CN109071845A - Protective film formation film and protective film formation composite sheet - Google Patents
Protective film formation film and protective film formation composite sheet Download PDFInfo
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- CN109071845A CN109071845A CN201780025032.9A CN201780025032A CN109071845A CN 109071845 A CN109071845 A CN 109071845A CN 201780025032 A CN201780025032 A CN 201780025032A CN 109071845 A CN109071845 A CN 109071845A
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- protective film
- film formation
- methyl
- film
- energy ray
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- YVUBWJOBCFNMES-UHFFFAOYSA-N formamide;pyridine Chemical compound NC=O.C1=CC=NC=C1 YVUBWJOBCFNMES-UHFFFAOYSA-N 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical class [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical class [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical class C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- 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
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
Abstract
The present invention provides a kind of protective film formation film; it forms for the protective film of energy ray-curable and uses film; the protective film formation film when irradiation energy ray is to be made protective film, it is with the protective film, according to JIS Z0237:2010 with the Rolling Ball Tack value of 30 ° of inclination angle measurement for 2 characteristics below.
Description
Technical field
The present invention relates to a kind of protective film formation film and protective film formation composite sheets.
The Japanese Patent Application 2016-092013 CLAIM OF PRIORITY that the application is proposed based on April 28th, 2016 in Japan, and
Its content is applied at this.
Background technique
In recent years, carrying out applying the semiconductor device of the Method for Installation referred to as upside-down mounting (face down) mode
Manufacture.In upside-down mounting mode, using the semiconductor chip with electrodes such as convex blocks in circuit face, the electrode connects with substrate
It closes.Therefore, semiconductor chip with circuit face be opposite side the back side expose sometimes.
It is formed with the resin film containing organic material as protective film at the back side of the semiconductor chip of the exposing, sometimes
Semiconductor device is packed into as the semiconductor chip with protective film.
It cracks to utilize protective film on a semiconductor die after cutting action or encapsulation in order to prevent.
In order to form such protective film, such as use a kind of protective film for having on support chip and being used to form protective film
The protective film formation composite sheet of formation film.In protective film formation composite sheet, protective film formation film can pass through solidification
And protective film is formed, support chip can be also used as to cutting sheet, can be made into protective film formation film and the integrated protection of cutting sheet
Composite sheet is used in film formation.
As such protective film formation composite sheet, such as mainly uses to have so far and carried out by heating
Solidify and be consequently formed the protective film formation composite sheet of the protective film formation film of the Thermocurable of protective film.At this point, for example
Protective film formation is attached at the back side of semiconductor crystal wafer (with electricity with composite sheet with film in the protective film formation using Thermocurable
Pole forming face is the face of opposite side) after, make the solidification of protective film formation film to which protective film be made by heating, it will by cutting
Semiconductor crystal wafer divides that semiconductor chip is made together with protective film.Later, semiconductor chip maintenance is made to be pasted with the guarantor
The state of cuticula simultaneously separates it from support chip, to be picked up.In addition, also being carried out sometimes with sequence contrary to the above
Protective film forms the solidification and cutting for using film.
However, being heating and curing for the protective film formation film of Thermocurable usually requires the long-time of hours or so, because
Curing time is shortened in this expectation.In this regard, studying can be by the cured protective film of irradiation of the energy-rays such as ultraviolet light
Formation is used for the formation of protective film with film.For example, the energy ray-curable protective film being formed on stripping film has been disclosed
(referring to patent document 1) and it is capable of forming high rigidity and to the energy-ray of the excellent protective film of the adherence of semiconductor chip
Solidify cake core protection with film (referring to patent document 2).
Existing technical literature
Patent document
Patent document 1: No. 5144433 bulletin of Japan's patent
Patent document 2: Japanese Unexamined Patent Publication 2010-031183 bulletin
Summary of the invention
The technical problem to be solved in the present invention
In order to, using the semiconductor chip with protective film after picking up, be packaged in sometimes such as figure in next process
In embossed carrier tape 102 shown in 7, and the embossed carrier tape 102 is taken care of with the state of wound in coils, carried or is traded.Quilt
When being accommodated in the embossed carrier tape 102, the semiconductor chip 101 with protective film after pickup is usually with the circuit of semiconductor chip
Surface side towards embossed carrier tape 102 pocket 102a bottom and protective film side towards the opening portion of the pocket 102a mode
It is contained, the lid band 103 of the cover of embossed carrier tape 102 is constituted by pasting, close the opening portion to packaged.By band
When the semiconductor chip 101 of protective film is used for next process, for example, the semiconductor chip 101 with protective film will be packaged with
Embossed carrier tape 102 is set to chip mounter together with reel, and the semiconductor chip 101 with protective film is installed on substrate.This
When, the lid band 103 is removed, the semiconductor chip 101 with protective film is taken out from the pocket 102a of embossed carrier tape 102, but have
When semiconductor chip 101 with protective film can be attached on lid band 103 because of protective film, hinder the semiconductor core with protective film
The process that piece 101 is installed on substrate.
In this regard, the purpose of the present invention is to provide a kind of can be formed at the back side of semiconductor crystal wafer or semiconductor chip to protect
Film, and when the semiconductor chip with protective film for being cut and being picked up is stored to the pocket of embossed carrier tape, having can press down
Semiconductor chip of the system with protective film is attached to the protective film formation film of the energy ray-curable of the characteristic of lid band and has
The protective film formation composite sheet of the protective film formation film.
Solve the technological means of technical problem
In order to solve the above technical problem, the present invention provides a kind of protective film formation films, are energy ray-curable
Protective film formed use film, to the protective film formation film irradiation energy ray to protective film is made when, the protection
Film, according to JIS Z0237:2010 with the Rolling Ball Tack value of 30 ° of inclination angle measurement for 2 or less.
In protective film formation film of the invention, the preferably described protective film formation film contain energy ray-curable at
Divide (a).
In protective film formation film of the invention, the preferably described protective film formation further includes photopolymerization with film and causes
Agent (c).
In protective film formation film of the invention, preferably with respect to 100 mass parts of energy ray-curable ingredient (a),
The content of the Photoepolymerizationinitiater initiater (c) is 2.0~12.0 mass parts.
In addition, the present invention provides a kind of protective film formation composite sheet, by having above-mentioned any note on support chip
The protective film formation of load is formed with film.
That is, the present invention includes following manner.
[1] a kind of protective film, which is formed, uses film, is that the protective film of energy ray-curable is formed with film, wherein protective film
Formation film irradiation energy ray to protective film is made when, with the protective film, according to JIS Z0237:2010 with
The Rolling Ball Tack value of the 30 ° of measurements in inclination angle is 2 characteristics below.
[2] protective film according to [1], which is formed, uses film, wherein the protective film formation film is solid comprising energy-ray
The property changed ingredient (a).
[3] protective film according to [2], which is formed, uses film, and the protective film formation further includes photopolymerization with film and causes
Agent (c).
[4] protective film according to [3], which is formed, uses film, wherein relative to 100 matter of energy ray-curable ingredient (a)
Part is measured, the content of the Photoepolymerizationinitiater initiater (c) is 2.0~12.0 mass parts.
[5] a kind of protective film, which is formed, uses composite sheet, by having described in any one of [1]~[4] on support chip
Protective film formation is formed with film.
Invention effect
According to the present invention, it is possible to provide a kind of when storing the semiconductor chip with protective film to the pocket of embossed carrier tape, tool
There is the protective film for the energy ray-curable for being able to suppress the characteristic that the semiconductor chip with protective film is attached to lid band to be formed to use
Film and the protective film formation composite sheet for having the protective film formation film.
Detailed description of the invention
Fig. 1 is the sectional view for schematically showing an embodiment of protective film formation film of the invention.
Fig. 2 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 3 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 4 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 5 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 6 is the sectional view for schematically showing an embodiment of protective film formation film of the invention.
Fig. 7 is to schematically show that the semiconductor chip with protective film is accommodated in the pocket of embossed carrier tape and pastes lid
Sectional view with the state to be covered and the state for peeling off the lid band.
Specific embodiment
Film is used in the formation of ◇ protective film
The protective film formation of the invention protective film formation film that film is energy ray-curable, to the protective film shape
At with film irradiation energy ray to protective film is made when, with the protective film, according to JIS Z0237:2010 to tilt
The Rolling Ball Tack value of the 30 ° of measurements in angle is 2 characteristics below.
Protective film formation film of the invention can have the first stripping film on the surface of at least side, can also be another
Further there is the second stripping film on the surface of side.Protective film formation film of the invention can be with the strip of wound into rolls
The form of shape film and provide.
Fig. 1 is the sectional view for schematically showing an embodiment of protective film formation film of the invention.In Fig. 1
In, it is sequentially laminated with the first stripping film 15 ', protective film is formed with film 13 and the second stripping film 15 ".
In the present specification, for protective film formation film, sometimes by be attached at semiconductor crystal wafer the back side (that is, with
Circuit face be opposite side surface) surface be known as " surface (α) ", will with the surface at the back side for being attached at semiconductor crystal wafer be phase
The surface tossed about is known as " surface (β) ".
To protective film formation film irradiation energy ray of the invention to protective film is made when, the protective film, extremely
The surface (β) of few side, according to JIS Z0237:2010 with the Rolling Ball Tack value of the 30 ° of measurements in inclination angle for 2 or less.
That is, protective film formation film of the invention is with energy ray-curable and for half as a side
The protective film that the back side of semiconductor wafer or semiconductor chip forms protective film, which is formed, uses film, preferably to the protective film formation film
Irradiation energy ray to protective film is made when, with the protective film, be attached at the semiconductor crystal wafer or semiconductor
The surface (α) of chip-side be the surface (β) of opposite side, according to JIS Z0237:2010 with the spin of 30 ° of inclination angle measurement
Viscosity value is 0 or more 2 characteristic below, and more preferably having the value is 0 characteristic more than and less than 2.
For the composition etc. of protective film formation film, described later.
Protective film formation of the invention is formed with the protective film that film can be used as constituting aftermentioned protective film formation composite sheet
Use film.
Furthermore it is possible to which protective film formation is attached at film and is partly led in a manner of without using protective film formation composite sheet
The back side of body wafer, and on support chip to be attached to the protective film formation film later, to carry out using guarantor at this time
Cuticula formation film and substrate sheets can suitably use the guarantor illustrated in the explanation in aftermentioned protective film formation composite sheet
Cuticula, which is formed, uses film and substrate sheets.
In the present invention, protective film formation film, can be with other than it can be used as aftermentioned protective film formation composite sheet
The back of the semiconductor crystal wafer is attached at as the protective film formation piece for being provided with protective film formation film on stripping film
Behind face, attach support chip and carry out using.
For example, Fig. 1 is to schematically show the protective film formation piece 2F for having used protective film formation film of the invention
An embodiment sectional view.
Protective film formation piece 2F shown here has protective film formation film 13 on the first stripping film 15 ', is protecting
Has the second stripping film 15 " on cuticula formation film 13.
Protective film formation shown in FIG. 1 carried out in the following manner with piece 2F using: in the second stripping for eliminating light removing side
In the state of film 15 ", protective film formation film 13 surface 13a (that is, protective film formation film 13 has the second stripping
Surface from the side of film 15 ") center side a part of region on attach semiconductor crystal wafer (illustration omitted) the back side, further
In the state of eliminating the first stripping film 15 ' for re-releasing side, what it is in protective film formation film 13 is opposite side with surface 13a
The other side surface 13b on attach substrate sheets, further attach the region near the peripheral part of protective film formation film 13
In on the fixtures such as annular frame.
Herein, the stripping film of the lesser side of peeling force is referred to as to the stripping film of light removing side, by peeling force biggish one
The stripping film of side is referred to as the stripping film for re-releasing side.If peeling force has differences, the stripping in the light removing side of only removing can be prevented
When from film, protective film formation film floats from the stripping film for re-release side, and prevents protective film formation film from following because being intended to
Two stripping films and stretcher strain occurs.
Composite sheet is used in the formation of ◇ protective film
Protective film formation composite sheet of the invention on support chip by having the protective film shape of energy ray-curable
It is formed at film.
In addition, in the present invention, " protective film forms film " refers to film before curing, and " protective film " is to instigate protective film
Film made of formation is solidified with film.
In the present specification, " energy-ray " refers to the ray in electromagnetic wave or charged particle beam with the quantum of energy, as
Its example can enumerate ultraviolet light, radioactive ray, electron beam etc..
Ultraviolet light for example can be by using high-pressure sodium lamp, fusion H lamp (fusion H lamp), xenon lamp, black light lamp or LED
Lamp etc. is irradiated as ultraviolet source.Electron beam can irradiate the electron beam using generations such as electron-beam accelerators.
In the present specification, " energy ray-curable ", which refers to, carries out cured property by irradiation energy ray, " non-
Energy ray-curable " refers to irradiation energy ray without cured property.
The support chip of the laminated body and the protective film formation are not particularly limited with the adhesion strength between film, such as can
Think 80mN/25mm or more, or 100mN/25mm or more, or 150mN/25mm or more, or
200mN/25mm or more, in addition, upper limit value is not particularly limited, it can be 10000mN/25mm or less, or 8000mN/
25mm or less, or 7000mN/25mm or less.
That is, adhesion strength between the support chip of the laminated body and the protective film formation film can for 80~
10000mN/25mm, or 150~8000mN/25mm, or 200~7000mN/25mm.
By the way that the adhesion strength is adjusted to the lower limit value or more, dispersing for the silicon chip in cutting can inhibit, also
It can prevent cutting water from infiltrating between protective film formation film and support chip.In addition, described by the way that the adhesion strength to be adjusted to
Upper limit value hereinafter, easily can suitably adjust later it is when being allowed to solidify to be made protective film by irradiation energy ray,
Adhesion strength between the protective film and the support chip.
The protective film formation film is solidified by the irradiation of energy-ray, becomes protective film.The protective film is for protecting
Protect the back side (being the face of opposite side with electrode forming surface) of semiconductor crystal wafer or semiconductor chip.It is soft that protective film, which is formed with film,
Matter can be simply attached to attach object.Also, to the protective film formation film irradiation energy ray to which guarantor be made
When cuticula, the adhesion strength between the protective film and the support chip is preferably 50~1500mN/25mm, more preferably 52~
1450mN/25mm, particularly preferably 53~1430mN/25mm.
By making the adhesion strength lower limit value or more, in the semiconductor chip of pick-up tape protective film, can inhibit
The pickup of the semiconductor chip with protective film outside target can pick up partly the leading with protective film as target with high selectivity
Body chip.By making the adhesion strength upper limit value hereinafter, in the semiconductor chip of pick-up tape protective film, half can inhibit
The rupture and defect of conductor chip.By this method, by making the adhesion strength in a specific range, protective film is formed with compound
Piece has good pickup adaptive.
