WO2021182554A1 - Feuille de formation de film de protection - Google Patents

Feuille de formation de film de protection Download PDF

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Publication number
WO2021182554A1
WO2021182554A1 PCT/JP2021/009704 JP2021009704W WO2021182554A1 WO 2021182554 A1 WO2021182554 A1 WO 2021182554A1 JP 2021009704 W JP2021009704 W JP 2021009704W WO 2021182554 A1 WO2021182554 A1 WO 2021182554A1
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WIPO (PCT)
Prior art keywords
protective film
bump
meth
acrylate
bumps
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PCT/JP2021/009704
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English (en)
Japanese (ja)
Inventor
拓 根本
桜子 田村
友尭 森下
圭亮 四宮
Original Assignee
リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN202180020576.2A priority Critical patent/CN115244654A/zh
Priority to JP2022507270A priority patent/JPWO2021182554A1/ja
Priority to KR1020227029886A priority patent/KR20220152208A/ko
Publication of WO2021182554A1 publication Critical patent/WO2021182554A1/fr

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    • 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
    • H01L23/293—Organic, e.g. plastic
    • 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
    • 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
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • 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
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • 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
    • 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
    • H01L23/3157—Partial encapsulation or coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/11—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector

Definitions

  • the present invention relates to a protective film forming sheet.
  • a convex electrode (hereinafter, also referred to as “bump”) is formed on the connection pad portion of the semiconductor chip. Things have been used. Then, by the so-called face-down method, a flip chip mounting method has been adopted in which those bumps are brought into contact with the corresponding terminal portions on the chip mounting substrate so as to face each other, and melt-bonded or diffuse-bonded.
  • Patent Documents 1 to 3 low ⁇ -dose solder is used to avoid a problem associated with high-density mounting, that is, a soft error in which the stored contents are rewritten due to ⁇ rays entering the memory cell of a semiconductor integrated circuit. The material has been proposed.
  • the present inventors have conducted diligent studies and have come to create a sheet for forming a protective film capable of suppressing the ball bumps from being crushed and spreading in the lateral direction. Further, even in a semiconductor chip having pillar bumps, it is considered that the pillar bumps may come into contact with each other to cause a short circuit due to bending or the like of the pillar bumps. The created sheet was also found to be effective in solving such problems in pillar bumps.
  • an object of the present invention is to provide a protective film forming sheet capable of suppressing a short circuit between bumps having a narrow pitch.
  • ⁇ 2 The bump pitch (BM P ) (unit: ⁇ m) and the bump width (BM w ) (unit: ⁇ m) satisfy the following formula (I). [(BM P ) / (BM w )] ⁇ 1.0 ... (I) A protective film forming sheet that satisfies the following requirements ( ⁇ 1) to ( ⁇ 3).
  • Requirement ( ⁇ 1) The tensile elastic modulus E'(23 ° C.) at 23 ° C. of the protective film (X) formed by curing the curable resin film (x) is 1 ⁇ 10 7 Pa to 1 ⁇ . It is 10 10 Pa.
  • Requirement ( ⁇ 2) The tensile elastic modulus E'(260 ° C.) of the protective film (X) formed by curing the curable resin film (x) at 260 ° C. is 1 ⁇ 10 5 Pa to 1 ⁇ . It is 10 8 Pa.
  • -Requirement ( ⁇ 3) The thickness (XT ) (unit: ⁇ m) of the protective film (X) formed by curing the curable resin film (x) at 23 ° C. and the height of the bumps (unit: ⁇ m).
  • BM h ) (unit: ⁇ m) satisfies the following formula (II). [( XT ) / (BM h )] ⁇ 0.2 ...
  • -Requirement ( ⁇ 3b) The height of the bump (BM h ) and the width of the bump (BM w ) satisfy the following formula (IIIb) 0.5 ⁇ [(BM h ) / (BM w )] ⁇ 5.0 ... (IIIb) [4]
  • -Requirement ( ⁇ 4) The height of the bump (BM h ) is 15 ⁇ m to 300 ⁇ m [5]
  • the support sheet (Y) is a back grind tape, any of [1] to [4].
  • a method for manufacturing a semiconductor wafer with a protective film Including the following steps (S1) to (S3), -Step (S1): Step of preparing a semiconductor wafer having a bump-forming surface provided with a plurality of bumps-Step (S2): Any one of [1] to [5] on the bump-forming surface of the semiconductor wafer.
  • Step / Step (S3) of attaching the protective film-forming sheet according to the above item to the protective film forming sheet with the curable resin film (x) as the affixing surface while pressing the sheet. ) Is formed.
  • a method for manufacturing a semiconductor wafer with a protective film wherein the semiconductor wafer prepared in the step (S1) satisfies the following requirements ( ⁇ 1) to ( ⁇ 2).
  • BM w The width (BM w ) (unit: ⁇ m) of the bump is 20 ⁇ m to 350 ⁇ m.
  • ⁇ 2 Pitch (BM P ) (unit: ⁇ m) of the bump and the width of the bump.
  • (BM w ) (unit: ⁇ m) satisfies the following formula (I) [(BM P ) / (BM w )] ⁇ 1.0 ... (I) [7]
  • a method for manufacturing a semiconductor chip with a protective film which comprises the following steps (T1) to (T2).
  • Step (T1) A step of obtaining a semiconductor wafer with a protective film by carrying out the manufacturing method according to [6]-Step (T2): A step of disassembling the semiconductor wafer with a protective film
  • Step (U2) A step of carrying out the manufacturing method according to [7] to obtain a semiconductor chip with a protective film
  • Step (U2) A wiring substrate and the semiconductor chip with a protective film are attached to each other via the bump.
  • Step (U3) A step of filling an underfill material between the wiring board and the semiconductor chip with a protective film.
  • the term "active ingredient” refers to a component contained in a target composition excluding a diluting solvent such as water or an organic solvent.
  • a diluting solvent such as water or an organic solvent.
  • (meth) acrylic acid means both “acrylic acid” and “methacrylic acid”, and other similar terms are also used.
  • the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • the lower limit value and the upper limit value described stepwise can be combined independently. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the “preferable lower limit value (10)" and the “more preferable upper limit value (60)” are combined to obtain “10 to 60". You can also do it.
  • the protective film forming sheet of the present invention has a laminated structure of a curable resin film (x) and a support sheet (Y).
  • the protective film forming sheet of the present invention has a plurality of bumps and is used for forming the protective film (X) on the bump forming surface of the semiconductor wafer that satisfies the following requirements ( ⁇ 1) to ( ⁇ 2).
  • -Requirement ( ⁇ 1) The width (BM w ) (unit: ⁇ m) of the bump is 20 ⁇ m to 350 ⁇ m.
  • the protective film forming sheet of the present invention satisfies the following requirements ( ⁇ 1) to ( ⁇ 3).
  • Requirement ( ⁇ 1) The tensile elastic modulus E'(23 ° C.) at 23 ° C. of the protective film (X) formed by curing the curable resin film (x) is 1 ⁇ 10 7 Pa to 1 ⁇ . It is 10 10 Pa.
  • Requirement ( ⁇ 2) The tensile elastic modulus E'(260 ° C.) of the protective film (X) formed by curing the curable resin film (x) at 260 ° C. is 1 ⁇ 10 5 Pa to 1 ⁇ . It is 10 8 Pa.
  • the protective film forming sheet of the present invention is used for the bump forming surface of a semiconductor wafer having narrow pitched bumps satisfying the above requirements ( ⁇ 1) to ( ⁇ 2).
  • the protective film-forming sheet of the present invention has a laminated structure of a curable resin film (x) and a support sheet (Y) as a specific configuration, and is related to the curable resin film (x). Satisfy requirements ( ⁇ 1) to ( ⁇ 3).
  • the present inventors have a laminated structure of a curable resin film (x) and a support sheet (Y), and satisfy the above requirements ( ⁇ 1) to ( ⁇ 3) related to the curable resin film (x).
  • the protective film (X) By forming the protective film (X) on the bump forming surface of the semiconductor wafer having the narrow pitched bumps satisfying the above requirements ( ⁇ 1) to ( ⁇ 2) by using the protective film forming sheet, the bumps are crushed. It was found that the deformation can be suppressed and the short circuit between the narrowed pitched bumps can be suppressed.
  • the above requirements ( ⁇ 1) to ( ⁇ 3) related to the protective film (X) defined in the protective film forming sheet of the present invention will be described.
  • the tensile elastic modulus E'(23 ° C.) at 23 ° C. is preferably 3 ⁇ 10 7 Pa to 8 ⁇ 10 9 Pa, more preferably 5 ⁇ 10 7 Pa to 7 ⁇ 10 9 Pa, and even more preferably 7 ⁇ 10 7 Pa to 6 ⁇ 10 9 Pa.
  • the protective film (X) having a tensile elastic modulus E'(23 ° C.) defined by the requirement ( ⁇ 1) is formed by curing the curable resin film (x).
  • the method for preparing the curable resin film (x) for forming the protective film (X) will be described later.
  • the protective film (X) cannot suppress the crushing and deformation of the bumps, and the bumps may come into contact with each other to cause a short circuit.
  • modulus E '(260 °C) is at 5 ⁇ 10 7 Pa, greater than the stress at the time of heating and cooling is increased, reliability and bondability given load to the bump decreases.
  • the protective film (X) formed by curing the curable resin film (x). The tensile elastic modulus E'(260 ° C.) at 260 ° C.
  • the protective film (X) having a tensile elastic modulus E'(260 ° C.) defined by the requirement ( ⁇ 2) is formed by curing the curable resin film (x). The method for preparing the curable resin film (x) for forming the protective film (X) will be described later.
  • the requirements ( ⁇ 3) are the thickness (XT ) (unit: ⁇ m) of the protective film (X) formed by curing the curable resin film (x) at 23 ° C. and the height of the bump (BM). h ) (Unit: ⁇ m) and the relationship is specified. Specifically, the following formula (II) is satisfied. [( XT ) / (BM h )] ⁇ 0.2 ... (II) When [( XT ) / (BM h )] ⁇ 0.2, the coating height of the protective film (X) with respect to the bump height (BM h ) is insufficient, and the protective film (X) is bumped.
