[go: up one dir, main page]

TW201130942A - Adhesive composition for semiconductor, semiconductor device and fabricating method thereof - Google Patents

Adhesive composition for semiconductor, semiconductor device and fabricating method thereof Download PDF

Info

Publication number
TW201130942A
TW201130942A TW099138874A TW99138874A TW201130942A TW 201130942 A TW201130942 A TW 201130942A TW 099138874 A TW099138874 A TW 099138874A TW 99138874 A TW99138874 A TW 99138874A TW 201130942 A TW201130942 A TW 201130942A
Authority
TW
Taiwan
Prior art keywords
semiconductor
adhesive
adhesive layer
resin
composition
Prior art date
Application number
TW099138874A
Other languages
Chinese (zh)
Inventor
Kazuyuki Mitsukura
Takashi Kawamori
Takashi Masuko
Shigeki Katogi
Shinjiro Fujii
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of TW201130942A publication Critical patent/TW201130942A/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of semiconductor or other solid state devices
    • H01L25/03—Assemblies consisting of a plurality of semiconductor or other solid state devices all the devices being of a type provided for in a single subclass of subclasses H10B, H10D, H10F, H10H, H10K or H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of semiconductor or other solid state devices all the devices being of a type provided for in a single subclass of subclasses H10B, H10D, H10F, H10H, H10K or H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/065—Assemblies consisting of a plurality of semiconductor or other solid state devices all the devices being of a type provided for in a single subclass of subclasses H10B, H10D, H10F, H10H, H10K or H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H10D89/00
    • H01L25/0657—Stacked arrangements of devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/27—Manufacturing methods
    • H01L2224/274—Manufacturing methods by blanket deposition of the material of the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/27—Manufacturing methods
    • H01L2224/274—Manufacturing methods by blanket deposition of the material of the layer connector
    • H01L2224/2741—Manufacturing methods by blanket deposition of the material of the layer connector in liquid form
    • H01L2224/27416—Spin coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/27—Manufacturing methods
    • H01L2224/274—Manufacturing methods by blanket deposition of the material of the layer connector
    • H01L2224/2741—Manufacturing methods by blanket deposition of the material of the layer connector in liquid form
    • H01L2224/27418—Spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
    • H01L2224/922—Connecting different surfaces of the semiconductor or solid-state body with connectors of different types
    • H01L2224/9222—Sequential connecting processes
    • H01L2224/92242—Sequential connecting processes the first connecting process involving a layer connector
    • H01L2224/92247—Sequential connecting processes the first connecting process involving a layer connector the second connecting process involving a wire connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2225/00—Details relating to assemblies covered by the group H01L25/00 but not provided for in its subgroups
    • H01L2225/03—All the devices being of a type provided for in the same main group of the same subclass of class H10, e.g. assemblies of rectifier diodes
    • H01L2225/04—All the devices being of a type provided for in the same main group of the same subclass of class H10, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L2225/065—All the devices being of a type provided for in the same main group of the same subclass of class H10
    • H01L2225/06503—Stacked arrangements of devices
    • H01L2225/0651—Wire or wire-like electrical connections from device to substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01004—Beryllium [Be]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01012—Magnesium [Mg]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01013—Aluminum [Al]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01015—Phosphorus [P]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0102—Calcium [Ca]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01023—Vanadium [V]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01027—Cobalt [Co]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01033—Arsenic [As]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0104—Zirconium [Zr]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01051—Antimony [Sb]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01067—Holmium [Ho]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01075—Rhenium [Re]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01084—Polonium [Po]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/049—Nitrides composed of metals from groups of the periodic table
    • H01L2924/0495—5th Group
    • H01L2924/04953—TaN
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/0665—Epoxy resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/07802—Adhesive characteristics other than chemical not being an ohmic electrical conductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]

Landscapes

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

Abstract

An adhesive composition for semiconductor of this invention includes: a radiation polymerizable compound (A), a photoinitiator (B), and thermosetting resin (C), wherein the component (A) includes a compound having a C-C double bond in its molecular, and the compound is liquid at 25 DEG C.

Description

201130942. 六、發明說明： 【發明所屬之技術領域】 本發明是有關於-種半導體用黏著劑組成物、使用該 半導體用黏著劑組成物之半導體裝置以及其製造方法。 【先前技術】 多級積層有多個晶片（ehip)之堆疊封裝（他制 package)型半導體裝置可用於記憶體等用途中。於紫造 ^體裝置時，為了料導體元件彼此之間或半導體元件盘 2體元件搭載用支撐部件黏著而適㈣膜狀黏著劑。i 2用零件之小型化、低背化，開始要求使該半 黏著劑進—步薄膜化1而，由於無法獲得 叫、針孔（pinhole)多發等原因而難以製造厚度 二μιη以下之薄膜狀黏著劑。而且，經薄膜化之 於晶圓上之貼附性成孰壓接 ' 降低，因此裝 外於上述異常而導致成品率 降低因此存在製造成本上升之問題。 號公題’例如如日本專利特開2GG7-110099 二二下之方法:塗佈奸溶劑之黏著 Β-階段（B-Stagj)化θ由加熱乾燥而使所塗佈之樹脂糊 問題含有溶劑之樹脂糊之情料存在如下之 者由於溶劑而污口;:，: Β’段化需要較長時間’或 劑揮發之乾^ ®。而且，由於用以進行使溶 、的加熱而存在如下之問題：於附有可剝離之 201130942 黏者帶的晶圓上塗佈樹脂糊之情形時，黏著帶變得不易剝 離或者產生晶圓之翹曲。若於低溫下崎乾燥，則雖然由 =熱所造成之異常得到某種程度之抑制，但於此 殘存溶劑變多，因此存在如下之傾向：於加熱硬化時產生 空隙（void)或剝離’可靠性降低。而且，若以降低乾燥 溫度為目㈣使用低彿點溶劑，則存在如下之傾向：於使 用中黏度產生較大變化，或者於乾燥時由於黏著劑表面之 溶劑揮發*造成_部殘存溶劑，因此可#性 【發明内容】 _ 本發明疋#於上述事實而成的，其目的在於提供一種 可=面充分地維持可靠性—面更薄地形成黏著劑層（所述 黏著劑層對半導體元件彼此之間或半導體元件鮮導體元 件搭載用支撐料進行㈣）之半導體_著敝成物、 使用該半導胸㈣聽成物之半導财置的製造方法以 及半導體裝置。 、為了解決上述課題’本發明提供—種半導_黏著劑 組成物’其包含⑷放射線聚合性化合物、（B)光起始 齊1、以及（C)熱硬化性樹脂，且（A)成分包含於Μ。。 為液，且於分子内具有！個碳·碳雙鍵之化合物。 藉由本叙明之半導體用黏著劑組成物，由於具有上述 構成二可不使用溶劑而塗佈於基材上，且可藉由對該塗膜 進行光照射㈣成薄狀黏著，即使於進行黏著劑層 之^階段化之情科’亦無需於塗佈後為了使溶劑乾燥而 進行加熱，可充分抑制由於熱流動或揮發成分而產生之針 4 201130942[Technical Field] The present invention relates to a semiconductor composition for an adhesive, a semiconductor device using the same as an adhesive composition for a semiconductor, and a method for producing the same. [Prior Art] A multi-layer laminated multi-chip (ehip) stacked package type semiconductor device can be used for applications such as a memory. In the case of the violet device, a film-like adhesive is applied to the conductor members or the semiconductor device disk 2 body element mounting support member. In the case of miniaturization and low-profile use of the parts, it has been demanded that the semi-adhesive agent is further film-formed, and it is difficult to obtain a film having a thickness of 2 μm or less due to the inability to obtain a large number of pinholes or the like. Adhesive. Further, since the adhesiveness of the film formed on the wafer is reduced, the yield is lowered due to the above-mentioned abnormality, and thus the manufacturing cost is increased. No. 2, for example, the method of Japanese Patent Laid-Open No. 2 GG7-110099 222: Adhesive-coated Β-stage (B-Stagj) θ is heated and dried to cause the problem of the resin paste to be coated to contain a solvent. In the case of the resin paste, the following ones are contaminated by the solvent;:,: The 段 'segmentation takes a long time' or the agent volatilizes dry ^ ® . Moreover, there is a problem in that when the resin paste is applied to the wafer with the peelable 201130942 adhesive tape, the adhesive tape is not easily peeled off or the wafer is produced. Warping. If it is dried at a low temperature, the abnormality caused by the heat is suppressed to some extent. However, since there are many residual solvents, there is a tendency to generate voids or peeling during heat hardening. reduce. Further, if the low-foam point solvent is used for the purpose of lowering the drying temperature, there is a tendency to cause a large change in viscosity during use, or a solvent remaining in the surface of the adhesive due to evaporation of the solvent on the surface of the adhesive during drying. The present invention has been made in view of the above facts, and an object thereof is to provide an adhesive layer capable of sufficiently maintaining the reliability-surface thinner (the adhesive layer to the semiconductor elements are mutually A manufacturing method and a semiconductor device in which a semiconducting material of the semiconducting thoracic (four) listener is used, and a semiconducting material (4) is used for the semiconductor element. In order to solve the above-mentioned problem, the present invention provides a semiconductive-adhesive composition comprising (4) a radiation polymerizable compound, (B) a photoinitiator 1, and (C) a thermosetting resin, and (A) a component. Included in Μ. . It is liquid and has it in the molecule! a compound of carbon and carbon double bonds. The adhesive composition for a semiconductor according to the present invention can be applied to a substrate without using a solvent as described above, and can be light-irradiated by the coating film (4) to form a thin adhesion, even if an adhesive layer is applied. It is also necessary to heat the solvent in order to dry the solvent after coating, and it is possible to sufficiently suppress the needle 4 due to heat flow or volatile components.

lL；fJ 杆Ϊ1ΪΙ而且，本發明之半導體用黏著劑組成物由於進 許化^者之熱時㈣性優異，因此可對被黏著 的丰：二：之？壓接。藉由本發明’可實現具有如下性質 倍盈㈣ί著舰成物m鐘紐以及耐熱性 麵《·可更薄地形絲著劑層，所述黏著劑層對半導體元 之間或轉體元件與半導體元件搭個支樓部件進 打黏著。 而^本發0狀半導體_著劑組成物可不使用溶劑 不進行加熱地以^3_時間形成薄膜之黏著劑層，因此可成 :可減低熱能量與揮發性有機化合物（電）且對環境之 負擔較先前小之材料。 本^月之半導體用黏著劑組成物較佳的是於25°C為 液狀且溶劑之含量為5質量％以下。 於本發明中，所謂液狀表示於25T：、1 atm下具有流 動性。 於本發明中’所謂溶劑是指不具有光反應性基以及熱 性基、分子量為5〇〇以下且於25。〇為液狀之有機化合 物0 八於本發明之半導體用黏著劑組成物中 ，上述放射線聚 :ί·生化合物較佳的是具有醯亞胺骨架或羥基之單官能（曱 稀酸1旨。此處所謂單官能是表示於分子内具有）個碳 炭又鍵，亦可具有除此之外之官能基。 而且’於本發明之半導體用黏著劑組成物中，自減低 201130942 曝，後之熱時逸氣之觀點考慮，較佳的是上述化合物之5% 重量損失溫度為15〇〇c以上。 β另外，於本發明之半導體用黏著劑組成物中，較佳的 是上述（Α)成分於25〇C之黏度為1000mPa.s以下。於此 ，形，，可調配固形或高黏度之熱硬化性樹脂而進一步提 冋黏著性。此處之黏度是使用東京計器製造所製造之EHD 型旋轉黏度計，於樣品量為G 4 mL、3。齡之條 件下，於25。(：測定之黏度值。 s而且於本發明之半導體用黏著劑組成物中，較佳的 疋上述（A)成分聚合得到之聚合物的巧為i〇〇〇c以下。 ^此it形時’可使B-階段化後之低溫熱璧接性以及熱時流 動性進一步提高。 較佳的是本發明之半導體用黏著劑組成物進一步含有 D)，自由基產生劑。藉此，可使曝光後未反應而殘存 )成分於熱硬化時騎聚合反應，因此可進 制，硬化狀發料者錢之熱餘咖聰…lL; fJ rod Ϊ 1 ΪΙ Moreover, the adhesive composition for a semiconductor of the present invention is excellent in the heat of the person (4), so it can be adhered to the abundance: two: Crimp. By the present invention, it is possible to realize a property of the following properties: (4) a ship's m-key and a heat-resistant surface, a thinner topographic wire layer, the adhesive layer between semiconductor elements or a rotating element and a semiconductor The components are attached to a branch building and glued. The present invention can reduce the thermal energy and volatile organic compounds (electricity) and the environment by using a solvent-free layer which can form a film without using a solvent without heating. The burden is smaller than the previous material. The adhesive composition for a semiconductor of the present invention is preferably liquid at 25 ° C and the content of the solvent is 5% by mass or less. In the present invention, the liquid state means that it has fluidity at 25T:, 1 atm. In the present invention, the term "solvent" means a photoreactive group and a thermal group, and has a molecular weight of 5 Å or less and 25 or less. In the adhesive composition for a semiconductor of the present invention, the above-mentioned radiation is preferably a monofunctional compound having a quinone imine skeleton or a hydroxyl group. Here, the monofunctional means that the carbon carbon has a bond in the molecule, and may have a functional group other than the above. Further, in the adhesive composition for a semiconductor of the present invention, it is preferable that the 5% weight loss temperature of the above compound is 15 〇〇c or more from the viewpoint of reducing exposure to 201130942 and outgassing after heat. Further, in the adhesive composition for a semiconductor of the present invention, it is preferred that the (Α) component has a viscosity at 25 ° C of 1000 mPa·s or less. Here, the shape, the thermosetting resin which can be adjusted to a solid shape or a high viscosity is further improved in adhesion. The viscosity here is an EHD type rotary viscometer manufactured by Tokyo Keiki Co., Ltd., and the sample amount is G 4 mL, 3. Under the age of 25, at 25. (The measured viscosity value is s. In the adhesive composition for a semiconductor of the present invention, it is preferred that the polymer obtained by polymerizing the above component (A) is below i〇〇〇c. The low-temperature heat-bonding property and the heat-time fluidity after the B-stage can be further improved. It is preferred that the adhesive composition for a semiconductor of the present invention further contains D) a radical generating agent. Thereby, the component which can be left unreacted after the exposure can be allowed to ride on the polymerization reaction during the heat hardening, so that it can be made into a hardened hairy person...

之發泡或剝離。 J 組成物之喷出性或者黏著劑層之薄膜化 25。。::二t，本發明之半導體用黏著劑組成物於 5C之黏度為i〇mPa.s〜3咖 射而將_域物構之藉= 6 201130942 損失溫度為15(TC以上。於此情形時，可更確實地防止將 階段化之黏著劑層壓接於被黏著體上之後進行熱硬化時 或回焊等熱歷程中被黏著體剝離。 自可更確實地防止於熱難巾觀著體_之觀點考 〜’較佳的是本發明之半導體祕著顯成物於藉由光照 射而將由該組成物構成之黏著劑層B-階段化、並進一步進 订加熱硬化時之5%重量損失溫度為細。c以上。 明_^^還提供—種半導體裝置，其具謂由上述本發 黏著劑組成物而將半導體元件彼此之間及/ 3 體7L件與半導體元件搭載用支撐料料之結構。 务明之半導體裝置藉由本發明之半導體用釉荽 成:而將半導趙元件彼此之_導== =搭載用支撑部件黏著，藉此可-面充分維ΐ可= 面減溥黏著劑層’因此能夠小型化、低背化。罪 於其包含: 而設置黏著劑層之步驟:對二 切斷二二將半導體晶圓與經光照射之所述黏著劑層-同 導:撕他半導體元件或半心 進行壓接而將劑層之半導體元件的輸 於半種半導體裝置的製造方法，其包含： ' 塗佈上34本發明之半導體用崎劑組成物 201130942. 而設置黏著劑層之步驟；對該黏著劑層進行光照射之步 驟；將具有經光照射之黏著劑層的半導體元件與其他半導 體元件或半導體元件搭載用支撐部件，夾著經光照射之黏 著劑層進行壓接而將其黏著之步驟。 本發明還提供一種半導體裝置的製造方法，其包含： 於半導體元件搭載用支撐部件上塗佈上述本發明之半導體 用黏著劑組成物而設置黏著劑層之步驟；對該黏著劑層進 行光照射之步驟；將具有經光照射之黏著劑層的半導體元 件搭載用支撐部件與半導體元件，夾著經光照射之黏著劑 層進行壓接而將其黏著之步驟。 [發明之效果] 藉由本發明，可提供一種可一面充分地維持可靠性一 面更薄地形成黏著劑層（所述黏著劑層對半導體元件彼此 之間或半導體元件與半導體元件搭載用支撐部件進行黏 著）之半導體用黏著劑組成物、使用該半導體用黏著劑組 成物之半導體裝置的製造方法以及半導體裝置。 【實施方式】 以下，對本發明之較佳實施形態加以詳細之說明。但 本發明並不限定於以下之實施形態。 以下，根據需要參照圖式對本發明之實施形態加以詳 細之說明。但本發明並不限定於以下之實施形態。另外， 於圖式中，對同一要素賦以同一符號，省略重複之說明。 而且，上下左右等位置關係若無特別之說明，則是基於圖 式所示之位置關係，圖式之尺寸比率並不限於圖示之比率。 8 201130942 本發明之半導體用黏著劑組成物之特徵在於包含（A) 放射線聚合性化合物、（B)缺始劑、以及（〇執硬化 性樹脂’ a U)成分包含（A1)於坑為液狀且ς分子 内具有1個石厌~碳雙鍵之化合物（以下，有時亦稱為「Α1 化合物」）。 ，本發明巾所謂之（Α)放射線聚合性化合物是表示烯 類或快類^具有碳原子間不飽和鍵之化合物。 於本發明中’所謂放射線是指電離性放射線或非電離 性放射線，例如可列舉ArF、KrF等準分子雷射光、電子 f 1紫外、線、真空紫外光、X射線、離子束或i線或g線 等各外光。自量紐之觀點考慮，放射線可較佳地使用i 線或g線等紫外光。 ，本發月之半導體用黏著劑組成物較佳的是於25。(^為 ，狀且溶劑之含量為5質量％以下之半導體用無溶劑型黏 著劑組成物。上稍謂之「無溶綱」是表轉著劑組成 物中所含有之溶劑量為5質量％以下。 ^上述所謂之溶劑是表示不具有放射線聚合性基或者月亏 酉曰基α胺基本乙酮、膦氧化物（ph〇Sphine oxjde)等光反 ，性基’環氧基、祕麟、祕、胺基、酸Sf、異氛酸 ，、1氡化物、重氮基、咪唑、烷氧基矽烷等熱反應性基， 分子量S 5GG以下且於室溫（25。〇下為液狀之有機化合 物。此種溶劑例如可列舉：二曱基曱醯胺、曱苯、笨、二 曱苯、丁酮、四氫呋喃、乙基溶纖劑、乙基溶纖劑乙酸酯、 一°惡烧、環己_、乙酸乙s旨、γ_丁内酯以及N_曱基_n比哈咬 201130942 酮等。 ，由，溶劑量為上述㈣，可藉由光歸而使黏性 (tack)減低，且可使光照射後之操作性提高。另外，可 抑制熱壓接或加熱硬化時之發泡。 本發明之半導體祕著劑組成物含有於25t：為液狀 ，於分子内具有1個碳·碳雙鍵之化合物作為必彡貞成分。於 «周配有;7子内具有2個以上碳·碳雙鍵之化合物的感光性 ^成物之情糾’若進行絲賴絲形成交聯結構之狀 悲，其後之熱時錄變難，且亦難表現出祕，因此存在 熱壓接變困難之傾向。相對於此，於本發日月之半導體用點 著劑組成物中’含有於分子内具有1個碳·碳雙鍵之化合 物’因此可充分獲得熱時流動性且熱壓接性提高。 而且，於本發明之半導體用黏著劑組成物中，亦可添 加於25。(：為錄且於分子内具有丨個碳·碳雙鍵之化合 物’且亦可調配固形之丙烯酸醋。於此情形時之（A)成 分之混合物較佳的是於25。(：為液狀。 自/蔓得更高水準之熱時流動性之觀點考慮，較佳的是 於黏著劑組成物中單獨含有於分子内具有1個碳-碳雙鍵 ^化合物作為放射線聚合性化合物。另外’於單獨使用於 二子内具有1個碳-碳雙鍵之化合物之情形時，可使光照射 後所得之聚合物的分子量為數萬以上 。此處，若含有於分 子内具有2個以上碳_碳雙鍵之化合物，則存在形成分子量 為數萬以上之聚合物彼此之間的網狀物（network)，熱時 之黏著性或流動性降低之傾向。 201130942 另一方面，為了提高耐熱性或者減低曝光後之黏著強 度’亦可以相對於分子内具有丨個碳_碳雙鍵之化合物而言 為0.1質量％〜50質量％之比例併用於分子内具有2個以 上碳-碳雙鍵之化合物。於此情形時，作為所併用之於分子 =具有2個以上碳.碳雙鍵之化合物，自熱時流動性之觀點 考慮，較佳的是碳數為1〇以上之脂肪族系丙烯酸醋，自熱 時之黏著性之無考慮，較佳的是官能基#量為 _ 以上，自低應力性之觀點考慮，更佳的是3〇〇 g/eq以上之 芳香族或者具有異三縣酸環或環己基等環狀結構的 酸酯。 八，作為上述（A)成分，自上述⑻成分以及⑹成 分等其他成分之溶解性的觀點考慮，較佳的是於25χ：之黏 度為5000 mPa.s以下，另外自薄膜化之觀點考慮，更佳的 是3000 mPa.s以下’進一步更佳的是2〇〇〇 mpa s以下另 1自較多地調配固形或高黏度之熱硬化樹脂而使黏著性提 尚之觀點考慮，最佳的是1000 mPa.s以下。此處所謂之黏 f是，著劑組成物中所含之（A)成分總體之值，使用東 不计态製造所製造之EHD型旋轉黏度計，於樣品量為〇 4 mL、3°圓錐之條件下，於25t：測定之黏度值。 若（A)成分之上述黏度超過5〇〇〇 mPa.s，則存在如 下之傾向：黏著劑組成物之黏度上升而造成薄膜化變困 難，或者變得難以自塗佈裝置等之喷嘴（n〇zzle)噴出。 自防止塗佈時產生針孔或者確保耐熱性之觀點考慮，較佳 的是（A)成分於乃它之黏度為1〇mPa.s以上。 11 201130942 。而且’上述（A)成分之5%重量損失溫度較佳的是 l〇〇°C以上’更佳的是i20°C以上’自可於熱硬化時抑制由 於未反應之（A)成分揮發所產生之剝離或空隙之方面考 慮，進—步更佳的是150。(：以上，最佳的是180。(：以上。此 處所明之5%重夏損失溫度是黏著劑組成物中所含之（a) 成分總體之值，是使用熱重/熱示差同步分析儀（sii NanoTechnology inc.製造；TG/DTA63〇〇)，於升溫速度為 l〇C/mm、氮氣流（4〇〇mi/min)下對（a)成分進行 時之5%重量損失溫度。 而且，自黏著劑組成物之低黏度化、塗佈後之表面凹 凸^抑制或者B-階段化後之熱時流動性之觀點考慮，較佳 的是以有機化合物為主體之材料設計，因此較佳的是上述 (A)成分之5%重量損失溫度為5⑻。◦以下。 而且，作為上述（A)成分，自B_階段化後之低溫熱 壓接性、熱時流動性之觀點考慮，較好的是上述（A)成 分聚合得到之聚合物的Tg ^跡c以下，自B階段化後 之操作性或拾取性之觀點考慮，較佳的是Tg &聰以上。 (A)成分之聚合物_^Tg是對如如下枝崎得之積層 體使用黏彈性測疋裝置（Rhe〇metric如哪她f e l纪 製造、商品名：ARES)而測定之於-50°C〜20(TC之taM 溫度：將於（A)成分中以組成物總量基準計而言為3 f量％之比例而溶解有光起始劑印舰（⑽坤⑽κ κ PET (p〇lyethylene terephthaJate , 承對本一甲酸乙—g旨）薄膜上以使膜厚成為^瓜，於空 12 201130942 氣下、25°C藉由高精度平行曝光機（〇RC MANUFACTURING Co.，LTD.製造、商品名： EXM-1172-B-oo)以l〇〇〇mj/cm2對該塗膜進行曝光，將所 付之薄膜進行積層以使膜厚成為150 μιη從而獲得所述積 層體。另外，測定板使用直徑為8 mm之平行板，測定條 件為：升溫速度為5°C/min、測定溫度為_5(TC〜20(TC、頻 率為1 Hz。 自與被黏著體之密接性、表面黏性之減低、切割性、 硬化後之高溫黏著性之提高之觀點考慮，較佳的是本發明 之半^體用黏著劑組成物包含於受到光照射時重量平均分 子量為50000〜1 〇〇〇〇〇〇的上述（A)成分之聚合物。而且， 自與被黏著體之熱壓接性之觀點考慮，較佳的是包含於受 到光照射時重量平均分子量為5〇〇〇〜5〇〇〇〇〇的上述（A) 成分之聚合物。另外，上述所謂重量平均分子量表示使用 島津製作所公司製造之高效液相層析儀「C_R4A」（商品 名），以聚本乙稀換算而測定時之重量平均分子量。 〃(A)成分之聚合物之重量平均分子量可藉由曝光條 件（氧濃度、溫度、強度）’光起始劑量或硫醇、雜經基、 胺或m合抑侧之添加，丙触g|之麵或熱硬化性 樹脂之調配量，黏著劑組成物之黏度而調整。 文約ft明巾所使用之（A)成分例如可縣具有乙烯性 化合物。乙烯性不飽和基可列舉乙烯基、柄 i射=Τ烯基、乙絲、苯基乙絲、馬來酿亞胺 基、耐地㈣絲、（甲基)丙_鱗。自反應性之觀點 13 201130942 考慮，較佳的是⑷成分包含單官能（甲基)丙稀酸醋作為 ==#合物。此處所謂之單宫能是表示於分子内具有 個石反-奴雙鍵，亦可具有除此之外之官能基。 議。「單官ΐ甲基)丙烯_較佳的是5%重量損失溫度為 c以上者，更佳的是12代以上，進-步更佳的是15(rc 最ί的是18Gt：以上。而且，自黏著劑組成物之低 二又、塗佈後之表面凹凸之抑制或者B_階段化後之熱時 =動性之觀點考慮’較佳的是財機化合物為主體之材料 设计，因此較佳的是單官能（甲基)丙婦酸醋之$ %重量 溫度為5〇叱以下。單官能（甲基)丙婦酸醋之5〇/〇重量損失 溫度是使賴_衫同步分㈣（sn N_TeehnFoaming or peeling. J The spurt of the composition or the thinning of the adhesive layer 25 . . ::2, the viscosity of the adhesive composition for a semiconductor of the present invention at 5C is i〇mPa.s~3, and the _ domain structure is borrowed = 6 201130942 The loss temperature is 15 (TC or more. In this case) In this case, it is possible to more reliably prevent the phased adhesive from being bonded to the adherend and then being thermally cured or peeled off by the adhesive during heat history such as reflow. OBJECTS OF THE EMBODIMENT - 'It is preferable that the semiconductor secret exhibit of the present invention is subjected to stepwise treatment of the adhesive layer B composed of the composition by light irradiation, and further 5% of heat hardening is performed. The weight loss temperature is fine or more. c. Further, a semiconductor device is provided which is characterized in that the semiconductor element is sandwiched between the semiconductor elements and the semiconductor element and the semiconductor element is supported by the above-described adhesive composition. Structure of the material. The semiconductor device of the present invention is formed by the glaze for semiconductors of the present invention: the semiconductor elements are bonded to each other by the support member, thereby enabling the surface to be fully smeared.溥Adhesive layer' can therefore be miniaturized and low-profiled. And the step of disposing the adhesive layer: the second semiconductor wafer and the light-irradiated adhesive layer-conducting: tearing the semiconductor element or the half core to crimp the semiconductor element of the layer a manufacturing method for a semiconductor device, comprising: 'coating 34 the sacrificial composition for semiconductor of the present invention 201130942. The step of providing an adhesive layer; and the step of irradiating the adhesive layer with light; The semiconductor element having the light-irradiated adhesive layer and the other semiconductor element or the semiconductor element mounting supporting member are bonded to each other via a light-irradiated adhesive layer, and are adhered thereto. The present invention also provides a semiconductor device. The manufacturing method includes the steps of: applying the above-described semiconductor adhesive composition to the semiconductor element mounting support member to provide an adhesive layer; and performing light irradiation on the adhesive layer; The support member for mounting the semiconductor element of the adhesive layer and the semiconductor element are bonded by a pressure-sensitive adhesive layer and adhered thereto. [Effect of the Invention] According to the present invention, it is possible to provide an adhesive layer which can be formed to be thinner while maintaining reliability (the adhesive layer is used for the semiconductor elements or the semiconductor element and the semiconductor element mounting supporting member). Adhesive composition for a semiconductor, a method for producing a semiconductor device using the semiconductor adhesive composition, and a semiconductor device. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The embodiments of the present invention are described in detail below with reference to the drawings. However, the present invention is not limited to the embodiments described below. In the drawings, the same elements are assigned the same. The description of the symbols is omitted, and the positional relationship such as up, down, left, and right is based on the positional relationship shown in the drawing, and the dimensional ratio of the drawings is not limited to the ratio shown. 8 201130942 The adhesive composition for a semiconductor of the present invention is characterized by comprising (A) a radiation-polymerizable compound, (B) a starter, and a (〇) curable resin 'a U) component containing (A1) in a pit as a liquid A compound having one stone-to-carbon double bond in the molecule (hereinafter, sometimes referred to as "Α1 compound"). The radiation-polymerizable compound of the present invention is a compound which represents an olefin or a group having an unsaturated bond between carbon atoms. In the present invention, the term "radiation" refers to ionizing radiation or non-ionizing radiation, and examples thereof include excimer laser light such as ArF and KrF, electron f 1 ultraviolet, line, vacuum ultraviolet light, X-ray, ion beam or i-line or G line and other external light. From the viewpoint of the amount of light, it is preferable to use ultraviolet light such as an i-line or a g-line for radiation. The semiconductor adhesive composition of this month is preferably at 25. (^ is a solvent-free adhesive composition for semiconductors having a solvent content of 5% by mass or less. The above-mentioned "no solute" means that the amount of the solvent contained in the composition of the transfer agent is 5 mass. % or less. ^ The above-mentioned solvent means a light-reactive group or a ruthenium-based alpha-amine basic ethyl ketone or a phosphine oxide (ph〇Sphine oxjde), etc. a thermoreactive group such as an amino group, an acid group, an acid Sf, an isophthalic acid, a hydrazine compound, a diazo group, an imidazole or an alkoxy decane, having a molecular weight of S 5GG or less and being liquid at room temperature (25. The organic compound. Examples of such a solvent include: decyl decylamine, fluorene benzene, stupid, diphenylbenzene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, and Burning, cyclohexanyl, acetic acid ethyl s, γ-butyrolactone, and N_mercapto _n than the bite 201130942 ketone, etc., by the amount of solvent is the above (four), can be made by light viscous (tack It is possible to reduce the operability after light irradiation, and to suppress foaming during thermocompression bonding or heat curing. The conductor secret agent composition is contained in 25t: a compound having one carbon-carbon double bond in the molecule as an essential component. It is contained in «weekly; there are two or more carbon-carbon doubles in 7 The sensitivity of the compound of the bond is the same as that of the compound. If the filament is formed into a crosslinked structure, the subsequent heat is difficult to record, and it is difficult to express the secret. Therefore, it is difficult to make the thermocompression bonding difficult. In contrast, the semiconductor-based dot composition of the present invention contains a compound having one carbon-carbon double bond in the molecule, so that the fluidity at the time of heat can be sufficiently obtained and the thermocompression property is improved. Further, in the adhesive composition for a semiconductor of the present invention, it may be added to 25. (: a compound which is recorded and has a carbon-carbon double bond in the molecule) and may be formulated with a solid acrylic vinegar. In this case, the mixture of the component (A) is preferably at 25. (: in the form of a liquid. From the viewpoint of fluidity at a higher level of heat, it is preferred to be separate from the adhesive composition. Containing one carbon-carbon double bond compound in the molecule as radiation polymerizability In the case where the compound having one carbon-carbon double bond in the two substrate is used alone, the molecular weight of the polymer obtained after the light irradiation can be tens of thousands or more. Here, if it is contained in the molecule A compound having two or more carbon-carbon double bonds tends to form a network between polymers having a molecular weight of tens of thousands or more, and the adhesiveness or fluidity tends to decrease during heat. 201130942 On the other hand, In order to improve the heat resistance or to reduce the adhesion strength after exposure, it may be in a ratio of 0.1% by mass to 50% by mass based on the compound having one carbon-carbon double bond in the molecule and may be used for two or more carbons in the molecule. A compound having a carbon double bond. In this case, as a compound to be used in combination with a compound having two or more carbon-carbon double bonds, it is preferred that the carbon number is 1 Å or more from the viewpoint of fluidity at the time of heat. The aliphatic acrylate vinegar has no adhesion at the time of self-heating, and it is preferred that the amount of the functional group is _ or more, and from the viewpoint of low stress, it is more preferably an aromatic of 3 〇〇 g/eq or more. Or have a different three Acid cyclic ester of cyclic structure or a cyclohexyl group and the like. In the above-mentioned (A) component, from the viewpoint of the solubility of the other components such as the component (8) and the component (6), the viscosity is preferably 5,000 mPa·s or less, and from the viewpoint of film formation, More preferably, it is below 3000 mPa.s. Further, it is better to use 2 〇〇〇 mpa s or less to adjust the solidity or high-viscosity thermosetting resin to make the adhesion improve. Below 1000 mPa.s. Here, the viscosity f is the total value of the component (A) contained in the composition of the composition, and the EHD type rotational viscometer manufactured by Dongwon Manufacturing Co., Ltd. is used, and the sample amount is 〇4 mL, 3° cone Under the conditions, at 25t: the viscosity value determined. When the viscosity of the component (A) exceeds 5 〇〇〇 mPa.s, there is a tendency that the viscosity of the adhesive composition rises to cause thinning, or it becomes difficult to apply a nozzle from a coating device or the like (n) 〇zzle) squirting. From the viewpoint of preventing occurrence of pinholes during coating or ensuring heat resistance, it is preferred that the component (A) has a viscosity of 1 〇 mPa.s or more. 11 201130942. Further, the temperature of the 5% weight loss of the above component (A) is preferably 10 ° C or more, and more preferably i 20 ° C or more, from the inhibition of the unreacted (A) component volatilization during thermal curing. In terms of the resulting peeling or voiding, the better step is 150. (: Above, the best is 180. (: Above. The 5% heavy summer loss temperature indicated here is the total value of the (a) component contained in the adhesive composition, and is a thermogravimetric/thermal differential synchronization analyzer. (Manufactured by sii NanoTechnology inc.; TG/DTA63〇〇), a temperature loss of 5% by weight of the component (a) at a heating rate of 10 ° C / mm and a nitrogen stream (4 〇〇 mi / min). From the viewpoint of low viscosity of the adhesive composition, surface irregularity after coating, or thermal fluidity after B-stage, it is preferable to design the material mainly composed of an organic compound, and therefore it is preferable. The 5% weight loss temperature of the component (A) is 5 (8) or less. Further, as the component (A), the low-temperature thermocompression property and the thermal fluidity after the B-stage are considered. It is preferred that the polymer obtained by polymerizing the above component (A) has a Tg trace c or less, and from the viewpoint of workability or pick-up property after the B-stage, it is preferable that Tg & The polymer _^Tg is a viscoelasticity measuring device for a laminate such as the following (Rhe〇metric Which fel production, trade name: ARES) is measured at -50 ° C ~ 20 (TC taM temperature: in the (A) component based on the total amount of the composition of the proportion of 3 f% The film was dissolved in a light-initiating agent (10) Kun (10) κ κ PET (p〇lyethylene terephthaJate), so that the film thickness became a melon, under the air 12 201130942 gas, 25 ° C The coating film was exposed by a high-precision parallel exposure machine (manufactured by 〇RC MANUFACTURING Co., LTD., trade name: EXM-1172-B-oo) at 10 μm/cm 2 to carry out the film to be applied. The laminate was laminated so that the film thickness became 150 μm to obtain the laminate. Further, the measurement plate was a parallel plate having a diameter of 8 mm, and the measurement conditions were as follows: the temperature increase rate was 5 ° C / min, and the measurement temperature was _ 5 (TC 20 (TC, frequency is 1 Hz. From the viewpoint of adhesion to the adherend, reduction in surface viscosity, cutting property, and high-temperature adhesion after hardening, it is preferred that the half body of the present invention is adhered. The composition of the agent is contained in the above (A) in which the weight average molecular weight is 50,000 to 1 〇〇〇〇〇〇 when irradiated with light. Further, it is preferable to include the above-mentioned (A) having a weight average molecular weight of 5 〇〇〇 5 〇〇〇〇〇 from the viewpoint of thermal compression bonding with the adherend. In addition, the weight average molecular weight is a weight average molecular weight measured by the high-performance liquid chromatography "C_R4A" (trade name) manufactured by Shimadzu Corporation, and measured in terms of polyethylene. The weight average molecular weight of the polymer of the cerium (A) component can be added by exposure conditions (oxygen concentration, temperature, strength) 'light starting dose or thiol, hetero group, amine or m-inhibiting side, The amount of the surface or the thermosetting resin is adjusted, and the viscosity of the adhesive composition is adjusted. The component (A) used in the defrosting towel, for example, can have an ethylenic compound. Examples of the ethylenically unsaturated group include a vinyl group, a saponin=decene group, an ethylene wire, a phenylethylene wire, a maleimine group, a ground-resistant (tetra) silk, and a (meth)acrylic-scale. From the viewpoint of self-reactivity 13 201130942 It is preferable that the component (4) contains a monofunctional (meth)acrylic acid vinegar as a ==# compound. Here, the single palace can have a stone anti-slave double bond in the molecule, and can have other functional groups. Negotiation. "Single-form ΐ methyl" propylene _ preferably 5% weight loss temperature is c or more, more preferably 12 generations or more, and further preferred is 15 (rc is 18 Gt: above). From the viewpoint of the second and second self-adhesive composition, the suppression of the surface unevenness after coating, or the thermal state after B_stage = the viewpoint of kinetics, it is preferable that the material of the organic compound is the main material design, so It is preferred that the monofunctional (methyl) propylene vinegar has a weight of less than 5 。. The weight loss temperature of the monofunctional (methyl) propyl vinegar 5 〇 / 〇 is to make the _ _ _ _ _ _ (sn N_Teehn

