WO2017061364A1 - Film de résine thermodurcissable et feuille destinée à former un premier film de protection - Google Patents

Film de résine thermodurcissable et feuille destinée à former un premier film de protection Download PDF

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Publication number
WO2017061364A1
WO2017061364A1 PCT/JP2016/079255 JP2016079255W WO2017061364A1 WO 2017061364 A1 WO2017061364 A1 WO 2017061364A1 JP 2016079255 W JP2016079255 W JP 2016079255W WO 2017061364 A1 WO2017061364 A1 WO 2017061364A1
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Prior art keywords
meth
acrylate
sensitive adhesive
pressure
group
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PCT/JP2016/079255
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English (en)
Japanese (ja)
Inventor
啓示 布施
正憲 山岸
明徳 佐藤
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リンテック株式会社
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Priority to JP2017544481A priority Critical patent/JP6821580B2/ja
Publication of WO2017061364A1 publication Critical patent/WO2017061364A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a thermosetting resin film and a first protective film forming sheet using the same.
  • a projecting electrode made of eutectic solder, high-temperature solder, gold or the like is formed as a semiconductor chip on its connection pad portion.
  • the flip chip mounting method has been employed in which the bumps are brought into contact with the corresponding terminal portions on the chip mounting substrate in a so-called face-down manner, and are melted / diffusion bonded. .
  • the semiconductor chip used in this mounting method can be obtained, for example, by grinding or dicing the surface opposite to the circuit surface of a semiconductor wafer having bumps formed on the circuit surface.
  • a curable resin film is applied to the bump forming surface, and the film is cured to form a protective film on the bump forming surface.
  • thermosetting resin film those containing a thermosetting component that is cured by heating are widely used, and as the protective film-forming sheet provided with such a thermosetting resin film, the film In which a thermoplastic resin layer having a specific thermoelastic modulus is laminated, and a thermoplastic resin layer non-plasticized at 25 ° C. is laminated on the uppermost layer of the thermoplastic resin layer ( Patent Document 1).
  • this protective film forming sheet is said to be excellent in bump filling property of the protective film, wafer processability, electrical connection reliability after resin sealing, and the like.
  • thermosetting resin film for forming the protective film has a part of the thermosetting component contained in the protective film forming sheet depending on the composition.
  • the problem that it is easy to move to the adjacent layer was found.
  • the thermosetting component moves from the thermosetting resin film to a layer adjacent to the thermosetting resin film, the composition of the thermosetting resin film changes, and a curing reaction occurs when a protective film is formed.
  • the thermosetting component migrates in this way, the thermosetting resin film has reduced fluidity during heating, and the bump does not sufficiently adhere to the entire target portion of the bump. As a result, the embedding of the bump becomes insufficient and the bump embedding property is lowered.
  • An object of the present invention is to provide a thermosetting resin film in which migration of a thermosetting component to an adjacent layer is sufficiently suppressed, and a protective film forming sheet using the same.
  • the present invention is a thermosetting resin film for forming a first protective film on the surface by sticking on a surface of a semiconductor wafer having bumps and thermosetting, the thermosetting resin film, A thermosetting containing a polymer component (A) and a thermosetting component (B0), wherein the thermosetting component (B0) has a weight average molecular weight of 450 or more and a dispersity of 10 or less.
  • a functional resin film is provided.
  • the thermosetting component (B0) may be composed of an epoxy resin (B01) and a thermosetting agent (B02).
  • this invention provides the sheet
  • thermosetting component in the thermosetting resin film migrates to the layer adjacent to the thermosetting resin film.
  • the thermosetting resin film of the present invention is a thermosetting resin film for forming a first protective film on the surface by sticking to a surface of a semiconductor wafer having bumps and thermosetting the film.
  • the curable resin film contains a polymer component (A) and a thermosetting component (B0), and the thermosetting component (B0) has a weight average molecular weight (Mw) of 450 or more and a dispersity ( Mw / Mn) is 10 or less.
  • Mw weight average molecular weight
  • Mw / Mn dispersity
  • Mn means a number average molecular weight.
  • seat for protective film formation of this invention equips the one surface of a 1st support sheet with the thermosetting resin film of said this invention.
  • the “thermosetting resin film” may be referred to as a “thermosetting resin layer”.
  • the first protective film-forming sheet of the present invention is used by being attached to a surface (that is, a circuit surface) having bumps of a semiconductor wafer via its thermosetting resin layer (thermosetting resin film). Then, the thermosetting resin layer after application increases in fluidity by heating, spreads between the bumps so as to cover the bumps, adheres to the circuit surface, and also on the surface of the bump, particularly in the vicinity of the circuit surface. Cover the surface and embed bumps. The thermosetting resin layer in this state is further thermoset by heating to finally form a first protective film, and protects the bumps in close contact with the surface on the circuit surface.
  • the first support sheet is removed, and then the thermosetting resin layer is heated.
  • the embedding of the bumps and the formation of the first protective film are performed, and finally, the semiconductor device is incorporated with the first protective film.
  • thermosetting resin film (thermosetting resin layer) of the present invention has, as a thermosetting component, a thermosetting component (B0) having a large weight average molecular weight and a dispersity of a specific range or less as described above.
  • the thermosetting resin film is used for the first protective film forming sheet immediately after its production and before the thermosetting resin film is cured during use.
  • the migration of the thermosetting component (B0) to the adjacent layer, that is, the first support sheet is sufficiently suppressed.
  • the change in the composition is suppressed, the curing reaction when forming the first protective film sufficiently proceeds, and the first protective film having a high degree of curing can be formed.
  • thermosetting resin film is excellent in bump embedding because a decrease in fluidity at the time of heating is suppressed and the bump is embedded in close contact with the entire target portion of the bump.
  • the thermosetting resin film of the present invention not only forms the first protective film having a high degree of curing as described above, but also has excellent bump embedding properties and has a very high bump protecting effect.
  • the configuration of the present invention will be described in detail.
  • the first support sheet may be composed of one layer (single layer) or may be composed 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” means “all layers may be the same or all layers. 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 thickness of each layer is different from each other ” "Means.
  • first support sheet for example, a sheet in which a first pressure-sensitive adhesive layer is laminated on a first substrate, a first intermediate layer is laminated on a first substrate, and a first intermediate layer is formed on the first intermediate layer.
  • first support sheet for example, a sheet in which a first pressure-sensitive adhesive layer is laminated on a first substrate, a first intermediate layer is laminated on a first substrate, and a first intermediate layer is formed on the first intermediate layer.
  • examples include one in which one pressure-sensitive adhesive layer is laminated, one made only of a first base material, and the like.
  • first protective film forming sheet of the present invention will be described below for each type of the first support sheet with reference to the drawings.
  • drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.
  • FIG. 1 is a cross-sectional view schematically showing one embodiment of the first protective film-forming sheet of the present invention.
  • seat 1 for protective film formation shown here uses as a 1st support sheet what laminated
  • the first support sheet 101 is a laminate of the first base material 11 and the first pressure-sensitive adhesive layer 13, and is on one surface 101 a of the first support sheet 101, that is, on one surface 13 a of the first pressure-sensitive adhesive layer 13.
  • thermosetting resin layer 12 is provided.
  • the transfer of the thermosetting component (B0) from the thermosetting resin layer 12 to the adjacent layer, ie, the 1st adhesive layer 13, is fully suppressed.
  • FIG. 2 is a cross-sectional view schematically showing another embodiment of the first protective film-forming sheet of the present invention.
  • the first protective film forming sheet 2 shown here is a first support sheet in which a first intermediate layer is laminated on a first base material, and a first adhesive layer is laminated on the first intermediate layer.
  • the first protective film forming sheet 2 includes the first intermediate layer 14 on the first base material 11, the first adhesive layer 13 on the first intermediate layer 14, and the first adhesive layer 13 Are provided with a thermosetting resin layer (thermosetting resin film) 12.