  • the upper limit of [( XT ) / (BM h )] is not particularly limited, but is preferably 1.0 or less, more preferably 1 from the viewpoint of exposing the bump top from the protective film (X). It is less than 0.0.
  • the requirement ( ⁇ 3) preferably satisfies the following formula (IIa).
  • P is 0.2, preferably 0.30, more preferably 0.40, and even more preferably 0.50.
  • Q is preferably 1.0, more preferably 0.90, and even more preferably 0.80.
  • the thickness of the curable resin film (x) satisfying the relationship specified in the requirement ( ⁇ 3) is the thickness of the curable resin film (x) and the protection formed by curing the curable resin film (x). It can be adjusted based on the relationship with the thickness of the film (X) and the height of bumps of the semiconductor wafer to be used.
  • FIG. 11 shows the height of the bump (BM h ) and the thickness (XT ) (unit: ⁇ m) of the protective film (X) formed by curing the curable resin film (x) at 23 ° C. The relationship is shown.
  • the thickness (XT ) (unit: ⁇ m) of the protective film (X) formed by curing the curable resin film (x) at 23 ° C. is the bump height (BM) as shown in FIG.
  • the position 50 farthest from the bump forming surface 41a is determined within the region where the protective film (X) formed on the bump forming surface 41a is continuously present. Therefore, for example, the protective film (X) partially present on the top of the bump, and the contact portion between the protective film (X) and the bump, which is removed by the exposure treatment (plasma etching treatment) described later, is a bump forming surface. The position 50 farthest from 41a is not determined.
  • the thickness of the protective film (X) after the retreat due to the exposure treatment must satisfy the above formula (II) (0.2 ⁇ m or more). There is. That is, regardless of the presence or absence of the exposure treatment described later, the thickness of the protective film (X) is naturally determined by the above formula (X) immediately before the step of electrically connecting the semiconductor chip and the wiring board via the ball bumps. II) must be satisfied (0.2 ⁇ m or more).
  • the bump height (BM h ) and the protective film (X) thickness ( XT ) pass, for example, a semiconductor wafer with the protective film (X) in a direction perpendicular to the bump forming surface and through the center of the bump. It can be measured by observing the cross section after cutting with an optical microscope.
  • the protective film forming sheet of the present invention will be described in detail with reference to a method for preparing a curable resin film (x) for forming a protective film (X) satisfying the requirement ( ⁇ 1) and the requirement ( ⁇ 2). do.
  • FIG. 1 shows a configuration example of the protective film forming sheet of the present invention.
  • the protective film-forming sheet of one aspect of the present invention is provided with a curable resin film (x) on one surface of the support sheet (Y) like the protective film-forming sheet 1 shown in FIG.
  • the curable resin film (x) can be transported as a product package, or the curable resin film (x) can be transported in the process.
  • the curable resin film (x) is stably supported and protected when it is used.
  • FIGS. 2 to 4 show structural examples of the protective film forming sheet according to one aspect of the present invention.
  • the support sheet (Y) is the base material 11, and a curable resin is formed on one surface of the base material 11.
  • a film (x) is provided.
  • the protective film forming sheet according to one aspect of the present invention is an adhesive sheet in which a base material 11 and an adhesive layer 21 are laminated, as in the protective film forming sheet 1b shown in FIG. Yes, the pressure-sensitive adhesive layer 21 of the pressure-sensitive adhesive sheet and the curable resin film (x) may be bonded together.
  • the support sheet (Y) includes the base material 11, the intermediate layer 31, and the adhesive layer 21.
  • the pressure-sensitive adhesive sheets are laminated in this order, and the pressure-sensitive adhesive layer 21 of the pressure-sensitive adhesive sheet and the curable resin film (x) may be bonded to each other.
  • the pressure-sensitive adhesive sheet in which the base material 11, the intermediate layer 31, and the pressure-sensitive adhesive layer 21 are laminated in this order can be suitably used as a back grind tape. That is, since the protective film forming sheet 1c shown in FIG.
  • the semiconductor wafer 4 has a back grind tape as the supporting sheet (Y), the curable resin film (x) of the protective film forming sheet 1c and the semiconductor wafer having a plurality of bumps.
  • Suitable for thinning a semiconductor wafer by grinding a surface of the semiconductor wafer opposite to the bump forming surface (hereinafter, also referred to as “back surface of the semiconductor wafer”) after bonding the bump forming surface of the semiconductor wafer. can be used for.
  • the curable resin film (x) is a film for protecting the bump-forming surface of a semiconductor wafer having a plurality of bumps, and forms the protective film (X) by curing by heating or energy ray irradiation. That is, the curable resin film (x) may be a thermosetting resin film (x1) that is cured by heating, or an energy ray-curable resin film (x2) that is cured by energy ray irradiation.
  • an "energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum. Examples thereof include ultraviolet rays, electron beams, and the like, and ultraviolet rays are preferable.
  • the physical characteristics of the curable resin film (x) can be adjusted by adjusting either or both of the types and amounts of the components contained in the curable resin film (x).
  • thermosetting resin film (x1) and the energy ray-curable resin film (x2) will be described.
  • the thermosetting resin film (x1) contains a polymer component (A) and a thermosetting component (B).
  • the thermosetting resin film (x1) is formed from, for example, a thermosetting resin composition (x1-1) containing a polymer component (A) and a thermosetting component (B).
  • the polymer component (A) is a component that can be regarded as being formed by a polymerization reaction of a polymerizable compound.
  • the thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction using heat as a trigger for the reaction.
  • the curing (polymerization) reaction also includes a polycondensation reaction.
  • thermosetting resin composition (x1-1) the content of each component in the total amount of the active component of the thermosetting resin composition (x1-1)
  • thermosetting resin composition (x1-1) the content of each component in the total amount of the active component of the thermosetting resin composition (x1-1)
  • thermosetting resin composition (x1-1) It is synonymous with “content of each component of the thermosetting resin film (x1) formed from”.
  • thermosetting resin film (x1) and the thermosetting resin composition (x1-1) contain the polymer component (A).
  • the polymer component (A) is a polymer compound for imparting film-forming property, flexibility, etc. to the thermosetting resin film (x1).
  • the polymer component (A) one type may be used alone, or two or more types may be used in combination. When two or more kinds of polymer components (A) are used in combination, their combinations and ratios can be arbitrarily selected.
  • polymer component (A) examples include polyvinyl acetal, acrylic resin (resin having (meth) acryloyl group), polyester, urethane resin (resin having urethane bond), acrylic urethane resin, and silicone resin (siloxane).
  • examples thereof include a resin having a bond), a rubber-based resin (a resin having a rubber structure), a phenoxy resin, and a thermosetting polyimide. These can be used alone or in combination of two or more. Among these, one or more selected from polyvinyl acetal and acrylic resin is preferable.
  • polyvinyl acetal and an acrylic resin which are preferable as the polymer component (A), will be described as an example.
  • the polyvinyl acetal used as the polymer component (A) is not particularly limited, and for example, a known polyvinyl acetal can be used.
  • a known polyvinyl acetal among the polyvinyl acetals, for example, polyvinyl formal, polyvinyl butyral and the like can be mentioned, and polyvinyl butyral is more preferable.
  • the polyvinyl butyral having the structural units represented by the following formulas (i-1), (i-2), and (i-3) is a semiconductor wafer having a bump forming surface and a protective film (X). It is preferable from the viewpoint of improving adhesion.
  • the weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5,000 to 200,000, more preferably 8,000 to 100,000, and further preferably 9,000 to 80,000. It is preferably 10,000 to 50,000, and even more preferably 10,000 to 50,000.
  • Mw weight average molecular weight
  • the content ratio p (degree of butyralization) of the structural unit of the butyral group represented by the above formula (i-1) is preferably 40 to 90 mol%, preferably 50 to 90 mol%, based on the total structural unit of the polymer component (A). 85 mol% is more preferable, and 60 to 76 mol% is further preferable.
  • the content ratio q of the structural unit having an acetyl group represented by the above formula (i-2) is preferably 0.1 to 9 mol%, preferably 0.5 to 9 mol%, based on all the structural units of the polymer component (A). 8 mol% is more preferable, and 1 to 7 mol% is further preferable.
  • the content ratio r of the structural unit having a hydroxyl group represented by the above formula (i-3) is preferably 10 to 60 mol%, more preferably 10 to 50 mol%, based on all the structural units of the polymer component (A). It is preferable, and more preferably 20 to 40 mol%.
  • the glass transition temperature (Tg) of polyvinyl acetal is preferably 40 to 80 ° C, more preferably 50 to 70 ° C.
  • Tg of polyvinyl acetal is in such a range, when the thermosetting resin film (x1) is attached to the bump forming surface of the bumped wafer, the protective film (X) on the upper portion of the bump remains. The effect of suppressing the film becomes higher, and the hardness of the protective film formed by thermosetting the thermosetting resin layer can be made sufficient.
  • the glass transition temperature (Tg) of the polymer (resin) is a value measured by the method described in Examples described later.
  • the content ratio of the above three types of structural units constituting polyvinyl butyral may be arbitrarily adjusted according to desired physical properties. Further, polyvinyl butyral may have a structural unit other than the above three types of structural units, but the content of the above three types of structural units is preferably 80 to 100 mol% based on the total amount of polyvinyl butyral. , More preferably 90 to 100 mol%, still more preferably 100 mol%.
  • the acrylic resin examples include known acrylic polymers.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000.
  • Mw weight average molecular weight
  • the thermosetting resin film (x1) can easily follow the uneven surface of the adherend, for example, the adherend and the thermosetting. It is easy to suppress the generation of voids and the like with the resin film (x1).
  • the glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, more preferably -30 to 50 ° C.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the acrylic resin is equal to or higher than the above lower limit, the adhesive force between the protective film (X) and the support sheet (Y) is suppressed, and the peelability of the support sheet (Y) becomes high. improves. Further, when the glass transition temperature (Tg) of the acrylic resin is not more than the above upper limit value, the adhesive force of the thermosetting resin film (x1) and the protective film (X) with the adherend is improved.