InC•製造；TG/DTA㈣〇)，於升溫速度為HTC/min、氮氣 流（_ml/min) τ進行測定時之5%重量損失溫度。 藉由调配5%重量損失溫度為上述溫度範圍的單官能 (甲基)丙稀酸。醋’可抑制於藉由曝光而Β_階段化之後所殘 存之未反鮮官能基)丙烯酸g旨於熱壓接或熱硬化時揮 發。 作為上述A U匕合物之單官能（曱基)丙稀酸醋，例如可 列舉如下化合物：於可使硬化物_化之方面而言較佳的 是^有縮水甘油基之（甲基)丙烯酸S旨或者曱基丙烯酸-4-經 基苯基S旨或3,5-二甲基_4·綠絲丙烯g罐等含有齡性經 基之（曱基）丙稀酸醋’ 2_曱基丙烯醯氧基乙基鄰苯二曱 酉夂2_曱基丙稀酿氧基丙基六氫鄰苯二曱酸、2_曱基丙稀 酸氧基曱基六氫鄰笨二甲酸等含有緩基之（曱基）丙烯酸 201130942. 酯；於可提高耐熱性之方面而言較佳的是苯酚E〇改性（甲 基)丙烯酸醋、苯紛PO改性（曱基)丙烯酸酯、壬盼E〇改 性（曱基)丙烯酸酯、壬酚PO改性（曱基)丙烯酸酯、（曱基) 丙烯酸苯氧基乙酯、笨氧基乙二醇（曱基)丙烯酸酯、苯氧 基二乙二醇（曱基）丙烯酸酯、羥乙基化苯基苯酚丙烯酸 酯、苯氧基聚乙二醇（曱基）丙烯酸酯、壬基苯氧基乙二醇 (甲基)丙烯酸酯、壬基苯氧基聚乙二醇（曱基)丙烯酸酯、壬 基苯氧基聚丙二醇（曱基)丙烯酸酯、（甲基)丙烯酸苄基酯、 2-曱基丙烯醯氧基乙基2-經丙基鄰苯二曱酸酯、苯基苯盼 縮水甘油醚丙烯酸酯等含有芳香族之（甲基）丙烯酸酯；於 可賦予B -階段化後之密接性或熱硬化後之黏著性之方面 而言，較佳的是（曱基)丙烯酸-2-羥基_3_苯氧基丙酯、〇_苯 基苯酚縮水甘油醚(曱基)丙烯酸酯、2_(曱基)丙烯醯氧基-2_ 羥丙基鄰苯二甲酸酯、2-(曱基)丙烯醯氧基乙基_2_羥乙基_ 鄰苯二甲酸、（曱基)丙烯酸_2_羥基苯氧基丙酯等下述通 式（A-1)或通式（A-2)所表示之含有羥基之（曱基）丙烯 酸酯，丙烯酸-2-(l，2-環己基羧基醯亞胺）乙酯等下述通式 (A-3)或通式（A-4)所表示之含有酸亞胺基之(甲基)丙 稀酸酯，於可使黏著劑組成物低黏度化之方面而言，較佳 的是含有異冰片基之（曱基)丙烯酸酯、含有二環戊二烯基 之（甲基)丙烯酸酯、（曱基)丙烯酸異冰片酯等。 [化1] 15 201130942InC•manufacturing; TG/DTA (four) 〇), 5% weight loss temperature at the time of temperature increase of HTC/min and nitrogen flow (_ml/min) τ. The monofunctional (meth)acrylic acid having a temperature of the above temperature range of 5% by weight was formulated. The vinegar 'suppresses the unreacted functional group remaining after the Β_staged by the exposure.) The acrylic acid g is volatilized during thermocompression bonding or thermosetting. As the monofunctional (fluorenyl) acrylate vinegar of the above AU composition, for example, a compound having a glycidyl group (meth)acrylic acid which is preferable in terms of a cured product can be mentioned.旨 曱 曱 曱 曱 曱 曱 曱 曱 经 经 经 经 经 经 经 经 经 经 经 经 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有Alkyl propylene oxyethyl phthalic acid 2 fluorenyl propylene oxypropyl hexahydrophthalic acid, 2 fluorenyl acryloxy fluorenyl hexahydro phthalic acid The (meth)acrylic acid 201130942. ester containing a slow solution; in terms of improving heat resistance, phenol E 〇 modified (meth) acrylate vine, benzene porphyrin PO modified (fluorenyl) acrylate, 〇 〇 〇 〇 〇 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO Oxydiethylene glycol (fluorenyl) acrylate, hydroxyethylated phenyl phenol acrylate, phenoxy polyethylene glycol (fluorenyl) acrylate, nonyl phenoxy ethylene glycol (meth) acrylate , nonylphenoxy polyethylene glycol (mercapto) acrylate, nonylphenoxy polypropylene glycol (fluorenyl) acrylate, benzyl (meth) acrylate, 2-mercapto propylene oxyethyl An aromatic (meth) acrylate such as 2-propyl phthalate or phenyl benzene, which is a glycidyl ether acrylate; it can impart adhesion after B-stage or adhesion after heat hardening. In terms of properties, (2-mercapto)acrylic acid 2-hydroxy-3-phenoxypropyl ester, hydrazine-phenylphenol glycidyl ether (mercapto) acrylate, 2-(indenyl) propylene oxime Oxy-2-hydroxypropyl phthalate, 2-(indenyl)propenyloxyethyl-2-hydroxyethyl-phthalic acid, (nonyl)acrylic acid 2-hydroxyphenoxy a hydroxy group-containing (mercapto) acrylate represented by the following formula (A-1) or formula (A-2), such as propyl ester, 2-(l,2-cyclohexylcarboxy sulfinimine) acrylate The (meth) acrylate having an acid imine group represented by the following formula (A-3) or formula (A-4), such as an ester, can be used to make the adhesive composition low in viscosity. In other words, it is preferred to contain an isobornyl group. Acrylate, isobornyl acrylate containing dicyclopentadienyl group of (meth) acrylate, (Yue-yl). [Chemical 1] 15 201130942

(A-1) [化2](A-1) [Chem. 2]

於通式（A-l)及通式（A-2)中，心表示氫原子或曱 基，R3表示1價之有機基，R2及R4分別表示2價之有機 基。自耐熱性之觀點考慮，較佳的是R3為芳香族基。自耐 熱性之觀點考慮，較佳的是R4具有芳香族基。 [化3]In the general formula (A-1) and the general formula (A-2), the core represents a hydrogen atom or a fluorenyl group, R3 represents a monovalent organic group, and R2 and R4 each represent a divalent organic group. From the viewpoint of heat resistance, it is preferred that R3 is an aromatic group. From the viewpoint of heat resistance, it is preferred that R4 has an aromatic group. [Chemical 3]

R6 Rr Ο (A-3) [化4] 16 201130942.R6 Rr Ο (A-3) [Chem. 4] 16 201130942.

(A-4) 於通式（A-3)及通式（A·4)中’ R1表示氫原子或曱 基’尺5表示2價之有機基，R6、R7、B·8、R9分別表示碳數 為1〜30之1價之烴基，R6及R7邡可分別相互鍵結而形 成環，Rs及R9亦可分別相互鍵結而形成環。於汉6及R7、 以及、Rs及R9形成環之情形時，例如可列舉笨環結構、 脂環式結構。苯環結構以及脂環式結構亦可具有綾基、盼 性經基、環氧基等熱硬化性基，且亦叮具有烷基等有機基。 上述通式（A-3)及通式（A-4)所表示之化合物例如 可藉由公知之方法使N_羥基烷基醯亞胺化合物與丙烯酸 ，或丙烯酸酯反應而合成，所述N—羥基烷基醯亞胺化合物 疋使單官能酸酐與乙醇胺反應而得。於此情形時，單官能 酸針可使用4-苯基乙炔基鄰苯二甲酸針、鄰笨二甲酸gf、匕 馬來酸酐、琥_酐、5-降冰片烯_2,3_二甲酸軒、2 5_降冰 片二烯-2,3-二甲酸酐、馬來酸酐、偏苯三曱酸酐、環己二 曱酸針、5-降冰片烯_2,3_二曱酸酐、順-降冰片稀_内_23· 苯二甲酸酐、六氣鄰苯二甲酸酐 ，四 虱郝本二甲酸酐、3,4,5,6-四氫鄰笨二甲酸 17 201130942 N-羥基烧基醯亞胺化合物例如可列舉N-經乙基鄰苯二甲 醯亞胺以及N-羥乙基琥珀醯亞胺等。 作為上述通式（A-3)及通式（A-4)所表示之化合物， 自保存穩定性、B-階段化後之低黏性、匕階段化後之密接 性、熱硬化後之耐熱性、黏著性、可靠性之觀點考慮，可 使用下述通式（A-5)〜通式（A-9)所表示之化合物作為 較佳之化合物；自低黏度之觀點考慮，可使用下述通式 (A-5)、通式（A-7)〜通式（A-9)所表示之化合物作為 更佳之化合物。 ~ [化5](A-4) In the general formula (A-3) and the general formula (A·4), 'R1 represents a hydrogen atom or a fluorenyl group'. The scale 5 represents a divalent organic group, and R6, R7, B8, and R9 are respectively A hydrocarbon group having a carbon number of 1 to 30, wherein R6 and R7 are each bonded to each other to form a ring, and Rs and R9 may be bonded to each other to form a ring. In the case where the rings are formed by the formation of the ring, the ring structure and the alicyclic structure are exemplified. The benzene ring structure and the alicyclic structure may have a thermosetting group such as a mercapto group, a desired trans group or an epoxy group, and also have an organic group such as an alkyl group. The compound represented by the above formula (A-3) and formula (A-4) can be synthesized, for example, by reacting an N-hydroxyalkyl quinone imine compound with acrylic acid or an acrylate by a known method. - A hydroxyalkyl quinone imine compound obtained by reacting a monofunctional acid anhydride with ethanolamine. In this case, the monofunctional acid needle may be a 4-phenylethynyl phthalic acid needle, an o-glycolic acid gf, a maleic anhydride, a succinic anhydride, a 5-norbornene-2,3-dicarboxylic acid. Xuan, 2 5_ norbornadiene-2,3-dicarboxylic anhydride, maleic anhydride, trimellitic anhydride, cyclohexanedicarboxylic acid needle, 5-norbornene_2,3_diphthalic anhydride, cis - borneol thin _ inner _23 · phthalic anhydride, hexaphthalic phthalic anhydride, tetrahydrofuran dicarboxylic anhydride, 3,4,5,6-tetrahydro o-phenyl dicarboxylic acid 17 201130942 N-hydroxy burn Examples of the quinoneimine compound include N-ethyl phthalimide and N-hydroxyethyl succinimide. As the compound represented by the above formula (A-3) and formula (A-4), self-storage stability, low viscosity after B-stage, adhesion after hydration, heat resistance after heat curing From the viewpoint of properties, adhesion, and reliability, a compound represented by the following formula (A-5) to formula (A-9) can be used as a preferred compound; from the viewpoint of low viscosity, the following can be used. The compound represented by the formula (A-5) and the formula (A-7) to the formula (A-9) is a more preferable compound. ~ [化5]

π上逆〜式㈤），R1A示氣原子或甲 被黏單官能(甲基)丙輪，自B階段化 黏者體之讀性、硬化後之黏著性、耐熱性之觀㈣ 18 201130942 L. 較佳的是具有胺基曱 ，崎、之任意基:特;;基、 基或經基之單官能（曱基旨讀刀子内具有醯亞胺 定性作有，氧基之單官能(甲基)丙缚酸醋 ，自保存穩 耐敎域相缝额顿裝的低逸氣性、 升成考慮，5%重量損失溫度於可抑制由於 面之加熱乾騎造成之揮發或偏析於表面上之方 氣所二ΐ ϋ是、15叱社，於可抑制由於熱硬化時之逸 是二。pt U Α 著性降低之方面而言更佳的 而古、*卩上’於可抑制熱歷財之空隙以關離之方面 —步更佳的是2(Κ^Χ±，於可抑伽焊時未反應 成^揮發所造成之空隙以及剝離之方面而言最佳的是 此種具有環氧基之單官能（曱基)㈣酸醋較佳 舌二於分子内具有芳香環之化合物。而且，可藉由將5% ^損失溫度為15Gt；以上之多官能環氧樹脂用作原料而 滿足上述耐熱性。 知具有環氧基之單官能（曱基)丙稀酸酯例如除曱基丙烯 酉文縮水甘油酯、丙烯酸縮水甘油酯、丙烯酸-4-羥基丁酯縮 水甘油醚、曱基丙烯酸-冬羥基丁酯縮水甘油醚之外，亦可 列舉使具有與環氧基反應之官能基及乙烯性不飽和基之化 合物與多官能環氧樹脂反應得到之化合物等。上述與環氧 基反應之官能基並無特別之限定，可列舉異氰酸酯基、敌 基、酚性羥基、羥基、酸酐、胺基、酼基、醯胺基等。該 些化合物可單獨使用1種或者將2種以上組合使用。更具 19 201130942 體而言，例如可於三笨基膦或四丁基溴化銨之存在下，使 於1分子中具有至少2個以上環氧基之多官能環氧樹脂、 與相對於1當量環氧基而言為0 i當量〜〇 9當量之（曱基) 丙稀酸反應而獲得。而且，可藉由於二丁基錫二月桂酸^ 之存在下，使多官能異氰酸酯化合物與含有羥基之（曱基) =烯酸料及含有錄之環氧化合物反應，或者使多官能 環氧樹脂與含有異氰酸醋基之（曱基)丙烯酸酯反應，從而 獲得含有縮水甘油基之（甲基)丙烯酸胺基甲酸酯等。 另外，作為具有環氧基之單官能（曱基)丙烯酸酯，自 防止電遷移（electromigrati〇n)或者防止金屬導體電路之 腐蝕之觀點考慮，較佳的是使用將作為雜質離子之鹼金屬 離子、鹼土金屬離子、鹵離子特別是氣離子或水解性氯等 減低為1000 ppm以下之高純度品。例如，可藉由將使鹼 金屬離子、驗土金屬離子、鹵離子等減低之多官能環氧樹 脂用作原料’可滿足上述雜質離子濃度。總氯含量可基於 JISK7243-3 而測定。 滿足上述耐熱性與純度之具有環氧基之單官能（甲基） 丙烯酸酯成分並無特別之限定’可列舉以雙紛A型（或 AD型、S型、F型）之縮水甘油醚、氫化雙酚A型之縮水 甘油醚、環氧乙烷加成物雙酚A及/或f型之縮水甘油醚、 環氧丙烷加成物雙酚A及/或F型之縮水甘油醚、酚系酚 酿清漆樹脂之縮水甘油醚、甲盼清漆樹脂之縮水甘油醚、 雙酚A酚醛清漆樹脂之縮水甘油醚、萘樹脂之縮水甘油 醚、3官能型（或4官能型）之縮水甘油醚、二環戍二婦 201130942. 甘t醚、二聚酸之縮水甘油酯、3官能型 (戈4 g此型）之縮水甘油妝 原料之成分。 、不樹脂之縮水甘油胺等為 特別是為了改善熱壓接性 * 佳的是環氧基之個數為3個峨力性以及黏著性，較 限定，可較佳地使肖下料彳。此種化合物並無特別之 ㈤广通式^”或通^^丨通式⑷广通式 於下述通式（Α·1)〜通式（A 物等。 子或曱暴，R10、Rn、Rl3及14 J R及11表不氧原 15 . ,a ^ A , 表不2價之有機基。而且， 為機基，R1、R18分別是其中1個為 具有乙1性不姊基之有機基，聽為具有環氧基之有= 基。另外’（A-4)中之f表示〇〜3之整數。 [4t 6]π上逆式~式(五)), R1A shows a gas atom or a viscous monofunctional (methyl) propylene wheel, the readability of the B-staged viscous body, the adhesion after hardening, and the heat resistance (4) 18 201130942 L It is preferred to have an amine group, an arbitrary group of a group, a base group, a base group or a base group, and a monofunctional group having a quinone imine in the knives. Base) B-bound acid vinegar, self-storing and stable 敎 相 相 相 的 的 的 的 的 的 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% The qi is the second ΐ ϋ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The gap between the financial resources and the aspect of the separation is better than 2 (Κ^Χ±, which is the best for the voids caused by the volatilization and the peeling caused by the suppression of the welding. The monofunctional (fluorenyl) oxy group of the oxy group is preferably a compound having an aromatic ring in the molecule, and the temperature can be reduced by 15 Gt by a 5% ^; The polyfunctional epoxy resin is used as a raw material to satisfy the above heat resistance. A monofunctional (fluorenyl) acrylate having an epoxy group, for example, a nonyl propylene glycol glycidyl ester, a glycidyl acrylate, an acrylic acid-4 is known. - Hydroxybutyl ester glycidyl ether, methacrylic acid-winter hydroxybutyl ester glycidyl ether, but also a compound having a functional group reactive with an epoxy group and an ethylenically unsaturated group, and a polyfunctional epoxy resin The functional group to be reacted with the epoxy group is not particularly limited, and examples thereof include an isocyanate group, an ester group, a phenolic hydroxyl group, a hydroxyl group, an acid anhydride, an amine group, a decyl group, a decylamino group, and the like. One type may be used alone or two or more types may be used in combination. Further, in the case of 19 201130942, for example, at least two or more rings may be contained in one molecule in the presence of triphenylphosphine or tetrabutylammonium bromide. The polyfunctional epoxy resin of the oxy group is obtained by reacting with 0 equivalents to 9 equivalents of (mercapto)acrylic acid relative to 1 equivalent of the epoxy group. Moreover, it can be obtained by dibutyltin dilaurate^ In the presence of The functional isocyanate compound is reacted with a hydroxyl group-containing (fluorenyl)=enoic acid and a recorded epoxy compound, or a polyfunctional epoxy resin is reacted with an isocyanate-containing (fluorenyl) acrylate to obtain a shrinkage-containing product. Glyceryl (meth) acrylate urethane, etc. In addition, as a monofunctional (fluorenyl) acrylate having an epoxy group, from the viewpoint of preventing electromigration or preventing corrosion of a metal conductor circuit In view of the above, it is preferred to use an alkali metal ion, an alkaline earth metal ion, a halogen ion, particularly a gas ion or a hydrolyzable chlorine, which is an impurity ion, to be reduced to a purity of 1000 ppm or less. For example, an alkali metal can be used. A polyfunctional epoxy resin having a reduced ion, a soil metal ion, a halogen ion or the like is used as a raw material to satisfy the above impurity ion concentration. The total chlorine content can be determined based on JIS K7243-3. The monofunctional (meth) acrylate component having an epoxy group satisfying the above heat resistance and purity is not particularly limited, and examples thereof include glycidyl ethers of a type A (or AD type, S type, and F type). Hydrogenated bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A and / or f type glycidyl ether, propylene oxide adduct bisphenol A and / or F type glycidyl ether, phenol a glycidyl ether of a phenolic varnish resin, a glycidyl ether of a acetal resin, a glycidyl ether of a bisphenol A novolac resin, a glycidyl ether of a naphthalene resin, a trifunctional (or tetrafunctional) glycidyl ether , two ring 戍 two women 201130942. Glycol ether, dimer acid glycidyl ester, trifunctional (go 4 g this type) of glycidol makeup ingredients. The non-resin glycidylamine or the like is particularly intended to improve the thermocompression bonding property. * The number of epoxy groups is preferably three toughness and adhesion, and is preferably limited. There is no particular compound of this kind. (5) A broad formula or a general formula (4) is broadly defined in the following formula (Α·1) to formula (A, etc.. Sub or halo, R10, Rn , Rl3 and 14 JR and 11 are non-oxygens 15. , a ^ A, which is not a divalent organic group. Moreover, for the machine base, R1 and R18 are each one of which has an organic group. The base is heard to have an epoxy group with a = group. In addition, f in '(A-4) represents an integer of 〇~3. [4t 6]

0—R”_ f a ，c=ch2 (A-1) [4t Ά0—R”_ f a ,c=ch2 (A-1) [4t Ά

[化8] 21 201130942[化8] 21 201130942

[化 ίο][化 ίο]

R18R18

O—R18 (Α-5) 上述單官能（曱基)丙烯酸酯之含量相對於（Α)成分總 量而言較佳的是20質量％〜100質量％，更佳的是40質量 %〜100質量％，最佳的是50質量％〜100質量％。藉由使 單官能（曱基)丙烯酸酯之調配量為上述範圍，可提高B-階 段化後與被黏著體之密接性以及熱壓接性。 於本發明之半導體用黏著劑組成物中，於25°C為液狀 且於分子内具有1個碳-碳雙鍵之化合物可單獨調配1種或 者將2種以上組合調配。 22 201130942 作為上述A1化合物，自上述（B)成分及（c)成分 等其他成分之溶解性之觀點考慮，於2 5它之黏度較佳的^ 5000 mPa.s以下；進一步自薄膜化之觀點考慮，更佳的是 3000 mPa.s以下’進一步更佳的是2〇〇〇mPa.s以下；進^ 步自較多地調配固形或高黏度之熱硬化樹脂而使黏著性提 尚之觀點考慮，最佳的是1000 mpa.s以下。此處所謂之黏 度，疋關於A1化合物之值，是使用東京計器製造所製造 之EHD型旋轉黏度計，於樣品量為〇 4 mL、3。圓錐之條 件下，於25°C所測定之黏度值。 若A1化合物之上述黏度超過5〇〇〇 mPa.s，則存在如 下之傾向：黏著劑組成物之黏度上升而造成薄膜化變困 難，或者變得難以自塗佈裝置等之喷嘴喷出。自防止塗佈 時之針孔產生或者確保耐熱性之觀點考慮，較佳的是Ai 化合物於25°C之黏度為1〇 mpa.s以上。 而且，作為A1化合物之上述黏度，自提高自噴嘴等 喷出黏著劑組成物時之喷出性、薄膜化之觀點考慮，較佳 的是1000 mPa.s以下，自減低逸氣之觀點考慮，較佳的是 5 mPa.s 以上。 而且’上述A1化合物之5%重量損失溫度較佳的是 100 C以上，更佳的是120¾以上，進一步更佳的是i50〇c 以上，最佳的是18(TC以上。此處所謂之5%重量損失溫度 疋使用熱重/熱示差同步分析儀（SH NanoTechnology Inc. 製造；TG/DTA6300 )，於升溫速度為丨〇°c /min、氮氣流（4〇〇 ml/mm)下對A1化合物進行測定時之5%重量損失溫度。 23 201130942 ί ’、自黏著劑組成物之低黏度化、塗佈後之表面凹 制或者Β-階段化後之熱時流動性之觀點考慮，較佳 有機化合物為主體之材料料，因此較佳的是上述 合物之5%重量損失溫度為500°C以下。 f外’作4 A1化合物，自B_階段化後之低溫熱壓接 f、熱時流紐之觀财慮，錄的是AHb合物聚合得 到之聚合物的Tg ^刚^以下；自B_階段化後之拾取性 之硯點考慮’較佳的是Tg為2叱以上。A1化合物之聚合 物=Tg是對藉由如下方式喊得之積層體，使用黏彈性 測疋裝置（RheometricScienetifkF.E. Ltd.製造、商品名： ARES)而測疋之於_5〇c〜2〇〇。〇之峰值溫度：將於 A1成分中以相對於A1成分而言為3質量％之比例而溶解 有光起始«I-379EG ( Ciba japan K.K.製造）的組成物塗佈 於 PET ( polyethylene terephthalate，聚對苯二甲酸乙二酯）O—R18 (Α-5) The content of the above monofunctional (fluorenyl) acrylate is preferably 20% by mass to 100% by mass, and more preferably 40% by mass to 100% by mass based on the total of the (Α) component. The mass% is preferably 50% by mass to 100% by mass. By setting the amount of the monofunctional (fluorenyl) acrylate to the above range, the adhesion to the adherend and the thermocompression bonding after the B-stage can be improved. In the adhesive composition for a semiconductor of the present invention, the compound which is liquid at 25 ° C and has one carbon-carbon double bond in the molecule may be used alone or in combination of two or more. 22 201130942 As the above-mentioned A1 compound, from the viewpoint of the solubility of the other components such as the above (B) component and (c) component, it is preferably less than 5,000 mPa.s of the viscosity of 25; further from the viewpoint of thin film formation It is considered that it is more preferable to be below 3000 mPa.s, and further preferably 2 〇〇〇mPa.s or less; the step of considering the adhesion of the solid or high-viscosity thermosetting resin to increase the adhesion is considered. The best is below 1000 mpa.s. The viscosity referred to herein is about the value of the A1 compound, which is an EHD type rotational viscometer manufactured by Tokyo Keiki Co., Ltd., and the sample amount is mL 4 mL, 3. Viscosity values measured at 25 ° C under conical conditions. When the above-mentioned viscosity of the A1 compound exceeds 5 〇〇〇 mPa.s, there is a tendency that the viscosity of the adhesive composition rises to cause thinning, or it becomes difficult to eject from a nozzle of a coating device or the like. From the viewpoint of preventing the occurrence of pinholes during coating or ensuring heat resistance, it is preferred that the viscosity of the Ai compound at 25 ° C is 1 〇 mpa.s or more. In addition, the viscosity of the A1 compound is preferably 1000 mPa·s or less from the viewpoint of improving the discharge property and film formation when the adhesive composition is ejected from a nozzle or the like, and from the viewpoint of reducing the outgassing, It is preferably 5 mPa.s or more. Further, the 5% weight loss temperature of the above A1 compound is preferably 100 C or more, more preferably 1203⁄4 or more, still more preferably i50 〇 c or more, and most preferably 18 (TC or more. % weight loss temperature 疋 using a thermogravimetric/thermal differential synchronization analyzer (manufactured by SH NanoTechnology Inc.; TG/DTA6300), at a heating rate of 丨〇°c / min, nitrogen flow (4 〇〇 ml / mm) to A1 The temperature at which the compound is measured is 5% by weight. 23 201130942 ί ', from the viewpoint of low viscosity of the adhesive composition, surface concave after coating, or thermal activity after enthalpy-staged, preferably The organic compound is a material material of the main body, and therefore it is preferred that the 5% weight loss temperature of the above compound is 500 ° C or less. f external 'as 4 A1 compound, low temperature thermocompression f, heat after B_stage At the time of the flow of the New Zealand, it is recorded that the Tg ^ ^ ^ of the polymer obtained by polymerization of the AHb compound is below; since the pick-up property after the B_stage is considered, it is preferable that the Tg is 2叱 or more. The polymer of the compound = Tg is a laminate that is shouted by the following method, using viscoelasticity The device (manufactured by Rheometric Scienetifk F. E. Ltd., trade name: ARES) was measured at _5 〇 c 〜 2 〇〇. The peak temperature of 〇 was 3% by mass relative to the A1 component in the A1 component. The composition of the light-initiated «I-379EG (manufactured by Ciba japan KK) was applied to PET (polyethylene terephthalate).