In addition, in the protective film formation composite sheet for an embodiment of the invention, by making the protective film
Formation is energy ray-curable with film, is formed with the previous protective film for the protective film formation film for having Thermocurable with multiple
It closes piece to compare, solidification can be carried out with the shorter time to form protective film.
The semiconductor crystal wafer of object or the thickness of semiconductor chip are used as protective film formation composite sheet of the invention
Degree is not particularly limited, due to can get more significant effect of the invention, so preferably 30~1000 μm, more preferably
100~300 μm.
Hereinafter, composition of the invention is described in detail.
◎ support chip
The support chip can be made of one layer (single layer), can also be made of two layers or more of multiple layers.Support chip by
When multiple layers of composition, these multiple layers constituent materials and thickness mutually the same can be can also be different, as long as not damaging this hair
Bright effect, these multiple layers combinations are not particularly limited.
In addition, in the present specification, the case where being not limited only to support chip, " multiple layers mutually the same can also be different "
Refer to " layer that can be all is identical, and layer that can also be all is different, can be identical with the layer of only a part ", in addition, " multiple layers
It is different from each other " refer to " at least one of constituent material and thickness of each layer are different from each other ".
As preferred support chip, such as adhering agent layer can be enumerated directly contact and be laminated on it with substrate and form
Support chip, adhering agent layer via middle layer support chip made of being laminated on substrate and the support chip being only made of substrate
Deng.
It protective film of the invention is formed uses hereinafter, accordinging to every kind of type of such support chip while referring to attached drawing
The example of composite sheet is illustrated.In addition, in order to which feature of the invention is more readily understood, for convenience, sometimes by following theory
The pith of figure used in bright expands display, and dimensional ratios of each component etc. are not necessarily identical as reality.
Fig. 2 is the sectional view for schematically showing an embodiment of protective film formation composite sheet of the invention.
Protective film formation composite sheet 1A shown here has adhering agent layer 12 on substrate 11, on adhering agent layer 12
Has protective film formation film 13.Support chip 10 is the laminated body of substrate 11 and adhering agent layer 12, and in other words, protective film is formed
Have on the surface 10a (for example, surface of 12 side of adhering agent layer of support chip 10) of the side of support chip 10 with composite sheet 1A
It is laminated with the composition of protective film formation film 13.In addition, protective film formation is enterprising in protective film formation film 13 with composite sheet 1A
One step has stripping film 15.
In protective film formation in composite sheet 1A, it is laminated with adhering agent layer 12 on the surface 11a of the side of substrate 11,
The surface 12a's (that is, face that the same side that it is contacted with substrate 11 of adhering agent layer 12 is opposite side) of adhering agent layer 12 is entire
Protective film formation film 13 is laminated on face, protective film formation film 13 surface 13a (that is, protective film is formed with film 13
The side contacted with adhering agent layer 12 with it is the face of opposite side) a part, i.e., on the region near the peripheral part of surface 13a
It is laminated with fixture adhesive phase 16, is not laminated fixture adhesive phase 16 in the surface 13a of protective film formation film 13
(same its of upper surface, i.e. fixture adhesive phase 16 is formed with protective film to be used the surface 16a of surface and fixture adhesive phase 16
Film 13 contact side be opposite side face and the fixture side of adhesive phase 16) on be laminated with stripping film 15.
In protective film formation in composite sheet 1A, the protective film after solidification is formed with film 13 (i.e. protective film) and support chip 10
Between adhesion strength, in other words, the adhesion strength between protective film and adhering agent layer 12 is preferably 50~1500mN/25mm.
Fixture adhesive phase 16 for example can be the single layer structure containing adhesive ingredients, or as core material
Sheet material two sides on be laminated with the multilayered structure of the layer containing adhesive ingredients.
Protective film formation shown in Fig. 2 carried out in the following manner with composite sheet 1A using: in the shape for eliminating stripping film 15
Under state, the back side that semiconductor crystal wafer (illustration omitted) is attached on surface 13a of the protective film formation with film 13 further makes to press from both sides
Upper surface in the surface 16a of tool adhesive phase 16 is attached on the fixtures such as annular frame.
Fig. 3 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
In addition, in Fig. 3 later figure, for constituent element identical with the constituent element shown in figure being explained, mark
Remember appended drawing reference identical with the figure that this is explained, and description is omitted.
Protective film formation composite sheet 1B shown here is not other than having fixture adhesive phase 16, and shown in Fig. 2
Protective film formed with composite sheet 1A it is identical.That is, in protective film formation in composite sheet 1B, on the surface of the side of substrate 11
Adhering agent layer 12 is laminated on 11a, adhering agent layer 12 surface 12a (that is, same its of adhering agent layer 12 is contacted with substrate 11
Side be opposite side face) entire surface on be laminated with protective film formation film 13, in the surface 13a of protective film formation film 13
It is laminated in the entire surface of (that is, its same side contacted with adhering agent layer 12 of protective film formation film 13 is the face of opposite side)
Stripping film 15.
Protective film formation shown in Fig. 3 carried out in the following manner with composite sheet 1B using: in the shape for eliminating stripping film 15
Under state, semiconductor crystal wafer is attached on a part of region of the center side in surface 13a of the protective film formation with film 13 and (saves sketch map
Show) the back side, be attached to protective film formation on the fixtures such as annular frame with the region near the peripheral part of film 13.
Fig. 4 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Protective film formation composite sheet 1C shown here is not other than having 12 this point of adhering agent layer, with Fig. 2 institute
The protective film formation composite sheet 1A shown is identical.That is, support chip 10 is only by 11 structure of substrate in protective film formation in composite sheet 1C
At.Also, it is laminated with protective film on the surface 11a of the side of substrate 11 (the surface 10a of the side of support chip 10) and forms use
Film 13, protective film formation film 13 surface 13a (that is, the same side that it is contacted with substrate 11 of protective film formation film 13
For the face of opposite side) a part, i.e., be laminated with fixture adhesive phase 16 on the region near the peripheral part of surface 13a,
The surface that fixture adhesive phase 16 is not laminated and fixture adhesive phase 16 in the surface 13a of protective film formation film 13
Surface 16a (upper surface, i.e. fixture with adhesive phase 16 it is same its with protective film formation with the side that film 13 contacts be opposite side
Face and the fixture side of adhesive phase 16) on be laminated with stripping film 15.
In protective film formation in composite sheet 1C, the protective film after solidification is formed with film 13 (i.e. protective film) and support chip 10
Between adhesion strength, in other words, the adhesion strength between protective film and substrate 11 is preferably 50~1500mN/25mm.
Identical with composite sheet 1A as protective film formation shown in Fig. 2, protective film shown in Fig. 4, which is formed, uses composite sheet 1C or less
The mode of stating carry out using: in the state of eliminating stripping film 15, attach on surface 13a of the protective film formation with film 13 and partly lead
The back side of body wafer (illustration omitted) further makes the upper surface in the surface 16a of fixture adhesive phase 16 be attached to annular
On the fixtures such as frame.
Fig. 5 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Protective film formation composite sheet 1D shown here is not other than having fixture adhesive phase 16, and shown in Fig. 4
Protective film formed with composite sheet 1C it is identical.That is, in protective film formation in composite sheet 1D, on the surface of the side of substrate 11
Protective film formation film 13 is laminated on 11a, protective film formation film 13 surface 13a (that is, protective film is formed with film 13
The side contacted with substrate 11 with it is the face of opposite side) entire surface on be laminated with stripping film 15.
Identical with composite sheet 1B as protective film formation shown in Fig. 3, protective film shown in fig. 5, which is formed, uses composite sheet 1D or less
The mode of stating carries out using center side in the state of eliminating stripping film 15, in surface 13a of the protective film formation with film 13
A part of region on attach semiconductor crystal wafer (illustration omitted) the back side, further make the peripheral part of protective film formation film 13
Neighbouring region is attached on the fixtures such as annular frame.
Fig. 6 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Protective film formation shown here with composite sheet 1E other than the shape difference this point of protective film formation film,
It is identical with composite sheet 1A as protective film formation shown in Fig. 2.That is, protective film formation composite sheet 1E has adhesion on substrate 11
Oxidant layer 12 has protective film formation film 23 on adhering agent layer 12.Support chip 10 is the stacking of substrate 11 and adhering agent layer 12
Body, in other words, protective film formation composite sheet 1E have in the surface 10a of the side of support chip 10 (for example, support chip 10
The surface of 12 side of adhering agent layer) on be laminated with the composition of protective film formation film 23.In addition, protective film formation is existed with composite sheet 1E
Protective film formation is with being further equipped with stripping film 15 on film 23.
In protective film formation in composite sheet 1E, adhering agent layer 12 is laminated on the surface 11a of the side of substrate 11.?
One of the surface 12a (that is, face that the same side that it is contacted with substrate 11 of adhering agent layer 12 is opposite side) of adhering agent layer 12
Point, i.e., protective film formation film 23 is laminated on the region of the center side of surface 12a.Also, on the surface of adhering agent layer 12
The surface 23a on the surface that protective film formation film 23 is not laminated and protective film formation film 23 in 12a (protect by upper surface
Its same side contacted with adhering agent layer 12 of film formation film 23 is the face of opposite side and the side of protective film formation film 23
Face) on be laminated with stripping film 15.
When overlooking protective film formation down from above with composite sheet 1E, protective film forms the surface area ratio sticker for using film 23
Layer 12 is small, for example, having the shapes such as circle.
In protective film formation in composite sheet 1E, the protective film after solidification is formed with film 23 (i.e. protective film) and support chip 10
Between adhesion strength, in other words, the adhesion strength between protective film and adhering agent layer 12 is preferably 50~1500mN/25mm.
Protective film formation shown in fig. 6 carried out in the following manner with composite sheet 1E using: in the shape for eliminating stripping film 15
Under state, the back side of semiconductor crystal wafer (illustration omitted) is attached on surface 23a of the protective film formation with film 23.Further make to adhere
The protective film formation that is not laminated in the surface 12a of oxidant layer 12 is attached on the fixtures such as annular frame with the surface of film 23.
In addition, protective film shown in fig. 6 is formed in composite sheet 1E, can in a manner of identical with shown in Fig. 2 and Fig. 4
Fixture adhesive phase is laminated on the surface that protective film formation film 13 is not laminated in the surface 12a of adhering agent layer 12 (to omit
Diagram).It is identical as protective film formation composite sheet shown in Fig. 2 and Fig. 4, such protective film shape for having fixture adhesive phase
At carried out with composite sheet 1E in the mode that is attached to the surface of fixture adhesive phase on the fixtures such as annular frame using.
As described previously for protective film formation composite sheet of the invention, no matter support chip and protective film formation with film are
What kind of form can have fixture adhesive phase.Wherein, usually as shown in Figures 2 and 4, has fixture adhesive
The protective film of the invention of layer, which is formed, uses composite sheet, preferably in protective film formation with having fixture adhesive phase on film.
Protective film formation of the invention is not limited to Fig. 2~protective film shown in fig. 6 formation composite sheet with composite sheet,
It does not damage in the range of effect of the invention, for change or Fig. 2~protective film shown in fig. 6 formation composite sheet can be deleted
The protective film formation composite sheet that constitutes of a part or may be the protective film formation composite sheet that is illustrated above
On the basis of further added other composition protective film formation composite sheet.
For example, Fig. 4 and protective film shown in fig. 5 are formed and are used in composite sheet, it can be in substrate 11 and protective film formation film 13
Between middle layer is set.As middle layer, arbitrary middle layer can be selected according to purpose.
In addition, in Fig. 2, Fig. 3 and protective film formation composite sheet shown in fig. 6, it can be in substrate 11 and adhering agent layer 12
Between middle layer is set.That is, support chip can stack gradually substrate, centre in protective film formation composite sheet of the invention
Layer and adhering agent layer form.Herein, middle layer refers to and can be arranged in Fig. 4 and protective film formation composite sheet shown in fig. 5
The identical middle layer of middle layer.
In addition, Fig. 2~protective film shown in fig. 6 formation composite sheet can be arranged on arbitrary position removes the middle layer
Layer in addition.
In addition, in protective film formation composite sheet of the invention, can directly contact in stripping film and with the stripping film
A part of gap is generated between layer.
In addition, in protective film formation composite sheet of the invention, can arbitrarily be adjusted according to purpose each layer size and
Shape.
In protective film formation composite sheet of the invention, as described later, it is preferably adhering agent layer etc., support chip with
Protective film formation is non-energy ray-curable with the layer that film directly contacts.Such protective film formation composite sheet can more be held
It changes places and picks up the semiconductor chip that the back side has protective film.
Support chip can be transparent, can also be opaque, can also be coloured according to purpose.
Wherein, in the present invention that protective film formation has energy ray-curable with film, preferably support chip penetrates energy
Ray.
For example, the transmitance of the light of wavelength 375nm is preferably 30% or more in support chip, more preferably 50% or more,
Particularly preferably 70% or more.By making the such range of transmitance of the light, protective film is formed through support chip and is used
When film irradiation energy ray (ultraviolet light), the curing degree of protective film formation film is further improved.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 375nm is not particularly limited, such as can
Think 95%.
That is, the transmitance of the light of wavelength 375nm is preferably 30~95% in support chip, and more preferably 50~95%, it is special
It You Xuanwei 70~95%.
In addition, the transmitance of the light of wavelength 532nm is preferably 30% or more in support chip, more preferably 50% or more,
Particularly preferably 70% or more.
By making the such range of transmitance of the light, protective film formation film or protective film are shone through support chip
It, being capable of more clearly lettering when penetrating laser to carry out lettering to it.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 532nm is not particularly limited, such as can
Think 95%.
That is, the transmitance of the light of wavelength 532nm is preferably 30~95% in support chip, and more preferably 50~95%, it is special
It You Xuanwei 70~95%.
In addition, the transmitance of the light of wavelength 1064nm is preferably 30% or more in support chip, more preferably 50% with
On, particularly preferably 70% or more.By making the such range of transmitance of the light, protective film is formed through support chip
It, being capable of more clearly lettering when with film or protective film irradiation laser to carry out lettering to it.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 1064nm is not particularly limited, such as can
Think 95%.
That is, the transmitance of the light of wavelength 1064nm is preferably 30~95% in support chip, more preferably 50~95%,
Particularly preferably 70~95%.Then, further each layer for constituting support chip is described in detail.
Zero substrate
The substrate is sheet or membranaceous, as its constituent material, such as can enumerate various resins.
