WO2022255165A1 - Film stratifié - Google Patents

Film stratifié Download PDF

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Publication number
WO2022255165A1
WO2022255165A1 PCT/JP2022/021273 JP2022021273W WO2022255165A1 WO 2022255165 A1 WO2022255165 A1 WO 2022255165A1 JP 2022021273 W JP2022021273 W JP 2022021273W WO 2022255165 A1 WO2022255165 A1 WO 2022255165A1
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WIPO (PCT)
Prior art keywords
adhesive layer
pressure
sensitive adhesive
separator
examples
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PCT/JP2022/021273
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English (en)
Japanese (ja)
Inventor
元気 越智
奈津子 沖田
弘司 野呂
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202280038843.3A priority Critical patent/CN117396572A/zh
Priority to KR1020237043634A priority patent/KR20240017845A/ko
Publication of WO2022255165A1 publication Critical patent/WO2022255165A1/fr

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/06Interconnection of layers permitting easy separation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/50Assembly 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
    • H01L21/52Mounting semiconductor bodies in containers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

  • the present invention relates to laminated films.
  • a semiconductor wafer is singulated by dicing in a state of being temporarily fixed on a dicing tape, and the singulated semiconductor chips are pushed by a pin member from the dicing tape side of the back surface of the wafer to form a collet. It is picked up by a suction jig called and mounted on a mounting board such as a circuit board (for example, Patent Document 1).
  • the present invention has been made in view of the above-mentioned problems, and its object is to prevent mistakes from occurring in the peeling process of the separator when temporarily fixing the semiconductor chip or the like to the carrier substrate to receive the semiconductor chip or the like on the mounting substrate.
  • the present inventors have made intensive studies to achieve the above object, and found that a surface protective film (first separator), a first adhesive layer for temporarily fixing fine electronic components such as semiconductor chips, and a substrate and a second adhesive layer for temporarily fixing to the carrier substrate, and a surface protection film (second separator), the peeling force F (1) of the first separator with respect to the first adhesive layer, the second The peeling force F (2) of the second separator to the adhesive layer, the adhesive force P (2) of the second adhesive layer to the glass plate, and the glass after 5 minutes at 160 ° C.
  • first separator a surface protective film
  • first adhesive layer for temporarily fixing fine electronic components such as semiconductor chips
  • second adhesive layer for temporarily fixing to the carrier substrate
  • second separator a surface protection film
  • the present invention is a laminated film in which a first separator, a first pressure-sensitive adhesive layer, a substrate, a second pressure-sensitive adhesive layer, and a second separator are laminated in this order, and the first pressure-sensitive adhesive layer consists of a low-adhesive pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer consists of a peelable pressure-sensitive adhesive layer.
  • H. and a 180° peeling force F(1) (N/50 mm) of the first separator against the first pressure-sensitive adhesive layer measured under the conditions of a peel speed of 0.3 m/min, 23°C, 50%R. H.
  • the laminated film preferably further satisfies the relationship of the following formula. F(2)/F(1) ⁇ 0.80 P(2)/F(1)>1.00
  • the above laminate film was dried at 23° C. and 50% R.I. H. and the 90° trigger peeling force T(1) (N/50 mm) of the first pressure-sensitive adhesive layer against the first separator measured under the conditions of a tensile speed of 0.3 m/min, 23°C, 50%R. H. And the 90-degree trigger peel force T (2) (N/50 mm) of the second adhesive layer against the second separator measured under the conditions of a tensile speed of 0.3 m / min, and the adhesive force P (2) , preferably satisfies the following formula. T(1)/T(2)>1.05 P(2)/T(1) ⁇ 1.00
  • the laminated film of the present invention does not cause an error in the peeling process of the separator when the semiconductor chip or the like is received by temporarily fixing it to the carrier substrate, does not peel off from the carrier substrate when the semiconductor chip or the like is transferred to the mounting substrate, and When a semiconductor chip or the like is transferred to a mounting substrate and then peeled off from the carrier substrate, it can be peeled off without contamination such as adhesive residue and is excellent in reworkability, so that work efficiency can be improved in the manufacturing process of the semiconductor device.
  • the laminated film of the present invention has a laminated structure in which a first separator, a first pressure-sensitive adhesive layer, a substrate, a second pressure-sensitive adhesive layer, and a second separator are laminated in this order. That is, the laminated film of the present invention is the adhesive surface of the double-sided adhesive film for transfer consisting of the first adhesive layer, the base material and the second adhesive layer (the adhesive surface of the first adhesive layer and the second adhesive layer). surface) has a laminated structure protected by the first separator and the second separator.
  • the first pressure-sensitive adhesive layer consists of a low-adhesive pressure-sensitive adhesive layer
  • the second pressure-sensitive adhesive layer consists of a peelable pressure-sensitive adhesive layer.
  • FIG. 4 is a schematic cross-sectional view showing the process from temporarily fixing the laminated film of the present invention to the carrier substrate to peeling it off.
  • the second separator 120 is peeled off from the adhesive layer 12 of the laminated film 1 adsorbed on the adsorption stage (not shown). At this time, no lifting occurs at the interface between the first separator 110 and the first pressure-sensitive adhesive layer 11 . After that, the adhesive surface of the second adhesive layer 12 is attached to the carrier substrate 22 (not shown).
  • the first separator 110 is peeled off from the adhesive layer 11. At this time, no lifting occurs at the interface of the second adhesive layer 22 .
  • a step of receiving the diced electronic component 21 of FIG. A step of transferring the electronic component 21 received by the first adhesive layer 11 of FIG. 3 to the mounting board 30 is performed.
  • the second adhesive layer 12 is peeled off from the carrier substrate 22 (not shown). Since the second pressure-sensitive adhesive layer 12 exhibits excellent reworkability in that it can be peeled off without contamination such as adhesive residue, the carrier substrate 22 can be easily reused.
  • F (2) / F (1) ratio of F (2) to F (1) is 1.00 or less (F (2) / F (1) ⁇ 1.00), preferably 0.90 or less (F(2)/F(1) ⁇ 0.90), more preferably less than 0.80 (F(2)/F(1) ⁇ 0.80), more preferably less than 0.50 (F(2)/F(1) ⁇ 0.50).
  • F(2)/F(1) is not particularly limited, but is preferably 0.10 or more (F(2)/F(1) ⁇ 0.10), for example.
  • F (1) is less than 0.50 N/50 mm (F (1) ⁇ 0.50 ), more preferably 0.40 N/50 mm or less (F(1) ⁇ 0.40), and still more preferably 0.35 N/50 mm or less (F(1) ⁇ 0.35).
  • it is preferably 0.04 N/50 mm or more (F(1) ⁇ 0.04), more preferably 0.05 N/50 mm or more (F(1) ⁇ 0.04).
  • 0.05 , more preferably 0.06 N/50 mm or more (F(1) ⁇ 0.06).
  • F(2) is preferably less than 0.20 N/50 mm (F(2) ⁇ 0.20) from the viewpoint of workability when peeling the second separator and balance with the first separator peeling force F(1). It is more preferably 0.15 N/50 mm or less (F(2) ⁇ 0.15 N), still more preferably 0.10 N/50 mm or less (F(2) ⁇ 0.10). In addition, from the viewpoint of separator floating during transfer sheet processing and transportation, it is preferably 0.01/50 mm or more (F(1) ⁇ 0.01), more preferably 0.02 N/50 mm or more (F(2) ⁇ 0.02), more preferably 0.04/50 mm or more (F(2) ⁇ 0.04).
  • P (2) / F (1) (ratio of P (2) to F (1)) is 1.00 or more (P (2) / F (1) ⁇ 1.00), preferably It is more than 1.00 (P(2)/F(1)>1.00), more preferably 1.20 or more (P(2)/F(1) ⁇ 1.20).
  • P(2)/F(1) is not particularly limited, but is preferably 4.50 or less (P(2)/F(1) ⁇ 4.50), for example.
  • P(2) is preferably less than 1.10 N/50 mm (P(2) ⁇ 1.10), more preferably less than 1.10 N/50 mm from the viewpoint of improving reworkability that can be peeled off from the carrier substrate without contamination such as adhesive residue. 1.00 N/50 mm or less (P(2) ⁇ 1.00), more preferably 0.90 N/50 mm or less (P(2) ⁇ 0.90). From the viewpoint of the adhesiveness of the carrier substrate to the second pressure-sensitive adhesive layer, it is preferably 0.10/50 mm or more (P(2) ⁇ 0.10), more preferably 0.20 N/50 mm or more (P(2) ⁇ 0.20), more preferably 0.30/50 mm or more (P(2) ⁇ 0.30).
  • P'(2)/P(2) (the ratio of P'(2) to P(2)) is the heat generated when the electronic component is transferred to the mounting substrate and mounted. From the viewpoint that the adhesive strength of the second pressure-sensitive adhesive layer to the carrier substrate does not increase even by press-fitting and that the second pressure-sensitive adhesive layer can be peeled off well and is excellent in reworkability, it is less than 1.20 (P'(2)/P(2) ⁇ 1.20). 20), preferably 1.0 or less (P'(2)/P(2) ⁇ 1.0), more preferably 0.8 or less (P'(2)/P(2) ⁇ 0.8 ).
  • P'(2)/P(2) is not particularly limited, for example, it is preferably 0.01 or more (P'(2)/P(2) ⁇ 0.01), more preferably 0.03 or more (P'(2)/P(2) ⁇ 0.03).
  • P'(2) is less than 1.00 N/50 mm (P '(2) ⁇ 1.00), preferably 0.6 N/50 mm or less (P'(2) ⁇ 0.6), more preferably 0.4 N/50 mm or less (P'(2) ⁇ 0.6). 4).
  • P′(2) is not particularly limited, for example, it is preferably 0.01/50 mm or more (P′(2) ⁇ 0.01), more preferably 0.02 N/50 mm or more (P′(2 ) ⁇ 0.02).
  • the double-sided adhesive film for transfer is difficult to peel off from the carrier substrate when transferring the semiconductor chip or the like to the mounting substrate, and the semiconductor chip or the like is mounted. After being transferred to the substrate, the double-sided adhesive film for transfer can be easily peeled off from the carrier substrate, and the adhesive residue is less likely to occur.
  • the temperature is 23° C., 50% R.I. H. and the 90° trigger peeling force T(1) (N/50 mm) of the first pressure-sensitive adhesive layer against the first separator measured under the conditions of a tensile speed of 0.3 m/min, 23°C, 50%R. H.
  • the 90-degree trigger peel force T (2) (N/50 mm) of the second adhesive layer against the second separator measured under the conditions of a tensile speed of 0.3 m / min, and the adhesive force P (2) preferably satisfies the following formula. T(1)/T(2)>1.05 P(2)/T(1) ⁇ 1.90
  • the trigger peel force T(1) means the maximum value (maximum stress) of the peel force recorded at the initial stage of peeling when the first separator is peeled from the first adhesive layer
  • the trigger peel force T(2) means the maximum peel force (maximum stress) recorded at the initial stage of peeling when the second separator is peeled from the second pressure-sensitive adhesive layer.
  • T(1)/T(2) ratio of T(1) to T(2) is the first From the viewpoint of making the separation of the first separator from the pressure-sensitive adhesive layer more difficult, it is preferably greater than 1.05 (T (1) / T (2) > 1.05), more preferably 1.10 or more. (T(1)/T(2) ⁇ 1.10), more preferably 1.15 or more (T(1)/T(2) ⁇ 1.15).
  • T(1)/T(2) is not particularly limited, it is preferably 3.50 or less (T(1)/T(2) ⁇ 3.50), for example.
  • P (2) / T (1) (ratio of P (2) to T (1)) is relative to the carrier substrate when peeling off the first separator from the first adhesive layer From the viewpoint of making it difficult for the second pressure-sensitive adhesive layer to peel off, it is preferably less than 1.90 (P (2) / T (1) ⁇ 1.90), more preferably 1.50 or less (P ( 2)/T(1) ⁇ 1.50), more preferably less than 1.00 (P(2)/T(1) ⁇ 1.00), particularly preferably 0.90 or less (P(2)/T (1) ⁇ 0.90). Also, P(2)/T(1) is not particularly limited, but is preferably 0.20 or more (P(2)/T(1) ⁇ 0.20), more preferably 0.20. 40 or more (P(2)/T(1) ⁇ 0.40).
