020 /007341
• the total value of the X value is, for example, 3759/69 below 350 9 /
• It may be either 6 or less and 3259/6 or less.
• the lower limit of the total value of the X values is not particularly limited.
• the total value of the above X values is 1009 from the viewpoint of suppressing deterioration of flexibility due to excessive crosslinking reaction. It is preferably 9 or more
• the total value of the X values can be appropriately adjusted within the range set by arbitrarily combining the lower limit value and the upper limit value.
• the sum of the above-mentioned values is 100-400/ ⁇ , 100-3759/6, 100-
• It may be any of 3503 X", and 100 to 3259/6.
• thermosetting resin films include those satisfying the conditions of the above-mentioned light transmittance and total X value.
• thermosetting resin film contains two or more thermosetting components other than the acrylic resin having an epoxy group, in the thermosetting resin film, the total mass of the thermosetting resin film
• the ratio of the total content of all types of the thermosetting components is 40% by mass or more
• thermosetting resin film having a thickness of 200, or composed of two or more layers of the thermosetting resin film having a thickness of less than 200, and having a total thickness of 200.
• ⁇ 1 is a laminated film, the wavelength of ⁇ 2020/175 428 15 ⁇ (: 170? 2020/007341
• thermosetting resin film For each of the thermosetting components contained in the thermosetting resin film, the following formula:
• thermosetting component [Equivalent of functional group involved in thermosetting reaction of thermosetting component (9 / 69)] X [Content of thermosetting component of thermosetting resin film (part by mass)] / [Thermosetting resin Total content of all thermosetting components of the film (parts by mass)]
• the total value of the X values in all types of the thermosetting components contained in the thermosetting resin film is calculated, the total value is preferably 40 or less. ..
• the breaking strength of the first protective film having a size of 200 1 111 X 1300 1 111 and a thickness of 40 measured by the following method is, for example, 5 It may be the following.
• the first protective film having the same composition as the first protective film having the breaking strength of not more than the upper limit value is easier to cut by the expand described later.
• the breaking strength of the first protective film is the distance between the gripping devices in the first protective film. As, it is possible to use the maximum stress measured when the first protective film is pulled by the gripping device in the direction parallel to the surface.
• thermosetting resin film obtained by thermosetting the thermosetting resin film at 1300° for 2 hours can be used.
• the breaking strength of the first protective film is, for example, 5 2.5 1 ⁇ /1 3 or less, The following may be either or and 47.5 1 ⁇ /1 3 or less.
• the lower limit of the breaking strength of the first protective film is not particularly limited. From the viewpoint that the protective ability of the first protective film becomes higher, the breaking strength of the first protective film is preferably not less than 0.1 IV! 3 .
• the breaking strength of the first protective film is obtained by arbitrarily combining the above lower limit value and upper limit value. ⁇ 2020/175428 16 ⁇ (: 170? 2020/007341
• the breaking strength of the first protective film is, for example, 0. 1 to 55 IV! 3, 0. 1 to 5 2.5 IV!, 0. 1 to 5 0 1 ⁇ /1? , And 0. 1 to 47.5 IV! 8 may be used.
• the breaking strength of the first protective film may be determined by, for example, the components contained in the composition for forming a thermosetting resin layer described later, particularly the polymer component (), the coupling agent (M), and the filler ( ⁇ ). ), etc., and the content, and the thickness of the first protective film (in other words, the thickness of the thermosetting resin film), etc., can be adjusted.
• a protective film containing an organic material may be formed on the back surface.
• the second protective film is used to prevent cracks from occurring in the workpiece after the workpiece is divided or packaged.
• the work piece with the second protective film having the second protective film on the back surface is finally taken into a target substrate device such as a semiconductor device.
• the second protective film may be required to have a function of marking information on the work piece with a laser and hiding the back surface of the work piece.
• a curable resin film in which a second protective film can be formed by curing and whose light transmission characteristics are adjusted is known.
• the second protective film for protecting the back surface of the work piece and the first protective film for protecting the protruding electrode forming surface of the work piece have different formation positions on the work piece, The required characteristics also differ from each other. Therefore, it is usually difficult to immediately use the thermosetting resin film capable of forming the second protective film immediately for forming the first protective film.
• Fig. 1 is a cross-sectional view schematically showing an example of a state in which a first protective film is formed on a protruding electrode formation surface using a thermosetting resin film in an embodiment of the present invention. ⁇ 2020/175 428 17 ⁇ (: 170? 2020/007341
• a plurality of projecting electrodes 91 are provided on the circuit surface 93 of the workpiece 90 shown here.
• the reference numeral 90 indicates the surface of the workpiece 90 opposite to the circuit surface 903 (rear surface).
• the projecting electrode 91 has a shape in which a part of a sphere is cut by a flat surface, and the flat surface corresponding to the cut and exposed portion is in contact with the circuit surface 93 of the work 90. Has become.
• the shape of the projecting electrode 91 is almost spherical.
• the first protective film 12' is formed by using the thermosetting resin film of the present embodiment, and covers the circuit surface 903 of the work 90, and further the protruding electrode 9 In the surface 9 13 of 1 of FIG. 1, the area other than the top portion 9 10 of the protruding electrode 9 1 and its vicinity is covered. In this way, the first protective film 12' adheres to the top surface 910 of the protruding electrode 91 and the surface 913 other than the vicinity thereof, and also adheres to the circuit surface 90-3 of the workpiece 90. Then, the protruding electrode 91 is embedded.
• the above-described substantially spherical shape of the projecting electrode 91 is particularly advantageous for forming the first protective film using the curable resin film.
• projecting electrodes 9 1 height 1-1 9 1 is not particularly limited, is preferably 5 0-5 0 0.
• the function of the protruding electrodes 91 can be further improved.
• the protruding electrode forming surface of the work 90 that is, the surface 9 13 of the protruding electrode 9 1 and the work 9 0
• the effect of suppressing the residual thermosetting resin film in the upper portion including the crown portion 9 10 of the projecting electrode 9 1 becomes higher.
• the effect of suppressing the formation of the first protective film 12′ on the upper portion of the projecting electrode 91 becomes higher.
• the “height of the protruding electrode” means the work height of the protruding electrodes. ⁇ 2020/175 428 18 ⁇ (: 170? 2020/007341
• projecting electrodes 9 1 of width ⁇ ⁇ / 9 1 is not particularly limited, 5 0-6 0 0 Dearuko and are preferred. Projecting electrodes 9 1 of width ⁇ ⁇ / 9 1 that is not less than the lower limit, it is possible to further improve the function of projecting electrodes 9 1.
• the protruding electrode forming surface of the work 9 0 i.e., the surface 9 1 3 projecting electrodes 9 1, the workpiece 9 0
• the effect of suppressing the residual thermosetting resin film in the upper portion including the crown portion 9 10 of the protruding electrode 9 1 becomes higher, As a result, the effect of suppressing the formation of the first protective film 12′ on the upper portion of the protruding electrode 91 becomes higher.
• the “width of the protruding electrode” means a work or a workpiece. This means the maximum value of the line segment obtained by connecting a straight line between two different points on the surface of the protruding electrode when looking down on the protruding electrode from a direction perpendicular to the circuit surface of.
• Distance 0 9 1 between projecting electrodes 9 1 adjacent is not particularly limited, 1 0 0-8
• the distance port 9! between the protruding electrodes 91 to be equal to or less than the upper limit value, the degree of freedom in the arrangement form of the protruding electrodes 91 becomes higher.
• the “distance between adjacent protruding electrodes” means the minimum value of the distance between the surfaces of adjacent protruding electrodes.
• the thickness sheets 9 0 sites excluding the projecting electrodes 9 1 of the workpiece 9 0 may be appropriately selected depending on the intended use of the work 9 0 is not particularly limited. ⁇ 2020/175 428 19 ⁇ (: 170? 2020/007341
• the thickness of sheets 9 0 after grinding the back surface 9 0 spoon workpiece 9 0 is preferably 5 0-5 0 0.
• the thickness sheets 9 0 of the work 9 0 after grinding the back surface 9 0 spoon is, that the at least as large as the lower limit, (in other words, pieces of the workpiece workpiece) splitting of the workpiece 9 at time 0, the work The effect of suppressing damage to the work piece is enhanced.
• the thickness sheets 9 0 of the work 9 0 after grinding the back surface 9 0 spoon is, that the it is not more than the upper limit, a thin workpiece workpiece is obtained.
• the thickness sheets 9 0 before grinding the back surface 9 0 spoon workpiece 9 0 is preferably 2 5 0-1 5 0 0.
• thermosetting resin film of the present embodiment is used is not limited to the one shown in FIG. 1, and a part of the composition is changed within a range not impairing the effects of the present invention. It may be deleted or added.
• the projecting electrode has a substantially spherical shape as described above (a shape in which a part of the sphere is cut off by a flat surface), but such a substantially spherical shape is shown.
• a shape that is stretched in the height direction in FIG. 1, a direction orthogonal to the circuit plane 903 of the work 90), that is, a shape of a spheroid that is almost a sphere (in other words, a sphere).
• a projecting electrode with an almost oblate spheroidal shape (in other words, a shape in which the part including one end in the minor axis direction of the oblate spheroid is cut off by a plane) is also used as a projecting electrode with a preferable shape.
• the projecting electrode having a substantially spheroidal shape also has the first protective film formed by using the thermosetting resin film of the present embodiment, similarly to the above-mentioned projecting electrode having a substantially spherical shape. It is particularly advantageous.
• examples of the protruding electrode include a columnar shape, an elliptic shape, a prism shape, an elliptical cone shape, a pyramid shape, a truncated cone shape, an elliptical truncated cone shape or a truncated pyramid shape; There is also a shape having a combination of a column, a prism, a truncated cone, a truncated ellipsoid or a truncated pyramid, and the above-mentioned substantially spherical or substantially spheroidal body.
• thermosetting in this embodiment.
• the first support sheet may be composed of one layer (single layer) or plural layers of two or more layers.
• the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
• 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”. May be different and only some of the layers may be the same", and "a plurality of layers are different from each other” means that "at least one of the constituent material and the thickness of each layer is different from each other”. It means that.
• a preferable first support sheet includes, for example, a first base material and a first adhesive layer provided on the first base material (in other words, the first base material and the first base material). 1 adhesive layer is laminated in these thickness directions), a first base material, a first intermediate layer provided on the first base material, and a first intermediate layer provided on the first intermediate layer.
• a pressure-sensitive adhesive layer i.e., a first base material, a first intermediate layer and a first pressure-sensitive adhesive layer, which are laminated in this order in the thickness direction
• And the like which include only the first base material.
• FIG. 2 is a cross-sectional view schematically showing an example of the first protective film forming sheet used in the embodiment of the present invention.
• the first protective film-forming sheet 1 shown here uses, as the first support sheet, the first base material and the first pressure-sensitive adhesive layer laminated in the thickness direction thereof. That is, the first protective film forming sheet 1 includes the first base material 11 and the first base material 11. ⁇ 2020/175428 21 ⁇ (: 170? 2020/007341
• thermosetting resin layer thermosetting resin film
• the first support sheet 10 1 is a laminated body of the first base material 11 and the first pressure-sensitive adhesive layer 13. Then, the first protective film forming sheet 1 is composed of the first support sheet 10 1 and one surface 10 1 3 of the first support sheet 10 1, that is, one of the first pressure-sensitive adhesive layer 13 It can be said that the thermosetting resin layer 12 provided on the surface 1 3 3 is provided.