薄膜上以使膜厚成為30 μιη，使用高精度平行曝光機（〇RC MANUFACTURING Co.，LTD.製造、商品名： EXM-1172-B-oo)以l〇〇〇mj/cm2對該塗膜進行曝光，將所 付之薄膜進行積層以使膜厚成為150 μηχ從而獲得所述積 層體。另外’測定板使用直徑為8 mm之平行板，測定條 件為：升溫速度為5°C/min、測定溫度為_5〇°c〜2〇〇<5c、頻 率為1 Hz。 本發明之半導體用黏著劑組成物除了上述A1化合物 以外，亦可含有2官能以上之（曱基)丙稀酸酯作為（a)放 射線聚合性化合物。此處所謂之2官能以上是表示於分子 24 201130942α 内具有2個以上碳-碳雙鍵。此種丙烯酸自旨並無特別之限 制，可列舉二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、 四乙二醇二丙稀酸酯、二乙二醇二曱基丙稀酸酯、三乙二 醇二曱基丙烯酸酯、四乙二醇二曱基丙烯酸酯、三羥曱基 丙烷二丙烯酸酯、三羥曱基丙烷三丙烯酸酯、三羥曱基丙 烷二曱基丙烯酸脂、三羥曱基丙烷三曱基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1，4-丁二醇二 曱基丙烯酸脂、1，6-己二醇二曱基丙烯酸脂、季戊四醇三 丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三曱基丙烯酸 酉旨、季戊四醇四甲基丙烯酸醋、二季戊四醇六丙烯酸自旨、 二季戊四醇六甲基丙烯酸酯、苯乙烯、二乙烯基苯、4-乙 烯基曱苯、4-乙烯基吡啶、Ν-乙烯基吡咯啶酮、丙烯酸-2-羥基乙酯、曱基丙烯酸-2-羥基乙酯、1,3-丙烯醯氧基-2-羥 基丙烷、1,2-曱基丙烯醯氧基-2-羥基丙烷、亞曱基雙丙烯 醯胺、Ν,Ν-二甲基丙烯醯胺、Ν-羥甲基丙烯醯胺、異三聚 氰酸三(β-羥乙基)酯之三丙烯酸酯、下述通式（Α-6)所表 示之化合物、丙烯酸胺基曱酸酯或甲基丙烯酸胺基曱酸 酉旨、以及丙烯酸脲S旨等。 Η 匕 11]The film was formed to have a film thickness of 30 μm, and the film was coated at 10 μm/cm 2 using a high-precision parallel exposure machine (manufactured by 〇RC MANUFACTURING Co., LTD., trade name: EXM-1172-B-oo). Exposure was carried out, and the film to be deposited was laminated so that the film thickness became 150 μηχ to obtain the laminate. Further, the measuring plate used a parallel plate having a diameter of 8 mm, and the measurement conditions were as follows: the heating rate was 5 ° C / min, the measurement temperature was _5 〇 ° c 2 〇〇 < 5 c, and the frequency was 1 Hz. The adhesive composition for a semiconductor of the present invention may contain, in addition to the above-mentioned A1 compound, a bifunctional or higher (fluorenyl) acrylate as (a) a radiation-polymerizable compound. Here, the bifunctional or higher means that two or more carbon-carbon double bonds are present in the molecule 24 201130942α. The acrylic acid is not particularly limited, and examples thereof include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and diethylene glycol dimercapto acrylate. , triethylene glycol dimercapto acrylate, tetraethylene glycol dimercapto acrylate, trihydroxy decyl propane di acrylate, trihydroxy decyl propane triacrylate, trihydroxy decyl propane di decyl acrylate, Trihydroxydecylpropane tridecyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimercapto acrylate, 1,6- Hexanediol dimercapto acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tridecyl acrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, benzene Ethylene, divinylbenzene, 4-vinylpyrene, 4-vinylpyridine, fluorene-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3- Propylene oxime-2-hydroxypropane, 1,2-mercaptopropenyloxy-2-hydroxypropane Alkane, fluorenyl bis acrylamide, hydrazine, hydrazine-dimethyl decylamine, hydrazine-hydroxymethyl acrylamide, tris(c-hydroxyethyl) ester triacrylate, under The compound represented by the formula (Α-6), the amino phthalic acid acrylate or the methic acid amide amide, and the urethane acrylate S. Η 匕 11]

Ria H2C—C一Ria H2C-C one

OCH2CH2i 於上述通式（A-6)中，R19及R2Q分別獨立地表示氫 25 20113094¾ 原子或甲基’ g及h分別獨立地表示1〜2〇之 而且’可列舉：上述式（A-3)之為具數。 飽和基之有機基的化合物、上述式（a_4：) ’^Rl7乙歸性不 以上為具有乙烯性不飽和基之有機基且農棘中之2個 之有機基的化合物、以及上述式（A-5)之汉二^有環氧基 上為具有乙烯性不飽和基之有機基且其餘林以 有機基的化合物。 衣氧基之 而且，為了減低曝光後之黏性或者提高黏著性 本發明之黏著劑組成物中含有下述結構式所表示之μ…& 馬來醯亞胺化合物。 ' 早s月b [化 12]OCH2CH2i In the above formula (A-6), R19 and R2Q each independently represent hydrogen 25 201130943⁄4 atom or methyl 'g and h each independently represent 1 to 2〇 and 'may be exemplified by the above formula (A-3) ) is a number. The compound of the organic group of the saturated group, the compound of the above formula (a-4:) 'R17, which is not more than the organic group having an ethylenically unsaturated group and two of the organic groups of the agricultural spines, and the above formula (A) -5) The compound having an organic group having an ethylenically unsaturated group on the epoxy group and an organic group in the remaining forest. Further, in order to reduce the viscosity after exposure or to improve the adhesion, the adhesive composition of the present invention contains a μ...&maleimide compound represented by the following structural formula. '早早月b [化12]

(A)成分之含量相對於黏著劑組成物總量而言較佳 的是10質量％〜95質量％，更佳的是2〇質量％〜9〇質量 %，最佳的是40質量％〜90質量％。若（A)成分之含量 不足10質量％’則存在曝光後之表面黏著力變大之傾向， 且若超過95質量％，則存在熱硬化後之黏著強度降低之傾 向，因此欠佳。 作為上述（B)光起始劑，對於波長為365 nm之光的 分子吸光係數於可階段化之方面而言較佳的是100 26 201130942 ml/gxm以上，於可進一步減低曝光後之黏性 士 更佳的是200 ml/g.cm以上，於可進一步減 而σ ，而言進-步更佳的是備· 直、短時間而進行B_階段化之方面而言最佳的是^ ml/g.cm以上。另外，B_階段化所需要之時間較佳的是⑼$ =内，於可更有效率地製造半導體材料之方面而言2佳的s S以内。上述分子吸光係數可藉由調製樣品°之0.001 質量％乙腈溶液’使用分光光度計（日立高新技術公司製 造、「U-3310」（商品名））對該溶液測定吸光度而求出。 上述（B)成分例如可列舉：1-羥基-環己基_苯基-酮、 2-經基苯基·丙烧销、丨例2•乙氧基)苯 基]-2-羥基-2-曱基-1-丙烧.μ酮、2_經基]_{4_[4 (2_經基_2_ 甲基-丙酿基)-节基]_苯基卜2-曱基_丙燒小嗣、氧基-苯基_ 乙酸2-[2-侧氧基_2-苯基-乙醯氧基-乙氧基]乙醋、苯基乙醛 酸曱醋、2-二曱基胺基_2_(4_甲基_节基)小⑷嗎琳冰基-苯 基)-丁烧-1-酮、2-乙基己基_4-二曱基胺基苯甲酸酉旨、2_节 基_2_二甲基胺基-1-(4_嗎啉代苯基)_丁_]、2,2_二甲氧基 -1,2-二苯基乙烷_1_酮、丨_羥基_環己基-苯基-酮、孓甲基 -1-(4-(甲硫基)苯基)-2_嗎啉代丙嗣心2,4_二乙基噻噸酮、 2-乙基慧醒、菲酿等芳香族@同，苯偶酿二甲基賴（benzii dimethyl ketal)等苯偶醯衍生物，2_(鄰氣苯基)_4,5_二苯基 t坐二聚體、2-(鄰氣苯基)_4,5_二(間甲氣基苯基坐二聚 體、2-(鄰氟苯基)-4,5-苯基咪唑二聚體、2_(鄰曱氧基苯 基)-4’5_二苯基咪唾二聚體、2_(對甲氧基苯基)_4>二苯基 27 201130942 味唾二聚體、2,4-二(對曱氧基苯基)-5-苯基咪吐二聚體、 2-(2,4-二甲氧基笨基)-4,5-二苯基咪唑二聚體等2,4,5-三芳 基咪唾二聚體’ 9-苯基吖啶、ι，7-雙(9,9，-吖啶基)庚烷等吖 σ定衍生物’雙(2,6-二甲氧基苯甲醯基)_2,4,4-三曱基-戊基膦 氧化物、雙(2,4,6,-三曱基苯曱醯基)-苯基膦氧化物等雙醯 基膦氧化物或者具有馬來醯亞胺之化合物等。該些化合物 可單獨使用或者將2種以上組合使用。 於上述光起始劑中，於不含溶劑之黏著劑組成物中之 溶解性之方面而言，可較佳地使用2,2_二曱氧基丨，^二苯 基乙烷-1-酮、2-苄基_2_二曱基胺基_1_(4_嗎啉代苯基)_丁酮 -1、2,2-二曱氧基_ι，2_二苯基乙烷+酮、2_曱基小(4_(甲硫 基)苯基)-2-嗎啉代丙烷小酮。 作為（B)光起始劑，於即使在空氣環境下（氧存在 下）中亦可藉由曝光而有效率地B_階段化之方面而言，較 佳的是於分子内具有肟酯骨架或嗎啉骨架之化合物。此種 化合物並無特別之限定，較佳的是下述通式（B4)所表示 之具有肟酯基之化合物及/或下述通式（B_2)、通式 或通式（B-4)所表示之具有嗎啉環之化合物。具體而言， 可較佳地使用2-苄基-2-二曱基胺基嗎啉代苯基)_丁 酉同-1、2,2-二曱氧基-1，2-二苯基乙燒+酉同、2_甲基(甲 硫基)苯基)-2-嗎淋代丙烧·1_酮。 [化 13] 28 201130942 R5、1The content of the component (A) is preferably 10% by mass to 95% by mass based on the total amount of the adhesive composition, more preferably 2% by mass to 9% by mass, most preferably 40% by mass. 90% by mass. When the content of the component (A) is less than 10% by mass, the surface adhesive strength after exposure tends to be large, and if it exceeds 95% by mass, the adhesive strength after thermal curing is lowered, which is not preferable. As the above (B) photoinitiator, the molecular absorption coefficient of light having a wavelength of 365 nm is preferably 100 26 201130942 ml/gxm or more in terms of staged, so as to further reduce the viscosity after exposure. It is better to be 200 ml/g.cm or more, and it is possible to further reduce σ. For the better, the best step is to prepare for B_stage. Ml/g.cm or more. In addition, the time required for the B_stage is preferably within (9)$=, which is within 2 s S in terms of more efficient fabrication of the semiconductor material. The molecular absorption coefficient can be determined by measuring the absorbance of the solution by using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, "U-3310" (trade name)) by preparing a 0.001% by mass acetonitrile solution of the sample. Examples of the component (B) include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-p-phenylene-propanoid, and anthracene 2•ethoxy)phenyl]-2-hydroxy-2-曱-l-1-propanol. μ ketone, 2 _ base] _{4_[4 (2_ mercapto_2_methyl-propyl aryl)-nodyl] phenylphenyl 2-mercapto-propyl Osmium, oxy-phenyl-acetic acid 2-[2-o-oxy-2-phenyl-ethoxycarbonyl-ethoxy]ethyl acetonate, phenylglyoxylate vinegar, 2-didecylamine Base 2_(4_methyl-nodal) small (4) morphine yl-phenyl)-butan-1-one, 2-ethylhexyl _4-didecylaminobenzoic acid, 2_ 1,2-dimethylamino-1-(4-morpholinophenyl)-butane, 2,2-dimethoxy-1,2-diphenylethane-1-one,丨_Hydroxy-cyclohexyl-phenyl-ketone, fluorenylmethyl-1-(4-(methylthio)phenyl)-2-morpholinopropanoid 2,4-diethylthioxanthone, 2 - Ethyl acetonide, phenanthrene and other aromatic @同, Benzene dimethyl butyl (benzii dimethyl ketal) and other benzoin derivatives, 2_(o-phenyl)_4,5_diphenyl t sit two Polymer, 2-(o-phenyl)_4,5_di(m-methylphenyl sitting dimer, 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2_( O-nonyloxyphenyl)-4'5-diphenyl Sodium salic dimer, 2_(p-methoxyphenyl)_4> diphenyl 27 201130942 taste saliva dimer, 2,4-di(p-methoxyphenyl)-5-phenylmipropene dimerization 2,4,5-triarylmeridene dimer 9-phenyl acridine such as 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolium dimer ι,7-bis(9,9,-acridinyl)heptane and other oxime-sigma derivatives 'bis(2,6-dimethoxybenzylidene)_2,4,4-tridecyl-pentyl a bisphosphonium phosphine oxide such as a phosphine oxide or a bis(2,4,6,-trimercaptophenyl)-phenylphosphine oxide or a compound having a maleimide or the like. It is used singly or in combination of two or more kinds. Among the above photoinitiators, 2,2-didecyloxy oxime can be preferably used in terms of solubility in a solvent-free adhesive composition. , diphenylethane-1-one, 2-benzyl-2-didecylamino-1_(4-morpholinophenyl)-butanone-1, 2,2-dimethoxy group ι, 2_diphenylethane + ketone, 2_fluorenyl small (4-(methylthio)phenyl)-2-morpholinopropane ketone. As (B) photoinitiator, even in air Under the environment (in the presence of oxygen), it can also be exposed by exposure. In terms of B-staged efficiency, a compound having an oxime ester skeleton or a morpholine skeleton in the molecule is preferred. The compound is not particularly limited, and is preferably a compound of the following formula (B4). A compound having an oxime ester group and/or a compound having a morpholine ring represented by the following formula (B-2), a formula or a formula (B-4). Specifically, 2-benzyl-2-didecylaminomorpholine phenyl)-butanthene-1,2,2-didecyloxy-1,2-diphenylethyl is preferably used. Burning + 酉, 2 - methyl (methylthio) phenyl) -2- hydrating, propyl ketone, 1-ketone. [Chem. 13] 28 201130942 R5, 1

Qzz—:JSJ-〇-Q-Qzz—: JSJ-〇-Q-

R -R53 (Β-1) 52 || ο [化 14]R -R53 (Β-1) 52 || ο [Chem. 14]

Q N- Ο >54 ,CH3Q N- Ο >54 ,CH3

R 55 CH3 (B-2)R 55 CH3 (B-2)

[化 16] >——, ch3o o ch3 (B-4) I II 57 II I /[化16] >——, ch3o o ch3 (B-4) I II 57 II I /

Q N—C—C—C—C—N CH, ch3 式中，R51及R52分別獨立地表示氫原子、碳數為1 29 201130942 表^數t系烴基之有機基，R53及R54及R55 R56及R57表# a -元^或包含芳香族系烴基之有機基， h包含㈣族系煙基之有機基。 述方香族系烴基並盔特别 以及萘基、安息香衍生物；’例如可列舉苯基 作為上述⑻光妓有取代基。 的分子吸光係數為1000 ml/g.c 溫度為航以上。 Μ上’而且5。/。重量損失 ㈣Ϊ種⑻光起始劑例如可列舉下述結構式㈤）〜 、〜構式（Β-9)所表示之化合物。 [化 17] 0 201130942, ο ^6^13QN-C-C-C-C-N CH, ch3 wherein R51 and R52 independently represent a hydrogen atom, the carbon number is 1 29 201130942, the number of t-based hydrocarbon groups, R53 and R54 and R55 R56 and R57 is a a-member or an organic group containing an aromatic hydrocarbon group, and h contains an organic group of a (iv) group of a ketone group. The aromatic hydrocarbon-based hydrocarbon group and the naphthyl group and the benzoin derivative are particularly exemplified by the above-mentioned (8) optical oxime-substituted substituent. The molecular absorption coefficient is 1000 ml/g.c. Μ上' and 5. /. Weight loss (4) The photoinitiator (8) The compound represented by the following structural formula (5)) ~, ~ configuration (Β-9). [化17] 0 201130942, ο ^6^13

=n_〇4-Q (B-5)=n_〇4-Q (B-5)

Ν—C一C / I ch3Ν—C-C / I ch3

/Ν' η3ιη3 C丨c—c OHnc «ο (Β·/Ν' η3ιη3 C丨c-c OHnc «ο (Β·

(B-8)(B-8)

O N- 0 ch2 丨丨1V 3O N- 0 ch2 丨丨1V 3

ii I n—C—C—I (B-9) ch2ch3 CH, 本發明之半導體用黏著劑組成物包含環氧樹脂之情形 時，（B)成分亦可含有光起始劑，所述光起始劑表現出藉 由放射線照射而促進環氧樹脂之聚合及/或反應的功能。此 種光起始劑例如可列舉藉由放射線照射而產生鹼之光鹼產 31 201130942 =驗=射線照射而產生酸之光酸產生劑等，特佳的 ，由使用光鹼產生劑’可使轉劑喊物於被黏著體 上之南溫黏著性以及耐濕性進—步提高。認為其理由是： 由光驗產生綱生成讀作為環氧樹脂之硬化觸媒而效率 良好地發揮作用’由此可使交聯密度進—步提高，而 生^之硬化觸媒對基板等造成之腐蝕較少。而且，藉由於 黏著劑組成财含有級產生劑，可提高交贿度且可 進-步減低高溫放置時之逸氣。另外，可使硬化處理溫度 低溫化、短時間化。 光鹼產生劑若為於放射線照射時產生鹼之化合物即 可。作為所產生之鹼，自反應性、硬化速度之方面而言較 佳的是強鹼性化合物。 ° 放射線照射時產生之驗例如可列舉：哺η坐、2 4-二曱 基咪唑、1-曱基咪唑等咪唑衍生物，哌嗪、2,5-二曱基哌嗪 等哌嗪衍生物，哌啶、1,2-二曱基哌啶等哌啶衍生物，脯 胺酸衍生物，三曱胺、三乙胺、三乙醇胺等三烷基胺衍生 物，4-曱基胺基吡啶、4-二甲基胺基吡啶等在4位取代有 胺基或炫基胺基之η比唆衍生物，π比Ι^π定、〜曱基吼洛咬等 吡咯啶衍生物，二氫吡啶衍生物，三乙二胺、二氮雜 雙環(5,4,0)十一烯-1 (DBU)等脂環族胺衍生物，节基甲 基胺、苄基二甲基胺、苄基二乙胺等苄胺衍生物等。 精由放射線照射而產生上述驗之光驗產生劑例如可使 用 Journal of Photopolymer Science and Technology 第 12 32 201130942 卷、第 313 〜314 項（ 1999 年）或 Chemistry of Materials 第 11卷、第170〜176項（ 1999年）等中所記載之四級銨鹽 衍生物。該些化合物藉由照射活性光線而生成高鹼性之三 烷基胺，因此適於環氧樹脂之硬化。 光鹼產生劑亦可使用Journal of American ChemicalIi I n—C—C—I (B-9) ch2ch3 CH, when the adhesive composition for a semiconductor of the present invention contains an epoxy resin, the component (B) may further contain a photoinitiator, the light The initiator exhibits a function of promoting polymerization and/or reaction of the epoxy resin by radiation irradiation. Examples of such a photoinitiator include a photobase generator which generates alkali by radiation irradiation. 31 201130942 = photo-acid generator which generates acid by irradiation = irradiation, and particularly, by using a photobase generator The transfer agent shook the object on the adhesive body and the south temperature adhesiveness and moisture resistance progressed step by step. The reason is considered to be: The photo-producing generation is read as an epoxy resin hardening catalyst and functions efficiently. Thus, the crosslinking density can be further improved, and the hardening catalyst of the raw material is caused to the substrate. Less corrosion. Moreover, by virtue of the adhesive composition of the grade-containing agent, the degree of bribery can be increased and the escape from high temperature can be further reduced. Further, the curing treatment temperature can be lowered and the time can be shortened. The photobase generator may be a compound which generates a base upon irradiation with radiation. As the base to be produced, a strongly basic compound is preferred from the viewpoints of reactivity and curing rate. ° Tests produced by radiation irradiation include, for example, imidazole derivatives such as η sitting, 2 4-dimercaptoimidazole, 1-mercaptoimidazole, piperazine derivatives such as piperazine and 2,5-dimercaptopiperazine; , piperidine derivatives such as piperidine, 1,2-dimercaptopiperidine, methionine derivatives, trialkylamine derivatives such as tridecylamine, triethylamine, triethanolamine, 4-mercaptoaminopyridine , 4-dimethylaminopyridine, etc., which are substituted with an amine group or a leucine group at the 4-position, and a pyrrolidine derivative such as π, Ι^π, 曱 曱 吼, and dihydrogen. Pyridine derivative, alicyclic amine derivative such as triethylenediamine, diazabicyclo(5,4,0)undecene-1 (DBU), benzylmethylamine, benzyldimethylamine, benzyl A benzylamine derivative such as diethyldiamine. For example, Journal of Photopolymer Science and Technology, Vol. 12 32 201130942, No. 313-314 (1999) or Chemistry of Materials, Vol. 11, No. 170-176 can be used for the photodetection agent which is irradiated by radiation. The quaternary ammonium salt derivative described in (1999) and the like. These compounds are suitable for hardening of epoxy resins by irradiating active light to form highly basic trialkylamines. Photobase generators can also be used in Journal of American Chemical

Society 第 118 卷第 12925 頁（ 1996 年）或 p〇iymer Journal 第28卷第795頁（1996年）等中所記載之胺基曱酸衍生 物。 猎由放射線照射而產生驗之光驗產生劑可使用2 4-二 曱氧基-1，2-二苯基乙烷-1-酮、1，2_辛二g同，(苯硫 基)-，2_(0-苯甲醯月亏)]或乙酮，1_[9_乙基_6_(2_甲基苯甲醯 基)-9Η-咔唑-3-基]-，1-(0-乙醯肟)等肟衍生物或作為光自由 基產生劑而市售之2-苄基-2-二甲基胺基_1_(4_嗎琳代苯 基)-丁酮-1、2,2-一曱氧基-1，2-二苯基乙烧酮、孓甲基 -1-(4-(曱硫基)苯基)-2-嗎啉代丙烷_1_酮、2_节基_2_二甲基 胺基-1-(4-嗎啉代苯基)-丁酮_；[、六芳基雙咪唑衍生物（亦 可於苯基上取代齒素、烷氧基、硝基、氰基等取代基）、苯 幷異噁唑啉酮衍生物等。 土 光驗產生劑亦可使用於高分子之主鍵及/或側鍵導入 有產生鹼之基的化合物。於此情形時之分子量，自作為黏 著劑之黏著性、流動性以及_^熱性之觀點考慮，較佳的是 重量平均分子量為10()()〜__，更佳的是5嶋〜議〇。 上述光驗產生劑於未曝光之狀態下並不顯示出 樹脂之反應性，因此於室溫下之儲存穩定_常優^ : 33 201130942. 起始劑之含量相對於（A)成分觸質量份而 份〜2。質量份，自_二= 質量份。若°·=份〜10 性降低’保存穩定性降低之二= 不足(Π質量份，則存在㈣段倾_之_。心里 於本發明之半導體用黏著劑組成物中，可視需要而併 用增，。該增感劑例如可列舉：樟職、苯‘要= 醯、本偶醯一甲基縮酮、苯偶醯二乙基縮酮、苯偶醯二0 曱氧基乙基)縮酮、4,4，_二曱基苯偶醯_二曱基縮酮、葱酿、 immm以苯幷蒽酿、l經基該、r甲基 蒽醌、2-乙基蒽醌、1 _溴蒽醌、嗟噸酮、2_異丙基嗟嘲酮、 2-硝基嗟噸酮、2-曱基噻噸酮、2,4-二曱基噻噸酮、2,4_二 乙基噻噸酮、2,4-二異丙基噻噸酮、2_氯_7_三氟曱基噻噸 酮、噻噸g同-10，10_二氧化物、噻噸酮_1〇_氧化物、安息香 曱醚、女息香乙鱗、異丙鱗、安息香異丁醚、二苯曱酮、 雙(4-二曱基胺基苯基)酮、4,4'-雙二乙基胺基二苯曱酮、含 有疊氮基之化合物等。該些化合物可單獨使用或者將2種 以上組合使用。 上述（C)熱硬化性樹脂若為由可藉由熱而產生交聯 反應之反應性化合物構成之成分則並無特別之限定，例如 可列舉環氧樹脂、氰酸酯樹脂、馬來醯亞胺樹脂、烯丙基 耐地醯亞胺樹脂、酚樹脂、脲樹脂、.三聚氰胺樹脂、醇酸 樹脂、丙烯酸樹脂、不飽和聚醋樹脂、鄰苯二曱酸二烯丙 34 201130942 ------- 酯樹脂、矽氧樹脂、間笨二酚曱醛樹脂、二曱苯樹脂、呋 喃樹脂、聚胺基甲酸酯樹脂、酮樹脂、氰尿酸三稀丙酯樹 脂、聚異氰酸酯樹脂、含有異氰尿酸三(2-羥乙基)酯之樹 月曰、含有二本六曱酸二稀丙基g旨之樹脂、由環戊二稀而合 成之熱硬化性樹脂、由於芳香族二氰胺之三聚作用而生成 之熱硬化性樹脂等。其中，於可具有於高溫下優異之黏著 力之方面而言’較佳的是環氧樹脂、馬來醯亞胺樹脂、以 及烯丙基耐地醯亞胺樹脂。另外，熱硬化性樹脂可單獨使 用或者將二種以上組合使用。 環氧樹脂較佳的是於分子内包含至少2個以上環氧基 之環氧樹脂’自熱壓接性或硬化性、硬化物特性之方面而 言，更佳的是酚之縮水甘油醚型環氧樹脂。此種樹脂例如 可列舉雙酚A型（或AD型、s型、F型）之縮水甘油醚、 氫化雙酚A型之縮水甘油醚、環氧乙烷加成物雙酚A型之 縮水甘油醚、環氧丙烷加成物雙酚A型之縮水甘油醚、酚 系_清漆樹脂之縮水甘油醚、脂之縮水甘油 醚、雙^祕清漆樹脂之缩水甘㈣、萘細旨之縮水甘 油醚、3官能型（或4官能型）之縮水甘㈣、二環戊二 稀苯紛樹脂之縮水甘油醚、二驗之縮水甘⑽旨、 变（H 型）之縮水甘油胺、蔡樹脂之縮水甘油胺等。 該些％可單獨使用或者將2種以上組合使用。 而反命作為環氧樹脂，自防止電遷移或者防止 體之觀點考慮，較佳的是使用將作為雜質離子 之驗金屬斜、驗土金屬離子、_子特別是 35 201130942 解性氣等減低為300 ppm以下之古 馬來醯亞胺樹脂例如可列槪二'、 馬來醯亞麟脂、下料# 料*⑴絲不之雙 來酿亞胺麟等。 UI)所表仏祕清漆型馬 [化 18]Aminophthalic acid derivatives as described in Society, Vol. 118, p. 12925 (1996) or p. iymer Journal, Vol. 28, p. 795 (1996). For the detection of radiation by radiation, 2 4-dimethoxy-1,2-diphenylethane-1-one, 1,2-di-di-g, (phenylthio) can be used. -, 2_(0-benzaldehyde oxime) or ethyl ketone, 1_[9_ethyl_6_(2_methylbenzhydryl)-9Η-oxazol-3-yl]-, 1-( 0-acetamidine) is an isomer derivative or a 2-benzyl-2-dimethylamino-1 - (4-morphinylphenyl)-butanone-1 commercially available as a photoradical generator. 2,2-monodecyloxy-1,2-diphenylacetone, fluorenylmethyl-1-(4-(indolylthio)phenyl)-2-morpholinopropan-1-one, 2 _ benzyl 2- dimethylamino-1-(4-morpholinophenyl)-butanone _; [, hexaarylbiimidazole derivative (also can replace dentate, alkoxy on phenyl) a substituent such as a nitro group or a cyano group), a benzoquinone isoxazolinone derivative or the like. The soil photodetecting agent can also be used as a compound in which a base of a base is introduced into a primary bond and/or a side bond of a polymer. The molecular weight in this case, from the viewpoints of adhesion, fluidity, and heat resistance of the adhesive, it is preferred that the weight average molecular weight is 10 () () ~ __, and more preferably 5 嶋 ~ 〇 . The photoinitiator does not exhibit reactivity of the resin in an unexposed state, and therefore is stable at room temperature _Changyou ^ 33 201130942. The content of the initiator is relative to the mass of the component (A) And the share ~ 2. Parts by mass, from _ two = parts by mass. If °·= parts to 10 is reduced, 'the storage stability is reduced by two = insufficient (the mass part is present, there is a (four) stage tilting_ _. In the adhesive composition of the semiconductor of the present invention, it can be used as needed. For example, the sensitizer may be exemplified by: 樟, 苯 '要 = 醯, 醯 醯 甲基 methyl ketal, benzoin diethyl ketal, benzoin oxime oxyethyl) ketal , 4,4,_dimercaptobenzophenone 曱-didecyl ketal, onion, immm, benzoquinone, l-based, r-methyl hydrazine, 2-ethyl hydrazine, 1 bromine蒽醌, xanthonone, 2-isopropylpyridinone, 2-nitroxanthone, 2-mercaptothioxanthone, 2,4-dimercaptothioxanthone, 2,4-diethyl Thioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluorodecylthioxanthone, thioxanthene-10,10-dioxide, thioxanthone_1〇_ Oxide, benzoin ether, dimethoate, isopropyl scale, benzoin isobutyl ether, dibenzophenone, bis(4-didecylaminophenyl) ketone, 4,4'-bisdiethyl Aminobenzophenone, a compound containing an azide group, and the like. These compounds may be used singly or in combination of two or more. The (C) thermosetting resin is not particularly limited as long as it is a component composed of a reactive compound capable of undergoing a crosslinking reaction by heat, and examples thereof include an epoxy resin, a cyanate resin, and a Malayan. Amine resin, allyl quinone imine resin, phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, phthalic acid diallyl 34 201130942 ---- --- Ester resin, oxime resin, m-diphenol phenolic resin, diphenyl benzene resin, furan resin, polyurethane resin, ketone resin, tri-propyl propyl urate resin, polyisocyanate resin, containing Tris(2-hydroxyethyl) isocyanurate, a resin containing two hexamethylene hexahydrate, a thermosetting resin synthesized from cyclopentadiene, due to aromatic dicyandiamide A thermosetting resin produced by the trimerization of an amine or the like. Among them, an epoxy resin, a maleimide resin, and an allyl ruthenium imine resin are preferred in terms of excellent adhesion at high temperatures. Further, the thermosetting resin may be used singly or in combination of two or more. The epoxy resin is preferably an epoxy resin containing at least two or more epoxy groups in the molecule, and is preferably a glycidyl ether type of phenol in terms of autothermal crimping property, hardenability, and hardened property. Epoxy resin. Examples of such a resin include glycidyl ether of bisphenol A type (or AD type, s type, and F type), hydrogenated bisphenol A type glycidyl ether, and ethylene oxide adduct bisphenol A type glycidol. Ether, propylene oxide adduct diglycidyl ether of bisphenol A type, glycidyl ether of phenolic varnish resin, glycidyl ether of fat, glycidyl condensate of bismuth varnish resin (IV), glycidyl ether of naphthalene , trifunctional (or 4-functional) glycidyl (tetra), dicyclopentadiene benzene resin glycidyl ether, two test of water shrinkage (10), change (H type) of glycidylamine, Cai resin shrinkage Glyceramine and the like. These % may be used singly or in combination of two or more. As an epoxy resin, from the viewpoint of preventing electromigration or preventing the body, it is preferable to use a metal slant which is an impurity ion, a soil metal sample, a smear, and especially a liquefied gas. The CMA yimimide resin below 300 ppm can be listed as 槪 槪 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 UI) The secret varnish type horse [Chemical 18]