As the resin, such as low density polyethylene (LDPE) (sometimes referred to simply as LDPE), the poly- second of linear low density can be enumerated
The polyethylene such as alkene (sometimes referred to simply as LLDPE), high density polyethylene (HDPE) (sometimes referred to simply as HDPE)；Polypropylene, polybutene, polybutadiene
The polyolefin in addition to polyethylene such as alkene, polymethylpentene, norbornene resin；Vinyl-vinyl acetate copolymer, ethylene-
The copolymerization of the vinyls such as (methyl) acrylic copolymer, ethylene-(methyl) acrylate copolymer, ethylene-norbornene copolymer
Object (uses ethylene as copolymer obtained from monomer)；The vinyl chloride resins such as polyvinyl chloride, vinyl chloride copolymer (use chlorine
Ethylene is as resin obtained from monomer)；Polystyrene；Polycyclic alkene；Polyethylene terephthalate, poly- naphthalenedicarboxylic acid second
Diol ester, polyethylene glycol isophthalate, poly- 2,6- (ethylene naphthalate), owns polybutylene terephthalate (PBT)
Structural unit there are the polyester such as Wholly aromatic polyester of aromatic series cyclic group；The copolymer of the two or more polyester；It is poly-
(methyl) acrylate；Polyurethane；Urethane acrylate；Polyimides；Polyamide；Polycarbonate；Fluororesin；Polyacetals；
Noryl；Polyphenylene sulfide；Polysulfones；Polyether-ketone etc..
In addition, as the resin, such as the polyester can also be enumerated and gathered with the mixture of resin etc. in addition to it
Close object alloy.It is preferred that the amount of the polyester and the resin in addition to polyester in the polymer alloy of resin in addition to it be compared with
On a small quantity.
In addition, as the resin, such as the one or more of the resin above illustrated can also be enumerated
Crosslinked resin made of crosslinking；The modified tree such as one or more kinds of ionomers of the resin above illustrated is used
Rouge.
In addition, in the present specification, " (methyl) acrylic acid " is comprising both " acrylic acid " and " methacrylic acid "
Concept.It is also identical as term as (methyl) acrylic compounds.
Constitute substrate resin can be only one kind, or it is two or more, for it is two or more when, their combination and
Ratio can be selected arbitrarily.
Substrate can be made of one layer (single layer), can also be made of two layers or more of multiple layers, when being made of multiple layers,
These multiple layers can be the same or different each other, these multiple layers combinations are not particularly limited.
The thickness of substrate is preferably 50~300 μm, and more preferably 60~100 μm.By make substrate with a thickness of such
Range, the pliability of the protective film formation composite sheet and to the adhesion of semiconductor crystal wafer or semiconductor chip be able into
One step improves.
Herein, " thickness of substrate " refers to the thickness of substrate entirety, for example, the thickness for the substrate being made of multiple layers refers to
Constitute the overall thickness of all layers of substrate.
In addition, " thickness " refers to the thickness with utilization contact thickness gauge in arbitrary five position findings in this specification
The value that the average value of degree indicates.
Preferred substrates are the high substrate of thickness and precision, no matter in the deviation of what part thickness are able to the substrate inhibited.
As it is in above-mentioned constituent material, can be used as constituting the material of the high substrate of such thickness and precision, such as poly- second can be enumerated
Alkene, the polyolefin in addition to polyethylene, polyethylene terephthalate, vinyl-vinyl acetate copolymer etc..
Substrate, can also be containing packing material, colorant, antistatic other than the main compositions material such as described resin
Various additives well known to agent, antioxidant, organic lubricant, catalyst, softening agent (plasticizer) etc..
As long as the optical characteristics of substrate meets the optical characteristics of support chip described above.That is, substrate can be saturating
It is bright, can also be opaque, it can also be coloured according to purpose, other layers can also be vapor-deposited with.
Also, in the present invention that protective film formation has energy ray-curable with film, preferred substrates make energy-ray
Through.
In order to improve and be set to the adherence of other layers such as the adhering agent layer on it, substrate can be for surface implementation
At further provided for contouring processing, Corona discharge Treatment, electron beam treatment with irradiation, plasma based on blasting treatment, solvent processing etc.
The substrate of the oxidation processes such as reason, the processing of ozone-ultraviolet line treatment with irradiation, flame treatment, chromic acid, hot wind processing etc..
In addition, substrate can also be substrate of the surface through prime treatment.
In addition, substrate also can have and prevent when overlapping antistatic coating, protective film formation composite sheet and being saved
The layer etc. that substrate and other sheet materials bond or prevent substrate and suction unit from bonding.
Wherein, the point of the generation of the part of the substrate caused by the friction of knife when inhibiting as cutting, particularly preferably
Substrate is the substrate that surface implements electron beam treatment with irradiation.
Substrate can be manufactured using well known method.For example, the substrate containing resin can be by that will contain the resin
Resin combination molding and manufacture.
Zero adhering agent layer
The adhering agent layer is sheet or membranaceous, and contains sticker.
As the sticker, for example, can enumerate acrylic resin, urethane based resin, rubber resin,
The adherences resin such as organic silicon resin, epoxylite, polyvinylether, polycarbonate, esters resin, preferably acrylic compounds tree
Rouge.
In addition, in the present specification, " adherence resin " is comprising the resin with adherence and with the tree of adhesiveness
The concept of both rouge.For example, not only include that resin itself has the resin of adherence, also comprising by with additive etc. other
It is used while ingredient and shows the resin of adherence or shown by the presence of heat or the triggers (trigger) such as water viscous
The resin etc. of conjunction property.
Adhering agent layer can be made of one layer (single layer), can also be made of two layers or more of multiple layers, by multiple layers of structure
Cheng Shi, these multiple layers mutually the same can also be different, these multiple layers combinations are not particularly limited.
The thickness of adhering agent layer is preferably 1~100 μm, more preferably 1~60 μm, particularly preferably 1~30 μm.
Herein, " thickness of adhering agent layer " refers to the thickness of adhering agent layer entirety, such as the sticker being made of multiple layers
The thickness of layer refers to the overall thickness for constituting all layers of adhering agent layer.
As long as the optical characteristics of adhering agent layer meets the optical characteristics of support chip described above.That is, sticker
Layer can be transparent, can also be opaque, can also be coloured according to purpose.
Also, in the present invention that protective film formation has energy ray-curable with film, preferably adhering agent layer makes energy
Radiolucent.
Adhering agent layer can be used energy ray-curable sticker and be formed, and non-energy ray-curable also can be used
Sticker and formed.It is preceding and solid that the adhering agent layer formed using energy ray-curable sticker can easily adjust solidification
Physical property after change.
<<adhesion agent composition>>
Adhering agent layer can be formed by the adhesion agent composition containing sticker.For example, by the way that adhesion agent composition is applied
Cloth is dried in the formation object surface of adhering agent layer and as needed, can form adhering agent layer in target site.Adhesion
The more specific forming method of oxidant layer will be described in detail below together with the forming method of other layers.Sticker combination
The mutual content of ingredient in object, not gasifying under room temperature compares phase with the mutual content of the ingredient of adhering agent layer than usually
Together.In addition, " room temperature " refers to the temperature for especially not cooled down or being heated, i.e. usual temperature, such as can in this specification
Enumerate 15~25 DEG C of temperature etc..
Using well known method carry out adhesion agent composition coating, such as can enumerate using Kohler coater,
Scraping blade coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain coater, die coating machine, knife type coater, silk screen
The method of the various coating machines such as coating machine (screen coater), Meyer rod coater, kiss painting machine (kiss coater).
The drying condition of adhesion agent composition is not particularly limited, but when adhesion agent composition contains aftermentioned solvent,
It is preferred that being thermally dried, at this point, being for example preferably dried with the condition of 70~130 DEG C, 10 seconds~5 minutes.
When adhering agent layer is energy ray-curable, as the sticker combination containing energy ray-curable sticker
The adhesion agent composition of object, i.e. energy ray-curable, such as can enumerate: the adherence tree containing non-energy ray-curable
Rouge (I-1a) (hereinafter, writing a Chinese character in simplified form work " adherence resin (I-1a) " sometimes) is combined with the sticker of energy ray-curable compound
Object (I-1)；Side chain containing the adherence resin (I-1a) in non-energy ray-curable is imported with the energy of unsaturated group
The adhesion agent composition of the adherence resin (I-2a) (hereinafter, writing a Chinese character in simplified form work " adherence resin (I-2a) " sometimes) of ray-curable
(I-2)；Adhesion agent composition (I-3) etc. containing the adherence resin (I-2a) Yu energy ray-curable compound.
<adhesion agent composition (I-1)>
As described above, adherence resin (I-1a) of the adhesion agent composition (I-1) containing non-energy ray-curable
And energy ray-curable compound.
[adherence resin (I-1a)]
It is preferred that the adherence resin (I-1a) is acrylic resin.
As the acrylic resin, such as can enumerate at least with the structure from (methyl) alkyl acrylate
The acrylic polymer of unit.
The structural unit that acrylic resin has can be only one kind, or and it is two or more, when being two or more,
Their combination and ratio can be selected arbitrarily.
In this specification, " coming from " refers to that chemical structure is changed to be polymerize.
As (methyl) alkyl acrylate, such as can enumerate the carbon atom number of the alkyl of composition Arrcostab is 1
~20 (methyl) alkyl acrylate, the preferably described alkyl are straight-chain or branched.
As (methyl) alkyl acrylate, more specifically, such as (methyl) methyl acrylate, (methyl) can be enumerated
Ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) third
Olefin(e) acid isobutyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) propylene
The own ester of acid, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) propylene
Sour n-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid
Hendecane base ester, (methyl) dodecylacrylate (also referred to as (methyl) lauryl acrylate), (methyl) acrylic acid 13
Arrcostab, (methyl) acrylic acid tetradecane base ester (also referred to as (methyl) myristyl ester), (methyl) acrylic acid pentadecane
Base ester, (methyl) aliphatic acrylate (also referred to as (methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester,
(methyl) octadecyl acrylate (also referred to as (methyl) stearyl acrylate acid esters), (methyl) acrylic acid nonadecane base ester, (first
Base) acrylic acid eicosane base ester etc..
From the point for the adhesion strength for improving adhering agent layer, the preferably described acrylic polymer, which has, comes from the alkyl
Carbon atom number be 4 or more (methyl) alkyl acrylate structural unit.Also, from further increasing the viscous of adhering agent layer
The point puted forth effort sets out, and the carbon atom number of the alkyl is preferably 4~12, and more preferably 4~8.Furthermore it is preferred that the carbon of the alkyl
(methyl) alkyl acrylate that atomicity is 4 or more is alkyl acrylate.
The acrylic polymer in addition to have from (methyl) alkyl acrylate structural unit other than, preferably into
One step has from the structural unit containing monomer.
Contain monomer as described, such as reacting by the functional group and aftermentioned crosslinking agent can be enumerated
The starting point or the functional group and the unsaturated group in the aftermentioned compound containing unsaturated group can be passed through that generation is crosslinked
Group reaction and the side chain of acrylic polymer import unsaturated group contain monomer.
As the functional group in the monomer containing functional group, such as hydroxyl, carboxyl, amino, epoxy group can be enumerated etc..
That is, as monomer is contained, such as hydroxyl monomer can be enumerated, carboxyl group-containing monomer, emulsion stability, contain ring
Oxygroup monomer etc..
As the hydroxyl monomer, such as (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl can be enumerated
Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (first
Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl；Vinyl alcohol, alkene
Non- (methyl) acrylic compounds unsaturated alcohol such as propyl alcohol (unsaturated alcohol for not having (methyl) acryloyl group skeleton) etc..
As the carboxyl group-containing monomer, such as the olefinics unsaturation unitary carboxylic such as can enumerate (methyl) acrylic acid, crotonic acid
Acid (i.e. with the monocarboxylic acid of ethylenic unsaturated bond)；The olefinics unsaturation dicarboxyl such as fumaric acid, itaconic acid, maleic acid, citraconic acid
Acid (dicarboxylic acids with ethylenic unsaturated bond)；The acid anhydrides of the ethylenically unsaturated dicarboxylic；Methacrylic acid 2- carboxyethyl
Deng (methyl) acrylic acid carboxyalkyl ester etc..
Monomer containing functional group is preferably hydroxyl monomer, carboxyl group-containing monomer, more preferably hydroxyl monomer.
Constitute the acrylic polymer can be only one kind containing monomer, or and it is two or more, be
When two or more, their combination and ratio can be selected arbitrarily.
In the acrylic polymer, relative to the total amount for the structural unit for constituting acrylic polymer, come from
The content of structural unit containing monomer is preferably 1~35 mass %, more preferably 2~32 mass %, and particularly preferably 3
~30 mass %.
The acrylic polymer is in addition to having structural unit from (methyl) alkyl acrylate and from containing
Other than the structural unit of monomer, can also further have the structural unit from other monomers.
As long as the other monomers are the monomer that can be copolymerized with (methyl) alkyl acrylate etc., do not limit especially
It is fixed.
As the other monomers, such as styrene, α-methylstyrene, vinyltoluene, vinyl formate can be enumerated
Ester, vinyl acetate, acrylonitrile, acrylamide etc..
The other monomers for constituting the acrylic polymer can be only one kind, or and it is two or more, be
When two or more, their combination and ratio can be selected arbitrarily.
The acrylic polymer can be used as the adherence resin (I-1a) of above-mentioned non-energy ray-curable.
On the other hand, make that there is containing for energy-ray polymerism unsaturated group (also referred to as energy-ray polymerizable group)
The substance for having the compound of unsaturated group and the functional group reactions in the acrylic polymer and generating, can be used as
The adherence resin (I-2a) for the energy ray-curable stated.
In addition, " energy-ray polymerism " refers to the property being polymerize by irradiation energy ray in this specification.
Adherence resin (I-1a) contained by adhesion agent composition (I-1) can be only one kind, or two kinds with
On, when being two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), relative to the gross mass of adhesion agent composition (I-1), adherence resin (I-
Content 1a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 15~90 mass %.
[energy ray-curable compound]
The energy ray-curable compound contained by as adhesion agent composition (I-1), can enumerate with energy
It measures ray polymerization unsaturated group and the cured monomer of irradiation or oligomer of energy-ray can be passed through.
As the monomer in energy ray-curable compound, such as trimethylolpropane tris (methyl) propylene can be enumerated
Acid esters, pentaerythrite (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylic acid
Polynary (methyl) acrylate such as ester, 1,4- butanediol two (methyl) acrylate, 1,6-HD (methyl) acrylate；Ammonia
Carbamate (methyl) acrylate；Polyester (methyl) acrylate；Polyethers (methyl) acrylate；Epoxy (methyl) acrylic acid
Ester etc..
As the oligomer in energy ray-curable compound, for example, the monomer polymerization above illustrated can be enumerated and
At oligomer etc..
Storage modulus larger with regard to molecular weight, adhering agent layer is not easy for reducing this point, energy ray-curable chemical combination
Object is preferably carbamate (methyl) acrylate, carbamate (methyl) acrylate oligomer.