• thermosetting resin layer 12 in the first protective film forming sheet 1 the content ratio of the thermosetting component may be 40% by mass or more.
• one thermosetting resin layer 12 having a thickness of 200 or a thermosetting resin layer 12 having a thickness of less than 200 is provided in the first protective film forming sheet 1.
• the laminated film having a total thickness of 200, which is formed by laminating two or more layers of, may have a transmittance of light having a wavelength of 1 3 4 2 n of 50% or more.
• thermosetting resin layer 12 in the first protective film forming sheet 1 contains two or more thermosetting components described above
• the thermosetting resin layer 12 for the thermosetting components contained in 12 the X value was determined for each type, and the total value of the X values in all types of the thermosetting components contained in the thermosetting resin layer 12 was determined. when the total value is, for example, it is a 4 0 0 9/6 9 below.
• FIG. 3 is a cross-sectional view schematically showing another example of the first protective film forming sheet used in the embodiment of the present invention.
• the first protective film forming sheet 2 shown here as the first supporting sheet, the first base material, the first intermediate layer and the first adhesive layer are laminated in this order in the thickness direction thereof. Is used. That is, the first protective film forming sheet 2 includes a first base material 11 and a first intermediate layer 14 provided on one surface of the first base material 11. ⁇ 2020/175 428 22 ⁇ (: 170? 2020 /007341
• thermosetting resin layer thermosetting resin film
• the first support sheet 102 is a laminate of the first base material 11, the first intermediate layer 14 and the first pressure-sensitive adhesive layer 13.
• the first protective layer forming sheet 2, the first support sheet - Bok 1 ⁇ 2 comprises a first supporting sheet 1 0 one side 1 of 2 0 2 3 on, other words the first adhesive layer 1 It can be said that the thermosetting resin layer 1 2 is provided on one surface 1 3 3 of the 3.
• the first protective film-forming sheet 2 is different from the first protective film-forming sheet 1 shown in FIG. 2 between the first base material 1 1 and the first pressure-sensitive adhesive layer 13 further.
• the first intermediate layer 14 is provided.
• thermosetting resin layer 12 in the first protective film forming sheet 2 the ratio of the total content of the above-mentioned thermosetting components may be 40% by mass or more. Further, in the first protective film-forming sheet 2, one thermosetting resin layer 12 having a thickness of 200 or a thermosetting resin layer 1 having a thickness of less than 200.
• the laminated film having a total thickness of 200 which is constituted by laminating two or more layers of 2, may have a transmittance of light having a wavelength of 1 of 50% or more. Further, when the thermosetting resin layer 12 in the first protective film forming sheet 2 contains two or more thermosetting components described above, the thermosetting resin layer 12 contains a thermosetting resin.
• the X value is determined for each type, and the total value of the X values for all types of thermosetting components contained in the thermosetting resin layer 12 is calculated.
• the total value may be, for example, 400 9 /69 or less.
• FIG. 4 is a cross-sectional view schematically showing still another example of the first protective film forming sheet used in the embodiment of the present invention.
• the first protective film forming sheet 3 shown here the first supporting sheet made of only the first base material is used. That is, the first protective film forming sheet 3 includes a first base material 11 and a thermosetting resin layer (thermosetting resin) provided on the first base material 11. ⁇ 2020/175428 23 ⁇ (: 170? 2020 /007341
• Resin film 1 and 2, and are configured.
• the first support sheet 103 is composed of only the first base material 11.
• the first protective film forming sheet 3 is provided with a first supporting sheet 103, and is provided on one surface 1033 of the first supporting sheet 103, in other words, one side of the first substrate 11 1. It can be said that the thermosetting resin layer 1 2 is provided on the surface 1 1 3 of the above.
• the first protective film forming sheet 3 is the first protective film forming sheet 1 shown in FIG. 2 in which the first pressure-sensitive adhesive layer 13 is omitted.
• thermosetting resin layer 12 in the first protective film forming sheet 3 the ratio of the total content of the above-mentioned thermosetting components may be 40% by mass or more.
• the laminated film having a total thickness of 200, which is constituted by laminating two or more layers of 2, may have a transmittance of light having a wavelength of 1 of 50% or more.
• the thermosetting resin layer 12 in the first protective film forming sheet 3 contains two or more thermosetting components described above, the thermosetting resin layer 12 contains a thermosetting resin.
• the X value is determined for each type, and the total value of the X values for all types of thermosetting components contained in the thermosetting resin layer 12 is calculated.
• the total value may be, for example, 400 9 /69 or less.
• the first support sheet a known one may be used, and the first support sheet can be appropriately selected according to the purpose.
• the first base material has a sheet shape or a film shape, and examples of the constituent material thereof include various resins.
• the resin constituting the first base material may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof may be arbitrarily selected.
• the first base material may be only one layer (single layer) or a plurality of layers of two or more layers. ⁇ 2020/175 428 24 ⁇ (: 170? 2020 /007341
• these layers may be the same or different from each other, and the combination of these layers is not particularly limited.
• the thickness of the first base material is preferably 50 to 200.
• the “thickness of the first base material” means the total thickness of the first base material, and for example, the thickness of the first base material composed of a plurality of layers means all the thicknesses of the first base material. Means the total thickness of the layers.
• the first base material is made of various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, a softening agent (plasticizer), in addition to the main constituent materials such as the resin. You may contain the additive.
• the first base material may be transparent or opaque, and may be colored depending on the purpose, or another layer may be vapor-deposited.
• the first base material is preferably one that transmits energy rays.
• the first base material may be, for example, a release film obtained by subjecting one side of a resin film to a release treatment by silicone treatment or the like, as described later in Examples.
• the first base material can be produced by a known method.
• the first base material containing a resin can be manufactured by molding a resin composition containing the resin.
• the first pressure-sensitive adhesive layer is in the form of a sheet or a film, and as the pressure-sensitive adhesive containing a pressure-sensitive adhesive, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate Examples thereof include adhesive resins such as sodium, and acrylic resins are preferable.
• adheresive resin is a concept that includes both a resin having adhesiveness and a resin having adhesiveness, and for example, the resin itself has adhesiveness. Not only this, but also includes resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness due to the presence of a trigger such as heat or water. ⁇ 2020/175 428 25 ⁇ (: 170? 2020/007341
• 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. In the case of a plurality of layers, these plurality of layers may be the same or different from each other. The combination of these plural layers is not particularly limited.
• the thickness of the first pressure-sensitive adhesive layer is preferably 3 to 40.
• the “thickness of the first pressure-sensitive adhesive layer” means the total thickness of the first pressure-sensitive adhesive layer, and for example, the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers means the first pressure-sensitive adhesive layer. It means the total thickness of all the layers that compose.
• the first pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive or may be formed using a non-energy ray-curable pressure-sensitive adhesive. ..
• the physical properties of the first pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can be easily adjusted before and after curing.
• energy ray means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, and electron rays.
• Ultraviolet rays can be emitted by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or a!
• the electron beam can be generated by an electron beam accelerator or the like.
• energy ray curable means a property of being cured by irradiation with energy rays
• non-energy ray curable means a property of not being cured even by irradiation of energy rays. To do.
• the first pressure-sensitive adhesive layer can be formed using the first pressure-sensitive adhesive composition containing a pressure-sensitive adhesive.
• the first pressure-sensitive adhesive composition can be formed on the target site by applying the first pressure-sensitive adhesive composition to the surface on which the first pressure-sensitive adhesive layer is to be formed and drying it if necessary.
• a more specific method for forming the first pressure-sensitive adhesive layer will be described later in detail together with a method for forming other layers.
• the first pressure-sensitive adhesive composition may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a mouth coater. ⁇ 2020/175 428 26 ⁇ (: 170? 2020/007341
• Examples of the method include various coaters such as a le coater, a mouth knife coater, a force coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
• various coaters such as a le coater, a mouth knife coater, a force coater, a die coater, a knife coater, 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, it is preferable to heat-dry it.
• the first pressure-sensitive adhesive composition containing a solvent may be dried, for example, under the conditions of 70 to 130 ° and 10 seconds to 5 minutes.
• the first pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive is, for example, A non-energy ray curable adhesive resin (_ _ 13) (hereinafter sometimes abbreviated as "adhesive resin (1-13)") and an energy ray curable compound, 1st pressure-sensitive adhesive composition (I 1 1);
• a non-energy ray curable adhesive resin (_ _ 13) (hereinafter sometimes abbreviated as "adhesive resin (1-13)") and an energy ray curable compound, 1st pressure-sensitive adhesive composition (I 1 1);
• Energy ray-curable adhesive resin in which an unsaturated group is introduced into the side chain of the pressure-sensitive adhesive resin ( ⁇ _ 13) ( ⁇ _ 23) hereinafter , Which may be abbreviated as “adhesive resin (I _ 2 3 )”
• a low-molecular compound and a first pressure-sensitive adhesive composition (I-3) containing
• the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive composition (I 1!!) to (I -3) includes non-energy-ray curable adhesives other than the energy-ray curable pressure-sensitive adhesive composition. Adhesive compositions are also included.
• non-energy ray curable first adhesive composition examples include a first adhesive composition ( ⁇ -4) containing the above-mentioned adhesive resin ( ⁇ 13). ⁇ 2020/175 428 27 ⁇ (: 170? 2020 /007341
• the first pressure-sensitive adhesive composition (C-14) preferably contains an acrylic resin as the pressure-sensitive adhesive resin (1-133), and further contains one or more cross-linking agents. More preferable.
• the first adhesive composition such as the first adhesive composition (I 1!!) to (I-4) is the first adhesive composition including the adhesive and, if necessary, components other than the adhesive. It is obtained by blending each component for constituting the agent composition.
• each component is not particularly limited, and two or more components may be added at the same time.
• a solvent When a solvent is used, it may be used by mixing the solvent with any compounding ingredient other than the solvent and diluting this compounding ingredient in advance, or by diluting any compounding ingredient other than the solvent in advance. Alternatively, the solvent may be used by mixing with the compounding ingredients.
• the method of mixing the components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing It may be selected appropriately.
• Temperature and time for addition and mixing of the components is not limited Ri particularly limited to each formulation component is not degraded, it may be appropriately adjusted, but it is preferable that the temperature is 1. 5 to 3 0 ° ⁇ .
• the first intermediate layer has a sheet shape or a film shape, and the constituent material thereof may be appropriately selected according to the purpose, and is not particularly limited.
• the first protective film it is possible to prevent the first protective film from being deformed by reflecting the shape of the protruding electrode existing on the circuit surface on the first protective film provided on the protruding electrode forming surface.
• urethane (meth)acrylate and the like can be mentioned from the viewpoint that the adhesiveness of the first intermediate layer is further improved.
• the first intermediate layer may be only one layer (single layer) or may be two or more layers. ⁇ 2020/175 428 28 ⁇ (: 170? 2020 /007341
• these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.
• the thickness of the first intermediate layer can be appropriately adjusted according to the height of the projecting electrodes present on the surface of the workpiece or workpiece workpiece to be protected.
