CN104798448B - Resin sheet - Google Patents

Resin sheet Download PDF

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Publication number
CN104798448B
CN104798448B CN201380060162.8A CN201380060162A CN104798448B CN 104798448 B CN104798448 B CN 104798448B CN 201380060162 A CN201380060162 A CN 201380060162A CN 104798448 B CN104798448 B CN 104798448B
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Prior art keywords
weight
mentioned
reduction rates
resin sheet
resin
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CN201380060162.8A
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CN104798448A (en
Inventor
宇圆田大介
丰田英志
鸟成刚
清水祐作
森弘幸
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4857—Multilayer substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68345—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used as a support during the manufacture of self supporting substrates
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump 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
    • H01L2224/16221—Disposition the bump 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
    • H01L2224/16225—Disposition the bump 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
    • H01L2224/16238—Disposition the bump 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 the bump connector connecting to a bonding area protruding from the surface 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
    • H01L2224/80—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
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/81001—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector involving a temporary auxiliary member not forming part of the bonding apparatus
    • H01L2224/81005—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector involving a temporary auxiliary member not forming part of the bonding apparatus being a temporary or sacrificial substrate
    • 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
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/8119—Arrangement of the bump connectors prior to mounting
    • H01L2224/81191—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed only on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49822—Multilayer substrates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

A kind of resin sheet, it is the resin sheet for forming the wired circuit board that can be connected with the electrode being formed on semiconductor chip, for the resin sheet after 180 DEG C carry out heat cure in 1 hour, the weight reduction rates after being impregnated 2400 seconds more than 20 DEG C and in less than 25 DEG C of MEK are below 1.0 weight %.

Description

Resin sheet
Technical field
The present invention relates to resin sheet.
Background technology
In recent years, in LSI mounting technique, CSP (Chip Size/Scale Package) technology attracts attention.The skill Among art, the envelope in the form of WLP (Wafer Level Package) is the only chip without using custom circuit substrate of representative Dress is one of encapsulation form that concern is particularly subject in miniaturization and highly integrated aspect.As WLP manufacture method, can enumerate The method for making the conductor part of wired circuit board corresponding with the electrode position of semiconductor chip and connecting both.
Above-mentioned wired circuit board is due to its flexible property, and the operability in the manufacturing process of chip installation etc. is not It is good.Therefore, in the past, as shown in patent document 1,2 etc., with the following method：First, formed on supporting substrates flexible Wired circuit board and be made with appropriate rigid wired circuit board, the shape of the operability in process is improved Chip installation is carried out under state, supporting substrates are removed after using the chip installation as rigid body.
Compared with only exposing the nude film of electrode pad, after chip is installed on wired circuit board and removes supporting substrates The semiconductor device of state is that possess to be easy to carry out the connection conductor with connection or the installation of external conductor (external circuit etc.) A kind of semiconductor device.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-349198 publications
Patent document 2：Japanese Unexamined Patent Publication 2001-44589 publications
The content of the invention
Problems to be solved by the invention
Above-mentioned wired circuit board can be by the base material application half formed with base insulating layer on supporting mass The known circuit substrate such as addition process, subtractive process or the manufacturing technology of interpolater are formed.However, in this method, by In the various solvents of use, thus it is expected the high solvent patience of base insulating layer.
The means used to solve the problem
Present inventors etc. are in order to solve the problems, such as above-mentioned point in the past, to the resin sheet for forming wired circuit board Studied.Its result is found, by using following compositions, it is possible to increase solvent resistance, so as to complete the present invention.
That is, resin sheet of the present invention is characterised by, is for formed can be with the electricity that is formed on semiconductor chip The resin sheet of the wired circuit board of pole connection,
The resin sheet impregnates after 180 DEG C carry out heat cure in 1 hour more than 20 DEG C and in less than 25 DEG C of MEK Weight reduction rates after 2400 seconds are below 1.0 weight %.
According to above-mentioned composition, resin sheet is after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 25 DEG C of first Weight reduction rates after being impregnated 2400 seconds in ethyl ketone are below 1.0 weight %.More than 20 DEG C and less than 25 DEG C of MEK Weight reduction rates of the middle dipping after 2400 seconds are below 1.0 weight %, it can be said that the dissolution in MEK receives Suppress.Therefore, if being suppressed using the dissolution in MEK and there is the above-mentioned resin sheet of solvent resistance, can manufacture The high wired circuit board of precision.
In above-mentioned composition, preferably after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 25 DEG C of 0.5 weight Weight reduction rates after being impregnated 60 seconds in amount % hydrofluoric acid are below 1.0 weight %.Have in the manufacture of above-mentioned wired circuit board When use sour (such as hydrofluoric acid).If impregnate 60 more than 20 DEG C and in less than 25 DEG C of 0.5 weight % hydrofluoric acid after heat cure Weight reduction rates after second are below 1.0 weight %, then also have acid resistance.If, can as a result, using above-mentioned resin sheet The higher wired circuit board of enough accuracies of manufacture.
In above-mentioned composition, preferably after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 25 DEG C of 3.0 weights The weight reduction rates after being impregnated 240 seconds in % tetramethylammonium hydroxide aqueous solution are measured as below 1.0% weight.Above-mentioned wiring electricity Sometimes alkali (such as tetramethylammonium hydroxide aqueous solution) is used in the manufacture of base board.If after heat cure more than 20 DEG C and 25 DEG C Weight reduction rates after being impregnated 240 seconds in the tetramethylammonium hydroxide aqueous solution of 3.0 following weight % for 1.0% weight with Under, then also there is alkali resistance.If, being capable of the higher wired circuit board of the accuracy of manufacture as a result, using above-mentioned resin sheet.
Brief description of the drawings
Fig. 1 is the diagrammatic cross-section of resin sheet of the present embodiment.
Fig. 2 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Fig. 3 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Fig. 4 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Fig. 5 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Fig. 6 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Fig. 7 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Fig. 8 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Fig. 9 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Figure 10 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Figure 11 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Figure 12 is the diagrammatic cross-section for being illustrated to the manufacture method of semiconductor device of the present embodiment.
Embodiment
Embodiments of the present invention are illustrated referring to the drawings, but the invention is not restricted to these examples.Fig. 1 is this implementation The diagrammatic cross-section for the resin sheet that mode is related to.It should be noted that it is unwanted to omit the description institute in this manual, in figure Part, in addition, for convenience of description, there is the part zoomed in or out etc. to be illustrated.It is it should be noted that of the invention Words and phrases above and below the expression such as middle " upper surface " used, " lower surface " are only for the position relationship for illustrating layer, do not limit wiring The posture up and down of circuit substrate or semiconductor device reality.
Resin sheet 20a is for forming the wiring that can be connected with the electrode being formed on semiconductor chip electricity (referring to Fig. 1) The resin sheet of base board.It should be noted that for forming the method for wired circuit board using resin sheet 20a, using wiring The method that circuit substrate manufactures semiconductor device, is hereinafter described in detail using Fig. 2~Figure 12.
Resin sheet 20a impregnates after 180 DEG C carry out heat cure in 1 hour more than 20 DEG C and in less than 25 DEG C of MEK Weight reduction rates after 2400 seconds are below 1.0 weight %.In MEK impregnate after above-mentioned weight reduction rates be preferably Below 0.8 weight %.In addition, in MEK impregnate after above-mentioned weight reduction rates it is preferably less, for example, 0 weight % with Upper, more than 0.01 weight %.Weight reduction rates after being impregnated 2400 seconds more than 20 DEG C and in less than 25 DEG C of MEK are Below 1.0 weight %, it can be said that the dissolution in MEK is inhibited.Therefore, if using molten in MEK Go out the resin sheet 20a being suppressed and with solvent resistance, then being capable of the high wired circuit board of the accuracy of manufacture.For above-mentioned heavy For measuring slip, by the content or the resin using high glass-transition temperature or the raising thermosetting that reduce elastomer It crosslink density after change, can decline above-mentioned weight reduction rates.