  • 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-methylol acrylamide, and the like. Examples thereof include copolymers of two or more kinds of monomers.
  • Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth).
  • N-butyl acrylate isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate Heptyl, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecy
  • acrylic resin for example, in addition to the (meth) acrylic acid ester, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like are copolymerized. It may be made of
  • the monomer constituting the acrylic resin may be one kind alone or two or more kinds. When there are two or more types of monomers constituting the acrylic resin, their combinations and ratios can be arbitrarily selected.
  • the acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group.
  • the functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound without a cross-linking agent (F). ..
  • F cross-linking agent
  • thermoplastic resin other than polyvinyl acetal and acrylic resin
  • thermoplastic resin may be simply abbreviated as "thermoplastic resin”
  • thermoplastic resin the peelability of the protective film (X) from the support sheet (Y) is improved, and the thermosetting resin film (x1) easily follows the uneven surface of the adherend, so that the cover can be covered. The generation of voids and the like may be further suppressed between the adherend and the thermosetting resin film (x1).
  • the weight average molecular weight of the thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.
  • the glass transition temperature (Tg) of the thermoplastic resin is preferably ⁇ 30 to 150 ° C., more preferably ⁇ 20 to 120 ° C.
  • thermoplastic resin examples include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene and the like.
  • thermoplastic resin One type of thermoplastic resin may be used alone, or two or more types may be used in combination. When there are two or more types of thermoplastic resins, their combinations and ratios can be arbitrarily selected.
  • the content of the polymer component (A) is a thermosetting resin composition from the viewpoint of facilitating the acquisition of the protective film (X) satisfying the requirements ( ⁇ 1) and the requirements ( ⁇ 2). Based on the total amount of the active ingredient of (x1-1), it is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, further preferably 15 to 70% by mass, and 15 to 15 to 70% by mass. It is even more preferably 60% by mass, and even more preferably 15 to 50% by mass.
  • polymer component (A) As described above, as the polymer component (A), one or more selected from polyvinyl acetal and acrylic resin is preferable, but requirements ( ⁇ 1) and requirements ( ⁇ 2) are satisfied. From the viewpoint of making it easier to obtain the protective film (X) to be filled, the polymer component (A) is preferably polyvinyl acetal.
  • the polymer component (A) may also correspond to the thermosetting component (B).
  • the thermosetting resin composition (x1-1) contains a component corresponding to both the polymer component (A) and the thermosetting component (B)
  • the thermosetting resin composition The product (x1-1) is considered to contain both the polymer component (A) and the thermosetting component (B).
  • thermosetting component (B) The thermosetting resin film (x1) and the thermosetting resin composition (x1-1) contain a thermosetting component (B).
  • the thermosetting component (B) is a component for curing the thermosetting resin film (x1) to form a hard protective film (X).
  • the thermosetting component (B) one type may be used alone, or two or more types may be used in combination. When there are two or more thermosetting components (B), their combinations and ratios can be arbitrarily selected.
  • thermosetting component (B) examples include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins. Among these, epoxy-based thermosetting resins are preferable.
  • the epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
  • B1 an epoxy resin
  • B2 a thermosetting agent
  • One type of epoxy thermosetting resin may be used alone, or two or more types may be used in combination. When there are two or more types of epoxy thermosetting resins, their combinations and ratios can be arbitrarily selected.
  • Epoxy resin (B1) examples include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, and dicyclopentadiene type epoxy resin. Examples thereof include biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and bifunctional or higher functional epoxy compounds.
  • epoxy resin (B1) an epoxy resin having an unsaturated hydrocarbon group may be used.
  • Epoxy resins having unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins having no unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the thermosetting resin film (x1) is improved.
  • Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of the polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof.
  • Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
  • the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, and a (meth) acryloyl group. ) Examples thereof include an acrylamide group. Of these, the acryloyl group is preferable.
  • the number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30, from the viewpoint of the curability of the thermosetting resin film (x1) and the strength and heat resistance of the protective film (X) after curing. It is preferably 000, more preferably 400 to 10,000, and even more preferably 500 to 3,000.
  • the epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1,000 g / eq, more preferably 300 to 800 g / eq.
  • One type of epoxy resin (B1) may be used alone, or two or more types may be used in combination. When two or more types of epoxy resin (B1) are used in combination, the combination and ratio thereof can be arbitrarily selected.
  • thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
  • thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule.
  • the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is annealed, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, and more preferably a phenolic hydroxyl group or an amino group.
  • examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins. ..
  • examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter, may be abbreviated as "DICY”) and the like.
  • the thermosetting agent (B2) may have an unsaturated hydrocarbon group.
  • examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of the phenol resin is replaced with a group having an unsaturated hydrocarbon group, or an aromatic ring of the phenol resin. , Compounds in which a group having an unsaturated hydrocarbon group is directly bonded, and the like can be mentioned.
  • the unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.
  • thermosetting agent (B2) When a phenolic curing agent is used as the thermosetting agent (B2), the thermosetting agent (B2) has a softening point or a softening point from the viewpoint of facilitating the improvement of the peelability of the protective film (X) from the support sheet (Y). Those having a high glass transition temperature are preferable.
  • the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene phenol resin, and aralkyl phenol resin shall be 300 to 30,000. , More preferably 400 to 10,000, and even more preferably 500 to 3,000.
  • the molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, but is preferably 60 to 500, for example.
  • thermosetting agent (B2) one type may be used alone, or two or more types may be used in combination. When there are two or more types of thermosetting agents (B2), their combinations and ratios can be arbitrarily selected.
  • the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (B1). It is preferably 1 to 200 parts by mass, and more preferably 1 to 200 parts by mass.
  • the content of the thermosetting agent (B2) is at least the above lower limit value, the curing of the thermosetting resin film (x1) becomes easier to proceed.
  • the content of the thermosetting agent (B2) is not more than the above upper limit value, the moisture absorption rate of the thermosetting resin film (x1) is reduced, and the thermosetting resin film (x1) can be used. The reliability of the package is improved.
  • the content of the thermosetting component (B) (the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is that of the polymer component (A).
  • the content is preferably 50 to 1000 parts by mass, more preferably 70 to 800 parts by mass, further preferably 80 to 600 parts by mass, and 90 to 500 parts by mass with respect to 100 parts by mass. It is even more preferable that the amount is 100 to 400 parts by mass.
  • the protective film (X) satisfying the requirement ( ⁇ 1) and the requirement ( ⁇ 2) can be easily obtained.
  • the amount of the thermosetting component (B) increases with respect to the polymer component (A)
  • the tensile elastic modulus E'tends to increase easily.
  • the amount of the thermosetting component (B) is reduced with respect to the polymer component (A)
  • the tensile elastic modulus E'tends to be lowered more easily.
  • the thermosetting resin film (x1) and the thermosetting resin composition (x1-1) may contain a curing accelerator (C).
  • the curing accelerator (C) is a component for adjusting the curing rate of the thermosetting resin composition (x1-1).
  • Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole.
  • 2-Phenyl-4-methylimidazole 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles (one or more hydrogen atoms other than hydrogen atoms) (Imidazole substituted with an organic group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Examples thereof include tetraphenylborone salts such as tetraphenylborate.
  • curing accelerator (C) one type may be used alone, or two or more types may be used in combination. When there are two or more types of curing accelerators (C), their combinations and ratios can be arbitrarily selected.
  • thermosetting resin composition (x1-1) when the curing accelerator (C) is used, the content of the curing accelerator (C) is based on 100 parts by mass of the content of the thermosetting component (B). The amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass.
  • the content of the curing accelerator (C) is at least the above lower limit value, the effect of using the curing accelerator (C) can be more remarkably obtained.
  • the highly polar curing accelerator (C) is a thermosetting resin film (x1) under high temperature and high humidity conditions. ), The effect of suppressing segregation by moving to the adhesion interface side with the adherend is enhanced, and the reliability of the package obtained by using the thermosetting resin film (x1) is further improved.
  • thermosetting resin film (x1) and the thermosetting resin composition (x1-1) may contain a filler (D).
  • a filler (D) By containing the filler (D), it becomes easy to adjust the coefficient of thermal expansion of the protective film (X) obtained by curing the curable resin film (x1) within an appropriate range, and the thermosetting resin film (x1) can be easily adjusted. The reliability of the package obtained by using x1) is further improved. Further, when the thermosetting resin film (x1) contains the filler (D), the hygroscopicity of the protective film (X) can be reduced and 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, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; Single crystal fibers of these inorganic fillers; Glass fibers and the like.
  • the inorganic filler is preferably silica or alumina.
  • filler (D) one type may be used alone, or two or more types may be used in combination. When there are two or more kinds of fillers (D), their combinations and ratios can be arbitrarily selected.
  • the content of the filler (D) is preferably 5 to 80% by mass based on the total amount of the active ingredients of the thermosetting resin composition (x1-1), 7 More preferably, it is in an amount of about 60% by mass.
  • the content of the filler (D) is in such a range, the above-mentioned coefficient of thermal expansion can be easily adjusted.
  • the average particle size of the filler (D) is preferably 5 nm to 1,000 nm, more preferably 5 nm to 500 nm, and even more preferably 10 nm to 300 nm.
  • the above average particle size is obtained by measuring the outer diameter of one particle at several places and obtaining the average value.
  • thermosetting resin film (x1) and the thermosetting resin composition (x1-1) 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 it is easy to improve the adhesiveness and adhesion of the thermosetting resin film (x1) to the adherend.
  • the protective film (X) obtained by curing the thermosetting resin film (x1) by using the coupling agent (E) does not impair the heat resistance and easily improves the water resistance. ..
  • the coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional groups of the polymer component (A), the thermosetting component (B) and the like, and is preferably a silane coupling agent. More preferred.
  • Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-( 3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethyl) Amino) propylmethyldiethoxysilane
  • the coupling agent (E) one type may be used alone, or two or more types may be used in combination. When there are two or more kinds of coupling agents (E), their combinations and ratios can be arbitrarily selected.
  • the content of the coupling agent (E) is the content of the polymer component (A) and the thermosetting component (B).