  • T(1) is preferably 0.10 N/50 mm or more (T(1) ⁇ 0.10), more preferably 0.15 N/50 mm or more (T(1) ⁇ 0.15), still more preferably 0.15 N/50 mm or more (T(1) ⁇ 0.15). 20 N/50 mm or more (T(1) ⁇ 0.20).
  • T(1) is not particularly limited, for example, it is preferably 1.00/50 mm or less (T(1) ⁇ 0.1.00), more preferably 0.85/50 mm or less (T(1) ⁇ 0.85), more preferably 0.70/50 mm or less (PT(1) ⁇ 0.70).
  • T(2) is preferably 0.50 N/50 mm or less (T(2) ⁇ 0.50), more preferably 0.45 N/50 mm or less (T(2) ⁇ 0.45), still more preferably 0.45 N/50 mm or less (T(2) ⁇ 0.45). It is 40 N/50 mm or less (T(2) ⁇ 0.40).
  • T(1) is not particularly limited, for example, it is preferably 0.10/50 mm or more (T(2) ⁇ 0.10), more preferably 0.15 N/50 mm or more (T(2) ⁇ 0 .15).
  • the overall configuration of the peel strength and adhesive strength is such that the above relationships are satisfied for F(1), F(2), P(2), P'(2), T(1) and T(2). can improve work efficiency in the manufacturing process of the semiconductor device.
  • the above F(1), F(2), P(2), P'(2), T(1) and T(2) constitute the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer. Adjustment of adhesive strength by agent type and composition, degree of cross-linking, etc., formation of WBL (Weak Boundary Layer) by blending light release agents and plasticizers, thickness of the first and second separators, constituent materials and release It can be adjusted by treatment or the like.
  • WBL Wood Boundary Layer
  • the first pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer for receiving and holding electronic components, and is composed of a low-adhesive pressure-sensitive adhesive layer.
  • the configuration in which the first pressure-sensitive adhesive layer is composed of a low-adhesive pressure-sensitive adhesive layer is preferable in that it can reduce the force applied to the electronic component when receiving, and can suppress damage to the electronic component.
  • the electronic component is received by the first pressure-sensitive adhesive layer in a non-contact manner, for example, the electronic component is separated from the dicing tape by pressing with a pin member or the like, and dropped onto the first pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer when the first pressure-sensitive adhesive layer receives the dropped electronic component, it may bounce and may not be received accurately. When this phenomenon occurs, the positional accuracy of the electronic product may be degraded, resulting in poor contact.
  • the structure in which the first pressure-sensitive adhesive layer consists of a low-adhesive pressure-sensitive adhesive layer makes it easy for the electronic component to be caught by the first pressure-sensitive adhesive layer without bouncing when the first pressure-sensitive adhesive layer receives the electronic component without contact. , can be received with high positional accuracy. Furthermore, it is also preferable in that the electronic component can be easily peeled off from the first adhesive layer when the electronic component received by the transfer double-sided pressure-sensitive adhesive film is mounted on the mounting substrate.
  • the first adhesive layer has a low adhesiveness by adjusting the type and composition of the adhesive that constitutes it, the degree of crosslinking, etc., and by forming a WBL (Weak Boundary Layer) by blending a light release agent and a plasticizer. It can be used as an agent layer.
  • WBL Wood Boundary Layer
  • AFM-DMA AFM: Atomic Force Microscope
  • nDMA nano Dynamic Mechanical Analysis
  • the storage modulus (E'1a) of is preferably 50 MPa or less. This configuration is preferable for reliably adhering the electronic component received by the first pressure-sensitive adhesive layer. If E′1a is too high, the adhesiveness of the electronic component to the first pressure-sensitive adhesive layer is lowered, which may cause problems such as misalignment and falling of the electronic component.
  • E′1a is preferably 40 MPa or less, more preferably 30 MPa or less, from the viewpoint of the adhesiveness of the electronic component to the first pressure-sensitive adhesive layer.
  • E′1a is preferably 0.1 MPa or more from the viewpoint of transferability from the first pressure-sensitive adhesive layer to the circuit board. If E'1a is too low, the adhesiveness of the electronic component to the first pressure-sensitive adhesive layer becomes too high, which may impair transferability when mounted on a mounting board.
  • E′1a is preferably 0.2 MPa or more, more preferably 0.5 MPa or more, from the viewpoint of transferability of the electronic component to the mounting board.
  • the storage elastic modulus (E'1b) of the first adhesive layer at a frequency of 1 kHz and 25°C by AFM-DMA is preferably 100 MPa or less.
  • This configuration is preferable in that when the first pressure-sensitive adhesive layer receives the electronic component in a non-contact manner, the electronic component is not repelled by the surface of the first pressure-sensitive adhesive layer and can be received with high positional accuracy. If the E'1b is too high, when the electronic component is dropped and received without contacting the surface of the first adhesive layer, the electronic component is repelled and shifted from a predetermined position or turned over, resulting in poor positional accuracy. tends to decrease.
  • E′1b is preferably 90 MPa or less, more preferably 80 MPa or less, from the viewpoint of the positional accuracy of the electronic component with respect to the first pressure-sensitive adhesive layer. Further, it may be 70 MPa or less, 60 MPa or less, 50 MPa or less, 40 MPa or less, 30 MPa or less, and particularly 20 MPa or less.
  • E'1b is preferably 0.5 MPa or more from the viewpoint of transferability from the first pressure-sensitive adhesive layer to the mounting substrate. If the E'1b is too low, the adhesiveness of the electronic component to the first adhesive layer increases, and when the electronic component falls, it is embedded in the first adhesive layer and mounted on the mounting substrate. transferability may be impaired.
  • E′1b is preferably 0.7 MPa or more, more preferably 1.0 MPa or more, from the viewpoint of the transferability of the electronic component to the mounting board.
  • the storage elastic modulus (E'1a) of the first pressure-sensitive adhesive layer at a frequency of 1 Hz and 25 ° C. by AFM-DMA of the first pressure-sensitive adhesive layer is measured by AFM-DMA at a frequency of 1 kHz and 25 ° C. is preferably greater than 1.00.
  • This configuration is preferable in that the adhesiveness of the electronic component to the first pressure-sensitive adhesive layer, the positional accuracy, the transferability to the mounting substrate, and the like are well balanced.
  • E'1b/E'1a is preferably 1.05 or more, more preferably 1.10 or more, from the viewpoint of balance of adhesiveness of electronic components, positional accuracy, transferability to a mounting substrate, and the like.
  • the upper limit of E'1b/E'1a is not particularly limited, it is preferably 3.00 or less from the viewpoint of the above balance.
  • the loss elastic modulus (E′′1a) of the first pressure-sensitive adhesive layer at a frequency of 1 Hz and 25° C. by AFM-DMA is preferably 7 MPa or less. It is preferable from the viewpoint of excellent transferability to the substrate. If the E′′1a is too high, the adhesiveness of the electronic component to the first pressure-sensitive adhesive layer becomes too high, impairing the transferability when mounted on the mounting substrate.
  • E′′1a is preferably 5 MPa or less, more preferably 3 MPa or less, from the viewpoint of transferability of electronic components to a mounting substrate. This may cause problems such as misalignment or dropping of electronic components. From the viewpoint of the adhesiveness of the electronic component to the first pressure-sensitive adhesive layer, E′′1a is preferably 0.01 MPa or more, more preferably 0.03 MPa or more.
  • the loss elastic modulus (E′′1a) of can be adjusted by the type and composition of the constituent pressure-sensitive adhesive, the degree of cross-linking, and the like.
  • the first pressure-sensitive adhesive layer preferably has a tack force of 10 to 250 gf/ ⁇ 5 mm SUS for a stainless steel plate (5 mm in diameter).
  • the configuration in which the tack force is 250 gf/ ⁇ 5 mm SUS or less is preferable from the viewpoint of transferability to the mounting board of the electronic component, and 200 gf/ ⁇ 5 mm SUS or less is more preferable.
  • the tack force of the first adhesive layer to a stainless steel plate (5 mm in diameter) can be adjusted by adjusting the type and composition of the constituent adhesive, the degree of cross-linking, and additives such as fatty acid esters and fluorosurfactants.
  • the surface force of the first pressure-sensitive adhesive layer is preferably -500 to -100 ⁇ N.
  • the surface strength of the first pressure-sensitive adhesive layer can be adjusted by the type and composition of the pressure-sensitive adhesive that constitutes it, the degree of cross-linking, and additives such as fatty acid esters and fluorosurfactants.
  • the thickness of the first pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more. When the thickness is equal to or greater than a certain value, the first pressure-sensitive adhesive layer can be easily received by the electronic component with high accuracy, which is preferable.
  • the upper limit of the thickness of the first pressure-sensitive adhesive layer is not particularly limited, it is preferably 100 ⁇ m, more preferably 75 ⁇ m. When the thickness is less than a certain value, the electronic component can be easily transferred to the mounting substrate with high accuracy, which is preferable.
  • the haze (according to JIS K7136) of the first pressure-sensitive adhesive layer is not particularly limited, but is preferably 10% or less, more preferably 5.0% or less. When the haze is 10% or less, excellent transparency can be obtained.
  • a pattern applied on the carrier substrate for example, a marker indicating the transfer position of the electronic component.
  • the haze can be measured by, for example, forming the first pressure-sensitive adhesive layer on the separator and allowing it to stand at normal conditions (23° C., 50% RH) for at least 24 hours. Transmittance 91.8%, haze 0.4%) is used as a sample, and measured using a haze meter (product name “HM-150”, manufactured by Murakami Color Research Laboratory). be able to.
  • the total light transmittance (according to JIS K7361-1) of the first adhesive layer in the visible light wavelength region is not particularly limited, but is preferably 85% or more, more preferably 88% or more. be. When the total light transmittance is 85% or more, excellent transparency can be obtained. It is preferable that the marker shown) can be visually recognized.
  • the above total light transmittance can be measured, for example, by forming a first pressure-sensitive adhesive layer on a separator and allowing it to stand in a normal state (23° C., 50% RH) for at least 24 hours, peeling off the separator, and applying a slide glass (for example, , total light transmittance of 91.8%, haze of 0.4%) is used as a sample, and a haze meter (product name “HM-150”, manufactured by Murakami Color Research Laboratory) is used.
  • HM-150 manufactured by Murakami Color Research Laboratory
  • the adhesive constituting the first adhesive layer is not particularly limited, but for example, silicone-based adhesive, urethane-based adhesive, acrylic-based adhesive, rubber-based adhesive, polyester-based adhesive, and polyamide-based adhesive. , epoxy-based adhesives, vinyl alkyl ether-based adhesives, fluorine-based adhesives, and the like.
  • silicone-based adhesives, urethane-based adhesives, and urethane-based adhesives which can be easily controlled to have low adhesiveness, can receive electronic components with high positional accuracy without damaging them, and from the viewpoint of good transferability to mounting substrates.
  • Acrylic adhesives are preferred, silicone adhesives and urethane adhesives are more preferred, and silicone adhesives are even more preferred.
  • the silicone-based pressure-sensitive adhesive is not particularly limited, and known or commonly used silicone-based pressure-sensitive adhesives can be used. agents and the like can be used.
  • the silicone pressure-sensitive adhesive may be either one-pack type or two-pack type.
  • the silicone pressure-sensitive adhesives can be used alone or in combination of two or more.
  • the addition-type silicone-based pressure-sensitive adhesive is generally prepared by an addition reaction ( A pressure-sensitive adhesive that generates a silicone-based polymer through a hydrosilylation reaction.
  • a peroxide-curable silicone-based pressure-sensitive adhesive is generally a pressure-sensitive adhesive that cures (crosslinks) organopolysiloxane with a peroxide to form a silicone-based polymer.
  • Condensation-type silicone-based pressure-sensitive adhesives are generally pressure-sensitive adhesives that generate a silicone-based polymer through a dehydration or dealcoholization reaction between polyorganosiloxanes having hydrolyzable silyl groups such as silanol groups or alkoxysilyl groups at their terminals. .