Resin sheet 20a is after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 25 DEG C of 0.5 weight % hydrogen fluorine Weight reduction rates after being impregnated 60 seconds in acid are preferably below 1.0 weight %, are more preferably below 0.8 weight %, are further excellent Elect as below 0.6 weight %.In addition, the above-mentioned weight reduction rates after being impregnated in 0.5 weight % hydrofluoric acid are preferably less, such as For more than 0 weight %, more than 0.01 weight %.Sometimes using sour (such as hydrofluoric acid) in the manufacture of wired circuit board.It is if hot Weight reduction rates after being impregnated 60 seconds more than 20 DEG C and in less than 25 DEG C of 0.5 weight % hydrofluoric acid after solidification are 1.0 weights Below % is measured, then also there is acid resistance.As a result, being capable of the higher wired circuit board of the accuracy of manufacture.Subtract for above-mentioned weight For few rate, after the content for reducing elastomer or the resin for using high glass-transition temperature or raising heat cure Crosslink density, can decline above-mentioned weight reduction rates.
Resin sheet 20a 180 DEG C carry out heat cure in 1 hour after, more than 20 DEG C and less than 25 DEG C of 3.0 weight % four Weight reduction rates after being impregnated 240 seconds in the ammonium hydroxide aqueous solution are preferably below 1.0% weight, are more preferably 0.8 weight Measure below %, more preferably below 0.6 weight %.In addition, soaked in 3.0 weight % tetramethylammonium hydroxide aqueous solution Above-mentioned weight reduction rates after stain are preferably less, for example, more than 0 weight %, more than 0.01 weight %.Wired circuit board Sometimes alkali (such as tetramethylammonium hydroxide aqueous solution) is used in manufacture.If after heat cure more than 20 DEG C and less than 25 DEG C Weight reduction rates after being impregnated 240 seconds in 3.0 weight % tetramethylammonium hydroxide aqueous solution are below 1.0% weight, then also With alkali resistance.As a result, being capable of the higher wired circuit board of the accuracy of manufacture.For above-mentioned weight reduction rates, pass through Reduce the content of elastomer or using the crosslink density after the resin of high glass-transition temperature or raising heat cure, energy Enough decline above-mentioned weight reduction rates.
Resin sheet 20a 180 DEG C carry out heat cure in 1 hour after, more than 20 DEG C and less than 80 DEG C SC-1 (form with weigh Amount is than meter, ammoniacal liquor (15 weight %)：Hydrogen peroxide：Water=1：2：5) weight reduction rates of the dipping after 100 seconds are preferably 1.0% in Below weight, it is more preferably below 0.8 weight %, more preferably below 0.6 weight %.In addition, above-mentioned weight reduction rates It is preferred that less, for example, more than 0 weight %, more than 0.01 weight %.Sometimes SC- is used in the matting of wired circuit board 1.If above-mentioned weight reduction rates are below 1.0% weight, also there is the patience to SC-1.As a result, can the accuracy of manufacture more High wired circuit board.For above-mentioned weight reduction rates, by reducing the content of elastomer or using high-vitrification Crosslink density after the resin of transition temperature or raising heat cure, can decline above-mentioned weight reduction rates.
Resin sheet 20a 180 DEG C carry out heat cure in 1 hour after, more than 20 DEG C and less than 80 DEG C SC-2 (form with weigh Amount is than meter, hydrochloric acid (38 weight %)：Hydrogen peroxide：Water=1：2：5) weight reduction rates of the dipping after 160 seconds are preferably 1.0% in Below weight, it is more preferably below 0.8 weight %, more preferably below 0.6 weight %.In addition, above-mentioned weight reduction rates It is preferred that less, for example, more than 0 weight %, more than 0.01 weight %.Sometimes SC- is used in the matting of wired circuit board 2.If above-mentioned weight reduction rates are below 1.0% weight, also there is the patience to SC-2.As a result, can the accuracy of manufacture more High wired circuit board.For above-mentioned weight reduction rates, by reducing the content of elastomer or using high-vitrification Crosslink density after the resin of transition temperature or raising heat cure, can decline above-mentioned weight reduction rates.
Resin sheet 20a 180 DEG C carry out heat cure in 1 hour after, more than 20 DEG C and less than 80 DEG C of 30 weight % mistake Weight reduction rates after being impregnated 840 seconds in hydrogen peroxide solution are preferably below 1.0% weight, more preferably below 0.8 weight %, More preferably below 0.6 weight %.In addition, above-mentioned weight reduction rates are preferably less, for example, more than 0 weight %, 0.01 More than weight %.Sometimes hydrogenperoxide steam generator is used in the manufacture of wired circuit board.If above-mentioned weight reduction rates are 1.0% weight Amount is following, then also has the patience to hydrogenperoxide steam generator.As a result, being capable of the higher wired circuit board of the accuracy of manufacture.It is right For above-mentioned weight reduction rates, by reduce elastomer content or using high glass-transition temperature resin or The crosslink density after heat cure is improved, can decline above-mentioned weight reduction rates.
Resin sheet 20a is after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 80 DEG C of degreasing solution Weight reduction rates of the dipping after 300 seconds are preferably 1.0% weight in (alkali, water solubility/water-insoluble solvent, surfactant etc.) Below, below 0.8 weight %, more preferably below 0.6 weight % are more preferably.In addition, above-mentioned weight reduction rates are preferred It is less, for example, more than 0 weight %, more than 0.01 weight %.Sometimes using degreasing solution in the manufacture of wired circuit board. If above-mentioned weight reduction rates are below 1.0% weight, also there is the patience to degreasing solution.As a result, essence can be manufactured Du Genggao wired circuit board.For above-mentioned weight reduction rates, by reducing the content of elastomer or using high glass Crosslink density after the resin of glass transition temperature or raising heat cure, can decline above-mentioned weight reduction rates.As upper Degreasing solution is stated, a day Rapid Clean P-1000 for ore deposit Metal Plating Co. Ltd. systems can be enumerated.
Resin sheet 20a 180 DEG C carry out heat cure in 1 hour after, more than 20 DEG C and less than 80 DEG C of 70 weight % nitre Weight reduction rates after being impregnated 30 seconds in aqueous acid are preferably below 1.0% weight, are more preferably below 0.8 weight %, enter One step is preferably below 0.6 weight %.In addition, above-mentioned weight reduction rates are preferably less, for example, more than 0 weight %, 0.01 weight Measure more than %.Sometimes using degreasing solution in the manufacture of wired circuit board.If above-mentioned weight reduction rates be 1.0% weight with Under, then also there is the patience to degreasing solution.As a result, being capable of the higher wired circuit board of the accuracy of manufacture.For above-mentioned For weight reduction rates, by reducing the content of elastomer or the resin or raising heat using high glass-transition temperature It crosslink density after solidification, can decline above-mentioned weight reduction rates.
Resin sheet 20a is after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 80 DEG C of plating pretreatment fluid (composition：Alkaline aqueous solution with metal salt) in weight reduction rates of the dipping after 30 seconds be preferably below 1.0% weight, be more excellent Elect as below 0.8 weight %, more preferably below 0.6 weight %.In addition, above-mentioned weight reduction rates are preferably less, such as For more than 0 weight %, more than 0.01 weight %.Sometimes zincate solution is used in the manufacture of wired circuit board.It is if above-mentioned heavy It is below 1.0% weight to measure slip, then also has the patience to zincate solution.As a result, can the accuracy of manufacture it is higher Wired circuit board.For above-mentioned weight reduction rates, by reducing the content of elastomer or using high glass transition Crosslink density after the resin of temperature or raising heat cure, can decline above-mentioned weight reduction rates.As above-mentioned zincate Solution, the SUPER ZINCATE PROCESS SZII of day ore deposit Metal Plating Co. Ltd. systems can be enumerated.