The energy ray-curable compound contained by adhesion agent composition (I-1) can be only one kind, can also be with
Be it is two or more, for it is two or more when, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), relative to the gross mass of the adhesion agent composition (I-1), the energy
The content for measuring ray-curable compound is preferably 1~95 mass %, more preferably 5~90 mass %, particularly preferably 10~
85 mass %.
[crosslinking agent]
It will be other than with the structural unit from (methyl) alkyl acrylate, further with from containing functional group
When the acrylic polymer of the structural unit of monomer is used as adherence resin (I-1a), preferred adhesive compositions (I-
1) further contain crosslinking agent.
Adherence resin (I-1a) for example by being cross-linked to each other by the crosslinking agent with the functional group reactions.
As crosslinking agent, such as toluene di-isocyanate(TDI), hexamethylene diisocyanate, phenylenedimethylidyne two can be enumerated
The isocyanates crosslinking agent such as addition product of isocyanates, these diisocyanate (i.e. with the crosslinking agent of isocyanate group)；
The epoxies such as ethylene glycol glycidyl ether crosslinking agent (i.e. with the crosslinking agent of glycidyl)；Six [1- (2- methyl) nitrogen third
Piperidinyl] triazines cross-linkings such as triphosphoric acid triazine (Hexa [1- (2-methyl)-aziridinyl] triphosphatriazine)
Agent (i.e. with the crosslinking agent of '-aziridino)；The metal-chelatings species such as aluminium chelate compound crosslinking agent (has metallo-chelate structure
Crosslinking agent)；Isocyanuric acid esters crosslinking agent (i.e. with the crosslinking agent of isocyanuric acid skeleton) etc..
The pointing out to improve the point of the adhesion strength of adhering agent layer and be easy to get etc. from the cohesiveness of raising sticker
Hair, preferably crosslinking agent are isocyanates crosslinking agent.
Crosslinking agent contained by adhesion agent composition (I-1) can be only one kind, or it is two or more, be two kinds with
When upper, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), relative to 100 mass parts of content of adherence resin (I-1a), crosslinking agent
Content be preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
[Photoepolymerizationinitiater initiater]
Adhesion agent composition (I-1) can also further contain Photoepolymerizationinitiater initiater.Even if to Photoepolymerizationinitiater initiater is contained
Adhesion agent composition (I-1) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater, such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin can be enumerated
The benzoins such as isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal
Close object；Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone etc.
Acetophenone compound；Bis- (2,4,6- trimethylbenzoyl) phosphine oxides of phenyl, 2,4,6- trimethyl benzoyl diphenyl base oxygen
Change the acylphosphine oxides compounds such as phosphine；The sulphur compounds such as benzyl phenyl thioether, tetramethylthiuram monosulfide；1- hydroxy cyclohexylphenyl
The α -one alcoholic compound such as base phenyl ketone；The azo-compounds such as azodiisobutyronitrile；The titanocenes compound such as titanocenes；Thioxanthones etc.
Thioxanthone compounds；Peroxide compound；The dione compounds such as biacetyl；Benzil；Two benzils；Benzophenone；2,4-
Diethyl thioxanthone；1,2- diphenyl methane；2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] acetone；2- chrloroanthracene
Quinone etc..
In addition, as the Photoepolymerizationinitiater initiater, such as the naphtoquinone compounds such as 1- chloroanthraquinone also can be used；The photosensitizers such as amine
Deng.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-1) can be only one kind, or and it is two or more, be
When two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), relative to 100 mass parts of content of the energy ray-curable compound,
The content of Photoepolymerizationinitiater initiater is preferably 0.01~20 mass parts, more preferably 0.03~10 mass parts, particularly preferably 0.05
~5 mass parts.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-1) can also be above-mentioned containing not corresponding to
Other additives of any ingredient.
As other described additives, such as antistatic agent, antioxidant, softening agent (plasticizer), filling can be enumerated
Material (filler), antirust agent, colorant (pigment, dyestuff), sensitizer, tackifier, response delay agent, crosslinking accelerator (catalysis
Agent) etc. well known to additive.
In addition, response delay agent refers to, such as pass through the effect of mixed catalyst in adhesion agent composition (I-1), suppression
The additive of the progress of the cross-linking reaction of the non-purpose in adhesion agent composition (I-1) in system preservation.As response delay
Agent, such as can enumerate and form chelate complex (chelate complex) using the chelate for catalyst
More specifically response delay agent can enumerate the response delay agent in 1 molecule with more than two carbonyls (- C (=O) -).
Other additives contained by adhesion agent composition (I-1) can be only one kind, or and it is two or more, it is two
Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type
Selection.
[solvent]
Adhesion agent composition (I-1) can also contain solvent.By containing solvent, adhesion agent composition (I-1) is to coating
The coating adaptive of object surface is improved.
It is preferred that the solvent is organic solvent, as the organic solvent, such as methyl ethyl ketone, acetone can be enumerated etc.
Ketone；The esters such as ethyl acetate (such as carboxylate)；The ethers such as tetrahydrofuran, dioxanes；The aliphatic hydrocarbons such as hexamethylene, n-hexane；Toluene,
The aromatic hydrocarbons such as dimethylbenzene；Alcohol such as 1- propyl alcohol, 2- propyl alcohol etc..
As the solvent, for example, when can not will manufacture adherence resin (I-1a) solvent that uses from adherence resin
(I-1a) it is removed in and is directly used in adhesion agent composition (I-1), can also in addition added when manufacturing adhesion agent composition (I-1)
Add the solvent with the identical or different type of solvent used when manufacture adherence resin (I-1a).
Solvent contained by adhesion agent composition (I-1) can be only one kind, or and it is two or more, it is two or more
When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), the content of solvent is not particularly limited, and can suitably be adjusted.
<adhesion agent composition (I-2)>
As described above, the adhesion agent composition (I-2) contains the adherence resin (I- in non-energy ray-curable
Side chain 1a) is imported with the adherence resin (I-2a) of the energy ray-curable of unsaturated group.
[adherence resin (I-2a)]
The adherence resin (I-2a) is for example by making have containing for energy-ray polymerism unsaturated group unsaturated
The compound of group is obtained with the functional group reactions in adherence resin (I-1a).
The compound containing unsaturated group be other than with the energy-ray polymerism unsaturated group,
Further having can be bonded and being reacted with the functional group in adherence resin (I-1a) with adherence resin (I-1a)
Group compound.
As the energy-ray polymerism unsaturated group, for example, can enumerate (methyl) acryloyl group, vinyl (
Referred to as ethylidine), allyl (also referred to as 2- acrylic) etc., preferably (methyl) acryloyl group.
As the group that can be bonded with the functional group in adherence resin (I-1a), such as can enumerate can be with hydroxyl or ammonia
The isocyanate group and glycidyl and the hydroxyl that can be bonded with carboxyl or epoxy group and amino etc. of base bonding.
As the compound containing unsaturated group, such as (methyl) acryloyl-oxyethyl isocyanic acid can be enumerated
Ester, (methyl) propenoyl isocyanate, (methyl) glycidyl acrylate etc..
Adherence resin (I-2a) contained by adhesion agent composition (I-2) can be only one kind, or two kinds with
On, when being two or more, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-2), relative to the gross mass of adhesion agent composition (I-2), adherence resin (I-
Content 2a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 10~90 mass %.
[crosslinking agent]
For example, will it is identical with adherence resin (I-1a), with from the structural unit containing monomer
When the acrylic polymer is used as adherence resin (I-2a), preferred adhesive compositions (I-2) are further containing crosslinking
Agent.
As the crosslinking agent in adhesion agent composition (I-2), can enumerate and the friendship in adhesion agent composition (I-1)
Join the identical crosslinking agent of agent.
Crosslinking agent contained by adhesion agent composition (I-2) can be only one kind, or it is two or more, be two kinds with
When upper, a combination thereof and ratio can be selected arbitrarily.
In the adhesion agent composition (I-2), relative to 100 mass parts of content of adherence resin (I-2a), crosslinking agent
Content be preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
[Photoepolymerizationinitiater initiater]
Adhesion agent composition (I-2) can also further contain Photoepolymerizationinitiater initiater.Even if to Photoepolymerizationinitiater initiater is contained
Adhesion agent composition (I-2) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater in adhesion agent composition (I-2), can enumerate and adhesion agent composition (I-1)
In the identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-2) can be only one kind, or and it is two or more, be
When two or more, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-2), relative to 100 mass parts of content of adherence resin (I-2a), photopolymerization
The content of initiator is preferably 0.01~20 mass parts, more preferably 0.03~10 mass, particularly preferably 0.05~5 mass
Part.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-2) can also be above-mentioned containing not corresponding to
Other additives of any ingredient.
As other described additives in adhesion agent composition (I-2), can enumerate with adhesion agent composition (I-1) in
Other identical additives of other additives.
Other additives contained by adhesion agent composition (I-2) can be only one kind, or and it is two or more, it is two
Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type
Selection.
[solvent]
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-2) can also contain molten
Agent.
As the solvent in adhesion agent composition (I-2), can enumerate and the solvent in adhesion agent composition (I-1)
Identical solvent.
Solvent contained by adhesion agent composition (I-2) can be only one kind, or and it is two or more, it is two or more
When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), the content of solvent is not particularly limited, and can suitably be adjusted.
<adhesion agent composition (I-3)>
As described above, the adhesion agent composition (I-3) contains the adherence resin (I-2a) and energy ray curing
Property compound.
In adhesion agent composition (I-3), relative to the gross mass of adhesion agent composition (I-3), adherence resin (I-
Content 2a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 15~90 mass %.
[energy ray-curable compound]
The energy ray-curable compound contained by as adhesion agent composition (I-3), can enumerate with energy
It measures ray polymerization unsaturated group and can be enumerated by the cured monomer of irradiation and oligomer of energy-ray
Energy ray-curable compound identical with the energy ray-curable compound contained by adhesion agent composition (I-1).
The energy ray-curable compound contained by adhesion agent composition (I-3) can be only one kind, can also be with
Be it is two or more, for it is two or more when, their combination and ratio can be selected arbitrarily.
It is described relative to 100 mass parts of content of adherence resin (I-2a) in the adhesion agent composition (I-3)
The content of energy ray-curable compound is preferably 0.01~300 mass parts, more preferably 0.03~200 mass parts, especially
Preferably 0.05~100 mass parts.
[Photoepolymerizationinitiater initiater]
Adhesion agent composition (I-3) can also further contain Photoepolymerizationinitiater initiater.Even if to Photoepolymerizationinitiater initiater is contained
Adhesion agent composition (I-3) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater in adhesion agent composition (I-3), can enumerate and adhesion agent composition (I-1)
In the identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-3) can be only one kind, or and it is two or more, be
When two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), relative to adherence resin (I-2a) and the energy ray-curable chemical combination
100 mass parts of total content of object, the content of Photoepolymerizationinitiater initiater are preferably 0.01~20 mass parts, more preferably 0.03~10 matter
Measure part, particularly preferably 0.05~5 mass parts.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-3) can also be above-mentioned containing not corresponding to
Other additives of any ingredient.
As other described additives, can enumerate it is identical with other additives in adhesion agent composition (I-1) its
His additive.
Other additives contained by adhesion agent composition (I-3) can be only one kind, or and it is two or more, it is two
Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type
Selection.
[solvent]
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-3) can also contain molten
Agent.
As the solvent in adhesion agent composition (I-3), can enumerate and the solvent in adhesion agent composition (I-1)
Identical solvent.
Solvent contained by adhesion agent composition (I-3) can be only one kind, or and it is two or more, it is two or more
When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), the content of solvent is not particularly limited, and can suitably be adjusted.
<adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3)>
So far, mainly to adhesion agent composition (I-1), adhesion agent composition (I-2) and adhesion agent composition (I-3)
It is illustrated, the substance being illustrated containing ingredient as them can be equally used for combining except these three stickers
All adhesion agent compositions other than object are (referred to as " viscous in addition to adhesion agent composition (I-1)~(I-3) in this specification
Agent composition ").
As the adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3), in addition to energy ray-curable
Other than adhesion agent composition, the adhesion agent composition of non-energy ray-curable can be also enumerated.
As the adhesion agent composition of non-energy ray-curable, such as can enumerate containing acrylic resin, amino
Formate ester resin, rubber resin, organic silicon resin, epoxylite, polyvinylether, polycarbonate, esters resin etc.
The adhesion agent composition (I-4) of the adherence resin (I-1a) of non-energy ray-curable, preferably comprises acrylic resin
The adhesion agent composition of non-energy ray-curable.
It is preferred that the adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3) contains one or more
Its content can be set as content identical with the situation of above-mentioned adhesion agent composition (I-1) etc. by crosslinking agent.
<adhesion agent composition (I-4)>
As the preference of adhesion agent composition (I-4), for example, can enumerate containing the adherence resin (I-1a) with
The adhesion agent composition of crosslinking agent.
[the adherence resin (I-1a) in adhesion agent composition (I-4)]
As the adherence resin (I-1a) in adhesion agent composition (I-4), can enumerate and adhesion agent composition (I-1)
In the identical adherence resin of adherence resin (I-1a).
Adherence resin (I-1a) contained by adhesion agent composition (I-4) can be only one kind, or two kinds with
On, when being two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), relative to the gross mass of adhesion agent composition (I-4), adherence resin (I-
Content 1a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 15~90 mass %.
[crosslinking agent]
It will be other than with the structural unit from (methyl) alkyl acrylate, further with from containing functional group
When the acrylic polymer of the structural unit of monomer is used as adherence resin (I-1a), preferred adhesive compositions (I-
4) further contain crosslinking agent.
As the crosslinking agent in adhesion agent composition (I-4), can enumerate and the crosslinking agent in adhesion agent composition (I-1)
Identical crosslinking agent.
Crosslinking agent contained by adhesion agent composition (I-4) can be only one kind, or it is two or more, be two kinds with
When upper, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-4), relative to 100 mass parts of content of adherence resin (I-1a), crosslinking
The content of agent is preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-4) can also be above-mentioned containing not corresponding to
Other additives of any ingredient.
As other described additives, can enumerate it is identical with other additives in adhesion agent composition (I-1) its
His additive.
Other additives contained by adhesion agent composition (I-4) can be only one kind, or and it is two or more, it is two
Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type
Selection.
[solvent]
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-4) can also contain molten
Agent.
As the solvent in adhesion agent composition (I-4), can enumerate and the solvent in adhesion agent composition (I-1)
Identical solvent.
Solvent contained by adhesion agent composition (I-4) can be only one kind, or and it is two or more, it is two or more
When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), the content of solvent is not particularly limited, and can suitably be adjusted.