  • the first support sheet 102 is a laminate in which the first base material 11, the first intermediate layer 14, and the first pressure-sensitive adhesive layer 13 are laminated in this order, and on the one surface 102a of the first support sheet 102, that is, A thermosetting resin layer 12 is provided on one surface 13 a of the first pressure-sensitive adhesive layer 13.
  • the first protective film forming sheet 2 further includes a first intermediate layer 14 between the first base material 11 and the first pressure-sensitive adhesive layer 13. It is equipped with.
  • the transfer of the thermosetting component (B0) from the thermosetting resin layer 12 to the adjacent layer, ie, the 1st adhesive layer 13, is fully suppressed.
  • FIG. 3 is a cross-sectional view schematically showing still another embodiment of the first protective film-forming sheet of the present invention.
  • a first support sheet made of only the first base material is used. That is, the first protective film forming sheet 3 includes a thermosetting resin layer (thermosetting resin film) 12 on the first base material 11 and is configured.
  • the first support sheet 103 includes only the first base material 11, and the thermosetting resin layer 12 is formed on one surface 103 a of the first support sheet 103, that is, on one surface 11 a of the first base material 11. Provided in direct contact.
  • the first protective film forming sheet 3 is obtained by removing the first pressure-sensitive adhesive layer 13 from the first protective film forming sheet 1 shown in FIG.
  • thermosetting component (B0) from the thermosetting resin layer 12 to the adjacent layer, ie, the 1st base material 11, is fully suppressed.
  • the said 1st base material is a sheet form or a film form
  • various resin is mentioned, for example.
  • the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin.
  • Polyolefins such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as a monomer)
  • a copolymer obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as polyesters, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalene dicarboxylates, wholly aromatic polyesters in which all the structural units have an aromatic cyclic group; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin
  • the polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
  • the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.
  • (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”.
  • (meth) acrylate is a concept including both “acrylate” and “methacrylate”
  • (meth) acryloyl group Is a concept including both an “acryloyl group” and a “methacryloyl group”.
  • the resin constituting the first base material may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the first substrate may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other, and a combination of these layers Is not particularly limited.
  • the thickness of the first base material is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, further preferably 15 to 300 ⁇ m, and particularly preferably 20 to 150 ⁇ m.
  • the “thickness of the first base material” means the thickness of the entire first base material.
  • the thickness of the first base material composed of a plurality of layers means all of the first base material. Means the total thickness of the layers.
  • the first substrate is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part.
  • materials that can be used to construct the first base material having such a high thickness precision include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. Examples include coalescence.
  • the first base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the resin. You may do it.
  • the first substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
  • the 1st adhesive layer or curable resin layer mentioned later has energy-beam sclerosis
  • the first substrate can be manufactured by a known method.
  • the 1st base material containing resin can be manufactured by shape
  • the said 1st adhesive layer is a sheet form or a film form, and contains an adhesive.
  • the pressure-sensitive adhesive include an acrylic resin (a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group), a urethane resin (a pressure-sensitive adhesive made of a resin having a urethane bond), and a rubber resin (a resin having a rubber structure). ), Silicone resins (adhesives composed of resins having a siloxane bond), epoxy resins (adhesives composed of resins having an epoxy group), polyvinyl ether, polycarbonate, and other adhesive resins. Based resins are preferred.
  • the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin.
  • the resin itself has an adhesive property
  • resins that exhibit tackiness 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.
  • the first pressure-sensitive adhesive layer may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other. The combination is not particularly limited.
  • the thickness of the first pressure-sensitive adhesive layer is preferably 1 to 1000 ⁇ m, more preferably 5 to 500 ⁇ m, and particularly preferably 10 to 100 ⁇ m.
  • the “thickness of the first pressure-sensitive adhesive layer” means the thickness of the entire first pressure-sensitive adhesive layer.
  • the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers means the first pressure-sensitive adhesive layer. Means the total thickness of all the layers that make up.
  • the first pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive.
  • the first pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
  • “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
  • Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp or the like as an ultraviolet ray source.
  • the electron beam can be emitted by an electron beam accelerator or the like.
  • energy ray curable means the property of being cured by irradiation with energy rays
  • non-energy ray curable means the property of not being cured even when irradiated with energy rays.
  • a 1st adhesive layer can be formed using the 1st adhesive composition containing an adhesive.
  • a 1st adhesive layer can be formed in the target site
  • a more specific method for forming the first pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers.
  • the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the first pressure-sensitive adhesive layer.
  • “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
  • the first pressure-sensitive adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
  • the drying conditions of the first pressure-sensitive adhesive composition are not particularly limited, but when the first pressure-sensitive adhesive composition contains a solvent described later, it is preferable to dry by heating.
  • the first pressure-sensitive adhesive composition containing the solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • the first pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive is, for example, non-energy First pressure-sensitive adhesive composition containing a linear curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound (I-1): energy ray curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray curable adhesive resin (I-1a) (hereinafter referred to as “adhesiveness”)
  • a first pressure-sensitive adhesive composition (I-2) which may be abbreviated as “resin (I-2a)”; the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low molecular weight compound; Examples thereof include the first pressure-sensitive adhesive composition (I-3).
  • the first pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound.
  • the adhesive resin (I-1a) is preferably an acrylic resin.
  • the acrylic resin the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
  • the acrylic resin may have only one type of structural unit, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred. More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-
  • the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms.
  • the alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
  • the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.
  • the acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
  • the functional group-containing monomer for example, the functional group reacts with a crosslinking agent to be described later to become a starting point of crosslinking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound, The thing which enables introduction
  • Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.
  • Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.
  • monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid maleic acid, citracone
  • Ethylenically unsaturated dicarboxylic acids such as acids (dica
  • the functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
  • the functional group-containing monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, and more preferably 3 to 32% by mass with respect to the total amount of the structural unit. It is particularly preferably 5 to 30% by mass.
  • the acrylic polymer may further have a structural unit derived from another monomer.
  • the other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester or the like.
  • Examples of the other monomer include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.
  • the other monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
  • the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).
  • energy beam polymerizability means a property of polymerizing by irradiation with energy rays.
  • the pressure-sensitive adhesive resin (I-1a) contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are as follows: Can be arbitrarily selected.
  • the content of the pressure-sensitive adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, It is particularly preferable that the content be ⁇ 90 mass%.
  • Examples of the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
  • examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4.
  • Polybutyl (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
  • examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
  • the energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that the molecular weight is relatively large and the storage elastic modulus of the first pressure-sensitive adhesive layer is difficult to be lowered.
  • the energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the energy ray-curable compound is preferably 1 to 95% by mass, more preferably 5 to 90% by mass. It is especially preferable that it is 85 mass%.
  • the first pressure-sensitive adhesive composition preferably further contains a crosslinking agent.
  • the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
  • a crosslinking agent for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( Cross-linking agent having a glycidyl group); Aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; Metal chelate-based cross-linking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent (
  • the cross-linking agent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the crosslinking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-1a).
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass.
  • the first pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator.
  • the first pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; 2-hydroxy-2 Acetophenone compounds such as methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal
  • 2-hydroxy-2 Acetophenone compounds such as methyl-1-phenyl-
  • Acyl phosphine oxide compounds such as benzyl phenyl sulfide and tetramethyl thiuram monosulfide; ⁇ -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; Azo compounds such as blanking Tirol carbonitrile; titanocene compounds such as titanocene; thioxanthone compounds of thioxanthone; peroxide compound; diketone compounds such as diacetyl, dibenzyl and the like.
  • a quinone compound such as 1-chloroanthraquinone
  • a photosensitizer such as amine
  • the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound.
  • the amount is more preferably 0.03 to 10 parts by weight, and particularly preferably 0.05 to 5 parts by weight.
  • the first pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers.
  • known additives such as reaction retarders and crosslinking accelerators (catalysts).
  • the reaction retarding agent means, for example, the purpose of the first pressure-sensitive adhesive composition (I-1) during storage due to the action of the catalyst mixed in the first pressure-sensitive adhesive composition (I-1).