Resin sheet 20a is after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 80 DEG C of nickel plating solution (group Into：Nickel sulfate, sodium hypophosphite, organic acid etc.) in dipping 1800 seconds after weight reduction rates be preferably below 1.0% weight, more Preferably below 0.8 weight %, more preferably below 0.6 weight %.In addition, above-mentioned weight reduction rates are preferably less, example Such as it is more than 0 weight %, more than 0.01 weight %.Sometimes using nickel plating solution in the manufacture of wired circuit board.It is if above-mentioned Weight reduction rates are below 1.0% weight, then also have the patience to nickel plating solution.As a result, can the accuracy of manufacture it is higher Wired circuit board.For above-mentioned weight reduction rates, by reducing the content of elastomer or being turned using high-vitrification Crosslink density after the resin of temperature or raising heat cure, can decline above-mentioned weight reduction rates.As above-mentioned nickel plating With solution, a day KG-535-0 for ore deposit Metal Plating Co. Ltd. systems can be enumerated：KG-535-1=3：1.
Resin sheet 20a 180 DEG C carry out heat cure in 1 hour after, more than 20 DEG C and less than 80 DEG C it is gold-plated use solution (group Into：Phosphate cpd, hydrosulfide, amines etc.) in dipping 1200 seconds after weight reduction rates be preferably 1.0% weight Amount is following, more preferably below 0.8 weight %, more preferably below 0.6 weight %.In addition, above-mentioned weight reduction rates are excellent Select it is less, for example, more than 0 weight %, more than 0.01 weight %.Sometimes using nickel plating with molten in the manufacture of wired circuit board Liquid.If above-mentioned weight reduction rates are below 1.0% weight, also there is the patience to nickel plating solution.As a result, it can manufacture The higher wired circuit board of precision.For above-mentioned weight reduction rates, by reducing the content of elastomer or using high Crosslink density after the resin of glass transition temperature or raising heat cure, can decline above-mentioned weight reduction rates.As It is above-mentioned it is gold-plated use solution, a day CF-500SS for ore deposit Metal Plating Co. Ltd. systems can be enumerated.
It it is preferably 100 DEG C in the glass transition temperature that 180 DEG C are carried out after heat cure in 1 hour for resin sheet 20a Above, more preferably more than 110 DEG C, more preferably more than 120 DEG C.Because resin sheet 20a possesses above-mentioned composition, therefore Solvent resistance, acid resistance, alkali resistance etc. can effectively be played.
The resin combination for forming resin sheet 20a as long as there is above-mentioned characteristic and can be used in being formed and can partly be led with being formed at The wired circuit board of electrode connection on body chip, is just not particularly limited, as preferable resin combination, can enumerate Such as the composition epoxy resin containing following A compositions to E compositions.It should be noted that C compositions can add as needed It can not add.
A compositions：Epoxy resin
B component：Phenolic resin
C compositions：Elastomer
D compositions：Inorganic filler
E compositions：Curing accelerator
(A compositions)
As epoxy resin (A compositions), it is not particularly limited.Such as triphenylmenthane type epoxy resin, cresols can be used Phenol aldehyde type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy Resin, modified bisphenol F types epoxy resin, dicyclopentadiene type epoxy resin, phenol novolak type epoxy, phenoxy resin etc. Various epoxy resin.These epoxy resin, which can be used alone, can also share two or more.
From the viewpoint of the toughness and the reactivity of epoxy resin after the solidification for ensuring epoxy resin, preferably epoxy is worked as Measure for 150~250, softening point or fusing point be 50~130 DEG C be at normal temperatures solid-state epoxy resin, wherein, from reliability From the viewpoint of, preferably triphenylmenthane type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin.
In addition, from the viewpoint of low stress, the preferably modification with the flexibility skeleton such as acetal radical, polyoxyalkylenes Bisphenol A type epoxy resin, there is the modified bisphenol A type epoxy resin of acetal radical to be liquid and operational good, therefore can be with Particularly suitable use.
The content of epoxy resin (A compositions) is preferably set to relative to composition epoxy resin generally 1~10 weight % Scope.
(B component)
Phenolic resin (B component) is just not particularly limited as long as curing reaction can occur between epoxy resin (A compositions). Can use for example phenol novolacs, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene type phenolic resin, Cresol novolac resin, resol etc..These phenolic resin can be used alone, and can also share two or more.
As phenolic resin, from from the viewpoint of the reactivity of epoxy resin (A compositions), being preferably using hydroxyl equivalent 70~250, softening point is 50~110 DEG C of phenolic resin, wherein from the viewpoint of solidification reactivity height, can suitably be made Use phenol novolacs.In addition, from the viewpoint of reliability, phenol aralkyl resin, biphenyl aralkyl can be suitably used The phenolic resin of the agent of low hygroscopicity of base resin etc.
From the viewpoint of solidification reactivity, the mixing ratio of epoxy resin (A compositions) and phenolic resin (B component) is preferred According to the hydroxyl in phenolic resin (B component) it is total relative to the equivalent of epoxy radicals 1 in epoxy resin (A compositions) be 0.7~ The mode of 1.5 equivalents coordinates, more preferably 0.9~1.2 equivalent.
(C compositions)
The elastomer (C compositions) being used together with epoxy resin (A compositions) and phenolic resin (B component) is to epoxy resin group Compound is assigned to the tracing ability of adherend (embedded (Mai め Write body) property) needed for flexibility, as long as being acted on as playing, just Its structure is not particularly limited.It can use for example：The various acrylic acid series copolymers such as polyacrylate；Styrene acrylic Ester based copolymer, butadiene rubber, butadiene-styrene rubber (SBR), vinyl-vinyl acetate copolymer (EVA), isoprene rubber, The rubber polymers such as acrylic-nitrile rubber.Wherein, from be easy into epoxy resin (A compositions) disperse and with epoxy resin (A into Point) reactivity it is also high, therefore from the viewpoint of the heat resistance of the resin sheet 20a obtained by can improving, intensity, preferably use Acrylic acid series copolymer.They can be used alone, and can also share two or more.
It should be noted that acrylic acid series copolymer for example can be by will be set as the acrylic acid series list after regulation mixing ratio Body mixture carries out radical polymerization to synthesize using conventional method.As the method for radical polymerization, can use with organic Solution polymerization process that solvent is carried out as solvent, the suspension polymerization for being dispersed in water starting monomer while being polymerize. As the polymerization initiator now used, such as 2 can be used, 2 '-azodiisobutyronitrile, 2, double (2, the 4- dimethyl of 2 '-azo Valeronitrile), the double -4- methoxyl group -2,4- methyl pentane nitriles of 2,2 '-azo, other azo systems or diazonium system polymerization initiator, peroxidating The peroxide such as benzoyl and methyl ethyl ketone peroxide system polymerization initiator etc..It should be noted that in the case of suspension polymerisation, reason What is thought is the dispersant for adding such as polyacrylamide, polyvinyl alcohol etc.
The content of elastomer (C compositions) is preferably 15~30 overall weight % of composition epoxy resin.Elastomer (C into Point) content when being more than 15 weight %, be readily obtained resin sheet 20a flexibility and flexibility.On the other hand, above-mentioned content is During below 30 weight %, the decline of the intensity and heat resistance of resin sheet 20a firming body can be suppressed.
In addition, elastomer (C compositions) relative to epoxy resin (A compositions) part by weight (weight of C compositions/A compositions Weight) it is preferably set to 3~4.7 scope.When above-mentioned part by weight is more than 3, easily controllable resin sheet 20a mobility, When less than 4.7, resin sheet 20a cementability can be made good.
(D compositions)
Inorganic filler (D compositions) is not particularly limited, and can use known various fillers, can enumerate example Such as quartz glass, talcum, silica (fused silica, crystallinity silica), aluminum oxide, aluminium nitride, silicon nitride Deng powder.They can be used alone, and can also share two or more.
Wherein, from solvent resistance, acid resistance, alkali resistance aspect, preferably using SiO 2 powder, silica Fused silica powder is more preferably used among powder.As fused silica powder, spheroidal fused dioxy can be enumerated SiClx powder, broken fused silica powder, from the viewpoint of mobility, particularly preferably use spheroidal fused silica Powder.Wherein, preferably using the powder for the scope that average grain diameter is 0.1~30 μm, particularly preferably using 0.3~15 μm of scope Powder.