  • the total content is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass with respect to 100 parts by mass. ..
  • the content of the coupling agent (E) is equal to or higher than the above lower limit, the dispersibility of the filler (D) in the resin is improved and the thermosetting resin film (x1) is adhered to the adherend.
  • the effect of using the coupling agent (E), such as improvement of the property can be obtained more remarkably. Further, when the content of the coupling agent (E) is not more than the above upper limit value, the generation of outgas is further suppressed.
  • the polymer component (A) has a functional group such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, or an isocyanate group that can be bonded to other compounds such as the above-mentioned acrylic resin.
  • the thermosetting resin film (x1) and the thermosetting resin composition (x1-1) contain a cross-linking agent (F) for bonding the functional group with another compound and cross-linking. You may. By cross-linking with the cross-linking agent (F), the initial adhesive force and cohesive force of the thermosetting resin film (x1) can be adjusted.
  • cross-linking agent (F) examples include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (a cross-linking agent having a metal chelate structure), and an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group). And so on.
  • organic polyvalent isocyanate compound examples include an aromatic polyvalent isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively abbreviated as "aromatic polyvalent isocyanate compound and the like”. ); Trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compounds with polyol compounds, etc. Can be mentioned.
  • the "adduct” includes the aromatic polyhydric isocyanate compound, the aliphatic polyhydric isocyanate compound, or the alicyclic polyvalent isocyanate compound, and low amounts of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include a xylylene diisocyanate adduct of trimethylolpropane.
  • organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4, 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane Compounds in which any one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxylates of the polyols such as lysine diis
  • organic polyvalent imine compound examples include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri- ⁇ -aziridinyl propionate, and tetramethylolmethane.
  • examples thereof include -tri- ⁇ -aziridinyl propionate and N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine.
  • the cross-linking agent (F) When an organic multivalent isocyanate compound is used as the cross-linking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A).
  • a hydroxyl group-containing polymer When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction between the cross-linking agent (F) and the polymer component (A) results in a thermosetting resin film (x1). The crosslinked structure can be easily introduced.
  • cross-linking agent (F) one type may be used alone, or two or more types may be used in combination. When there are two or more cross-linking agents (F), their combinations and ratios can be arbitrarily selected.
  • the content of the cross-linking agent (F) is 0 with respect to 100 parts by mass of the content of the polymer component (A). It is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass.
  • the content of the cross-linking agent (F) is at least the lower limit value, the effect of using the cross-linking agent (F) is more remarkable. Further, when the content of the cross-linking agent (F) is not more than the upper limit value, the excessive use of the cross-linking agent (F) is suppressed.
  • thermosetting resin film (x1) and the thermosetting resin composition (x1-1) may contain an energy ray-curable resin (G). Since the thermosetting resin film (x1) contains the energy ray-curable resin (G), the characteristics can be changed by irradiation with energy rays.
  • the energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
  • the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth) acryloyl group are preferable.
  • acrylate-based compound examples include trimethylolpropantri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (meth).
  • the weight average molecular weight of the energy ray-curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.
  • the energy ray-curable compound used for polymerization one type may be used alone, or two or more types may be used in combination. When there are two or more energy ray-curable compounds used for polymerization, their combinations and ratios can be arbitrarily selected.
  • the content of the energy ray-curable resin (G) is 1 to 95% by mass based on the total amount of the active ingredients of the thermosetting resin composition (x1-1). It is preferably 5 to 90% by mass, more preferably 10 to 85% by mass.
  • thermosetting resin film (x1) and the thermosetting resin composition (x1-1) contain the energy ray-curable resin (G), the polymerization reaction of the energy ray-curable resin (G) is efficiently promoted. Therefore, the thermosetting resin film (x1) and the thermosetting resin composition (x1-1) may contain a photopolymerization initiator (H).
  • 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.
  • photopolymerization initiator (H) one type may be used alone, or two or more types may be used in combination. When there are two or more photopolymerization initiators (H), their combinations and ratios can be arbitrarily selected.
  • the content of the photopolymerization initiator (H) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable resin (G). It is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass.
  • thermosetting resin film (x1) and the thermosetting resin composition (x1-1) may contain the 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 may be arbitrarily selected depending on the intended purpose, and is not particularly limited.
  • Preferred general-purpose additives (I) include, for example, plasticizers, antistatic agents, antioxidants, colorants (dye, pigment), gettering agents and the like.
  • the general-purpose additive (I) one type may be used alone, or two or more types may be used in combination. When there are two or more general-purpose additives (I), their combinations and ratios can be arbitrarily selected.
  • the content of the general-purpose additive (I) is not particularly limited, and may be appropriately selected depending on the intended purpose.
  • the thermosetting resin composition (x1-1) preferably further contains a solvent.
  • the thermosetting resin composition (x1-1) containing a solvent has good handleability.
  • the solvent is not particularly limited, but preferred ones are, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; Examples thereof include 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 one type may be used alone, or two or more types may be used in combination. When there are two or more solvents, their combinations and ratios can be arbitrarily selected.
  • the solvent is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the thermosetting resin composition (x1-1) can be mixed more uniformly.
  • thermosetting resin composition (x1-1) is prepared by blending each component for constituting the thermosetting resin composition (x1-1).
  • the order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
  • the solvent may be mixed with any compounding component other than this solvent and the compounding component may be diluted in advance, or any compounding component other than the solvent may be used in advance. You may use it by mixing the solvent with these compounding components without diluting.
  • the method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
  • the temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
  • the energy ray-curable resin film (x2) contains the energy ray-curable component (a).
  • the energy ray-curable resin film (x2) is formed from, for example, an energy ray-curable resin composition (x2-1) containing an energy ray-curable component (a).
  • the energy ray-curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably uncured and has adhesiveness.
  • “energy ray-curable resin composition (x2)" It is synonymous with "content of each component of the energy ray-curable resin film (x2) formed from -1)".
  • the energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming property, flexibility, and the like to the energy ray-curable resin film (x2).
  • Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and an energy ray-curable group. Examples thereof include a compound (a2) having a molecular weight of 100 to 80,000.
  • the polymer (a1) may be at least partially crosslinked by a crosslinking agent or may not be crosslinked.
  • Polymer (a1) examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer having a functional group capable of reacting with a group of another compound.
  • An acrylic resin (a1) obtained by polymerizing (a11), a group that reacts with the functional group, and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond. -1) can be mentioned.
  • the functional group capable of reacting with the group of another compound examples include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom. Group), an epoxy group, and the like.
  • the functional group is preferably a group other than a carboxy group.
  • the functional group is preferably a hydroxyl group.
  • the acrylic polymer (a11) having a functional group examples include those obtained by copolymerizing an acrylic monomer having a functional group and an acrylic monomer having no functional group, and other than these monomers. Further, a monomer other than the acrylic monomer (non-acrylic monomer) may be copolymerized. Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer.
  • acrylic monomer having a functional group examples include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic.
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acid, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturateds such as vinyl alcohols and allyl alcohols.
  • Alcohol (unsaturated alcohol having no (meth) acrylic skeleton) and the like can be mentioned.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, and citraconic acid.
  • ethylenically unsaturated dicarboxylic acid dicarboxylic acid having an ethylenically unsaturated bond
  • anhydride of the ethylenically unsaturated dicarboxylic acid (meth) acrylic acid carboxyalkyl ester such as 2-carboxyethyl methacrylate. ..
  • acrylic monomer having a functional group a hydroxyl group-containing monomer or a carboxy group-containing monomer is preferable, and a hydroxyl group-containing monomer is more preferable.
  • acrylic monomer having a functional group constituting the acrylic polymer (a11) one type may be used alone, or two or more types may be used in combination. When there are two or more kinds of acrylic monomers having a functional group constituting the acrylic polymer (a11), their combinations and ratios can be arbitrarily selected.
  • acrylic monomer having no functional group examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
  • acrylic monomer having no functional group examples include an alkoxyalkyl group such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
  • (Meta) acrylic acid ester (meth) acrylic acid ester having an aromatic group, including (meth) acrylic acid aryl ester such as (meth) phenyl acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; Examples thereof include (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as (meth) acrylic acid N, N-dimethylaminoethyl and (meth) acrylic acid N, N-dimethylaminopropyl.
  • acrylic monomer having no functional group constituting the acrylic polymer (a11) one type may be used alone, or two or more types may be used in combination.
  • acrylic polymer (a11) one type may be used alone, or two or more types may be used in combination.
  • non-functional acrylic monomers constituting the acrylic polymer (a11) their combinations and ratios can be arbitrarily selected.
  • non-acrylic monomer examples include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.
  • non-acrylic monomer constituting the acrylic polymer (a11) one type may be used alone, or two or more types may be used in combination.
  • the combination and ratio thereof can be arbitrarily selected.
  • the ratio (content) of the amount of the structural unit derived from the acrylic monomer having a functional group to the total mass of the constituent units constituting the polymer is 0.1 to 50% by mass. It is preferably 1 to 40% by mass, more preferably 3 to 30% by mass.
  • the content of the group can be easily adjusted to a preferable range for the degree of curing of the protective film (X).
  • acrylic polymer (a11) constituting the acrylic resin (a1-1) one type may be used alone, or two or more types may be used in combination. When there are two or more kinds of acrylic polymers (a11) constituting the acrylic resin (a1-1), their combinations and ratios can be arbitrarily selected.
  • the content of the acrylic resin (a1-1) is preferably 1 to 60% by mass, preferably 3 to 50% by mass, based on the total amount of the active ingredients of the energy ray-curable resin composition (x2-1). More preferably, it is more preferably 5 to 40% by mass.
  • the energy ray-curable compound (a12) is one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11).
  • the one having an isocyanate group is preferable, and the one having an isocyanate group as the group is more preferable.
  • the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
  • the energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably 1 to 2 energy ray-curable groups.
  • Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl) ethyl.
  • Examples thereof include acryloyl monoisocyanate compounds.
  • the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
  • the energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be used alone or in combination of two or more. When there are two or more types of energy ray-curable compounds (a12) constituting the acrylic resin (a1-1), their combinations and ratios can be arbitrarily selected.