In protective film formation composite sheet of the invention, preferably adhering agent layer is non-energy ray-curable.This be by
In, if adhering agent layer is energy ray-curable, when the irradiation by energy-ray solidifies protective film formation film,
Solidification while can not inhibiting adhering agent layer.If adhering agent layer solidifies simultaneously with protective film formation film, after will lead to solidification
Protective film formation film and adhering agent layer the attaching that not can be carried out the degree of removing occurs on their interface.At this point, difficult
The back side to be had to the semiconductor chip of the protective film formation film after solidifying, i.e. protective film (in the present specification, sometimes referred to as
" semiconductor chip with protective film ") it is removed from the support chip for having the adhering agent layer after solidifying, lead to not normally pick up
Semiconductor chip with protective film.It can by making adhering agent layer non-energy ray-curable for support chip of the invention
Definitely avoid such undesirable condition, is capable of the semiconductor chip of more easily pick-up tape protective film.
Herein, effect when being non-energy ray-curable to adhering agent layer is illustrated, however, even if support chip
It is layer in addition to adhering agent layer with protective film formation with the layer that film directly contacts, as long as the layer is non-energy ray-curable,
Then play same effect.
<<preparation method of adhesion agent composition>>
Adhesion agent composition (I-1)~(I-3) and adhesion agent composition (I-4) etc. except adhesion agent composition (I-1)~
(I-3) adhesion agent composition other than can constitute each ingredient of the adhesion agent composition, i.e., by described in blending by blending
Sticker and the ingredient in addition to the sticker as needed and obtain.
Order of addition when blending each ingredient is not particularly limited, and can also add two or more ingredients simultaneously.
It, can be pre- by the blending ingredient and mixing solvent with any blending ingredient in addition to solvent when using solvent
Dilution is to carry out using can not also be by any blending ingredient pre-dilution in addition to solvent but by by solvent and this
It is a little blend ingredients mixing to carry out using.
The method that each ingredient is mixed when blending is not particularly limited, and suitably selects: making from following well known methods
Blender or stirring blade etc. rotate and mixed method；The method mixed using blender；Apply ultrasonic wave and
Mixed method etc..
As long as respectively blending ingredient not deteriorate, the temperature and time when adding and mix each ingredient are not particularly limited,
Suitably adjust, but preferable temperature is 15~30 DEG C
Film is used in the formation of ◎ protective film
In protective film formation composite sheet of the invention, protective film obtained from protective film formation film is solidified and branch
Adhesion strength between blade is preferably 50~1500mN/25mm, more preferably 52~1450mN/25mm, and further preferably 53
~1430mN/25mm.By making the adhesion strength lower limit value or more, in the semiconductor chip of pick-up tape protective film,
It can inhibit the pickup of the semiconductor chip with protective film outside target, the band protective film as target can be picked up with high selectivity
Semiconductor chip.In addition, by make the adhesion strength upper limit value hereinafter, pick-up tape protective film semiconductor chip
When, it can inhibit the rupture and defect of semiconductor chip.By this method, it by making the adhesion strength in a specific range, protects
Film formation has good pickup adaptive with composite sheet.
In addition, in the present specification, even if after protective film formation film solidifies, as long as maintaining support chip and protective film shape
At the stepped construction of the solidfied material (in other words, support chip and protective film) with film, then the laminate structure is thus referred to as " protection
Film, which is formed, uses composite sheet ".
The adhesion strength between protective film and support chip is measured using the following method.
That is, being 25mm by width, the arbitrary protective film formation of length is attached by its protective film formation with film with composite sheet
On adherend.
Then, irradiation energy ray solidified protective film formation film after forming protective film, with 300mm/ minutes
Peeling rate removes support chip from the protective film being attached on adherend.Removing at this time is set as 180 ° of removings, i.e.,
By support chip (protection along its length in such a way that the face for contacting with each other protective film and support chip is in 180 ° of angle each other
Film forms the length direction for using composite sheet) removing.Later, the load (peeling force) when this 180 ° removings is measured, and is measured
Value is used as the adhesion strength (mN/25mm).
As long as the length of the protective film formation composite sheet for measurement is in the range of steadily can detect adhesion strength
It is not particularly limited, but preferably 100~300mm.In addition, preferably making protective film formation composite sheet when being measured
The state being attached on adherend, and make attaching in stable conditionization of protective film formation composite sheet.
In the present invention, the adhesion strength between protective film formation film and the support chip is not particularly limited, such as can
Think 80mN/25mm with first-class, but preferably 100mN/25mm or more, more preferably 150mN/25mm or more, particularly preferably
200mN/25mm or more.By making the adhesion strength 100mN/25mm or more, when being cut, can inhibit protective film and formed
With the removing of film and support chip, fly from support chip for example, can inhibit the semiconductor chip that the back side has protective film formation film
It dissipates.
On the other hand, the upper limit value of the adhesion strength between protective film formation film and the support chip is not particularly limited,
It such as can be any of 4000mN/25mm, 3500mN/25mm, 3000mN/25mm etc..But these values are only an example
Son.
That is, as a side, adhesion strength between protective film formation film and the support chip can for 80~
4000mN/25mm, preferably 100~3500mN/25mm are even more preferably 150~3500mN/25mm, particularly preferably
200~3000mN/25mm.
In addition to do not carry out the protective film formation film for measurement, irradiation based on energy-ray solidification this point with
Outside, protective film formation film and support can be measured by the identical method of adhesion strength between above-mentioned protective film and support chip
Adhesion strength between piece.
Adhesion strength and protective film between above-mentioned protective film and support chip are formed with the adhesion strength between film and support chip
Such as the setting protective film formation film in the type containing ingredient and amount, support chip of adjusting protective film formation film can be passed through
The constituent material of layer and the surface state etc. of this layer be adjusted.
For example, the type containing ingredient and amount of protective film formation film can pass through aftermentioned protective film formation composition
The type containing ingredient and amount be adjusted.Also, in ingredient, example is contained by adjusting protective film formation composition
Do not have the type and content of polymer (b), the content of packing material (d) or the crosslinking agent of energy ray-curable group such as
(f) content can more easily adjust the adhesion strength between protective film or protective film formation film and support chip.
In addition, for example, adjusting can be passed through when the layer for being provided with protective film formation film in support chip is adhering agent layer
The type and amount containing ingredient of adhering agent layer, to suitably adjust its constituent material.Also, adhering agent layer contains ingredient
Type and amount can be adjusted by the type containing ingredient and amount of above-mentioned adhesion agent composition.
On the other hand, when the layer for being provided with protective film formation film in support chip is substrate, protective film or protective film
Formed with adhesion strength between film and support chip, except through substrate constituent material be adjusted other than, substrate can also be passed through
Surface state be adjusted.Also, the surface state of substrate for example can be by implementing to improve base in conduct listed above
Material and the surface treatment of the adherence of other layers are adjusted, that is, can be by implementing based on the recessed of blasting treatment, solvent processing etc.
Convexification processing；Corona discharge Treatment, electron beam treatment with irradiation, corona treatment, ozone-ultraviolet line treatment with irradiation, at flame
The oxidation processes such as reason, chromic acid processing, hot wind processing；Any one in prime treatment etc. is adjusted.
Protective film formation has energy ray-curable with film, such as can enumerate containing energy ray-curable ingredient
(a) film is used in protective film formation.
Energy ray-curable ingredient (a) is preferably uncured, preferably has adherence, more preferably uncured and have
Adherence.
Protective film formation film can be only made of one layer (single layer), can also be made of two layers or more of multiple layers, be
At multiple layers, these multiple layers mutually the same can be can also be different, these multiple layers combinations are not particularly limited.
The thickness of protective film formation film is preferably 1~100 μm, more preferably 5~75 μm, particularly preferably 5~50 μm.
By make protective film formation film with a thickness of above-mentioned lower limit value more than, be capable of forming the higher protective film of protective capability.In addition,
By make protective film formation film with a thickness of the upper limit value hereinafter, can inhibit thickness as excessive thickness.
Herein, the thickness that " thickness of protective film formation film " refers to protective film formation film entirety, for example, by multiple layers
The thickness of the protective film formation film of composition refers to the overall thickness for constituting all layers of protective film formation film.
As long as protective film become fully play its function degree curing degree, make protective film formation film solidification from
And condition of cure when forming protective film is not particularly limited, and suitably select i.e. according to the type of protective film formation film
It can.
For example, the illumination of energy-ray when solidifying protective film formation film is preferably 4~280mW/cm2.Also, it is described
The light quantity of energy-ray when solidification is preferably 3~1000mJ/cm2。
<<protective film, which is formed, uses composition>>
Protective film formation film can be used the protective film formation composition containing its constituent material and be formed.For example, logical
It crosses and protective film formation is coated in the formation object surface of protective film formation film with composition and is dried as needed, energy
It is enough to form protective film formation film in target site.The ingredient not gasified under room temperature in protective film formation composition is mutual
Content is than usually with the mutual content of the ingredient of protective film formation film than identical.Herein, " room temperature " with hereinbefore say
Bright is identical.
Using well known method carry out adhesion agent composition coating, such as can enumerate using Kohler coater,
Scraping blade coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain coater, die coating machine, knife type coater, silk screen
The method of the various coating machines such as coating machine, Meyer rod coater, kiss painting machine.
The drying condition of protective film formation composition is not particularly limited, but after protective film formation composition contains
It when the solvent stated, is preferably thermally dried, at this point, for example preferably being carried out with the condition of 70~130 DEG C, 10 seconds~5 minutes
It is dry.
<protective film, which is formed, uses composition (IV-1)>
As protective film formation composition, such as the guarantor containing the energy ray-curable ingredient (a) can be enumerated
Cuticula is formed with composition (IV-1) etc..
[energy ray-curable ingredient (a)]
Energy ray-curable ingredient (a) is the cured ingredient of irradiation by energy-ray, also for for protection
Film formation film assigns the ingredient for making film property or pliability etc..
As energy ray-curable ingredient (a), such as it can enumerate with energy ray-curable group and divide equally again
Polymer (a1) that son amount be 80000~2000000 and with energy ray-curable group and molecular weight is 100~80000
Compound (a2).The polymer (a1) can be its at least part substance made of the crosslinking of aftermentioned crosslinking agent (f),
Or uncrosslinked substance.
In addition, in the present specification, unless otherwise indicated, " weight average molecular weight ", which refers to, utilizes gel permeation chromatography (GPC)
The polystyrene scaled value of method measurement.
(with energy ray-curable group and polymer (a1) that weight average molecular weight is 80000~2000000)
As with energy ray-curable group and polymer (a1) that weight average molecular weight is 80000~2000000, example
There is the acrylic polymer (a11) for the functional group that can be reacted with group possessed by other compounds as that can enumerate
With the energy with energy ray-curables groups such as the group reacted with the functional group and energy ray-curable double bonds
The acrylic resin (a1-1) that amount ray-curable compound (a12) is polymerized.
As the official that can be reacted with group possessed by other compounds in acrylic polymer (a11)
Can group, such as hydroxyl, carboxyl, amino, substituted-amino can be enumerated (one or two hydrogen atom of amino is by addition to hydrogen atom
Group replace made of group), epoxy group etc..Wherein, from the corrosion for preventing the circuits such as semiconductor crystal wafer, semiconductor chip
Point sets out, and the preferably described functional group is the group in addition to carboxyl.
Wherein, the preferably described functional group is hydroxyl.
Acrylic polymer (a11) with functional group
As the acrylic polymer (a11) with functional group, such as can enumerate with the functional group
Acrylic monomer and polymer made of the acrylic monomer copolymerization for not having the functional group, or remove these lists
Further copolymerization has the polymer of the monomer (non-acrylic monomer) in addition to acrylic monomer other than body.
In addition, the acrylic polymer (a11) can be random copolymer, or block copolymer.
As the acrylic monomer with the functional group, such as hydroxyl monomer can be enumerated, carboxyl group-containing monomer, contained
Amino monomers, monomer containing substituted-amino, containing epoxy based monomers etc..
As the hydroxyl monomer, such as (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl can be enumerated
Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (first
Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl；Vinyl alcohol, alkene
Non- (methyl) acrylic compounds unsaturated alcohol such as propyl alcohol (unsaturated alcohol for not having (methyl) acryloyl group skeleton) etc..
As the carboxyl group-containing monomer, such as the olefinics unsaturation unitary carboxylic such as can enumerate (methyl) acrylic acid, crotonic acid
Acid (i.e. with the monocarboxylic acid of ethylenic unsaturated bond)；The olefinics unsaturation dicarboxyl such as fumaric acid, itaconic acid, maleic acid, citraconic acid
Acid (i.e. with the dicarboxylic acids of ethylenic unsaturated bond)；The acid anhydrides of the ethylenically unsaturated dicarboxylic；Methacrylic acid 2- carboxyl second
Ester etc. (methyl) acrylic acid carboxyalkyl ester etc..
It is preferred that the acrylic monomer with the functional group is hydroxyl monomer, carboxyl group-containing monomer, more preferably contain hydroxyl
Base monomer.
Constitute the acrylic polymer (a11), the acrylic monomer with the functional group can be only one
Kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
As the acrylic monomer for not having the functional group, it is 1 that the alkyl for preferably comprising Arrcostab, which is carbon atom number,
(methyl) alkyl acrylate of~18 chain structure etc., such as (methyl) methyl acrylate, (methyl) propylene can be enumerated
Acetoacetic ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid
Isobutyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid oneself
Ester, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid are just
Monooctyl ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid 11
Arrcostab, (methyl) dodecylacrylate (also referred to as (methyl) lauryl acrylate), (methyl) acrylic acid tridecyl
Ester, (methyl) acrylic acid tetradecane base ester (also referred to as (methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester,
(methyl) aliphatic acrylate (also referred to as (methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (first
Base) octadecyl acrylate (also referred to as (methyl) stearyl acrylate acid esters) etc..
In addition, as the acrylic monomer for not having the functional group, such as (methyl) acrylic acid first can also be enumerated
Oxygroup methyl esters, (methyl) methoxyethyl acrylate, (methyl) ethioxy methyl esters, (methyl) ethoxyethyl acrylate
Deng (methyl) acrylate containing alkoxyalkyl；Including (methyl) phenyl acrylate etc. (methyl) benzyl acrylate etc.,
(methyl) acrylate with aromatic group；(methyl) acrylamide and its derivative of non-crosslinked property；(methyl) propylene
The non-crosslinked property such as sour N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester with tertiary amino
(methyl) acrylate etc..
Constitute the acrylic polymer (a11), the acrylic monomer without the functional group can be only
It is a kind of, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
As the non-acrylic monomer, such as the alkene such as ethylene, norbornene can be enumerated；Vinyl acetate；Benzene
Ethylene etc..
The non-acrylic monomer for constituting the acrylic polymer (a11) can be only one kind, or
Two or more, when being two or more, their combination and ratio can be selected arbitrarily.