  • silicone-based pressure-sensitive adhesive for example, a silicone-based pressure-sensitive adhesive composition containing a silicone rubber and a silicone resin can be used because it is easy to control the adhesiveness to be low.
  • the silicone rubber is not particularly limited as long as it is a silicone-based rubber component, but for example, organopolysiloxane having dimethylsiloxane, methylphenylsiloxane, etc. as main structural units can be used.
  • silicone rubber having alkenyl groups bonded to silicon atoms alkenyl group-containing organopolysiloxane; in the case of addition reaction type), silicone rubber having at least methyl groups (peroxide curing type ), a silicone rubber having a terminal silanol group or a hydrolyzable alkoxysilyl group (in the case of condensation type) can be used.
  • the weight average molecular weight of the organopolysiloxane in the silicone rubber is usually 150,000 or more, preferably 280,000 to 1,000,000, and more preferably 500,000 to 900,000.
  • the silicone resin is not particularly limited as long as it is a silicone-based resin that is used in silicone-based pressure -sensitive adhesives. 2 ”, T units consisting of the structural unit “RSiO 3/2 ”, and D units consisting of the structural unit “R 2 SiO”.
  • Examples include silicone resins made of organopolysiloxane.
  • R in the above structural unit represents a hydrocarbon group or a hydroxyl group.
  • examples of the above hydrocarbon groups include aliphatic hydrocarbon groups (alkyl groups such as methyl and ethyl), alicyclic hydrocarbon groups (cycloalkyl groups such as cyclohexyl), aromatic hydrocarbon groups ( phenyl group, aryl group such as naphthyl group, etc.) and the like.
  • Various functional groups such as a vinyl group may be introduced into the organopolysiloxane in such a silicone resin, if necessary.
  • the functional group to be introduced may be a functional group capable of causing a cross-linking reaction.
  • an MQ resin composed of M units and Q units is preferred.
  • the weight average molecular weight of the organopolysiloxane in the silicone resin is usually 1,000 or more, preferably 1,000 to 20,000, and more preferably 1,500 to 10,000.
  • the mixing ratio of the silicone rubber and the silicone resin is not particularly limited, but from the point of view of easy control of low tackiness, for example, 100 parts by weight of the silicone rubber and 100 to 220 parts by weight of the silicone resin (especially 120 parts by weight of the silicone resin) ⁇ 180 parts by weight).
  • the silicone rubber and the silicone resin may be in a mixed state in which they are simply mixed, and react with each other to form condensates (especially partial condensate), a cross-linking reaction product, an addition reaction product, or the like.
  • a silicone pressure-sensitive adhesive composition containing a silicone rubber and a silicone resin usually contains a cross-linking agent in order to form a cross-linked structure, since it is easy to control the adhesiveness to be low.
  • a cross-linking agent is not particularly limited, but siloxane-based cross-linking agents (silicone-based cross-linking agents) and peroxide-based cross-linking agents can be preferably used.
  • a crosslinking agent can be used individually or in combination of 2 or more types.
  • siloxane-based cross-linking agent for example, polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule can be suitably used.
  • various organic groups other than hydrogen atoms may be bonded to silicon atoms to which hydrogen atoms are bonded.
  • the organic group include alkyl groups such as a methyl group and an ethyl group; aryl groups such as a phenyl group; and halogenated alkyl groups.
  • the skeleton structure of the polyorganohydrogensiloxane may have a linear, branched, or cyclic skeleton structure, but is preferably linear.
  • peroxide-based crosslinking agent examples include diacyl peroxide, alkylperoxyester, peroxydicarbonate, monoperoxycarbonate, peroxyketal, dialkyl peroxide, hydroperoxide, and ketone peroxide.
  • addition-type silicone pressure-sensitive adhesives include trade names “KR-3700”, “KR-3701”, “X-40-3237-1”, “X-40-3240”, and “X-40-3291-1.” ” and “X-40-3306” (manufactured by Shin-Etsu Chemical Co., Ltd.) are commercially available.
  • peroxide-curable silicone-based adhesives for example, trade names “KR-100”, “KR-101-10", “KR-130” (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are commercially available. It is
  • the addition-type silicone pressure-sensitive adhesive composition preferably contains a curing catalyst such as a platinum catalyst.
  • a platinum catalyst for example, trade name "CAT-PL-50T” (manufactured by Shin-Etsu Chemical Co., Ltd.), trade name “DOWSIL NC-25 Catalyst”, “DOWSIL SRX212 Catalyst” (manufactured by Dow Toray Industries, Inc. ) are commercially available.
  • the content of the curing catalyst is It is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight.
  • the urethane-based pressure-sensitive adhesive is not particularly limited, and a known or commonly used urethane-based pressure-sensitive adhesive can be used, and from the viewpoint of easy control of low adhesiveness, a urethane containing a polyol, a polyfunctional isocyanate compound, and a catalyst is used. system adhesive compositions are preferred.
  • any appropriate polyol can be adopted as the polyol as long as it has two or more hydroxyl groups.
  • examples of such polyols include polyols having two hydroxyl groups (diols), polyols having three hydroxyl groups (triols), polyols having four hydroxyl groups (tetraols), and polyols having five hydroxyl groups. (pentaol), polyol (hexaol) having six hydroxyl groups, and the like.
  • a polyol can be used individually or in combination of 2 or more types.
  • the above polyol preferably contains a polyol having a number average molecular weight (Mn) of 400 to 20,000.
  • the content of polyols having a number average molecular weight (Mn) of 400 to 20000 in the total amount of polyols is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and still more preferably 90 to 100% by weight. 100% by weight, particularly preferably 95-100% by weight, most preferably substantially 100% by weight.
  • polyols examples include polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols.
  • the above polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
  • polyol component examples include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like.
  • the acid component examples include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1 ,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid acids, acid anhydrides thereof, and the like.
  • polyether polyols examples include water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcinol, hydroquinone, etc.).
  • Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., as initiators. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
  • polycaprolactone polyols examples include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ⁇ -caprolactone and ⁇ -valerolactone.
  • polycarbonate polyol examples include polycarbonate polyol obtained by subjecting the polyol component and phosgene to a polycondensation reaction; the polyol component, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate , propylene carbonate, diphenyl carbonate, dibenzyl carbonate, and other carbonic acid diesters through transesterification condensation; copolymerized polycarbonate polyols obtained by combining two or more of the above polyol components; various polycarbonate polyols and carboxyl groups above.
  • Polycarbonate polyol obtained by esterification reaction with the containing compound Polycarbonate polyol obtained by etherification reaction of the above various polycarbonate polyols and hydroxyl group-containing compounds; Obtained by transesterifying the above various polycarbonate polyols and ester compounds.
  • Polycarbonate polyols obtained by transesterification of various polycarbonate polyols and hydroxyl group-containing compounds Polyester-based polycarbonate polyols obtained by polycondensation reaction of various polycarbonate polyols and dicarboxylic acid compounds;
  • Various polycarbonates above A copolymerized polyether-based polycarbonate polyol obtained by copolymerizing a polyol and an alkylene oxide may be mentioned.
  • castor oil-based polyols examples include castor oil-based polyols obtained by reacting castor oil fatty acids with the above polyol components. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.
  • the above polyol it is preferable to use a polyol (triol) having three hydroxyl groups as an essential component from the viewpoint of low adhesion and wettability of the first pressure-sensitive adhesive layer to electronic parts.
  • the content of the polyol (triol) having three hydroxyl groups is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, based on the total amount of components constituting the polyol.
  • polyfunctional isocyanate compounds examples include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanate compounds.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4- and trimethylhexamethylene diisocyanate.
  • alicyclic polyisocyanate examples include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene Isocyanate Hydrogenated tetramethylxylylene diisocyanate and the like can be mentioned.
  • aromatic polyisocyanate examples include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4 ,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.
  • aliphatic polyisocyanates and modified products thereof are preferred.
  • Aliphatic polyisocyanates and modified products thereof have a more flexible crosslinked structure than other isocyanate-based crosslinkers, and can be easily controlled to have low tackiness.
  • Hexamethylene diisocyanate and its modified form are particularly preferred as the aliphatic polyisocyanate and its modified form.
  • the polyfunctional isocyanate compound and the polyol are selected from the viewpoints of low adhesion and wettability to electronic parts of the first pressure-sensitive adhesive layer, and the isocyanate group of the polyfunctional isocyanate compound and the hydroxyl group of the polyol.
  • the equivalent ratio (NCO/OH) is preferably 1-5, more preferably 1.1-3, even more preferably 1.2-2.
  • the urethane-based pressure-sensitive adhesive composition preferably contains a catalyst such as an iron-based compound and/or a tin-based compound.
  • a catalyst such as an iron-based compound and/or a tin-based compound.
  • tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetonate)iron, tris(hexane-2,4-dionato)iron, tris(heptane-2,4-dionato)iron , tris(heptane-3,5-dionato)iron, tris(5-methylhexane-2,4-dionato)iron, tris(octane-2,4-dionato)iron, tris(6-methylheptane-2,4 -dionato)iron, tris(2,6-dimethylheptane-3,5-dionato)iron, tris(nonane-2,
  • the content (use amount) of the catalyst contained in the urethane pressure-sensitive adhesive composition is preferably 0.002 to 0.5 parts by weight, preferably 0.005 to 0.3 parts by weight, with respect to 100 parts by weight of the polyol. More preferably, 0.01 to 0.1 parts by weight is even more preferable. Within this range, the speed of the cross-linking reaction is high when the pressure-sensitive adhesive layer is formed, and the pot life of the pressure-sensitive adhesive composition is lengthened, which is a preferred embodiment.
  • a urethane-based adhesive composition containing a urethane prepolymer is also preferable because it is easy to control the adhesiveness to be low.
  • Urethane-based pressure-sensitive adhesive compositions containing urethane prepolymers include, for example, pressure-sensitive adhesive compositions containing polyurethane polyols as urethane prepolymers and polyfunctional isocyanate-based compounds.
  • a urethane prepolymer can be used individually or in combination of 2 or more types.
  • a polyfunctional isocyanate compound can be used individually or in combination of 2 or more types.
  • a polyurethane polyol as a urethane prepolymer is preferably obtained by reacting a polyester polyol and a polyether polyol with an organic polyisocyanate compound in the presence or absence of a catalyst.
  • polyester polyol Any appropriate polyester polyol can be used as the polyester polyol.
  • polyester polyols include polyester polyols obtained by reacting an acid component and a glycol component.
  • acid components include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
  • glycol components include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, Examples include polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components such as glycerin, trimethylolpropane, and pentaerythritol. Polyester polyols also include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly( ⁇ -methyl- ⁇ -valerolactone) and polyvalerolactone.
  • the molecular weight of the polyester polyol can range from low molecular weight to high molecular weight.
  • the number average molecular weight is preferably 500 to 5,000. If the number average molecular weight is less than 500, the reactivity becomes high and gelation may easily occur. If the number-average molecular weight exceeds 5,000, the reactivity may become low, and the cohesive strength of the polyurethane polyol itself may become small.
  • the amount of the polyester polyol used is preferably 10 to 90 mol % of the polyol constituting the polyurethane polyol.
  • polyether polyol can be used as the polyether polyol.
  • polyether polyols include water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and other low-molecular-weight polyols as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and other oxirane compounds.
  • examples include polyether polyols obtained by polymerization.
  • Specific examples of such polyether polyols include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.
  • the molecular weight of the polyether polyol can range from low molecular weight to high molecular weight.
  • the number average molecular weight is preferably 1,000 to 5,000. If the number average molecular weight is less than 1,000, the reactivity becomes high and gelation may easily occur. If the number-average molecular weight exceeds 5,000, the reactivity may become low, and the cohesive strength of the polyurethane polyol itself may become small.
  • the amount of polyether polyol used is preferably 20 to 80 mol % of the polyols constituting the polyurethane polyol.
  • Part of the polyether polyol is ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, glycols such as pentaerythritol, ethylenediamine, N - Polyvalent amines such as aminoethylethanolamine, isophoronediamine, and xylylenediamine can be substituted and used in combination.
  • the polyether polyol only a bifunctional polyether polyol may be used, or a polyether polyol having a number average molecular weight of 1000 to 5000 and at least 3 or more hydroxyl groups in one molecule is used. Part or all may be used.