Ο) 包含芳香族環及/或直鏈、分支或 機基。]Ο) Contains aromatic rings and/or linear, branched or organic groups. ]

[式（II)中，n表示〇〜2〇之整數。] [式（I)中，R5表示 環狀脂肪族烴之2價之有 [化 19] 其中’於可賦予點著薄膜之硬化後之耐熱性以及高溫 黏著力之方面而言’可較佳地使用下述結構式（m)所表 示之雙馬來醯亞麟脂及/或上述通式⑻所表示之祕 清漆型馬來醯亞胺樹脂。 36 201130942 [化 20][In the formula (II), n represents an integer of 〇~2〇. [In the formula (I), R5 represents a divalent valence of a cyclic aliphatic hydrocarbon. [In the case of imparting heat resistance after hardening of the film and high-temperature adhesion, it is preferable. The sclerotherapy-type maleic imine resin represented by the following formula (m) and/or the varnish-type maleic imine resin represented by the above formula (8) are used. 36 201130942 [Chem. 20]

為了使上述馬來醯亞胺樹脂硬化，亦可併用婦丙基化 又盼A、亂酸g旨化合物專’或者添加過氧化物等觸媒。關 於上述化合物及觸媒之添加量、以及添加之有無，於可確 保目標特性之範圍内適宜調整。 烯丙基耐地醯亞胺樹脂可使用於分子内包含2個以上 烯丙基耐地酿亞胺基之化合物’例如可列舉下述通式（IV) 所表示之雙烯丙基耐地醯亞胺樹脂。 [化 21]In order to cure the above-mentioned maleimide resin, it is also possible to use a combination of a pro-propylation and a compound of a compound or a peroxide. The amount of the above-mentioned compound and the catalyst to be added, and the presence or absence of the addition are appropriately adjusted within the range in which the target characteristics can be ensured. The allyl quinone imine resin can be used for a compound containing two or more allyl-resistant imino groups in the molecule, and examples thereof include a bisallyl-resistant guanidine represented by the following formula (IV). Imine resin. [Chem. 21]

、[式（Iv)中，Ri表示包含芳香族環及/或直鏈、分支 或環狀脂肪族烴之2價之有機基。] ^其中，下述結構式（V)所表示之液狀之伸己基型雙 ，丙基耐地醯亞胺、以及、下述結構式（VI)所表示之低 熔點（熔點：4(TC )固體狀之苯二甲基型雙烯丙基耐地醯 37 201130942 良好之熱時流動性之方面而言較佳。而且， 良好之熱日^mflene)型雙稀丙基耐賴亞胺除了 上升，且於可㈣㈣段化狀黏著性之 割後之切斷面再融;:::==易剝離性、切 [化 22]In the formula (Iv), Ri represents a divalent organic group containing an aromatic ring and/or a linear, branched or cyclic aliphatic hydrocarbon. ] Among them, the liquid-like hexyl type bis represented by the following structural formula (V), propyl dysinimide, and the low melting point represented by the following structural formula (VI) (melting point: 4 (TC) Solid benzene-dimethyl bisallyl-resistant lanthanum 37 201130942 Good in terms of fluidity in terms of good heat. Moreover, good hot day ^mflene) type bis propyl lysine Rising, and re-melting at the cut surface after the cutting of the (4) (4) segmental adhesiveness;:::==easy peeling, cutting [22]

上述雙烯丙基耐地醯亞胺可單獨使用或者將二種以上 組合使用。 另外’上述烯丙基耐地醯亞胺樹脂於無觸媒下單獨硬 化時，必須25(TC以上之硬化溫度，且於實用化時成為較 大之問題；而且，即使於使用觸媒之系中，亦只能使用強 酉义或麵I鹽專於電子材料中成為重大缺點之金屬腐儀性觸 媒，且最終硬化必須250°C前後之溫度，但藉由將上述烯 丙基耐地酿亞胺樹脂與2官能以上之丙烯酸酯化合物、或 曱基丙烯酸酯化合物、或馬來酿亞胺樹脂之任意種併用， 38 201130942 可於200°C以下之低溫下硬化（文獻： A.Renner,A.Kramer,ctAUylnadic-Imides · A New Class ofThe above bisallyl lysine may be used singly or in combination of two or more. Further, when the above-mentioned allyl quinone imine resin is cured alone without a catalyst, it is necessary to have a curing temperature of 25 or more, and it becomes a problem in practical use; moreover, even in the case of using a catalyst. In the middle, only the strong sputum or surface I salt is used in the metal material to become a major defect in the electronic material, and the final hardening must be before and after the temperature of 250 ° C, but by the above allyl resistance The imide resin can be used in combination with any of a bifunctional or higher acrylate compound, or a mercapto acrylate compound, or a maleic imide resin. 38 201130942 can be hardened at a low temperature of 200 ° C or lower (literature: A. Renner) , A.Kramer, ctAUylnadic-Imides · A New Class of

Heat-Resistant Thermosets”， J.Polym.Sci.,Part AHeat-Resistant Thermosets”, J.Polym.Sci., Part A

Polym.Chem.，27，1301 (1989))。 (C)熱硬化性樹脂可於室溫下無論液狀、固形地使 用。於液狀熱硬化性樹脂之情形時，可進一步低黏度化； 於固形熱硬化性樹脂之情形時，可進一步減低光照射後之 黏性。而且’亦可將液狀熱硬化性樹脂與固形熱硬化性樹 脂併用。 於使用液狀熱硬化性樹脂之情形時，其黏度較佳的是 10000 mPa’s以下’更佳的是5000 mPa.s以下，進一步更 佳的是3000mPa.s以下’最佳的是2000mPa.s以下。若黏 度超過10000 mPa’s，則存在黏著劑組成物之黏度上升，薄 膜化變困難之傾向。此種液狀熱硬化性樹脂並無特別之限 定，自黏著性、耐熱性之觀點而言較佳的是環氧樹 別是可較佳地㈣3官能型（或4官能型）3^油= 或雙酚A型（或AD型、S型、F型）之縮水甘油醚。 於使用固形熱硬化性樹脂之情形時，例如可使其溶解 於（A)成分中而使用。固形熱硬化性樹脂並無特別之阳 定，自熱壓接性與黏度之觀點考慮，分子量較佳'的是如⑻ 以下，更佳的是1000以下，而且軟化點較佳的是以 下’更佳的是80W。而且，自黏著性、耐熱性 考慮’較佳的是3官能以上之環氧樹脂。此種環氡例 如可較佳地使用下述結構之環氧樹脂。 曰1 39 201130942 [化 23] ch3 τ ch2 [化 24]Polym. Chem., 27, 1301 (1989)). (C) The thermosetting resin can be used in a liquid or solid form at room temperature. In the case of a liquid thermosetting resin, the viscosity can be further lowered; in the case of a solid thermosetting resin, the viscosity after light irradiation can be further reduced. Further, a liquid thermosetting resin may be used in combination with a solid thermosetting resin. In the case of using a liquid thermosetting resin, the viscosity is preferably 10,000 mPa's or less, more preferably 5,000 mPa.s or less, still more preferably 3,000 mPa.s or less, and most preferably 2000 mPa.s or less. . When the viscosity exceeds 10,000 mPa's, the viscosity of the adhesive composition increases, and the film formation tends to be difficult. The liquid thermosetting resin is not particularly limited, and from the viewpoints of adhesion and heat resistance, it is preferred that the epoxy tree is preferably (tetra) trifunctional (or tetrafunctional) 3 oil = Or a glycidyl ether of bisphenol A type (or AD type, S type, F type). When a solid thermosetting resin is used, it can be used, for example, by dissolving it in the component (A). The solid thermosetting resin is not particularly positive, and the molecular weight is preferably from (8) or less, more preferably 1,000 or less, and the softening point is preferably the following from the viewpoint of thermocompression bonding property and viscosity. The best is 80W. Further, from the viewpoint of self-adhesiveness and heat resistance, a trifunctional or higher epoxy resin is preferred. As such a ring, for example, an epoxy resin having the following structure can be preferably used.曰1 39 201130942 [Chem. 23] ch3 τ ch2 [Chem. 24]

而且’（C)熱硬化性樹脂較佳的是5%重量損失溫度 為150 C以上，更佳的是18〇°c以上，進一步更佳的是2〇〇°c 以上。此處所謂熱硬化性樹脂之5%重量損失溫度，是使 用熱重/熱示差同步分析儀（SII Nan〇Techn〇1〇gy Inc製造； TG/DTA6300) ’於升溫速度為1〇〇c/min、氮氣流（4〇〇 ml/min)下對熱硬化性樹脂進行測定時之5%重量損失溫 201130942 度 制孰;5/°重$知失溫度高之熱硬化性樹脂，可抑 ;硬彳_’發。科此種耐熱性之紐化性樹 月曰可列舉於分㈣具有料縣之縣氣，自黏著性、 二熱考慮，特別是可較佳地使用3官能型(或4 =:=油胺，A型(…、S型- μ 化性樹脂之含量相對於⑷成分質量 t'1/量份〜刚質量份，更佳的是2質量 二地μ ·Γ刀° t其含量超過1〇0質量份，則存在曝光後 ”上升之傾向。另一方面’若上述含量不足巧量份， 則存在無法獲得充分之高溫黏著性之傾向。 於本發月之半導體用黏著劑組成物中，較佳的是進一 步含有硬化促_。硬化促進劑若為可藉由加熱而促進環 氧樹脂之硬化/聚合之化合物則並無特別之限制，例如可列 舉紛系化合物、脂肪族胺、脂環族胺、芳香族多胺、聚醯 ，、脂肪族酸酐、脂環族酸酐、芳香族酸Sf、二氰基二醯 胺、有機酸二⑽、三氟化侧胺錯合物、味嗤類、二氰基 二酸胺衍生物、二紐二醯肼、三苯基膦、四笨基鱗^ 基删酸鹽、2-乙基-4-曱基咪唾-四苯基石朋酸鹽、^8-二氮雜 雙環[5.4_0]十-烯_7_四苯基鑛鹽、三級胺等。於該些化 合物中，自不含溶劑時之溶解性、分散性之觀點考慮了可 較佳地使用咪唑類。硬化促進劑之含量相對於環g樹脂 100質罝份而言較佳的是0 01質量份〜50質量份。而且， 自黏著性、耐熱性、保存穩定性之觀點考慮，特佳的是咪 41 201130942 唑類 咪销較佳的是反蘭始溫度為5(rc以上 8〇°C以上。若反應開始溫度為5〇〇c以下則保 二：此樹脂組成物之黏度上升而造成膜厚之控制變 而欠隹。 ' 作為味偏，較佳的是使用溶解於環氧樹 ;ΐΐί=用此種•坐可獲得凹凸少之塗佈膜。此種，嗤 類並無特別之限定，可列舉2_十一院基味嗤、 喃嗤、1，2-二曱基咪嗤' 2_乙基冰甲基味唾、【·节基 乙1美Ί苯基咪唾、1_氰乙基-2'曱基味：、氰 乙基-2-乙基-4-甲基咪唑、i_氰？其9纪 .. ^ 亂乙基-2-本基咪唑等。自保存 基觀點考慮，特別是可較佳地使 以下而更且佳可使用粉碎為平均粒捏較佳的是1〇阿 夢由使用此錄7 以下最佳的是5 μηι以下之化合物。 猎由使用此種粒徑之咪嗤類 變化，且可抑制侧上 減低表面之凹凸，且可由其:得膜時，了 化合物作為 少2個以上雜經基之2=更佳的是於分子令具有至 舉紛系祕清漆、甲齡清漆、^物^種化合物例如可列 環戊二烯㈣清漆、二環祕清漆、二 戍一烯酚糸酚醛清漆、苯二甲基 42 201130942 改性盼系祕清漆、萘盼系化合物、三紛系化合物、四紛 系盼路清漆、伽a祕清漆、聚對乙絲雜、苯酿芳 烧基樹脂等。該些化合物巾較佳的是數量平均分子量為 4〇〇 4咖之範圍内者。藉此可抑制於半導體裝置組裝加 ，時成為半導體元件或裝置等之污染原因的加熱時之逸 ^上述1%化合物較麵是液狀，烯丙基改㈣系祕 清漆為液狀且高耐熱，因此可較佳地使用。 二酚系化合物之含量相對於熱硬化性樹脂1〇〇質量份而 吕較佳的是5〇質量份〜刚f量份，更佳的是6q質量份 〜95質量份。 本务明之半導體用黏著劑組成物可進一步含有（D) …自由基產生劑。熱自由基產生劑較佳的是有機過氧化 物。有機過氧㈣較佳的是丨分鐘半衰期溫度為 80°C 以 上’更佳的是loom，最佳的是12(rc以上。有機過氧 化物可考慮黏著触成物之雛條件、細溫度、壓接、 硬化條件、其他製程條件、儲存穩定轉而選擇。可使用 之過氧化物並無制之限定，例如可列舉25_二曱其_25_ 二(第三丁基過氧基己烧）、過氧化二異丙苯、己酸ί三丁 基過氧基-2-乙醋、己酸第三己基過氧基_2_乙醋、^韻第 =基過氧基似^曱基環己烧吖崎第王己基過氧 巧私三Τ基環已烧、雙㈣三丁基環 酸=等，可單獨使_些化合物中之丨種或者將2種以上 混:使用。藉由含有上述有機過氧化物，可使曝光後殘存 之未反應之放射線聚合性化合物反應，且可實現低逸氣 43 201130942 化、高黏著化。 鐘半絲溫度為阶以上讀自由基產生劑例如 :=MeXa 25Β(曰油公司製造)、2,5二甲基_2,5二(第 土過氧基己烧)〇分鐘半衰期溫度：⑽。㈡、p猶㈣ 17二由A司製造）、過氧化二異丙苯（1分鐘半衰期溫度： 175 C )等。 (D)熱自由基產生劑之含量相對於（A)放射線聚合 化5物總i而s較佳的是〇 〇1質量〇/。〜2〇質量，更佳 。的是W質量％〜1〇質量％ ’最佳的是〇 5 f量％〜5質量 /〇。右熱自由基產生劑之含量不足〇 01質量％，則硬化性 降低、添加效果變小；若超過5質量％，則逸氣量增加、 保存穩定性降低。 自使塗佈後之膜厚均勻性、B—階段化後之熱壓接性、 熱硬化後之低應力性、與被黏著體之密接性提高之方面考 慮，本發明之半導體用黏著劑組成物亦可進一步含有（E 熱塑性樹脂。 (E)成分之Tg較佳的是i5〇°c以下，更佳的是ι2(Γ(： 以下，進一步更佳的是100ΐ以下，最佳的是8〇ΐ以下。 於其Tg超過150°C之情形時，存在黏著劑組成物之黏度上 升之傾向。而且’於熱壓接於被黏著體上時需要 上之尚溫’存在容易於半導體晶圓上產生輕曲之傾向。 此處，（E)成分之「Tg」表示於將（E)成分薄膜化 時之主分散峰值溫度。具體而言，對（E)成分之薄犋， 使用Rheometrics公司製造之黏彈性分析儀「RSA-2」（商 44 201130942 品名），於溥膜厚為100 μηι、升溫速度為5°C/min、頻率為 1 Hz、測定溫度為-150 C〜300°C之條件下進行測定，求出 Tg附近之tan5峰值溫度作為Tg。 (E)成分之重量平均分子量較佳的是控制於5〇〇〇〜 500000之範圍内。另外，於可高度地兼顧熱壓接性與高溫 黏著性之方面而言’（E)成分之重量平均分子量更佳的是 10000〜300000。此處所謂之「重量平均分子量」是表示使 用島津製作所公司製造之高效液相層析儀「C_R4A」（商品 名），以聚苯乙婦換算進行測定時之重量平均分子量。 (E)成分例如除聚酯樹脂、聚醚樹脂、聚酿亞胺樹 脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、 聚胺基曱酸酯樹脂、聚胺基曱酸酯醢亞胺樹脂、聚胺基曱 I酯醯胺醯亞胺樹脂、矽氧烷聚醯亞胺樹脂、聚 樹脂、該㈣狀共㈣、齡概之前驅物（聚醯胺酸 =)之外，可列舉聚苯幷噁唑樹脂、苯氡樹脂、聚砜樹脂、 聚㈣樹脂、聚笨硫醚樹脂、聚輯脂、聚嘯脂、聚礙 酸_脂、聚醚酮樹脂、重量平均分子量為i萬〜應萬 之（曱基)丙烯酸系共聚物、祕清漆樹脂、盼樹脂等。該 些細脂可單獨使用丨種或者將2種以上組合使用。而且， =可為於該些樹脂之主鏈及/或側鍵賦予有乙二醇、丙二醇 寻一醇基、羧基及/或羥基者。 ，些樹財’自高溫黏著性、咖性之韻考慮，較 ⑻成分為具㈣亞胺基之樹脂。具㈣亞胺基 之祕月曰例如可列舉聚齡贿脂、㈣舰亞胺樹脂、聚 45 201130942 醚醯亞胺樹脂、聚胺基曱酸酯醯亞胺樹脂、聚胺基甲酸酉旨 醯胺醯亞胺樹脂、矽氧烷聚醯亞胺樹脂、聚酯醯亞胺樹脂、 該些樹脂之共聚物、具有醯亞胺基之單體的聚合物。 聚醯亞胺樹脂及/或聚醯胺醯亞胺樹脂例如可藉由公 知之方法使四羧酸二酐與二胺進行縮合反應而獲得。即， 於有機溶劑使四羧酸二酐與二胺等莫耳或者視需要在 相對於四幾酸二針之合計1.0 mol而言二胺之合計較佳的 是0.5 mol〜2.0 mo卜更佳的是〇.8 mol〜1.0 m〇l之範圍内 調整組成比（各成分之添加順序任意），於反應溫度為8(rc 以下、較佳的是0°C〜60°C進行加成反應。隨著反應之進 行，反應液之黏度緩緩上升，生成聚醯亞胺樹脂之前驅物 即聚酸胺酸。另外，為了抑制樹脂組成物之諸特性之降低， 較佳的是上述四羧酸二酐為於乙酸酐中進行了再結晶純化 處理者。 關於上述縮合反應中之四羧酸二酐與二胺之組成比， 若相對於四羧酸二酐之合計丨.0 m〇1而言二胺之合計超過 ^0」η〇卜則存在於所得之聚醯亞胺樹脂中胺末端之聚醯亞 安泰聚物之1變多之傾向，且存在聚醯亞胺樹脂之重量平 句分子量變低、樹脂組成物之包括耐熱性之各種特性變得 不充分=傾向。m，若相對於喊酸二酐之合計ι〇 =而言二胺之合計不;^ G5福，則存在酸末端之聚酿亞 寡㈣之量歸之傾向，且存在㈣亞胺樹脂及/ 祕亞賴脂之重量平均分子量、樹脂組成物 包括耐熱性之各種特性變得不充分之傾向。 46 201130942t 聚醯亞胺樹脂及/或聚醯胺醯亞胺樹脂可藉由使上述 反應物（聚醯胺酸）進行脫水閉環而獲得。可藉由進行加 熱處理之熱閉環法、使用脫水劑之化學閉環法等而進行脫 水閉環。 作為聚醯亞胺樹脂之原料而使用之四羧酸二酐例如可 較佳地使用均苯四甲酸二酐，於可降低線膨脹係數之方面 而吕可較佳地使用3,3，4,4’-聯苯四曱酸二酐、2,2，，3,3'-聯苯 四曱酸二酐、2,3,3，4 -聯笨四曱酸二酐、3,4,3，，4L聯苯四曱 酸一酐等具有聯苯骨架之酸二酐，萘四曱酸二酐、 M，5,8-萘四曱酸二酐、2,3,6,7-萘四曱酸二酐、;ι,2,4,5-萘四 曱酸二料具有萘基骨架之酸二酐。而且，於可使匕階段 化之感光度提高之方面而言，可較佳地使用3,4,3，，4,二苯 曱_四曱酸二酐、2,3,2，，3，、二苯甲酮四曱酸二酐、3,3,3，，4，_ -笨曱酮四甲酸一酐等具有二苯曱酮骨架之酸二軒。而 且，自透明性之觀點考慮，可較佳地使用 1，2,3,4-丁烷四曱 -义一酐、十氫化奈_1，4,5,8_四曱酸二酐、二曱基 -1，2,3,5,6,7-六氫化蒽萘义2,5,6_四甲酸二針、環戊烧 _，2:3,4-四甲酸二酐、⑵木環丁烷四曱酸二酐、雙(外_ 雙％[2,2，1]庚烷-2,3-二甲酸二酐、雙環_[2,2,2]_辛_7_烯 =，3,5,6·四甲酸謂等具有月旨環式骨架之酸二㈣者❻ :(3二4-一幾，苯基)六氟丙燒二奸、2,2-雙[4_(3,4,二羧基苯 二苯基]六氟丙烧二酐、I，4、雙(2_經基六1異丙基)笨雙(偏 =甲酸酐）、以雙(2邊基六μ丙基)苯雙(偏笨三甲酸 酉千）等具有氤烧基之酸二軒。 47 201130942 而且，自對於365 nm之透明性之觀點考慮’守較佳 地使用下述通式（1)所表示之四羧酸二酐等。下述通式（1) 中，a表示2〜20之整數。 [化 25]Further, the (C) thermosetting resin preferably has a 5% weight loss temperature of 150 C or more, more preferably 18 〇 ° C or more, still more preferably 2 〇〇 ° C or more. Here, the 5% weight loss temperature of the thermosetting resin is a thermogravimetric/thermal differential synchronization analyzer (manufactured by SII Nan〇Techn〇1〇gy Inc; TG/DTA6300)' at a temperature rising rate of 1〇〇c/ Min, nitrogen flow (4〇〇ml/min), the 5% weight loss temperature when the thermosetting resin is measured, 201130942 degrees 孰; 5/° weight, the heat-hardening resin with high temperature, can be suppressed; Hard 彳 _ ' hair. This kind of heat-resistant neoformed tree can be listed in the sub-district (4) with the county gas of the county, self-adhesive, two heat considerations, especially the trifunctional type (or 4 =: = oleylamine) , the content of type A (..., S type - vibrating resin is relative to the mass of (4) component t'1/volume to just mass part, more preferably 2 mass two ground μ · sickle ° t content exceeds 1〇 When the amount is 0 parts by mass, there is a tendency to rise after exposure. On the other hand, if the above content is less than a sufficient amount, there is a tendency that sufficient high-temperature adhesion cannot be obtained. In the adhesive composition for semiconductors of this month, It is preferable to further contain a hardening accelerator. The hardening accelerator is not particularly limited as long as it can accelerate the hardening/polymerization of the epoxy resin by heating, and examples thereof include a compound, an aliphatic amine, and an alicyclic ring. Amine, aromatic polyamine, polyfluorene, aliphatic acid anhydride, alicyclic acid anhydride, aromatic acid Sf, dicyanodiamine, organic acid di(10), trifluorinated amine complex, miso , dicyandiamine derivative, dinonion, triphenylphosphine, tetraphenyl sulfonate a salt, 2-ethyl-4-mercapto-imidazo-tetraphenyl-tibate, a bis-diazabicyclo[5.4_0]de-ene-7-tetraphenyl ore salt, a tertiary amine, etc. Among these compounds, imidazoles can be preferably used from the viewpoint of solubility and dispersibility in the absence of a solvent. The content of the hardening accelerator is preferably 0 01 with respect to the mass of the ring g resin 100. In parts by mass, it is preferably 50 parts by weight. Above C. If the reaction starting temperature is 5 〇〇c or less, the second: the viscosity of the resin composition rises and the control of the film thickness becomes unsatisfactory. 'As a taste bias, it is preferred to use a solvent dissolved in an epoxy tree. ;ΐΐί=This type of coating can be used to obtain a coating film with less unevenness. This type of cockroach is not particularly limited, and examples include 2_11 yards of glutinous rice, simmering, 1,2-dioxime嗤' 2_Ethyl ice methyl scent, [··························· Imidazole, i_cyano? 9th.. ^ Ordinary ethyl-2-benzazole and the like. From the viewpoint of the preservation group, in particular, it is preferable to use the pulverization to the average granules, and it is preferable to use the granules. The best is a compound of 5 μηι or less. Hunting is changed by using a quinone of such a particle size, and it is possible to suppress the unevenness of the surface on the side, and it is possible to: when the film is obtained, the compound is less than two or more kinds of impurities. Base 2 = more preferable in the molecular order to have a variety of secret varnish, age-old varnish, compound compounds such as cyclacyclopentadiene (four) varnish, two ring secret varnish, diterpene phenol phenolic phenolic Varnish, Benzyl dimethyl 42 201130942 Modified anti-clear varnish, naphthene compound, three compounds, four confession varnish, gamma secret varnish, poly-p-Si, benzene-based aryl resin . Preferably, the compound towels are those having a number average molecular weight of 4 to 4 coffees. Therefore, it is possible to suppress the semiconductor device from being assembled and added, and the above-mentioned 1% compound is liquid when the semiconductor element or the device is contaminated, and the allyl compound is liquid and highly heat-resistant. Therefore, it can be preferably used. The content of the diphenol-based compound is preferably 5 parts by mass to just f parts by weight, more preferably 6 parts by mass to 95 parts by mass, per part by mass of the thermosetting resin. The semiconductor adhesive composition of the present invention may further contain (D) a radical generating agent. The thermal radical generating agent is preferably an organic peroxide. The organic peroxygen (IV) preferably has a half-life temperature of 80 ° C or more. More preferably, it is a loom, and most preferably 12 (rc or more. The organic peroxide can be considered as a condition of the adhesive, a fine temperature, Crimp, hardening conditions, other process conditions, storage stability and selection. The peroxides that can be used are not limited by the method, for example, 25_二曱_25_2 (t-butylperoxyhexanone) , dicumyl peroxide, butyl tributylperoxy-2-ethyl hexanoate, hexanohexylperoxy-2-ethyl hexanoate, hexanyl = hydroxy-like oxime ring己 吖 第 第 第 第 第 过 过 过 过 过 过 过 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第The organic peroxide can react with unreacted radiation-polymerizable compound remaining after exposure, and can realize low outgassing, high adhesion, and high-adhesion. The temperature of the clock half-length is more than the order reading radical generating agent, for example: MeXa 25 Β (manufactured by Oyster Sauce), 2,5 dimethyl 2,5 bis (terti-peroxy hexane) 〇 minute half-life temperature: (10). (b), p (46) 17 (manufactured by Division A), dicumyl peroxide (1 minute half-life temperature: 175 C) and so on. (D) The content of the thermal radical generating agent is preferably 〇 〇 1 mass 〇 / with respect to (A) the total mass i of the radiation polymerization product. ~ 2 〇 quality, better. The W mass % ~ 1 〇 mass % ' is the best 〇 5 f amount % ~ 5 mass / 〇. When the content of the right thermal radical generator is less than 质量01% by mass, the hardenability is lowered and the effect of addition is small. When the content is more than 5% by mass, the amount of outgas is increased and the storage stability is lowered. The semiconductor adhesive composition of the present invention is considered in view of uniformity of film thickness after coating, thermocompression bonding after B-stage, low stress property after heat curing, and adhesion to an adherend. The material may further contain (E thermoplastic resin. The Tg of the component (E) is preferably i5 〇 °c or less, more preferably ι 2 (Γ (hereinafter, more preferably 100 ΐ or less, and most preferably 8) 〇ΐThe following. When the Tg exceeds 150 ° C, there is a tendency for the viscosity of the adhesive composition to rise, and 'the temperature required for thermocompression bonding to the adherend' is easy to exist in the semiconductor wafer. Here, the "Tg" of the component (E) is expressed as the main dispersion peak temperature when the component (E) is thinned. Specifically, for the thinness of the component (E), Rheometrics Co., Ltd. is used. The viscoelastic analyzer "RSA-2" (trade name 44 201130942) has a thickness of 100 μηι, a heating rate of 5 °C/min, a frequency of 1 Hz, and a measurement temperature of -150 C to 300 °C. The measurement was carried out under the conditions, and the peak temperature of tan5 in the vicinity of Tg was determined as Tg. The weight average molecular weight is preferably controlled within a range of from 5 Å to 500,000. Further, the weight average molecular weight of the (E) component is more excellent in terms of both thermocompression bonding and high-temperature adhesion. It is 10,000 to 300,000. The "weight average molecular weight" is a weight average molecular weight measured by a polystyrene conversion using a high performance liquid chromatography "C_R4A" (trade name) manufactured by Shimadzu Corporation. The component (E) is, for example, a polyester resin, a polyether resin, a polyanilin resin, a polyamide resin, a polyamidimide resin, a polyether oxime resin, a polyamino phthalate resin, a polyamine曱 曱 醢 imine resin, polyamine 曱 I ester amide amine imide resin, decyl oxy phthalimide resin, poly resin, the (four) shape (four), age precursor (poly phthalic acid) In addition to polystyrene oxazole resin, benzoquinone resin, polysulfone resin, poly(tetra) resin, polystyrene sulfide resin, polymer grease, polyglycol, poly(acid) fat, polyether ketone resin , the weight average molecular weight is i million ~ 10,000 (mercapto) acrylic a polymer, a varnish resin, a resin, etc. These fine fats may be used singly or in combination of two or more. Further, = may be imparted with ethylene glycol to the main chain and/or side bonds of the resins. Propylene glycol is an alcoholic group, a carboxyl group and/or a hydroxyl group. Some of the trees are considered to have a (4) imine-based resin compared with the high-temperature adhesiveness and the rhyme of the coffee. (4) The imide of the imine group For example, it can be exemplified by poly-age brittle fat, (4) imine resin, poly 45 201130942 ether quinone imine resin, polyamino phthalate quinone imine resin, polyamino phthalic acid hydrazine imine resin, decane A polymer of a polyimide, a polyesterimide resin, a copolymer of the resins, and a monomer having a quinone imine group. The polyimine resin and/or the polyamidimide resin can be obtained, for example, by a condensation reaction of a tetracarboxylic dianhydride with a diamine by a known method. That is, in the organic solvent, the total amount of the diamine such as the tetracarboxylic dianhydride and the diamine or the 1.0 mol of the total of the two needles is preferably 0.5 mol to 2.0 mo. The composition ratio is adjusted within the range of 8.8 mol to 1.0 m〇l (the order of addition of each component is arbitrary), and the addition reaction is carried out at a reaction temperature of 8 (rc or less, preferably 0 ° C to 60 ° C). As the reaction progresses, the viscosity of the reaction liquid gradually rises to form a polyamic acid prior to the production of the polyimine resin. Further, in order to suppress the decrease in the properties of the resin composition, the above tetracarboxylic acid is preferred. The acid dianhydride is subjected to recrystallization purification treatment in acetic anhydride. The composition ratio of the tetracarboxylic dianhydride to the diamine in the above condensation reaction is 丨.0 m〇1 with respect to the total of the tetracarboxylic dianhydride. In the case where the total amount of the diamine exceeds 0 〇 〇 则 则 则 则 则 则 则 则 则 则 则 所得 倾向 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得 所得The molecular weight of the sentence becomes low, and various properties including heat resistance of the resin composition become insufficient. m, if the total of diamines is not relative to the total of yttrium dianhydrides; ^ G5 Fu, there is a tendency for the amount of the acid-terminated oligomers (4) to be present, and (iv) imine resin and / The weight average molecular weight of the lysine and the resin composition include various properties of heat resistance which are insufficient. 46 201130942t Polyimine resin and/or polyamidoximine resin can be obtained by reacting the above reactants ( Polylysine is obtained by dehydration ring closure. The dehydration ring closure can be carried out by a thermal ring closure method using heat treatment or a chemical ring closure method using a dehydrating agent. The tetracarboxylic acid used as a raw material of the polyimine resin As the anhydride, for example, pyromellitic dianhydride can be preferably used, and 3,3,4,4'-biphenyltetracarboxylic dianhydride, 2, 2 can be preferably used in terms of lowering the coefficient of linear expansion. , 3,3'-biphenyltetraphthalic acid dianhydride, 2,3,3,4-diphenyl phthalic anhydride, 3,4,3,,4L biphenyl tetradecanoic acid anhydride, etc. Acid dianhydride, naphthalene tetraphthalic acid dianhydride, M, 5,8-naphthalene tetraphthalic acid dianhydride, 2,3,6,7-naphthalene tetraphthalic acid dianhydride, i,2,4,5-naphthalene Tetraphthalic acid dichloride has naphthyl The acid dianhydride of the skeleton. Moreover, 3,4,3,4,diphenylfluorene-tetradecanoic acid dianhydride, 2,3 can be preferably used in terms of improving the sensitivity of the hydrazine stage. , 2,, 3, benzophenone tetradecanoic acid dianhydride, 3,3,3,,4, _ - alkanoic acid tetracarboxylic acid monoanhydride and the like having a diphenyl fluorenone skeleton. From the viewpoint of transparency, 1,2,3,4-butane tetraindole-yiic anhydride, decahydronaphthalene, 4,5,8-tetradecanoic acid dianhydride, dimercapto- can be preferably used. 1,2,3,5,6,7-hexahydroquinone naphthalene 2,5,6-tetracarboxylic acid two-needle, cyclopentane _, 2:3,4-tetracarboxylic dianhydride, (2) wood cyclobutane IV Decanoic acid dianhydride, double (external_double%[2,2,1]heptane-2,3-dicarboxylic acid dianhydride, bicyclo-[2,2,2]-octyl-7-ene =, 3,5 ,6. Tetraformic acid, etc., which has the acidity of the ring-shaped skeleton of the moon (4): (3 2 - 4, phenyl) hexafluoropropanil, 2,2-bis [4_(3,4, Dicarboxy phenyl diphenyl] hexafluoropropane dianhydride, I, 4, bis (2 _ yl hexa 1 isopropyl) bis ( partial = formic anhydride), bis (2 aryl hexyl propyl) An acid bismuth having a fluorinated group such as benzoic acid (partially ternary trimethyl hydrazide). 47 201130942 Further, from the viewpoint of the transparency of 365 nm, the tetracarboxylic dianhydride represented by the following general formula (1) or the like is preferably used. In the following general formula (1), a represents an integer of 2 to 20. [Chem. 25]