It should be noted that average grain diameter can export as follows：Using the sample of the haphazard selection from sampled population, It is measured using laser diffraction and scattering formula particle size distribution device.
The content of inorganic filler (D compositions) is preferably 70~95 overall weight % of composition epoxy resin, more preferably For 72~93 weight %, more preferably 75~90 weight %.By making the content of inorganic filler (D compositions) be 70 weights More than % is measured, solvent resistance, acid resistance, alkali resistance can be made good.On the other hand, by making above-mentioned content be 90 weight %, Resin sheet 20a flexibility and the variation of mobility can be suppressed.
(E compositions)
Curing accelerator (E compositions) is as long as promote the solidification of epoxy resin and phenolic resin to be just not particularly limited, from admittedly From the viewpoint of the property changed and keeping quality, preferably using triphenylphosphine, tetraphenylphosphoniphenolate tetraphenylborate (テ ト ラ Off ェ ニ Le ホ ス ホ ニ ウ system テ ト ラ Off ェ ニ Le ボ レ ー ト) etc. organic phosphorus series compound, imidazole compound.These curing accelerators can To be used alone, can also be shared with other curing accelerators.
The content of curing accelerator (E compositions) is relative to the total of epoxy resin (A compositions) and phenolic resin (B component) 100 parts by weight are preferably 0.1~5 parts by weight.
(other compositions)
In addition, flame retardant constituent can also be added in addition to A compositions~E compositions in composition epoxy resin.As fire-retardant Agent composition, such as aluminium hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, stannic hydroxide, Composite metallic hydrogen can be used The various metal hydroxides such as oxide.From can be played with less addition anti-flammability in terms of and the viewpoint of cost go out Hair, preferably using aluminium hydroxide or magnesium hydroxide, particularly preferably using aluminium hydroxide.
As the average grain diameter of metal hydroxides, from ensuring suitably to flow when having carried out heating to composition epoxy resin Property from the viewpoint of, preferably average grain diameter be 1~10 μm, more preferably 2~5 μm.The average grain diameter of metal hydroxides During less than 1 μm, it is difficult to it is dispersed in composition epoxy resin, and have and can not fill in the heating of composition epoxy resin Get the trend of mobility.In addition, when average grain diameter is more than 10 μm, the unit addition of metal hydroxides (E compositions) Surface area diminishes, it can thus be seen that flame retardant effect downward trend.
In addition, as flame retardant constituent, phosphazene compound can also be used beyond above-mentioned metal hydroxides.As phosphorus Nitrile compound, SPR-100, SA-100, SP-100 (above, great mound chemistry strain formula meetings for example as commercially available product can be obtained Society), FP-100, FP-110 (above, Fushimi Pharmaceutical Company, Limited) etc..
From the viewpoint of even if can also play flame retardant effect on a small quantity, preferably by formula (1) or the phosphonitrile chemical combination of formula (2) expression Thing, the content of the P elements contained in these phosphazene compounds is preferably more than 12 weight %.
【Change 1】
(in formula (1), n be 3~25 integer, R1And R2It is identical or different, be have selected from alkoxy, phenoxy group, amino, Any monovalent organic radical of functional group in hydroxyl and pi-allyl.)
【Change 2】
(in formula (2), n and m are each independently 3~25 integer.R3And R5It is identical or different, it is to have to be selected from alcoxyl Any monovalent organic radical of functional group in base, phenoxy group, amino, hydroxyl and pi-allyl.R4Be have selected from alkoxy, phenoxy group, The divalent organic base of functional group in amino, hydroxyl and pi-allyl.)
In addition, from the viewpoint of stability and suppression space (ボ イ De) generation, preferably use what is represented by formula (3) Cyclic phosphazene oligomer.
【Change 3】
(in formula (3), n be 3~25 integer, R6And R7It is identical or different, it is that hydrogen, hydroxyl, alkyl, alkoxy or shrink are sweet Oil base.)
The above-mentioned cyclic phosphazene oligomer represented by formula (3) can obtain FP-100, FP-110 for example as commercially available product (above, Fushimi Pharmaceutical Company, Limited) etc..
The content of phosphazene compound is preferably comprising epoxy resin (A compositions), the phenolic aldehyde contained in composition epoxy resin Resin (B component), elastomer (D compositions), the organic principle of curing accelerator (E compositions) and phosphazene compound (other compositions) are whole 10~30 weight % of body.That is, when the content of phosphazene compound is less than 10 overall weight % of organic principle, it can be seen that resin sheet 20a anti-flammability downward trend.When above-mentioned content is more than 30 overall weight % of organic principle, resin sheet 20a surface holds It is also easy to produce tacky, it can be seen that workability downward trend.
Alternatively, it is also possible to share above-mentioned metal hydroxides and phosphazene compound, so as to ensure needed for piece encapsulation Flexibility while obtain the resin sheet 20a of excellent in flame retardance.By sharing both, can obtain that metal hydroxides is used only When abundant anti-flammability and using only sufficient flexibility during phosphazene compound.
For both content when sharing metal hydroxides and phosphazene compound, the preferred total amount of two-component For 70~90 overall weight % of composition epoxy resin, more preferably 75~85 weight %.Above-mentioned total amount is less than 70 weights When measuring %, resin sheet 20a is difficult to obtain sufficient anti-flammability, during more than 90 weight %, becomes easy on resin sheet 20a surface Produce tacky, it can be seen that workability downward trend.
It should be noted that composition epoxy resin can also suitably coordinate with charcoal as needed beyond above-mentioned each composition It is black for other additives such as the pigment of representative.
(preparation method of resin sheet)
Illustrate resin sheet 20a preparation method below.First, by the way that above-mentioned each composition is mixed to prepare epoxy resin group Compound.As long as the method that each composition is uniformly dispersed mixing by mixed method is just not particularly limited.Afterwards, such as coating will Each composition is dissolved or dispersed in the varnish formed in organic solvent etc., to form sheet.Or kneader etc. can also be utilized straight Connect and each gradation composition is kneaded to prepare mixture, so obtained mixture is extruded into sheet.
As the specific make step using varnish, according to conventional method by above-mentioned A~E compositions and as needed other Additive suitably mixes, and is equably dissolved or dispersed in organic solvent, so as to prepare varnish.Then, above-mentioned varnish is coated with In on the supporting masses such as polyester and being allowed to drying, it is hereby achieved that resin sheet 20a.Then, as needed can also be in order to protect Resin sheet 20a surface and be bonded the stripping films such as polyester film.
As above-mentioned organic solvent, it is not particularly limited, known various organic solvents, such as first and second can be used Ketone, acetone, cyclohexanone, dioxane, metacetone, toluene, ethyl acetate etc..They can be used alone, and can also share 2 More than kind.In addition, it is usually preferred to the solid component concentration according to varnish reach 30~60 weight % range mode use it is organic Solvent.
The thickness that organic solvent is dried is not particularly limited, from the uniformity of thickness and the viewpoint of residual solvent amount Set out, it is usually preferred to be set as 5~100 μm, more preferably 20~70 μm.
On the other hand, in the case of using being kneaded, using method known to blender etc. by above-mentioned A~E compositions and root Mixed according to each composition of other additives of needs, afterwards, carry out melting mixing, thus prepare mixture.As melting mixing Method, be not particularly limited, can enumerate for example, by kneading machine known to mixing mill, adding pressure type kneader, extruder etc. Method for carrying out melting mixing etc..As compounding conditions, as long as temperature is more than the softening point of above-mentioned each composition just no special Limitation, such as 30~150 DEG C, if considering the Thermocurable of epoxy resin, preferably 40~140 DEG C, more preferably 60 ~120 DEG C, the time is, for example, 1~30 minute, is preferably 5~15 minutes.Thereby, it is possible to prepare mixture.
