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KR-102962785-B1 - Film, laminate, semiconductor wafer with film layer attached, substrate for mounting semiconductor with film layer attached, and semiconductor device

KR102962785B1KR 102962785 B1KR102962785 B1KR 102962785B1KR-102962785-B1

Abstract

A film comprising a propenyl group-containing resin (A) having a constituent unit represented by the following formula (1) at the end of the molecule, a radical polymerizable resin or compound (B) other than the propenyl group-containing resin (A), and a curing accelerator (C), wherein the radical polymerizable resin or compound (B) comprises at least one type selected from the group consisting of maleimide groups and citraconimide groups. In Equation (1), -* represents the coupling loss.

Inventors

  • 세키도 다카히토
  • 오카니와 마사시
  • 스기야마 겐키
  • 다카노 겐타로
  • 기다 츠요시

Assignees

  • 미츠비시 가스 가가쿠 가부시키가이샤

Dates

Publication Date
20260508
Application Date
20200626
Priority Date
20190628

Claims (20)

  1. A propenyl group-containing resin (A) comprising a constituent unit represented by the following formula (1) at the end of the molecule, and A radical polymerizable resin or compound (B) other than the above propenyl group-containing resin (A), and Curing accelerator (C) and, A thermosetting compound (F) other than the above propenyl group-containing resin (A) and the above radical polymerizable resin or compound (B), and The above radical polymerizable resin or compound (B) comprises at least one selected from the group consisting of maleimide groups and citraconimide groups, and The above thermosetting compound (F) comprises a benzoxazine compound, and The ratio (propenyl group: polymerizable functional group) of the propenyl group in the above propenyl group-containing resin (A) to the ratio of the polymerizable functional group in the above radical polymerizable resin or compound (B) is 1:1 to 1:7, and The content of the above curing accelerator (C) is 0.05 to 10 parts by mass per 100 parts by mass of the total of the propenyl group-containing resin (A) and the radical polymerizable resin or compound (B), Pre-applied underfill film. (In Equation (1), -* represents a coupling loss)
  2. In Article 1, A film having a mass average molecular weight of the above propenyl group-containing resin (A) of 300 to 10,000.
  3. In Article 1, A film comprising the above propenyl group-containing resin (A), which is a resin represented by the following formula (2). (In Equation (2), W represents, each independently, a hydrocarbon group having 6 to 15 carbon atoms that may have a substituent. U represents, each independently, a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. n1 represents the number of repetitions, and the average value is a real number from 1 to 20.)
  4. In Article 1, A film comprising the above propenyl group-containing resin (A), which is a resin represented by the following formula (3). (In Equation (3), Y independently represents a hydrocarbon group having 1 to 6 carbon atoms. X independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. n² represents the number of repetitions, and the average value is a real number from 1 to 20.)
  5. In Article 1, A film comprising at least one selected from the group consisting of the radical polymerizable resin or compound (B), 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, a maleimide compound represented by the following formula (4), a maleimide compound represented by the following formula (5), a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), and a maleimide compound represented by the following formula (9). (In Equation (4), R1 independently represents a hydrogen atom or a methyl group, and n3 represents an integer from 1 to 10) (In Equation (5), n 4 represents an integer from 1 to 30) (In Equation (6), R2 independently represents a hydrogen atom, a methyl group, or an ethyl group, and R3 independently represents a hydrogen atom or a methyl group) (In formula (7), R4 each independently represents a hydrogen atom, a C1-C5 alkyl group, or a phenyl group, l each independently represents an integer from 1 to 3, and n5 represents an integer from 1 to 10) (In Equation (8), R5 and R7 each independently represent a hydrocarbon group in which 8 or more atoms are connected in a straight chain, R6 each independently represents a cyclic hydrocarbon group that may include a heteroatom having 4 to 10 atoms forming the ring, whether substituted or unsubstituted, and n6 represents an integer from 1 to 10) (In formula (9), R8 each independently represents an alkylene group, R9 each independently represents an alkylene group, a group represented by the following formula (10), a group represented by the formula “ -SO₂- ”, a group represented by the formula “-CO-”, a group represented by the following formula (11), an oxygen atom, or a single bond, and n7 represents an integer from 1 to 10) (In formula (10), Z is a hydrocarbon group having 6 to 30 carbon atoms containing an alkylene group or an aromatic ring, and n8 represents an integer from 0 to 5)
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  7. In Article 1, A film comprising at least one type selected from the group consisting of the above-mentioned curing accelerator (C), a thermal radical polymerization initiator (D), and an imidazole compound (E).
  8. In Article 7, A film in which the 10-hour half-life temperature of the above-mentioned thermal radical polymerization initiator (D) is 100°C or higher.
  9. In Article 7, The above thermal radical polymerization initiator (D) comprises an organic peroxide, in a film.
  10. In Article 7, The above thermal radical polymerization initiator (D) is a film having a peroxyester, peroxyketal, dialkyl peroxide, or hydroperoxide backbone.
  11. In Article 7, A film comprising at least one selected from the group consisting of the above-mentioned thermal radical polymerization initiator (D), which is dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutylhydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexine-3, and tert-butylhydroperoxide.
  12. delete
  13. delete
  14. In Article 1, A film in which the above thermosetting compound (F) has a molecular weight of 400 or more.
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  16. In Article 1, A film comprising at least one type selected from the group consisting of the above benzoxazine compound, the compound represented by the following formula (12), the compound represented by the following formula (13), the compound represented by the following formula (14), and the compound represented by the following formula (15). (In formula (12), R 10 each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, R 11 represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or an organic group of 1 to 4 valence represented by the following general formulas (a) to (t), and n 9 represents an integer from 1 to 4) (In formula (13), R 12 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, R 13 represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or an organic group of 1 to 4 valence represented by the following general formulas (a) to (t), and n 10 represents an integer from 1 to 4) (In formula (14), R 14 represents an alkyl group, a cycloalkyl group, or a phenyl group that may have a substituent) (In formula (15), R 15 represents an alkyl group, a cycloalkyl group, or a phenyl group that may have a substituent) (In formulas (a) to (t), R a represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R b represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group)
  17. In Article 1, A film comprising at least one selected from the group consisting of the above benzoxazine compound, the compound represented by the following formula (23) and the compound represented by the following formula (24). (In formula (23), R 16 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, o each independently represents an integer from 1 to 4, R 17 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, p each independently represents an integer from 1 to 4, and T 1 represents an alkylene group, a group represented by the following formula (10), a group represented by the formula "-SO 2 -", a group represented by "-CO -", an oxygen atom, or a single bond) (In formula (24), R 18 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; q each independently represents an integer from 1 to 3; R 19 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; r each independently represents an integer from 1 to 5; and T 2 represents an alkylene group, a group represented by the following formula (10), a group represented by the formula "-SO 2 -", a group represented by "-CO -", an oxygen atom, or a single bond) (In formula (10), Z is a hydrocarbon group having 6 to 30 carbon atoms containing an alkylene group or an aromatic ring, and n8 represents an integer from 0 to 5)
  18. In Article 1, A film having a content of the thermosetting compound (F) of 1 to 100 parts by mass relative to 100 parts by mass of the total of the propenyl group-containing resin (A) and the radical polymerizable resin or compound (B).
  19. In Article 1, A film further comprising an inorganic filler (G).
  20. In Article 19, A film having an average particle size of the above-mentioned inorganic filler (G) of 3 μm or less.