上述通式（1)所表示之四叛酸二酐例如<由偏本一甲 酸酐單醯氯以及對應之二醇而合成，具體可列奉ι，2 (伸 基)雙(偏苯三甲酸酐）、1，3-(伸丙基)雙(偏苯三甲酸80、 1，4-(伸丁基)雙(偏苯三甲酸酐）、1，5-(伸戊基)雙(偏苯二甲 酸酐）、1，6-(伸己基)雙(偏苯三甲酸酐）、1，7-(伸庚基)雙(偏 苯三曱酸酐）、1，8-(伸辛基)雙(偏苯三甲酸酐）、1，9-(伸壬基) 雙（偏苯三曱酸酐）、1，1〇_(伸癸基）雙（偏苯三甲酸酐）、 1，12-(伸十二烷基)雙(偏苯三甲酸酐）、1，16-(伸十六烷基) 雙(偏苯三曱酸酐）、1，18-(伸十八烷基)雙(偏苯三曱酸酐) 等。該些化合物可不損及耐熱性地使Tg降低。 而且，自賦予於（A)成分中之良好之溶解性、對於 365 nm光之透明性、熱壓接性之觀點考慮，四叛酸二酐較 佳的是下述通式（2)或通式（3)所表示之四羧酸二酐。 [化 26] 48 201130942The tetrahydro acid dianhydride represented by the above formula (1), for example, is synthesized from a mono-n-carboxylic acid monothiocyanate and a corresponding diol, and specifically may be listed as ι, 2 (extension) bis (p-benzoic acid) Anhydride), 1,3-(propyl)bis (trimellitic acid 80, 1,4-(butylene) bis(trimellitic anhydride), 1,5-(amyl) bis(phenylene) Dicarboxylic anhydride), 1,6-(extended hexyl)bis(trimellitic anhydride), 1,7-(heptyl)bis(trimellitic anhydride), 1,8-(exetylene) bis ( Trimellitic anhydride), 1,9-(extended fluorenyl) bis(trimellitic anhydride), 1,1 〇 _ (extended fluorenyl) bis(trimellitic anhydride), 1,12-(extension twelve Alkyl) bis(trimellitic anhydride), 1,16-(hexadecyl)bis(trimellitic anhydride), 1,18-(exetyl octadecyl)bis(trimellitic anhydride) In addition, these compounds can lower the Tg without impairing the heat resistance. Further, from the viewpoint of imparting good solubility in the component (A), transparency to 365 nm light, and thermocompression bonding, tetrazoic acid The dianhydride is preferably a tetracarboxylic dianhydride represented by the following formula (2) or formula (3). [Chem. 26] 48 201130942

如上所述之四羧酸二酐可單獨使用1種或者將2種以 上組合使用。 於使黏著強度上升之方面而言，（E)成分可進一步使 用含有羧基及/或酚性羥基之聚醯亞胺樹脂。可作為上述含 有羧基及/或羥基之聚醯亞胺樹脂之原料而使用的二胺較 佳的是包含下述通式（4)、通式（5)、通式（6)或通式（7) 所表示之芳香族二胺。 [化 27] 49 201130942The tetracarboxylic dianhydride as described above may be used singly or in combination of two or more. In order to increase the adhesion strength, the (E) component may further use a polyimine resin containing a carboxyl group and/or a phenolic hydroxyl group. The diamine which can be used as a raw material of the above polyvalent imide resin containing a carboxyl group and/or a hydroxyl group preferably contains the following general formula (4), formula (5), formula (6) or formula ( 7) The aromatic diamine represented. [Chem. 27] 49 201130942

作為上述聚醯亞胺樹脂之原料而使用之其他二胺並無 特別之限定，為了調整聚合物之Tg以及溶解性，可使用 以下之二胺。例如，於可提高耐熱性以及黏著性之方面而 言，可較佳地使用鄰苯二胺、間苯二胺、對苯二胺、雙(4_ 胺基-3,5_二甲基苯基）曱烷、雙(4_胺基_3,5_二異丙基苯基) 曱烷、2,2_雙〇胺基苯基）丙烷、2,2，_(3,4，_二胺基二苯基) 丙烷、2,2-雙(4-胺基苯基)丙烷、1，3_雙(3_胺基苯氧基)苯、 1，4-雙(3-胺基苯氧基）苯、1，4_雙(4-胺基苯氧基）苯、 3,3’-(1，4-伸笨基雙(1-甲基亞乙基))雙苯胺、3，-(1，4-伸苯基 雙(1-曱基亞乙基))雙苯胺、4,4’-(1，4-伸苯基雙(1-曱基亞乙 基))雙苯胺、2,2-雙(4-(3-胺基苯氧基)苯基)丙烷、2,2-雙(4-胺基苯氧基苯基)丙烧。於可降低線膨服係數之方面而言， 可較佳地使用3,3^二胺基二苯基醚、3,4’-二胺基二苯基 50 201130942 趟、4,4'-二胺基二苯基醚、3,3，-二胺基二苯基甲烷、3,4，-一胺基一笨基曱梡、4,4'-二胺基二苯基醚曱烧、3,3'-二胺 基二苯基砜、3,4，-二胺基二苯基颯、4,4，-二胺基二苯基颯、 雙(4-(3-胺基烯氧基)苯基)砜、雙(4-(4-胺基烯氧基)苯基) =風、3,3’-二羥基_4,4，_二胺基聯苯。於可提高與金屬等被黏 著體之密接性之方面而言，可較佳地使用3,3,_二胺基二苯 巧醚、3,4’_二胺基二苯硫醚、4,4，_二胺基二苯硫醚、雙 私·基婦氧基)苯旬賴、雙(4_(4_縣騎基)苯基)硫謎。 =且’可使Tg降低之二胺可列舉M省胺基甲基)環己 、元了述通式（8)所表示之脂肪族醚二胺、下述通式 所表示之矽氧烷二胺等。 [化 28]The other diamine used as a raw material of the above polyimine resin is not particularly limited, and in order to adjust the Tg and solubility of the polymer, the following diamine can be used. For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, bis(4-amino-3,5-dimethylphenyl) can be preferably used in terms of heat resistance and adhesion. ) decane, bis(4-amino-3,5-diisopropylphenyl)decane, 2,2-bis-guanidinophenyl)propane, 2,2,_(3,4,_2 Aminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminobenzene) Oxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-(1,4-extended bis(1-methylethylidene))diphenylamine, 3, -(1,4-phenylphenylbis(1-mercaptoethylidene))diphenylamine, 4,4'-(1,4-phenylphenylbis(1-indenylethylene))diphenylamine, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-aminophenoxyphenyl)propane. In terms of lowering the coefficient of linear expansion, 3,3 diaminodiphenyl ether, 3,4'-diaminodiphenyl 50 201130942 趟, 4, 4'-two can be preferably used. Aminodiphenyl ether, 3,3,-diaminodiphenylmethane, 3,4,-monoamino-phenylidene, 4,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl sulfone, 3,4,-diaminodiphenyl fluorene, 4,4,-diaminodiphenyl fluorene, bis(4-(3-amino)alkenyloxy Phenyl)sulfone, bis(4-(4-aminoalkenyloxy)phenyl) = wind, 3,3'-dihydroxy-4,4,-diaminobiphenyl. 3,3,-diaminobiphenyl ether, 3,4'-diaminodiphenyl sulfide, 4, can be preferably used in terms of improving the adhesion to an adherend such as a metal. 4, _ diaminodiphenyl sulfide, bis, thiophene oxy) benzoate, bis (4 _ (4_ county riding base) phenyl) sulfur puzzle. And the 'diamine which can lower the Tg can be exemplified by M-aminomethyl) cyclohexyl, the aliphatic ether diamine represented by the formula (8), and the oxane 2 represented by the following formula Amines, etc. [化 28]

H2N—Ri~^〇~_R2 —R3-nh2 ) ⑴中別獨立地表示碳數為 1〇之伸烧基’ b表示2〜80之整數。 [化 29]H2N-Ri~^〇~_R2 - R3-nh2) (1) independently represents a stretching group having a carbon number of 1 Å, and b represents an integer of 2 to 80. [化29]

於通式（9)中，R4及R9分 別獨立地表示碳數為1 51 201130942 之伸烧基或亦可具有取代基之伸苯基，R5、R6、R7及；R8 分別獨立地表示碳數為1〜5之烷基、苯基或苯氧基，d表 示1〜5之整數。 上述二胺中，於賦予與其他成分之相溶性之方面而 言’較佳的是通式（8)所表示之脂肪族醚二胺，更佳的是 乙二醇及/或丙二醇系二胺。In the formula (9), R4 and R9 each independently represent a stretching group having a carbon number of 1 51 201130942 or a stretching phenyl group which may have a substituent, and R5, R6, R7 and R8 each independently represent a carbon number. It is an alkyl group of 1 to 5, a phenyl group or a phenoxy group, and d represents an integer of 1 to 5. Among the above diamines, preferred is an aliphatic ether diamine represented by the formula (8), more preferably an ethylene glycol and/or a propylene glycol-based diamine, in terms of compatibility with other components. .

此種脂肪族醚二胺具體可列舉SUN TECHNO CHEMICAL Co·，LTD.製造之 JEFFAMINE D-230、D-400、 D-2000、D-4000、ED-600、ED-900、ED-2000、EDR-148、 BASF (製）聚醚胺D-230、D-400、D-2000等聚氧伸烧基 二胺等脂肪族一胺。该些二胺較佳的是所有二胺之2〇 mol%以上，於與（A)放射線聚合性化合物或熱硬 化性樹脂等其他調配成分之相溶性、且可高度地兼顧熱壓 接性與高溫黏著性之方面而言’更佳的是5〇m〇l%以上。 而且，於可賦予於室溫下之密接性、黏著性之方面而 言，上述二胺較佳的是上述通式（9)所表示之矽氧烷二胺。 〇亥些·一胺較佳的疋所有一胺之0.5 mol%〜80 mol%， 於可高度地兼顧熱壓接性與高溫黏著性之方面而言更佳的 是1 mol%〜50 mol%。若低於〇.5 m〇1%，則添加矽氧烷二 胺之效果變小；若超過80 m〇l%，則存在與其他成分之相 漆性、局溫黏著性降低之傾向。 上述二胺可單獨使用1種或者將2種以上組合使用。 而且，上述聚酿亞胺樹脂可單獨使用丨種或者視需要 將2種以上混合（biend)使用。 52 201130942, 而且’如上所述，於決定聚酿亞胺樹脂之組成時，較 佳的是設計為#Tg415G。⑶下，特佳的是使用上述通式 (8 )所表示之&肪族㈣二胺作為聚醯亞胺樹脂之原料二 胺。 於上述聚釀亞胺樹脂之合成時，藉由將下述通式 (10)、通式（11)或通式（12)所表示之化合物之類的單 官能酸酐及/或單官能胺投人至縮合反應液中 ，可於聚合物 „或二胺以外之官能基。而且，藉此可降低聚 合物U1:、使轉劑細旨組絲絲度降低、使熱壓 接性提南。 [化 30]Specific examples of such an aliphatic ether diamine include JEFFAMINE D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2000, EDR manufactured by SUN TECHNO CHEMICAL Co., Ltd. -148, BASF (made) polyetheramine D-230, D-400, D-2000 and other polyoxyalkylene diamines and other aliphatic monoamines. These diamines are preferably at least 2 mol% or more of all diamines, and are compatible with other compounding components such as (A) a radiation polymerizable compound or a thermosetting resin, and are highly compatible with thermocompression bonding. In terms of high temperature adhesion, 'better than 5〇m〇l%. Further, the diamine is preferably a nonoxyldiamine represented by the above formula (9) in terms of adhesion to the room temperature and adhesion. Preferably, the lanthanide-monoamine is preferably 0.5 mol% to 80 mol% of all the amines, and more preferably 1 mol% to 50 mol% in terms of high thermal compatibility and high temperature adhesion. . If it is less than 〇.5 m〇1%, the effect of adding a decane diamine becomes small; if it exceeds 80 m〇l%, the lacquer property and the local temperature adhesiveness with other components tend to decrease. These diamines may be used alone or in combination of two or more. Further, the above-mentioned polyienimine resin may be used singly or in combination of two or more kinds as needed. 52 201130942, and as described above, it is preferable to design #Tg415G when determining the composition of the polyimide resin. (3) It is particularly preferable to use the & aliphatic (tetra)diamine represented by the above formula (8) as a raw material diamine of the polyimine resin. In the synthesis of the above-mentioned polyamidiamine resin, a monofunctional acid anhydride and/or a monofunctional amine such as a compound represented by the following formula (10), formula (11) or formula (12) is used. In the human condensation reaction liquid, a functional group other than the polymer „ or diamine can be used. Further, the polymer U1 can be lowered, the filament fineness of the transfer agent can be lowered, and the thermocompression bonding property can be increased. [化30]

、（E)熱塑性樹脂亦可於其主鏈及/或側鏈含有具有促 進咪唾等之環氧樹驗化之功能的官祕。含有♦坐之聚 酿f胺例如可使用如下述結構式所示之含有料基之二胺 獲传其-部分而作為上述所示之二胺成分。此種於侧鍵具 53 201130942 有咪唾之聚合物可提高相溶性或保存穩定性而較佳。 [化 31]Further, the (E) thermoplastic resin may have an official function of promoting the function of the epoxy tree in the main chain and/or the side chain. For example, a diamine containing a base as shown in the following structural formula may be used as the diamine component. Such a polymer having a side-to-side fastener 53 201130942 is preferred to improve compatibility or storage stability. [化31]

ch3. 作，上述聚酿亞胺樹脂，自可均勻地B-階段化之方面 車父佳的是於成形為30叫時對於365 nm之透射率 f以上:於可藉由更低曝光量進行B-階段化之方面而 吕、，更佳的是20%以上。此種聚醯亞麟脂例何藉由使 上述通式（2)所表示之麟、與上述通式⑻所表示之 201130942 脂肪族醚二胺及/或上述通式（9)所表示之 應而合成。 /礼沉一胺反 一而且，作為（E)熱塑性樹脂，於抑制黏度上 一步減低黏著劑組成物中之溶解殘留之方面 是使用於常溫⑽)下為液狀之液狀熱塑性二較 ，贿不使用溶劑地進行加熱而反應，二： 並不適用溶劑之黏著劑組成物中，於削減溶劑除 驟、減低殘存溶劑、削減再沈殿步驟之方面而： 夕 2熱塑性樹脂亦容易自反應爐中取出。此種= 树月曰例如可列舉聚丁二烯、丙稀腈.丁二稀寡聚物、^ 二烯、聚丁烯等樹膠狀聚合物，聚酸聚合物戊 石夕氧聚合物、聚胺基曱酸自旨、祕亞胺、聚 其中可較佳地使用聚醯亞胺樹脂。 。 液狀之聚醯亞胺樹脂例如可藉由使上述酸酐、盥 族喊二胺切魏二胺反應轉得。合成方法可列^曰 添加溶劑而使酸酐分散於脂肪族醚二胺或矽氧烷二1中， 進行加熱之方法。 女 ⑻熱塑性樹脂之含量相對於⑷成分而言較 是〇.1質量％〜50質量％，自成膜性或膜厚均句性、抑制 黏度上升之觀點而言更佳的是〇5質量％〜2〇質量％。若 熱塑性樹脂之含量不^ (H質量％，則存在不能表現出添 加效果之傾向，若超過50質量％，則存在由於溶解殘留等 而使膜厚均勻性降低，黏度上升而變得難以薄膜化之傾向。 於本發明之半導體用黏著劑組成物中，為了賦予保存 55 201130942 性、製程適應性或抗氧化性 範圍内進—步添加_、多_、2於^及硬化性之 類等聚合抑制劑或抗氧化劑。、 科酸酯類、硫 宜之填料。半導體用黏著劑組成物中亦可含有適 金屬填科，氧^=舉··絲、金粉、銅粉、錄粉等 鎂、石夕酸約、石夕酸碧1匕鋁、氫氧化鎂、碳酸舞、碳酸 結晶性二氧化 破璃、氧化鐵、陶营i曰i；；氧夕、氮化娜、二氧化鈦、 填料等，無論種類、形t等^^碳、樹膠系填料等有機 了物==所導::之r分開使用。例如，為 屬填料，$ 了賦二導熱性、觸變性等而添加金 性等而添加非金屬盈& 1性、低熱膨脹性、低吸濕 添加有機填料。·，，、機填枓，為了賦予黏著劑層韌性等而 或者將2種機填料或有機填料可單獨使用1種 黏著材料所要求之&用。其中，於可賦予半導體裝置用 等之方面而言n f、導熱性、低吸濕特性、絕緣性 填料；於無機“或填料、無機填料、或絕緣性 之分散性良好且可触不也性填料中，於對於黏著劑組成物 佳的是二氧化砂^熱時較高之黏著力之方面而言，更 為30^1^較H是平均粒捏為10㈣以下且最大粒徑 佳的是平均粒徑為5 μιη以下且最大粒 56 201130942 =20 μιη叮超過i(^或者最大粒徑超 向。而則存在無法充分獲得提高破壞韋刃，欧之效果的傾 +均粒梭以及最大粒徑之下限並無特別之限制， 仁千均粒㈣及最錄徑均難的是議丨哗以上。 上述填料之含量可根據賦予之特性或功能而決定，相 f於包含填料之黏著劑组成物總量而言較佳的是50質量 2下’更佳的是1質量％〜4〇質量％，進一步更佳的是3 。貝罝％〜30質量％。藉由使填料增量，可實現低α化、低 吸濕化、高彈性模數化，且可有效地提高切割性（切刃之 切斷性）、打線接合性（超音波效率）、熱時之黏著強度。 若使填料增量至必要量以上，則存在黏度上升、損及熱壓 接性之傾向，因此較佳的是填料之含量位於上述之範圍 内。為了獲得所要求之特性的平衡，可決定最佳填料含量。 使用填料之情形時之混合、混練可將通常之攪拌機、研磨 攪拌機、三輥研磨機、球磨機等分散機適宜組合而進行。 於本發明之半導體用黏著劑組成物中，為了使不同種 材料間之界面耦合良好，亦可添加各種偶合劑。偶合劑例 如可列舉矽烷系、鈦系、鋁系等，其中於效果較高之方面 而言’較佳的是矽烷系偶合劑’更佳的是具有環氧基等熱 硬化性基或曱基丙烯酸酯及/或丙烯酸酯等放射線聚合性 基之化合物。 而且，上述矽烷系偶合劑之沸點及/或分解溫度較佳的 是150°C以上，更位的是180°C以上，進一步更佳的是2〇〇。〇 以上。特別是可最佳地使用沸點及/或分解溫度為200°c以 57 201130942 ~ 分— * — f i i酸性基_絲_戈丙 席w曰專放射線聚合性基之石夕燒系偶合劑。 之方Γϊί述r合劑之使用量’自其效果或耐熱性及成本 兮為〇3旦=圭的是相對於黏著劑組成物100質量份而 。局υ·〇1質量份〜2〇質量份。 為了制離子_質、使吸濕時之 =本發明之半導嶋著劑組成物中進-二子 t劑。此種離子捕獲劑並無特別之限制，例如可列舉三 嗪硫醇化合物、_還原轉作為用以防止銅產生離子化 之銅毒抑·而為人所知之化合物，粉末狀之叙 2、録系’系、紹系、鍅系、約系、鈦系、錫系以及該 二，混合轉無機化合物。具體财東亞合成股份有限公 司製造之無機離子捕獲劑、商品名、IXE_300 (銻系）、 IXE-500 (叙系）、IXE_6GG (録、叙混合系）、ιχΕ•彻（鎮、 紹混合系）、IXE-800 (錯系）、IXE]綱（約系）等。該些 離子捕獲劑可翔使用或者將2種以上混合使用。自添力—〇 之，果或耐熱性、成本等方面而言，上述離子捕獲劑之使 用里相對於黏著劑組成物1〇〇質量份而言較佳的是〇 〇1質 量份〜10質量份。 本發明之半導體用黏著劑組成物較佳的是含有具有醯 亞胺基之化合物。具有醯亞胺基之化合物例如可含有作為 上述Α1化合物而列舉之具有醯亞胺基之單官能（甲基)丙 烯酸酯等低分子化合物、或者作為上述（Ε)成分而列舉 之聚醯亞胺樹脂等具有醯亞胺基之樹脂。 58 201130942 、作為本發明之半導體用黏著劑組成物，自提高黏著劑 組成物之1性、薄臈化之觀財慮，較佳的是於25°C之 黏度為 10 mPa.s〜300〇〇 mPa.s，更佳的是 3〇 mPa s〜2〇〇〇〇 mPa s ’自黏著劑組成物之耐熱性或硬化後之黏著性、塗佈 時之膜厚均勾性讀點考慮，進-步更佳的是5G mPa.s〜 10000 mPa s ’ 最佳的是 1〇〇 mpa.s〜5〇〇〇 mpa.s。若上述黏 度不足10 mPa.s，則存在黏著劑組成物之保存穩定性或耐 熱性降低’或者於塗佈黏著劑組成物時容易產生針孔之傾 1。而且，亦存在利用曝光進行B-階段化變困難之傾向。 若上述黏度超過30000 mPa.s，則存在塗佈時薄膜化變困難 ，傾向或f自喷嘴之噴出變困難之傾向。此處所謂之黏度 是，用東料ϋ製造所製造之腦型旋轉黏度計，於樣 品里為0‘4mL、3。圓錐之條件下，於^它測定之黏度值。 本發明之半導體用黏著劑組成物可形成薄膜之黏著劑 層。於此情形時，將黏著劑組成物於溫度25〇c進行塗佈， 加以曝光後之膜厚較佳的是5〇μιηατ，自低應力化之觀 點考慮更佳的是30 μιη以下，自膜料自性之觀點考慮進 -步更佳的是20μιη以下，自可更薄地封裝（package)考 慮最，的是10 μηι以下。而且，為了確保良好之熱壓接性 與黏著性，上述膜厚較佳的是〇 5 μιη以上；為了減低灰塵 或切割時之切斷渣所造成之空隙等壓接不良，更佳的是i μιη以上。 而且，於使用本發明之半導體用歸劑組成物而於半 導體晶圓上形成黏著劑層之情形時，自晶片之操作性、翹 59 201130942 曲等應力、熱壓接時之晶月變形（可相對於基材而平行地 麼，）硬彳b時之aa#保持性（硬化時之熱炼融所造成之變 形）之觀點考慮，較佳的是晶圓之厚度χ與黏著劑層之厚 度y之關係滿足Xgy，更佳的是滿足x^2xy。 此處之膜厚可藉由以下方法而測定。藉由旋塗將黏著 劑組成物塗佈於石夕晶圓上，於所得之塗膜層麼進行了脫模 處理之PET薄膜，藉由高精度平行曝光機（㈣ MANUFACTUIUNG Co” LTD.製造、「EXM_lm如」（商 _mWit行曝光。其後，使用表面粗糖度 測疋盗（小阪研究所製造）測定黏著劑層之厚度。 作為本發明之半導體用黏著劑組成物，較佳的是藉由 ^射而㈣段化之黏細域物之5%重量損失溫度為 HOC以上，更佳的是⑽。c以上，最佳的是雇。c以上。 纽度錄15Gt，财在於壓触黏著體後 之熱硬化時或回焊等熱歷程時被黏著體剝離之傾向，且於 诊熱賴。μ，自_齡成物之低 mi 面凹凸之抑制或者Β-階段化後之熱時 設計:因，的是5%重量損失二 =/°重_失溫度為該翻’較佳岐黏著劑組成物中 所含之溶劑量為5質量％以下，更 5中 最佳的是1質量％以下。 M/WT’ 此，所謂之5%重量損失溫度域由如下 之值。猎由旋塗⑽0rpm/10s、侧rpm/20s)將^ 201130942 劑組成物塗佈於矽晶圓上，將進行了脫模處理之pET薄膜 於室溫下用手壓輥（hand roller)層壓於所得之塗膜上，藉 由高精度平行曝光機（ORC MANUFACTURING Co.，LTD 製k、EXM-1172-B-oo」（商品名））以 1000 mJ/cm2 進行 曝光。其後’使用熱重/熱示差同步分析儀（SII NanoTechnologylnc.製造、商品名 rTG/DTA63〇〇」），於升 溫速度為10°C/min、氮氣流（400 ml/min)下對匕階段化 之黏著劑測定5%重量損失溫度。 至於本發明之半導體用黏著劑組成物之階段化，自 插作性之觀點考慮，較佳的是將黏著劑組成物塗佈於基材 上進行曝光後’於30°C之表面黏著力為200gf/cm2以下； 自熱壓接時之黏著性之觀點考慮，更佳的是15〇 gf/cm2以 下；自切割膠帶之剝離性之觀點考慮，進一步更佳的是1〇〇 gf/cm2以下；自拾取性之觀點考慮，最佳的是5〇沙咖2以 下。而且，為了抑制切割時晶片飛出等，較佳的是表面黏 著力為0.1 gf/cm2以上。若上述於3(rc之表面黏著力超過 200 gf/cm2’則存在所得之黏著劑層於室溫下之表面之黏著 性變高，且操作性變差之傾向。而且，存在變得容易產生 如下問題之傾向而欠佳：於切割時黏著劑與被黏著體之界 面浸入水而產生晶片飛出，與切割後之切割膜之剝離性降 低而造成拾取性降低。 此處之表面黏著力是藉由如下方式而測定之值。藉由 旋塗（2000 rpm/l〇 s、4000 rpm/2〇 s)將黏著劑組成物塗 佈於矽晶圓上，將進行了脫模處理之PET薄膜層壓於所$ 61 201130942f 之塗膜上，藉由高精度平行曝光機（ORC MANUFACTURING Co.，LTD.製造、「EXM-1172_B-〇o」（商 品名））以1000 mJ/cm2進行曝光。其後，對於30°C以及 120°C之表面之黏著強度（tack strength )，使用RHESCA Corporation製造之探針式黏性試驗機，藉由探針直徑：5.1 mm、剝離速度：10 mm/s、接觸荷重：100 gf/cm2、接觸時 間：1 s，測定5次30〇C之黏著力，算出其平均值。 本發明之半導體用黏著劑組成物較佳的是使用高精度 平行曝光機（ORC MANUFACTURING Co.，LTD.製造、 「EXM-1172-B-oo」（商品名））進行曝光後，於2〇。〇〜300 °C之最低熔融黏度為30000 Pa.s以下。 此處所謂之最低熔融黏度表示使用黏彈性測定裝置 ARES( Rheometric Scienetific F.E. Ltd.製造）而測定以 1〇〇〇 mJ/cm2之光量進行曝光後之樣品時，於2〇°c〜300°C之炫 融黏度之最低值。另外，測定板是直徑為8 mm之平行板， 測定條件為：升溫5°C/min，測定溫度20°C〜300°C，頻率 1 Hz。 上述最低熔融黏度自熱壓接性之觀點考慮更佳的是 10000 Pa.s以下，於可於形成薄膜時熱壓接之方面而言進 步更佳的疋5000 Pa.s以下’於可藉由更低溫且短時間而 熱壓接之方面而言特佳的是3〇〇〇 pa_s以下。藉由具有上述 範圍内之最低熔融黏度，可確保充分之低溫熱壓接性，且 了賦予即使對於具有凹凸之基板等亦良好之密接性。上述 最低熔融黏度之下限值並未特別設定，於操作性或賦予熱 62 201130942 時之黏著性等方面而言較理想的是1〇pa.s以上β 本發明之半導體用黏著劑組成物之藉由光照射而Β_ 階段化、進一步進行加熱硬化後之5%重量損失溫度，於 可抑制由於熱歷程而剝離之方面而言較佳的是2&它以 上，於可抑制由於熱歷程而造成之空隙之方面而言更佳的 是280°c以上，自耐吸濕回焊性之觀點考慮最佳的是3⑽。cCh3. For the above-mentioned poly-imine resin, the B-stage can be uniformly B-staged. It is better than the transmittance of 365 nm when forming into 30: for lower exposure. In terms of B-stage, Lu, and more preferably 20% or more. Such a polypyrene resin is exemplified by the lining represented by the above formula (2) and the 201130942 aliphatic ether diamine represented by the above formula (8) and/or the above formula (9). And synthesis. In addition, as the (E) thermoplastic resin, the solubility residue in the adhesive composition is reduced in the first step of suppressing the viscosity, and the liquid thermoplasticity is used in the liquid state at room temperature (10). The reaction is carried out without heating using a solvent. Secondly, the adhesive composition which is not suitable for the solvent is used in the steps of reducing the solvent, reducing the residual solvent, and reducing the step of re-sinking: the second thermoplastic resin is also easily used in the reaction furnace. take out. Such a sapphire may, for example, be a polybutadiene, a acrylonitrile, a butyl diene oligomer, a diene, a polybutene or the like, a polyamic polymer, a pentylene oxide polymer, or a poly Aminophthalic acid is preferably used as the aminoguanidine acid, and the polyimine resin is preferably used. . The liquid polyimine resin can be obtained, for example, by reacting the above-mentioned acid anhydride and sulfonium diamine cleavage. The synthesis method may be a method in which a solvent is added to disperse an acid anhydride in an aliphatic ether diamine or a decane alkane 1, and heating is carried out. The content of the female (8) thermoplastic resin is 〇1% by mass to 50% by mass based on the component (4), and more preferably 〇5 mass% from the viewpoint of film forming property or film thickness uniformity and suppression of viscosity increase. ~ 2 〇 mass%. When the content of the thermoplastic resin is not more than (% by mass), the addition effect tends not to be exhibited. When the content is more than 50% by mass, the film thickness uniformity is lowered due to dissolution or the like, and the viscosity is increased to make it difficult to form a film. In the adhesive composition for a semiconductor of the present invention, in order to impart a property such as _, _, 2, and hardenability in order to impart a property of 55 201130942, process adaptability or oxidation resistance, etc. Inhibitors or antioxidants, acid esters, sulfur-based fillers. The adhesive composition for semiconductors may also contain suitable metal filling materials, oxygen ^= lifting silk, gold powder, copper powder, recording powder, etc.夕夕酸约,石夕酸碧1匕 aluminum, magnesium hydroxide, carbonic acid dance, carbonic acid crystalline oxidized glass, iron oxide, Taoying i曰i;; oxygen eve, nitriding, titanium dioxide, filler, etc. Regardless of the type, shape t, etc., organic matter such as carbon, gum filler, etc. == the guide:: r is used separately. For example, it is a filler, and the addition of gold, such as thermal conductivity and thixotropy, is added. Add non-metallic surplus & 1 property, low thermal expansion, low Wet addition of organic fillers, etc., in order to impart toughness of the adhesive layer, etc., or to use two kinds of organic fillers or organic fillers, which can be used alone or in combination with one type of adhesive material. In terms of equipment, etc., nf, thermal conductivity, low moisture absorption property, insulating filler; in inorganic "or filler, inorganic filler, or insulating dispersibility and inaccessible filler, for adhesives The composition is better than the higher adhesion of the silica sand when it is hot, and the average particle size is less than 10 μm, and the average particle size is less than 10 μm. And the maximum particle 56 201130942 = 20 μιη叮 exceeds i (^ or the maximum particle size super direction. However, there is no special reason for the inability to obtain the effect of improving the damage of the Wei blade, the effect of the European gradient and the maximum particle size. Restrictions, Renqianjun (4) and the most recorded diameter are difficult to discuss. The content of the above fillers may be determined according to the characteristics or functions imparted, and the phase f is preferably the total amount of the adhesive composition containing the filler. Is 50 quality 2 under 'more It is 1% by mass to 4% by mass, and more preferably 3. It is 3% by mass to 30% by mass. By increasing the amount of filler, low α, low moisture absorption, and high elastic modulus can be achieved. Moreover, the cutting property (cutting property of the cutting edge), the wire bonding property (ultrasonic efficiency), and the bonding strength during heat can be effectively improved. If the filler is increased to a necessary amount or more, the viscosity is increased and the hot pressing is damaged. The tendency of the connection is preferred, so that the content of the filler is within the above range. In order to obtain the balance of the required characteristics, the optimum filler content can be determined. In the case of using the filler, the usual mixer, A dispersing machine such as a grinding mixer, a three-roll mill, or a ball mill is suitably combined. In the adhesive composition for a semiconductor of the present invention, various coupling agents may be added in order to achieve good interfacial coupling between different materials. Examples of the coupling agent include a decane type, a titanium type, and an aluminum type. Among them, a preferred one is a decane coupling agent, and a thermosetting group such as an epoxy group or a fluorenyl group is more preferable. A compound of a radiation polymerizable group such as an acrylate or/or an acrylate. Further, the boiling point and/or decomposition temperature of the above decane-based coupling agent is preferably 150 ° C or higher, more preferably 180 ° C or higher, and still more preferably 2 Torr. 〇 Above. In particular, it is preferable to use a boiling point and/or a decomposition temperature of 200 ° C to 57 201130942 ~ min - * - f i i acidic group - silk _ _ _ _ _ _ 曰 曰 曰 曰 曰 曰 曰 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The amount of use of the mixture is 'from its effect or heat resistance and cost 兮 旦 3 = = 圭 is relative to the adhesive composition 100 parts by mass. Bureau υ·〇 1 part by mass to 2 〇 parts by mass. In order to produce ion-quality, when it is moisture-absorbing, the semi-conductive agent composition of the present invention is a two-component t-agent. Such an ion trapping agent is not particularly limited, and examples thereof include a triazine thiol compound, a compound which is known as a copper poison to prevent copper from being ionized, and a powdery form. The system is a system of 'systems, Shaoxing, lanthanides, yttrium, titanium, tin and the second, mixed with inorganic compounds. Inorganic ion trapping agent, trade name, IXE_300 (锑), IXE-500 (syntax), IXE_6GG (recorded, Syrian mixed system), ιχΕ•Che (town, Shao mixed system) manufactured by Tokayo Synthetic Co., Ltd. , IXE-800 (wrong system), IXE] (about) and so on. These ion trapping agents may be used in combination or in combination of two or more. The use of the above ion trapping agent is preferably 1 part by mass to 10 parts by mass based on 1 part by mass of the adhesive composition, in terms of the strength, the heat, the cost, and the like. Share. The adhesive composition for a semiconductor of the present invention preferably contains a compound having a ruthenium group. The compound having a quinone imine group may, for example, contain a low molecular compound such as a monofunctional (meth) acrylate having a quinone imine group as the above quinone 1 compound, or a polyimine which is exemplified as the above (Ε) component. A resin having a quinone imine group such as a resin. 58 201130942 As the adhesive composition for a semiconductor of the present invention, it is preferable to increase the viscosity of the adhesive composition by 10 mPa.s to 300 自 from the viewpoint of improving the properties of the adhesive composition. 〇mPa.s, more preferably 3〇mPa s~2〇〇〇〇mPa s 'The heat resistance of the self-adhesive composition or the adhesion after hardening, and the film thickness at the time of coating are considered. The better step is 5G mPa.s~ 10000 mPa s ' The best is 1〇〇mpa.s~5〇〇〇mpa.s. If the viscosity is less than 10 mPa.s, the storage stability or heat resistance of the adhesive composition may be lowered or the pinhole may be easily formed when the adhesive composition is applied. Moreover, there is also a tendency to make B-stage transformation difficult by exposure. When the viscosity is more than 30,000 mPa·s, the film formation becomes difficult during coating, and the tendency to f or the ejection from the nozzle tends to be difficult. The viscosity referred to here is a brain-type rotational viscometer manufactured by Tohoku Manufacturing Co., Ltd., which is 0 '4 mL, 3 in the sample. Under the condition of the cone, the viscosity value determined by it. The adhesive composition for a semiconductor of the present invention can form an adhesive layer of a film. In this case, the adhesive composition is applied at a temperature of 25 〇c, and the film thickness after exposure is preferably 5 〇 μηη ατ, and more preferably 30 μηη or less from the viewpoint of low stress. From the point of view of material self-optimization, it is better to be 20 μm or less, and the package is considered to be the thinner than 10 μηι. Further, in order to secure good thermocompression bonding and adhesion, the film thickness is preferably 〇5 μm or more; in order to reduce the pressure difference such as voids caused by dust or cutting slag during cutting, it is more preferable that i Ιιη or more. Further, in the case where the adhesive composition layer is formed on the semiconductor wafer by using the reductant composition for a semiconductor of the present invention, the operability from the wafer, the stress such as the warp, and the crystal deformation at the time of thermocompression bonding can be The thickness of the wafer χ and the thickness of the adhesive layer are preferably considered to be parallel to the substrate, and the aa# retention of the hard 彳b (deformation caused by thermal smelting during hardening). The relationship of y satisfies Xgy, and it is better to satisfy x^2xy. The film thickness here can be determined by the following method. The PET film which was subjected to release treatment on the obtained coating layer by spin coating was applied to the Shi Xi wafer, and was manufactured by a high-precision parallel exposure machine ((4) MANUFACTUIUNG Co” LTD. "EXM_lm" (the _mWit line exposure. Thereafter, the thickness of the adhesive layer is measured using the surface roughness tester (manufactured by Kosaka Research Institute). As the adhesive composition for a semiconductor of the present invention, it is preferred to borrow The 5% weight loss temperature of the (4) segmented viscose domain is above HOC, more preferably (10). c or more, the best is hired. c or more. New Zealand Lu 15Gt, the wealth lies in pressure contact The tendency of the adhesive to be peeled off during the thermal hardening of the body or during the thermal history such as reflow, and the diagnosis is based on the μ. The suppression of the low-mi surface irregularities of the aging-aged product or the thermal design after the Β-stage : 5% weight loss two = / ° weight _ loss temperature is the preferred amount of the solvent contained in the adhesive composition is 5% by mass or less, and the most preferred one is 1% by mass. Below. M/WT' This, the so-called 5% weight loss temperature domain is determined by the following values: Hunting by spin coating (10) 0rpm/10 s, side rpm/20s) The composition of the 201130942 was applied to a ruthenium wafer, and the pET film subjected to the release treatment was laminated on the obtained coating film by a hand roller at room temperature. Exposure was performed at 1000 mJ/cm2 by a high-precision parallel exposure machine (manufactured by ORC MANUFACTURING Co., LTD. k, EXM-1172-B-oo (trade name)). Thereafter, the thermogravimetric/thermal differential synchronization analysis was performed. The instrument (manufactured by SII NanoTechnology Lnc., trade name: rTG/DTA63®) was used to measure the 5% weight loss temperature of the crucible-staged adhesive at a heating rate of 10 ° C/min and a nitrogen flow (400 ml/min). As for the stage of the adhesive composition for a semiconductor of the present invention, it is preferred that the adhesive composition is applied to a substrate after exposure for exposure, and the surface adhesion at 30 ° C is 200 gf / cm 2 or less; more preferably 15 〇 gf / cm 2 or less from the viewpoint of adhesion at the time of thermocompression bonding; further preferably 1 〇〇 gf / cm 2 or less from the viewpoint of the detachability of the dicing tape From the point of view of picking, the best is 5 〇 沙 咖 2 or less. Also, in order to suppress When the wafer is flying out during cutting, etc., it is preferable that the surface adhesion force is 0.1 gf/cm2 or more. If the surface adhesion force exceeds 200 gf/cm2 in 3 (the surface of the adhesive layer is present at room temperature) The adhesiveness is high and the workability is deteriorated. Moreover, there is a tendency that the following problems tend to occur, and it is unsatisfactory: the wafer is immersed in water at the interface between the adhesive and the adherend at the time of cutting, and the wafer is ejected and cut. The peeling property of the latter dicing film is lowered to cause a decrease in pick-up property. The surface adhesion here is a value measured by the following method. The adhesive composition was applied to the tantalum wafer by spin coating (2000 rpm/l〇s, 4000 rpm/2〇s), and the release film PET film was laminated on the coating of $61 201130942f. The film was exposed to light at 1000 mJ/cm 2 by a high-precision parallel exposure machine (manufactured by ORC MANUFACTURING Co., LTD., "EXM-1172_B-〇o" (trade name)). Thereafter, for the tack strength of the surface at 30 ° C and 120 ° C, a probe type viscosity tester manufactured by RHESCA Corporation was used, with a probe diameter of 5.1 mm and a peeling speed of 10 mm/s. Contact load: 100 gf/cm2, contact time: 1 s, the adhesion of 30 times 30 〇C was measured, and the average value was calculated. The adhesive composition for a semiconductor of the present invention is preferably subjected to exposure using a high-precision parallel exposure machine (manufactured by ORC MANUFACTURING Co., LTD., "EXM-1172-B-oo" (trade name)). . The lowest melt viscosity of 〇~300 °C is below 30,000 Pa.s. The lowest melt viscosity referred to herein is a sample obtained by measuring a light amount of 1 μm/cm 2 using a viscoelasticity measuring apparatus ARES (manufactured by Rheometric Scienetific FE Ltd.) at 2 ° C to 300 ° C. The lowest value of the viscous viscosity. Further, the measuring plate was a parallel plate having a diameter of 8 mm, and the measurement conditions were as follows: a temperature rise of 5 ° C / min, a measurement temperature of 20 ° C to 300 ° C, and a frequency of 1 Hz. The above-mentioned minimum melt viscosity is more preferably 10,000 Pa.s or less from the viewpoint of thermocompression bonding, and is more preferably 疋5000 Pa.s or less in terms of thermocompression bonding at the time of film formation. Particularly preferred in terms of lower temperature and short time and thermocompression bonding is 3 〇〇〇pa_s or less. By having the lowest melt viscosity within the above range, sufficient low-temperature thermocompression bonding property can be ensured, and good adhesion to a substrate having irregularities or the like can be imparted. The lower limit of the minimum melt viscosity is not particularly set, and it is preferable that the adhesiveness of the semiconductor of the present invention is 1 〇 pa.s or more in terms of workability or adhesion to heat 62 201130942. The 5% weight loss temperature after the light irradiation and the further heat hardening is preferably 2&suppering from the viewpoint of suppressing the peeling due to the heat history, thereby suppressing the heat history More preferably, it is 280 ° C or more in terms of voids, and 3 (10) is the most preferable from the viewpoint of moisture absorption reflow resistance. c