Resulting mixture is formed by using extrusion molding, resin sheet 20a can be obtained.Specifically, Keep carrying out extrusion molding under the condition of high temperature by the mixture after melting mixing is not cooled down, resin sheet 20a can be formed. As such extrusion method, be not particularly limited, can enumerate T moulds extrusion molding, roller rolling process, roller be kneaded method, coetrusion, Calender method of forming etc..As extrusion temperature, as long as more than the softening point of above-mentioned each composition just it is not particularly limited, if considering The Thermocurable and formability of epoxy resin, then for example, 40~150 DEG C, be preferably 50~140 DEG C, more preferably 70~ 120℃.Thus, it is possible to form resin sheet 20a.
So obtained resin sheet 20a can also make after being laminated in the way of as desired thickness as needed With.That is, resin sheet 20a can be used with single layer structure, the layered product that can also be formed with being laminated into more than 2 layers of sandwich construction Form use.
(manufacture method of semiconductor device)
Hereinafter, 2~Figure 12 of reference picture, an example of the manufacture method of semiconductor device of the present embodiment is entered Row describes in detail.Fig. 2~Figure 12 is cutd open for what is illustrated to the manufacture method of semiconductor device of the present embodiment Face schematic diagram.
(preparation with the supporting mass of peel ply)
First, prepare supporting mass 1 (referring to Fig. 2).Supporting mass 1 preferably has the intensity more than certain.
As supporting mass 1, it is not particularly limited, can enumerates：The compounds such as silicon wafer, SiC wafer, GaAs chips are brilliant Piece；Chip glass, SUS, 6-4Alloy；The metal foils such as Ni paper tinsels, Al paper tinsels；Etc..When using top view to be circular in the case of, It is preferred that silicon wafer or chip glass.In addition, in the case of being rectangle during top view, preferably SUS plates or glass plate.
In addition, as supporting mass 1, can also use for example：Low density polyethylene (LDPE), straight chain shaped polyethylene, the poly- second of Midst density Alkene, high density polyethylene (HDPE), ultra-low density polyethylene, atactic copolymerized polypropene, block copolymerization polypropylene, HOPP, poly- fourth The polyolefin such as alkene, polymethylpentene；Vinyl-vinyl acetate copolymer, from polyimide precursor resin, ethene-(methyl) acrylic acid copolymer Thing, ethene-(methyl) acrylate (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, poly- ammonia The polyester such as ester, polyethylene terephthalate, PEN, makrolon, polyimides, polyether-ether-ketone, Polyimides, PEI, polyamide, fully aromatic polyamide, polyphenylene sulfide, aromatic polyamide (paper), glass, glass Fiber cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose-based resin, silicones, paper etc..
Supporting mass 1 may be used singly or in combination of two or more.The thickness of supporting mass is not particularly limited, example Such as it is usually 10 μm~20mm or so.
Then, peel ply 5 is formed on supporting mass 1.
Dipping 60 seconds in 50 DEG C of METHYLPYRROLIDONE (NMP) of peel ply 5, after 150 DEG C are dried 30 minutes Weight reduction rates be preferably more than 1.0 weight %, more preferably more than 1.2 weight %, more preferably 1.3 weight % with On.In addition, above-mentioned weight reduction rates are preferably larger, but for example, below 50 weight %, below 30 weight %.In 50 DEG C of N- first Dipping 60 seconds in base -2-Pyrrolidone (NMP), the weight reduction rates after being dried 30 minutes at 150 DEG C are more than 1 weight %, Therefore the dissolution of peel ply 5 is in METHYLPYRROLIDONE, it may be said that weight is substantially reduced.Its result is that can utilize N- first Base -2-Pyrrolidone easily peels off peel ply 5.The above-mentioned weight reduction rates of peel ply 5 can for example be existed by raw material Dissolubility in NMP is controlled.That is, as raw material, the raw material that dissolubility is high in NMP is more selected at, use this The peel ply that raw material obtain is higher to NMP dissolubility.
The impact hardness of peel ply 5 is preferably less than 10, more preferably less than 9, more preferably less than 8.On in addition, It is preferably smaller to state impact hardness, for example, more than 0.001.When above-mentioned impact hardness is less than 10, peel ply 5 can be made to being glued Thing has enough bonding forces.
The case hardness of peel ply 5 be preferably below 10GPa, more preferably below 8GPa, more preferably 6GPa with Under.In addition, above-mentioned case hardness is preferably smaller, but for example, more than 0.05GPa.When above-mentioned case hardness is below 10GPa, energy Enough control the bonding force of the peel ply 5 and adherend.
Weight reduction rates after peel ply 5 impregnates 5 minutes in 3% tetramethylammonium hydroxide aqueous solution are preferably smaller than 1 Weight %, more preferably less than 0.9 weight %, it is further preferably no larger than 0.8 weight %.In addition, above-mentioned weight reduction rates preferably compared with It is small, for example, more than 0 weight %, more than 0.001 weight %.After being impregnated 5 minutes in 3% tetramethylammonium hydroxide aqueous solution Weight reduction rates when being less than 1 weight %, the dissolution in 3% tetramethylammonium hydroxide aqueous solution is few, therefore can improve Solvent resistance (especially to the solvent resistance of tetramethylammonium hydroxide aqueous solution).The above-mentioned weight reduction rates of peel ply 5 are for example It can be controlled by the composition (dissolubility of the diamines to tetramethylammonium hydroxide aqueous solution) of used diamines.
Peel ply 5 when being peeled off after fitting in silicon wafer, silicon wafer it is unilateral on more than 0.2 μm of particle increasing Dosage, relative to fit in before silicon wafer be preferably less than 1000/6 inch wafers, more preferably less than 900/6 inch wafers, Further preferably it is less than 800/6 inch wafers.Fit in after silicon wafer when being peeled off, silicon wafer it is unilateral on 0.2 μm More than particle incrementss, relative to fit in be less than 1000/6 inch wafer before silicon wafer when, after stripping being suppressed Adhesive residue.
Peel ply 5 kept for 1 minute at 200 DEG C after, the shear bond power of silicon wafer to the temperature be preferably 0.25kg/ 5 × more than 5mm, more preferably 0.30kg/5 × more than 5mm, more preferably 0.50kg/5 × more than 5mm.In addition, peel off Any temperature of the layer 5 in the temperature province more than 200 DEG C and less than 500 DEG C kept for 3 minutes after, silicon wafer to the temperature Shear bond power be preferably smaller than 0.25kg/5 × 5mm, more preferably less than 0.10kg/5 × 5mm, be further preferably no larger than 0.05kg/5×5mm.The shear bond power of the silicon wafer to the temperature after being kept for 1 minute at 200 DEG C is 0.25kg/5 × 5mm More than, any temperature in the temperature province more than 200 DEG C and less than 500 DEG C kept for 3 minutes after, silicon wafer to the temperature When the shear bond power of piece is less than 0.25kg/5 × 5mm, the peel ply 5 for showing fissility at a higher temperature can be formed. The above-mentioned shear bond power of peel ply can be for example controlled by the functional group number contained by peel ply.
In addition, above-mentioned peel ply realizes that being less than 0.25kg/5 × 5mm (is preferably less than to the shear bond power of silicon wafer 0.10kg/5 × 5mm, more preferably less than 0.05kg/5 × 5mm) temperature, as long as more than 200 DEG C and less than 500 DEG C of temperature Any temperature in degree region is just not particularly limited, preferably greater than 220 DEG C and less than 480 DEG C, more preferably higher than 240 DEG C And less than 450 DEG C.
It should be noted that for above-mentioned peel ply, even if below 200 DEG C but when keeping for a long time, to silicon wafer The above-mentioned shear bond power of piece is sometimes less than 0.25kg/5 × 5mm.In addition, even if above-mentioned peel ply is maintained at more than 200 DEG C Temperature, but if if being the short time, then the above-mentioned shear bond power of silicon wafer will not be also less than sometimes 0.25kg/5 × 5mm。
That is, " any temperature in the temperature province more than 200 DEG C and less than 500 DEG C kept for 3 minutes after, to the temperature It is the index for evaluating the fissility under high temperature that the shear bond power of the silicon wafer of degree, which is less than 0.25kg/5 × 5mm ", is not to represent When being set to " being more than any temperature in 200 DEG C and less than 500 DEG C of temperature province ", to the shear bond power of silicon wafer just immediately Become less than 0.25kg/5 × 5mm.In addition, nor represent if being not set to " be more than 200 DEG C and less than 500 DEG C of humidity province Any temperature in domain " can not just show fissility.