  • a polyether polyol having an average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule is partially or wholly used as the polyether polyol, the adhesive strength and removability are well balanced. obtain.
  • the number average molecular weight is less than 1000, the reactivity becomes high and there is a possibility that gelation is likely to occur.
  • the number average molecular weight of such polyether polyols is more preferably 2500-3500.
  • organic polyisocyanate compound can be used as the organic polyisocyanate compound.
  • organic polyisocyanate compounds include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.
  • aromatic polyisocyanates examples include 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 - tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4′′-triphenylmethane triisocyanate and the like.
  • aliphatic polyisocyanates examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.
  • araliphatic polyisocyanates include ⁇ , ⁇ '-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene , 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
  • alicyclic polyisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 ,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane and the like. be done.
  • organic polyisocyanate compound a trimethylolpropane adduct, a water-reacted burette, a trimer having an isocyanurate ring, and the like can also be used in combination.
  • Any suitable catalyst can be used as the catalyst that can be used in obtaining the polyurethane polyol.
  • Examples of such catalysts include tertiary amine compounds and organometallic compounds.
  • tertiary amine compounds include triethylamine, triethylenediamine, 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU), and the like.
  • organometallic compounds examples include tin-based compounds and non-tin-based compounds.
  • tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin Tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
  • DBTDL dibutyltin dilaurate
  • dibutyltin diacetate dibutyltin sulfide, tributyltin sulfide, tributyltin oxide
  • non-tin-based compounds include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
  • titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride
  • lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
  • iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate
  • cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate
  • zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate
  • zirconium compounds such as zirconium nap
  • a catalyst When a catalyst is used to obtain a polyurethane polyol, in a system in which two kinds of polyols, a polyester polyol and a polyether polyol, are present, gelation or a reaction solution may occur in a single catalyst system due to the difference in reactivity. The problem of turbidity is likely to occur. Therefore, by using two kinds of catalysts when obtaining a polyurethane polyol, the reaction rate, the selectivity of the catalyst, etc. can be easily controlled, and these problems can be solved. Combinations of such two types of catalysts include, for example, tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably.
  • tin 2-ethylhexanoate is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate.
  • the weight ratio of tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the compounding ratio is 1 or more, gelation may tend to occur due to the balance of catalytic activity.
  • the amount of catalyst used is preferably 0.01 to 1.0% by weight with respect to the total amount of the polyester polyol, polyether polyol and organic polyisocyanate compound.
  • the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. If the temperature is 100° C. or higher, it may become difficult to control the reaction rate and the crosslinked structure, and it may become difficult to obtain a polyurethane polyol having a predetermined molecular weight.
  • a catalyst may not be used when obtaining polyurethane polyol.
  • the reaction temperature is preferably 100° C. or higher, more preferably 110° C. or higher.
  • Methods for obtaining polyurethane polyol include, for example, 1) a method of charging a polyester polyol, a polyether polyol, a catalyst, and an organic polyisocyanate into a volumetric flask, and 2) a method of charging a polyester polyol, a polyether polyol, and a catalyst into a flask to produce an organic polyisocyanate. can be added dropwise.
  • the method 2) is preferable from the viewpoint of controlling the reaction.
  • Any suitable solvent can be used to obtain the polyurethane polyol.
  • suitable solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene and acetone. Among these solvents, toluene is preferred.
  • polyfunctional isocyanate compound those mentioned above can be used.
  • any suitable method may be used as long as it is a method for producing a polyurethane-based resin composition using a so-called "urethane prepolymer" as a raw material. Manufacturing methods may be employed.
  • the acrylic pressure-sensitive adhesive is not particularly limited, and a known or commonly used acrylic pressure-sensitive adhesive can be used. agent compositions.
  • the above acrylic polymer is a polymer that contains structural units derived from acrylic monomers (monomer components having (meth)acryloyl groups in the molecule) as polymer structural units.
  • the acrylic polymer is preferably a polymer containing the largest proportion of structural units derived from (meth)acrylic acid ester.
  • an acrylic polymer can be used individually or in combination of 2 or more types.
  • "(meth)acrylic” means “acrylic” and/or "methacrylic” (either one or both of "acrylic” and “methacrylic"), and others are the same.
  • Examples of the (meth)acrylic acid esters include hydrocarbon group-containing (meth)acrylic acid esters.
  • Hydrocarbon group-containing (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid cycloalkyl esters, (meth)acrylic acid aryl esters, and the like.
  • Examples of the (meth)acrylic acid alkyl esters include (meth)acrylic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester (lauryl ester), tridecyl ester, tetradecyl ester , hexadecyl ester, octadecyl ester, eicosyl ester and the like.
  • Examples of the (meth)acrylic acid cycloalkyl esters include cyclopentyl esters and cyclohexyl esters of (meth)acrylic acid.
  • Examples of the (meth)acrylic acid aryl esters include phenyl esters and benzyl esters of (meth)acrylic acid.
  • the above hydrocarbon group-containing (meth)acrylic acid esters can be used alone or in combination of two or more. All monomer components for forming an acrylic polymer because the basic properties such as adhesiveness of the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the first adhesive layer and it is easy to control the adhesiveness to be low.
  • the ratio of the hydrocarbon group-containing (meth)acrylic acid ester is preferably 40% by mass or more, more preferably 60% by mass or more.
  • the acrylic polymer contains structural units derived from other monomer components copolymerizable with the hydrocarbon group-containing (meth)acrylic acid ester for the purpose of improving cohesive strength, heat resistance, adhesiveness, etc.
  • Other monomer components include carboxy group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, acrylamide, acrylonitrile, and other functional group-containing monomers. monomers, vinyl ester monomers, and the like.
  • carboxy group-containing monomers examples include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • acid anhydride monomer examples include maleic anhydride and itaconic anhydride.
  • Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate and the like.
  • Examples of the glycidyl group-containing monomer include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate.
  • Examples of the sulfonic acid group-containing monomer include styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth) ) acryloyloxynaphthalenesulfonic acid and the like.
  • Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acryloyl phosphate and the like.
  • Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl cyclohexanecarboxylate, and vinyl benzoate.
  • the above other monomer components can be used alone or in combination of two or more. All monomer components for forming an acrylic polymer because the basic properties such as adhesiveness of the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the first adhesive layer and it is easy to control the adhesiveness to be low.
  • the total ratio of the other monomer components is preferably 60% by mass or less, more preferably 40% by mass or less.
  • the above acrylic polymer may contain a structural unit derived from a polyfunctional monomer copolymerizable with the monomer component forming the acrylic polymer in order to form a crosslinked structure in the polymer skeleton.
  • the polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, penta Erythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy (meth)acrylate (e.g.
  • polyglycidyl (meth)acrylate examples thereof include monomers having a (meth)acryloyl group and other reactive functional groups in the molecule such as (meth)acrylate and urethane (meth)acrylate.
  • the above polyfunctional monomers can be used alone or in combination of two or more. All monomer components for forming an acrylic polymer because the basic properties such as adhesiveness of the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the first adhesive layer and it is easy to control the adhesiveness to be low. is preferably 40% by mass or less, more preferably 30% by mass or less.
  • An acrylic polymer is obtained by subjecting one or more monomer components including an acrylic monomer to polymerization.
  • Polymerization methods include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like.
  • the mass average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 200,000 to 3,000,000.
  • weight average molecular weight is 100,000 or more, the amount of low-molecular-weight substances in the pressure-sensitive adhesive layer tends to be small, and contamination of electronic parts and the like can be further suppressed.
  • the acrylic pressure-sensitive adhesive composition forming the first pressure-sensitive adhesive layer may contain a cross-linking agent.
  • the acrylic polymer can be crosslinked to further reduce low-molecular-weight substances in the first pressure-sensitive adhesive layer.
  • the mass average molecular weight of the acrylic polymer can be increased to control the adhesiveness to be low.
  • the cross-linking agent include polyisocyanate compounds, epoxy compounds, polyol compounds (polyphenol-based compounds, etc.), aziridine compounds, melamine compounds, etc., and isocyanate-based cross-linking agents and/or epoxy-based cross-linking agents are preferred.
  • the amount used is preferably about 10 parts by mass or less, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the acrylic polymer.
  • isocyanate-based cross-linking agents include aliphatic isocyanates, alicyclic isocyanates, and aromatic isocyanates.
  • Aliphatic isocyanates include, for example, trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and dimer acid diisocyanate.
  • Cycloaliphatic isocyanates include, for example, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.
  • Aromatic isocyanates include, for example, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.
  • isocyanate-based cross-linking agents include trimethylolpropane adducts of tolylene diisocyanate (trade name: "Coronate L", manufactured by Tosoh Corporation) and isocyanurate of hexamethylene diisocyanate (trade name: "Coronate HX", manufactured by Tosoh Corporation). ) made) are also included.
  • epoxy-based cross-linking agents include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylamino methyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether,
  • the adhesive composition that constitutes the first adhesive layer preferably contains a light release agent.
  • a WBL Wood Boundary Layer
  • the light release agent is not particularly limited, and known light release agents can be used without limitation. Examples thereof include silicone release agents, fluorosurfactants, aliphatic esters, etc. It can be used alone or in combination of two or more.
  • the silicone-based release agent is not particularly limited, but includes, for example, a thermosetting silicone-based release agent, an ionizing radiation-curable silicone-based release agent, and the like.
  • the silicone-based release agent may be either a solvent-free type that does not contain a solvent or a solvent-type that is dissolved or dispersed in an organic solvent.
  • the silicone release agent can be used alone or in combination of two or more.
  • thermosetting silicone-based release agent is not particularly limited, but preferably contains an organohydrogenpolysiloxane and an organopolysiloxane having an aliphatic unsaturated group. Further, the above silicone-based release agent is preferably a thermal addition reaction-curable silicone-based release agent that is cured by cross-linking caused by a thermal addition reaction.
  • the heat addition reaction-curable silicone-based release agent is not particularly limited, but polysiloxane (Si—H group-containing polysiloxane) having a hydrogen atom (H) bonded to a silicon atom (Si) in the molecule, and a molecule Polysiloxane (Si-H group reactive polysiloxane) containing a functional group (Si-H group reactive functional group) having reactivity to Si-H bond (covalent bond between Si and H) in A release agent containing is preferably exemplified. This release agent is cured by cross-linking through an addition reaction between the Si—H group and the reactive functional group of the Si—H group.
  • the Si to which H is bonded may be either Si in the main chain or Si in the side chain.
  • the Si—H group-containing polysiloxane is preferably polysiloxane containing two or more Si—H groups in the molecule.
  • Polysiloxanes containing two or more Si—H groups preferably include dimethylhydrogensiloxane-based polymers such as poly(dimethylsiloxane-methylsiloxane).
  • the Si—H group-reactive polysiloxane a Si—H group-reactive functional group or a side chain containing such a functional group forms the main chain (skeleton) of the siloxane-based polymer (for example, the main chain Preferred examples include polysiloxanes in a mode in which Si at the terminal and Si in the main chain are bonded. Among them, polysiloxane in which the Si—H group-reactive functional group is directly bonded to Si in the main chain is preferred. Furthermore, as the Si—H group-reactive polysiloxane, a polysiloxane containing two or more Si—H group-reactive functional groups in the molecule is also preferable.
  • Si—H group-reactive functional groups in the above Si—H group-reactive polysiloxane include alkenyl groups such as vinyl groups and hexenyl groups.
  • Examples of the siloxane-based polymer forming the main chain portion of the Si—H group-reactive polysiloxane include polydialkylsiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polymethylethylsiloxane (the two alkyl groups are the same).
  • polyalkylarylsiloxane poly(dimethylsiloxane-methylsiloxane); a polymer obtained by polymerizing a plurality of Si-containing monomers; Among them, polydimethylsiloxane is preferable as the siloxane-based polymer forming the main chain portion.
  • the thermal addition reaction-curable silicone-based release agent contains a polysiloxane containing two or more Si—H groups in the molecule and a polysiloxane containing two or more Si—H reactive functional groups in the molecule. It is preferably a heat-addition-curable silicone-based release agent to be contained.
  • the ionizing radiation-curable silicone-based release agent is not particularly limited, but preferably includes a UV-curable silicone-based release agent that is cured by a crosslinking reaction caused by ultraviolet (UV) irradiation.