• the thickness of the first intermediate layer is preferably 50 to 6001 in terms of easily absorbing the effect of the protruding electrode having a relatively high height.
• the “thickness of the first intermediate layer” means the total thickness of the first intermediate layer, and for example, the thickness of the first intermediate layer composed of a plurality of layers constitutes the first intermediate layer. It means the total thickness of all layers.
• the first intermediate layer can be formed by using the composition for forming the first intermediate layer containing the constituent material. For example, by coating the composition for forming the first intermediate layer on the surface on which the first intermediate layer is to be formed, and drying it as necessary, or curing it by irradiation with energy rays, the first site is formed on the target site. An intermediate layer can be formed. A more specific method of forming the first intermediate layer will be described later in detail together with a method of forming the other layers.
• the first intermediate layer-forming composition can be applied, for example, by the same method as in the case of the first pressure-sensitive adhesive composition.
• the drying conditions for the first intermediate layer-forming composition are not particularly limited, and may be the same as the drying conditions for the first adhesive composition, for example.
• the first intermediate layer forming composition When the first intermediate layer forming composition has an energy ray curability, it may be further cured by irradiation with an energy ray after being dried.
• composition for forming the first intermediate layer can be produced, for example, by the same method as in the case of the first pressure-sensitive adhesive composition except that the components are different.
• thermosetting resin film thermosetting resin layer
• thermosetting resin film is a film (layer) for protecting the circuit surface of the workpiece and the workpiece workpiece, and the protruding electrodes provided on the circuit surface. ⁇ 2020/175 428 29 ⁇ (: 170? 2020/007341
• thermosetting resin film forms a first protective film by thermosetting.
• thermosetting resin film is cured (in other words, after the first protective film is formed), the first support sheet and the thermosetting resin As long as the laminated structure of the cured product of the resin film (in other words, the first support sheet and the first protective film) is maintained, this laminated structure is referred to as a “first protective film forming sheet”.
• thermosetting resin film may or may not have energy ray-curable properties in addition to thermosetting properties.
• thermosetting resin film has energy ray curable characteristics
• the contribution of the thermosetting resin film to the formation of the first protective film from the thermosetting resin film is It should be larger than the contribution of curing.
• the thermosetting resin film may be composed of one layer (single layer) or may be composed of two or more layers regardless of the presence or absence of energy ray curability. Good.
• the thermosetting resin film is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
• the thickness of the thermosetting resin film is preferably 1 to 10001, more preferably 3 to 800!, regardless of the presence or absence of energy ray curability. , 5 to 60 are particularly preferable.
• the first protective film having higher protective ability can be formed.
• the thickness of the thermosetting resin film is equal to or less than the above upper limit, when the thermosetting resin film is attached to the protruding electrode forming surface of the work, the thermosetting resin film above the protruding electrodes is The effect of suppressing the remaining becomes higher. Furthermore, when the thickness of the thermosetting resin film is equal to or less than the above upper limit value, the first protective film can be cut better when the work is divided.
• the “thickness of the thermosetting resin film” means the total thickness of the thermosetting resin film, for example, the thickness of the thermosetting resin film composed of a plurality of layers. ⁇ 2020/175 428 30 ⁇ (: 170? 2020/007341
• thermosetting resin film Means the total thickness of all layers constituting the thermosetting resin film.
• thermosetting resin layer Composition for forming thermosetting resin layer
• the thermosetting resin film can be formed by using the thermosetting resin layer-forming composition containing the constituent material.
• the thermosetting resin film can be formed by applying the composition for forming a thermosetting resin layer to the surface on which the thermosetting resin film is to be formed, and drying the composition if necessary.
• the content ratio of the components that do not vaporize at room temperature is usually the same as the content ratio of the components in the thermosetting resin film.
• the composition for forming a thermosetting resin layer may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coat Yuichi, a mouth coater, a mouth knife.
• a known method for example, an air knife coater, a blade coater, a bar coater, a gravure coat Yuichi, a mouth coater, a mouth knife.
• the method using various coaters such as a coater, a force coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater can be used.
• thermosetting resin layer-forming composition The drying conditions of the thermosetting resin layer-forming composition are not particularly limited, regardless of whether the thermosetting resin film has energy-ray curability. However, when the thermosetting resin layer-forming composition contains the solvent described below, it is preferable to heat-dry the composition.
• the thermosetting resin layer-forming composition containing a solvent may be dried, for example, under the conditions of 70 to 130° and 10 seconds to 5 minutes. However, the thermosetting resin layer-forming composition is preferably dried by heating so that the composition itself and the thermosetting resin film formed from the composition are not thermoset.
• the curing conditions for thermosetting the thermosetting resin film to form the first protective film are not particularly limited, as long as the curing degree is such that the first protective film sufficiently exhibits its function. However, it may be appropriately selected according to the type of the thermosetting resin film.
• the heating temperature during thermosetting of the thermosetting resin film is preferably 100 to 200 ° ⁇ , more preferably 110 to 180 ° ⁇ , more preferably 120 It is particularly preferable that it is ⁇ 170°. And during heating during the thermosetting ⁇ 2020/175 428 31 ⁇ (: 170? 2020/007341
• the time interval is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.
• thermosetting resin film examples include those containing the polymer component (8) and the thermosetting component (M).
• the polymer component () is a component that can be regarded as formed by the polymerization reaction of the polymerizable compound.
• the thermosetting component (Mitsumi) is a component that can undergo a curing (polymerization) reaction by using heat as a reaction trigger.
• the polymerization reaction also includes a polycondensation reaction.
• thermosetting resin layer (I ⁇ I -1) ⁇ Composition for forming thermosetting resin layer (I ⁇ I -1)>
• thermosetting resin layer forming composition for example, a thermosetting resin layer forming composition (I 11-1) containing the polymer component (8) and the thermosetting component (8) In the present specification, it may be simply referred to as “composition (hereinafter referred to as “(composition) — 1”)” and the like.
• the polymer component () is a polymer compound for imparting film-forming property and flexibility to the thermosetting resin film.
• the polymer component () has thermoplasticity and does not have thermosetting property.
• composition ( ⁇ I-1) and the polymer component (8) contained in the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds. In that case, those combinations and ratios can be arbitrarily selected.
• Examples of the polymer component (8) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.
• the polymer component (8) is preferably polyvinyl acetal or acrylic resin.
• Examples of the polyvinyl acetal in the polymer component (8) include known ones.
• polyvinyl acetals include, for example, polyvinyl formal, polyvinyl butyral, and the like, and polyvinyl butyral is more preferable. ⁇ 2020/175 428 32 ⁇ (: 170? 2020 /007341
• polyvinyl petitral examples include those having the structural units represented by the following formulas (()) _ 1, (()) _ 2 and (I) _ 3.
• n is independently an integer of 1 or more.
• the polyvinyl acetal has a weight average molecular weight (IV!) of 5,000 to 2,000.
• thermosetting resin film is preferably 0 0, and more preferably 800 0 to 100 0 0 0.
• weight average molecular weight of the polyvinyl acetal is within such a range, when the thermosetting resin film is attached to the protruding electrode forming surface, the thermosetting resin film is prevented from remaining on the upper portion of the protruding electrode. The effect of doing this is higher.
• the polyvinyl acetal has a glass transition temperature (Choose 9) of preferably 40 to 80°, more preferably 50 to 70°.
• Choose 9 glass transition temperature
• the ratio of three or more kinds of monomers constituting the polyvinyl acetal can be arbitrarily selected.
• the acrylic resin in the polymer component (8) means a resin having a structural unit derived from (meth)acrylic acid or a derivative thereof.
• (meth)acrylic acid includes both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth)acrylic acid, for example, "(meth)acryloyl group” ⁇ 2020/175 428 33 ⁇ (: 170? 2020 /007341
• the “derivative” of a specific compound means a compound having a structure in which one or more hydrogen atoms of the compound are substituted with a group (substituent) other than a hydrogen atom.
• (meth)acrylic acid ester is a derivative of (meth)acrylic acid.
• Examples of the acrylic resin in the polymer component (8) include known acrylic polymers.
• the weight average molecular weight (IV!) of the acrylic resin is preferably 100,000 to 200,000, more preferably 100,000, and more preferably 1,500. I like it.
• the weight average molecular weight of the acrylic resin is at least the above lower limit, the shape stability (temporal stability during storage) of the thermosetting resin film is improved.
• the weight average molecular weight of the acrylic resin is equal to or less than the above upper limit, the thermosetting resin film easily follows the uneven surface of the adherend, and the void between the adherend and the thermosetting resin film is increased. And the like are further suppressed.
• the “weight average molecular weight” is a polystyrene-converted value measured by gel permeation chromatography (° ⁇ ) method unless otherwise specified.
• the glass transition temperature (Choose 9) of the acrylic resin is preferably from 60 to 70°, more preferably from 30 to 50°.
• the amount of the acrylic resin 9 is not less than the above lower limit, for example, the adhesive force between the cured product of the thermosetting resin film and the support sheet is suppressed, and the peelability of the support sheet is appropriately improved.
• the amount of the acrylic resin 9 is less than or equal to the above upper limit, the adhesive force between the thermosetting resin film and the cured product thereof to the adherend is improved.
• acrylic resin examples include polymers of one or more kinds of (meth)acrylic acid ester; (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and ! ⁇ 1-methylol acrylic. Selected from amide, etc. ⁇ 0 2020/175 428 34 ⁇ (: 17 2020 /007341
• Examples thereof include copolymers of two or more kinds of monomers.
• Examples of the (meth)acrylic acid ester constituting the acrylic resin include (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid 11-propyl, and (meth)acrylic acid.
• (Meth)acrylic acid cycloalkyl esters such as isobornyl acrylate and (meth)dicyclopentanyl acrylate;
• (Meth)acrylic acid containing substituted amino groups such as 1 ⁇ 1-methylaminoethyl (meth)acrylic acid ester containing substituted amino groups such as 1 ⁇ 1-methylaminoethyl (meth)acrylic acid ester.
• substituted amino group means a group obtained by substituting one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.
• the acrylic resin is selected from, for example, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and 1 ⁇ 1 _methylol acrylic amide in addition to the (meth)acrylic acid ester. It may be a copolymer of one or more monomers.
• the monomer constituting the acrylic resin may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof may be arbitrarily selected.
• the acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group.
• the functional group of the acrylic resin may be bonded to another compound via the crosslinking agent () described below, or may be directly bonded to another compound without the crosslinking agent ().
• the acrylic resin is bound to another compound by the functional group, the reliability of the package obtained by using the first protective film forming sheet tends to be improved.
• thermoplastic resin other than polyvinyl acetal and an acrylic resin (hereinafter sometimes simply abbreviated as "thermoplastic resin”) It may be used alone without using the acetal and the acrylic resin, or may be used in combination with the polyvinyl acetal or the acrylic resin.
• thermoplastic resin By using the thermoplastic resin, the first support sheet of the first protective film ⁇ 2020/175 428 36 ⁇ (: 170? 2020 /007341
• thermosetting resin film easily follows the uneven surface of the adherend, further suppressing the occurrence of voids between the adherend and the thermosetting resin film.