  • reaction retarder examples include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C ( ⁇ O) —) in one molecule. Can be mentioned.
  • the other additive contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of other additives is not particularly limited, and may be appropriately selected depending on the type.
  • the first pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the first pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
  • the solvent is preferably an organic solvent.
  • organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane and n-hexane and the like.
  • ketones such as methyl ethyl ketone and
  • the solvent for example, the one used in the production of the adhesive resin (I-1a) is used as it is in the first adhesive composition (I-1) without being removed from the adhesive resin (I-1a).
  • the same or different type of solvent used in the production of the adhesive resin (I-1a) may be added separately during the production of the first pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the first pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • the first pressure-sensitive adhesive composition (I-2) is an energy ray-curable pressure-sensitive adhesive in which an unsaturated group is introduced into the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). Containing a functional resin (I-2a).
  • the adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
  • the unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.
  • a compound having a group examples include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
  • Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. Etc.
  • Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate, and the like.
  • the pressure-sensitive adhesive resin (I-2a) contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are as follows: Can be arbitrarily selected.
  • the content of the pressure-sensitive adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass. It is particularly preferable that the content be ⁇ 90 mass%.
  • the first adhesive composition may further contain a crosslinking agent.
  • Examples of the crosslinking agent in the first pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the first pressure-sensitive adhesive composition (I-1).
  • the cross-linking agent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the crosslinking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-2a).
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass.
  • the first pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator.
  • the first pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the first pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the photopolymerization initiator is 0.01 to 20 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). Is preferable, 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.
  • the first pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • Examples of the other additive in the first pressure-sensitive adhesive composition (I-2) include the same additives as those in the first pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the first pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the first pressure-sensitive adhesive composition (I-2) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the first pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • the first pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low molecular weight compound.
  • the content of the pressure-sensitive adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, It is particularly preferable that the content be ⁇ 90 mass%.
  • Examples of the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) include monomers and oligomers that have an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays. And the same energy ray-curable compound contained in the first pressure-sensitive adhesive composition (I-1).
  • the energy ray-curable low molecular weight compound contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and when two or more types, the combination and ratio thereof are as follows: Can be arbitrarily selected.
  • the content of the energy ray-curable low molecular weight compound is 0.01 to 300 with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a).
  • the amount is preferably part by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.
  • the first pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator.
  • the first pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
  • Examples of the photopolymerization initiator in the first pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators as those in the first pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the photopolymerization initiator is based on 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable low molecular weight compound.
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the first pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components within a range that does not impair the effects of the present invention.
  • the other additives include the same additives as the other additives in the first pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the first pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of other additives is not particularly limited, and may be appropriately selected depending on the type.
  • the first pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the first pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the first pressure-sensitive adhesive composition (I-3) include the same solvents as those in the first pressure-sensitive adhesive composition (I-1). Only 1 type may be sufficient as the solvent which 1st adhesive composition (I-3) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
  • the content of the solvent is not particularly limited and may be appropriately adjusted.
  • first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) has been mainly described.
  • first pressure-sensitive adhesive compositions (I-1) to (I-) It is also possible to use the same in the first pressure-sensitive adhesive composition other than 3).
  • Examples of the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions other than energy-ray-curable pressure-sensitive adhesive compositions. Also mentioned.
  • Non-energy ray curable adhesive compositions include, for example, acrylic resins (resins having (meth) acryloyl groups), urethane resins (resins having urethane bonds), rubber resins (resins having a rubber structure).
  • Silicone resins (resins having a siloxane bond), epoxy resins (resins having an epoxy group), polyvinyl ethers, or resins containing an adhesive resin such as polycarbonate, and those containing acrylic resins are preferred. .
  • the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more crosslinking agents, and the content thereof is as described above. This can be the same as in the case of the first pressure-sensitive adhesive composition (I-1) and the like.
  • the first pressure-sensitive adhesive composition such as the first pressure-sensitive adhesive compositions (I-1) to (I-3) includes the first pressure-sensitive adhesive, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive as necessary. It is obtained by blending each component for constituting the composition. The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • middle layer is a sheet form or a film form
  • the constituent material should just be suitably selected according to the objective, and is not specifically limited.
  • the protective film covering the semiconductor surface is intended to suppress the deformation of the protective film by reflecting the shape of the bump existing on the semiconductor surface
  • the preferred constituent material of the first intermediate layer examples thereof include urethane (meth) acrylate and the like 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. In the case of a plurality of layers, these layers may be the same or different from each other, and a combination of these layers. Is not particularly limited.
  • the thickness of the first intermediate layer can be adjusted as appropriate according to the height of the bump on the surface of the semiconductor to be protected.
  • the thickness of the first intermediate layer is 50 to 600 ⁇ m because the influence of the relatively high bump can be easily absorbed. It is preferably 70 to 500 ⁇ m, more preferably 80 to 400 ⁇ m.
  • the “thickness of the first intermediate layer” means the thickness of the entire first intermediate layer.
  • the thickness of the first intermediate layer composed of a plurality of layers means all of the first intermediate layer. Means the total thickness of the layers.
  • middle layer can be formed using the composition for 1st intermediate
  • the first intermediate layer-forming composition is applied to the surface of the first intermediate layer and dried as necessary, or cured by irradiation with energy rays, so that the first intermediate layer is formed on the target site. Layers can be formed. A more specific method for forming the first intermediate layer will be described in detail later along with methods for forming other layers.
  • the ratio of the content of components that do not vaporize at room temperature in the first intermediate layer forming composition is usually the same as the content ratio of the components of the first intermediate layer.
  • “normal temperature” is as described above.
  • the first intermediate layer forming composition may be applied by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife.
  • a method using various coaters such as a coater, a screen coater, a Meyer bar coater, and a kiss coater.
  • the drying conditions for the first intermediate layer forming composition are not particularly limited.
  • the composition for forming a first intermediate layer containing a solvent described later is preferably heat-dried, and in this case, for example, it is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • the composition for forming the first intermediate layer has energy ray curability, it is preferably cured by irradiation with energy rays after drying.
  • Examples of the first intermediate layer forming composition include a first intermediate layer forming composition (II-1) containing urethane (meth) acrylate.
  • the first intermediate layer forming composition (II-1) contains urethane (meth) acrylate.
  • Urethane (meth) acrylate is a compound having at least a (meth) acryloyl group and a urethane bond in one molecule, and has energy ray polymerizability.
  • the urethane (meth) acrylate may be monofunctional (having only one (meth) acryloyl group in one molecule) or bifunctional or more ((meth) acryloyl group in one molecule). Having two or more), that is, a polyfunctional one. However, in the present invention, it is preferable to use at least a monofunctional urethane (meth) acrylate.
  • Examples of the urethane (meth) acrylate contained in the first intermediate layer forming composition include, for example, a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound and a polyvalent isocyanate compound, a hydroxyl group and What was obtained by making the (meth) acrylic-type compound which has a (meth) acryloyl group react is mentioned.
  • the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.
  • the urethane (meth) acrylate contained in the first intermediate layer forming composition (II-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule.
  • the said polyol compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • polyol compound examples include alkylene diol, polyether type polyol, polyester type polyol, and polycarbonate type polyol.
  • the polyol compound may be any of a bifunctional diol, a trifunctional triol, a tetrafunctional or higher polyol, etc., but a diol is preferable in terms of easy availability and excellent versatility and reactivity. .
  • the polyether type polyol is not particularly limited, but is preferably a polyether type diol, and examples of the polyether type diol include compounds represented by the following general formula (1). It is done.
  • n is an integer of 2 or more; R is a divalent hydrocarbon group, and a plurality of R may be the same or different from each other.
  • n represents the number of repeating units of the group represented by the general formula “—RO—”, and is not particularly limited as long as it is an integer of 2 or more. Among these, n is preferably 10 to 250, more preferably 25 to 205, and particularly preferably 40 to 185.