  • UV ultraviolet
  • the above UV-curable silicone-based release agent is a release agent that is cured by chemical reactions such as cationic polymerization, radical polymerization, radical addition polymerization, hydrosilylation reaction, etc., by UV irradiation.
  • the UV-curable silicone release agent is particularly preferably a UV-curable silicone release agent that cures by cationic polymerization.
  • the cationic polymerization type UV curable silicone release agent is not particularly limited, but at least two epoxy groups form the main chain (skeleton) of the siloxane polymer (for example, Si at the main chain terminal, main Si in the chain) and / or Si contained in the side chain, respectively, directly or via a divalent group (alkylene group such as methylene group and ethylene group; alkyleneoxy group such as ethyleneoxy group and propyleneoxy group) Release agents containing epoxy-group-containing polysiloxanes bound together are preferred.
  • the bonding modes of these at least two epoxy groups to Si may be the same or different. That is, release agents containing polysiloxane containing two or more side chains containing one or more epoxy groups are preferred.
  • epoxy group-containing side chains examples include glycidyl group, glycidoxy group (glycidyloxy group), 3,4-epoxycyclohexyl group, 2,3-epoxycyclopentyl group and the like.
  • Epoxy-group-containing polysiloxanes may be linear, branched, or mixtures thereof.
  • the silicone-based pressure-sensitive adhesive preferably contains a thermosetting silicone-based release agent from the viewpoint that the first pressure-sensitive adhesive layer can be easily controlled to have a low adhesiveness. More preferably, it contains a reaction-curable silicone-based release agent.
  • the content of the silicone-based release agent is not particularly limited, but 100 parts by weight of the silicone-based polymer that is the base polymer. is preferably 0.5 parts by weight or more and 100 parts by weight or less.
  • the content is 0.5 parts by weight or more, the effect of easily controlling the adhesiveness of the first pressure-sensitive adhesive layer to be low can be easily obtained. Department or above.
  • the content is 100 parts by weight or less, sufficient adhesiveness cannot be obtained, and it becomes easy to suppress the problem that electronic components are difficult to receive.
  • it is 25 parts by weight or less.
  • the fluorine-based surfactant as a light release agent, it is possible to exhibit a light release effect due to the low surface free energy of the fluorine site.
  • the fluorine-based surfactant is not particularly limited, but examples include fluorine-based oligomers, perfluorobutanesulfonates, perfluoroalkyl group-containing carboxylates, hexafluoropentane trimer derivative-containing sulfonates, and hexafluoropentane trimers. Derivative-containing carboxylates, hexafluoropentane trimer derivative-containing quaternary ammonium salts, hexafluoropentane trimer derivative-containing betaine, hexafluoropentane trimer derivative-containing polyoxyethylene ethers, and the like, among others, fluorine-based oligomers are preferred. In addition, a fluorine-type surfactant can be used individually or in combination of 2 or more types.
  • fluorine-based surfactants include commercially available products such as "Megafac F (1) 14" and “Megafac F-410” (manufactured by DIC Corporation), the product name " Surflon S-211", “Surflon S-221", “Surflon S-231", “Surflon S-232", “Surflon S-233", “Surflon S-241", “Surflon S-242", “Surflon S-243", “Surflon S-420” (manufactured by AGC Seimi Chemical Co., Ltd.), trade names “Futergent 100", “Futergent 100C”, “Futergent 110", “Futergent 150”, “ Futergent 150CH”, “Ftergent 300”, “Ftergent 310”, “Ftergent 320”, “Ftergent 400SW”, “Ftergent 251”, “Ftergent 212M”, “Ftergent 215M”, “Ftergent 250”, “Ftergent 20
  • the weight average molecular weight (Mw) of the fluorine-based oligomer is preferably 3,500 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more.
  • the weight-average molecular weight of the fluorine-based oligomer is 3500 or more, it becomes easy to control the adhesiveness to be low. Furthermore, when the weight-average molecular weight is 20,000 or more, foaming can be suppressed when the pressure-sensitive adhesive (composition) is blended, and the appearance after the pressure-sensitive adhesive is applied is excellent, which is preferable.
  • the upper limit of the weight average molecular weight (Mw) of the fluorine-based oligomer is preferably 200,000, more preferably 100,000. By setting the upper limit to 200,000, the fluorine-based oligomer tends to be unevenly distributed on the surface, making it easier to exhibit the effect of light release, which is preferable.
  • fluorine-based oligomer for example, commercial products such as "Megafac F(2)51”, “Megafac F(2)53”, “Megafac F(2)81”, “Megafac F-410", “Megafuck F-430", “Megafuck F-444", “Megafuck F-477”, “Megafuck F-510", “Megafuck F-511”, “Megafuck F- 551”, “Megafuck F-552", “Megafuck F-553”, “Megafuck F-554”, “Megafuck F-555”, “Megafuck F-556", “Megafuck F-557” , “Megafuck F-558", "Megafuck F-559”, “Megafuck F-560”, “Megafuck F-561”, “Megafuck F-562”, “Megafuck F-563”, “ Megafac F-565”, “Megafac F-568", “Megafac F-569",
  • the content of the fluorosurfactant is not particularly limited, but the silicone polymer 100, which is the base polymer, is not particularly limited. It is preferably 0.01 parts by weight or more and 5 parts by weight or less. When the content is 0.01 parts by weight or more, the effect of easily controlling the adhesiveness of the first pressure-sensitive adhesive layer to be low can be easily obtained, and the content is more preferably 0.05 parts by weight or more, and even more preferably. It is 0.1 part by weight or more. In addition, if the content is 5 parts by weight or less, sufficient adhesiveness cannot be obtained, and it becomes easy to suppress the problem that it becomes difficult to receive electronic parts. It is more preferably 3 parts by weight or less, and even more preferably 2 parts by weight or less.
  • the adhesive composition that constitutes the first adhesive layer By including a fatty acid ester in the adhesive composition that constitutes the first adhesive layer, low adhesion and wettability of the first adhesive layer to electronic components can be expected.
  • fatty acid ester examples include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, isopropyl myristate, Isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl cocoate, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, penta erythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate,
  • the content of the fatty acid ester contained in the urethane-based pressure-sensitive adhesive composition is, for example, polyol 100 from the viewpoint of low adhesion to electronic parts of the first pressure-sensitive adhesive layer, wettability, and staining of adherends. It is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and even more preferably 3 to 30 parts by weight.
  • the content (total amount) of the pressure-sensitive adhesive layer should From the viewpoint of staining, for example, 0.1 parts by weight or more is preferable, 1 part by weight or more is more preferable, and 3 parts by weight or more is even more preferable with respect to 100 parts by weight of the base polymer. From the viewpoint of preventing coloring of the first pressure-sensitive adhesive layer, it is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 10 parts by weight or less.
  • the pressure-sensitive adhesive composition that constitutes the first pressure-sensitive adhesive layer preferably contains anti-degradation agents such as antioxidants and ultraviolet absorbers.
  • anti-degradation agents such as antioxidants and ultraviolet absorbers.
  • UV absorber examples include, but are not limited to, triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.
  • UV absorbers and the like can be mentioned, and these can be used alone or in combination of two or more.
  • triazine-based UV absorbers and benzotriazole-based UV absorbers are preferred, triazine-based UV absorbers having two or less hydroxyl groups in one molecule, and benzotriazole having one benzotriazole skeleton in one molecule.
  • At least one UV absorber selected from the group consisting of triazole-based UV absorbers has good solubility in the monomer used to form the acrylic pressure-sensitive adhesive composition and has a wavelength of around 380 nm. It is preferable because it has a high ultraviolet absorption capacity at .
  • triazine-based UV absorbers having two or less hydroxyl groups in one molecule include 2,4-bis-[ ⁇ 4-(4-ethylhexyloxy)-4-hydroxy ⁇ -phenyl]-6 -(4-methoxyphenyl)-1,3,5-triazine (trade name “Tinosorb S”, manufactured by BASF), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4 -dibutoxyphenyl)-1,3,5-triazine (trade name “TINUVIN 460”, manufactured by BASF), 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine -2-yl)-5-hydroxyphenyl and [(C 10 -C 16 (mainly C 12 -C 13 )alkyloxy)methyl]oxirane reaction product (trade name “TINUVIN400”, manufactured by BASF), 2 -[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin
  • benzophenone-based ultraviolet absorber (benzophenone-based compound) and oxybenzophenone-based ultraviolet absorber (oxybenzophenone-based compound)
  • examples of the benzophenone-based ultraviolet absorber (benzophenone-based compound) and oxybenzophenone-based ultraviolet absorber (oxybenzophenone-based compound) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy -4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2, 2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone and the like can be mentioned.
  • salicylic acid ester-based ultraviolet absorbers examples include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, and phenyl-2-acryloyloxy.
  • cyanoacrylate-based ultraviolet absorbers examples include alkyl-2-cyanoacrylates, cycloalkyl-2-cyanoacrylates, alkoxyalkyl-2-cyanoacrylates, alkenyl-2-cyanoacrylates, alkynyl- 2-cyanoacrylate and the like can be mentioned.
  • the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength range of 300-400 nm, more preferably in the wavelength range of 320-380 nm.
  • antioxidants examples include phenol-based, phosphorus-based, sulfur-based and amine-based antioxidants, and at least one selected from these is used. Among these, phenolic antioxidants are preferred, and hindered phenolic antioxidants are particularly preferred.
  • phenolic antioxidants include monocyclic phenol compounds such as 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6 -dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol , 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl -6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL- ⁇ -tocopherol
  • the above deterioration inhibitors can be used alone or in combination of two or more.
  • the content of the anti-deterioration agent contained in the pressure-sensitive adhesive composition is, for example, based on 100 parts by weight of the first pressure-sensitive adhesive composition from the viewpoint of suppressing deterioration such as discoloration during storage and workability of the double-sided pressure-sensitive adhesive film for transfer. , preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, even more preferably 0.1 to 3 parts by weight.
  • the pressure-sensitive adhesive composition that constitutes the first pressure-sensitive adhesive layer can contain any other appropriate component within a range that does not impair the effects of the present invention.
  • Such other components include, for example, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, conductive agents, surface lubricants, leveling agents, and heat-stabilizing agents. agents, polymerization inhibitors, lubricants, solvents and the like.
  • the second pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer for temporarily fixing to the carrier substrate, and is composed of a peelable pressure-sensitive adhesive layer.
  • the configuration in which the second pressure-sensitive adhesive layer consists of a peelable pressure-sensitive adhesive layer is preferable in that the second pressure-sensitive adhesive layer can be peeled off from the carrier substrate without contamination such as adhesive residue, and reworkability can be improved.
  • the second pressure-sensitive adhesive layer is formed by adjusting the pressure-sensitive adhesive by adjusting the type and composition of the pressure-sensitive adhesive, the degree of cross-linking, etc., and reducing the pressure-sensitive adhesive strength by physical stimuli such as heat and electromagnetic waves such as ultraviolet rays.
  • physical stimuli such as heat and electromagnetic waves such as ultraviolet rays.
  • the adhesive strength of the second pressure-sensitive adhesive layer can be adjusted by adjusting the type and composition of the pressure-sensitive adhesive that constitutes it, the degree of cross-linking, etc., or by forming a WBL (Weak Boundary Layer) by blending a light release agent or a plasticizer. can be adjusted.
  • WBL Wood Boundary Layer
  • the thickness of the second pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more. When the thickness is at least a certain value, the second pressure-sensitive adhesive layer can be stably and easily fixed to the carrier substrate, which is preferable. Moreover, although the upper limit of the thickness of the second pressure-sensitive adhesive layer is not particularly limited, it is preferably 30 ⁇ m, more preferably 20 ⁇ m. When the thickness is less than a certain value, the second pressure-sensitive adhesive layer can be easily peeled off from the carrier substrate, and reworkability is improved, which is preferable.