Description

Film, laminate, semiconductor wafer with film layer attached, substrate for mounting semiconductor with film layer attached, and semiconductor device The present invention relates to a film, a laminate using the film, a semiconductor wafer with a film layer attached, a substrate for mounting a semiconductor with a film layer attached, and a semiconductor device. More specifically, the present invention relates to a film useful as a pre-applied underfill material. Recently, with the miniaturization and increased performance of semiconductor devices, flip-chip mounting has attracted attention as a method for mounting a semiconductor chip (hereinafter abbreviated as "chip") onto a semiconductor mounting substrate (hereinafter abbreviated as "substrate"). In flip-chip mounting, a process is generally used in which the chip and the substrate are bonded, and then an underfill material is filled into the gap between the chip and the substrate and cured. However, with the miniaturization and increased performance of semiconductor devices, the pitch of electrodes arranged on the chip and the gap between electrodes have become narrower, leading to problems such as deterioration of workability due to the prolonged filling of the underfill material and the occurrence of filling defects such as incomplete filling. In response to this, a process is being considered in which a pre-applied underfill material is supplied to the chip or the substrate, and the bonding of the chip and the substrate and the filling of the underfill material are performed simultaneously. As the underfill material is a component that comes into direct contact with the chip and the substrate, important characteristics required of the underfill material include suppression of unfilled underfill between the chip and the substrate and the underfill material in the environment in which the semiconductor device is manufactured and used (hereinafter referred to as "low voidness") and good adhesion between the chip and the substrate and the underfill material (hereinafter referred to as "chip adhesion"). Patent Document 1 describes a pre-applied underfill material using a radical polymerizable monomer in the main resin. This Patent Document 1 describes the formulation of a silane coupling agent for the purpose of improving adhesion to the chip. Patent Document 2 describes an underfill material comprising an epoxy resin, an imidazole compound, and a maleimide compound. Patent Document 3 describes a pre-applied underfill material using an epoxy compound and a carboxyl group-containing flux component, and mentions adhesion. Patent Document 4 describes a resin composition having a maleimide compound, an epoxy resin, and an epoxy resin curing agent as essential components, and states that high adhesion was obtained in the resin composition after heat curing. Patent document 5 describes a resin composition for a printed circuit board, comprising a maleimide compound having a specific structure, a benzoxazine compound, and an inorganic filler (C), as a thermosetting resin composition used to form an insulating layer in a printed circuit board. Patent Document 6 describes an adhesive for electronic components that contains an aliphatic epoxy compound and a benzoxazine compound as a curing agent, and also contains a phenolic curing agent. Patent document 7 describes an adhesive composition comprising a thermosetting compound, a polymer containing a functional group capable of reacting with the thermosetting compound, and a thermosetting agent, wherein the melt viscosity at the bonding temperature is 10 Pa·s to 15000 Pa·s, the gel time at the bonding temperature is 10 seconds or more, and the gel time at 240°C is 1 second to 10 seconds. Patent document 8 describes a method for manufacturing a semiconductor device using a sheet-like thermosetting resin composition. In addition, when joining a chip and a substrate with a metal that is prone to oxidation, such as solder or copper, there are cases where a flux component derived from a carboxylic acid is added to the pre-applied underfill material for the purpose of removing the metal oxide film, which is a factor hindering the joining, from the joining area and obtaining a good metal joining. Hereinafter, a form for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described. Furthermore, the following present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment. According to one embodiment of the present invention, the film comprises a specific propenyl group-containing resin (A), a specific radical polymerizable resin or compound (B), and a curing accelerator (C). The film is preferably used as a pre-applied underfill material in order to more effectively and reliably exhibit the effects according to the present invention. Another aspect of the present embodiment is a film further compri