In the acrylic polymer (a11), relative to the structure list for constituting the acrylic polymer (a11)
The gross mass of member, the ratio (content) of the structural unit as derived from the acrylic monomer with the functional group is preferably 0.1
~50 mass %, more preferably 1~40 mass %, particularly preferably 3~30 mass %.By making the such model of the ratio
It encloses, is obtained according to by the acrylic polymer (a11) and the copolymerization of the energy ray-curable compound (a12)
The acrylic resin (a1-1) in energy ray-curable group content, can easily consolidating the first protective film
Change degree is adjusted to preferred range.
The acrylic polymer (a11) for constituting the acrylic resin (a1-1) can be only one kind, can also
Think it is two or more, for it is two or more when, their combination and ratio can be selected arbitrarily.
Energy ray-curable compound (a12)
It is preferred that the energy ray-curable compound (a12), which has, selects free isocyanate group, epoxy group and carboxyl group
At one or more of group as can be reacted with functional group possessed by the acrylic polymer (a11)
Group, more preferably have isocyanate group as the group.For example, working as the energy ray-curable compound (a12)
When with isocyanate group as the group, which is easy and has acrylic acid of the hydroxyl as the functional group
The hydroxyl of quasi polymer (a11) is reacted.
It is preferred that the energy ray-curable compound (a12) is described energy ray curing with 1~5 in 1 molecule
Property group, more preferably have 1~3 energy ray-curable group.
As the energy ray-curable compound (a12), such as 2- methylacryoyloxyethyl isocyanide can be enumerated
Acid esters, isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate, methacryloyl isocyanate, allyl iso cyanurate, 1,
1- (double acryloyloxymethyls) ethyl isocyanate；
It is obtained by diisocyanate cpd or polyisocyanate compound with reacting for (methyl) hydroxy-ethyl acrylate
The acryloyl group monoisocyanate compound arrived；
Pass through diisocyanate cpd or polyisocyanate compound, polyol compound and (methyl) acrylic acid hydroxyl second
Acryloyl group monoisocyanate compound etc. obtained from the reaction of ester.
Wherein, the preferably described energy ray-curable compound (a12) is 2- methylacryoyloxyethyl isocyanates.
The energy ray-curable compound (a12) for constituting the acrylic resin (a1-1) can be only one
Kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
Relative to the protective film formation gross mass in addition to solvent of composition (IV-1), acrylic resin (a1-1)
Content be preferably 1~40 mass %, more preferably 2~30 mass %, particularly preferably 3~20 mass %.
In the acrylic resin (a1-1), the energy from the energy ray-curable compound (a12) is penetrated
The content of line curative group is excellent relative to the ratio of the content of the functional group from the acrylic polymer (a11)
It is selected as 20~120 moles of %, more preferably 35~100 moles of %, particularly preferably 50~100 moles of %.By making described contain
The ratio of amount is such range, is become much larger by the bonding force for the protective film being solidified to form.In addition, when the energy is penetrated
When line curability compound (a12) is simple function (having 1 group in 1 molecule) compound, the ratio of the content
Upper limit value be 100 moles of %, and when the energy ray-curable compound (a12) be it is multifunctional (in 1 molecule have 2 with
On the group) compound when, the upper limit value of the ratio of the content is sometimes more than 100 moles of %.
The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000~2000000, more preferably 300000~
1500000。
When the polymer (a1) is that its at least part is crosslinked substance made of agent (f) crosslinking, the polymer
(a1) can be not belonging to as the monomer for constituting the acrylic polymer (a11) and any in the above-mentioned monomer illustrated
Person and there is the monomer of group reacted with crosslinking agent (f) to be copolymerized, and is reacted with the crosslinking agent (f)
Group at be crosslinked made of polymer, can also for from the energy ray-curable compound (a12), with it is described
Polymer made of being crosslinked at the group that functional group is reacted.
Protective film, which forms to be formed with composition (IV-1) and protective film, uses the polymer (a1) contained by film can be only
For one kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
(there is the compound (a2) that energy ray-curable group and molecular weight are 100~80000)
As with energy ray-curable group and energy possessed by compound (a2) that molecular weight is 100~80000
Ray-curable group is measured, the group comprising energy ray-curable double bond can be enumerated, as preferred group, can be enumerated
(methyl) acryloyl group, vinyl etc..
The compound (a2) is not particularly limited as long as meeting above-mentioned condition, can enumerate with energy ray curing
Property the low molecular weight compound of group, the epoxy resin with energy ray-curable group, there is energy ray-curable base
The phenol resin etc. of group.
As the low molecular weight compound with energy ray-curable group in the compound (a2), such as can arrange
Polyfunctional monomer or oligomer etc. are enumerated, preferably with the acrylic ester compound of (methyl) acryloyl group.
As the acrylic ester compound, such as 2- hydroxyl -3- (methyl) acryloxypropyl first can be enumerated
Base acrylate, polyethylene glycol two (methyl) acrylate, propoxylation Ethoxylated bisphenol A bis- (methyl) acrylate, 2,
2- bis- [4- ((methyl) acryloxy polyethoxy) phenyl] propane, Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2-
Bis- [4- ((methyl) acryloxy diethoxy) phenyl] propane, the bis- [4- (2- (methyl) acryloyloxyethoxy) of 9,9-
Phenyl] fluorenes, 2,2- bis- [4- (the poly- propoxyl group of (methyl) acryloxy) phenyl] propane, Tricyclodecane Dimethanol two (methyl) third
Olefin(e) acid ester (also referred to as tristane dihydroxymethyl two (methyl) acrylate), 1,10- decanediol two (methyl) acrylate, 1,
6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate,
Tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) propylene
Acid esters, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid
Ester, 2,2- bis- [4- ((methyl) acryloyloxyethoxy) phenyl] propane, neopentyl glycol two (methyl) acrylate, ethyoxyl
Change the difunctionalities (methyl) third such as polypropylene glycol two (methyl) acrylate, 2- hydroxyl -1,3- two (methyl) acryloxy propane
Olefin(e) acid ester；
Modified three (2- (methyl) the acryloyl-oxy second of three (2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters, 6-caprolactone
Base) isocyanuric acid ester, ethoxylated glycerol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, trihydroxy methyl
Propane three (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, ethoxylation pentaerythrite four (methyl)
Poly- (methyl) acrylate of acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol, six (first of dipentaerythritol
Base) multifunctional (methyl) acrylates such as acrylate；
Multifunctional (methyl) acrylates oligomer such as carbamate (methyl) acrylate oligomer etc..
As the epoxy resin with energy ray-curable group, solid with energy-ray in the compound (a2)
The phenol resin of the property changed group, such as be able to use and recorded in the 0043rd section etc. of " Japanese Unexamined Patent Publication 2013-194102 bulletin "
Resin.Such resin also corresponds to constitute the resin of aftermentioned thermosetting component (h), but describedization is regarded as in the present invention
It closes object (a2).
The weight average molecular weight (Mw) of the compound (a2) is preferably 100~30000, and more preferably 300~10000.
Protective film, which forms to be formed with composition (IV-1) and protective film, uses the compound (a2) contained by film can be only
For one kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
[polymer (b) without energy ray-curable group]
Protective film formation uses composition (IV-1) and protective film formation that film is used to contain the compound (a2) as the energy
When measuring ray-curable ingredient (a), preferably further contain the polymer (b) without energy ray-curable group.
The polymer (b) can be crosslinked substance made of agent (f) crosslinking at least part, or uncrosslinked
Substance.
As the polymer (b) for not having energy ray-curable group, such as acrylic polymer, benzene can be enumerated
Oxygroup resin, carbamate resins, polyester, rubber resin, propenoic methyl carbamate resin, polyvinyl alcohol (PVA), fourth
Urea formaldehyde, polyester urethane resin etc..
Wherein, the preferably described polymer (b) is acrylic polymer (hereinafter, writing a Chinese character in simplified form work " acrylic polymer sometimes
(b-1)”)。
Acrylic polymer (b-1) can be well known acrylic polymer, such as can be a kind of acrylic compounds
The homopolymer of monomer, or the copolymer of two or more acrylic monomers can also be one or more kinds of
The copolymerization of acrylic monomer and one or more kinds of monomers (non-acrylic monomer) in addition to acrylic monomer
Object.
As the acrylic monomer of composition acrylic polymer (b-1), such as (methyl) propylene can be enumerated
Acid alkyl ester, (methyl) acrylate with cyclic skeleton, (methyl) acrylate containing glycidyl, hydroxyl
(methyl) acrylate, (methyl) acrylate containing substituted-amino etc..Herein, " substituted-amino " and the phase being illustrated above
Together.
As (methyl) alkyl acrylate, the alkyl for preferably comprising Arrcostab is chain that carbon atom number is 1~18
(methyl) alkyl acrylate of shape structure etc., for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate,
(methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (first
Base) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) n-octyl,
The positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid undecyl
Ester, (methyl) dodecylacrylate (also referred to as (methyl) lauryl acrylate), (methyl) tridecyl acrylate,
(methyl) acrylic acid tetradecane base ester (also referred to as (methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (first
Base) aliphatic acrylate (also referred to as (methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) third
Olefin(e) acid stearyl (also referred to as (methyl) stearyl acrylate acid esters) etc..
As described (methyl) acrylate with cyclic skeleton, such as (methyl) isobomyl acrylate can be enumerated
(methyl) the acrylate base esters such as ester, (methyl) dicyclopentyl acrylate；
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester；
(methyl) acrylic acid cyclenes base ester such as (methyl) acrylic acid dicyclopentenyl ester；
(methyl) acrylic acid cycloalkenyl oxy Arrcostab such as (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester etc..
As described (methyl) acrylate containing glycidyl, such as (methyl) glycidyl can be enumerated
Ester etc..
As (methyl) acrylate of the hydroxyl, such as (methyl) acrylate, (methyl) can be enumerated
Acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2-
Hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl etc..
As described (methyl) acrylate containing substituted-amino, such as (methyl) acrylic acid N- methylamino can be enumerated
Ethyl ester etc..
As the non-acrylic monomer of composition acrylic polymer (b-1), such as ethylene, drop ice can be enumerated
The alkene such as piece alkene；Vinyl acetate；Styrene etc..
As being crosslinked agent (f) crosslinking, the polymer without energy ray-curable group at least partially
(b), for example, the reactive functional groups that can enumerate in the polymer (b) reacted with crosslinking agent (f) obtained from polymer.
The reactive functional groups are suitably selected according to progress such as the types of crosslinking agent (f), are not particularly limited.Example
Such as, when crosslinking agent (f) is polyisocyanate compounds, as the reactive functional groups, hydroxyl, carboxyl, ammonia can be enumerated
Base etc., wherein preferably with the hydroxyl with high reactivity of isocyanate group.In addition, when crosslinking agent (f) is epoxy compounds,
As the reactive functional groups, carboxyl, amino, amide groups etc. can be enumerated, wherein preferably with high reactivity with epoxy group
Carboxyl.However, from the point of the corrosion for the circuit for preventing semiconductor crystal wafer or semiconductor chip, the preferably described reactive functional
Group is the group in addition to carboxyl.
It, such as can as with the reactive functional groups and not having the polymer (b) of energy ray-curable group
Enumerate polymer obtained from at least monomer polymerization with the reactive functional groups of sening as an envoy to.For acrylic polymer
(b-1) when, the monomer with the reactive functional groups is used to arrange as the monomer for constituting the acrylic polymer (b-1)
It is lifting, in the acrylic monomer and non-acrylic monomer any one or both.For example, as with hydroxyl
As the polymer (b) of reactive functional groups, such as (methyl) acrylic ester polymerization by hydroxyl can be enumerated and obtained
The polymer arrived can enumerate the acrylic monomer or non-acrylic monomer that will hereinbefore enumerate in addition to this
One or two of more than hydrogen atom be substituted by polymer obtained from monomer polymerization made of the reactive functional groups.
In the polymer (b) with reactive functional groups, relative to the structural unit for constituting the polymer (b)
Gross mass, be preferably 1~25 mass % by the ratio (content) of the structural unit of the monomer derived with reactive functional groups,
More preferably 2~20 mass %.By making the such range of the ratio, in the polymer (b), the degree of crosslinking at
For preferred range.
The more good point of film property is made from protective film formation composition (IV-1), is not had energy ray curing
The weight average molecular weight (Mw) of the polymer (b) of property group is preferably 10000~2000000, more preferably 100000~
1500000。
Protective film formed with composition (IV-1) and protective film formed with it is contained by film, do not have energy ray-curable
The polymer (b) of group can be only one kind, or two or more, when being two or more, their combination and ratio can
Arbitrarily to select.
As protective film formation with composition (IV-1), can enumerate containing the polymer (a1) and the compound
(a2) in any one or both protective film formation use composition.Also, it when containing the compound (a2), preferably protects
Cuticula, which is formed, further contains the polymer (b) without energy ray-curable group with composition (IV-1), at this point, also excellent
Choosing is further containing (a1).In addition, protective film, which is formed, can also not contain the compound (a2) with composition (IV-1)
And simultaneously containing the polymer (a1) and without the polymer (b) of energy ray-curable group.
Protective film, which is formed, to be contained the polymer (a1), the compound (a2) with composition (IV-1) and not to have energy
When the polymer (b) of ray-curable group, by the polymer (a1) and polymerization without energy ray-curable group
When the total content of object (b) is set as 100 mass parts, protective film forms the content with the compound (a2) in composition (IV-1)
Preferably 10~400 mass parts, more preferably 30~350 mass parts.
In protective film formation in composition (IV-1), gross mass relative to the ingredient in addition to solvent, described energy
The total content of ray-curable ingredient (a) and the polymer (b) without energy ray-curable group is measured (that is, relative to guarantor
Cuticula forms energy ray-curable ingredient (a) that use the gross mass of film, described and without energy ray-curable group
The total content (quality) of polymer (b)) it is preferably 5~90 mass %, more preferably 10~80 mass %, particularly preferably 15~
70 mass %.By making the such range of ratio of the total content, protective film is formed to be become with the energy ray-curable of film
It obtains better.
In total content (gross mass) of the protective film formation in composition (IV-1), relative to the ingredient in addition to solvent
, the content of the energy ray-curable ingredient (a) is (that is, gross mass relative to protective film formation film, the energy
The content of ray-curable ingredient (a)) be preferably 6~50 mass %, more preferably 10~40 mass %, still more preferably for
15~30 mass %, particularly preferably 19.5~27 mass %.It, can by making the such range of ratio of the total content
Suitably solidify, so that making film property becomes more good, can prevent reliability caused by excessively shrinking when solidification from reducing.