  • the pressure-sensitive adhesive that constitutes the second pressure-sensitive adhesive layer is not particularly limited. adhesives, polyester-based adhesives, polyamide-based adhesives, epoxy-based adhesives, vinyl alkyl ether-based adhesives, fluorine-based adhesives, and the like. Among these, silicone-based adhesives, urethane-based adhesives, and acrylic-based adhesives are preferable from the viewpoint of improving reworkability, as they can be removed from the carrier substrate without contamination such as adhesive residue, and urethane-based adhesives and acrylic adhesives are preferred. PSA is more preferred, and acrylic PSA is even more preferred.
  • the second pressure-sensitive adhesive layer in the double-sided pressure-sensitive adhesive film for transfer according to the present invention is a pressure-sensitive adhesive layer capable of intentionally reducing the pressure-sensitive adhesive force by an external action during the process of using the double-sided pressure-sensitive adhesive film for transfer (reduction of pressure-sensitive adhesive force It may be a flexible adhesive layer), or it may be an adhesive layer (adhesive strength non-reducing type adhesive layer) whose adhesive force is hardly or not reduced by external action during the use process of the double-sided adhesive film for transfer. It can be selected as appropriate according to the method, conditions, etc. for transferring an electronic component using the double-sided pressure-sensitive adhesive film for transfer according to the present invention.
  • the second pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer capable of reducing the pressure-sensitive adhesive strength
  • the state in which the pressure-sensitive adhesive layer exhibits relatively high pressure-sensitive adhesive strength in the process of manufacturing or using the double-sided pressure-sensitive adhesive film for transfer according to the present invention. and a state in which the adhesive strength is relatively low can be properly used.
  • the second pressure-sensitive adhesive layer in the step of receiving the electronic component with the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer exhibits relatively high adhesive strength, and the carrier substrate is It is possible to suppress and prevent the transfer double-sided adhesive film from floating.
  • the reworkability can be improved by reducing the adhesive strength of the second pressure-sensitive adhesive layer.
  • Examples of adhesives that form such an adhesive layer capable of reducing adhesive strength include radiation-curable adhesives and heat-foamable adhesives.
  • the pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer capable of reducing the pressure-sensitive adhesive strength can be used alone or in combination of two or more.
  • the radiation-curable adhesive for example, an adhesive that is cured by irradiation with electron beams, ultraviolet rays, ⁇ -rays, ⁇ -rays, ⁇ -rays, or X-rays can be used.
  • Adhesives ultraviolet curable adhesives
  • the same acrylic polymer as the first adhesive layer can be used as the base polymer.
  • the basic properties such as adhesiveness of the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the second adhesive layer, and the adhesiveness and peelability are easily controlled.
  • the ratio of the hydrocarbon group-containing (meth)acrylic acid ester in the monomer component is preferably 40% by mass or more, more preferably 60% by mass or more.
  • the acrylic polymer may contain a hydroxy group-containing monomer.
  • the second pressure-sensitive adhesive layer tends to have an appropriate cohesive strength.
  • the proportion of the hydroxy group-containing monomer in the acrylic polymer is, for example, 0.1 to 30% by mass, preferably 0.1% by mass. 5 to 20% by mass.
  • the acrylic polymer may contain a carboxy group-containing monomer.
  • the second pressure-sensitive adhesive layer tends to have adequate adhesion reliability.
  • the proportion of the carboxy group-containing monomer in the acrylic polymer is, for example, 0.1 to 30% by mass, preferably 0.5 to 30% by mass. 20% by mass.
  • the acrylic polymer may contain a vinyl ester monomer.
  • the second pressure-sensitive adhesive layer tends to have an appropriate cohesive strength.
  • the proportion of the vinyl ester monomer in the acrylic polymer is, for example, 0.1 to 60% by mass, preferably 0.5 to 50%. % by mass.
  • the acrylic pressure-sensitive adhesive composition forming the second pressure-sensitive adhesive layer may contain a cross-linking agent.
  • the acrylic polymer can be crosslinked to further reduce low-molecular-weight substances in the second pressure-sensitive adhesive layer.
  • the cross-linking agent include polyisocyanate compounds, epoxy compounds, polyol compounds (polyphenol-based compounds, etc.), aziridine compounds, melamine compounds, and the like, and isocyanate-based cross-linking agents and/or epoxy-based cross-linking agents are preferred cross-linking agents.
  • the amount used is preferably about 10 parts by mass or less, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the acrylic polymer.
  • a cross-linking accelerator may be used in the acrylic pressure-sensitive adhesive composition forming the second pressure-sensitive adhesive layer.
  • the type of cross-linking accelerator can be appropriately selected according to the type of cross-linking agent used.
  • the term "crosslinking accelerator” refers to a catalyst that increases the speed of the cross-linking reaction by the cross-linking agent.
  • Such crosslinking accelerators include tin (Sn)-containing compounds such as dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, tetra-n-butyltin, trimethyltin hydroxide;
  • Sn tin
  • examples include amines such as N',N'-tetramethylhexanediamine and triethylamine, and N-containing compounds such as imidazoles.
  • Sn-containing compounds are preferred.
  • cross-linking accelerators are particularly effective when a hydroxyl group-containing monomer is used as the secondary monomer and an isocyanate-based cross-linking agent is used as the cross-linking agent.
  • the amount of the cross-linking accelerator contained in the adhesive composition is, for example, about 0.001 to 0.5 parts by mass (preferably about 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the acrylic polymer. ).
  • Examples of the radiation-polymerizable monomer component include urethane (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta ( meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate and the like.
  • the radiation-polymerizable oligomer component examples include various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based oligomers, and those having a molecular weight of about 100 to 30,000 are preferred.
  • the content of the radiation-curable monomer component and oligomer component in the radiation-curable adhesive that forms the second adhesive layer is, for example, 5 to 500 parts by mass, preferably 40 parts by mass, with respect to 100 parts by mass of the base polymer. It is about 150 parts by mass.
  • the additive-type radiation-curable pressure-sensitive adhesive for example, one disclosed in JP-A-60-196956 may be used.
  • an internal radiation-curable adhesive containing a base polymer having a radiation-polymerizable carbon-carbon double bond or other functional group in the polymer side chain, in the polymer main chain, or at the polymer main chain end. Also included are adhesives. When such an internal radiation-curable adhesive is used, it tends to be possible to suppress unintended changes over time in adhesive properties due to migration of low-molecular-weight components within the formed second adhesive layer. be.
  • an acrylic polymer is preferable as the base polymer contained in the internal radiation-curable pressure-sensitive adhesive.
  • a method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer for example, an acrylic polymer is obtained by polymerizing (copolymerizing) raw material monomers containing a monomer component having a first functional group. After that, a compound having a second functional group capable of reacting with the first functional group and a radiation polymerizable carbon-carbon double bond is added to an acrylic polymer while maintaining the radiation polymerizability of the carbon-carbon double bond. and condensation reaction or addition reaction method.
  • Combinations of the first functional group and the second functional group include, for example, a carboxy group and an epoxy group, an epoxy group and a carboxy group, a carboxy group and an aziridyl group, an aziridyl group and a carboxy group, a hydroxy group and an isocyanate group, An isocyanate group, a hydroxy group, and the like can be mentioned.
  • a combination of a hydroxy group and an isocyanate group, and a combination of an isocyanate group and a hydroxy group are preferred from the viewpoint of ease of reaction tracking.
  • the first functional group is A preferred combination is a hydroxy group and the second functional group is an isocyanate group.
  • Compounds having an isocyanate group and a radiation-polymerizable carbon-carbon double bond, that is, radiation-polymerizable unsaturated functional group-containing isocyanate compounds include, for example, methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate and the like.
  • acrylic polymer having a hydroxy group those containing structural units derived from the above-mentioned hydroxy group-containing monomers and ether compounds such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. is mentioned.
  • the radiation-curable adhesive preferably contains a photopolymerization initiator.
  • the photopolymerization initiator include ⁇ -ketol compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, camphorquinone, halogenated ketone, acylphosphinate, acylphosphonate and the like.
  • Examples of the ⁇ -ketol compounds include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxy propiophenone, 1-hydroxycyclohexylphenyl ketone, and the like.
  • Examples of the acetophenone compounds include methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2 -Morpholinopropane-1 and the like.
  • Examples of the benzoin ether compounds include benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether.
  • Examples of the ketal compounds include benzyl dimethyl ketal.
  • Examples of the aromatic sulfonyl chloride compounds include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime compound include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime.
  • Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone.
  • thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropyl. thioxanthone and the like.
  • the content of the photopolymerization initiator in the radiation-curable adhesive is, for example, 0.05 to 20 parts by weight with respect to 100 parts by weight of the base polymer.
  • the heat-expandable pressure-sensitive adhesive is a pressure-sensitive adhesive containing components that foam or expand when heated (foaming agent, thermally expandable microspheres, etc.).
  • foaming agent include various inorganic foaming agents and organic foaming agents.
  • the inorganic foaming agent include ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, and azides.
  • organic foaming agent examples include alkane hydrochlorides such as trichloromonofluoromethane and dichloromonofluoromethane; azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate; and paratoluene.
  • alkane hydrochlorides such as trichloromonofluoromethane and dichloromonofluoromethane
  • azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate
  • paratoluene examples include paratoluene.
  • Hydrazine compounds such as sulfonyl hydrazide, diphenylsulfone-3,3'-disulfonyl hydrazide, 4,4'-oxybis(benzenesulfonylhydrazide), allylbis(sulfonylhydrazide); p-toluylenesulfonyl semicarbazide, 4,4'- Semicarbazide compounds such as oxybis (benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl- Examples include N-nitroso compounds such as N,N'-dinitrosoterephthalamide.
  • heat-expandable microspheres examples include microspheres having a structure in which a substance that easily gasifies and expands upon heating is encapsulated in the shell.
  • Isobutane, propane, pentane, and the like are examples of substances that easily gasify and expand when heated.
  • Thermally expandable microspheres can be produced by encapsulating a substance that is easily gasified and expanded by heating in a shell-forming substance by a coacervation method, an interfacial polymerization method, or the like.
  • the shell-forming substance a substance exhibiting thermal melting properties and a substance capable of bursting due to the action of thermal expansion of the enclosed substance can be used.
  • Examples of such substances include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, and the like.
  • non-reducing adhesive layer examples include a pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive layer an adhesive layer formed from the radiation-curable adhesive described above with respect to the adhesive force-reducing adhesive layer is cured by irradiation in advance and has a certain adhesive force.
  • An adhesive layer is included.
  • the pressure-sensitive adhesives forming the non-reducing pressure-sensitive adhesive layer can be used alone or in combination of two or more.
  • the whole second pressure-sensitive adhesive layer may be a non-adhesive force-reducing pressure-sensitive adhesive layer, or a part thereof may be a non-adhesive force-reducing pressure-sensitive adhesive layer.
  • the entire second pressure-sensitive adhesive layer may be a non-adhesion-reducing pressure-sensitive adhesive layer, or a specific portion of the second pressure-sensitive adhesive layer may It may be a non-reducing type pressure-sensitive adhesive layer and the other portion may be a pressure-sensitive adhesive layer capable of reducing the pressure-sensitive adhesive force.
  • all the pressure-sensitive adhesive layers in the laminated structure may be non-adhesive strength-reducing pressure-sensitive adhesive layers, or some of the pressure-sensitive adhesive layers in the laminated structure may be adhesive layers. It may be a non-force-reducing pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer formed by pre-curing the pressure-sensitive adhesive layer (radiation-unexposed radiation-curable pressure-sensitive adhesive layer) formed from a radiation-curable pressure-sensitive adhesive by irradiation with radiation Even if the adhesive strength is reduced by irradiation, it exhibits adhesiveness due to the contained polymer component, and it is possible to exhibit the minimum required adhesive strength for the double-sided adhesive film for transfer according to the present invention.
  • the entire second pressure-sensitive adhesive layer may be the irradiated radiation-curable pressure-sensitive adhesive layer in the surface spreading direction of the second pressure-sensitive adhesive layer.
  • a portion of the agent layer may be a radiation-curable pressure-sensitive adhesive layer that has been exposed to radiation, and the other portion may be a radiation-curable pressure-sensitive adhesive layer that has not been exposed to radiation.
  • radiation-curable pressure-sensitive adhesive layer refers to a pressure-sensitive adhesive layer formed from a radiation-curable pressure-sensitive adhesive. It includes both the radiation-cured radiation-curable pressure-sensitive adhesive layer after the agent layer has been cured by irradiation.