  • the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is , 20 to 120 mol%, more preferably 35 to 100 mol%, and even more preferably 50 to 100 mol%.
  • the content ratio is in such a range, the adhesive force of the protective film (X) after curing becomes larger.
  • the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule)
  • the upper limit of the content ratio is 100 mol%, but the energy.
  • the linear curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule)
  • the upper limit of the content ratio may exceed 100 mol%.
  • the weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000.
  • the polymer (a1) is any of the above-mentioned monomers described as constituting the acrylic polymer (a11).
  • a monomer having a group that reacts with the cross-linking agent may be polymerized and cross-linked at the group that reacts with the cross-linking agent, or is derived from the energy ray-curable compound (a12).
  • the group that reacts with the functional group may be crosslinked.
  • polymer (a1) one type may be used alone, or two or more types may be used in combination. When there are two or more kinds of polymers (a1), their combinations and ratios can be arbitrarily selected.
  • Compound (a2) Examples of the energy ray-curable group contained in the compound (a2) having an energy ray-curable group and having a weight average molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred ones. , (Meta) acryloyl group, vinyl group and the like.
  • the compound (a2) is not particularly limited as long as it satisfies the above conditions, but has a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, and an energy ray-curable group.
  • Examples include phenol resin.
  • examples of the low molecular weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and acrylate compounds having a (meth) acryloyl group are preferable.
  • examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4-.
  • Bifunctional (meth) acrylate tris (2- (meth) acryloxyethyl) isocyanurate, ⁇ -caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, penta Elythritol tri (meth) acrylate, trimethylolpropantri (meth) acrylate, ditrimethylolpropantetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) Polyfunctional (meth) acrylates such as acrylates and dipentaerythritol hexa (meth) acrylates; polyfunctional (meth) acrylate oligomers such as urethane (meth
  • the weight average molecular weight of compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.
  • the compound (a2) may be used alone or in combination of two or more.
  • the combination and the ratio thereof can be arbitrarily selected.
  • the energy ray-curable resin composition (x2-1) and the energy ray-curable resin film (x2) contain the compound (a2) as the energy ray-curable component (a), they further have an energy ray-curable group. It is preferable that the polymer (b) that does not contain the polymer (b) is also contained.
  • the polymer (b) having no energy ray-curable group may have at least a part thereof crosslinked by a crosslinking agent or may not be crosslinked.
  • polymer (b) having no energy ray-curable group examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.
  • the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").
  • the acrylic polymer (b-1) may be a known one, and may be, for example, a homopolymer of one kind of acrylic monomer or a copolymer of two or more kinds of acrylic monomers. May be good. Further, the acrylic polymer (b-1) is a copolymer of one or more kinds of acrylic monomers and one or more kinds of monomers other than the acrylic monomers (non-acrylic monomers). It may be.
  • acrylic monomer constituting the acrylic polymer (b-1) examples include (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, and (meth) acrylic acid ester containing a glycidyl group. Examples thereof include a hydroxyl group-containing (meth) acrylic acid ester and a substituted amino group-containing (meth) acrylic acid ester.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n-butyl (meth) acrylic acid.
  • Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl ester such as (meth) acrylic acid isobornyl and (meth) acrylic acid dicyclopentanyl; and (meth) acrylic acid benzyl and the like.
  • (Meta) Acrylic acid cycloalkenyloxyalkyl such as (meth) Acrylic acid dicyclopentenyloxyethyl ester Esters and the like can be mentioned.
  • Examples of the glycidyl group-containing (meth) acrylic acid ester include glycidyl (meth) acrylic acid.
  • Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Examples thereof include propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylic acid.
  • non-acrylic monomer constituting the acrylic polymer (b-1) examples include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.
  • Examples of the polymer (b) having no energy ray-curable group, which is at least partially crosslinked by a cross-linking agent include those in which the reactive functional group in the polymer (b) has reacted with the cross-linking agent. ..
  • the reactive functional group may be appropriately selected depending on the type of the cross-linking agent and the like, and is not particularly limited.
  • examples of the reactive functional group include a hydroxyl group, a carboxy group, an amino group and the like, and among these, a hydroxyl group having a high reactivity with an isocyanate group is preferable. ..
  • the reactive functional group include a carboxy group, an amino group, an amide group and the like, and among these, a carboxy group having high reactivity with an epoxy group is used. preferable. However, in terms of preventing corrosion of circuits of semiconductor wafers and semiconductor chips, the reactive functional group is preferably a group other than a carboxy group.
  • Examples of the polymer (b) having a reactive functional group and not having an energy ray-curable group include those obtained by polymerizing at least a monomer having a reactive functional group.
  • the acrylic polymer (b-1) if one or both of the acrylic monomer and the non-acrylic monomer listed as the monomers constituting the polymer is used, those having a reactive functional group may be used. good.
  • the polymer (b) having a hydroxyl group as a reactive functional group for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester can be mentioned, and in addition to this, the above-mentioned polymer (b) mentioned above can be mentioned.
  • examples thereof include acrylic monomers and non-acrylic monomers obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the reactive functional groups.
  • the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total mass of the constituent units constituting the polymer (b) is 1 to 20. It is preferably by mass, more preferably 2 to 10% by mass. When the ratio is in such a range, the degree of cross-linking in the polymer (b) becomes a more preferable range.
  • the weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is 10,000 to higher because the film-forming property of the energy ray-curable resin composition (x2-1) becomes better. It is preferably 2,000,000, more preferably 100,000 to 1,500,000.
  • polymer (b) having no energy ray-curable group one type may be used alone, or two or more types may be used in combination. When there are two or more polymers (b) having no energy ray-curable group, their combinations and ratios can be arbitrarily selected.
  • Examples of the energy ray-curable resin composition (x2-1) include those containing either one or both of the polymer (a1) and the compound (a2).
  • the energy ray-curable resin composition (x2-1) contains the compound (a2)
  • the energy ray-curable resin composition (x2-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. You may.
  • the energy ray-curable resin composition (x2-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group
  • the compound (a2) is contained.
  • the amount is preferably 10 to 400 parts by mass, preferably 30 to 350 parts by mass, based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. More preferably.
  • the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group is 5 to 5 based on the total amount of the active ingredients of the energy ray-curable resin composition (x2-1). It is preferably 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass. When the content of the energy ray-curable component is in such a range, the energy ray-curable property of the energy ray-curable resin film (x2) becomes better.
  • the energy ray-curable resin composition (x2-1) contains a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a cross-linking agent, and a general-purpose additive, depending on the purpose. It may contain one kind or two or more kinds selected from the group consisting of.
  • the energy ray-curable resin film (x2) formed by using the energy ray-curable resin composition (x2-1) containing the energy ray-curable component and the thermosetting component is adhered by heating.
  • the adhesive force to the body is improved, and the strength of the protective film (X) formed from the energy ray-curable resin film (x2) is also improved.
  • thermosetting component, photopolymerization initiator, filler, coupling agent, cross-linking agent, and general-purpose additive in the energy ray-curable resin composition (x2-1) are energy ray-curable resin compositions (respectively). Same as the thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), cross-linking agent (F), and general-purpose additive (I) in x2-1). Can be mentioned.
  • thermosetting component In the energy ray-curable resin composition (x2-1), one kind of thermosetting component, photopolymerization initiator, filler, coupling agent, cross-linking agent and general-purpose additive may be used alone. However, two or more types may be used in combination. When two or more types are used in combination, their combinations and ratios can be arbitrarily selected.
  • the contents of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the cross-linking agent, and the general-purpose additive in the energy ray-curable resin composition (x2-1) can be appropriately adjusted according to the purpose. Well, there is no particular limitation.
  • the energy ray-curable resin composition (x2-1) is preferably further containing a solvent because its handleability is improved by dilution.
  • the solvent contained in the energy ray-curable resin composition (x2-1) include the same solvents as those in the thermosetting resin composition (x1-1).
  • seeds may be used alone, or two or more kinds may be used in combination. When two or more types are used in combination, their combinations and ratios can be arbitrarily selected.
  • thermosetting resin film (x1) in addition to the above energy ray-curable component, as in the case of the thermosetting resin film (x1) described above, a component other than the curable component, that is, An appropriate amount of the curing accelerator (C), the filler (D), the coupling agent (E) and the like can be contained.
  • the energy ray-curable resin composition (x2-1) can be obtained by blending each component for constituting the energy ray-curable resin composition (x2-1).
  • the order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
  • the solvent may be mixed with any compounding component other than this solvent and the compounding component may be diluted in advance, or any compounding component other than the solvent may be used in advance. You may use it by mixing the solvent with these compounding components without diluting.
  • the method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
  • the temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
  • Support sheet (Y) functions as a support for supporting the curable resin film (x).
  • the support sheet (Y) may be composed of only the base material 11, or may be a laminate of the base material 11 and the pressure-sensitive adhesive layer 21 as shown in FIG. , As shown in FIG. 4, the base material 11, the intermediate layer 31, and the pressure-sensitive adhesive layer 21 may be laminated in this order. A laminate in which the base material 11, the intermediate layer 31, and the pressure-sensitive adhesive layer 21 are laminated in this order is suitable for use as a back grind tape.
  • the base material of the support sheet (Y), the adhesive layer that the support sheet (Y) may have, and the intermediate layer will be described.
  • the base material is in the form of a sheet or a film, and examples of the constituent material thereof include the following various resins.
  • the resin constituting the base material include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin, and the like.
  • Polyethylenes other than polyethylene ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-norbornene copolymers and other ethylene-based copolymers.
  • Polymer obtained by using ethylene as a monomer Vinyl chloride-based resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer); Polystyrene; Polycycloolefin; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, polymers such as all aromatic polyesters in which all constituent units have aromatic cyclic groups; two or more Examples thereof include the polymer of the polyester; poly (meth) acrylic acid ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; polyether ketone and the like.
  • the resin constituting the base material for example, a polymer alloy such as a mixture of the polyester and other resins can be mentioned.
  • the polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.
  • the resin constituting the base material for example, a crosslinked resin in which one or more of the resins exemplified so far is crosslinked; one or two of the resins exemplified so far. Modified resins such as ionomer using the above can also be mentioned.