For peel ply 5, as long as impregnating 60 seconds in 50 DEG C of METHYLPYRROLIDONE (NMP), 150 DEG C dry 30 minutes after weight reduction rates be more than 1.0 weight %, its formation material be just not particularly limited, can enumerate poly- Imide resin, silicones, acrylic resin, fluororesin, epoxy resin, carbamate resins, rubber resin etc..
Above-mentioned polyimide resin generally can be by carrying out imidizate (dehydration contracting to the polyamic acid for being used as its precursor Close) obtain.As the method that imidizate is carried out to polyamic acid, for example known heating imidizate can be used Method, azeotropic dehydration, chemical imidization method etc..Wherein, imidizate method is preferably heated.Using the feelings of heating imidizate method Under condition, in order to prevent being deteriorated caused by oxidation for polyimide resin, preferably under nitrogen atmosphere, the medium torpescence atmosphere of vacuum Under heated.
Above-mentioned polyamic acid can obtain as follows：Thrown in the solvent suitably selected by substantial equimolar than in the way of Enter acid anhydrides and diamines, be allowed to react.
As above-mentioned polyimide resin, preferably there are the Component units from diamines, the diamines has ether structure.It is above-mentioned Diamines with ether structure, as long as with ether structure and with the compound of at least two ends for possessing amine structure, just do not have It is particularly limited to.Among the above-mentioned diamines with ether structure, the preferred diamines with two ol skeletons.In above-mentioned polyimide resin In the case of with following Component units, if peel ply is heated into high temperature (such as more than 200 DEG C), shearing can be reduced Bonding force, the Component units are the Component units from the diamines with ether structure, especially from two ol skeletons The Component units of diamines.On the phenomenon, the present inventor speculates：Due to being heated to high temperature, therefore above-mentioned ether structure or above-mentioned Two ol skeletons depart from from the resin for forming solvent release sheet, and shear bond power declines because of the disengaging.
It should be noted that depart from this from the resin for forming solvent release sheet for above-mentioned ether structure or above-mentioned two ol skeleton For a bit, such as can be by comparing the FT-IR spectrograms before and after being heated 30 minutes at 300 DEG C, 2800~3000 spectrogram exists The situation of reduction is confirmed before and after heating.
As the above-mentioned diamines with two ol skeletons, can enumerate for example：With polypropylene glycol structure and two ends The respective diamines with an amino, with polyethylene glycol structures and in diamines of two ends each with an amino, have There is polytetramethylene glycol structure and each there is the diamines of an amino two ends.Furthermore it is possible to enumerate with multiple above-mentioned two Alcohol structure and the diamines each two ends with an amino.
The molecular weight of the above-mentioned diamines with ether structure is preferably in the range of 100~5000, more preferably 150~ 4800.The molecular weight of the above-mentioned diamines with ether structure be 100~5000 in the range of when, the bonding force that is readily obtained under low temperature It is high and play the peel ply 5 of fissility in high temperature.
In the formation of above-mentioned polyimide resin, in addition to the diamines with ether structure, additionally it is possible to share without ether knot Other diamines of structure.As other diamines without ether structure, aliphatic diamine, aromatic diamine can be enumerated.It is logical Cross and share other diamines without ether structure, the closing force with adherend can be controlled.As the diamines with ether structure It is preferably 100 with molar ratio computing with the mixed proportion of other diamines without ether structure：0~20：80th, 99 are more preferably： 1~30：70.
As above-mentioned aliphatic diamine, for example, ethylenediamine, hexamethylene diamine, 1,8- diamino-octanes, 1,10- diaminos Double (the 3- aminopropyls) -1,1 of base decane, 1,12- diamino dodecanes, 4,9- dioxa -1,12- diamino dodecanes, 1,3-, 3,3- tetramethyl disiloxanes (α, ω-bis- aminopropyls tetramethyl disiloxane) etc..The molecular weight of above-mentioned aliphatic diamine leads to Often it is 50~1,000,000, is preferably 100~30,000.
As aromatic diamine, for example, 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 3,3 '- Diaminodiphenyl ether, m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diamino-diphenyl propane, 3,3 '-diaminodiphenyl-methane, 4, 4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenyl sulfide, 4,4 '-diaminodiphenylsulfone, 3,3 '-diaminodiphenylsulfone, 1, Double (4- amino-benzene oxygens) benzene of 4-, double (4- amino-benzene oxygens) benzene of 1,3-, double (3- amino-benzene oxygens) benzene of 1,3-, the double (4- of 1,3- Amino-benzene oxygen) -2,2- dimethylpropanes, 4,4 '-diaminobenzophenone etc..The molecular weight of above-mentioned aromatic diamine is usually 50~1000, it is preferably 100~500.It should be noted that in this specification, molecular weight refers to utilize GPC (gel infiltration colors Spectrum) value (weight average molecular weight) that is measured, is calculated by polystyrene.
As above-mentioned acid anhydrides, for example, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic acid Acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 4,4 '-epoxide are double Double (2,3- dicarboxyphenyis) hexafluoropropane dianhydrides of O-phthalic acid dianhydride, 2,2-, double (3,4- dicarboxyphenyis) hexafluoros of 2,2- Propane dianhydride (6FDA), double (2,3- dicarboxyphenyis) methane dianhydrides, double (3,4- dicarboxyphenyis) methane dianhydrides, double (2,3- Dicarboxyphenyi) sulfone dianhydride, double (3,4- dicarboxyphenyis) sulfone dianhydrides, pyromellitic acid anhydride, the double trimellitic acids two of ethylene glycol Acid anhydride etc..They can be used alone, and can also share two or more.
As solvent when making above-mentioned acid anhydrides and above-mentioned diamine reactant, can enumerate DMA, N- methyl- 2-Pyrrolidone, N,N-dimethylformamide, cyclopentanone etc..They can be used alone, and can also be used in mixed way a variety of.Separately Outside, in order to adjust the dissolubility of raw material, resin, the nonpolar solvent such as toluene, dimethylbenzene can be suitably used in mixed way.
Peel ply 5 is for example carried out as follows making.First, the solution containing above-mentioned polyamic acid is made.Then, will be above-mentioned molten Liquid is coated on base material after formation coated film according to regulation thickness, the coated film is dried under prescribed conditions.As upper Base material is stated, can be used：The metal foils such as SUS304,6-4 alloy, aluminium foil, copper foil, Ni paper tinsels；Polyethylene terephthalate (PET), polyethylene, polypropylene；Surface painting is carried out using removers such as fluorine system remover, chain alkyl acrylate series stripping agents Plastic foil or paper after covering etc..In addition, as coating method, be not particularly limited, for example, roller coat, silk screen coating, Intaglio plate coating, spin coating etc..In addition, as drying condition, such as in 50~150 DEG C of drying temperature, 3~30 minutes drying times In the range of carry out.Thus, it can obtain peel ply 5 of the present embodiment.
For the supporting mass 1 with peel ply 5, peel ply 5 can be transferred to supporting mass 1 and peeled off to make to have The supporting mass 1 of layer 5.In addition, the supporting mass 1 with peel ply 5 can also make as follows：Solution containing polyamic acid is direct After being coated on the formation coated film of supporting mass 1, the coated film is set to be dried under prescribed conditions.
(formation of wired circuit board)
Then, wired circuit board 2 is formed on the peel ply 5 of supporting mass 1.Formed on the supporting mass with peel ply The method of wired circuit board can also apply the manufacture of the known circuit substrates such as semi-additive process, subtractive process or interpolater Technology.Due to forming wired circuit board on supporting mass, thus in manufacturing process, dimensional stability becomes good, in addition The operability of thin wired circuit board improves.An example of the forming method of wired circuit board is illustrated below.