  • R is not particularly limited as long as it is a divalent hydrocarbon group, but is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, an ethylene group, a propylene group, or a tetra group.
  • a methylene group is more preferable, and a propylene group or a tetramethylene group is particularly preferable.
  • the compound represented by the formula (1) is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol, and more preferably polypropylene glycol or polytetramethylene glycol.
  • the terminal isocyanate urethane prepolymer having an ether bond represented by the following general formula (1a) is obtained.
  • the urethane (meth) acrylate has the ether bond part, that is, the structural unit derived from the polyether type diol. .
  • polyester type polyol is not specifically limited, For example, what was obtained by performing esterification reaction using a polybasic acid or its derivative (s), etc. are mentioned.
  • derivative means a compound in which one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified.
  • group includes not only an atomic group formed by bonding a plurality of atoms but also one atom.
  • polybasic acid and its derivative As said polybasic acid and its derivative (s), the polybasic acid normally used as a manufacturing raw material of polyester and its derivative (s) are mentioned.
  • the polybasic acid include saturated aliphatic polybasic acids, unsaturated aliphatic polybasic acids, aromatic polybasic acids, and the like, and dimer acids corresponding to any of these may be used.
  • saturated aliphatic polybasic acid examples include saturated aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
  • unsaturated aliphatic polybasic acid examples include unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid.
  • aromatic polybasic acid examples include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid; aromatic tribasic acids such as trimellitic acid; pyromellitic acid and the like And aromatic tetrabasic acids.
  • Examples of the derivative of the polybasic acid include the above-mentioned saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid and acid anhydride of aromatic polybasic acid, and hydrogenated dimer acid.
  • any of the polybasic acids or derivatives thereof may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be arbitrarily selected. .
  • the polybasic acid is preferably an aromatic polybasic acid in that it is suitable for forming a coating film having an appropriate hardness.
  • a known catalyst may be used as necessary.
  • the catalyst include tin compounds such as dibutyltin oxide and stannous octylate; alkoxy titanium such as tetrabutyl titanate and tetrapropyl titanate.
  • the polycarbonate type polyol is not particularly limited, and examples thereof include those obtained by reacting the same glycol as the compound represented by the formula (1) with an alkylene carbonate.
  • each of glycol and alkylene carbonate may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected. .
  • the number average molecular weight calculated from the hydroxyl value of the polyol compound is preferably 1000 to 10,000, more preferably 2000 to 9000, and particularly preferably 3000 to 7000.
  • the number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated from the following formula.
  • the polyol compound is preferably a polyether type polyol, and more preferably a polyether type diol.
  • the polyvalent isocyanate compound to be reacted with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.
  • a polyvalent isocyanate compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • polyvalent isocyanate compound examples include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2.
  • chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate
  • isophorone diisocyanate norbornane diisocyanate
  • dicyclohexylmethane-4,4′-diisocyanate dicyclohexylmethane-2.
  • Cycloaliphatic diisocyanates such as 4,4′-diisocyanate, ⁇ , ⁇ ′-diisocyanate dimethylcyclohexane, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, naphthalene-1, And aromatic diisocyanates such as 5-diisocyanate.
  • the polyvalent isocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate or xylylene diisocyanate from the viewpoint of handleability.
  • the (meth) acrylic compound to be reacted with the terminal isocyanate urethane prepolymer is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth) acryloyl group in one molecule.
  • the said (meth) acrylic-type compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • Examples of the (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyl-3-phenyloxypropyl, hydroxyl group-containing (meth) acrylate such as pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; N-methylol (meth) acrylamid Hydroxyl group-containing (meth) acrylamide and the like; vinyl alcohol, vinyl phenol or bisphenol A diglycidyl ether (
  • the (meth) acrylic compound is preferably a hydroxyl group-containing (meth) acrylic ester, more preferably a hydroxyl group-containing (meth) acrylic acid alkyl ester, and (meth) acrylic acid 2- Particularly preferred is hydroxyethyl.
  • the reaction between the terminal isocyanate urethane prepolymer and the (meth) acrylic compound may be performed using a solvent, a catalyst, or the like, if necessary.
  • Conditions for reacting the terminal isocyanate urethane prepolymer with the (meth) acrylic compound may be appropriately adjusted.
  • the reaction temperature is preferably 60 to 100 ° C.
  • the reaction time is 1 to It is preferably 4 hours.
  • the urethane (meth) acrylate may be an oligomer, a polymer, or a mixture of an oligomer and a polymer, but is preferably an oligomer.
  • the urethane (meth) acrylate has a weight average molecular weight of preferably from 1,000 to 100,000, more preferably from 3000 to 80,000, and particularly preferably from 5,000 to 65,000. Due to the intermolecular force between the structures derived from urethane (meth) acrylate in the polymer of urethane (meth) acrylate and a polymerizable monomer described later, the weight average molecular weight is 1000 or more. Optimization of layer hardness is facilitated.
  • the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
  • the first intermediate layer forming composition (II-1) may contain a polymerizable monomer in addition to the urethane (meth) acrylate, from the viewpoint of further improving the film forming property.
  • the polymerizable monomer is a compound having energy ray polymerizability and excluding oligomers and polymers having a weight average molecular weight of 1000 or more and having at least one (meth) acryloyl group in one molecule. It is preferable.
  • Examples of the polymerizable monomer include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester is a chain having 1 to 30 carbon atoms; a hydroxyl group, an amide group, an amino group, an epoxy group, or the like (Meth) acrylic compound having a functional group of (meth) acrylic ester having an aliphatic cyclic group; (meth) acrylic ester having an aromatic hydrocarbon group; having a heterocyclic group ( (Meth) acrylic acid ester; compound having vinyl group; compound having allyl group.
  • Examples of the (meth) acrylic acid alkyl ester having a chain alkyl group having 1 to 30 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( Isopropyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic acid Isononyl, decy
  • Examples of the functional group-containing (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid.
  • Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (Meth) acrylamides such as N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and the like
  • a derivative having an amino group ( A) Acrylic acid ester hereinafter sometimes referred to as “amino group-containing (meth) acrylic acid
  • amino group-containing (meth) acrylic acid ester means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with an amino group (—NH 2 ).
  • monosubstituted amino group-containing (meth) acrylic acid ester means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a monosubstituted amino group
  • disubstituted amino group-containing (meth) acrylic acid ester means a compound in which one or two or more hydrogen atoms of (meth) acrylic acid ester are substituted with a disubstituted amino group.
  • the group other than the hydrogen atom in which the hydrogen atom is substituted in the “monosubstituted amino group” and the “disubstituted amino group” include an alkyl group.
  • Examples of the (meth) acrylic acid ester having an aliphatic cyclic group include, for example, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and (meth) acrylic acid. Examples include dicyclopentenyloxyethyl, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate, and the like.
  • Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenylhydroxypropyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. Can be mentioned.
  • the heterocyclic group in the (meth) acrylic acid ester having a heterocyclic group may be either an aromatic heterocyclic group or an aliphatic heterocyclic group.
  • Examples of the (meth) acrylic acid ester having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and (meth) acryloylmorpholine.
  • Examples of the compound having a vinyl group include styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinyl pyrrolidone, N-vinyl caprolactam and the like.
  • Examples of the compound having an allyl group include allyl glycidyl ether.
  • the polymerizable monomer preferably has a relatively bulky group from the viewpoint of good compatibility with the urethane (meth) acrylate.
  • examples of such a polymerizable monomer include (meth) acrylic acid ester having an aliphatic cyclic group, (meth) acrylic acid ester having an aromatic hydrocarbon group, and (meth) acrylic acid having a heterocyclic group. (Meth) acrylic acid ester having an aliphatic cyclic group is more preferable.
  • the polymerizable monomer contained in the first intermediate layer forming composition (II-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrarily selected. it can.