  • the resin constituting the base material one type may be used alone, or two or more types may be used in combination.
  • the combination and ratio thereof can be arbitrarily selected.
  • the base material may be only one layer (single layer) or may have two or more layers.
  • the base material has a plurality of layers, 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.
  • the thickness of the base material is preferably 5 ⁇ m to 1,000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, further preferably 15 ⁇ m to 300 ⁇ m, and even more preferably 20 ⁇ m to 150 ⁇ m.
  • the "thickness of the base material” means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.
  • the base material has a high thickness accuracy, that is, a material in which the variation in thickness is suppressed regardless of the part.
  • a high thickness accuracy that is, a material in which the variation in thickness is suppressed regardless of the part.
  • materials having high thickness accuracy that can be used to form a base material include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers. And so on.
  • the base material contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). You may.
  • the base material may be transparent, opaque, colored depending on the purpose, or another layer may be vapor-deposited.
  • the curable resin film (x) is an energy ray-curable resin film (x2)
  • the pressure-sensitive adhesive layer is an energy-curable pressure-sensitive adhesive layer
  • the base material transmits energy rays. It is preferable to have.
  • the base material can be produced by a known method.
  • a base material containing a resin can be produced by molding a resin composition containing the resin.
  • the pressure-sensitive adhesive layer is in the form of a sheet or a film and contains a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive include an acrylic resin (a pressure-sensitive adhesive made of a resin having a (meth) acryloyl group), a urethane-based resin (a pressure-sensitive adhesive made of a resin having a urethane bond), and a rubber-based resin (a resin having a rubber structure).
  • an acrylic resin is preferable.
  • the "adhesive resin” is a concept including both a resin having adhesiveness and a resin having adhesiveness.
  • a resin having adhesiveness for example, not only the resin itself has adhesiveness but also the resin itself has adhesiveness. It also includes a resin that exhibits adhesiveness when used in combination with other components such as additives, and a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.
  • the adhesive layer may be only one layer (single layer), or may be two or more layers.
  • the pressure-sensitive adhesive layer is a plurality of layers, 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.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m to 1,000 ⁇ m, more preferably 5 ⁇ m to 500 ⁇ m, and even more preferably 10 ⁇ m to 100 ⁇ m.
  • the "thickness of the pressure-sensitive adhesive layer” means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the sum of all the layers constituting the pressure-sensitive adhesive layer. Means the thickness of.
  • the pressure-sensitive adhesive layer may be formed by using an energy ray-curable pressure-sensitive adhesive or may be formed by using a non-energy ray-curable pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer formed by using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
  • the intermediate layer is in the form of a sheet or a film, and the constituent material thereof may be appropriately selected depending on the intended purpose and is not particularly limited.
  • the intermediate layer is preferable.
  • the constituent material include urethane (meth) acrylate and the like from the viewpoint of improving the unevenness followability, improving the bump penetration property, and further improving the stickability of the intermediate layer.
  • the intermediate layer may be only one layer (single layer), or may be two or more layers.
  • the intermediate layer is a plurality of layers, 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.
  • the thickness of the intermediate layer can be appropriately adjusted according to the height of the bumps on the surface of the semiconductor to be protected, but it may be 50 ⁇ m to 600 ⁇ m because the influence of the bumps having a relatively high height can be easily absorbed. It is preferably 70 ⁇ m to 500 ⁇ m, more preferably 80 ⁇ m to 400 ⁇ m.
  • the "thickness of the intermediate layer” means the thickness of the entire intermediate layer, and for example, the thickness of the intermediate layer composed of a plurality of layers is the total thickness of all the layers constituting the intermediate layer. means.
  • the protective film forming sheet can be produced by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. For example, when a pressure-sensitive adhesive layer or an intermediate layer is laminated on a base material when manufacturing a support sheet, a pressure-sensitive adhesive composition or a composition for forming an intermediate layer is applied on the base material, and if necessary.
  • the pressure-sensitive adhesive layer or the intermediate layer can be laminated by drying and irradiating with energy rays.
  • the coating method include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a roll knife coating method, a blade coating method, a die coating method, and a gravure coating method.
  • the pressure-sensitive adhesive composition may be applied on the intermediate layer to directly form the pressure-sensitive adhesive layer. It is possible.
  • the composition is further applied on the layer formed from the composition to form a new layer. Is possible to form.
  • the layer to be laminated afterwards is formed in advance on another release film using the composition, and the side of the formed layer that is in contact with the release film is It is preferable to form a laminated structure of two continuous layers by laminating the exposed surface on the opposite side with the exposed surface of the remaining layers that have already been formed. At this time, it is preferable that the composition is applied to the peeled surface of the peeling film. The release film may be removed if necessary after the laminated structure is formed.
  • the method for manufacturing a semiconductor wafer with a protective film of the present invention will be described in detail with respect to the semiconductor wafer to be applied.
  • FIG. 5 shows an example of a semiconductor wafer having a bump forming surface provided with a plurality of bumps, which is used in the method for manufacturing a semiconductor wafer with a protective film of the present invention.
  • the semiconductor wafer 40 provided with bumps includes a plurality of bump BMs on the bump forming surface (circuit surface) 41a of the semiconductor wafer 41.
  • the "semiconductor wafer having bumps” is also referred to as a "wafer with bumps”.
  • the “semiconductor wafer” is also simply referred to as a "wafer”.
  • the wafer 41 has circuits such as wiring, capacitors, diodes, and transistors formed on the surface thereof, for example.
  • the material of the wafer is not particularly limited, and examples thereof include silicon wafers, silicon carbide wafers, compound semiconductor wafers, sapphire wafers, and glass wafers.
  • the size of the wafer 41 is not particularly limited, but is usually 8 inches (diameter 200 mm) or more, preferably 12 inches (diameter 300 mm) or more from the viewpoint of improving batch processing efficiency.
  • the shape of the wafer is not limited to a circle, and may be a square shape such as a square or a rectangle. In the case of a square wafer, the size of the wafer 41 is preferably such that the length of the longest side is equal to or larger than the above size (diameter) from the viewpoint of increasing batch processing efficiency.
  • the thickness of the wafer 41 is not particularly limited, but is preferably 100 ⁇ m to 1,000 ⁇ m, more preferably 200 ⁇ m or more, from the viewpoint of facilitating the suppression of warpage of the wafer 41 due to curing of the curable resin film (x). It is 900 ⁇ m, more preferably 300 ⁇ m to 800 ⁇ m.
  • the shape of the bump BM is not particularly limited, and may be any shape as long as it can be brought into contact with and fixed to an electrode or the like on a substrate for mounting the chip.
  • the bump BM has a ball shape, but the bump BM may be a spheroid.
  • the spheroid may be, for example, a spheroid stretched in the direction perpendicular to the bump forming surface 41a of the wafer 41, or may be pulled in the horizontal direction with respect to the bump forming surface 41a of the wafer 41. It may be a stretched spheroid.
  • the bump BM may have a pillar shape as shown in FIG. Examples of the material of the bump BM include solder.
  • a semiconductor wafer having narrow pitched bumps defined by the requirements described below is applied. That is, in the present invention, by forming the protective film (X) on the bump forming surface of the semiconductor wafer having the narrow pitched bumps by using the protective film forming sheet, the narrowed pitched bumps can be crushed. Deformation is suppressed and short circuits between bumps are prevented.
  • the semiconductor wafer to which the present invention is applied is a semiconductor having narrow pitched bumps, which may be short-circuited due to crushing or deformation of the bumps when the protective film (X) is not formed. It is a wafer.
  • the semiconductor wafer described below is a semiconductor wafer having narrow pitched bumps, which may cause a short circuit due to crushing or deformation of the bumps when the protective film (X) is not formed.
  • the protective film forming sheet of the present invention is used to form the protective film (X) on the bump forming surface of the semiconductor wafer satisfying the following requirements ( ⁇ 1) to ( ⁇ 2). Further, the method for manufacturing a semiconductor wafer with a protective film of the present invention is carried out using semiconductor wafers that satisfy the following requirements ( ⁇ 1) to ( ⁇ 2).
  • -Requirement ( ⁇ 1) The width (BM w ) (unit: ⁇ m) of the bump is 20 ⁇ m to 350 ⁇ m.
  • the above requirements ( ⁇ 1) to ( ⁇ 2) are indexes indicating that the wafer is a semiconductor wafer having narrow pitched bumps. That is, it is an index showing that a short circuit due to crushing or deformation of the bump is likely to occur.
  • the bump pitch (BM P ) is the shortest distance between two bumps. In Figure 7, the shortest distance of the bump BM_a and bumps BM_b is P 1.
  • the shortest distance between bump BM_b and bump BM_c is P 2 .
  • Bump width (BM w) is the straight line P 1 connecting the bumps BM_a and bumps BM_b, the contact b 1 between the bumps BM_b, linear P 2 connecting the bump BM_b and the bump BM_c, contact b of the bump BM_b It is the length of a straight line b 1- b 2 connecting 2 and 2.
  • the bump pitch (BM P ) (unit: ⁇ m) and the bump width (BM w ) (unit: ⁇ m) can be measured, for example, by observation with an optical microscope based on the above definitions.
  • the wafer to which the present invention is applied is a wafer that satisfies the above requirements ( ⁇ 1) to ( ⁇ 2) between at least one of the plurality of bumps existing on the wafer.
  • the bump width (BM w ) (unit: ⁇ m) defined by the requirement ( ⁇ 1) is 20 ⁇ m to 350 ⁇ m. That is, according to the present invention, it is also possible to target a wafer having a plurality of bumps having a small bump width (BM w ) of 20 ⁇ m or more and less than 150 ⁇ m (particularly, 20 ⁇ m to 100 ⁇ m). In other words, a wafer having a narrow pitch and having a plurality of minute bumps can be targeted. Further, it is also possible to target a wafer having a plurality of bumps having a large bump width (BM w) of 150 ⁇ m to 350 ⁇ m.
  • BM w large bump width
  • Wafers having a plurality of bumps having a narrow pitch and a large width are particularly prone to short circuits between bumps, but according to the present invention, short circuits between bumps in such a wafer can be suppressed.