• the weight average molecular weight of the thermoplastic resin is preferably 1,000 to 100,000, and more preferably 3000 to 80,000.
• the glass transition temperature (C9) of the thermoplastic resin is preferably 30 to 150 ° C, more preferably _20 to 120°O.
• thermoplastic resin examples include polyester resin, polyurethane resin, phenoxy resin, polybutene, polybutadiene, polystyrene and the like.
• thermoplastic resin contained in the composition ( ⁇ I-1) and the thermosetting resin film may be only one kind, may be two kinds or more, and may be two kinds or more. In some cases, their combination and ratio can be arbitrarily selected.
• the ratio of the content of the polymer component () to the total mass of the curable resin film) is, for example, 5 to 60% by mass, regardless of the type of the polymer component (8),
• It may be any of 5 to 45% by mass, 5 to 30% by mass, and 5 to 15% by mass.
• the polymer component () may also correspond to the thermosetting component (Mitsumi).
• the composition ( ⁇ ⁇ ⁇ _ 1) contains both the polymer component () and the thermosetting component (Mitsumi)
• the composition (III _ 1 ) Is considered to contain a polymer component () and a thermosetting component (M).
• thermosetting component (M) has thermosetting properties and is a component for thermosetting the thermosetting resin film to form the hard first protective film.
• thermosetting resin film both of the “thermosetting component” that defines the above-mentioned content ratio and the “thermosetting component” whose X value is calculated are ⁇ 2020/175 428 37 ⁇ (: 170? 2020 /007341
• thermosetting component (Mitsumi) is applicable.
• composition (II 1-1) and the thermosetting component (M) contained in the thermosetting resin film may be only one kind, or may be two or more kinds, or two kinds. In the above cases, the combination and ratio of them can be arbitrarily selected.
• thermosetting component examples include epoxy-type thermosetting resins, polyimide resins, unsaturated polyester resins, and the like.
• thermosetting component (Mitsumi) is preferably an epoxy thermosetting resin.
• Epoxy thermosetting resin consists of epoxy resin (Min 1) and thermosetting agent (Min 2).
• thermosetting resin film both of the "thermosetting component” that defines the above-mentioned content ratio and the "thermosetting component” whose X value is to be calculated are epoxy resin (1 ) And thermosetting agent (Mimi 2) are both applicable.
• composition (II 1 _ 1) and the thermosetting resin film may contain only one type of epoxy resin, or two or more types, or two or more types. If so, the combination and ratio thereof can be arbitrarily selected.
• Epoxy resin (Mimi 1)
• Examples of the epoxy resin include known ones. Examples include bifunctional or higher functional epoxy compounds such as pentene type epoxy resin, biphenyl type epoxy resin, bisphenol octa type epoxy resin, bisphenol type epoxy resin, and phenylene skeleton type epoxy resin.
• an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (Min 1).
• An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, ⁇ 0 2020/175 428 38 ⁇ (: 17 2020 /007341
• the reliability of the work piece with the first protective film obtained by using the production sheet is improved.
• Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a part of the epoxy groups of the polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition-reacting (meth)acrylic acid or its derivative with an epoxy group.
• examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting an epoxy resin.
• the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), 2-proberenyl group (allyl group), and (meth)acryloyl group. , (Meth) acrylic amide group and the like, and acryloyl group is preferable.
• the number average molecular weight of the epoxy resin (Min 1) is not particularly limited, but from the viewpoint of the thermosetting resin film curability, and the strength and heat resistance of the resin film after curing,
• It is preferably from 300 to 300, more preferably from 300 to 100, and particularly preferably from 300 to 300.
• Rukoto preferably, 1 and more preferably 5_ ⁇ _ ⁇ 9 7 0 9 / & a is.
• the epoxy resin (Mitsumi 1) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof may be arbitrarily selected. ..
• thermosetting agent functions as a curing agent for the epoxy resin (Mimi 1).
• thermosetting agent examples include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule.
• the functional group examples include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and an acid group. ⁇ 2020/175 428 39 ⁇ (: 170? 2020 /007341
• Examples thereof include a group in which the group is dehydrated, and a phenolic hydroxyl group, an amino group, or a group in which the acid group is dehydrated is preferable, and a phenolic hydroxyl group or an amino group is more preferable.
• thermosetting agents examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins and aralkyl type phenolic resins. Examples thereof include enol resin.
• thermosetting agents examples of the amine-based curing agent having an amino group include dicyandiamide and the like.
• thermosetting agent may have an unsaturated hydrocarbon group.
• thermosetting agent having an unsaturated hydrocarbon group (Min 2) examples include, for example, a compound obtained by substituting a part of a hydroxyl group of a phenol resin with a group having an unsaturated hydrocarbon group, and an aromatic compound of a phenol resin. Examples thereof include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to the ring.
• the unsaturated hydrocarbon group in the thermosetting agent (Mimi 2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
• the heat-curing agent (Min 2) softens because the peelability of the first protective film from the first support sheet is improved. Those having a high point or glass transition temperature are preferable.
• thermosetting agents for example, the resin component such as polyfunctional phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin has a number average molecular weight of 30 It is preferably from 0 to 300,0, more preferably from 400 to 100, and particularly preferably from 500 to 300.
• the molecular weight of the non-resin component such as biphenol or dicyandiamide in the thermosetting agent (Mitsumi 2) is not particularly limited, it is preferably, for example, 60 to 500.
• thermosetting agent (Mimi 2) may be used alone or in combination of two or more kinds. ⁇ 2020/175 428 40 ⁇ (: 170? 2020/007341
• thermosetting agent ( ⁇ _ 1) and the thermosetting resin film, a thermosetting agent ( ⁇ _ 1) and the thermosetting resin film, a thermosetting agent ( ⁇ _ 1) and the thermosetting resin film, a thermosetting agent ( ⁇ _ 1) and the thermosetting resin film, a thermosetting agent ( ⁇ _ 1) and the thermosetting resin film, a thermosetting agent ( ⁇ _ 1) and the thermosetting resin film, a thermosetting agent (
• the content of 2) is, for example, 0.1 to 500 parts by mass, 1 to 250 parts by mass, 1 to 15 parts by mass relative to the content of 100 parts by mass of the epoxy resin (Mitsumi 1). 0 parts by mass,! To 100 parts by mass, 1 to 75 parts by mass, and 1 to 50 parts by mass.
• the content of the thermosetting agent (Mitsumi 2) is at least the lower limit value, the thermosetting resin film will be more easily cured.
• the content of the thermosetting agent (Mimi 2) is less than or equal to the upper limit value, the moisture absorption rate of the thermosetting resin film is reduced, and the package obtained using the first protective film forming sheet is reduced. Reliability is further improved.
• the content of the thermosetting component (B) (for example, the total content of the epoxy resin (M1) and the thermosetting agent (M2))
• the amount is, for example, 300 to 1400 parts by mass, 400 to 1300 parts by mass, and 500 to 1 part with respect to the content of the polymer component () of 100 parts by mass. It may be any one of 100 parts by mass, 600 to 100 parts by mass, and 700 to 900 parts by mass.
• the content of the thermosetting component (M) is within such a range, for example, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is reduced. Is improved.
• the composition ( ⁇ _1) and the thermosetting resin film may contain a curing accelerator ( ⁇ 3).
• the curing accelerator ( ⁇ 3) is a component for adjusting the curing speed of the composition (IIII-1).
• preferable curing accelerators ( ⁇ ) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methyl imidazole, 2 —Phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2 ⁇ 2020/175 428 41 ⁇ (: 170? 2020 /007341
• Imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); tributylphosphine, diphenylphosphine, triphenylphosphine Organic phosphines such as innes (phosphines in which one or more hydrogen atoms are substituted with organic groups); Tetraphenylphosphonium tetraphenylborate, tetraphenylboron salts such as triphenylphosphinetetraphenylborate, etc. To be mentioned.
• composition ( ⁇ I-1) and the curing accelerator ( ⁇ ) contained in the thermosetting resin film may be only one kind, or may be two or more kinds, or two kinds. In the above cases, the combination and ratio of them can be arbitrarily selected.
• the content of the curing accelerator ( ⁇ 3) in the composition (III-1) and the thermosetting resin film is the same as that of the thermosetting component (M). It may be, for example, any one of 0.01 to 100 parts by mass and 0.1 to 7 parts by mass with respect to the amount of 100 parts by mass.
• the content of the curing accelerator ( ⁇ 3) is equal to or more than the lower limit value, the effect of using the curing accelerator ( ⁇ ) can be more remarkably obtained.
• the content of the curing accelerator ( ⁇ 3) is less than or equal to the above upper limit value, for example, the highly polar curing accelerator ( ⁇ 3) may be contained in the thermosetting resin film under high temperature and high humidity conditions. The effect of suppressing the segregation by moving to the adhesive interface with the adherent is enhanced. As a result, the reliability of the work piece with the first protective film obtained by using the sheet for forming the first protective film is further improved.
• the composition ( ⁇ I-1) and the thermosetting resin film may contain a filler (mouth). Since the thermosetting resin film contains the filler (mouth), the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin film can be easily adjusted. Then, by optimizing this thermal expansion coefficient for the object to be formed with the first protective film, the reliability of the work piece with the first protective film obtained using the sheet for forming the first protective film is improved. To improve. In addition, since the thermosetting resin film contains the filler (mouth), the moisture absorption rate of the first protective film can be reduced, ⁇ 2020/175428 42 ⁇ (: 170? 2020 /007341
• the filler (mouth) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
• Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc.; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Quality products; single crystal fibers of these inorganic fillers; glass fibers and the like.
• the inorganic filler is preferably silica or alumina, and more preferably silica.
• the average particle size of the filler (mouth) may be appropriately selected according to the purpose and is not particularly limited, and may be, for example, 0.02 to 2.
• the term “average particle size” means the value of particle size (port 50 ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified.
• composition ( ⁇ I-1) and the thermosetting resin film may contain only one kind of filler (mouth), or two or more kinds, or two or more kinds. If so, their combination and ratio can be arbitrarily selected.
• the ratio of the content of the filler ( ⁇ ) to the total content of all components other than the solvent ie, in the thermosetting resin film.
• the ratio of the content of the filler ( ⁇ ) with respect to the total mass of the thermosetting resin film is, for example, 3 to 60 mass%, 4 to 40 mass%, 5 to 30 mass%, 5 to 20 mass%. %, and 5 to 15% by mass.
• the ratio is within such a range, it becomes easier to adjust the thermal expansion coefficient of the first protective film described above.
• the composition ( ⁇ _1) and the thermosetting resin film may contain a coupling agent (Mitsumi).
• a coupling agent (Mitsumi) having a functional group capable of reacting with an inorganic compound or an organic compound, a thermosetting resin can be obtained.
• the adhesiveness and adhesion of the oil film to the adherend can be improved. Further, by using the coupling agent (Mitsumi), the cured product of the thermosetting resin film has improved water resistance without impairing heat resistance.
• the coupling agent (Mitsumi) is preferably a compound having a functional group capable of reacting with a functional group of the polymer component (H), thermosetting component (Mitsumi), etc. More preferably, it is an agent.