  • the content of the polymerizable monomer is preferably 10 to 99% by mass, more preferably 15 to 95% by mass, and 20 to 90% by mass. % Is more preferable, and 25 to 80% by mass is particularly preferable.
  • the first intermediate layer forming composition (II-1) may contain a photopolymerization initiator in addition to the urethane (meth) acrylate and the polymerizable monomer.
  • the first intermediate layer-forming composition (II-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; 2-hydroxy-2 Acetophenone compounds such as methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal
  • 2-hydroxy-2 Acetophenone compounds such as methyl-1-phenyl-
  • Acyl phosphine oxide compounds such as benzyl phenyl sulfide and tetramethyl thiuram monosulfide; ⁇ -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; Azo compounds such as blanking Tirol carbonitrile; titanocene compounds such as titanocene; thioxanthone compounds of thioxanthone; peroxide compound; diketone compounds such as diacetyl, dibenzyl and the like.
  • a quinone compound such as 1-chloroanthraquinone
  • a photosensitizer such as amine
  • the photopolymerization initiator contained in the first intermediate layer forming composition (II-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the photopolymerization initiator is 0.01 to 20 with respect to 100 parts by mass of the total content of the urethane (meth) acrylate and the polymerizable monomer.
  • the amount is preferably part by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the first intermediate layer forming composition (II-1) may contain a resin component other than the urethane (meth) acrylate as long as the effects of the present invention are not impaired.
  • the kind of the resin component and the content in the first intermediate layer forming composition (II-1) may be appropriately selected according to the purpose, and are not particularly limited.
  • the first intermediate layer forming composition (II-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • the other additives include known crosslinking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), and the like.
  • An additive is mentioned.
  • the chain transfer agent includes a thiol compound having at least one thiol group (mercapto group) in one molecule.
  • thiol compound examples include nonyl mercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, triazinedithiol, triazinetrithiol, 1,2,3-propanetrithiol, Tetraethylene glycol-bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakisthioglucorate, dipentaerythritol hexa Kiss (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,4-bis (3-mercaptobutyryloxy) butane, pen Erythritol tetrakis (3-mercapt
  • the other additive contained in the first intermediate layer forming composition (II-1) may be only one kind, two or more kinds, and in the case of two or more kinds, the combination and ratio thereof are arbitrary. You can choose.
  • the content of other additives is not particularly limited, and may be appropriately selected depending on the type.
  • the first intermediate layer forming composition (II-1) may contain a solvent. Since the first intermediate layer forming composition (II-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
  • the first intermediate layer forming composition such as the first intermediate layer forming composition (II-1) can be obtained by blending the components for constituting the first intermediate layer forming composition.
  • the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • thermosetting resin layer (thermosetting resin film) is a layer for protecting bumps on the semiconductor surface, and forms a first protective film by curing.
  • the thermosetting resin layer contains a polymer component (A) and a thermosetting component (B0), and the thermosetting component (B0) has a weight average molecular weight of 450 or more and a dispersity of 10. It is as follows.
  • the polymer component (A) is a component that can be regarded as formed by polymerization reaction of the polymerizable compound.
  • the thermosetting component (B0) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger.
  • the polymerization reaction includes a polycondensation reaction.
  • thermosetting resin layer can be formed using the composition for thermosetting resin layer formation containing the constituent material.
  • a thermosetting resin layer can be formed at a target site by applying a thermosetting resin layer forming composition to the surface on which the thermosetting resin layer is to be formed and drying it as necessary.
  • the ratio of the contents of components that do not vaporize at room temperature is usually the same as the ratio of the contents of the components of the thermosetting resin layer.
  • “normal temperature” is as described above.
  • thermosetting resin layer forming composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, Examples include a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
  • thermosetting resin layer forming composition The drying conditions of the thermosetting resin layer forming composition are not particularly limited, but when the thermosetting resin layer forming composition contains a solvent described later, it is preferable to heat dry.
  • the composition for forming a thermosetting resin layer containing a solvent is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes, for example.
  • thermosetting resin layer forming composition (III-1) a thermosetting resin layer forming composition (III-1) containing a polymer component (A) and a thermosetting component (B0) (in this specification) May be simply abbreviated as “resin layer forming composition (III-1)”).
  • the polymer component (A) is a polymer compound for imparting film-forming properties, flexibility and the like to the thermosetting resin layer.
  • the polymer component (A) contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • Examples of the polymer component (A) include an acrylic resin (a resin having a (meth) acryloyl group), a polyester, a urethane resin (a resin having a urethane bond), an acrylic urethane resin, and a silicone resin (having a siloxane bond). Resin), rubber resin (resin having a rubber structure), phenoxy resin, thermosetting polyimide and the like, and acrylic resin is preferable.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1500,000.
  • Mw weight average molecular weight
  • the shape stability of the thermosetting resin layer time stability during storage
  • the thermosetting resin layer easily follows the uneven surface of the adherend, and between the adherend and the thermosetting resin layer. Generation of voids and the like is further suppressed.
  • the glass transition temperature (Tg) of the acrylic resin is preferably ⁇ 60 to 70 ° C., and more preferably ⁇ 30 to 50 ° C.
  • Tg of the acrylic resin is equal to or more than the lower limit value, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.
  • adhesive force with the to-be-adhered body of a thermosetting resin layer and a 1st protective film improves because Tg of acrylic resin is below the said upper limit.
  • the acrylic resin is selected from, for example, a polymer of one or more (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like. Examples include copolymers of two or more monomers.
  • Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (me
  • the acrylic resin is, for example, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like in addition to the (meth) acrylic ester. May be obtained by copolymerization.
  • Only one type of monomer constituting the acrylic resin may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the acrylic resin may have a functional group that can be bonded 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 a cross-linking agent (F) described later, or may be directly bonded to another compound not via the cross-linking agent (F). .
  • F cross-linking agent
  • thermoplastic resin other than an acrylic resin
  • thermoplastic resin is used alone without using an acrylic resin.
  • it may be used in combination with an acrylic resin.
  • thermoplastic resin By using the thermoplastic resin, the peelability of the first protective film from the first support sheet is improved, and the thermosetting resin layer can easily follow the uneven surface of the adherend. Occurrence of voids or the like may be further suppressed between the curable resin layer.
  • the weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.
  • the glass transition temperature (Tg) of the thermoplastic resin is preferably ⁇ 30 to 150 ° C., and more preferably ⁇ 20 to 120 ° C.
  • thermoplastic resin examples include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.
  • thermoplastic resin contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one kind, two kinds or more, and when two or more kinds are combined, The ratio can be arbitrarily selected.
  • the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the polymer component (A) of the thermosetting resin layer) Content) is preferably 5 to 85% by mass, more preferably 5 to 80% by mass, for example 5 to 70% by mass, regardless of the type of the polymer component (A). It may be any of ⁇ 60 mass%, 5 ⁇ 50 mass%, 5 ⁇ 40 mass%, and 5 ⁇ 30 mass%.
  • the polymer component (A) may also correspond to the thermosetting component (B0).
  • the resin layer forming composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B0)
  • the composition (III-1) is considered to contain a polymer component (A) and a thermosetting component (B0).
  • thermosetting component (B0) is a component for curing the thermosetting resin layer to form a hard first protective film.
  • the thermosetting component (B0) contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one type, two or more types, and when two or more types, These combinations and ratios can be arbitrarily selected.
  • thermosetting component (B0) is not particularly limited as long as the weight average molecular weight is 450 or more and the degree of dispersion is 10 or less.
  • a thermosetting component (B0) is, as described above, in the first protective film forming sheet of the present invention, immediately after its production, the thermosetting resin film (thermosetting resin layer) is used at the time of use. The transition from the thermosetting resin film to the layer adjacent to the thermosetting resin film (first support sheet) is sufficiently suppressed before curing.
  • the weight average molecular weight of the thermosetting component (B0) is preferably 20000 or less, more preferably 15000 or less, and particularly preferably 10,000 or less, for example, 8000 or less, 6000 or less, 4000 or less, And 2000 or less.