  • the adhesive that forms the pressure-sensitive adhesive layer a known or commonly used pressure-sensitive adhesive can be used, and an acrylic adhesive that uses an acrylic polymer as a base polymer can be preferably used.
  • the acrylic polymer is a polymer containing the structural unit derived from (meth)acrylic acid ester as the largest structural unit in terms of mass ratio. is preferred.
  • the acrylic polymer for example, the acrylic polymer described as the acrylic polymer that can be included in the additive-type radiation-curable pressure-sensitive adhesive can be employed.
  • the substrate in the double-sided pressure-sensitive adhesive film for transfer according to the present invention is an element that functions as a support in the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer.
  • Substrates include, for example, plastic substrates (especially plastic films).
  • the base material may be a single layer or a laminate of the same or different base materials.
  • Examples of the resin constituting the plastic substrate include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymerized polypropylene, block copolymerized polypropylene, and homopolypropylene.
  • polybutene polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester (random, alternating) copolymer, ethylene- Polyolefin resins such as butene copolymers and ethylene-hexene copolymers; polyurethanes; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT); polycarbonates; polyimides; polyamide such as aramid and wholly aromatic polyamide; polyphenyl sulfide; fluorine resin; polyvinyl chloride; polyvinylidene chloride; cellulose resin;
  • EVA ethylene-vinyl acetate copolymer
  • EVA ethylene-vinyl acetate copolymer
  • ionomer ethylene-(meth)acrylic
  • the heat-resistant resin such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), polyetheretherketone (PEEK), etc. It preferably contains polyimide as a main component, and more preferably contains polyimide as a main component. In addition, let the main component of a base material be a component which occupies the largest mass ratio in a structural component. The above resins may be used alone or in combination of two or more.
  • the second pressure-sensitive adhesive layer is a radiation-curable pressure-sensitive adhesive layer as described above, the substrate preferably has radiation transparency.
  • the plastic film may be non-oriented, or may be oriented in at least one direction (uniaxial direction, biaxial direction, etc.). It is preferable because it is difficult to exhibit contractility.
  • the first pressure-sensitive adhesive layer and/or the second pressure-sensitive adhesive layer side surface of the base material may be subjected to, for example, corona discharge treatment, plasma treatment, sand matting treatment, Physical treatments such as ozone exposure treatment, flame exposure treatment, high voltage shock exposure treatment, and ionizing radiation treatment; chemical treatment such as chromic acid treatment; coating agent (undercoat); surface treatment such as easy adhesion treatment by silicone primer treatment. may be applied.
  • a conductive deposition layer containing a metal, an alloy, an oxide thereof, or the like may be provided on the substrate surface, or a conductive polymer such as PEDOT-PSS may be coated.
  • the surface treatment for enhancing adhesion is preferably applied to the entire surface of the adhesive layer side of the substrate.
  • the thickness of the substrate is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 10 ⁇ m or more, from the viewpoint of ensuring strength for the substrate to function as a support in the double-sided pressure-sensitive adhesive film for transfer according to the present invention. 15 ⁇ m or more, particularly preferably 20 ⁇ m or more. From the viewpoint of achieving appropriate flexibility in the double-sided pressure-sensitive adhesive film for transfer according to the present invention, the thickness of the substrate is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less, and still more preferably 150 ⁇ m or less. .
  • ⁇ Separator> The pressure-sensitive adhesive layer surfaces (the pressure-sensitive adhesive surfaces of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer) of the double-sided pressure-sensitive adhesive film for transfer according to the present invention are protected by a release liner (separator) until use.
  • the separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when the pressure-sensitive adhesive film is attached to the adherend.
  • a conventional release paper or the like can be used.
  • a fluoropolymer e.g., polytetrafluoroethylene, Low-adhesive substrates made of polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.
  • non-polar polymers for example, a low-adhesive base material made of olefin resins such as polyethylene and polypropylene can be used.
  • a separator having a release layer formed on at least one surface of a separator substrate can be suitably used.
  • Base materials for such separators include polyester films (polyethylene terephthalate films, etc.), olefin resin films (polyethylene films, polypropylene films, etc.), polyvinyl chloride films, polyimide films, polyamide films (nylon films), rayon films, and the like.
  • plastic base film synthetic resin film
  • paper wooden paper, Japanese paper, kraft paper, glassine paper, synthetic paper, top coat paper, etc.
  • these are multi-layered by lamination or co-extrusion. (composite of 2 to 3 layers) and the like.
  • the release agent that constitutes the release layer is not particularly limited, but for example, a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, a fatty acid amide-based release agent, or the like can be used. Among them, a silicone-based release agent is preferable.
  • the release agents can be used alone or in combination of two or more. Since the first pressure-sensitive adhesive layer is composed of a low-adhesive pressure-sensitive adhesive layer, it is also possible to use a base material that has not been treated with a release treatment agent as a separator.
  • the thickness of the release layer of the first separator is preferably 10 to 2000 nm, more preferably 20 to 500 nm, and even more preferably 30 nm, from the viewpoint of keeping F(1) and T(1) within the numerical ranges described above. to 150 nm, particularly preferably 40 to 80 nm.
  • the thickness of the release layer of the second separator is preferably 10 to 2000 nm from the viewpoint that F(2), P(2), P'(2) and T(2) are within the numerical ranges described above. It is more preferably 30 to 500 nm, still more preferably 50 to 250 nm, particularly preferably 70 to 150 nm.
  • the thickness of the release layer of the first separator is preferably less than the thickness of the release layer of the second separator.
  • the separator may have an antistatic layer formed on at least one surface of the separator substrate in order to prevent adverse effects on electronic components.
  • the antistatic layer may be formed on one side of the separator (release-treated side or untreated side) or may be formed on both sides of the separator (release-treated side and untreated side).
  • Antistatic agents contained in the antistatic resin include quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic functional groups such as primary, secondary and tertiary amino groups, and sulfonates. and anionic antistatic agents having anionic functional groups such as sulfates, phosphonates and phosphates, alkylbetaines and derivatives thereof, imidazoline and derivatives thereof, amphoteric antistatic agents such as alanine and derivatives thereof, Nonionic antistatic agents such as aminoalcohols and derivatives thereof, glycerin and derivatives thereof, polyethylene glycol and derivatives thereof, and monomers having cationic, anionic, and zwitterionic ion conductive groups are polymerized or An ion-conductive polymer obtained by copolymerization can be mentioned. These compounds can be used alone or in combination of two or more.
  • the thickness of the first separator is preferably 1 to 150 ⁇ m, more preferably 5 to 100 ⁇ m, still more preferably 10 to 80 ⁇ m, from the viewpoint of keeping F(1) and T(1) within the numerical ranges described above. .
  • the thickness of the second separator is preferably 10 to 150 ⁇ m, more preferably 15 ⁇ m, from the viewpoint of keeping F(2), P(2), P′(2) and T(2) within the numerical ranges described above. ⁇ 100 ⁇ m, more preferably 20-80 ⁇ m.
  • the method for producing the laminated film according to the present invention varies depending on the composition of the pressure-sensitive adhesive composition, etc., and is not particularly limited, and known forming methods can be used. and other methods.
  • the adhesive composition is applied (coated) on a substrate to form a composition layer, and the composition layer is cured (for example, cured by heat curing or irradiation with active energy rays such as ultraviolet rays).
  • the adhesive composition is applied (coated) on a separator to form a composition layer, and the composition layer is cured (for example, A method of producing an adhesive film by forming an adhesive layer by heat curing or curing by irradiation with active energy rays such as ultraviolet rays, and then transferring the adhesive layer onto a substrate to produce an adhesive film (3). , A method of producing an adhesive film by coating (coating) on a substrate and drying to form an adhesive layer. (4) The adhesive composition is coated (coated) on a separator and dried. A method of producing an adhesive film by forming an adhesive layer with a method of transferring the adhesive layer onto a substrate
  • a heat curing method is preferable in terms of excellent productivity and in terms of forming a uniform pressure-sensitive adhesive layer with a smooth surface.
  • a known coating method can be employed, and is not particularly limited, but examples include roll coating, kiss roll coating, gravure coating, and reverse coating. , roll brush, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, and extrusion coating using a die coater.
  • the thickness (total thickness) of the double-sided pressure-sensitive adhesive film for transfer according to the present invention is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more. When the thickness is at least a certain value, the first pressure-sensitive adhesive layer can easily receive electronic components with high accuracy, which is preferable.
  • the upper limit of the thickness (total thickness) of the double-sided pressure-sensitive adhesive film for transfer according to the present invention is not particularly limited, but is preferably 500 ⁇ m, more preferably 300 ⁇ m. When the thickness is less than a certain value, the electronic component can be easily transferred to the mounting substrate with high accuracy, which is preferable.
  • the double-sided pressure-sensitive adhesive film for transfer according to the present invention is suitably used in a method for mounting electronic components onto a mounting substrate.
  • a method for mounting an electronic component on a mounting substrate using the transfer double-sided pressure-sensitive adhesive film according to the present invention preferably includes the following steps.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment of the first step in a method for mounting an electronic component onto a mounting substrate using the transfer double-sided pressure-sensitive adhesive film according to the present invention.
  • the transfer double-sided adhesive film 1 is attached to the carrier substrate 22 with the adhesive surface of the second adhesive layer 12 .
  • a marking pattern for arranging electronic components may be provided on the surface of the carrier substrate 22 that is adhered to the second adhesive layer 12 . Since the transfer double-sided pressure-sensitive adhesive film 1 has high transparency, the marking pattern applied to the carrier substrate 22 can be visually recognized.
  • a plurality of electronic components 21 separated into individual pieces by dicing are attached to the dicing tape 20, and the first adhesive layer is formed. 11 and are spaced apart from each other.
  • the electronic component 21 is pushed by the pin member 23 from the side of the dicing tape 20 to which the electronic component 21 is not attached, and the electronic component 21 is brought close to the adhesive surface of the first adhesive layer 11. , the adhesive surface of the first adhesive layer 11 receives.
  • the receiving may be performed by bringing the electronic component 21 into contact with the first adhesive layer 11 or may be performed without contact.
  • the electronic component 21 is pushed until the electronic component 21 is separated from the dicing tape 20 and dropped onto the adhesive surface of the electronic component 21 .
  • the stress applied when the electronic component 21 is received is weak, so damage to the electronic component 21 can be suppressed.
  • the adhesive surface of the first adhesive layer 11 has low adhesiveness, so the dropped electronic component 21 can be caught with high positional accuracy.
  • the electronic component 21 may be peeled off from the dicing tape 20 by irradiating radiation such as ultraviolet rays or laser beams instead of the pin member 23 .
  • FIG. 2(c) is a schematic cross-sectional view showing a state in which all the electronic components 21 of the dicing tape 20 are received on the adhesive surface of the first adhesive layer 11 of the transfer double-sided adhesive film 1.
  • FIG. 3 is a schematic cross-sectional view showing the second step in the method of mounting an electronic component onto a mounting substrate using the double-sided pressure-sensitive adhesive film for transfer according to the present invention.
  • FIG. 3( a ) they are arranged on the adhesive surface of the first adhesive layer 11 of the transfer double-sided adhesive film 1 so as to face the circuit surface 31 (the circuit pattern is not shown) of the mounting substrate 30 , while being spaced apart. Then, the electronic component 21 is arranged. Next, as shown in FIG. 4B, the circuit surface 31 of the mounting substrate 30 and the electronic components 21 arranged on the adhesive surface of the first adhesive layer 11 of the transfer double-sided adhesive film 1 are brought close to each other, The electronic component 21 and the circuit surface 31 of the mounting board 30 are brought into contact with each other.
  • the transfer of the electronic component 21 to the circuit surface 31 of the mounting substrate 30 may be performed by thermocompression bonding (for example, 150° C. for 1 minute). Since the substrate 10, the first adhesive layer 11, and/or the second adhesive layer 12, which constitute the transfer double-sided adhesive film 1, are excellent in heat resistance, they expand, contract, and adhere to each other by thermocompression. is less likely to change, the electronic component 21 can be transferred onto the circuit surface 31 of the mounting board 30 with high accuracy.