以上。若5%重量損失溫度不足26(TC，則存在由於回焊步 驟等熱歷程而產生剝離之傾向。 V 而且，本發明之半導體用黏著劑組成物之進行B_階段 化後，藉由烘箱於140〇C加熱1小時、繼而於18〇。〇加熱3 小時之時（加熱硬化時）的逸氣量，於可抑制剝離之方面 而言較佳的是10%以下，於可抑制空隙之方面而言更佳的 是7%以下，於可進一步抑制由於硬化後之熱歷程所造成 之空隙或剝離之方面而言最佳的是5%以下。若上述逸氣 量超過10%，則存在於加熱硬化時產生空隙或剝離之傾向。 此處所謂之逸氣量是藉由如下之方式而測定之值。藉 由旋塗（2000 rpm/10 s、4000 rpm/20 s)將黏著劑組成物 塗佈於矽晶圓上，將進行了脫模處理之PET薄膜於室溫下 用手壓輥（handroller)層壓於所得之塗膜上，藉由高精度 平行曝光機（ORC MANUFACTURING Co_，LTD.製造、 「EXM-1172-B-〇〇」（商品名））以 l〇〇〇mJ/cm2 進行曝光。 其後，使用熱重/熱示差同步分析儀（SII NanoTechnology Inc.製造、商品名「TG/DTA6300」），於氮氣流（400 ml/min ) 下進行如下之程式（program)時之5%重量損失溫度之值： 63 201130942 以50〇C/min之升溫速度使B_階段 =，rr°c保持1小時，進—步以節 速度使其升溫至18叱，於⑽。C保持3小時。开 本發明之半導翻料敝絲較佳的是以段 接後’於1〇〇°C〜15〇t實施5分鐘〜120分鐘 :二匕處理之方式而使用。藉由此種熱硬化處理，可抑 奸之=熱歷程步驟所造成之空隙或剝離，可 狻传同可罪性之半導體裝置。 本發明之半導體用黏著劑組成物之the above. If the 5% weight loss temperature is less than 26 (TC, there is a tendency for peeling due to a heat history such as a reflow step. V. Further, after the B_stage of the adhesive composition for a semiconductor of the present invention is carried out, it is dried by an oven. 140 〇C is heated for 1 hour and then at 18 Torr. The amount of outgassing when heated for 3 hours (when heat-hardened) is preferably 10% or less in terms of suppressing peeling, and the void can be suppressed. More preferably, it is 7% or less, and it is preferably 5% or less in terms of further suppressing voids or peeling due to heat history after hardening. If the above-mentioned outgas amount exceeds 10%, it is present in heat hardening. The tendency to cause voids or peeling occurs. The amount of outgassing referred to herein is a value measured by the following method: The adhesive composition is applied by spin coating (2000 rpm/10 s, 4000 rpm/20 s) On the crucible wafer, the PET film subjected to the release treatment was laminated on the obtained coating film by hand roller at room temperature, and manufactured by ORC MANUFACTURING Co., LTD. "EXM-1172-B-〇〇" (trade name)) l〇〇〇mJ/cm2 was exposed. Thereafter, a thermogravimetric/thermal differential sync analyzer (manufactured by SII NanoTechnology Inc., trade name "TG/DTA6300") was used, and the following was carried out under a nitrogen stream (400 ml/min). 5% weight loss temperature value during program: 63 201130942 B_stage =, rr °c is maintained for 1 hour at a heating rate of 50 ° C / min, and the temperature is raised to 18 at a node speed.叱, at (10). C for 3 hours. The semi-conductive turning yarn of the present invention is preferably carried out after 5 minutes to 120 minutes at a temperature of 1 〇〇 ° C to 15 〇 t: By using such a heat hardening treatment, the gap or peeling caused by the thermal history step can be circulated, and the sinister semiconductor device can be circulated. The adhesive composition for a semiconductor of the present invention