• Examples of the preferable silane coupling agent include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyljetoxysilane, 2-(3 , 4-Epoxycyclohexyl) Ethyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-Aminopropyltrimethoxysilane, 3-(2-Aminoethylamino)propyltrimethoxysilane, 3-(2-Aminoethylamino)propylmethyl jetoxy Silane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxys
• composition (II 1 _ 1) and the coupling agent (M) contained in the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds. In the case of the above, those combinations and ratios can be arbitrarily selected.
• the content of the coupling agent (Mitsumi) in the composition (II 1 -1) and the thermosetting resin film is the polymer component (8) and the thermosetting resin.
• the polymer component () one having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group or an isocyanate group, which can be bonded to other compounds, such as the above-mentioned acrylic resin is used.
• the composition ( ⁇ -1) and the thermosetting resin film may contain a cross-linking agent ().
• the cross-linking agent () is a component for bonding the functional group in the polymer component () with other compound to cross-link, and by such cross-linking, the initial adhesive force of the thermosetting resin film is increased. And the cohesive force can be adjusted.
• cross-linking agent () examples include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate cross-linking agents (cross-linking agents having a metal chelate structure), aziridine cross-linking agents (cross-linking agents having an aziridinyl group. ) Etc.
• organic polyvalent isocyanate compound examples include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compound”). May be abbreviated as “isocyanate compound etc.”); trimer of the above-mentioned aromatic polyvalent isocyanate compound etc., isocyanurate body and adduct body; obtainable by reacting the above-mentioned aromatic polyvalent isocyanate compound etc. with a polyol compound Examples thereof include a terminal isocyanate isocyanate prepolymer.
• the "adduct” means the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. And a low molecular weight active hydrogen-containing compound of 1.
• Examples of the adduct include trimethylolpropane xylylene diisocyanate as described below. ⁇ 2020/175 428 45 ⁇ (: 170? 2020 /007341
• terminal isocyanate urethane prepolymer means a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.
• the organic polyisocyanate compound is, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate.
• Compounds: lysine diisocyanate and the like can be mentioned.
• organic polyvalent imine compound examples include, for example, 1 ⁇ 1, 1 ⁇ 1'-diphenylmethan-4,4'-bis(1-aziridinecarboxamide), trimethylol propantry/3-aziridinylprobio. , Tetramethylolmethanoltri/3/3-aziridinylprobionate, 1 ⁇ 1, 1 ⁇ 1, -toluene_2,4-bis(1-aziridinecarboxamide)triethylenemelamine and the like.
• cross-linking agent () When an organic polyisocyanate compound is used as the cross-linking agent (), it is preferable to use a hydroxyl group-containing polymer as the polymer component ().
• a hydroxyl group-containing polymer When the cross-linking agent () has an isocyanate group and the polymer component () has a hydroxyl group, the cross-linking structure can be easily introduced into the thermosetting resin film by the reaction between the cross-linking agent () and the polymer component (). ..
• the crosslinking agent () contained in the composition ( ⁇ I-1) and the thermosetting resin film may be only one kind, may be two kinds or more, and may be two kinds or more. In some cases, their combination and ratio can be arbitrarily selected. ⁇ 2020/175 428 46 ⁇ (: 170? 2020 /007341
• the content of the cross-linking agent () in the composition ( ⁇ 1-1) is, for example, based on 100 parts by mass of the polymer component (), It may be any one of 0.01 to 20 parts by mass, 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass.
• the content of the cross-linking agent () is at least the lower limit value, the effect of using the cross-linking agent () is more remarkably obtained.
• the content of the cross-linking agent () is less than or equal to the upper limit value, excessive use of the cross-linking agent () is suppressed.
• the composition ( ⁇ I-1) and the thermosetting resin film may contain an energy ray-curable resin ( ⁇ ). Since the thermosetting resin film contains the energy ray-curable resin ( ⁇ ), its characteristics can be changed by irradiation with energy rays.
• the energy ray-curable resin ( ⁇ ) is obtained by polymerizing (curing) an energy ray-curable compound.
• Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferable.
• Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acryloyl-, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol.
• Chain-like aliphatic skeletons such as tall monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (Meth)acrylate; Dicyclopentanyldi(meth)acrylate and other cycloaliphatic skeleton-containing (meth)acrylate; Polyethylene glycol di(meth)acrylate and other polyalkylene glycol (meth)acrylate; Oligoester (meth) Acrylate; Urethane (meth) acrylate oligomer; Epo ⁇ 2020/175428 47 ⁇ (: 170? 2020/007341
• the weight average molecular weight of the energy ray-curable compound is preferably 100 to 300,000, and more preferably 300 to 100.
• the energy ray-curable compound used for the polymerization may be only one type, or may be two or more types. In the case of two or more types, their combination and ratio are arbitrarily selected. it can.
• the energy ray curable resin ( ⁇ ) contained in the composition (II 1 _ 1) and the thermosetting resin film may be only one kind, or may be two or more kinds. When there are more than one species, their combination and ratio can be arbitrarily selected.
• the energy ray curable resin ( ⁇ ) when used, the energy ray curable resin ( ⁇ ) relative to the total mass of the composition ( ⁇ _1) in the composition ( ⁇ 1-1)
• the content ratio of may be, for example, any one of 1 to 95% by mass, 5 to 90% by mass, and 10 to 85% by mass.
• composition ( ⁇ I-1) and the thermosetting resin film contain the energy ray-curable resin ( ⁇ ), in order to promote the polymerization reaction of the energy ray-curable resin ( ⁇ ) efficiently, It may contain a polymerization initiator (1 to 1).
• Examples of the photopolymerization initiator (1 to 1) in the composition ( ⁇ ⁇ ⁇ _ 1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isoptyl ether, and benzoin Benzoin compounds such as benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyloxypropane _ 1-one, 2,2-dimethoxy _ 1, 2-diphenylethane
• -Acetophenone compounds such as 1-one; Acyl such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Phosphine oxide ⁇ 2020/175 428 48 ⁇ (: 170? 2020 /007341
• sulfide compounds such as benzyl phenyl sulfide and tetramethyl thiuram mono sulfide; 1-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisoptyronitrile; titanocene such as titanocene Compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzil; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy_2-methyl-1— [4 — (1-Methylvinyl)phenyl]propanone; 2-chloroanthraquinone and the like.
• the photopolymerization initiator also include quinone compounds such as 1-chloroanthraquinone; and photosensitizers such as amine
• the photopolymerization initiator (1 to 1) contained in the composition ( ⁇ I-1) and the thermosetting resin film may be only one kind, or may be two or more kinds. , And when there are two or more kinds, their combination and ratio can be arbitrarily selected.
• the content of the photopolymerization initiator (! !) in the composition ( ⁇ ⁇ _ _ 1) is the same as that of the energy ray curable resin ( ⁇ ).
• the content of 100 parts by mass any one of, for example, 0.1 to 20 parts by mass, 1 to 10 parts by mass, and 2 to 5 parts by mass may be used.
• composition ( ⁇ I-1) and the thermosetting resin film may contain a colorant ( ⁇ ).
• Examples of the colorant (I) include known pigments such as inorganic pigments, organic pigments and organic dyes.
• organic pigments and organic dyes examples include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyriquinones.
• Ndolinone dyes examples include dyes, azomethine dyes, benzimidazolone dyes, piranslone dyes and slene dyes.
• examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments. , Tadano ⁇ (indium tin oxide) type dyes, and Hachio ⁇ (antimony tin oxide) type dyes.
• the colorant ( ⁇ ) contained in the composition ( ⁇ I-1) and the thermosetting resin film may be only one kind, or may be two or more kinds, or two or more kinds. If so, their combination and ratio can be arbitrarily selected.
• the content of the colorant () in the thermosetting resin film may be appropriately adjusted according to the purpose.
• the ratio of the content of the colorant ( ⁇ ) to the total content of all components other than the solvent (that is, the thermosetting resin film) may be 0.1 to 5 mass%.
• the ratio is equal to or more than the lower limit value, the effect of using the coloring agent () is more remarkable.
• the ratio is equal to or less than the upper limit value, an excessive decrease in light transmittance of the thermosetting resin film is suppressed.
• composition (I I-1) and the thermosetting resin film may contain a general-purpose additive (") as long as the effects of the present invention are not impaired.
• the general-purpose additive (" may be a known one and can be arbitrarily selected according to the purpose and is not particularly limited, but preferable examples include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, etc. Is mentioned.
• thermosetting resin film ⁇ 2020/175 428 50 ⁇ (: 170? 2020/007341
• ]) may be only one kind, or may be two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.
• composition ( ⁇ I-1) and the general-purpose additive (") of the thermosetting resin film are not particularly limited and may be appropriately selected depending on the purpose.
• composition ( ⁇ _1) preferably further contains a solvent.
• the composition containing the solvent ( ⁇ _1) has good handleability.
• the solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isoptyl alcohol (2-methylpropane _1-ol), 1-butanol.
• hydrocarbons such as toluene and xylene
• alcohols esters such as ethyl acetate; ketones such as acetone and methylethylketone; ethers such as tetrahydrofuran; dimethylformamide,
• Examples include amides (compounds having an amide bond) such as 1 ⁇ !-methylpyrrolidone.
• the solvent contained in the composition ( ⁇ _ 1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are arbitrarily selected. it can.
• the solvent contained in the composition ( ⁇ _ 1) is preferably methyl ethyl ketone or the like, since the components contained in the composition ( ⁇ ⁇ _ 1) can be mixed more uniformly.
• the content of the solvent of the composition (IIII-1) is not particularly limited and may be appropriately selected depending on, for example, the type of components other than the solvent.
• thermosetting resin layer-forming composition [0203]
• composition for forming a thermosetting resin layer such as the composition (I II-1) can be obtained by blending each component for constituting the composition.
• each component is not particularly limited, and two or more components may be added at the same time.
• This blending component may be used by diluting it in advance, or the solvent may be mixed with these blending components without preliminarily diluting any of the blending components other than the solvent.
• the method of mixing the components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing It may be selected appropriately.
• Temperature and time for addition and mixing of the components is not limited Ri particularly limited to each formulation component is not degraded, it may be appropriately adjusted, but it is preferable that the temperature is 1. 5 to 3 0 ° ⁇ .
• the first protective film forming sheet can be manufactured by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship.
• the method for forming each layer is as described above.
• the first pressure-sensitive adhesive layer or the first intermediate layer when the first pressure-sensitive adhesive layer or the first intermediate layer is laminated on the first base material when manufacturing the first support sheet, the above-mentioned first pressure-sensitive adhesive composition is formed on the first base material.
• the first pressure-sensitive adhesive layer or the first intermediate layer can be laminated by applying the composition for forming the first intermediate layer and, if necessary, drying it or irradiating it with energy rays.
• thermosetting resin layer thermosetting resin film
• the thermosetting resin layer-forming composition can be applied onto the agent layer to directly form the thermosetting resin layer.
• first pressure-sensitive adhesive layer when further laminating the first pressure-sensitive adhesive layer on the first intermediate layer that has already been laminated on the first substrate, apply the first pressure-sensitive adhesive composition on the first intermediate layer. It is possible to directly form the first adhesive layer.
• another composition is applied onto the layer formed from the composition and a new composition is formed. It is possible to form a layer on.