When protective film formation containing the energy ray-curable ingredient (a) and does not have energy with composition (IV-1)
When the polymer (b) of ray-curable group, is formed and used in film in protective film formation composition (IV-1) and protective film, relatively
In 100 mass parts of content of energy ray-curable ingredient (a), the content of the polymer (b) is preferably 3~160 mass parts,
More preferably 6~130 mass parts.By making the such range of the content of the polymer (b), film is used in protective film formation
Energy ray-curable become more good.
In addition to containing energy ray-curable ingredient (a) and polymer (b) without energy ray-curable group with
Outside, protective film is formed can also be contained according to purpose selected from by Photoepolymerizationinitiater initiater (c), packing material with composition (IV-1)
(d), in the group of coupling agent (e), crosslinking agent (f), colorant (g), Thermocurable ingredient (h) and universal additive (z) composition
It is one or more kinds of.For example, by using containing the energy ray-curable ingredient (a) and Thermocurable ingredient (h)
Protective film, which is formed, uses composition (IV-1), is formed by protective film formation film and improves to the bonding force of adherend because of heating,
It is also improved by the protection film strength that the protective film formation is formed with film.
[Photoepolymerizationinitiater initiater (c)]
As Photoepolymerizationinitiater initiater (c), such as can to enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin different
The benzoins chemical combination such as propyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal
Object；The benzene such as acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone
Ethanone compounds；Bis- (2,4,6- trimethylbenzoyl) phosphine oxides of phenyl, the oxidation of 2,4,6- trimethyl benzoyl diphenyl base
The acylphosphine oxides compound such as phosphine；The sulphur compounds such as benzyl phenyl thioether, tetramethylthiuram monosulfide；1- hydroxy-cyclohexyl
The α -one alcoholic compound such as phenyl ketone；The azo-compounds such as azodiisobutyronitrile；The titanocenes compound such as titanocenes；The thiophenes such as thioxanthones
Ton ketone compound；Benzophenone, 2- (dimethylamino) -1- (4- morpholinyl phenyl) -2- benzyl -1- butanone, 1- [9- ethyl -6-
(2- methyl benzoyl) -9H- carbazole -3- base] benzophenone cpds such as ethyl ketone 1- (O- acetyl oxime)；Peroxide chemical combination
Object；The dione compounds such as biacetyl；Benzil；Two benzils；2,4- diethyl thioxanthone；1,2- diphenyl methane；2- hydroxyl-
2- methyl-1-[4- (1- methyl ethylene) phenyl] acetone；2- chloroanthraquinone etc..
In addition, as Photoepolymerizationinitiater initiater (c), such as the naphtoquinone compounds such as 1- chloroanthraquinone also can be used；Photosensitizers such as amine etc..
It can be only one kind that protective film, which is formed with the Photoepolymerizationinitiater initiater (c) contained by composition (IV-1), or
Two or more, when being two or more, their combination and ratio can be selected arbitrarily.
When using Photoepolymerizationinitiater initiater (c), in protective film formation in composition (IV-1), relative to energy ray curing
100 mass parts of content of property compound (a), the content of Photoepolymerizationinitiater initiater (c) is preferably 0.01~20 mass parts, more preferably
2.0~12.0 mass parts, particularly preferably 2~10 mass parts.
[packing material (d)]
By making protective film formation film contain packing material (d), protection obtained from protective film formation film is solidified
The adjusting of the thermal expansion coefficient of film becomes easy, by keeping the thermal expansion coefficient most suitable relative to the formation object of protective film
Change, is further increased using the reliability of protective film formation encapsulation obtained from composite sheet.In addition, by forming protective film
Contain packing material (d) with film, also can reduce the hydroscopicity of protective film, or can be improved thermal diffusivity.
As packing material (d), such as the packing material being made of thermally-conductive materials can be enumerated.
Packing material (d) can be any one of organic filler material and inorganic filling material, preferably inorganic fill
Material.
As preferred inorganic filling material, for example, can enumerate silica, aluminium oxide, talcum, calcium carbonate, titanium white,
The powder such as colcother, silicon carbide, boron nitride；By pearl made of these inorganic filling material spheroidizations；These inorganic filling materials
The modified product in surface；The mono-crystlling fibre of these inorganic filling materials；Glass fibre etc..
Wherein, inorganic filling material is preferably silica or aluminium oxide, more preferably through epoxy-modified silica.
The average grain diameter of packing material (d) is not particularly limited, but preferably 0.01~20 μm, more preferably 0.08~15
μm, more preferably 0.1~15 μm, more preferably 0.1~10 μm, more preferably 0.3~10 μm, particularly preferably 0.5~8 μm.
By making the such range of average grain diameter of packing material (d), it is able to maintain that the adhesiveness of the formation object to protective film,
And inhibit the reduction of the transmitance of the light of protective film simultaneously.
In addition, unless otherwise indicated, " average grain diameter " in this specification refers to be acquired using laser diffraction scattering method
In size distribution curve, accumulated value is the partial size (D at 50%50) value.
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the packing material (d) contained by film,
Kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
When using packing material (d), in protective film formation in composition (IV-1), relative to all in addition to solvent
The total content (gross mass) of ingredient, packing material (d) content (filling i.e. relative to the gross mass of protective film formation film
The content of material (d)) it is preferably 5~83 mass %, more preferably 7~78 mass %.By the content for making packing material (d)
The adjusting of such range, above-mentioned thermal expansion coefficient becomes easier to.
As a side of the invention, relative to the gross mass of protective film formation film, the content of packing material (d) is excellent
It is selected as 5~83 mass %, more preferably 5~70 mass %.
As another side of the invention, when the average grain diameter of packing material (d) is 0.08~0.15 μm, relative to
Protective film forms the gross mass for using film, and the content of packing material (d) is preferably 5~83 mass %, more preferably 5~70 matter
Measure %.
As another side of the invention, when the average grain diameter of packing material (d) is 0.5~8 μm, relative to protection
Film forms the gross mass for using film, and the content of packing material (d) is preferably 5~8 mass %.
By the such range of content for making packing material (d), it is easier to by at least side of protective film formation film
Surface (β) surface roughness (Ra) be adjusted to 0.04 μm or more, more preferably 0.049 μm or more, it is easier to by the table
The surface roughness (Ra) in face (β) is adjusted to 0.15 μm hereinafter, more preferably 0.129 μm or less.
That is, when the content of packing material (d) is adjusted to above range, it is easier to by least the one of protective film formation film
The surface roughness (Ra) on the surface (β) of side is preferably adjusted to 0.04~0.15 μm, is more preferably adjusted to 0.049~0.129 μm.
[coupling agent (e)]
Coupling is used as by using the substance with the functional group that can be reacted with inorganic compound or organic compound
Agent (e) can be improved protective film formation film to the adhesiveness and adherence of adherend.In addition, by using coupling agent (e),
The water resistance of protective film obtained from protective film formation is solidified with film is improved and is not damaging heat resistance.
Coupling agent (e) preferably have can with energy ray-curable ingredient (a), do not have energy ray-curable group
Polymer (b) etc. possessed by the compound of functional group that is reacted of functional group, more preferably silane coupling agent.
As the preferred silane coupling agent, such as 3- glycydoxy trimethoxy silicon can be enumerated
Alkane, 3- glycydoxy methyldiethoxysilane, 3- glycidyl ether oxypropyltriethoxysilane, 3- contracting
Water glycerin ether oxygroup methyldiethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- methacryl
Oxygroup propyl trimethoxy silicane, 3- TSL 8330,3- (2- aminoethylamino) propyl trimethoxy silicon
Alkane, 3- (2- aminoethylamino) hydroxypropyl methyl diethoxy silane, 3- (phenyl amino) propyl trimethoxy silicane, 3- aniline
Base propyl trimethoxy silicane, 3- urea propyl-triethoxysilicane, 3- mercaptopropyl trimethoxysilane, 3- mercapto hydroxypropyl methyl diformazan
Oxysilane, bis- (3- triethoxysilylpropyltetrasulfide) tetrasulfides, methyltrimethoxysilane, methyltriethoxy silane
Alkane, vinyltrimethoxysilane, vinyltriacetoxy silane, imidizole silane etc..
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the coupling agent (e) contained by film,
Kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
When using coupling agent (e), is formed in protective film formation composition (IV-1) and protective film in film, energy is penetrated
When the total content of line curability composition (a) and the polymer (b) without energy ray-curable group is set as 100 mass parts,
The content of coupling agent (e) is preferably 0.03~20 mass parts, more preferably 0.05~10 mass parts, particularly preferably 0.1~5 matter
Measure part.More than the content lower limit value by making coupling agent (e), packing material (d) can be obtained more significantly and is being set
The raising of dispersibility in rouge, raising of adhesiveness etc. of protective film formation film and adherend, by using coupling agent (e) and
The effect of generation.In addition, by making the content upper limit value of coupling agent (e) hereinafter, degassing can be further suppressed
It generates.
[crosslinking agent (f)]
Above-mentioned energy ray-curable ingredient (a) is made by using crosslinking agent (f) or does not have energy ray-curable
The polymer (b) of group is crosslinked, and can adjust the initial bond power and cohesiveness of protective film formation film.
As crosslinking agent (f), such as organic polyisocyanate compound, organic multicomponent group with imine moiety, gold can be enumerated
Belong to chelates crosslinking agent (crosslinking agent with metallo-chelate structure), (friendship with '-aziridino of aziridines crosslinking agent
Join agent) etc..
As the organic polyisocyanate compound, such as aromatic polyisocyanate compound, fat can be enumerated
Race's polyisocyanate compound and alicyclic polyisocyanates compound are (hereinafter, uniformly write a Chinese character in simplified form work " virtue for these compounds sometimes
Fragrant race's polyisocyanate compound etc. ")；The tripolymer of the aromatic polyisocyanate compound etc., isocyanuric acid ester body and
Addition product；Terminal isocyanate ammonia obtained from reacting described aromatic polyisocyanate compound etc. with polyol compound
Carbamate prepolymer etc.." addition product " refers to the aromatic polyisocyanate compound, aliphatic polyisocyante
Compound or alicyclic polyisocyanates compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil etc.
The reactant of low molecule active hydrogen-contg compound can enumerate the benzene two of trimethylolpropane as described later as its example
Methylene diisocyanate addition product etc..In addition, " terminal isocyanate carbamate prepolymer " refers to carbamic acid
Ester bond and the terminal part of molecule have isocyanate group prepolymer.
As the organic polyisocyanate compound, more specifically, such as 2,4- toluene diisocynate can be enumerated
Ester；2,6- toluene di-isocyanate(TDI)；1,3- benzene dimethylene diisocyanate；1,4- xylene diisocyanate；Diphenylmethyl
Alkane -4,4 '-diisocyanate；Diphenyl methane -2,4 '-diisocyanate；3- Dimethyl diphenylmethane diisocyanate；Six is sub-
Methyl diisocyanate；Isophorone diisocyanate；Dicyclohexyl methyl hydride -4,4 '-diisocyanate；Dicyclohexyl methyl hydride-
2,4 '-diisocyanate；Addition has toluene diisocynate on all or part of hydroxyl of the polyalcohols such as trimethylolpropane
In ester, hexamethylene diisocyanate and benzene dimethylene diisocyanate any one or it is two or more made of chemical combination
Object；Lysine diisocyanate etc..
As the organic multicomponent group with imine moiety, such as N can be enumerated, diphenyl methane -4 N ' -, 4 '-bis- (1- nitrogen third
Pyridine formamide) ,-three-β of trimethylolpropane-'-aziridino propionic ester ,-three-β of tetramethylol methane-'-aziridino propionic ester,
N, N '-Toluene-2,4-diisocyanate, bis- (1- aziridine formamide) triethylenemelanins of 4- etc..
When using organic polyisocyanate compound as crosslinking agent (f), as energy ray-curable ingredient (a) or not
Polymer (b) with energy ray-curable group, it is preferable to use hydroxyl polymer.When crosslinking agent (f) has isocyanide
When perester radical, energy ray-curable ingredient (a) or the polymer (b) without energy ray-curable group have hydroxyl,
By crosslinking agent (f) with energy ray-curable ingredient (a) or the polymer (b) without energy ray-curable group it is anti-
It answers, cross-linked structure simply can be imported into protective film formation film.
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the crosslinking agent (f) contained by film,
Kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
When using crosslinking agent (f), in protective film formation in composition (IV-1), by energy ray-curable ingredient (a)
And the total content of the polymer (b) without energy ray-curable group is when being set as 100 mass parts, the content of crosslinking agent (f)
Preferably 0.01~20 mass parts, more preferably 0.1~10 mass parts, particularly preferably 0.5~5 mass parts.By making to be crosslinked
The content of agent (f) is the lower limit value or more, can obtain the effect generated by using crosslinking agent (f) more significantly.
In addition, by making the content upper limit value of crosslinking agent (f) hereinafter, can inhibit being excessively used for crosslinking agent (f).
[colorant (g)]
As colorant (g), such as well known to inorganic pigment, organic pigment, organic dyestuff being enumerated etc.
Toner.
As the organic pigment and organic dyestuff, such as amine can be enumerated(aminium) class pigment, cyanine class
Pigment, merocyanine class pigment, crocic acid (croconium) class pigment, sour cyanines (squarylium) the class pigment in side, azulene
(azulenium) class pigment, polymethine class pigment, naphthalene Quinone Pigments, pyransClass pigment, phthalocyanines pigment, naphthalene cyanines class pigment,
Naphthalene lactim (naphtholactam) class pigment, azo pigment, condensation azo pigment, indigoid type pigment, purple cyclic ketones
(perinone) class pigment, class pigment, dioxazine pigment, quinacridine ketone pigment, isoindoline ketone pigment, quinophthalone
Class pigment, pyroles pigment, thioindigo class pigment, metal complex species pigment (metal complex salt dyestuff), dithiol metal complexing
Species pigment, indoles phenol sulfonate, triallyl methane class pigment, anthraquinone pigments, aphthols pigment, azomethine class pigment,
Benzimidazole ketone pigment, pyranthrone pigment and intellectual circle (threne) class pigment etc..
As the inorganic pigment, such as carbon black, cobalt class pigment, iron class pigment, chromium class pigment, titanium class color can be enumerated
Element, vanadium class pigment, zirconium class pigment, molybdenum class pigment, ruthenium class pigment, platinum class pigment, ITO (i.e. tin indium oxide) class pigment, ATO are (i.e.
Antimony tin) class pigment etc..