St??之黏著劑層，黏著半導^ 面而占著強度’於抑制由於熱歷程而剝離之方 ，而“父佳的疋0.2廳以上，更佳的是〇 5廳以上， 自耐吸濕轉性之觀时錢佳的是1.0 MPa以上。而 Ϊ之ί Ϊ Γ切黏著強度較佳的是％顺以下。為了使260 二度為5〇 MPa以上’必須大量調配熱硬化 機粒子，且存在損及塗佈後之膜厚均勻性或黏著 劑、，且成物之保存穩定性、賴硬化後之應力增大之傾向。 ,、此處所谓之剪切黏著強度，與膜厚測定時同樣，準備 =成有黏著劑組成物之石夕晶圓，對黏著薄膜整個面進行曝 魅t出石夕晶圓使其為3 _3麵見方。將切出之附有 之石夕晶片置於預先切出為5 mmx5職見方之石夕晶 心-©以2GG gf進行加壓—面於12(rc進行2秒之壓 /、後，於烘箱中於14〇。〇加熱〗小時，繼而於1⑽。◦加 ”、、】時彳隻彳于黏著樣品。關於所得之樣品，使用剪切黏 64 20113094¾ 著力試驗機「Dage-4GG0」（商品名）而測定於·。c之煎 切黏著力，將其作為剪切黏著強度之值。 以下’使用圖式對使用本發明之半導體用黏著劑組成 物而製造之半導财置以及其製造綠加以具體之說明。 近年來挺出了各種結構之半導體裝置，本發明之半導體用 黏著劑組成物之用途並不限定於以下所說明之結構的半導 體裝置以及其製造方法。 a圖1〜圖13是表示半導體裂置的製造方法之-實施形 ‘4的模式圖。本實施形態之製造方法包括以下步驟。 步驟1 .在形成於半導體晶圓i内之半導體晶片（半 導體元件）2之電路面S1上積層可_之黏著帶（背面研 磨膠帶）4 (參照圖1)。 一步驟2:自與電路面S1為相反側之面（背面）以對 半導體晶圓1進行研磨而使半導體晶目i變薄（參照圖 步驟3:於與半導體晶圓！之電路面S1為相反側之面 S2塗佈本發明之半導體用黏著劑組成物5 (參照圖3及圖 4)。 步驟4:自由所塗佈之黏著劑組成物而構成之黏著劑 層5側進行曝光，使黏著劑層5 B_階段化（參照圖。 步驟5 :於黏著劑層5上積層可剝離之黏著帶（切割 膠帶）6 (參照圖6)。 步驟6 .將可剝離之黏著帶4剝離（參照圖7 )。 步驟7 :藉由切割將半導體晶圓丨切分為多個半導體 晶片（半導體元件）2 (參照圖8)。 65 201130942 步驟8 :拾取半導體晶片2而將其壓接（安裝）於半 導體裝置用支撐部件（半導體元件搭載用支撐部件）7或 半導體晶片上（參照圖9、圖10、圖11)。 步驟9 :使所安裝之半導體晶片經由導線16而與支撐 部件7上之外部連接端子連接（參照圖12)。 步驟10:藉由密封材17而密封包含多個半導體晶片2 之積層體’獲得半導體裝置100 (參照圖13)。 以下’對（步驟1)〜（步驟丨〇)加以詳述。 (步驟1) 於表面形成有電路之半導體晶圓1的電路面S1側積 層可剝離之黏著帶4。黏著帶4之積層可藉由對預先成形 為薄膜狀之薄膜進行層壓之方法而進行。 (步驟2) 對半導體晶圓1的與黏著帶4為相反侧之面S2進;f 研磨」使半導體晶圓1變薄為預定之厚度。於藉由黏著;? 4將半導體晶圓1固定於研磨用夾具上之狀態下，使用石 磨裝置8進行研磨。 (步驟3) 於與半導體晶圓1之電路㈣為相反側之面幻璧 ft明之半導體用黏義組成物5。於箱2G内，將貼押 j者帶4之半導體晶圓1固定於夾具21上之狀態下進；p :及自印刷法、旋塗法、噴塗法、喷射點用 二及贺墨法料獅。該些方法巾，自薄魏以及 勻性之觀點考慮，較佳的是旋塗法（圖3 )或喷塗法（圖< 66 201130942 -Γ1Ι 旋塗敦置之吸附台上形成孔，吸附台亦可為網 “ f以殘留吸附痕跡之方面考慮，較佳的是吸附台為 、 、了防止0曰圓之不平整以及邊緣部隆起，利用旋塗 法之塗佈較佳的是於500卬m〜5000 rpm之轉速下進行。 自同樣之觀點考慮，更佳的是轉速為1000 rpm〜4000 rpm。為了調整黏著劑组成物之黏度，亦可於旋塗台上具 有溫度調節器。 、黏著劑組成物可於注射器（syringe)等中保存，於旋 塗裝置之注射器設置部分亦可具有溫度調節器。 藉由例如旋塗法將黏著劑組成物塗佈於半導體晶圓上 時’有時會於半導體晶圓之邊緣部分附著多餘之黏著劑組 成物、。可於旋塗後用溶劑等將此種多餘之黏著劑清洗除 去^清洗方法並無特別之限定，較佳的是—面使半導體晶 =塗，-面使溶劑自喷嘴喷出至附著有多餘之黏著劑= 部分的方法。清洗所使用之溶縣為可溶解黏著劑之溶劑 即可，例如可使用選自丁酮、丙酮、異丙醇以及 沸點溶劑。 低 (步驟4) 自猎由塗佈而由本發明之半導體用简触成物所形 ，之黏著劑層5舰肺性光線（典_是料線），_ 著劑組成物Βϋ化。藉此可將黏著騎5固定於半導^ 晶，1上，且可減低黏著劑層5表面之黏性。可於真空下胆 氮氣下、空氣下等環境下進行曝光。為了減低氧抑制，亦 可於將進行了脫模處理之PET薄膜或聚丙烯薄膜等基材積 67 201130942 層於黏著劑層5上之狀態下進行曝光。而且，亦可藉由如 下方式而簡略化步驟5 :於將聚氣乙烯、聚烯烴或黏著帶 (切割膠帶）6積層於黏著劑層5上之狀態下進行曝光。 而且’亦可經由圖案化之遮罩進行曝光。藉由使用圖案化 之遮罩’可形成熱壓接時之流動性不同的黏著劑層。自黏 性之減低以及節拍時間之觀點考慮，曝光量較佳的是2〇 ml/em2〜2_ mj/cm2。而且，為了減低B_階段化後之黏性 以及減低逸氣，亦可於曝光後於1〇〇t：以下之溫度下進行 加熱。 彆π傻之胰厚較佳的是5〇 μιη以下，自低應力化之 點考慮更佳的是Μμη^ητ，自膜厚㈣性之觀點考慮 一步更佳的是20 μπι以下，自可使封裝更薄考慮最佳的 10 μιη以下。而且，為了確保良好之熱壓接性與黏著性 上述膜厚較佳的是〇.5 μιη以上；為了減低由於灰塵或切 時之切斷渣而造成之空隙等壓接不良，更佳的是丨 上。膜厚之測定可與上述同樣地進行。 而且’自晶片之操作性、_等之應力、敎壓 晶片變形（可相對於基材平行地壓接) 徂 性⑷匕時之編所造成之變形)之觀點考夺 厚度y之關係較佳的恤‘， 68 201130942 的是100 gf/cm2 U下’自拾取性之觀點考慮最佳的是5〇 gf/cm2以下。而且，為了抑制切割時之晶片飛出等，表面 黏著力較㈣是0.1 gf/emHx上。表面黏著力之測定可與 上述同樣地進行。 (步驟5) 曝光後’於黏著劑層5上貼附切割膠帶等可剝離之黏 著帶6。可藉由層壓航成形為薄膜狀之黏著帶之方法而 貼附黏著帶6。 (步驟6) 繼而，將貼附於半導體晶圓i之電路面上的黏著帶l 剝離。例如可使用藉由照射活性光線（典型的是紫 =著性降低之㈣帶，自黏著帶4側進行曝光後，將 剥離。 (步驟7) 1與黏著劑層5 —同切 切分為於各自之背面設 2。於藉由黏著帶（切 圓環）10上之狀態下， 沿著切割線D將半導體晶圓 斷。藉由該切割，將半導體晶圓1 置有黏著劑層5之多個半導體晶片 割膠帶）6而將整體固定於框（晶 使用切割刀片11進行切割。 (步驟8) 分之片藉==:，广同_ =二=财置_部以導載 掠縣）7或其他半導體晶片2上。較佳的是一面進 69 201130942 行加熱一面進行壓接。 。(:之剪切二支擇部件或其他半導體晶片於260 較佳的是〇. 2 Mp= W抑制由於熱歷程而剝離之方面而言 濕回焊性之觀財廣更佳的是0.5 MPa以上’自财吸 剪切黏著二ΐΪf的是M MPa以上。而且，上述 定可與上述同^地進廳以下。剪切黏著強度之測 (步驟9) 上之==撐各^ (步驟1G) 上之外部連制子連接° 獲得密封包含半導體晶片2之積層體，由此 獲付+導體裝置100。 經過如上所述之步驟，可藉由 ==製造具有如下結構之半導體裝置 ^ B及/或、半導體兀件與半導體元件搭載用支撐 獅著之結構。半導《置之構成以及製造方== =於以上之貫施形態，只要不偏離本發明之主旨則可適宜 ’艾更0 丄例如’可視需要替換步驟丨〜步驟7之順序^更具體 而σ可於預先切割之半導體晶圓的背面塗佈本發明之半 導體用黏著劑組成物，其後照射活性光線（典型的是紫外 線）而使黏著劑組成物Β-階段化。此時，亦可使用經圖案 化之遮罩。 ° 、 201130942 亦。可將所塗佈之黏著劑組成物於曝光前或曝光後力口熱 至120 c以下、較佳的是1〇〇。〇以下、更佳的是阶以下。 藉此可減低殘存之㈣彳、水分，且可進―步減低曝光後之 黏性。 [實例] 以下列舉貫例對本發明加以更具體之說明。但本發 明並不限定於以下實例。 x < (E)成分：熱塑性樹脂之調製〉。 (PM) 於具有攪拌機、溫度計以及氮氣置換裝置之燒瓶内， 裝入作為二胺之MBAA (和歌山精化製造、商品名 「MBAA」、分子量 286) 5 72 g(〇〇2m〇1)、「D 4〇〇」（商 品名「D·400」（分子量：433)、BASF 製造）13.57 g (0.03 m〇l「）、1，1，3,3-四曱基q，3_雙(3-胺基丙基)二矽氧烷（商品 名「BY16-871EG」、東麗道康寧股份有限公司製造）2 48 g (0.01 mol)以及丨，4_丁二醇雙(3_胺基丙基）醚（商品名 「B-12」、東京化成公司製造、分子量為2〇4 31)8 17g(〇 〇4 mol)以及作為溶劑2NMpil〇g，進行攪拌使二胺溶解於 溶劑中。 一面將上述燒瓶於冰浴中冷卻，一面將作為酸酐之 4,4’-氧雙鄰笨二曱酸二酐（以下簡稱為r〇DpA」）29.35 g (0_09mol)以及偏苯三曱酸酐（TAA) 3 84 g (〇 〇2mQl) 每次少量地添加於燒瓶内之溶液中。添加結束後，於室溫 下攪拌5小時。其後，於燒瓶上安裝附有水分接受器之回 71 201130942 流冷凝器，添加二甲苯70.5 g，一面吹入氮氣一面使溶液 升溫至180°C而保溫5小時，將二曱笨與水一同共沸除去， 獲付聚酿亞胺樹脂（PI-1)。進行（PI_ 1)之GPC測定，結 果是以聚苯乙烯換算計Mw = 21000。而且，（pi_i)之Tg 為 55°C β 使用純水對所得之聚醯亞胺清漆進行3次再沈殿純 化，使用真空烘箱於60〇C進行3日之加熱乾燥，獲得聚醯 亞胺固形物。 (PI-2 ) 於具有攪拌機、溫度計以及氮氣置換裝置（氮氣流入 管）之500ml燒瓶内，於作為二胺之聚氧化丙烯二胺（商 品名「D-2000」（分子量：約2000)、BASF製造）140 g (0.〇7 mol)以及U，3,3,甲基…先3胺基丙基)二矽氡 烧（商品名「BY16_871EG」、東麗道康寧股份有限公司製 造）3.72 g (0.015 m〇l)中’將 〇DpA31 〇 g (〇] m〇1)每 次少量地添加於燒瓶内之溶液中。添加結束後，於室溫下 擾拌5小時。紐’於燒紅絲附有水分接受ϋ之回流 冷凝器，一面吹入氮氣一面使溶液升溫至18〇。〇，保溫5 小時而除去水’獲得液狀聚醯亞胺樹脂（ρΙ_2 )。進行（Η。） 之GPC測定，結果是以聚苯乙烯換算計重量平均分子量 (Mw) 。而且，（ρι_2)之巧為抓以下。 <黏著劑組成物之調製> 使用上述所得之聚醯亞胺樹脂（Η-。及聚醯亞胺樹 脂（H-2)，藉由下述表i〜表3中所示之組成比（單位： 72 201130942 質量份）調配各成分’獲得實m〜實例18之黏著劑組成 物以及比㈣1〜比㈣4之黏著敝成物（黏著劑層形 成用組成物）。 於表1〜表3中，各記號表示下述者。 M-140 :東亞合成公司製造、丙烯酸_2_(1，2-環己基羧 基醯亞胺）乙酯（含有醯亞胺基之單官能丙烯酸酯、5%重 量損失溫度：200°C、於25°C之黏度：450 mPa.s)。 AMP-20GY :新中村化學工業公司製造、苯氧基二乙 二醇丙烯酸酯（單官能丙烯酸酯、5%重量損失溫度： 175 C、於 25 C 之黏度：16 mPa.s)。 702A :新中村化學工業公司製造、丙烯酸_2_羥基_3_ 苯氧基丙酯（含有羥基之單官能丙烯酸酯、5%重量損失溫 度：175°C、黏度：160mPa.s)。 401P :新中村化學工業公司製造、鄰苯基苯酚縮水甘 油醚丙烯酸酯（含有羥基之單官能丙烯酸酯、5%重量損失 溫度：160 C、黏度：10000 mPa. s )。 HOA-MPE :共榮社化學公司製造、2-曱基丙烯醯氧基 乙基-2-經乙基-鄰苯二曱酸（含有經基之單官能丙烯酸 酯、5%重量損失溫度：175°C、黏度·· 1200mPa.s)。 HO-MPP :共榮社化學公司製造、鄰苯二曱酸-2-曱基 丙浠醯氧基乙基-2-經丙酯（含有經基之單官能丙烯酸酯、 5%重量損失溫度：175°C、黏度：1〇〇〇 mPa‘s)。 PQMA .昭和兩分子公司製造、甲基丙稀酸-4-經基苯 基酯（含有羥基之單官能丙烯酸酯、5%重量損失溫度：> 73 201130942 260°C、固形）。 A-BPE4:新中村化學工業公司製造、乙氧基化雙酚A 型丙烯酸酯（2官能丙烯酸酯、5%重量損失溫度：330°C、 於 25°C 之黏度：980mPa，s)。 1-651 : CibaJapanK.K.製造、2,2-二曱氧基-1，2-二苯基 乙烷-1-酮（5%重量損失溫度：170°C、i線吸光係數：400 ml/gcm)。 I-379EG : Ciba Japan K.K.製造、2-二甲基胺基-2-(4-曱基-节基)-1-(4-嗎嚇*-4-基-苯基)-丁烧-1·•嗣（5%重量損失 溫度：260°C、i線吸光係數：8000 ml/gcm)。 1-907 : Ciba Japan K.K.製造、2-曱基-1-(4-(甲硫基)苯 基)-2-嗎啉代丙烷-1-酮（5%重量損失溫度：220°C、於365 nm下之分子吸光係數·· 450 ml/g.cm)。 I-OXE02 : Ciba Japan K.K.製造、乙酮，1-[9-乙基-6-(2-曱基苯曱醯基)-9H-咔唑-3-基]-，1-(鄰乙醯肟）、（5%重量損 失溫度：370°C、於365 nm下之分子吸光係數：7700 ml/g-cm)。 YDF-8170C :東都化成公司製造、雙酚F型雙縮水甘 油醚（5%重量損失溫度：270°C、於25°C之黏度：1300 mPa.s)。 630LSD :日本環氧樹脂股份有限公司製造、縮水甘油 胺型環氧樹脂（5%重量損失溫度·· 240°C、於25°C之黏度： 600 mPa.s )。 1032H60 :日本環氧樹脂股份有限公司製造、三(羥基 74 201130942 本基）曱烧型固形環氧樹脂（5%重量損失溫度：35〇°c、固 形、熔點60°C ；)。 2PHZ-PW ··四國化成公司製造、2_苯基_4,5_二羥基曱 基咪唑（平均粒徑：約3 μιη)。 1Β2ΡΖ:四國化成公司製造、卜苄基_2_苯基咪唑。St??'s adhesive layer, which adheres to the semi-conducting surface and occupies the strength' to inhibit the peeling due to the thermal history, and "the father's 疋 厅 0.2 or more, more preferably 〇 5 halls or more, self-resistant moisture absorption The view of the transition is better than 1.0 MPa, while the 黏 ί 黏 Γ 黏 黏 黏 黏 黏 黏 黏 黏 。 。 。 。 。 。 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 260 There is a tendency to impair the uniformity of the film thickness after coating or the adhesive, and the storage stability of the product and the stress after the hardening is increased. Here, the shear adhesive strength and the film thickness are measured. Similarly, prepare = a stone wafer with an adhesive composition, and expose the entire surface of the adhesive film to a 3 _3 square square. The cut-off stone wafer is placed in advance. Cut out as a 5 mmx5 job square stone core -© pressurize with 2GG gf - face at 12 (rc for 2 seconds pressure /, then in the oven at 14 〇. 〇 heat 〗 hours, then at 1 (10) When you add ",", you only have to stick to the sample. For the sample obtained, use the shear bond 64 201130943⁄4 The test machine "Dage-4GG0" (trade name) was measured for the adhesive strength of the c. The shear adhesive strength was used as the value of the shear adhesive strength. The following is a description of the use of the adhesive composition for a semiconductor of the present invention. The manufacturing of the semi-conducting material and the manufacturing of the green are specifically described. In recent years, semiconductor devices of various structures have been developed, and the use of the adhesive composition for semiconductors of the present invention is not limited to the semiconductor device having the structure described below and Fig. 1 to Fig. 13 are schematic views showing a method of manufacturing semiconductor cracking-implementation type 4. The manufacturing method of the present embodiment includes the following steps: Step 1. Formed in a semiconductor wafer i An adhesive tape (back grinding tape) 4 (see FIG. 1) is laminated on the circuit surface S1 of the semiconductor wafer (semiconductor element) 2. One step 2: a surface opposite to the circuit surface S1 (back surface) to the semiconductor The wafer 1 is polished to thin the semiconductor crystal substrate i (see FIG. 3: the semiconductor adhesive composition 5 of the present invention is applied to the surface S2 opposite to the circuit surface S1 of the semiconductor wafer! 3 and 4) Step 4: Exposure is carried out on the side of the adhesive layer 5 which is formed by freely applying the adhesive composition, and the adhesive layer 5 is stepped (see Fig. 5: Adhesive) A peelable adhesive tape (cut tape) 6 is laminated on the layer 5 (refer to Fig. 6). Step 6. Peel the peelable adhesive tape 4 (refer to Fig. 7) Step 7: Cut the semiconductor wafer by cutting A plurality of semiconductor wafers (semiconductor elements) 2 (see FIG. 8). 65 201130942 Step 8: Picking up the semiconductor wafer 2 and bonding (mounting) the semiconductor wafer 2 to a semiconductor device supporting member (semiconductor element mounting supporting member) 7 or semiconductor On the wafer (see Figures 9, 10, and 11). Step 9: The mounted semiconductor wafer is connected to the external connection terminal on the support member 7 via the wire 16 (refer to Fig. 12). Step 10: Sealing the laminated body including the plurality of semiconductor wafers 2 by the sealing member 17 to obtain the semiconductor device 100 (refer to FIG. 13). The following 'step (1) to (step 丨〇) will be described in detail. (Step 1) A peelable adhesive tape 4 is laminated on the circuit surface S1 side of the semiconductor wafer 1 on which the circuit is formed. The laminate of the adhesive tape 4 can be carried out by laminating a film formed in advance into a film. (Step 2) The surface S2 of the semiconductor wafer 1 opposite to the adhesive tape 4 is advanced; f is polished to thin the semiconductor wafer 1 to a predetermined thickness. The semiconductor wafer 1 is fixed to the polishing jig by adhesion; and the polishing is performed using the stone grinding device 8. (Step 3) On the opposite side to the circuit (4) of the semiconductor wafer 1, the viscous composition 5 for the semiconductor is used. In the case 2G, the semiconductor wafer 1 with the tape holder 4 is fixed on the jig 21; p: and the self-printing method, the spin coating method, the spray coating method, the ejection point 2, and the He ink method. lion. The method towel, from the viewpoint of thinness and uniformity, is preferably a spin coating method (Fig. 3) or a spraying method (Fig. < 66 201130942 - Γ1Ι spin coating, forming a hole on the adsorption table, adsorption The table can also be considered as a residual adsorption trace for the mesh "f. It is preferable to prevent the unevenness of the round and the edge portion from rising, and the coating by spin coating is preferably 500. It is carried out at a speed of 卬m to 5000 rpm. From the same viewpoint, it is more preferable that the rotation speed is 1000 rpm to 4000 rpm. In order to adjust the viscosity of the adhesive composition, a temperature regulator may be provided on the spin coating stage. The adhesive composition may be stored in a syringe or the like, and may have a temperature regulator in the syringe setting portion of the spin coating device. When the adhesive composition is applied to a semiconductor wafer by, for example, spin coating method' The excess adhesive composition may be attached to the edge portion of the semiconductor wafer. The excess adhesive may be removed by a solvent or the like after spin coating. The cleaning method is not particularly limited, and preferably, Surface semiconductor crystal = coating, - surface The solvent is ejected from the nozzle to a method in which an excess of the adhesive = part is attached. The solvent used for the cleaning is a solvent which can dissolve the adhesive, and for example, a solvent selected from the group consisting of methyl ethyl ketone, acetone, isopropyl alcohol, and a boiling point can be used. Low (Step 4) Self-hunting is formed by the coating of the semi-contact of the semiconductor of the present invention, and the adhesive layer 5 is a ship's lung light (code _ is a material line), and the composition of the agent is deuterated. The adhesive ride 5 can be fixed on the semi-conductive crystal, 1 and can reduce the viscosity of the surface of the adhesive layer 5. It can be exposed under vacuum under nitrogen and under air, etc. In order to reduce oxygen inhibition, The base film 67 201130942 such as a PET film or a polypropylene film which has been subjected to release treatment may be exposed to the adhesive layer 5, and the step 5 may be simplified by the following method: The ethylene, polyolefin or adhesive tape (cut tape) 6 is exposed to the adhesive layer 5 and exposed. It can also be exposed through a patterned mask. It can be formed by using a patterned mask. Adhesive with different fluidity during thermocompression bonding The layer is preferably 2〇ml/em2~2_mj/cm2 from the viewpoint of the decrease in self-adhesiveness and the tact time. Moreover, in order to reduce the viscosity after B_stage and reduce the outgassing, After the exposure, the heating is performed at a temperature of 1 〇〇 t: or less. The thickness of the pancreas is preferably 5 〇 μηη or less, and more preferably Μμη^ητ from the point of low stress, from the film thickness (4) The viewpoint of the nature is preferably 20 μm or less, and the optimum thickness of 10 μmη or less can be considered from the viewpoint of making the package thinner. Moreover, in order to ensure good thermal crimping property and adhesion, the film thickness is preferably 〇.5. In order to reduce the pressure-bonding failure such as voids caused by dust or cutting slag at the time of cutting, it is more preferable to use it. The measurement of the film thickness can be carried out in the same manner as described above. Moreover, the relationship between the operability of the wafer, the stress of the wafer, the deformation of the rolled wafer (which can be pressed in parallel with respect to the substrate), and the deformation caused by the braiding of the crucible (4) is preferable. The shirt's '68 201130942' is 100 gf/cm2 U under the 'self-picking point of view, the best is 5 〇gf/cm2 or less. Further, in order to suppress the flying of the wafer at the time of cutting, etc., the surface adhesion force is (0.1) at 0.1 gf/emHx. The measurement of the surface adhesive force can be carried out in the same manner as described above. (Step 5) After the exposure, a peelable adhesive tape 6 such as a dicing tape is attached to the adhesive layer 5. The adhesive tape 6 can be attached by laminating a film formed into a film-like adhesive tape. (Step 6) Then, the adhesive tape 1 attached to the circuit surface of the semiconductor wafer i is peeled off. For example, it is possible to use a strip of active light (typically purple = reduced (four) tape, which is exposed from the adhesive tape 4 side, and then peeled off. (Step 7) 1 and the adhesive layer 5 are equally divided into The back surface is provided with 2. The semiconductor wafer is broken along the dicing line D by the adhesive tape (cut ring) 10. By this dicing, the semiconductor wafer 1 is placed with the adhesive layer 5 The semiconductor wafer is cut into tape 6 and the whole is fixed to the frame (the crystal is cut using the cutting blade 11) (Step 8) The piece is divided by ==:, Guangtong _ = 2 = Finance _ Department to guide the county 7 or other semiconductor wafer 2 on. It is preferable to press the side while heating on the side of the 2011, 2011,942. . (: The shearing of the second selected component or other semiconductor wafer is preferably 260. 2 Mp = W suppresses the wet reflow property due to the thermal history and is more preferably 0.5 MPa or more. 'It is M MPa or more that is self-ficked and sheared. It is more than M MPa. Moreover, the above can be entered in the same place as above. The shear adhesion strength is measured (step 9) == 撑^ (Step 1G) The external connection sub-connection is obtained. The laminated body including the semiconductor wafer 2 is sealed, whereby the +-conductor device 100 is obtained. Through the steps as described above, the semiconductor device having the following structure can be fabricated by == and / Or, the semiconductor element and the semiconductor element are mounted to support the lion. The semi-conducting structure and the manufacturing side == = the above-mentioned configuration, as long as it does not deviate from the gist of the present invention, it is suitable for 'Ai Mo 0 丄For example, the order of the steps 丨 to 7 can be replaced. More specifically, σ can be applied to the back surface of the pre-cut semiconductor wafer with the adhesive composition for semiconductor of the present invention, followed by irradiation with active light (typically ultraviolet). Adhesive composition At this time, a patterned mask can also be used. ° , 201130942 Also, the applied adhesive composition can be heated to 120 c or less before exposure or after exposure, preferably 1 〇. 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 However, the present invention is not limited to the following examples: x < (E) component: preparation of a thermoplastic resin. (PM) In a flask having a stirrer, a thermometer, and a nitrogen gas displacement device, an MBAA as a diamine is added (Wakayama Chemical production, trade name "MBAA", molecular weight 286) 5 72 g (〇〇2m〇1), "D 4〇〇" (trade name "D·400" (molecular weight: 433), manufactured by BASF) 13.57 g (0.03 M〇l"), 1,1,3,3-tetradecyl q,3_bis(3-aminopropyl)dioxane (trade name "BY16-871EG", manufactured by Toray Dow Corning Co., Ltd. ) 2 48 g (0.01 mol) and 丨, 4_butanediol bis(3_aminopropyl) ether (trade name "B-12", Tokyo Chemical Industry Co., Ltd. Manufactured, the molecular weight was 2〇4 31)8 17g (〇〇4 mol) and 2NMpil〇g as a solvent, and the diamine was dissolved in a solvent. The flask was cooled in an ice bath while being used as an acid anhydride. , 4'-oxybis-succinyl phthalic anhydride (hereinafter referred to as r〇DpA)) 29.35 g (0_09 mol) and trimellitic anhydride (TAA) 3 84 g (〇〇2mQl) are added in small amounts each time In the solution in the flask, after the addition was completed, the mixture was stirred at room temperature for 5 hours. Thereafter, a 71 201130942 flow condenser equipped with a water receiver was attached to the flask, and 70.5 g of xylene was added thereto, and the solution was heated to 180 ° C while being blown with nitrogen gas for 5 hours, and the second solution was mixed with water. Azeotropic removal, the obtained polyamidene resin (PI-1) was obtained. The GPC measurement of (PI_1) was carried out, and the result was Mw = 21,000 in terms of polystyrene. Further, the Tg of (pi_i) was 55 ° C. The obtained polyimine varnish was purified three times with pure water, and dried by heating in a vacuum oven at 60 ° C for 3 days to obtain a solid polyimide. Things. (PI-2) In a 500 ml flask equipped with a stirrer, a thermometer, and a nitrogen gas replacement device (nitrogen inflow pipe), a polyoxypropylene diamine (trade name "D-2000" (molecular weight: about 2000), BASF as a diamine. Manufactured) 140 g (0.〇7 mol) and U,3,3,methyl...first 3 aminopropyl) dioxin (trade name "BY16_871EG", manufactured by Toray Dow Corning Co., Ltd.) 3.72 g ( In 0.015 m〇l), 〇DpA31 〇g (〇] m〇1) was added in small portions to the solution in the flask. After the addition was completed, the mixture was stirred at room temperature for 5 hours. The neon was heated with a water-receiving reflux condenser, and the solution was heated to 18 Torr while blowing nitrogen gas. 〇, heat is kept for 5 hours to remove water' to obtain a liquid polyimine resin (ρΙ_2). The GPC measurement of (Η.) was carried out, and the result was a weight average molecular weight (Mw) in terms of polystyrene. Moreover, the trick of (ρι_2) is to catch the following. <Preparation of Adhesive Composition> The composition ratios shown in the following Tables i to 3 were used by using the polyimine resin (H- and Polyimine resin (H-2) obtained above. (Unit: 72 201130942 parts by mass) The ingredients of each of the ingredients 'obtained to obtain the adhesive composition of the actual m to the case 18 and the adhesive composition of the (four) 1 to the ratio (4) 4 (the composition for forming the adhesive layer) are shown in Table 1 to Table 3. In the following, each symbol indicates the following: M-140: Manufactured by Toagosei Co., Ltd., 2-(1,2-cyclohexylcarboxyimine)ethyl acrylate (monofunctional acrylate containing sulfimine group, 5% by weight) Loss temperature: 200 ° C, viscosity at 25 ° C: 450 mPa.s) AMP-20GY : Manufactured by Xinzhongcun Chemical Industry Co., Ltd., phenoxy diethylene glycol acrylate (monofunctional acrylate, 5% weight loss) Temperature: 175 C, viscosity at 25 C: 16 mPa.s) 702A: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., 2-hydroxyl_3_phenoxypropyl acrylate (monofunctional acrylate containing hydroxyl group, 5% by weight Loss temperature: 175 ° C, viscosity: 160 mPa.s). 401P: manufactured by Xinzhongcun Chemical Industry Co., Ltd., o-phenylphenol shrinkage Glycidyl ether acrylate (hydroxyl-containing monofunctional acrylate, 5% weight loss temperature: 160 C, viscosity: 10000 mPa·s) HOA-MPE: manufactured by Kyoeisha Chemical Co., Ltd., 2-mercaptopropenyloxy Ethyl-2-ethyl-phthalic acid (monofunctional acrylate containing a thiol group, 5% weight loss temperature: 175 ° C, viscosity · 1200 mPa·s) HO-MPP: Kyoeisha Chemical Manufactured, phthalic acid 2-mercaptopropenyloxyethyl 2-propyl propyl ester (containing mono-functional acrylate, 5% weight loss temperature: 175 ° C, viscosity: 1 〇 〇〇mPa's). PQMA. Manufactured by Showa Molecular Co., Ltd., 4-methylphenyl methacrylate (monofunctional acrylate containing hydroxyl group, 5% weight loss temperature: > 73 201130942 260 ° C A-BPE4: ethoxylated bisphenol A type acrylate manufactured by Xinzhongcun Chemical Industry Co., Ltd. (2-functional acrylate, 5% weight loss temperature: 330 ° C, viscosity at 25 ° C: 980 mPa, s) 1-651 : CibaJapanK.K. Manufacture, 2,2-dimethoxy-1,2-diphenylethane-1-one (5% weight loss temperature: 170 ° C, i-line absorption coefficient : 400 ml/gcm) I-379EG : Manufactured by Ciba Japan KK, 2-dimethylamino-2-(4-indolyl-benzyl)-1-(4-infrared-4-yl-benzene Base) - Ding Shao-1·•嗣 (5% weight loss temperature: 260 ° C, i-line absorption coefficient: 8000 ml/gcm). 1-907 : 2-mercapto-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one manufactured by Ciba Japan KK (5% weight loss temperature: 220 ° C, Molecular absorption coefficient at 365 nm · · 450 ml / g. cm). I-OXE02 : manufactured by Ciba Japan KK, ethyl ketone, 1-[9-ethyl-6-(2-mercaptophenyl)-9H-indazol-3-yl]-, 1-(o-ethylidene)肟), (5% weight loss temperature: 370 ° C, molecular absorption coefficient at 365 nm: 7700 ml / g-cm). YDF-8170C: bisphenol F type double-shrinkage glycerol ether manufactured by Dongdu Chemical Co., Ltd. (5% weight loss temperature: 270 ° C, viscosity at 25 ° C: 1300 mPa·s). 630LSD: Made by Japan Epoxy Resin Co., Ltd., glycidylamine amine epoxy resin (5% weight loss temperature · · 240 ° C, viscosity at 25 ° C: 600 mPa.s). 1032H60: Japan Epoxy Resin Co., Ltd., three (hydroxy 74 201130942 base) calcined solid epoxy resin (5% weight loss temperature: 35 ° C, solid, melting point 60 ° C;). 2PHZ-PW ··2-Phenyl-4,5-dihydroxyindolizole (average particle size: about 3 μηη) manufactured by Shikoku Chemicals Co., Ltd. 1Β2ΡΖ: Made by Shikoku Chemicals Co., Ltd., benzyl-2-phenylimidazole.

Percumyl D :曰油公司製造、過氧化二異丙苯（1分 鐘半衰期溫度：175。(：）。 乃 <含有醯亞胺基之單官能丙烯酸酯A-1之合成> 於300 L可分離式燒瓶中加入5_降冰片烯_2,3_二甲酸 酐（日立化成工業股份有限公司製造、商品名：納迪克峻 酐）100 g與曱笨130 g，設置攪拌機、氮氣導入管、滴液 漏斗、溫度計。以40 ml/min於其中導入氮氣，一面攪掉 一面使用滴液漏斗滴加單乙醇胺38.4 g。滴加結束後，將 滴液漏斗替換為Dean-Stark水分定量器而開始加溫，以使 液溫成為100°C之方式回流3小時。 上述反應後，放入曱基丙烯酸乙酯91·5 g、作為聚合 抑制劑之對甲氧基苯酚0.088 g而設置精餾塔，一面以二 ml/min導入氮氣一面將液温調節為75。〇，除去系統内之水 分。確認系統内之水分為300 ppm以下後，放入作為觸媒 之四異丙醇鈦0.8 g’將反應溫度控制為9(rc。對反應液進 行加熱回流，使生成之乙醇與曱基丙烯酸乙酯以及曱笨於 75°C共沸4小時。 、 對反應液進行氣相層析分析，於酯轉換率成為99%時 結束反應。繼而，添加17質量％食鹽水1 g而使觸媒（四 75 201130942 異丙醇妖）水解。靜置15分鐘後，藉由 將有機層取人以形燒瓶中，使倾轉蒸 去過剩之曱基丙稀酸乙醋以及甲苯 ^ L ^ 形燒沲“、、後猎由抽濾過濾茄Percumyl D: Dicumyl peroxide manufactured by Oyster Oil Co., Ltd. (1 minute half-life temperature: 175. (:). It is <Synthesis of monofunctional acrylate A-1 containing quinone imine> at 300 L In a separate flask, 5_norbornene-2,3-dicarboxylic anhydride (manufactured by Hitachi Chemical Co., Ltd., trade name: Nadickic anhydride) 100 g and 130 g of hydrazine were added, and a stirrer, a nitrogen introduction tube, and the like were placed. A dropping funnel and a thermometer were introduced, and nitrogen gas was introduced thereinto at 40 ml/min, and 38.4 g of monoethanolamine was added dropwise using a dropping funnel. After the dropwise addition, the dropping funnel was replaced with a Dean-Stark moisture meter. The mixture was heated to reflux for 3 hours so that the liquid temperature became 100 ° C. After the above reaction, a rectification column was set by adding 91. 5 g of ethyl methacrylate and 0.088 g of p-methoxyphenol as a polymerization inhibitor. While introducing nitrogen gas at two ml/min, the liquid temperature was adjusted to 75. 〇, the moisture in the system was removed. After confirming that the moisture in the system was 300 ppm or less, the titanium tetraisopropoxide 0.8 g as a catalyst was placed. Control the reaction temperature to 9 (rc. Add the reaction solution The mixture was heated to reflux, and the resulting ethanol was azeotroped with ethyl methacrylate and hydrazine at 75 ° C for 4 hours. The reaction solution was subjected to gas chromatography analysis, and the reaction was terminated when the ester conversion rate became 99%. 17 g of salt water 1 g was used to hydrolyze the catalyst (four 75 201130942 isopropyl alcohol demon). After standing for 15 minutes, the organic layer was taken into a flask to allow the distillate to distill off excess thiol Dilute acid vinegar and toluene ^ L ^ shape burning 沲 ", after hunting by suction filtration filter

14 J 990/0 η 貝失溫度為赋’於抑之黏度為屬 儀熱示差同步分析 NanoTechnology Inc.製造、 口 m「ir)T=匕於升溫速度為⑽咖、氮氣流°_ ml/min )下對樣σσ進行測定。 轉黏二了二咖型旋 。〇進行測定。巧.4mL 3圓錐之條件下，於25 76 201130942 J-a0s9e 【Id |實例9 1 1 1 1 1 1 g 1 1 ΠΊ 1 1 1 1 1 1—Η 1 t 1200 1200 實例8 1 1 1 1 g 1 1 I ΓΟ 1 1 1 1 宕 1 r-H 1 1 ϊ-Η 〇 500 in 實例7 1 1 1 § 1 1 t 1 m 1 1 1 1 1 r—Η 1 1 10000 iT) yr) 8000 沄 實例6 〇 〇〇 1 1 1 1 1 1 1 1 m 1 1 1 1 ί-Η 1 1 450 § 600 實例5 〇 〇〇 1 1 1 1 1 1 1 cn 1 1 1 1 1 Η ι—Η 1 1 450 § 600 實例4 1 1 1 1 1 1 CO 1 1 1 1 1 1 1 1 450 s 600 實例3 〇 〇〇 1 1 1 1 1 i 1 cn 1 1 1 1 1 Η 1 1 450 s 1200 o 實例2 〇 00 1 1 1 1 1 t 1 m 1 幽 1 1 1 τ-Η 1 450 s 3200 in (N 實例1 g 1 1 1 1 1 1 1 m 1 1 1 1 1 1 450 § 4500 Μ-140 A-1 AMP-20GY 401P 702A HOA-MPE HO-MPP 1-651 I-379EG 1-907 I-OXE02 YDF-8170C 630LSD 1032H60 2PHZ-PW 1Β2ΡΖ Percumyl D PI-1 PI-2 (A)成分之黏度（mPa-s) (A)成分聚合物之Tg (°c) 黏著劑組成物之黏度（mPa‘s) 膜厚（μιη) (Α)放射線聚合性化合 物 (B)光起始劑 (C)熱硬化性樹脂 硬化劑 (D)熱自由基產生劑 (E)熱塑性樹脂 201130942 j-bh?99£ Ο m <3000 1 <ί 260 〇 ο m <3000 C 1 260 1 〇 ο ο m <3000 C _240 1 〇 d in 1-Η ο ro <3000 C 260 ο 1-Η Ο τ-Μ <3000 C 260 CN 1 >200 I <3000 < 240 Τ-Η Ο 1 <3000 1 280 ^Τ) CN ιη r—H Ο ΓΟ <3000 < 260 1 〇〇 τ-Η ο ΓΟ <3000 C 260 τ-Η 光照射後之黏性（gf) 於空氣下進行光照射後之黏性（gf) 最低溶融黏度（Pa-s) 熱壓接性 光照射後之5%重量損失溫度（°C ) 260°C黏著強度（MPa) 20113094214 J 990/0 η 失 失 失 为 于 于 于 于 于 于 于 于 属 属 属 属 属 属 N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N The sample σσ is measured. The viscous squeezing squeezing squeezing sputum. The sputum is measured. In the condition of 4 mL 3 cone, at 25 76 201130942 J-a0s9e [Id | Example 9 1 1 1 1 1 1 g 1 1 ΠΊ 1 1 1 1 1 1—Η 1 t 1200 1200 Example 8 1 1 1 1 g 1 1 I ΓΟ 1 1 1 1 宕1 rH 1 1 ϊ-Η 〇500 in Example 7 1 1 1 § 1 1 t 1 m 1 1 1 1 1 r—Η 1 1 10000 iT) yr) 8000 沄Example 6 〇〇〇1 1 1 1 1 1 1 1 m 1 1 1 1 ί-Η 1 1 450 § 600 Example 5 〇〇〇1 1 1 1 1 1 1 cn 1 1 1 1 1 Η ι—Η 1 1 450 § 600 Example 4 1 1 1 1 1 1 CO 1 1 1 1 1 1 1 1 450 s 600 Example 3 〇〇〇1 1 1 1 1 i 1 cn 1 1 1 1 1 Η 1 1 450 s 1200 o Example 2 〇00 1 1 1 1 1 t 1 m 1 幽1 1 1 τ-Η 1 450 s 3200 in (N Example 1 g 1 1 1 1 1 1 1 m 1 1 1 1 1 1 450 § 4500 Μ-140 A-1 AMP-20GY 401P 702A HOA-MPE HO-MPP 1-651 I-379EG 1-907 I-OXE02 YDF- 8170C 630LSD 1032H60 2PHZ-PW 1Β2ΡΖ Percumyl D PI-1 PI-2 (A) Viscosity (mPa-s) (A) Component Tg (°c) Adhesive Composition Viscosity (mPa's) Membrane Thick (μιη) (Α) Radiation Polymerizable Compound (B) Photoinitiator (C) Thermosetting Resin Hardener (D) Thermal Radical Producer (E) Thermoplastic Resin 201130942 j-bh?99£ Ο m &lt 3000 1 < ί 260 〇ο m <3000 C 1 260 1 〇ο ο m <3000 C _240 1 〇d in 1-Η ο ro <3000 C 260 ο 1-Η Ο τ-Μ < 3000 C 260 CN 1 >200 I <3000 < 240 Τ-Η Ο 1 <3000 1 280 ^Τ) CN ιη r-H Ο ΓΟ <3000 < 260 1 〇〇τ-Η ο ΓΟ &lt ; 3000 C 260 τ-Η Viscosity after light irradiation (gf) Viscosity after light irradiation in air (gf) Minimum melt viscosity (Pa-s) 5% weight loss temperature after thermocompression light irradiation (°C) 260°C adhesion strength (MPa) 201130942