  • the weight average molecular weight of the thermosetting component (B0) is less than or equal to the above upper limit, the first protective film having a high degree of curing and more excellent characteristics can be formed, and the bump embedding property of the thermosetting resin film Will be improved.
  • the degree of dispersion of the thermosetting component (B0) is 10 or less, preferably 7 or less, and more preferably 5 or less. When the degree of dispersion of the thermosetting component (B0) is not more than the above upper limit value, a first protective film having a high degree of curing can be formed, and the bump embedding property of the thermosetting resin film is further improved.
  • the lower limit of the degree of dispersion of the thermosetting component (B0) is not particularly limited, but is preferably 1.
  • thermosetting component (B0) examples include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like, and epoxy-based thermosetting resins are preferable.
  • the epoxy thermosetting resin includes an epoxy resin (B01) and a thermosetting agent (B02). That is, both of the epoxy resin (B01) and the thermosetting agent (B02) have a weight average molecular weight of 450 or more and a dispersity of 10 or less, and preferable numerical ranges of the weight average molecular weight and dispersity are as follows. As described above.
  • the epoxy-type thermosetting resin contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one type, or two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • Epoxy resin (B01) examples include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.
  • an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (B01).
  • An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the 1st sheet
  • Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
  • the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned, An acryloyl group is preferable.
  • the epoxy equivalent of the epoxy resin (B01) is preferably 100 to 1000 g / eq, more preferably 200 to 900 g / eq, for example, 300 to 800 g / eq.
  • the epoxy resin (B01) may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected.
  • thermosetting agent (B02) functions as a curing agent for the epoxy resin (B01).
  • a thermosetting agent (B02) the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example.
  • the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
  • thermosetting agents (B02) examples include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins.
  • examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
  • the thermosetting agent (B02) may have an unsaturated hydrocarbon group.
  • the thermosetting agent (B02) having an unsaturated hydrocarbon group for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
  • the unsaturated hydrocarbon group in the thermosetting agent (B02) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
  • thermosetting agent (B02) When a phenolic curing agent is used as the thermosetting agent (B02), the thermosetting agent (B02) has a softening point or a glass transition temperature from the viewpoint of improving the peelability of the first protective film from the first support sheet. A high one is preferred.
  • thermosetting agent (B02) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • the content of the thermosetting agent (B02) is 0.1 to 500 with respect to 100 parts by mass of the epoxy resin (B01). It is preferably part by mass, more preferably 1 to 200 parts by mass, and for example, it may be any of 10 to 150 parts by mass and 20 to 100 parts by mass.
  • the content of the thermosetting agent (B02) is equal to or more than the lower limit value, the thermosetting resin layer is more easily cured.
  • the moisture absorption rate of a thermosetting resin layer is reduced because the said content of a thermosetting agent (B02) is below the said upper limit, The package obtained using the sheet
  • the content of the thermosetting component (B0) (for example, the total content of the epoxy resin (B01) and the thermosetting agent (B02)) is
  • the content of the polymer component (A) is preferably 50 to 1000 parts by weight, more preferably 100 to 900 parts by weight, and particularly preferably 150 to 800 parts by weight with respect to 100 parts by weight of the polymer component (A). preferable.
  • the content of the thermosetting component (B0) is in such a range, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.
  • the resin layer forming composition (III-1) and the thermosetting resin layer may contain a curing accelerator (C).
  • the curing accelerator (C) is a component for adjusting the curing rate of the resin layer forming composition (III-1).
  • Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are other than hydrogen atoms)
  • the curing accelerator (C) contained in the resin layer forming composition (III-1) and the thermosetting resin layer may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • the content of the curing accelerator (C) in the resin layer forming composition (III-1) and the thermosetting resin layer is the content of the thermosetting component (B0).
  • the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass.
  • the effect by using a hardening accelerator (C) is acquired more notably because the said content of a hardening accelerator (C) is more than the said lower limit.
  • the highly polar curing accelerator (C) is deposited in the thermosetting resin layer under high temperature and high humidity conditions. The effect of suppressing segregation by moving toward the adhesion interface with the body is enhanced, and the reliability of the package obtained using the first protective film forming sheet is further improved.
  • the resin layer forming composition (III-1) and the thermosetting resin layer may contain a filler (D).
  • the thermosetting resin layer contains the filler (D)
  • the first protective film obtained by curing the thermosetting resin layer can easily adjust the thermal expansion coefficient.
  • seat for 1st protective film formation improves more by optimizing this thermal expansion coefficient with respect to the formation object of a 1st protective film.
  • the thermosetting resin layer contains the filler (D) the moisture absorption rate of the first protective film can be reduced or the heat dissipation can be improved.
  • the filler (D) 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, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the inorganic filler is preferably silica or alumina.
  • the resin layer forming composition (III-1) and the filler (D) contained in the thermosetting resin layer may be only one type, two or more types, and combinations of two or more types.
  • the ratio can be arbitrarily selected.
  • the ratio of the content of the filler (D) to the total content of all components other than the solvent in the resin layer forming composition (III-1) that is, the thermosetting resin
  • the content of the filler (D) in the layer is preferably 5 to 80% by mass, more preferably 7 to 60% by mass. Adjustment of said thermal expansion coefficient becomes easier because content of a filler (D) is such a range.
  • the resin layer forming composition (III-1) and the thermosetting resin layer may contain a coupling agent (E).
  • a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound the adhesion and adhesion of the thermosetting resin layer to the adherend can be improved.
  • the coupling agent (E) the first protective film obtained by curing the thermosetting resin layer has improved water resistance without impairing heat resistance.
  • the coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (A), the thermosetting component (B0), etc., and is preferably a silane coupling agent. More preferred. Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (pheny
  • the resin layer forming composition (III-1) and the coupling agent (E) contained in the thermosetting resin layer may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • the content of the coupling agent (E) in the resin layer forming composition (III-1) and the thermosetting resin layer is such that the polymer component (A) and the thermosetting
  • the content is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the total content of the component (B0). It is particularly preferred.
  • the content of the coupling agent (E) is equal to or higher than the lower limit, the dispersibility of the filler (D) in the resin and the adhesion of the thermosetting resin layer to the adherend are improved.
  • the effect by using a coupling agent (E) etc. is acquired more notably.
  • production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.
  • Cross-linking agent (F) As the polymer component (A), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin.
  • the resin layer forming composition (III-1) and the thermosetting resin layer may contain a crosslinking agent (F).
  • the cross-linking agent (F) is a component for cross-linking the functional group in the polymer component (A) with another compound to cross-link, and by this cross-linking, initial adhesion of the thermosetting resin layer Force and cohesion can be adjusted.
  • crosslinking agent (F) examples include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.
  • organic polyvalent isocyanate compound examples include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”).
  • a trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc.
  • the “adduct body” includes the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a molecularly active hydrogen-containing compound.
  • Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane as described later.
  • the “terminal isocyanate urethane prepolymer” is as described above.
  • organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.
  • a polyol such as propane.
  • organic polyvalent imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and tetramethylolmethane.
  • -Tri- ⁇ -aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.
  • crosslinking agent (F) When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A).
  • a cross-linked structure is formed on the thermosetting resin layer by a reaction between the crosslinking agent (F) and the polymer component (A). Easy to introduce.
  • composition for forming a resin layer (III-1) and the crosslinking agent (F) contained in the thermosetting resin layer may be one kind, two kinds or more, and combinations of two or more kinds.
  • the ratio can be arbitrarily selected.
  • the content of the crosslinking agent (F) is 0. 0 parts by mass relative to 100 parts by mass of the polymer component (A).
  • the amount is preferably 01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.
  • the effect by using a crosslinking agent (F) is acquired more notably because the said content of a crosslinking agent (F) is more than the said lower limit.
  • the excessive use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.
  • the resin layer forming composition (III-1) may contain an energy ray curable resin (G). Since the thermosetting resin layer contains the energy ray curable resin (G), the characteristics can be changed by irradiation with energy rays.