(formation of base insulating layer)
As shown in figure 3, the resin sheet 20a as base insulating layer is pasted onto on the peel ply 5 of supporting mass 1.Resin sheet 20a thickness is preferably 3~50 μm.
Then, form opening h1 in the position that should form external connection conductor portion 22 (referring to Fig. 4).As opening h1's Forming method, known method can be used.For example, being exposed development by using photosensitive material, can be formed Be open h1.Opening shape is not particularly limited, preferably circular, and diameter also can suitably be set, but can be set to such as 5 μm~ 500μm.Afterwards, heat cure is carried out.As heating-up temperature it is preferably 20 DEG C~150 DEG C, more preferably as the condition of heat cure 40 DEG C~120 DEG C, as the heat time preferably using 0.5 minute~60 minutes, more preferably using 1 minute~30 minutes.
(formation of the metal film of contact)
Then, the metal film 211 of contact is formed in opening h1 (referring to Fig. 5).By forming metal film 211, Neng Gougeng It is electrically connected well, improves corrosion resistance.The forming method of metal film 211 is not particularly limited, preferably plating, as the gold Belong to the material of film, the single metal such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium can be enumerated or by upper State alloy of two or more composition etc..Among them, as preferred material, gold, tin, nickel etc. can be enumerated, as preferable metal The scheme of film, double-decker that bottom is Ni, top layer is Au etc. can be enumerated.
(kind film (Japanese：Seed films), the formation of the conductive path of downside, conductor layer)
Then, formed as needed in conductor layer 23 and by the wall as the part of conductive path 25 for making metal material Expect kind film (metallic film) 23a well accumulated (referring to Fig. 6).Kind film 23a can for example be formed by sputtering.As kind of a film Material, metal single such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium or by above-mentioned 2 can be used Alloy formed more than kind etc..The thickness of conductor layer 23 is not particularly limited, and can suitably be selected in 1~500nm scope. In addition, for conductive path 25, cylindric is preferable shape, its a diameter of 5~500 μm, preferably 5~300 μm.It Afterwards, the conductor layer 23 with defined wiring pattern, conductive path 25 are formed.Wiring pattern can for example be formed by electroplating. Afterwards, the kind film of the part of no conductor layer 23 is removed.
Then, as shown in fig. 7, being covered using the r1 of resistance to platedresist on conductor layer 23 (does not include that conductive path will be formed The part in footpath), and using the whole lower surface of resist r2 covering supporting masses 1, conductive path 24 is formed by plating.
(formation of gluing oxidant layer)
Then, the r1 of resistance to platedresist, r2 are removed, the shape in the way of conductor layer 23 and conductive path 24 that embedding is exposed Into using epoxy and polyimides as the gluing oxidant layer 20b of main component, the adhesive linkage is etched using alkaline solution etc., made The upper surface for obtaining conductive path 24 is exposed to adhesive linkage upper surface as portion of terminal (referring to Fig. 8).
(formation of the metal film on end face of connection conductor portion)
Then, as shown in figure 9, forming connection conductor portion for example, by being electrolysed plating in the upper surface of conductive path 24 21.Connection is formed with conductor portion 21 such as using nickel film, golden film.It is consequently formed wired circuit board.Above-mentioned wired circuit Sometimes using various solvents (particularly MEK) in the formation process of substrate.However, resin sheet 20a is carried out 1 hour at 180 DEG C After heat cure, the weight reduction rates after being impregnated 2400 seconds more than 20 DEG C and in less than 25 DEG C of MEK are 1.0 weight % Below.Therefore, it can be said that the dissolution in MEK is inhibited.If as a result, using resin sheet 20a, can make The high wired circuit board of manufacturing accuracy.
In addition, in resin sheet 20a, after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 25 DEG C of 0.5 weight When weight reduction rates after being impregnated 60 seconds in amount % hydrofluoric acid are below 1.0 weight %, also with acid resistance.Now, even if , also being capable of the higher wired circuit board of the accuracy of manufacture using acid in the formation process of above-mentioned wired circuit board.
In addition, in resin sheet 20a, after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C and less than 25 DEG C of 3.0 weights When measuring the weight reduction rates after being impregnated 240 seconds in % tetramethylammonium hydroxide aqueous solution as below 1.0% weight, also with resistance to Alkalescence.Now, also being capable of the higher wiring electricity of the accuracy of manufacture even if using alkali in the formation process of above-mentioned wired circuit board Base board.
(installation procedure, stripping process, scribing (Dicing))
Then, wired circuit board 2 (in a releasable manner with supporting mass 1) chip to above obtaining. Specifically, the electrode 31 of semiconductor chip 3 is matched somebody with somebody according to the opposed mode of the connection conductor portion 21 with wired circuit board 2 Postpone (referring to Figure 10), both connections, semiconductor chip 3 (referring to Figure 11) is installed on wired circuit board 2.Need what is illustrated It is that connection conductor portion 21,31 respective projection of electrode after installing are eliminated in Figure 11 diagram.Afterwards, adhesive is carried out Layer 20b aging, and then resin-encapsulated (not shown) is implemented to each chip 3 on wired circuit board 2.It should be noted that Resin-encapsulated can use the encapsulation resin sheet of sheet, can also use the resin-encapsulated material of liquid.Afterwards, with peel ply 5 With the face of the opposite side of supporting mass 1 as interface, supporting mass 1 is peeled off together with peel ply 5.As stripping means, Ke Yiju Go out and peeled off using the solvent of METHYLPYRROLIDONE, utilize the stripping of heating.In the case of stripping using heating, heating The lower limit of temperature can be set to such as 50 DEG C, 80 DEG C, 100 DEG C, 150 DEG C, 180 DEG C.In addition, temperature during above-mentioned stripping process The upper limit be preferably 260 DEG C, more preferably 230 DEG C, more preferably 200 DEG C.In addition, maintained in above-mentioned stripping process The time stated under temperature conditionss is different according to temperature, but preferably 0.05~120 minute, more preferably 0.1~30 minute.Need It is noted that more than 260 DEG C of heat is preferably not exposed in the later process of above-mentioned installation procedure.Thereby, it is possible to suppress to weld Material etc. melts.Thus, it can obtain the semiconductor device that semiconductor chip 3 is provided with wired circuit board 2.
It should be noted that the wired circuit board 2 after stripping supporting mass 1 can also be implemented to assign solder ball etc Processing.
More than, an example of the manufacture method of semiconductor device of the present embodiment is illustrated, but this The manufacture method of semiconductor device in invention is not limited to above-mentioned example, and it is appropriate to be carried out in the range of the purport of the present invention Change.
Embodiment
Below, a preferred embodiment of the present invention is illustrated by way of example.But limited as long as no special Property record, material, use level described in the embodiment etc. are not intended to the purport of the present invention being only defined in these materials, matched somebody with somebody Resultant etc..In addition, part refers to parts by weight.
(embodiment 1)
The making ＞ of ＜ resin sheets
Following (a)~(f) is dissolved in MEK, obtain the weight % of concentration 26.8 resin composition solution.This is set Oil/fat composition solution coating after silicon demoulding processing has been carried out is 38 μm of polyethylene terephthalate film structure by thickness Into demoulding process film (release liner) on, then 130 DEG C dry 2 minutes.Thus, the resin sheet of 100 μm of thickness has been made.