  • the value of [(BM P ) / (BM w )] specified in the requirement ( ⁇ 2) is one of the indexes indicating the ease of short-circuiting between bumps, and this value is 0.9. It may be less than or equal to or less than or equal to 0.8.
  • the wafer may further satisfy the following requirement ( ⁇ 3a) or the following requirement ( ⁇ 3b).
  • -Requirement ( ⁇ 3a) The height of the bump (BM h ) and the width of the bump (BM w ) satisfy the following formula (IIIa) 0.2 ⁇ [(BM h ) / (BM w )] ⁇ 1.0 ...
  • the above requirement ( ⁇ 3a) is an index indicating that the bump is a ball bump, and the closer the value of [(BM h ) / (BM w )] is to 1.0, the closer to a spherical shape, 0.2.
  • a semiconductor wafer having such ball bumps is individualized into a semiconductor chip, and in the process of electrically connecting the semiconductor chip and the wiring substrate via the ball bumps, the ball bumps are crushed in the lateral direction. The problem arises that the ball bumps come into contact with each other and cause a short circuit.
  • the above requirement ( ⁇ 3b) is an index indicating that the bump is a pillar bump, and the closer the value of [(BM h ) / (BM w )] is to 5.0, the higher the aspect ratio of the pillar bump, which is 0. The closer it is to .5, the lower the aspect ratio of the pillar bumps.
  • a semiconductor wafer having such a pillar bump is separated into a semiconductor chip, and in a process of electrically connecting the semiconductor chip and a wiring board via a ball bump, the pillar bump is deformed and bent, and the pillar bump is bent. There is a problem that they come into contact with each other and cause a short circuit. In addition, there is a problem that the pillar bump is deformed and bent, resulting in poor connection.
  • the pillar bumps are gradually deformed by the weight of the semiconductor package. In some cases, it may lead to a short circuit. According to the present invention, a short circuit due to contact between pillar bumps can be suppressed. In addition, poor connection that may be caused by deformation of the pillar bumps can be suppressed.
  • the bump height (BM h ) is a straight line connecting the contact point of the bump forming surface with the bump and the part of the bump farthest from the bump forming surface when focusing on one bump. Means the distance of. Specifically, the bump height (BM h ) may be a value specified by the following requirement ( ⁇ 4). -Requirement ( ⁇ 4):
  • the bump height (BM h ) is 15 ⁇ m to 300 ⁇ m. That is, in one aspect of the present invention, the bump height (BM h ) is low, 20 ⁇ m or more and less than 150 ⁇ m (particularly, 20 ⁇ m to 20 ⁇ m). Wafers having a plurality of bumps of 100 ⁇ m) can also be targeted.
  • BM h bump height
  • the bump height (BM h ) can be measured, for example, by observing a cross section of a bumped semiconductor wafer in a direction perpendicular to the bump forming surface and passing through the center of the bump with an optical microscope. can.
  • Step (S2) The outline of the step (S2) is shown in FIG.
  • the protective film forming sheet 1 of the present invention described above is attached to the bump forming surface 41a of the semiconductor wafer 41 while pressing the curable resin film (x) as the attaching surface.
  • the bump forming surface 41a of the semiconductor wafer 41 is covered with the curable resin film (x), and the curable resin film (x) is also filled between the plurality of bumps BM.
  • the pressing force when the protective film forming sheet 1 is attached to the bump forming surface 41a of the semiconductor wafer 41 is from the viewpoint of satisfactorily filling the curable resin film (x) between the plurality of bump BMs. It is preferably 1 kPa to 200 kPa, more preferably 5 kPa to 150 kPa, and even more preferably 10 kPa to 100 kPa.
  • the pressing force when the protective film forming sheet 1 is attached to the bump forming surface 41a of the semiconductor wafer 41 may be appropriately changed from the initial stage to the final stage of the attachment. For example, from the viewpoint of better filling the curable resin film (x) between the plurality of bumps BM, it is preferable to lower the pressing force at the initial stage of application and gradually increase the pressing force.
  • the curable resin film (x) is a thermosetting resin film (x1)
  • a plurality of bump BMs From the viewpoint of more satisfactorily filling the curable resin film (x) between the two, it is preferable to perform heating.
  • the thermosetting resin film (x1) is temporarily increased in fluidity by heating, and is cured by continuing heating. Therefore, by heating within the range in which the fluidity of the thermosetting resin film (x1) is improved, the thermosetting resin film (x1) can be easily distributed among the plurality of bump BMs, and the plurality of bump BMs can be easily distributed.
  • thermosetting resin film (x1) in between is further improved.
  • the specific heating temperature (sticking temperature) is preferably 50 ° C. to 150 ° C., more preferably 60 ° C. to 130 ° C., and even more preferably 70 ° C. to 110 ° C.
  • the heat treatment performed on the thermosetting resin film (x1) is not included in the curing treatment of the thermosetting resin film (x1).
  • the protective film forming sheet 1 when attached to the bump forming surface 41a of the semiconductor wafer 41, it may be performed in a reduced pressure environment. As a result, a negative pressure is generated between the plurality of bump BMs, and the curable resin film (x) is easily distributed between the plurality of bumps BMs. As a result, the filling property of the curable resin film (x) between the plurality of bumps BM is more likely to be improved.
  • the specific pressure in the reduced pressure environment is preferably 0.001 kPa to 50 kPa, more preferably 0.01 kPa to 5 kPa, and even more preferably 0.05 kPa to 1 kPa.
  • the step (S3) is carried out. Specifically, as shown in FIG. 9, the curable resin film (x) is cured to obtain a semiconductor wafer with a protective film.
  • the protective film (X) formed by curing the curable resin film (x) becomes stronger than the curable resin film (x) at room temperature (23 ° C.). Therefore, by forming the protective film (X), the bump neck is well protected.
  • the protective film forming sheet satisfying the above requirements ( ⁇ 1) to ( ⁇ 3) is used, as described above, the pitch is narrowed so that a short circuit may occur due to crushing or deformation of the bump. For a semiconductor wafer having bumps, it is possible to suppress crushing and deformation of the bumps, and it is possible to avoid a short circuit due to contact between the bumps.
  • the curable resin film (x) can be cured by either thermosetting or curing by irradiation with energy rays, depending on the type of the curable component contained in the curable resin film (x).
  • the curing temperature is preferably 90 ° C. to 200 ° C.
  • the curing time is preferably 1 hour to 3 hours.
  • the conditions for curing by energy ray irradiation are appropriately set depending on the type of energy ray to be used.
  • the illuminance is preferably 170 mw / cm 2 to 250 mw / cm 2
  • the amount of light is preferably is 300mJ / cm 2 ⁇ 3000mJ / cm 2.
  • the curable resin film (x) is preferably a thermosetting resin film (x1). That is, when the curable resin film (x) is a thermosetting resin film (x1), the thermosetting resin film (x1) is temporarily increased in fluidity by heating, and is cured by continuing heating. do. By utilizing this phenomenon, when the fluidity of the thermosetting resin film (x1) is increased, air bubbles that may enter when filling between a plurality of bumps BM with the thermosetting resin film (x1). Etc.
  • the curable resin film (x) is preferably an energy ray-curable resin film (x1).
  • the support sheet (Y) is peeled off before the curable resin film (x) is cured, and the curable resin film (x) is cured to form a protective film (X), whereby a semiconductor with a protective film is formed.
  • a wafer is obtained.
  • the present invention is not limited to such an embodiment, and a semiconductor with a protective film is formed by curing the curable resin film (x) to form a protective film (X) and then peeling off the support sheet (Y). A wafer may be obtained.
  • the surface of the semiconductor wafer 41 opposite to the bump forming surface 41a that is, the back surface of the semiconductor wafer 41
  • the back grind treatment may be performed before the curing of the curable resin film (x), or may be performed after the curing of the curable resin film (x). Further, when the back grind treatment is performed, the support sheet (Y) is preferably a back grind tape from the viewpoint of satisfactorily performing the back grind treatment.
  • the protective film (X) covering the top of the bump or the protective film (X) adhering to a part of the top of the bump is removed to expose the top of the bump.
  • the exposure treatment for exposing the top of the bump include an etching treatment such as a wet etching treatment and a dry etching treatment.
  • examples of the dry etching process include a plasma etching process and the like.
  • the method for manufacturing a semiconductor chip with a protective film of the present invention includes the following steps (T1) to (T2). -Step (T1): A step of carrying out the method for manufacturing a semiconductor wafer with a protective film of the present invention to obtain a semiconductor wafer with a protective film-Step (T2): A step of individualizing the semiconductor wafer with a protective film.
  • Step (T1) the method for manufacturing a semiconductor wafer with a protective film of the present invention described above is carried out to obtain a semiconductor wafer with a protective film.
  • the semiconductor wafer with a protective film obtained in the step (T1) is fragmented.
  • the method of individualization is not particularly limited, and a known individualization method can be appropriately adopted. Specific examples thereof include laser dicing, blade dicing, stealth dicing (registered trademark) and the like.
  • a step of forming a back surface protective film on the back surface (the surface opposite to the bump forming surface) of the semiconductor wafer with the protective film may be included.
  • the method for manufacturing a semiconductor package of the present invention includes the following steps (U1) to (U2).
  • Step (U1) A step of carrying out the method for manufacturing a semiconductor chip with a protective film of the present invention to obtain a semiconductor chip with a protective film.
  • Step (U2) A wiring substrate and the semiconductor chip with a protective film are attached to the bump. The process of electrically connecting via
  • Step (U1) the method for manufacturing a semiconductor chip with a protective film of the present invention described above is carried out to obtain a semiconductor chip with a protective film.
  • the wiring board (Z) having the wiring Z1 and the semiconductor chip CP with the protective film are electrically connected via the bump BM. More specifically, heating is performed in a state where the bump forming surface of the semiconductor chip CP with a protective film and the forming surface of the wiring Z1 of the wiring board (Z) are opposed to each other via the bump BM (hereinafter, "heating connection”). Also called “process”). As a result, the top of the bump BM and the wiring Z1 can be electrically and satisfactorily connected.