  • the energy beam curable resin (G) is obtained by polymerizing (curing) an energy beam curable compound.
  • 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.
  • the acrylate compound examples include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; polyethylene Polyalkylene glycol (meth) acrylate such as glycol di (meth) acrylate; oligoester (meth) acrylate; urethane (meth) acrylate oligomer; Modified (meth) acrylate; the polyalky
  • the weight average molecular weight of the energy ray curable compound is preferably 100 to 30000, and more preferably 300 to 10000.
  • the energy ray-curable compound used for the polymerization may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the energy ray curable resin (G) contained in the resin layer forming composition (III-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof are as follows: Can be arbitrarily selected.
  • the content of the energy ray curable resin (G) in the resin layer forming composition (III-1) is preferably 1 to 95% by mass. It is more preferably 90% by mass, and particularly preferably 10 to 85% by mass.
  • Photopolymerization initiator (H) When the resin layer forming composition (III-1) contains the energy beam curable resin (G), the photopolymerization initiator (H) is used to efficiently advance the polymerization reaction of the energy beam curable resin (G). ) May be contained.
  • photopolymerization initiator (H) examples include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4 -Diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1- [4- (1-Methylvinyl) phenyl] propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-chloroanthrac Emissions, and the like
  • the photopolymerization initiator (H) contained in the resin layer forming composition (III-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the photopolymerization initiator (H) is 100 parts by mass of the energy ray curable resin (G). Is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.
  • the resin layer forming composition (III-1) and the thermosetting resin layer may contain a general-purpose additive (I) as long as the effects of the present invention are not impaired.
  • the general-purpose additive (I) may be a known one, and can be arbitrarily selected according to the purpose.
  • the general-purpose additive (I) is not particularly limited, but preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye Pigments), gettering agents and the like.
  • the resin layer forming composition (III-1) and the general-purpose additive (I) contained in the thermosetting resin layer may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • the contents of the resin layer forming composition (III-1) and the general-purpose additive (I) in the thermosetting resin layer are not particularly limited, and may be appropriately selected depending on the purpose.
  • thermosetting component (B9) The resin layer forming composition (III-1) and the thermosetting resin layer are within the range not impairing the effects of the present invention, and other thermosetting components (B9) other than the above-mentioned thermosetting component (B0). May be contained.
  • the other thermosetting component (B9) is not particularly limited as long as it is other than the thermosetting component (B0).
  • the thermosetting component (B0) has been exemplified as the thermosetting component (B0), and the weight average molecular weight and dispersity Or the like in which at least one of the above does not satisfy the above-mentioned conditions.
  • an epoxy-based thermosetting composition containing either or both of an epoxy resin (B91) not corresponding to the epoxy resin (B01) and a thermosetting agent (B92) not corresponding to the thermosetting agent (B02).
  • the resin is handled as another thermosetting component (B9).
  • the resin layer forming composition (III-1) and the other thermosetting component (B9) contained in the thermosetting resin layer may be one type, two or more types, or two or more types. These combinations and ratios can be arbitrarily selected.
  • thermosetting component (B9) with respect to the total content of the thermosetting component (B0) and the other thermosetting components (B9).
  • ) Content is preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less, and may be 0% by mass.
  • the effect by using a thermosetting component (B0) is acquired more notably because the ratio of the said content of another thermosetting component (B9) is below the said upper limit.
  • the resin layer forming composition (III-1) preferably further contains a solvent.
  • the resin layer forming composition (III-1) containing a solvent has good handleability.
  • the solvent is not particularly limited. Preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
  • the solvent contained in the resin layer forming composition (III-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the solvent contained in the resin layer forming composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components in the resin layer forming composition (III-1) can be mixed more uniformly.
  • thermosetting resin layer forming composition such as the resin layer forming composition (III-1) can be obtained by blending each component for constituting the composition.
  • the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • the first protective film forming sheet can be produced by sequentially laminating the above-described layers so as to have a corresponding positional relationship.
  • the method for forming each layer is as described above.
  • the first support sheet when the first pressure-sensitive adhesive layer or the first intermediate layer is laminated on the first base material, the above-mentioned first pressure-sensitive adhesive composition or A 1st adhesive layer or a 1st intermediate
  • thermosetting resin layer when a thermosetting resin layer is further laminated on the first pressure-sensitive adhesive layer that has been laminated on the first base material, a composition for forming a thermosetting resin layer on the first pressure-sensitive adhesive layer. It is possible to directly form a thermosetting resin layer by coating an object.
  • the first pressure-sensitive adhesive composition when further laminating the first pressure-sensitive adhesive layer on the first intermediate layer already laminated on the first base material, the first pressure-sensitive adhesive composition is applied on the first intermediate layer.
  • the first pressure-sensitive adhesive layer can be directly formed.
  • the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed.
  • the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers already formed.
  • the composition is preferably applied to the release-treated surface of the release film.
  • the release film may be removed as necessary after forming the laminated structure.
  • a first protective film forming sheet (a first support sheet is a first support sheet) is formed by laminating a first pressure-sensitive adhesive layer on a first base material and laminating a thermosetting resin layer on the first pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive composition is applied onto the first base material, and dried as necessary.
  • thermosetting resin layer is formed on the release film, and the exposed surface of the thermosetting resin layer is bonded to the exposed surface of the first pressure-sensitive adhesive layer laminated on the first substrate, and thermosetting is performed.
  • a first protective film-forming sheet is obtained by laminating the adhesive resin layer on the first pressure-sensitive adhesive layer.
  • the first substrate In the case of producing a first support sheet in which a first intermediate layer is laminated on a first substrate and a first pressure-sensitive adhesive layer is laminated on the first intermediate layer, the first substrate The first intermediate layer-forming composition is applied on top and dried as necessary, so that the first intermediate layer is laminated on the first substrate, and the first pressure-sensitive adhesive is separately provided on the release film.
  • a first pressure-sensitive adhesive layer is formed on the release film by applying the composition and drying as necessary, and the exposed surface of the first pressure-sensitive adhesive layer is already laminated on the first substrate.
  • the first support sheet is obtained by laminating the first pressure-sensitive adhesive layer on the first intermediate layer by laminating the exposed surface of the first intermediate layer.
  • thermosetting resin layer forming composition is applied onto the release film, and if necessary, dried to form a thermosetting resin layer on the release film.
  • thermosetting resin layer is laminated on the first pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive composition or the first intermediate layer forming composition is applied onto the release film, and dried as necessary, whereby the first pressure-sensitive adhesive composition is applied onto the release film.
  • An adhesive layer or a first intermediate layer is formed, and the exposed surface of these layers is bonded to one surface of the first base material, whereby the first pressure-sensitive adhesive layer or the first intermediate layer is formed on the first base material. May be laminated.
  • the release film may be removed at an arbitrary timing after the target laminated structure is formed.
  • seat for 1st protective film formation is normally stored in the state in which the peeling film was bonded together on the surface of the outermost layer (for example, thermosetting resin layer) on the opposite side to the 1st support sheet.
  • a composition for forming a layer constituting the outermost layer such as a composition for forming a thermosetting resin layer, is applied on the release film (preferably the release-treated surface), and if necessary, By drying, a layer constituting the outermost layer is formed on the release film, and each of the remaining layers is placed on the exposed surface of the layer 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 and leaving the laminated film without removing the release film.