(a) 50 parts of acrylic resin (Nagase ChemteX Co. Ltd. systems, Teisan Resin SG-70L)
(b) 4.752 parts of cresol novolak type epoxy resin (Nippon Kayaku K. K's system, EOCN 1020-4P)
(c) 4.848 parts of biphenylene type phenolic resin (bright and chemical conversion Co. Ltd. system, MEH-7851SS)
(d) 17.78 parts of silica filler (Admatechs Co. Ltd. systems, SE2050MC (60%))
(e) silane coupler (0.08 part of (Shin-Etsu Chemial Co., Ltd's system, KBM-303)
(f) 0.101 part of the imidazolium compounds (four countries' chemical conversion Co. Ltd. system, 2PHZ-PW) as curing accelerator
(embodiment 2)
The making ＞ of ＜ resin sheets
Following (a)~(f) is mixed using blender, is kneaded 2 minutes under conditions of 120 DEG C using twin screw compounder, Then, extruded from mould, thus obtain the resin sheet of 20 μm of thickness.
(a) 280 parts of epoxy resin (chemical company of Nippon Steel system, YSLV-80XY)
(b) 300 parts of phenolic resin (bright and chemical conversion company system, MEH-7851-SS)
(c) 330 parts of silica filler (electrochemical industry company system, FB-9454)
(d) 10 parts of silane coupler (Shin-Etsu Chemial Co., Ltd's system, KBM-403)
(e) 6 parts of curing accelerator (four countries' chemical conversion industry company system, 2P4MHZ-PW)
(f) 10 parts of carbon (Mitsubishi Chemical Ind's system, #40)
(measure of weight reduction rates when being impregnated in hydrofluoric acid)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 23 DEG C of 0.5% hydrogen Dipping 60 seconds in fluoric acid (HF).After room temperature (23 DEG C) carries out the cleaning of 3 minutes twice with ultra-pure water, 30 points are dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in tetramethylammonium hydroxide aqueous solution)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 23 DEG C of 3% tetramethyl Dipping 5 minutes in base ammonium hydroxide aqueous solution (TMAH).After room temperature (23 DEG C) carries out the cleaning of 3 minutes twice with ultra-pure water, Dried 30 minutes at 120 DEG C.Afterwards, room temperature is returned in drier, determines weight (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in SC-1)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 23 DEG C of SC-1 (compositions Using weight ratio meter as ammoniacal liquor (15 weight %)：Hydrogen peroxide：Water=1：2：5) dipping 100 seconds in.In room temperature (23 DEG C) with ultrapure After water carries out the cleaning of 3 minutes twice, dried 30 minutes at 120 DEG C.Afterwards, room temperature is returned in drier, determines weight Measure (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in SC-2)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 23 DEG C of SC-2 (compositions Using weight ratio meter as hydrochloric acid (38 weight %)：Hydrogen peroxide：Water=1：2：5) dipping 160 seconds in.In room temperature (23 DEG C) with ultrapure After water carries out the cleaning of 3 minutes twice, dried 30 minutes at 120 DEG C.Afterwards, room temperature is returned in drier, determines weight Measure (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in hydrogenperoxide steam generator)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 23 DEG C of 30% peroxide Change and impregnated 840 seconds in hydrogen solution.After room temperature (23 DEG C) carries out the cleaning of 3 minutes twice with ultra-pure water, 30 points are dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in MEK)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 23 DEG C of MEK (MEK) dipping 2400 seconds in.After room temperature (23 DEG C) carries out the cleaning of 3 minutes twice with ultra-pure water, 30 points are dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in degreasing solution)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 50 DEG C of degreasing solution Dipping 300 seconds in (day ore deposit Metal Plating Co. Ltd. system, Rapid Clean P-1000).It is super in (23 DEG C) use of room temperature After pure water carries out the cleaning of 3 minutes twice, dried 30 minutes at 120 DEG C.Afterwards, room temperature is returned in drier, is determined Weight (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in aqueous solution of nitric acid)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 23 DEG C of 70% nitric acid Impregnated 30 seconds in the aqueous solution.After room temperature (23 DEG C) carries out the cleaning of 3 minutes twice with ultra-pure water, dried 30 minutes at 120 DEG C. Afterwards, room temperature is returned in drier, determines weight (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in plating pretreatment fluid)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, the plating at 23 DEG C pre-processes Dipping 30 seconds in liquid (day ore deposit Metal Plating Co. Ltd. system, SUPER ZINCATE PROCESS SZII).In room temperature After (23 DEG C) carry out the cleaning of 3 minutes twice with ultra-pure water, dried 30 minutes at 120 DEG C.Afterwards, room is returned in drier Temperature, determine weight (weight after dipping).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(measure of weight reduction rates when being impregnated in nickel plating solution)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, in 80 DEG C of nickel plating solution (day ore deposit Metal Plating Co. Ltd. system, KG-535-0：KG-535-1=3：1) dipping 1800 seconds in.At room temperature (23 DEG C) After carrying out the cleaning of 3 minutes twice with ultra-pure water, dried 30 minutes at 120 DEG C.Afterwards, room temperature is returned in drier, is surveyed Weight (weight after dipping) is determined.
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
(in the measure of the gold-plated weight reduction rates with when being impregnated in solution)
First, the resin sheet that embodiment 1 and embodiment 2 are related to is cut into 30mm × 100mm, 30 points is dried at 120 DEG C Clock.Afterwards, room temperature is returned in drier, determines weight (weight before dipping).Then, solution is used in 75 DEG C gold-plated Dipping 1200 seconds in (day ore deposit Metal Plating Co. Ltd. system, CF-500SS).In room temperature (23 DEG C) two are carried out with ultra-pure water After the cleaning of secondary 3 minutes, dried 30 minutes at 120 DEG C.Afterwards, room temperature is returned in drier, determines weight (after dipping Weight).
Weight reduction rates are obtained according to following formula.As a result it is shown in table 1.
(weight reduction rates (weight %))=[1- ((weight after dipping)/(weight before dipping))] × 100
【Table 1】
(measure of the glass transition temperature (Tg) of resin sheet)
The measure of storage tensile modulus uses solid determination of viscoelasticity device (Rheometric Scientific company systems： Pattern：RSA-III) carry out.Specifically, resin sheet is made to carry out heat cure within 1 hour in 180 DEG C of heating, using sample size as length Degree 400mm × width 10mm × 200 μm of thickness is obtained after determining sample from the solidfied material, and measure sample is installed on into film stretching surveys Surely fixture is used, drawing of the measure within the temperature range of -50~300 DEG C under conditions of frequency 1Hz, 10 DEG C/min of programming rate Storage modulus and loss modulus are stretched, vitrifying is obtained by calculating tan δ (G " (loss modulus)/G ' (storage modulus)) value Transition temperature (Tg).As a result, the glass transition temperature of the resin sheet of embodiment 1 is 105 DEG C.In addition, the resin of embodiment 2 The glass transition temperature of piece is 110 DEG C.
Symbol description
1 supporting mass
2 wired circuit boards
20a resin sheets (base insulating layer)
The gluing oxidant layer of 20b
21 connection conductor portions
22 external connection conductor portions
23 conductor layers
23a kind films
24 conductive paths
25 conductive paths
211 metal films
3 semiconductor chips
31 electrodes
4 semiconductor devices
5 peel plies
R1 resists
R2 resists

Claims (3)

1. a kind of resin sheet, it is characterised in that be for forming the wiring that can be connected with the electrode being formed on semiconductor chip The resin sheet of circuit substrate,
The resin sheet includes epoxy resin and phenolic resin, its glass transition temperature after carrying out heat cure in 1 hour at 180 DEG C Spend for more than 100 DEG C, after 180 DEG C carry out heat cure in 1 hour, impregnate 2400 more than 20 DEG C and in less than 25 DEG C of MEK Weight reduction rates after second are below 1.0 weight %.
2. resin sheet as claimed in claim 1, it is characterised in that after 180 DEG C carry out heat cure in 1 hour, more than 20 DEG C And the weight reduction rates after being impregnated 60 seconds in less than 25 DEG C of 0.5 weight % hydrofluoric acid are below 1.0 weight %.
3. resin sheet as claimed in claim 1 or 2, it is characterised in that 180 DEG C carry out heat cure in 1 hour after, 20 DEG C with Weight reduction rates after being impregnated 240 seconds in upper and less than 25 DEG C of 3.0 weight % tetramethylammonium hydroxide aqueous solution are 1.0% Below weight.
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