Juo寸9汔Juo inch 9汔

SI 實例18 〇 1 〇 1 1 1 1 1 I ΓΟ 1 1 t 1 Ο I (Ν 200 Ο 850 卜 實例17 § 1 1 1 1 1 1 1 m 1 1 1 1 1 300 ο in 650 o 實例16 〇 〇〇 1 1 1 1 1 1 1 1 cn 1 1 1 I 1 r—Η Η 450 s 550 in 宕 實例15 g 1 1 1 1 1 1 1 1 m 1 1 1 1 1 450 s 650 o 實例14 g 1 1 1 1 1 1 1 1 1 1 〇 t 1 1 Η Η 450 s 700 o 實例13 § 1 1 1 1 1 1 1 1 1 1 ro 1 1 1 »—Η τ-Η 450 s 650 o 實例12 1 1 1 1 1 1 g 1 1 m 1 1 1 1 1 r-H Η 1000 o 1000 o o 實例11 1 1 § 1 幽 1 1 1 m 1 1 1 1 Ο 1 CN 1-^ Ο τ—Η in (N 500 yr) 100 實例10 1 § 1 1 1 1 1 $ 1 m 1 1 1 1 1 τ-Η 1200 g 1300 in o Μ-140 A-1 AMP-20GY 401P 702A HOA-MPE HO-MPP PQMA 1-651 I-379EG 1-907 I-OXE02 YDF-8170C 630LSD 1032Η60 2PHZ-PW 1Β2ΡΖ Percumyl D (Α)成分之黏度（mPa_s) (A)成分聚合物之Tg (°C) 黏著劑組成物之黏度（mPa-s) 膜厚（μηι) 光照射後之黏性（gf) (Α)放射線聚合性化合 物 (B)光起始劑 (C)熱硬化性樹脂 硬化劑 (D)熱自由基產生劑 201130942 J-a0s9e <3000 < 260 (N cn <3000 < 280 ri I <3000 1 < 240 I <3000 1 < 260 Os Ο <3000 < 250 t> ο <3000 < 260 1-H | <3000 I < 1 Ο 1 >200 1 <3000 < | 240 I Ο τ-Η | <3000 | < 270 ν〇 r-H 於空氣下進行光照射後之黏性（gf) 最低熔融黏度（Pa-s) 熱壓接性 光照射後之5%重量損失溫度（°C) 260°C黏著強度（MPa) 201130942 J-a0s9e 比較例4 1 § 1 m 1 1 1000 〇 >30000 U >300 剝離 比較例3 g 1 1 m 1 1 1 1 500 Ο ι-Η 0 <3000 <ί 260 <0.2 比較例2 1 1 1 ro τ-Η 1 1 Ο 12000 Ο cn >200 >200 <3000 <ί 260 cn 比較例1 1 1 CO 1—Η 1 1 * 1 * 1 * 1 * 1 * 1 * I * 1 * 1 Μ-140 A-BPE4 0 P-. I-379EG YDF-8170C 1B2PZ Percumyl D PI-1 PI-2 黏著劑組成物之黏度（mPa-s) 膜厚（μιη) 光照射後之黏性（gf) 於空氣下進行光照射後之黏性（gf) 最低溶融黏度（Pa-s) 熱壓接性 光照射後之5%重量損失溫度（°C ) 260°C黏著強度（MPa) (Α)放射線聚合性化合物 (Β)光起始劑 (C)熱硬化性樹脂 硬化劑 (D)熱自由基產生劑 (E)熱塑性樹脂 s 100 201130942 關於上述所得之黏著劑組成物，依照下述方法評價點 度、（A)成分聚合物之Tg、膜厚、光照射後之黏性、於 空氣下進行光照射後之黏性、最低熔融黏度、熱壓接性、 光照射後之5%重量損失溫度、以及26〇。〇黏著強度。 < (A)成分之黏度以及黏著劑組成物之黏度> 使用東京計器製造所製造之EHD型旋轉黏度計，於 樣品量為0.4mL、3。圓錐之條件下測定25°C之黏度。 < (A)成分聚合物之Tg> 對藉由如下方式所得之積層體，使用黏彈性測定裴置 (Rheometric Scienetific F.E. Ltd.製造、商品名：ARES) 測定-50°C〜200°C之tan3峰值溫度，求出（A)成分之聚 合物之Tg :將於（A)成分中以組成物總量基準計成為3 質量％之比例溶解有I-379EG ( Ciba Japan K.K.製造）的组 成物塗佈於PET (聚對苯二甲酸乙二酯）薄膜上以使祺厚 成為30 μιη，藉由高精度平行曝光機（ MANUFACTURING Co·，LTD.製造、商品名. EXM-1172-B-co)以l〇〇〇mj/cm2對該塗膜進行曝光 得之薄膜進行積層以使膜厚成為15〇 μιη而獲得 體。另外，測定板錢直徑為8mm之平行板， 為·升溫速度5°C/min、測定溫度_5〇t 〜2〇〇t、頻讨 <臈厚> 、WZ。 “藉由旋塗（200〇rpm/l〇s、進而侧rpm/2〇 者劑組成物塗佈於秒晶®上’於所得之塗膜上層壓' 脫模處理之PET薄膜，藉由高精度平行曝光機（〇丁^ 82 201130942t MANUFACTURING Co” LTD.製造、「EXM-1172-B-oo」（商 品名））以1000 mJ/cm2進行曝光。其後，使用表面粗糙度 測定器（小阪研究所製造）測定黏著劑層之厚度。 <光照射後之黏性（表面黏著力）>SI Example 18 〇1 〇1 1 1 1 1 I ΓΟ 1 1 t 1 Ο I (Ν 200 Ο 850 卜 Example 17 § 1 1 1 1 1 1 1 m 1 1 1 1 1 300 ο in 650 o Example 16 〇〇 〇1 1 1 1 1 1 1 1 cn 1 1 1 I 1 r—Η Η 450 s 550 in 宕Example 15 g 1 1 1 1 1 1 1 1 m 1 1 1 1 1 450 s 650 o Example 14 g 1 1 1 1 1 1 1 1 1 1 〇t 1 1 Η Η 450 s 700 o Example 13 § 1 1 1 1 1 1 1 1 1 1 ro 1 1 1 »—Η τ-Η 450 s 650 o Example 12 1 1 1 1 1 1 g 1 1 m 1 1 1 1 1 rH Η 1000 o 1000 oo Example 11 1 1 § 1 幽1 1 1 m 1 1 1 1 Ο 1 CN 1-^ Ο τ—Η in (N 500 yr) 100 Example 10 1 § 1 1 1 1 1 $ 1 m 1 1 1 1 1 τ-Η 1200 g 1300 in o Μ-140 A-1 AMP-20GY 401P 702A HOA-MPE HO-MPP PQMA 1-651 I-379EG 1 -907 I-OXE02 YDF-8170C 630LSD 1032Η60 2PHZ-PW 1Β2ΡΖ Percumyl D (Α) Component Viscosity (mPa_s) (A) Component Polymer Tg (°C) Adhesive Composition Viscosity (mPa-s) Film Thickness (μηι) Viscosity after light irradiation (gf) (Α) Radiation polymerizable compound (B) Photoinitiator (C) Thermosetting resin hardener (D) Thermal radical generator 20113094 2 J-a0s9e <3000 < 260 (N cn <3000 < 280 ri I < 3000 1 < 240 I < 3000 1 < 260 Os Ο <3000 < 250 t> ο <3000 < 260 1-H | < 3000 I < 1 Ο 1 >200 1 <3000 < | 240 I Ο τ-Η | <3000 | < 270 ν〇rH After light irradiation in air Viscosity (gf) Minimum Melt Viscosity (Pa-s) 5% Weight Loss Temperature after Thermocompression Light Irradiation (°C) 260°C Adhesion Strength (MPa) 201130942 J-a0s9e Comparative Example 4 1 § 1 m 1 1 1000 〇>30000 U >300 Peeling Comparative Example 3 g 1 1 m 1 1 1 1 500 Ο ι-Η 0 <3000 < ί 260 <0.2 Comparative Example 2 1 1 1 ro τ-Η 1 1 Ο 12000 Ο cn >200 >200 <3000 < ί 260 cn Comparative Example 1 1 1 CO 1—Η 1 1 * 1 * 1 * 1 * 1 * 1 * I * 1 * 1 Μ-140 A -BPE4 0 P-. I-379EG YDF-8170C 1B2PZ Percumyl D PI-1 PI-2 Adhesive composition viscosity (mPa-s) Film thickness (μιη) Viscosity after light irradiation (gf) under air Viscosity after light irradiation (gf) Minimum melt viscosity (Pa-s) 5% weight loss temperature after thermocompression light irradiation (°C) 260°C Adhesive strength (MPa) (Α) Radiation polymerizable compound (Β) Photoinitiator (C) Thermosetting resin hardener (D) Thermal radical generator (E) Thermoplastic resin s 100 201130942 The adhesive composition obtained above was evaluated for the degree, the Tg of the (A) component polymer, the film thickness, the viscosity after light irradiation, the viscosity after light irradiation under air, and the lowest melting. Viscosity, thermocompression bonding, 5% weight loss temperature after light irradiation, and 26 〇. 〇 Adhesive strength. <Viscosity of the component (A) and viscosity of the adhesive composition> An EHD type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used, and the sample amount was 0.4 mL and 3. The viscosity at 25 ° C was measured under the conditions of a cone. <Tg of the polymer of the component (A)> The layered body obtained as follows was measured using a viscoelasticity measuring device (manufactured by Rheometric Scienetific FE Ltd., trade name: ARES) at -50 ° C to 200 ° C. The Tg of the polymer of the component (A) is determined by the peak temperature of tan3, and the composition of I-379EG (manufactured by Ciba Japan KK) is dissolved in a ratio of 3% by mass based on the total amount of the component (A). Coated on a PET (polyethylene terephthalate) film to have a thickness of 30 μm, manufactured by MANUFACTURING Co., LTD., trade name. EXM-1172-B-co The film obtained by exposing the coating film at 10 μm/cm 2 was laminated to have a film thickness of 15 μm to obtain a body. Further, a parallel plate having a plate diameter of 8 mm was measured, and the temperature rise rate was 5 ° C/min, the measurement temperature was _5 〇 t 〜 2 〇〇 t, and the frequency was < 臈 & 、 and WZ. "Laminating the PET film by spin coating (200 rpm / l 〇 s, and then side rpm / 2 〇 涂布 涂布 ' 秒 秒 秒 秒 秒 秒 秒 秒 秒 秒 秒 秒 秒 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 秒 秒 秒The precision parallel exposure machine (manufactured by Kenting ^ 82 201130942t MANUFACTURING Co" LTD., "EXM-1172-B-oo" (trade name) was exposed at 1000 mJ/cm2. Thereafter, the surface roughness measuring device (Kosaka) was used. Manufactured by the Institute) The thickness of the adhesive layer was measured. <Viscosity after light irradiation (surface adhesion)>

藉由旋塗（2000 rpWlO s、進而4000 rpm/20 s)將黏 著劑組成物塗佈於石夕晶圓上，於所得之塗膜上層壓進行了 脫模處理之PET薄膜，藉由高精度平行曝光機（〇RC MANUFACTURING Co” LTD.製造、「EXM-1172-B-oo」（商 品名）、強度：13 mW/cm2)以1000 mJ/cm2進行曝光。其 後’對於30°C之表面黏著強度，使用RHESCA Corporation 製造之探針式黏性試驗機’藉由探針直徑：5.1 mm、剝離 速度：10 mm/s、接觸荷重：1〇〇 gf/cm2、接觸時間：1 s， 測定5次30°C之黏著力，算出其平均值。 <於空氣下進行光照射後之黏性（表面黏著力）> 藉由旋塗（2000 rpm/10 s、進而 4000 rpm/20 s )將點 著劑組成物塗佈於矽晶圓上。於室溫空氣下藉由高精度平 行曝光機（ORC MANUFACTURING Co.，LTD.製造、 「丑1]^-1172-；6-〇〇」（商品名））以1〇〇〇111：1/〇1112對所得之塗 膜進行曝光。其後’使用RHESCA Corporation製造之探針 式黏性试驗機’藉由探針直徑：5.1 mm、剝離速度： mrn/s、接觸荷重：1〇〇 gf/cm2、接觸時間：1 s，測定5次 於30°C之黏著劑層表面之黏著強度，算出其平均值。 <最低熔融黏度> 將黏著劑組成物塗佈於PET薄膜上以使膜厚成為5〇 83The adhesive composition was applied to the Shixi wafer by spin coating (2000 rpW10 s, and further 4000 rpm/20 s), and the release film was laminated on the obtained coating film with high precision. The parallel exposure machine (manufactured by 〇RC MANUFACTURING Co" LTD., "EXM-1172-B-oo" (trade name), strength: 13 mW/cm2) was exposed at 1000 mJ/cm2. Thereafter, for the surface adhesion strength at 30 ° C, a probe type viscosity tester manufactured by RHESCA Corporation was used' by probe diameter: 5.1 mm, peeling speed: 10 mm/s, contact load: 1 〇〇 gf / Cm2, contact time: 1 s, the adhesion of 30 times 30 ° C was measured, and the average value was calculated. <Adhesiveness after surface light irradiation in air (surface adhesion)> The coating composition was applied onto a tantalum wafer by spin coating (2000 rpm/10 s, and further 4000 rpm/20 s) . By high-precision parallel exposure machine (manufactured by ORC MANUFACTURING Co., LTD., "Ugly 1]^-1172-; 6-〇〇" (trade name)) at room temperature under air at 1〇〇〇111:1/ The resulting coating film was exposed to 〇1112. Thereafter, 'Probe-type viscometric tester manufactured by RHESCA Corporation' was used to measure by probe diameter: 5.1 mm, peeling speed: mrn/s, contact load: 1〇〇gf/cm2, contact time: 1 s. The average value of the adhesion strength of the surface of the adhesive layer at 30 ° C was calculated five times. <Minimum melt viscosity> The adhesive composition was applied onto a PET film to have a film thickness of 5 〇 83

201130942 _ L201130942 _ L

μιη。於室溫空氣下藉由高精度平行曝光機（〇RC MANUFACTURING Co” LTD.製造、「EXM-1172-B-oo」（商 品名））以1000 mJ/cm2對所得之塗膜進行曝光。將所得之 黏著片於鐵氟龍（註冊商標）薄板上，使黏著劑層為鐵氟 龍（註冊商標）薄板側而藉由輥（溫度6〇。〇、線壓4kgf/cm、 進給速度0.5 m/min)進行加壓，進行積層以使厚度成為約 200 μιη。使用黏彈性測定裝置（Rheometric Scienetific F.E. Ltd.製造、商品名：ARES)測定所得之樣品。測定板為直 徑25 111111之平行板，測定條件設定為升溫1〇。(：/1^11、頻率 1 Hz。將於20°C〜200°C之熔融黏度之最低值作為最低熔 融黏度。 <熱壓接性> 藉由旋塗（2000 rpm/l〇 s、進而 4000 rpm/20 s)將黏 著劑組成物塗佈於石夕晶圓上。於所得之塗膜上層壓進行了 脫模處理之PET薄膜，藉由高精度平行曝光機（〇Rc MANUFACTURING Co.，LTD.製造、「EXM-1172-B_〇〇」（商 品名））以1000 mJ/cm2進行曝光後，切出石夕晶圓使其為3 mm><3 mm見方。將切出之附有黏著劑之矽晶片置於預先 切出為5 mmx5 mm見方之矽晶片上，一面以2〇〇 gf進行 加壓一面於120°C進行2秒之壓接。關於所得之樣品，使 用剪切黏著力試驗機「Dage-4000」（商品名）而測定於室 溫下之剪切黏著力’將1 MPa以上者記為「a」，將低於1 MPa者記為「C」。 <光照射後之5%重量損失溫度> 84 201130942 藉由旋塗（2000 rpm/10 s、進而 4〇〇〇 rpm/20 s)將黏 著劑組成物塗佈於矽晶圓上。於所得之塗膜上層壓進行了 脫模處理之PET薄膜，藉由高精度平行曝光機（〇RC MANUFACTURING Co., LTD.製造、「EXM-1172-B-oo」（商 品名））以1000mJ/cm2進行曝光。其後，對於所得之黏著 劑’使用熱重/熱示差同步分析儀（SII NanoTechnology Inc. 製造、商品名「TG/DTA6300」），於升溫速度i〇°c/min、 氮氣流（400ml/min)下測定5%重量損失溫度。 <260°C黏著強度（剪切黏著強度）> 藉由旋塗（2000 rpm/10 s、進而 4000 rpm/20 s)將黏Ιιη. The obtained coating film was exposed at 1000 mJ/cm 2 by a high-precision parallel exposure machine (manufactured by 〇RC MANUFACTURING Co. LTD., "EXM-1172-B-oo" (trade name)) at room temperature under air. The obtained adhesive sheet was placed on a Teflon (registered trademark) sheet so that the adhesive layer was on the side of the Teflon (registered trademark) sheet and the roller was used (temperature 6 〇. 线, line pressure 4 kgf/cm, feed rate) Pressurization was carried out at 0.5 m/min, and lamination was carried out so that the thickness became about 200 μm. The obtained sample was measured using a viscoelasticity measuring apparatus (manufactured by Rheometric Scienetific F. E. Ltd., trade name: ARES). The measuring plate was a parallel plate having a diameter of 25 111111, and the measurement conditions were set to a temperature rise of 1 Torr. (:/1^11, frequency 1 Hz. The lowest value of the melt viscosity from 20 ° C to 200 ° C is taken as the lowest melt viscosity. <Hot compression bonding> by spin coating (2000 rpm/l〇s And further, the adhesive composition was applied to the Shixi wafer at 4000 rpm/20 s. The PET film which was subjected to release treatment was laminated on the obtained coating film by a high-precision parallel exposure machine (〇Rc MANUFACTURING Co ., LTD., "EXM-1172-B_〇〇" (trade name)), after exposure at 1000 mJ/cm2, cut out the Shihwa wafer to 3 mm><3 mm square. The wafer with the adhesive attached thereto was placed on a wafer of 5 mm x 5 mm square, which was pre-cut, and pressed at 2 ° gf for 2 seconds at 120 ° C. For the obtained sample, use The shear adhesion tester "Dage-4000" (trade name) was measured and the shear adhesion at room temperature was measured as "a" for those above 1 MPa, and "C" for those below 1 MPa. <5% weight loss temperature after light irradiation> 84 201130942 The adhesive composition was applied to twin crystal by spin coating (2000 rpm/10 s, and further 4 rpm/20 s) The PET film which was subjected to release treatment was laminated on the obtained coating film by a high-precision parallel exposure machine (manufactured by 〇RC MANUFACTURING Co., LTD., "EXM-1172-B-oo" (trade name)) Exposure was performed at 1000 mJ/cm 2 . Thereafter, a thermogravimetric/thermal differential synchronization analyzer (manufactured by SII NanoTechnology Inc., trade name "TG/DTA6300") was used for the obtained adhesive, at a temperature increase rate i 〇 ° c / min 5% weight loss temperature was measured under a nitrogen stream (400 ml/min). <260 ° C Adhesion Strength (Shear Adhesion Strength)> By spin coating (2000 rpm/10 s, and thus 4000 rpm/20 s) sticky

著劑組成物塗佈於石夕晶圓上。於所得之塗膜上層壓進行了 脫模處理之PET薄膜，藉由高精度平行曝光機（〇RC MANUFACTURING Co·，LTD.製造、「EXM_1172-B-〇〇」（商 品名））以ioo〇mj/cm2進行曝光後，切出矽晶圓使其為3 mmx3 mm見方。將切出之附有黏著劑之矽晶片置於預先 切出為5 mmx5 mm見方之珍晶片上，一面以⑽gf進行 加壓一面於120°C進行2秒之壓接。其後，於烘箱中以14〇它 加熱1小時，繼而以18〇〇c加熱3小時而獲得黏著樣品。 關於所得之樣品，使用剪切黏著力試驗機「Dage_4〇〇〇」 品名）而測定於26Gd_著力。將其作 著The composition of the coating is applied to the Shi Xi wafer. A PET film which has been subjected to release treatment is laminated on the obtained coating film, and is manufactured by a high-precision parallel exposure machine (manufactured by 〇RC MANUFACTURING Co., LTD., "EXM_1172-B-〇〇" (trade name)). After exposure to mj/cm2, the germanium wafer was cut to a 3 mm x 3 mm square. The cut wafer with the adhesive attached was placed on a wafer of 5 mm x 5 mm square which was previously cut out, and pressed at 120 ° C for 2 seconds while being pressurized with (10) gf. Thereafter, it was heated in an oven at 14 Torr for 1 hour, and then heated at 18 ° C for 3 hours to obtain an adhesive sample. The obtained sample was measured at 26 Gd_ using a shear adhesion tester "Dage_4" (product name). Make it

強度之值。 I 【圖式簡單說明】 圖 形態賴=糊之半魏謂_之一實施 85 201130942 圖2是表示本發明之半導體裝置的製造方法之貫施 形態的模式圖。 圖3是表示本發明之半導體裝置的製造方法之貫施 形態的模式圖。 圖4是表示本發明之半導體裝置的製造方法之其他只 施形態的模式圖。 圖5是表示本發明之半導體裝置的製造方法之實她 形態的模式圖。 圖6是表示本發明之半導體裝置的製造万法之實訑 形態的模式圖。 + 圖7是表示本發明之半導體裝置的數益方法之貫施 形態的模式圖。 圖8是表示本發明之半導體裝置的製邊方法之貝施 形態的模式圖。 圖9是表示本發明之半導體裝之貫施 形態的模式圖。 圖1〇是表示本發明之半導體裝置的象这方法之貫 施形態的模式圖。 圖U是表示本發明之半導體裝ί的製瓜方法之實 施形態的模式圖。 圖12是表示本發明之半導體裝J：的氟这方法之貝 施形態的模式圖。 圖13是表示本發明之半導體裝置的製这方法之實 施形態的模式圖。 86 201130942. 【主要元件符號說明】 I :半導體晶圓 2:半導體晶片 4:黏著帶（背面研磨膠帶） 5 :黏著劑組成物（黏著劑層） 6:黏著帶（切割膠帶） 7:支撐部件 8 :研磨裝置 9:曝光裝置 10 :晶圓環 II :切割刀片 12 :固晶裝置 14、15 :熱盤 16 :導線 17 :密封材 18 :連接端子 20 :箱 21 :夾具 100 :半導體裝置 D :切割線 51 :半導體晶圓之電路面 52 :半導體晶圓之背面 87The value of the intensity. I. [Embodiment of the drawings] Fig. 2 is a schematic view showing a form of a method of manufacturing a semiconductor device according to the present invention. Fig. 3 is a schematic view showing a form of a method of manufacturing a semiconductor device of the present invention. Fig. 4 is a schematic view showing another embodiment of a method of manufacturing a semiconductor device of the present invention. Fig. 5 is a schematic view showing the form of the method for fabricating the semiconductor device of the present invention. Fig. 6 is a schematic view showing a state in which the semiconductor device of the present invention is manufactured. Fig. 7 is a schematic view showing a mode of the digital method of the semiconductor device of the present invention. Fig. 8 is a schematic view showing a form of a bedding method of a semiconductor device according to the present invention. Fig. 9 is a schematic view showing a state in which the semiconductor package of the present invention is applied. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a schematic view showing a configuration of a method of the semiconductor device of the present invention. Fig. U is a schematic view showing an embodiment of a method for producing a melon according to the semiconductor device of the present invention. Fig. 12 is a schematic view showing the form of the method of the fluorine in the semiconductor package J of the present invention. Fig. 13 is a schematic view showing an embodiment of the method for fabricating the semiconductor device of the present invention. 86 201130942. [Explanation of main component symbols] I : Semiconductor wafer 2: Semiconductor wafer 4: Adhesive tape (back grinding tape) 5 : Adhesive composition (adhesive layer) 6: Adhesive tape (cut tape) 7: Supporting member 8: polishing apparatus 9: exposure apparatus 10: wafer ring II: cutting blade 12: solid crystal device 14, 15: hot plate 16: wire 17: sealing material 18: connection terminal 20: case 21: jig 100: semiconductor device D : Cutting line 51: circuit surface 52 of the semiconductor wafer: back side of the semiconductor wafer 87

Claims (1)

201130942 —1 七、申請專利範圍： 賴祕_域物，其包含··⑷放射線 ί5性化&物、⑻光起始劑、以及⑻熱硬化性樹脂， 所述（Α)成分包含於坑為餘且於分子内 個石反-碳雙鍵之化合物。 /、有 ^ 1*丨♦丄θ 斗導體用㈣劑組成物於2 5 〇C為液狀且溶 劑之含量為5質量％以7^ ^狀1冷 著劑===1項或第2項所述之半導體用黏 基之單甲基I轉 =§u)成分料㈣亞胺基或經 4. 如申請專利範圍第i項至箆 ;體用卿且成物，其中，所述⑷成分之二ΐ 失溫度為150〇C以上。 里里才貝 5. 如中請專利範圍第^至第4項中任—項所 =用黏著劑組成物，其中，所述（A)成分於25 = 度為1000 mPa.s以下。 6. 如申請專利範圍第丨項至第5項中任_ 導^黏著劑組成物，其中，所述⑷成分聚 聚合物的Tg為loot：以下。 丨之 道7.如申請專利範圍第1項至第6項中任-項所述之本 :體用黏著劑組成物，其進一步含有(D)熱自由= 88 201130942 一 8.如申睛專利範圍第1項至第7項中任—項所述之半 導體用黏著劑組成物，其中’所述半導體用黏著劑組成物 於 25 C 之黏度為 1〇 mpa.s〜30000 mpa.s。 9.如申請專利範圍第1項至第8項中任—項所述之半 著劑組成物，其中，所述半導體用黏著劑組成物 ;错光照射而將由該組成物構成之黏著劑層B_階段化 時之5%重量損失溫度為150〇C以上。 半導職圍第1項至第9項巾任—項所述之 物於錢物’其中，所述半導體用黏著劑組成 =由•射㈣由該組成物構成之黏著劑層B·階段 】上進—步進行加熱硬化時之抓重量損失溫度為·。c 11. 項至第in種Λ導體装置’其具有藉由如申請專利範圍第1 半導體亓：分中任—項所述之半導體用黏著劑組成物而將 用支㈣谢彻元件搭載 種半導體裝置的製造方法，其包含： 至第；10 ^日曰圓之一個面上塗佈如申讀'專利範圍第1項 黏著劑層之步^1所叙半導縣黏著聽成物而設置 對所述黏著劑層進行光照射之步驟； 斷而===與經光照射之所述黏著劑層-同切 脸,Ιϋ有劑層之半導體元件之步驟； :附有黏著劑層之半導體元件與其他半導體元件 89 201130942, 或半導體元件搭载用支撐部件，夾著所述附有黏著劑層之 半導體元件的黏著劑層進行壓接，藉此將其黏著之步驟。 13. —種半導體裝置的製造方法，其包含： 於半導體元件上塗佈如申請專利範圍第1項至第1〇 項中任一項所述之半導體用黏著劑組成物而設置黏著劑層 之步驟； 對所述黏著劑層進行光照射之步驟； 將具有經光照射之所述黏著劑層的所述半導體元件與 其他半導體元件或半導體元件搭載用支料件，夾著經光 照射之所述黏著劑層進行壓接，藉此將其黏著之步驟。 14. 一種半導體裝置的製造方法，其包含： ★於半導體元件搭載用支撐部件上塗佈如申請專利範圍 ^ 1項至产1。項中任—項所述之半導體雜著劑組成物而 设置黏著劑層之步驟； 對所述黏著劑層進行S照射之步驟； 載用二劑層的所述半導體元件搭 層進行壓接，藉此之:經光照射之所述勒著劑201130942 —1 VII. Patent application scope: Dependent _ domain, which includes (4) radiation 55 chemical & material, (8) photoinitiator, and (8) thermosetting resin, the (Α) component is included in the pit A compound of the anti-carbon double bond of the stone in the molecule. /, ^1*丨♦丄θ The composition of the (four) agent for the bucket conductor is liquid at 25 〇C and the content of the solvent is 5% by mass in the form of 7^^1 cold refrigerant ===1 or 2nd The monomethyl I-transfer of the semiconductor for the term "§u" component (4) imine group or by 4. as claimed in the scope of item i to 箆; body use and composition, wherein (4) The second component of the component has a temperature loss of 150 〇C or more.里里贝贝 5. As claimed in paragraphs 至 to 4 of the patent scope, the adhesive composition is used, wherein the component (A) is at 25 = degrees below 1000 mPa.s. 6. The adhesive composition according to any of the above-mentioned claims, wherein the polymer of the (4) component has a Tg of loot: or less.丨之道 7. The invention as claimed in any one of claims 1 to 6 wherein the body adhesive composition further contains (D) thermal freedom = 88 201130942 - 8. The adhesive composition for a semiconductor according to any one of the preceding claims, wherein the adhesive composition for the semiconductor has a viscosity at 25 C of 1 〇 mPa.s to 30000 mpa.s. 9. The semi-drug composition according to any one of the preceding claims, wherein the semiconductor adhesive composition comprises an adhesive layer composed of the composition by stray light irradiation. The 5% weight loss temperature at the time of B_stage is 150 〇C or more. Item No. 1 to Item 9 of the semi-guided occupation is in the case of money, wherein the composition of the semiconductor adhesive is composed of: (4) the adhesive layer B consisting of the composition. The temperature at which the weight is lost during the heating and hardening step is . c 11. The item to the in-thin conductor device, which has a semiconductor semiconductor adhesive composition as described in the first patent of the patent application: The manufacturing method of the device comprises: applying a pair to the first surface of the 10th day of the round, such as applying the adhesive article of the first layer of the adhesive layer of the patent range a step of performing light irradiation on the adhesive layer; a step of breaking the === the adhesive layer irradiated with light - a face-cutting, a semiconductor component having a layer of a coating; a semiconductor component with an adhesive layer The step of adhering the other semiconductor element 89 201130942 or the support member for mounting the semiconductor element to the adhesive layer of the semiconductor element with the adhesive layer is carried out by pressure bonding. 13. A method of manufacturing a semiconductor device, comprising: applying an adhesive layer for a semiconductor according to any one of claims 1 to 1 above; a step of irradiating the adhesive layer with light; and the semiconductor element having the adhesive layer irradiated with light and the other semiconductor element or the semiconductor element mounting member are sandwiched by the light irradiation The step of bonding the adhesive layer to bond it. A method of manufacturing a semiconductor device, comprising: applying a coating member for mounting a semiconductor element to a product 1 of the patent application. The step of providing an adhesive layer for the semiconductor hybrid composition according to any one of the preceding claims; the step of irradiating the adhesive layer with S; and carrying the two component layers of the semiconductor device layer for crimping, By this: the light agent is irradiated by light
TW099138874A 2009-11-13 2010-11-11 Adhesive composition for semiconductor, semiconductor device and fabricating method thereof TW201130942A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2009260410 2009-11-13
JP2009260421 2009-11-13
JP2010138634 2010-06-17

Publications (1)

Publication Number Publication Date
TW201130942A true TW201130942A (en) 2011-09-16

Family

ID=43991655

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099138874A TW201130942A (en) 2009-11-13 2010-11-11 Adhesive composition for semiconductor, semiconductor device and fabricating method thereof

Country Status (4)

Country Link
JP (1) JP5477389B2 (en)
CN (1) CN102576681A (en)
TW (1) TW201130942A (en)
WO (1) WO2011058997A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI540659B (en) * 2011-08-11 2016-07-01 Denka Company Ltd A semiconductor block bonding apparatus, a semiconductor block bonding method, and a method of manufacturing a semiconductor wafer
JP6193663B2 (en) * 2013-07-26 2017-09-06 日東電工株式会社 Die-bonding film with dicing tape and method for manufacturing semiconductor device
JP6129696B2 (en) * 2013-09-11 2017-05-17 デクセリアルズ株式会社 Underfill material and method for manufacturing semiconductor device using the same
JP6605846B2 (en) 2015-06-03 2019-11-13 日東電工株式会社 Masking adhesive tape
EP3877449A1 (en) * 2018-11-09 2021-09-15 3M Innovative Properties Company Curable sealant compositions, seal cap, and methods of making and using the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1732408B (en) * 2002-12-28 2010-04-21 Jsr株式会社 Radiation Sensitive Resin Composition
KR101068372B1 (en) * 2005-07-05 2011-09-28 히다치 가세고교 가부시끼가이샤 Photosensitive adhesive, and the adhesive film obtained by using this, the adhesive sheet, the semiconductor wafer with an adhesive bond layer, a semiconductor device, and electronic components
JP5524465B2 (en) * 2007-10-24 2014-06-18 日立化成株式会社 Adhesive sheet, semiconductor device using the same, and manufacturing method thereof
JP5353064B2 (en) * 2008-02-19 2013-11-27 日立化成株式会社 Photosensitive adhesive composition, adhesive film obtained using the same, adhesive sheet, adhesive pattern, and semiconductor device
JP2009239190A (en) * 2008-03-28 2009-10-15 Sekisui Chem Co Ltd Dicing die-bonding tape

Also Published As

Publication number Publication date
JP5477389B2 (en) 2014-04-23
WO2011058997A1 (en) 2011-05-19
CN102576681A (en) 2012-07-11
JPWO2011058997A1 (en) 2013-04-04

Similar Documents

Publication Publication Date Title
TWI333501B (en)
TW201125948A (en) Semiconductor device and fabricating method thereof, and semiconductor wafer with adhesive layer
TWI411655B (en) A photosensitive adhesive composition, a film-like adhesive using the same, an adhesive sheet, an adhesive pattern, a semiconductor wafer with an adhesive layer, and a semiconductor device
JP5505421B2 (en) Method for manufacturing film adhesive, adhesive sheet, semiconductor device, and method for manufacturing the same
TWI473867B (en) Semiconductor device manufacturing method and semiconductor device
JP5035476B2 (en) Adhesive composition, semiconductor device using the same, and manufacturing method thereof
TW200907004A (en) Photosensitive adhesive composition, film-like adhesive, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device and semiconductor device manufacturing method
TW201639939A (en) Kit, and laminate body
JP5488001B2 (en) Method for manufacturing semiconductor chip with adhesive and method for manufacturing semiconductor device
TW201122075A (en) Liquid adhesive composition for semiconductor, semiconductor device and fabricating method thereof
JP5648514B2 (en) Photosensitive adhesive composition, adhesive pattern, semiconductor wafer with adhesive layer, and manufacturing method of semiconductor device.
TW200941548A (en) Photosensitive adhesive, semiconductor device and method for manufacturing semiconductor device
TW201130942A (en) Adhesive composition for semiconductor, semiconductor device and fabricating method thereof
TWI613517B (en) Photosensitive resin composition, film adhesive, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive layer, and semiconductor device
TW201246280A (en) Semiconductor wafer with adhesive layer, fabricating method of semiconductor device and semiconductor device
TW201250873A (en) Manufacturing method of semiconductor apparatus, manufacturing method of semiconductor wafer with semiconductor device, manufacturing method of semiconductor wafer with adhesive layer and manufacturing method of semiconductor wafer laminate
JP5092719B2 (en) Semiconductor device and manufacturing method thereof
TW201207960A (en) Fabricating method of semiconductor wafer with adhsive layer, photosensitive adhsion agent and semiconductor device
JP2009141017A (en) Semiconductor device and manufacturing method thereof
JP2011155195A (en) Method of manufacturing semiconductor chip with adhesive, and method of manufacturing semiconductor device
JP2023145374A (en) Laminate, method for manufacturing laminate, and method for manufacturing semiconductor device
JP2012238700A (en) Semiconductor wafer with adhesive layer manufacturing method, semiconductor device manufacturing method and semiconductor device