  • the protective film of the present invention although a semiconductor chip obtained from a semiconductor wafer having narrow pitched bumps, which may be short-circuited due to crushing or deformation of the bumps, is used, for forming the protective film of the present invention.
  • a semiconductor chip obtained from a semiconductor wafer having narrow pitched bumps which may be short-circuited due to crushing or deformation of the bumps.
  • the conditions of the heating connection step are, for example, a temperature of 250 ° C. to 270 ° C. for 30 seconds to 5 minutes.
  • Step (U3) A step of filling an underfill material between the wiring board and the semiconductor chip with a protective film. It can be suppressed. In other words, it is possible to suppress the proximity of bumps due to crushing or deformation of bumps. Conventionally, when bumps are close to each other, even if an attempt is made to fill the underfill material, the gap between the bumps is narrow, and it is difficult to fill the gap with the underfill material. However, in the present invention, since the proximity of the bumps is also suppressed, it is possible to satisfactorily fill the space between the protective film (X) and the wiring board (Z) with the underfill material including the gap between the bumps. be.
  • the glass transition temperature (Tg) of the polymer component (A), which will be described later, is a temperature of ⁇ 70 ° C. to 150 ° C. at a lifting temperature rate of 10 ° C./min using a differential scanning calorimeter (PYRIS Diamond DSC) manufactured by PerkinElmer Co., Ltd. Measurements were performed using the profile, and the points of variation were confirmed and determined.
  • Tg glass transition temperature
  • ⁇ Average particle size The particles to be measured are dispersed in water by ultrasonic waves, and the particle size distribution of the particles is measured on a volume basis by a dynamic light scattering method particle size distribution measuring device (LB-550, manufactured by Horiba Seisakusho Co., Ltd.), and the median diameter thereof is measured. (D 50 ) was defined as the average particle size.
  • thermosetting resin composition (x1-1) used for producing the thermosetting resin film (x1) used in the examples was prepared by the following method.
  • thermosetting resin composition (x1-1) > (Polymer component (A)) Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., Eslek® B BL-) having a structural unit represented by the following formula (i-1), the following formula (i-2), and the following formula (i-3) 10. Weight average molecular weight 25,000, glass transition temperature 59 ° C., in the following formula, p is 68 to 74 mol%, q is 1 to 3 mol%, and r is about 28 mol%).
  • Epoxy resin (B1) The following two types of epoxy resins were used.
  • Epoxy resin (B1-1) Liquid bisphenol A type epoxy resin (manufactured by DIC Corporation, EPICLON (registered trademark) EXA-4850-1000, epoxy equivalent 404-412 g / eq)
  • Epoxy resin (B1-2) Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, EPICLON (registered trademark) HP-7200, epoxy equivalent 254 to 264 g / eq)
  • thermosetting agent (B2) A novolak type phenol resin (manufactured by Showa Denko KK, Shonor (registered trademark) BRG-556) was used.
  • Fill (D) Spherical silica modified with an epoxy group (manufactured by Admatex Co., Ltd., Admanano® YA050C-MKK, average particle size 0.05 ⁇ m) was used.
  • thermosetting resin composition (x1-1) The polymer component (A), epoxy resin (B1-1), epoxy resin (B1-2), thermosetting agent (B2), curing accelerator (C), and filler (D) are composed of a thermosetting resin.
  • the active ingredient (solid content) concentration is increased by dissolving or dispersing in methyl ethyl ketone and stirring at 23 ° C. so that the content is as shown below based on the total amount (100% by mass) of the substance (x1-1).
  • a thermosetting resin composition (x1-1) having an amount of 55% by mass was prepared.
  • the protective film (X) was formed using the thermosetting resin composition (x1-1) prepared in Formulation 1 shown below.
  • thermosetting resin composition (x1-1) prepared in Formulation 2 shown below.
  • (Formulation 1) -Polymer component (A): 41.4% by mass -Epoxy resin (B1-1): 23.2% by mass -Epoxy resin (B1-2): 15.2% by mass -Thermosetting agent (B2): 11.2% by mass -Curing accelerator (C): 0.2% by mass -Filler (D): 8.8% by mass
  • thermosetting resin film (x1) ⁇ Manufacturing of thermosetting resin film (x1)>
  • a product (x1-1) was applied and dried by heating at 120 ° C. for 2 minutes to obtain a thermosetting resin film (x1: compounding 1) having a thickness of 30 ⁇ m.
  • a thermosetting resin film (x1: formulation 2) having a thickness of 50 ⁇ m was obtained by the same method except that the composition was changed to the thermosetting resin composition (x1-1) prepared in formulation 2.
  • a sticking tape (Lintec) formed by laminating a base material (thickness: 100 ⁇ m), an intermediate layer (thickness: 400 ⁇ m), and an adhesive layer (thickness: 10 ⁇ m) in this order.
  • the adhesive layer of this sticking tape and a thermosetting resin film (x1: compounding 1) having a thickness of 30 ⁇ m formed on the release material are bonded to each other to form a support sheet (1).
  • Y), a thermosetting resin film (x1), and a release material were laminated in this order to produce a protective film forming sheet 1.
  • a protective film forming sheet 2 was produced by the same procedure.
  • thermosetting resin film (x1) was cured, the tensile elastic modulus E'of the protective film (X) was measured by the following method.
  • thermosetting resin films (x1: compounding 1) having a thickness of 30 ⁇ m are laminated to prepare a sample having a thickness of 0.18 mm, a width of 4.5 mm, and a length of 20.0 mm, and the sample is pressed.
  • a protective film (X) was obtained by heat treatment in an oven (RAD-9100 manufactured by Lintec Corporation) under heating conditions of temperature: 130 ° C., time: 2 hours, and furnace pressure: 0.5 MPa.
  • the protective film (X) is subjected to a protective film using a dynamic viscoelasticity measuring device (manufactured by TA instruments, product name "DMA Q800") in a tensile mode at a frequency of 11 Hz, 23 ° C., and in an air atmosphere.
  • the tensile elastic modulus E'(23 ° C.) of (X) was measured.
  • the tensile elastic modulus E'(260 ° C.) of the protective film (X) was measured under the same conditions except that the temperature at the time of measurement was set to 260 ° C.
  • the heat-curable resin film (x1: compounding 2) is protected by the same procedure except that four heat-curable resin films (x1: compounding 2) having a thickness of 50 ⁇ m are stacked to make the thickness 0.20 mm.
  • a film (X) was obtained, and the tensile elastic modulus E'(23 ° C.) of the protective film (X) and the tensile elastic modulus E'(260 ° C.) of the protective film (X) were measured.
  • the semiconductor wafer By removing the release material from the protective film forming sheet obtained above and pressing the exposed surface (exposed surface) of the thermosetting resin layer against the bump forming surface of the wafer with ball bumps, the semiconductor wafer can be obtained.
  • a protective film forming sheet was attached to the bump forming surface.
  • the protective film forming sheet is attached using a pasting device (roller type laminator, "RAD-3510 F / 12" manufactured by Lintec Corporation), a table temperature of 90 ° C., a sticking speed of 2 mm / sec, and a sticking pressure of 0. This was performed while heating the thermosetting resin film (x1) under the condition of 5.5 MPa.
  • Table 1 shows the details (requirements ( ⁇ 1), ( ⁇ 2), ( ⁇ 3a), and ( ⁇ 4)) of the wafer with ball bumps to which the protective film forming sheets 1 and 2 are attached.
  • the support sheet (Y) of the protective film forming sheet was peeled off by irradiating with ultraviolet rays.
  • a wafer with bumps to which a thermosetting resin film (x1) is attached is heated in a pressure oven (RAD-9100 manufactured by Lintec Co., Ltd.) at a temperature of 130 ° C., a time of 2 hours, and a furnace pressure of 0.5 MPa.
  • thermosetting resin film (x1) was heat-cured to obtain semiconductor wafers (Examples 1 to 4) with a protective film (X).
  • the thickness ( XT ) of the protective film (X) is obtained by cutting a semiconductor wafer with the protective film (X) in a direction perpendicular to the bump forming surface and passing through the center of the bump, and dividing the cross section after cutting. , Measured by observing with an optical microscope. Then, a heat treatment (heat connection step) at 260 ° C. for 1 minute is performed in a state where the bump forming surface of the semiconductor wafer with the protective film (X) and the wiring forming surface of the wiring board are opposed to each other via the bumps.

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une feuille de formation de film de protection qui est capable de supprimer un court-circuit entre des bosses à pente étroite. Le problème est résolu par une feuille de formation de film de protection qui : a une structure stratifiée comprenant un film de résine durcissable (x) et une feuille de support (Y) ; a une pluralité de bosses ; est utilisée pour former un film de protection (X) sur une surface de formation de bosse d'une tranche semi-conductrice qui satisfait une exigence prescrite qui indique la présence de bosses à pas étroit ; et satisfait une exigence prescrite spécifiée par le module de traction E'.
PCT/JP2021/009704 2020-03-12 2021-03-11 Feuille de formation de film de protection WO2021182554A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002359446A (ja) * 2001-05-31 2002-12-13 Hitachi Ltd 配線基板およびその製造方法
JP2012196906A (ja) * 2011-03-22 2012-10-18 Lintec Corp 基材フィルムおよび該基材フィルムを備えた粘着シート

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KR100958652B1 (ko) 2005-07-01 2010-05-20 닛코킨조쿠 가부시키가이샤 고순도 주석 또는 주석 합금 및 고순도 주석의 제조방법
JP5822250B2 (ja) 2010-03-31 2015-11-24 Jx日鉱日石金属株式会社 α線量が少ない銀又は銀を含有する合金及びその製造方法
SG192717A1 (en) 2011-03-07 2013-09-30 Jx Nippon Mining & Metals Corp Copper or copper alloy, bonding wire, method of producing the copper, method of producing the copper alloy, and method of producing the bonding wire.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002359446A (ja) * 2001-05-31 2002-12-13 Hitachi Ltd 配線基板およびその製造方法
JP2012196906A (ja) * 2011-03-22 2012-10-18 Lintec Corp 基材フィルムおよび該基材フィルムを備えた粘着シート

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