  • Polymer component Polymer component (A) -1 butyl acrylate (hereinafter abbreviated as “BA”) (55 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) (10 parts by mass)
  • BA butyl acrylate
  • MA methyl acrylate
  • GMA glycidyl methacrylate
  • HOA 2-hydroxyethyl acrylate
  • Polymer component (A) -2 Polyester (Toyobo "Byron 220", thermoplastic resin) Epoxy resin Epoxy resin (B01) -1: polyfunctional aromatic epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight 1000, dispersity 1.5) Epoxy resin (B01) -2: aromatic epoxy resin (“EXA-4850-150” manufactured by DIC, weight average molecular weight 900, dispersity 1.1) Epoxy resin (B01) -3: Liquid bisphenol A type epoxy resin (“JER834” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 250 g / eq, weight average molecular weight 470, dispersity 2) Epoxy resin (B01) -4: Bisphenol A type epoxy resin (“JER1055” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800-900 g / eq, weight average molecular weight 1600, dispersity 3.5) Epoxy resin (B91) -1: Mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles (“BPA
  • Example 1 ⁇ Manufacture of sheet for forming first protective film> (Production of thermosetting resin layer forming composition) Polymer component (A) -1, Polymer component (A) -2, Epoxy resin (B01) -1, Epoxy resin (B01) -2, Thermosetting agent (B02) -1, Curing accelerator (C)- 1.
  • thermosetting resin layer is prepared by dissolving in methyl ethyl ketone so that the content ratio becomes the value shown in Table 2 (described as “content ratio” in Table 2) and stirring at 23 ° C.
  • a resin layer forming composition III-1) (methyl ethyl ketone solution) having a solid content concentration of 50% by mass was obtained.
  • the description of “-” in the column of the content component in Table 2 means that the thermosetting resin layer forming composition does not contain the component.
  • Photopolymerization initiator (“Irgacure 651”, benzyldimethyl ketal, manufactured by Ciba Specialty Chemicals) (3 parts by mass) with respect to the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 1 ), Acetylacetone (1 part by mass) as a reaction retarding agent was added and stirred well, and then a tolylene diisocyanate trimer adduct of trimethylolpropane (“Coronate HL” manufactured by Nippon Polyurethane Co., Ltd.) was used as an isocyanate crosslinking agent.
  • the first pressure-sensitive adhesive composition obtained above is applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment.
  • the first pressure-sensitive adhesive layer having a thickness of 10 ⁇ m was formed by heating and drying at 120 ° C. for 2 minutes.
  • an ethylene-vinyl acetate copolymer film having a thickness of 120 ⁇ m was bonded to the exposed surface of the first pressure-sensitive adhesive layer to obtain a first support sheet.
  • thermosetting resin layer obtained above on the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment
  • SP-PET 381031 manufactured by Lintec Co., Ltd., thickness 38 ⁇ m
  • the product was applied and dried at 100 ° C. for 2 minutes to prepare a thermosetting resin film (thermosetting resin layer) having a thickness of 7 ⁇ m.
  • the release film is removed from the first pressure-sensitive adhesive layer of the first support sheet obtained above, and the exposed surface of the thermosetting resin film obtained above is bonded to the exposed surface of the first pressure-sensitive adhesive layer.
  • the 1st base material, the 1st adhesive layer, the thermosetting resin layer, and the peeling film obtained the 1st sheet
  • thermosetting resin layer is peeled off, and the exposed surface of the first pressure-sensitive adhesive layer is applied with the total reflection measurement method (ATR method) and red. Analysis was performed by external spectroscopy (IR). As the analytical instrument, “spectrum one” manufactured by PerkinElmer was used.
  • the thermosetting components transferred from the thermosetting resin layer to the first pressure-sensitive adhesive layer that is, the epoxy resin and the thermosetting agent (phenolic resin) due to the presence or absence of an increase in the intensity of the peak at 1510 cm ⁇ 1 peculiar to the aromatic ring ) was confirmed. A case where a peak of 1510 cm ⁇ 1 was not confirmed was marked with “ ⁇ ”, and a case where a peak was confirmed was marked with “x”. The results are shown in Table 2.
  • Examples 2 to 3, Comparative Example 1 A first protective film-forming sheet was produced and evaluated in the same manner as in Example 1 except that the components and content of the thermosetting resin layer-forming composition were as shown in Table 2. The results are shown in Table 2.
  • thermosetting component has a weight average molecular weight and a dispersity both in the above ranges
  • the migration of the thermosetting component from the curable resin layer to the first pressure-sensitive adhesive layer was suppressed.
  • thermosetting component in the first protective film forming sheet of Comparative Example 1 in which both the weight average molecular weight and the dispersity are outside the above range, the above thermosetting component is used. The transition was not suppressed.
  • the present invention can be used for manufacturing a semiconductor chip or the like having bumps in connection pad portions used in a flip chip mounting method.
  • thermosetting resin layer thermosetting resin Film
  • first adhesive layer 13 ... surface of the first adhesive layer
  • 14 ... first intermediate layer 101,102,103 ... first support sheet, 101a, 102a , 103a ... surface of the first support sheet

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

La présente invention concerne une feuille permettant de former un premier film de protection comprenant une première feuille de substrat et un film de résine thermodurcissable disposé sur une surface de cette dernière, le film de résine thermodurcissable étant destiné à former un premier film de protection sur une surface d'une tranche de semi-conducteur qui présente des bosses, par application du film de résine thermodurcissable à la surface et durcissement thermique du film. Le film de résine thermodurcissable comprend un constituant polymère (A) et un constituant thermodurcissable (B0), le constituant thermodurcissable (B0) ayant un poids moléculaire moyen en poids de 450 ou plus et un rapport de polydispersité de 10 ou moins.
PCT/JP2016/079255 2015-10-08 2016-10-03 Film de résine thermodurcissable et feuille destinée à former un premier film de protection WO2017061364A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2020195761A1 (fr) * 2019-03-27 2020-10-01 リンテック株式会社 Film de résine thermodurcissable, feuille de formation de premier film de protection, kit et procédé de fabrication de pièce à usiner fixée à un premier film de protection
JP2021195451A (ja) * 2020-06-15 2021-12-27 信越化学工業株式会社 エポキシ樹脂組成物

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JP2002371262A (ja) * 2001-06-14 2002-12-26 Nitto Denko Corp ウエハ加工用粘着シート用粘着剤およびウエハ加工用粘着シート
JP2013075989A (ja) * 2011-09-30 2013-04-25 Shin-Etsu Chemical Co Ltd 仮接着材組成物及びこれを用いた薄型ウエハの製造方法
JP2014070191A (ja) * 2012-09-28 2014-04-21 Fujifilm Corp 半導体装置製造用仮接着剤、並びに、それを用いた接着性支持体、及び、半導体装置の製造方法。
JP2015164197A (ja) * 2015-03-31 2015-09-10 積水化学工業株式会社 バックグラインド−アンダーフィル一体型テープ、及び、半導体チップの実装方法

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Publication number Priority date Publication date Assignee Title
JP2002371262A (ja) * 2001-06-14 2002-12-26 Nitto Denko Corp ウエハ加工用粘着シート用粘着剤およびウエハ加工用粘着シート
JP2013075989A (ja) * 2011-09-30 2013-04-25 Shin-Etsu Chemical Co Ltd 仮接着材組成物及びこれを用いた薄型ウエハの製造方法
JP2014070191A (ja) * 2012-09-28 2014-04-21 Fujifilm Corp 半導体装置製造用仮接着剤、並びに、それを用いた接着性支持体、及び、半導体装置の製造方法。
JP2015164197A (ja) * 2015-03-31 2015-09-10 積水化学工業株式会社 バックグラインド−アンダーフィル一体型テープ、及び、半導体チップの実装方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020195761A1 (fr) * 2019-03-27 2020-10-01 リンテック株式会社 Film de résine thermodurcissable, feuille de formation de premier film de protection, kit et procédé de fabrication de pièce à usiner fixée à un premier film de protection
JP7451495B2 (ja) 2019-03-27 2024-03-18 リンテック株式会社 熱硬化性樹脂フィルム、第１保護膜形成用シート、キット、及び第１保護膜付きワーク加工物の製造方法
JP2021195451A (ja) * 2020-06-15 2021-12-27 信越化学工業株式会社 エポキシ樹脂組成物
JP7337462B2 (ja) 2020-06-15 2023-09-04 信越化学工業株式会社 エポキシ樹脂組成物

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