• the layer to be laminated later is formed beforehand on another release film using the composition, and the side of the formed layer which is in contact with the release film is Exposed surface on the other side ⁇ 2020/175 428 52 ⁇ (: 170? 2020 /007341
• the composition is preferably applied to the release-treated surface of the release film.
• the release film may be removed as needed after the laminated structure is formed.
• a first protective film-forming sheet in which a first adhesive layer is laminated on a first substrate and a thermosetting resin layer is laminated on the first adhesive layer Is a laminate of the first base material and the first pressure-sensitive adhesive layer), the first pressure-sensitive adhesive composition is coated on the first base material, and The first pressure-sensitive adhesive layer is laminated on the first base material by drying according to the above conditions, and the thermosetting resin layer-forming composition is separately applied on the release film and dried if necessary.
• a thermosetting resin layer is formed on the release film, and the exposed surface of this thermosetting resin layer is attached to the exposed surface of the first adhesive layer already laminated on the first base material.
• the first protective film forming sheet can be obtained.
• the first base material is used.
• the composition for forming the first intermediate layer on the above, by drying as necessary, or by irradiating with an energy ray, the first intermediate layer is laminated on the first substrate, separately,
• the first pressure-sensitive adhesive composition is applied onto the release film, and dried if necessary to form the first pressure-sensitive adhesive layer on the release film, and the exposed surface of the first pressure-sensitive adhesive layer is removed.
• the first support sheet is obtained by laminating the first pressure-sensitive adhesive layer on the exposed surface of the first intermediate layer that has already been laminated on the first base material, and laminating the first adhesive layer on the first intermediate layer.
• a thermosetting resin layer-forming composition is separately applied onto a release film, and dried if necessary to form a curable resin layer on the release film.
• the first pressure-sensitive adhesive composition or the composition for forming the first intermediate layer is formed on the release film.
• the first pressure-sensitive adhesive layer or the first intermediate layer is formed on the release film by applying the composition for forming and drying it as necessary, or by irradiating with energy rays.
• the first adhesive layer or the first intermediate layer may be laminated on the first substrate by bonding the exposed surface to one surface of the first substrate.
• the release film may be removed at any timing after the intended laminated structure is formed.
• any of the layers other than the first base material forming the first protective film-forming sheet is formed on the release film in advance and is attached to the surface of the target layer. Since it can be laminated by, the layer for which such a step is adopted can be appropriately selected as necessary to manufacture the first protective film forming sheet.
• the first protective film-forming sheet is usually stored with a release film attached to the surface of the outermost layer (eg, thermosetting resin layer) on the side opposite to the first support sheet. It Therefore, a composition for forming a layer constituting the outermost layer, such as a thermosetting resin layer-forming composition, is coated on this release film (preferably the release treatment surface), and if necessary, And drying to form a layer constituting the outermost layer on the release film, and the remaining layers are formed on the exposed surface of the layer on the side opposite to the side in contact with the release film.
• the first protective film-forming sheet can also be obtained by laminating by the method described above and leaving the release film in a bonded state without removing it.
• the first support sheet a commercially available product may be used.
• FIGS. 58 to 50 and FIGS. 68 to 6 are enlarged cross-sectional views for schematically explaining the method for manufacturing the workpiece.
• a manufacturing method using the first protective film forming sheet 1 shown in FIG. 2 will be described.
• thermosetting resin film 1 On the protruding electrode forming surface of the work 90 (that is, the surface 9 13 of the protruding electrode 91 and the circuit surface 90 3 of the work 90), Attach the thermosetting resin film 1 2.
• the thermosetting resin film 12 spreads among a large number of projecting electrodes 91, and adheres to the projecting electrode forming surface, as well as the surface 9 1 of the projecting electrode 9 1. 3.
• the surface 913 of the workpiece 90 which is in the vicinity of the circuit surface 903, can be covered and the projecting electrodes 91 can be embedded to cover these regions.
• the upper portion of the protruding electrode 91 including the crown portion 910 penetrates the thermosetting resin film 12 and projects from the thermosetting resin film 12.
• thermosetting resin film 12 may be used alone, but as shown here, the thermosetting resin film 12 may be formed on the first support sheet 10 1 and the first support sheet 10 1. It is preferable to use the first protective film forming sheet 1 including the thermosetting resin film 12 and the thermosetting resin film 12. As will be described later, when grinding the back surface 90 of the work 90, a back grinding surface protection tape can be used as the first support sheet 10 1.
• thermosetting resin film 12 in the first protective film-forming sheet 1 is attached to the work sheet 90 by the protrusion of the work 90.
• the first protective film forming sheet 1 itself may be attached to the protruding electrode forming surface of the workpiece 90 by attaching the first protective film forming sheet 1 to the protruding electrode forming surface.
• first laminated structure body a structure in which the first protective film forming sheet is attached to the protruding electrode forming surface of the work as shown here is referred to as "first laminated structure body". It may be called.
• the first laminated structure body 201 is formed by adhering the first protective film forming sheet 1 to the projecting electrode forming surface of the work 90.
• the exposed surface of the thermosetting resin film 12 facing the workpiece 90 may be referred to as "first surface” in the present specification.
• 1 2 3 is the surface of the workpiece 90 on which the protruding electrode is formed (that is, the surface of the protruding electrode 9 1 ⁇ 2020/175 428 55 ⁇ (: 170? 2020 /007341
• thermosetting resin film 12 can be attached to the protruding electrode forming surface by pressing the surface 91 3 and the circuit surface 90 3) of the workpiece 90.
• thermosetting resin film 12 is attached to the surface on which the protruding electrodes are formed while heating.
• the thermosetting resin film 12 and the protruding electrode forming surface that is, between the thermosetting resin film 12 and the circuit surface 903 of the work 90.
• the heating temperature of the thermosetting resin film 12 at the time of attachment need not be an excessively high temperature, and is preferably, for example, 60 to 100 ° .
• “excessively high temperature” means a temperature at which the thermosetting resin film 12 exhibits an unintended action, for example, thermosetting of the thermosetting resin film 12 progresses. ..
• thermosetting resin film 12 when the thermosetting resin film 12 is attached to the protruding electrode forming surface (in the present specification, it may be referred to as "attaching pressure"). Is preferably 0.3 to 1 IV! 3.
• the first laminated structure 201 After forming the first laminated structure 201 by the attaching step, the first laminated structure 201 may be used as it is in the next step, but if necessary, the work 90 The thickness of the workpiece 90 may be adjusted by grinding the back surface 9013 of the workpiece.
• the first laminated structure 20 1 after grinding the back surface 90 of the work 90 is also in the state shown in FIG. 58, except that the thickness of the work 90 is different.
• the back surface 90 of the work 90 can be ground by a known method such as a method using a grinder.
• the thickness of the portion of the work 90 excluding the protruding electrodes 91 before and after grinding the back surface 90 of the work 90 is as described above.
• the first laminated structure is
• thermosetting resin film 12 is provided on the projecting electrode forming surface of the work 90, and the first supporting sheet 10 1 is provided.
• a second laminated structure (in other words, a work with a thermosetting resin film) 202 which is configured without the above is obtained.
• the upper portion of the protruding electrode 91 including the crown portion 910 penetrates the thermosetting resin film 12, projects, and is exposed.
• the first pressure-sensitive adhesive layer 13 is energy ray-curable, the first pressure-sensitive adhesive layer 13 is cured by irradiation with energy rays so that the pressure-sensitive adhesiveness of the first pressure-sensitive adhesive layer 13 is increased. After lowering, it is preferable to remove the first supporting sheet 10 1 from the thermosetting resin film 12.
• the thermosetting resin film 12 after being attached is thermally cured to form a first protective film 12' as shown in FIG.
• the first protective film forming step can be performed after removing the first support sheet 10 1.
• the first protective film forming step can be performed after the back surface 90 is ground.
• the third laminated structure having the first protective film 12 ′ on the protruding electrode forming surface of the work 90 (in other words, the work with the first protective film) is formed. 2 0 3 is obtained.
• Fig. 50 Indicates the contact surface of the first protective film 12 ′ with the work 90 (may be referred to as “first surface” in this specification).
• thermosetting resin film 12 The curing conditions of the thermosetting resin film 12 are not particularly limited as long as the first protective film 12' has a degree of curing sufficient to exert its function, and the thermosetting resin film 1 2 It may be appropriately selected according to the type of.
• thermosetting resin film 12 when the thermosetting resin film 12 is thermally cured, the heating temperature and the heating ⁇ 2020/175 428 57 ⁇ (: 170? 2020/007341
• the heat time is as described above.
• the curable resin film 12 may be pressurized, and the pressure applied in that case is preferably 0.3 to 11 ⁇ 13.
• thermosetting resin film was formed on the upper part including the crown 910 of the protruding electrode 91. The remaining of 1 2 is suppressed. Therefore, after the completion of this step, the first protective film 12' is also prevented from remaining on the upper portion of the protruding electrode 91.
• a laser is applied to the work 90 from the side having the first protective film 12′ through the first protective film 12′.
• the modified layer 900 is formed inside the workpiece 90.
• the modified layer forming step is performed in the third laminated structure (first work with protective film) 203. It is preferable that the dicing sheet or the second protective film forming sheet is attached to the back surface 90 of the work 90 after the work.
• the protruding electrode forming surface of the work is provided with the first protective film, and the back surface of the work is provided with the dicing sheet or the second protective film forming sheet.
• What is referred to as a “fourth laminated structure” is sometimes called.
• a structure having a modified layer formed inside the work in the fourth laminated structure may be referred to as a “fifth laminated structure”.
• the first protective film 12' is provided on the projecting electrode forming surface of the work 90, and the second protective film is formed on the back surface 9013 of the work 90.
• the figure shows a structure including a production sheet 8 and a modified layer 900 formed inside a work 90.
• the second protective film forming sheet 8 shown here is the second base material 81, the second pressure-sensitive adhesive layer 8 3 provided on the second base material 81, and the second pressure-sensitive adhesive layer 8 1. Resin provided on 3 ⁇ 2020/175 428 58 ⁇ (: 170? 2020 /007341
• the layer (resin film) 82 is provided.
• the laminated body of the second base material 81 and the second pressure-sensitive adhesive layer 83 is the second support sheet 8O1.
• the second protective film forming sheet 8 includes the second supporting sheet 8 01 and one surface 8 01 3 of the second supporting sheet 8 01, in other words, one of the second adhesive layer 8 3 and the second supporting sheet 8 01. It can be said that it is provided with a resin layer (resin film) 82 provided on the surface 8 3 3.
• the resin layer (resin film) 82 is for forming the second protective film on the back surface 9013 of the work 90.
• the second protective film covers and protects the back surface 90 of the work 90. More specifically, the second protective film is used to process the work during the division of the work or during the process of packaging the work processed product obtained by dividing the work into the target substrate device. Prevents cracks from occurring in objects.
• the resin layer 82 may have a property of only one of thermosetting property and energy beam curable property, may have both properties, or may have both properties. It does not have to have.
• the resin layer 82 is curable (that is, has at least one of thermosetting property and energy ray curable property)
• the cured product is the second protective film.
• the resin layer 8 2 is non-curable (that is, does not have both thermosetting property and energy ray-curable property)
• the resin layer 8 2 was attached to the back surface 90 of the work 90. At the stage, it is considered that the second protective film is provided.