  • the electronic component 21 is peeled off from the first adhesive layer 11, and the circuit surface 31 of the mounting substrate 30 is removed. transcribed to Since the first adhesive layer 11 is composed of a low-adhesive adhesive layer, the electronic component 21 can be easily peeled off and efficiently mounted on the mounting substrate 30 without damaging the electronic component 21. .
  • the transfer double-sided adhesive film 1 in FIG. 3(c) after the electronic component 21 has been mounted on the mounting board 30 may be peeled off from the carrier board 22 (not shown). Since the second pressure-sensitive adhesive layer 12 is composed of a peelable pressure-sensitive adhesive layer, it can be peeled off without leaving an adhesive residue and is excellent in reworkability, so that the carrier substrate 22 can be easily reused.
  • the electronic component to be mounted on the mounting board is not particularly limited, but it can be suitably used for fine and thin semiconductor chips and LED chips.
  • Silicone release agent manufactured by Shin-Etsu Chemical Co., Ltd., KS-847: 100 parts by weight, catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 3.0 weight A part thereof was diluted with toluene to 1.0% by weight to obtain a silicone-based stripping liquid.
  • the resulting silicone-based release treatment liquid was applied to the surface of a base film (thickness 50 ⁇ m, trade name “Diafoil T100-50S”, manufactured by Mitsubishi Chemical Corporation) as a release layer, and the thickness after drying with a wire bar.
  • a separator (1) consisting of a laminate of
  • ⁇ Production Example 4 Production of separator (2) Using a base film (thickness 25 ⁇ m, trade name “Diafoil T100-25”, manufactured by Mitsubishi Chemical Corporation), the release layer has a thickness of 100 nm after drying.
  • a separator (2) consisting of a laminate of [release layer (thickness: 100 nm, release treatment B)]/[base material layer] was produced in the same manner as in Production Example 3 except that the coating was performed in the above manner.
  • separators used as the second separator were produced by changing the thickness of the base film as shown in Table 1.
  • Silicone adhesive (addition reaction type silicone adhesive, trade name "X-40-3306", manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by weight, platinum catalyst 1 (trade name "CAT-PL-50T”, Shin-Etsu Chemical Co., Ltd.) 1.4 parts by weight, silicone-based release agent 1 (addition reaction type silicone-based release agent containing dimethylpolysiloxane as a main component, trade name “KS-776A” and Shin-Etsu Chemical Co., Ltd. ) was added, diluted with toluene so that the total solid content was 25% by weight, and mixed with a disper to prepare a silicone pressure-sensitive adhesive composition.
  • a base film (polyester film with one side treated with a silicone primer, thickness 75 ⁇ m, trade name "Diafoil MRF #75", manufactured by Mitsubishi Plastics Co., Ltd.) was coated with a silicone-based pressure-sensitive adhesive composition on the silicone-primed side.
  • the product was applied so that the glue thickness after drying was 10 ⁇ m, and cured by drying under the conditions of a drying temperature of 120° C. and a drying time of 5 minutes.
  • a film having a silicone pressure-sensitive adhesive layer on the silicone primer-treated layer of the base film was obtained.
  • the release layer side of the separator (1) produced in Production Example 3 is attached to the silicone-based pressure-sensitive adhesive layer to protect it, [first separator layer] / [silicone-based pressure-sensitive adhesive layer] / A laminate (1) having a laminate structure of [base film layer] was obtained.
  • TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • a cross-linking agent is added to 100 parts by weight of the solid content in terms of solid content.
  • 6 parts by weight of the second separator (separator (2)) diluted with ethyl acetate so that the total solid content is 25% by weight, and stirred with a disper. It was coated on the release layer side with a fountain roll so as to have a thickness of 5 ⁇ m after drying, and cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds.
  • an acrylic pressure-sensitive adhesive layer (1) was formed on the second separator.
  • the base film side (silicone primer-untreated surface) of the laminate (1) obtained above is attached to the surface of the acrylic pressure-sensitive adhesive layer (1), [first separator layer] / [silicone-based A laminated film having a laminated structure of adhesive layer (first adhesive layer)]/[base film layer]/[acrylic adhesive (1) layer (second adhesive layer)]/[second separator layer] got
  • Example 2 The thickness of the adhesive after drying the silicone-based pressure-sensitive adhesive in the first pressure-sensitive adhesive layer is set to 25 ⁇ m, and the base film in the separator (2) is used instead of the separator (2) for the second separator (thickness 38 ⁇ m, product A laminated film was obtained in the same manner as in Example 1, except that a separator changed to the name "Diafoil T100C38" (manufactured by Mitsubishi Chemical Corporation) was used.
  • Example 3 The thickness of the adhesive after drying the silicone-based pressure-sensitive adhesive in the first pressure-sensitive adhesive layer is 50 ⁇ m, and the second separator is replaced with the base film (thickness 50 ⁇ m, commercial product) in place of the separator (2).
  • a laminate film was obtained in the same manner as in Example 1, except that a separator changed to the name "Diafoil T100-50S" (manufactured by Mitsubishi Chemical Corporation) was used.
  • Example 4 The thickness of the adhesive after drying the silicone-based pressure-sensitive adhesive in the first pressure-sensitive adhesive layer is set to 75 ⁇ m, and the base film in the separator (2) is used instead of the separator (2) for the second separator (thickness 75 ⁇ m, product A laminated film was obtained in the same manner as in Example 1, except that a separator with the name "Diafoil T100-75S" (manufactured by Mitsubishi Chemical Corporation) was used.
  • Example 5 A laminate film was obtained in the same manner as in Example 1, except that the adhesive thickness of the silicone-based pressure-sensitive adhesive in the first pressure-sensitive adhesive layer after drying was 50 ⁇ m, and the separator (2) was used as the first separator.
  • Example 6> A laminated film was obtained in the same manner as in Example 5, except that the adhesive thickness of the silicone adhesive in the first adhesive layer after drying was 75 ⁇ m.
  • Example 7 The adhesive thickness of the silicone adhesive in the first adhesive layer after drying is 25 ⁇ m, the separator (3) is used as the first separator, and the acrylic adhesive (1) is replaced with the acrylic adhesive for the first adhesive layer.
  • a laminated film was obtained in the same manner as in Example 1, except that the adhesive (2) was used.
  • Example 8> A laminated film was obtained in the same manner as in Example 7, except that the adhesive thickness of the silicone-based pressure-sensitive adhesive in the first pressure-sensitive adhesive layer after drying was 50 ⁇ m.
  • Example 9 A laminated film was obtained in the same manner as in Example 7, except that the adhesive thickness of the silicone-based pressure-sensitive adhesive in the first pressure-sensitive adhesive layer after drying was 75 ⁇ m.
  • the separator of the second pressure-sensitive adhesive layer was peeled off, and the pressure was applied at 23°C and 50% R.I. H.
  • the surface of the second adhesive layer was laminated to a glass plate (trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.) with a roller of 0.25 MPa and 0.3 m / min, and then a universal tensile tester (product Using the name "TCM-1kNB", manufactured by Minebea Co., Ltd.), the peeling force F ( 1) was measured.
  • the separator of the first pressure-sensitive adhesive layer was peeled off and placed at 23°C and 50% R.I. H.
  • the surface of the first adhesive layer was laminated to a glass plate (trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.) with a roller of 0.25 MPa and 0.3 m / min, and then a universal tensile tester (product Using the name "TCM-1kNB", manufactured by Minebea Co., Ltd.), the peeling force F ( 2) was measured.
  • the surface of the second adhesive layer from which the separator of the evaluation sample has been peeled is applied to a glass plate (trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.) with a roller of 0.25 MPa and 0.3 m / min.
  • a glass plate trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.
  • TCM-1kNB universal tensile tester
  • the second adhesive was applied from the glass plate at a peeling angle of 180 degrees and a tensile speed of 0.3 m / min.
  • the peel adhesion P(2) was measured by peeling off the agent layer.
  • the surface of the second adhesive layer from which the separator of the evaluation sample has been peeled is applied to a glass plate (trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.) with a roller of 0.25 MPa and 0.3 m / min. Affixed and cured for 30 minutes.
  • the separator of the second adhesive layer is peeled off, and the surface of the second adhesive layer is applied to a glass plate (trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.) at 23 ° C. and 50% at 0.25 MPa and 0.3 m. /min, then 23°C, 50% R.I. H. 315 (trade name, 19 mm width, manufactured by Nitto Denko Corporation) was crimped to the center of the back surface of the surface protection film in the width direction with a hand roller.
  • a glass plate trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.
  • the first separator was peeled from the first pressure-sensitive adhesive layer under the conditions of a tensile speed of 0.3 m / min and a peeling angle of 90 degrees, and the maximum stress applied at the beginning of peeling was the trigger peel strength T (1) [N / 50 mm].
  • the separator of the second pressure-sensitive adhesive layer was peeled off, and the pressure was applied at 23°C and 50% R.I. H.
  • the surface of the second pressure-sensitive adhesive layer was laminated to a glass plate (trade name “S200423”, manufactured by Matsunami Glass Industry Co., Ltd.) with a roller of 0.25 MPa and 0.3 m / min, and then 23 ° C. ⁇ 50% R . H. 315 (trade name, 19 mm width, manufactured by Nitto Denko Corporation) is crimped to the center of the back of the surface protective film in the width direction with a hand roller.
  • the second separator was peeled from the second pressure-sensitive adhesive layer under the conditions of a tensile speed of 0.3 m / min and a peeling angle of 90 degrees, and the maximum stress applied at the beginning of peeling was the trigger peel strength T (2) [N / 50 mm].
  • the separator of the second pressure-sensitive adhesive layer was peeled off, and the pressure was applied at 23°C and 50% R.I. H.
  • the surface of the second adhesive layer was attached to a glass plate (trade name "S200423", manufactured by Matsunami Glass Industry Co., Ltd.) with a roller of 0.25 MPa and 0.3 m / min, and then the right angle part of the evaluation sample 23° C., 50% R.I. H.
  • the first separator was peeled from the first pressure-sensitive adhesive layer at a peel angle of 180 degrees and a peel speed of 0.3 m/min, and the peelability of the first separator was evaluated according to the following criteria.
  • the evaluation sample was fixed by placing it on the adsorption stage with the first separator side down and sucking it.
  • An acrylic adhesive tape (trade name: "NO.31B", manufactured by Nitto Denko Corporation) was pressed with a hand roller to the right-angled part of the fixed sample for evaluation, and was held at 23°C and 50% RH. H.
  • the second separator was peeled from the second pressure-sensitive adhesive layer at a peel angle of 180 degrees and a peel speed of 0.3 m/min, and the peelability of the second separator was evaluated according to the following criteria.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Die Bonding (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film stratifié susceptible d'améliorer le rendement des opérations dans un procédé de production d'un dispositif à semiconducteurs. Le film stratifié selon la présente invention est tel qu'un premier séparateur, une première couche adhésive composée d'une couche adhésive à faible pégosité, un matériau de base, une seconde couche adhésive composée d'une couche adhésive antiadhésive et un second séparateur sont appliqués en couches dans l'ordre indiqué, la résistance au pelage à 180 ° F(1), F(2) du premier et du second séparateurs par rapport à la première et à la seconde couches adhésives, la force d'adhérence après pelage à 180 ° P(2) de la seconde couche adhésive par rapport à une plaque de verre et la force d'adhérence par pelage à 180 ° P'(2) après cinq minutes à 160 °C (N/50 mm) satisfaisant aux formules suivantes. F(2) ≤ F(1) P(2) ≥ F(1) P'(2)/P(2) < 1,20P'(2) < 1,00 Comme « F(1) ≤ F(2) » dans la revendication 1 est une erreur typographique pour « F(2) ≤ F(1) », eu égard aux descriptions des paragraphes [0009], [0015] et [0018]-[0022], les exemples, et la revendication 2, l'examen a été mené par utilisation de « F(2) ≤ F(1) ».
PCT/JP2022/021273 2021-05-31 2022-05-24 Film stratifié WO2022255165A1 (fr)

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WO2020162331A1 (fr) * 2019-02-06 2020-08-13 日東電工株式会社 Feuille adhésive sensible à la pression
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KR20240017845A (ko) 2024-02-08
CN117396572A (zh) 2024-01-12

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