• the second pressure-sensitive adhesive layer 8 3 may be either energy-ray curable or non-energy-ray curable, as with the first pressure-sensitive adhesive layer 13.
• the energy ray-curable second pressure-sensitive adhesive layer 83 can easily adjust the physical properties before and after curing.
• the second base material 81 is, for example, the first base material in the first protective film forming sheet described above (for example, the first base material 11 in the first protective film forming sheet 1). May be the same as. ⁇ 2020/175 428 59 ⁇ (: 170? 2020/007341
• a sheet other than the second protective film forming sheet 8 may be used as the second protective film forming sheet.
• the second protective film forming sheet 8 not only the second protective film forming sheet 8 but also known sheets can be used as the second protective film forming sheet.
• a known dicing sheet can be used.
• a focus is set on a specific region inside the work 90, which is a division point of the work 90, and laser _ light ⁇ is irradiated so as to focus the focus. To do.
• the modified layer 900 is formed in the irradiation region.
• thermosetting resin film 12 and the first protective film 12' have transparency to light having a wavelength of 1 3 4 2 n , and preferably the thermosetting resin film 12 and the first protective film.
• the transmittance of the light of wavelength 1 3 4 2 n of 1 2' is high as described above, the laser light of wavelength 1 3 4 2 n transmits well through the first protective film 1 2'. To do. Therefore, even if the laser beam is applied to the workpiece 90 from the side having the first protective film 12′ through the first protective film 12′, the inside of the workpiece 90 is modified.
• the layer 900 can be well formed.
• the work 90 after forming the modified layer 900 is formed with the first protective film 12 ′, in other words, the fifth laminated structure 20 5 with respect to the circuit surface 90 3 .
• the work 90 is divided at the modified layer 900 to obtain a work product 9.
• the processed product 990 is immediately obtained (in this case, this process is sometimes referred to as the "dividing/cutting process").
• the manufacturing method is such that, in the dividing step (in other words, a step of obtaining a workpiece processed product), the work is divided at the portion of the modified layer and the first protective film is cut. Good.
• reference numeral 120 indicates a contact surface of the first protective film 120′ after cutting with the workpiece 9 (may be referred to as “first surface” in this specification)
• the reference numeral 9 indicates the back surface of the work piece 9 to be processed.
• the first protective film 12' is cut along the dividing position of the work 90, and finally cut along the outer periphery of the workpiece 9 .
• the first protective film 12' is cut at the same time when the work 90 is divided depends on the composition of the first protective film 12', in other words, the thermosetting resin film 12'. Or, it is determined by the expanding conditions.
• the first protective film 12' is formed of the thermosetting resin film 12 satisfying the condition of the total value of X values
• the first protective film 1' is formed in the dividing step. 2'can be easily cut (splitting/cutting process).
• the work piece 9 provided with the first protective film 120' after cutting the protruding electrode forming surface with high efficiency.
• the cutting step is, for example, a step of picking up the workpiece 9 (more specifically, the workpiece that has the uncut first protective film) by separating it from the second support sheet 8 01 and picking it up at the same time. It can be carried out.
• the workpiece 9 is not necessarily cut into the first work piece 9 in the cutting step as shown in FIG. 2
• the protective film forming sheet 8 is not always provided as it is.
• the expanding is preferably performed under a temperature condition of 15 to 5 ° C.
• the temperature at the time of expanding is not more than the upper limit value, the first protective film 12′ can be cut more easily.
• the temperature during expansion is at least the above lower limit value, excessive cooling can be avoided.
• the resin layer 8 2 in the second protective film forming sheet 8 is also cut by performing the dividing step (or dividing/cutting step) is shown.
• the cutting may be performed separately by a known method after the dividing step (or dividing/cutting step).
• the resin layer 82 after cutting is denoted by reference numeral 820.
• the resin layer 82 is not cut at the stage of the resin layer 82, and the second protective film obtained by curing the resin layer 82 is cut. Good.
• the resin layer 82 or the second protective film is cut along the divided portions of the work 90, as in the case of the first protective film 12'.
• the laminated structure of the second supporting sheet and the resin layer (in other words, the second supporting sheet and the resin layer after cutting) is maintained even after the resin layer is cut.
• This laminated structure is referred to as a "second protective film forming sheet" as long as it is provided.
• a first processed protective film including a workpiece and a first protective film formed on a surface of the workpiece having a projecting electrode are provided.
• thermosetting resin film A step of attaching a thermosetting resin film to the surface of the work piece having the protruding electrodes, ⁇ 2020/175 428 62 ⁇ (: 170? 2020 /007341
• thermosetting resin film After attachment to form a first protective film
• thermosetting resin film In the step of adhering the thermosetting resin film, the thermosetting resin film is heated at 60 to 100 ° ⁇ , and a pressure of 0.3 to 1 IV! 3 is applied to the thermosetting resin film.
• thermosetting resin film is attached to the surface of the work having the protruding electrodes.
• a first protective film including a workpiece and a first protective film formed on a surface of the workpiece having a protruding electrode are provided.
• thermosetting resin film A step of attaching a thermosetting resin film to the surface of the work having the protruding electrodes, and a step of thermosetting the thermosetting resin film after attachment to form a first protective film
• thermosetting resin film comprises a polymer component (), an epoxy resin other than an acrylic resin having an epoxy group, an epoxy resin (Min 1), and a thermosetting agent (Min 2) ⁇ 2020/175 428 63 ⁇ (: 170? 2020 /007341
• the ratio of the total content of the epoxy resin (Min 1) and the thermosetting agent (Min 2) to the total mass of the thermosetting resin film is 40% by mass or more.
• thermosetting resin film the ratio of the content of the polymer component () with respect to the total mass of the thermosetting resin film is 5 to 30 mass%, in the thermosetting resin film, A method for producing a work piece with a first protective film, wherein the ratio of the content of the filler (mouth) with respect to the total mass of the curable resin film is 5 to 20 mass %.
• Another example of the preferred manufacturing method of the present embodiment is a first protective film including a workpiece and a first protective film formed on a surface of the workpiece that has a protruding electrode.
• thermosetting resin film A step of attaching a thermosetting resin film to the surface of the work having the protruding electrodes, and a step of thermosetting the thermosetting resin film after attachment to form a first protective film
• the thermosetting resin film contains a polymer component (), an epoxy resin other than an acrylic resin having an epoxy group, an epoxy resin (Min 1), a thermosetting agent (Min 2), and a filler (mouth). ,
• thermosetting resin film relative to the total mass of the thermosetting resin film, the total content of the epoxy resin (Min 1) and the thermosetting agent (Min 2) ⁇ 0 2020/175 428 64 ⁇ (: 17 2020 /007341
• thermosetting resin film the ratio of the content of the polymer component () with respect to the total mass of the thermosetting resin film is 5 to 30 mass% in the thermosetting resin film, The ratio of the content of the filler (mouth) to the total mass of the thermosetting resin film is 5 to 20% by mass, and the thickness is 200.
• One layer of the thermosetting resin film. Or a laminated film composed of two or more layers of the thermosetting resin film having a thickness of less than 200, and having a total thickness of 200,01,
• Another example of the preferred manufacturing method of the present embodiment is a first protective film including a workpiece and a first protective film formed on a surface of the workpiece that has a protruding electrode.
• thermosetting resin film A step of attaching a thermosetting resin film to the surface of the work having the protruding electrodes, and a step of thermosetting the thermosetting resin film after attachment to form a first protective film
• thermosetting resin film In the step of adhering the thermosetting resin film, the thermosetting resin film is heated at 60 to 100 ° ⁇ , and a pressure of 0.3 to 1 IV! 3 is applied to the thermosetting resin film. While adding, affix the thermosetting resin film to the surface of the work having the protruding electrodes, ⁇ 2020/175 428 65 ⁇ (: 170? 2020 /007341
• the thermosetting resin film contains a polymer component (), an epoxy resin other than an acrylic resin having an epoxy group, an epoxy resin (Min 1), a thermosetting agent (Min 2), and a filler (mouth). ,
• the ratio of the total content of the epoxy resin (Min 1) and the thermosetting agent (Min 2) to the total mass of the thermosetting resin film is 40% by mass or more.
• thermosetting resin film the ratio of the content of the polymer component () with respect to the total mass of the thermosetting resin film is 5 to 30% by mass.
• thermosetting resin film In the thermosetting resin film, the ratio of the content of the filler (mouth) with respect to the total mass of the thermosetting resin film is 5 to 20 mass% and the thickness is 200. 1 A layer of the thermosetting resin film, or a laminate of two or more layers of the thermosetting resin film having a thickness of less than 200, a total thickness of 200 0 1. Film, wavelength
• the work piece with the first protective film (in other words, the sixth laminated layer structure) is obtained by the above-described manufacturing method
• the work piece with the first protective film is subjected to the circuit surface of the substrate by a known method.
• the target substrate device can be manufactured by using this package after flip-chip connecting to the package (not shown).
• the semiconductor chip with the first protective film after manufacturing the semiconductor package, the intended semiconductor device can be manufactured by using this semiconductor package. Further, when the semiconductor chip having the first protective film and the second protective film is used, the semiconductor chip with the protective film can be flip-chip connected to manufacture a target semiconductor device.
• the present invention is not limited to the examples shown below.
• each target product manufactured in the comparative examples shown below has the same name as each target product manufactured in the examples.
• thermosetting resin layer-forming composition The components used in the production of the thermosetting resin layer-forming composition are shown below.
• (Min 1) -2 Dicyclopentadiene type epoxy resin ("Men 1 ⁇ !_ ⁇ 1 ⁇ 1 7200" manufactured by 0 ⁇ company, Epoxy equivalent 2659/6)
• (Min 1) -4 Mixture of liquid bisphenol octadecyl epoxy resin and fine particles of acrylic rubber (“Min 328” manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent)
• (o)-1 Silane coupling agent (Mitsubishi Chemical Corporation Silicate IV! 3M 2", silicate compound with arglycidoxypropyltrimethoxysilane added)
• Polymer component () 1 (9.9 mass parts), Epoxy resin (Mitsumi 1)-1 (37.8 mass parts), Epoxy resin (Mami 1) -2 (25.0 mass parts), thermosetting Agent ⁇ 2020/175 428 68 ⁇ (: 170? 2020 /007341
• thermosetting resin layer-forming composition (III — 1) in which the total concentration of the 6 components other than the above-mentioned methyl ethyl ketone was 55 mass% by diluting with methyl ethyl ketone and stirring at 23 °
• Table 1 the description of "1" in the column of the contained components in Table 1 means that the components for the thermosetting resin layer forming composition are the same.
• the “content ratio (% by mass) of the thermosetting component” in Table 1 means “the total mass of the thermosetting resin film in the thermosetting resin film”. To the ratio of the content of thermosetting component"
• thermosetting resin film ⁇ Production of thermosetting resin film>
• a release film in which one side of a polyethylene terephthalate film is peeled off by silicone treatment (“3 Ichiba 3 8 1 0 3 1" manufactured by Lintec Co., Ltd.)
• thermosetting resin layer-forming composition ( ⁇ ⁇ I-1) obtained above was applied to the release-treated surface, and the temperature was maintained at 100 ° 2 minutes for 2 minutes. By drying, a thermosetting resin film having a thickness of 30 was produced.
• thermosetting resin film in other words, the surface opposite to the side provided with the release film
• a surface protection tape for backgrinding (“Hachiman, Minami” manufactured by Lintec Co., Ltd. by bonding one face one 8 1 8 0 1 ⁇ 1 [ 3 ⁇ 4 ") to produce a first protective layer forming sheet.
• the surface protection tape corresponds to the first support sheet.
• thermosetting resin film in the first protective film forming sheet obtained above the release film is removed, and the exposed surface of the thermosetting resin film generated in this way (in other words, the surface protective tape is provided.
• the first protective film forming sheet was attached to the bump forming surface of the semiconductor wafer by pressure-bonding the surface opposite to the bump forming surface) to the bump forming surface of the semiconductor wafer. At this time, for forming the first protective film ⁇ 2020/175 428 69 ⁇ (: 170? 2020 /007341
• the sheet was pasted using a pasting device (mouth-roller type laminator, "[3 ⁇ 48 0-3 5 1 0/1 2" manufactured by Lintec Co., Ltd.), table temperature 90 ° ⁇ , pasting speed 2
• the application was performed while heating the thermosetting resin film under the conditions of application pressure of 0.51 ⁇ /1 3.
• the height of bumps is 210
• the width of bumps is 250
• the distance between adjacent bumps is 400!
• the thickness of the parts excluding bumps is A value of 750 was used.
• the surface protection tape (in other words, the first support sheet) was removed from the thermosetting resin film in the first laminated structure.
• the second laminated structure semiconductor wafer with thermosetting resin film having the thermosetting resin film on the bump formation surface of the semiconductor wafer was obtained.
• thermosetting resin film in the second laminated structure obtained above was used.
• the thermosetting resin film in the second laminated structure obtained above was used.
• the third laminated structure (in other words, the semiconductor wafer with the first protective film) having the first protective film on the bump formation surface of the semiconductor wafer was obtained.
• a dicing tape (“8 ⁇ ⁇ ⁇ -841" manufactured by Lintec Co., Ltd.) was applied to the back surface (in other words, ground surface) of the semiconductor wafer.
• a fourth laminated structure having a first protective film on the bump formation surface of the semiconductor wafer and a dicing tape on the back surface was obtained.
• the dicing tape corresponds to the second support sheet. ⁇ 2020/175 428 70 ⁇ (: 170? 2020/007341
• a dicing device (“0 !_ 7 3 6 1" manufactured by Disco Co., Ltd.) was used to focus the semiconductor wafer in the fourth laminated structure at a focus set inside the semiconductor wafer. Then, the modified layer was formed inside the semiconductor wafer by irradiating laser light from the side having the first protective film through the first protective film. At this time, the wavelength of the laser light is 1 3 4 2 n , The output is ⁇ , and the frequency is did.
• the fifth laminated structure having a structure in which the modified layer was formed inside the semiconductor wafer in the fourth laminated structure was obtained.
• the semiconductor wafer (in other words, the fifth laminated structure) on which the modified layer was formed was placed in a direction parallel to the circuit surface of the first protective film.
• the semiconductor wafer was divided at the modified layer and the first protective film was cut along the division of the semiconductor wafer.
• a die separator (“0 0 3 2 3 0 0” manufactured by Disco Co., Ltd.) was used to place the second support sheet in the fifth laminated structure on the table in the die separator, and the fifth laminated structure.
• the peripheral edge of the body is fixed, and in this state, the semiconductor wafer and the first protective film are expanded by pushing up the table under the conditions of a push-up speed of 5001 01/3600 and a push-up amount of 2000011. did.
• the size of the obtained semiconductor chip is
• thermosetting resin film on the upper part of the bump ⁇ Confirmation of residual curability of the thermosetting resin film on the upper part of the bump>
• thermosetting resin film The boundary between the bump and the thermosetting resin film can be confirmed, and it can be confirmed that the thermosetting resin film does not remain above the bump.
• Mami The boundary between the bump and the thermosetting resin film cannot be confirmed, and it can be confirmed that the thermosetting resin film remains on the upper part of the bump.
• thermosetting resin layer-forming composition (I I I-1) Except that the coating amount of the thermosetting resin layer-forming composition (I I I-1) was changed, the thermosetting resin for test was prepared in the same manner as in the production of the thermosetting resin film described above. Five films (thickness 40) were produced.
• thermosetting resin films for a test were laminated in the thickness direction to obtain a laminated film (thickness 200).
• the spectrophotometer 3 1 ⁇ 1 IMADZ ⁇ J company "11 ⁇ 1 3-1 ⁇ 1 1 [3 ⁇ 4 3
• the first region exists approximately in the center of the first line segment that connects the second and third regions, and the first region approximately exists in the center of the second line segment that connects the fourth and fifth regions.
• the second ⁇ 2020/175428 72 ⁇ (: 170? 2020/007341
• the semiconductor wafer is normally divided in all 5 areas (all areas 1 to 5).
• At least one region (at least one of the first to fifth regions) has a portion where the semiconductor wafer is not normally divided.
• the first protective film is normally cut in all five areas (all areas from the first area to the fifth area).
• At least one region (at least one of the first to fifth regions) has a part where the first protective film is not normally cut.
• thermosetting resin layer-forming composition (I I I-1) Except that the coating amount of the thermosetting resin layer-forming composition (I I I-1) was changed, the thermosetting resin for test was prepared in the same manner as in the production of the thermosetting resin film described above. A film (thickness 40) was produced.
• thermosetting resin film for this test was heated at 130 ° C. for 2 hours to be thermoset.
• thermosetting resin film and sheet for forming first protective film [0271] ⁇ Production of thermosetting resin film and sheet for forming first protective film>
• thermosetting resin film and a first protective film-forming sheet were produced in the same manner as in Example 1 except that the resin layer-forming composition obtained above was used.
• thermosetting resin film and first protective film Evaluation of thermosetting resin film and first protective film
• thermosetting resin film and the first protective film produced in this example were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Polymer component () I 3 (21.0 parts by mass), Epoxy resin (Min 1) -4 (10.0 parts by mass), Epoxy resin (Min 1) -5 (2.0 parts by mass), Epoxy ⁇ 2020/175 428 74 ⁇ (: 170? 2020/007341
• Resin (1)-6 (5.6 parts by mass), thermosetting agent (2)-2 (20.5 parts by mass), curing accelerator ( ⁇ 3)-1 (0.5 parts by mass), filling Material (mouth) I 2 (6.0 mass parts), Filler (mouth) _ 3 (5 4.0 parts by mass), Coupling agent (Mitsumi) _ 1 ( ⁇ 0.4 parts by mass) and colorant ( I) _ 1 (1.9 parts by mass) is mixed, further diluted with methyl ethyl ketone and stirred at 23 °C to obtain a total concentration of 10 components other than the above methyl ethyl ketone of 55% by mass.
• a resin layer forming composition was prepared. Table 1 shows these components and their contents.
• thermosetting resin film and sheet for forming first protective film ⁇ Production of thermosetting resin film and sheet for forming first protective film>
• thermosetting resin film and a first protective film-forming sheet were produced in the same manner as in Example 1 except that the resin layer-forming composition obtained above was used.
• thermosetting resin film and first protective film
• thermosetting resin film and the first protective film produced in this comparative example were evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Example 1 a semiconductor chip, that is, a semiconductor chip with a first protective film could be favorably manufactured from a semiconductor wafer having a first protective film on the bump formation surface.
• thermosetting resin film has preferable characteristics because it can suppress the residual on the upper part of the bump when it is attached to the bump forming surface of the semiconductor wafer. ⁇ 02020/175428 76 ⁇ (: 17 2020/007341
• Example 1 in the thermosetting resin film, the ratio of the content of the thermosetting component to the total mass of the thermosetting resin film was 80.9% by mass.
• Example 1 the dividability of the semiconductor wafer was good.
• thermosetting resin film the wavelength 1 342 n high transparently of light is m
• the transmittance of light of the first protective film formed from the film is similarly high
• Example 1 the cutting property of the first protective film at the time of dividing the semiconductor wafer is also good, and the first protective film can also be cut at the time of dividing the semiconductor wafer by the expansion, and the dividing step (that is, In the division/cutting process), the semiconductor chip with the first protective film was immediately obtained.
• the semiconductor chip could be favorably manufactured from the semiconductor wafer having the first protective film on the bump formation surface.
• thermosetting resin film had favorable characteristics because it was possible to suppress the residual on the upper part of the bump when it was attached to the bump forming surface of the semiconductor wafer.
• Example 2 the ratio of the content of the thermosetting component in the thermosetting resin film to the total mass of the thermosetting resin film was 78.8% by mass.
• Example 2 Also in Example 2, the dividability of the semiconductor wafer was good.
• thermosetting resin film transparently of light having a wavelength of 1 342 n m high, so that the transmission of light of a first protective film formed from the film ⁇ 2020/175 428 77 ⁇ (: 170? 2020/007341
• the rate was also high, and when the semiconductor wafer was irradiated with laser light through the first protective film, the modified layer could be formed well inside the semiconductor wafer.
• Example 2 the cutability of the first protective film at the time of dividing the semiconductor wafer was poor. However, this first protective film can be cut in the subsequent steps, and the semiconductor with the first protective film is cut. It was possible to manufacture a chip (a semiconductor chip having a cut first protective film).
• thermosetting resin film when the thermosetting resin film was attached to the bump forming surface of the semiconductor wafer, it was not possible to suppress the residual thermosetting resin film on the bumps.
• thermosetting resin film had a low transmittance of light having a wavelength of 1 342 n, and as a result, the first protective film formed from this film also had a low transmittance of light.
• the semiconductor wafer was irradiated with the laser beam through the protective film, the modified layer could not be properly formed inside the semiconductor wafer. As a result, the semiconductor wafer could not be divided normally.
• the first protective film could not be cut at the time of dividing the semiconductor wafer, but it was not possible to determine to what extent the characteristics of the first protective film itself had an effect on this result, and the semiconductor wafer The cutability of the first protective film at the time of division could not be evaluated. However, since the breaking strength of the first protective film was as small as 251 ⁇ / 1 3, cause could not be cut first protective layer is mainly in the division of the semiconductor wafer was inferior, and guess Was done. ⁇ 2020/175 428 78 ⁇ (: 170? 2020/007341 Industrial availability
• the present invention can be used for manufacturing a work piece or the like which is used in a flip-chip mounting method and has a protruding electrode on the connection pad portion.
• Thermosetting resin layer thermosetting resin film
• 1 2′ 1st protective film 1 20′ 1st protective film after cutting
• 1 3rd 1 Adhesive layer 1 33 ⁇ 01 1 3, 10 23 033 ⁇ 1st support sheet surface, 201 ⁇ 1st laminated structure, 202 ⁇ 2nd laminated structure, 203 ⁇ 3rd laminated structure, 205--5th laminated structure, 206 ⁇ 6th Laminated structure, 90 ⁇ work, circuit surface of 90 3 work, 9 1 ⁇ ⁇ ⁇ protruding electrode, 9 1 3---surface of protruding electrode, 900 modified layer, 990 Workpiece with first protective film Stuff, Laser light

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