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the colorant (g) contained by film,
Kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
When using colorant (g), the content that protective film forms the colorant (g) of film suitably adjust i.e. according to purpose
It can.For example, protective film is subjected to lettering sometimes through laser irradiation, pass through containing for the colorant (g) to protective film formation film
Amount is adjusted and the translucency of protective film is adjusted, and can adjust lettering visuality.At this point, in protective film formation group
It closes in object (IV-1), the total content relative to all the components in addition to solvent, colorant (g) content is (i.e. relative to guarantor
Cuticula forms the content of the colorant (g) of the gross mass of film) it is preferably 0.1~10 mass %, more preferably 0.4~7.5 matter
Measure %, particularly preferably 0.8~5 mass %.It more than the content lower limit value by making colorant (g), can be more aobvious
Land the effect for obtaining and being generated by using colorant (g).In addition, by make the content of colorant (g) it is described on
Limit value is hereinafter, can inhibit being excessively used for colorant (g).
[Thermocurable ingredient (h)]
Protective film, which forms to be formed with composition (IV-1) and protective film, uses the Thermocurable ingredient (h) contained by film can be only
For one kind, or two or more, when being two or more, a combination thereof and ratio can be selected arbitrarily.
As Thermocurable ingredient (h), for example, can enumerate epoxies heat-curing resin, Thermocurable polyimides,
Polyurethane, unsaturated polyester (UP), organic siliconresin etc., preferably epoxies heat-curing resin.
(epoxies heat-curing resin)
Epoxies heat-curing resin is made of epoxy resin (h1) and thermal curing agents (h2).
Protective film is formed can with the epoxies heat-curing resin contained by composition (IV-1) and protective film formation film
To be only one kind, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
Epoxy resin (h1)
As epoxy resin (h1), well known epoxy resin can be enumerated, for example, can enumerate multifunctional based epoxy resin,
Biphenol compound, bisphenol A diglycidyl ether and its hydride, o-cresol phenolic resin varnish, dicyclopentadiene type ring
Oxygen resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin etc.
Epoxide more than difunctionality.
As epoxy resin (h1), the epoxy resin with unsaturated alkyl can be used.With do not have unsaturated alkyl
Epoxy resin is compared, and the compatibility of epoxy resin and acrylic resin with unsaturated alkyl is high.Therefore, by using tool
There is the epoxy resin of unsaturated alkyl, is improved using the reliability of protective film formation encapsulation obtained from composite sheet.
As the epoxy resin with unsaturated alkyl, for example, can enumerate multifunctional based epoxy resin epoxy group one
Partial Transformation is at compound made of the group with unsaturated alkyl.Such compound for example can be by making (methyl) propylene
Acid or derivatives thereof carries out addition reaction with epoxy group and obtains.
In addition, as the epoxy resin with unsaturated alkyl, such as can enumerate in the aromatic rings for constituting epoxy resin
There is the compound etc. of the group with unsaturated alkyl Deng upper Direct Bonding.
Unsaturated alkyl is that the unsaturated group with polymerism can enumerate ethylidine (also referred to as its concrete example
Vinyl), 2- acrylic (also referred to as allyl), (methyl) acryloyl group, (methyl) acrylamido etc., preferably acryloyl
Base.
The number-average molecular weight of epoxy resin (h1) is not particularly limited, curability, Yi Jibao from protective film formation film
The point of shield film strength and heat resistance sets out, and preferably 300~30000, more preferably 400~10000, particularly preferably 500
~3000.
In the present specification, unless otherwise indicated, " number-average molecular weight " is referred to be surveyed using gel permeation chromatography (GPC) method
The number-average molecular weight that fixed standard polystyren scaled value indicates.
The epoxide equivalent of epoxy resin (h1) is preferably 100~1000g/eq, more preferably 150~800g/eq.
In the present specification, " epoxide equivalent " refers to the grams (g/ of the epoxide comprising 1 gram equivalent of epoxy group
Eq), can be measured according to the method for JIS K 7236:2001.
Epoxy resin (h1) can be used alone, can also be simultaneously using two or more, while using two or more
When, their combination and ratio can be selected arbitrarily.
Thermal curing agents (h2)
Thermal curing agents (h2) play a role as the curing agent for epoxy resin (h1).
As thermal curing agents (h2), such as can enumerate has two or more can be with the official of epoxy reaction in 1 molecule
The compound that can be rolled into a ball.As the functional group, such as phenolic hydroxyl group, alcohol hydroxyl group, amino, carboxyl, acidic group acid anhydrides can be enumerated
Group made of group made of change etc., preferably phenolic hydroxyl group, amino or acidic group acid anhydrides, more preferably phenolic hydroxyl group or
Amino.
As the phenols curing agent with phenolic hydroxyl group in thermal curing agents (h2), such as multifunctional phenol tree can be enumerated
Rouge, '-biphenyl diphenol, novolak type phenol resin, bicyclopentadiene class phenol resin, aralkyl-phenol resin etc..
As the amine curing agent with amino in thermal curing agents (h2), such as dicyandiamide can be enumerated (hereinafter, sometimes
Write a Chinese character in simplified form work " DICY ") etc..
Thermal curing agents (h2) can have unsaturated alkyl.
As the thermal curing agents (h2) with unsaturated alkyl, for example, can enumerate phenol resin hydroxyl a part through having
Compound made of having the group of unsaturated alkyl to replace, Direct Bonding has unsaturated alkyl on the aromatic rings of phenol resin
Compound obtained from group etc..
In the unsaturated alkyl and the above-mentioned epoxy resin with unsaturated alkyl in thermal curing agents (h2) not
Saturated hydrocarbyl is identical.
When using phenols curing agent as thermal curing agents (h2), from improving protective film pointing out from the fissility of support chip
Hair, thermal curing agents (h2) are preferably softening point or the high thermal curing agents of glass transition temperature.
Phenol resin in thermal curing agents (h2), for example multifunctional, novolak type phenol resin, bicyclopentadiene class phenol tree
The number-average molecular weight of the resin components such as rouge, aralkyl-phenol resin is preferably 300~30000, and more preferably 400~10000, especially
Preferably 500~3000.
In thermal curing agents (h2), the molecular weight of non-resin ingredient such as '-biphenyl diphenol, dicyandiamide is not particularly limited,
Such as preferably 60~500.
Thermal curing agents (h2) can be used alone, can also be simultaneously using two or more, while using two or more
When, their combination and ratio can be selected arbitrarily.
When using Thermocurable ingredient (h), protective film is formed to be formed with composition (IV-1) and protective film and be used in film, relatively
In 100 mass parts of content of epoxy resin (h1), the content of thermal curing agents (h2) is preferably 0.01~20 mass parts.
When using Thermocurable ingredient (h), is formed and used in film in protective film formation composition (IV-1) and protective film, phase
For not having 100 mass parts of content of the polymer (b) of energy ray-curable group, the content of Thermocurable ingredient (h)
(for example, total content of epoxy resin (h1) and thermal curing agents (h2)) is preferably 1~500 mass parts.
[universal additive (z)]
Universal additive (z) can be well known additive, can arbitrarily be selected, be not particularly limited according to purpose, as
Preferred additive, such as plasticizer, antistatic agent, antioxidant, capturing agent (gettering agent) can be enumerated etc..
Protective film forms composition (IV-1) and protective film formation with the universal additive (z) contained by film
It is a kind of, or two or more, when being two or more, their combination and ratio can be selected arbitrarily.
When using universal additive (z), protective film forms general the adding with composition (IV-1) and protective film formation film
Add the content of agent (z) to be not particularly limited, suitably select according to purpose.
[solvent]
Protective film, which is formed, preferably further contains solvent with composition (IV-1).Protective film containing solvent is formed with combination
The operability of object (IV-1) becomes good.
The solvent is not particularly limited, and as preferred solvent, such as can enumerate the hydrocarbon such as toluene, dimethylbenzene；Methanol,
The alcohol such as ethyl alcohol, 2- propyl alcohol, isobutanol (2- methylpropane -1- alcohol), n-butyl alcohol；The esters such as ethyl acetate；Acetone, methyl ethyl ketone etc.
Ketone；The ethers such as tetrahydrofuran；Amides such as dimethylformamide, N-Methyl pyrrolidone (compound with amido bond) etc..
It can be only one kind that protective film, which is formed with the solvent contained by composition (IV-1), or and it is two or more, be
When two or more, their combination and ratio can be selected arbitrarily.
From can by the point that containing ingredient more uniformly mixes of the protective film formation in composition (IV-1), protect
It is preferably methyl ethyl ketone, toluene or ethyl acetate etc. that film, which is formed with the solvent contained by composition (IV-1),.
<<protective film forms the preparation method for using composition>>
Protective film is formed can be by blending for constituting its with the protective films formation such as composition (IV-1) composition
Each ingredient and obtain.
Order of addition when blending each ingredient is not particularly limited, and can also add two or more ingredients simultaneously.
It, can be pre- by the blending ingredient and mixing solvent with any blending ingredient in addition to solvent when using solvent
Dilution is to carry out using can not also be by any blending ingredient pre-dilution in addition to solvent, and by by solvent and these
Blend ingredient mixing to carry out using.
The method that each ingredient is mixed when blending is not particularly limited, and suitably selects: making from following well known methods
Blender or stirring blade etc. rotate and mixed method；The method mixed using blender；Apply ultrasonic wave and
Mixed method etc..
As long as respectively blending ingredient not deteriorate, the temperature and time when adding and mix each ingredient are not particularly limited,
Suitably adjust, but preferable temperature is 15~30 DEG C.
As it is identical with protective film formation composite sheet of the invention, be attached at and semiconductor crystal wafer or semiconductor chip
Circuit face be the back side of opposite side, and have on support chip the composite sheet of the layer of display adhesiveness, there is cutting chip engagement
Piece (dicing die bonding sheet).
However, the adhesive phase that cutting chip joint fastener has is picked up from support chip together with semiconductor chip
Afterwards, the adhesive phase is as the bonding whens semiconductor chip to be attached to substrate, lead frame or other semiconductor chips etc.
Agent and play a role.On the other hand, of the invention for it is picked up this point from support chip together with semiconductor chip
Protective film, which forms to be formed with the protective film in composite sheet, uses film identical as described adhesive layer, but it becomes eventually by solidification
Protective film has the function of protecting the back side of attached semiconductor chip.In this way, protective film formation film of the invention with cut
The purposes for cutting the adhesive phase in chip joint fastener is different, and the performance sought is certainly also different.Moreover, usually with cutting chip
Adhesive phase in joint fastener is compared, and protective film formation film has hard and is difficult to the tendency picked up, this also reflects above-mentioned use
The difference on way.Therefore, usually the adhesive phase cut in chip joint fastener is directly converted and is made in protective film formation composite sheet
Protective film formation with film be very difficult.For protective film formation composite sheet of the invention, as having energy-ray
The protective film of curability forms the composite sheet for using film, has picking up for the previous unexistent excellent semiconductor chip with protective film
Take adaptive.
◇ protective film forms the manufacturing method for using composite sheet
This hair can be manufactured being successively laminated in a manner of making above-mentioned each layer become corresponding positional relationship
Composite sheet is used in bright protective film formation.The forming method of each layer is identical as what is be illustrated above.
For example, when adhering agent layer is laminated on substrate, above-mentioned adhesion agent composition is coated on base when manufacture support chip
It is dried on material and as needed.
On the other hand, such as when protective film formation film is further laminated on adhering agent layer on base material has been laminated,
Protective film formation can be coated on adhering agent layer with composition and directly form protective film formation film.For removing protective film shape
At with the layer other than film, same method can be also utilized, be laminated on adhering agent layer using the composition for being used to form this layer
The layer.It like this, can be in the layer formed by the composition when forming continuous two layers of stepped construction using arbitrary composition
Upper further coating composition is to form new layer.
Wherein, it is preferable to use the composition is pre-formed the layer of the rear stacking in above-mentioned two layers on other stripping films,
By by the side of the established layer contacted with the stripping film be opposite exposed surface, with formed another
The exposed surface fitting of layer, is consequently formed continuous two layers of stepped construction.At this point, it is preferred that the composition is coated on stripping film
On lift-off processing face.After forming stepped construction, stripping film is removed as needed.
For example, manufacture on substrate be laminated adhering agent layer and on the adhering agent layer be laminated protective film formation film and
Obtained protective film formation is with composite sheet (the protective film formation composite sheet that support chip is the sandwich of substrate and adhering agent layer)
When, by the way that adhesion agent composition is coated on substrate and is dried as needed, sticker is thus laminated on substrate
Thus layer, is in addition being removed by being coated on protective film formation on stripping film with composition and being dried as needed again
Protective film formation is formed on film uses film.Later, by by the exposed surface of the protective film formation film be laminated it is on base material
The exposed surface of adhering agent layer is bonded, and protective film formation is stacked on adhering agent layer with film layer, and protective film can be obtained and formed with multiple
Close piece.
In addition, adhesion agent composition can also be coated on stripping film and be replaced such as when adhering agent layer is laminated on substrate
Upper described is coated with method on base material by adhesion agent composition and is dried as needed, thus the shape on stripping film
It is bonded at adhering agent layer, and by the exposed surface of this layer with the surface of the side of substrate, thus adhering agent layer can be layered in substrate
On.
In arbitrary method, the arbitrary opportunity after forming target stepped construction removes stripping film.
As noted previously, as removing can be previously formed in by constituting the layer in addition to substrate of protective film formation composite sheet
It on film, and is laminated in the method for being fitted in the surface of destination layer, therefore appropriate selection uses such process as needed
Layer manufacture protective film formation composite sheet.
In addition, protective film formation with composite sheet usually with the most surface layer of its support chip opposite side (such as protective film shape
At with film) surface be fitted with the state of stripping film and taken care of.Therefore, even if by protective film formation composition etc., use
It is coated on stripping film (preferably its lift-off processing face) in forming the composition for constituting the layer on most surface layer, and carries out as needed
It is dry, thus form the layer for constituting most surface layer on stripping film, and using above-mentioned arbitrary method in this layer and same stripping film
The side of contact is the other each layers of stacking in the exposed surface of opposite side, when holding does not remove and is bonded the state of stripping film,
Protective film formation composite sheet can be obtained.
◇ protective film forms the application method for using composite sheet
Protective film formation of the invention can for example be carried out using method as shown below with composite sheet using.
That is, making protective film formation composite sheet by its protective film formation film to be attached at the back side of semiconductor crystal wafer
(being the face of opposite side with electrode forming surface).Then, to protective film formation film irradiation energy ray, make protective film formation film
Solidification is to be made protective film.Then, by cutting, semiconductor crystal wafer is divided together with protective film, semiconductor chip is made.
Then, to be pasted with the state (that is, as semiconductor chip with protective film) of the protective film, by semiconductor chip from support chip
Upper separation is simultaneously picked up.
Later, using method identical with previous method, by the semiconductor of the obtained semiconductor chip with protective film
After flip-chip is connected in the circuit face of substrate, semiconductor packages is made.Then, using the semiconductor packages, target is made
Semiconductor device.
In addition, herein, although to making protective film formation solidify the case where protective film is made and then cuts with film
When being illustrated, but being formed using protective film of the invention with composite sheet, the sequence for carrying out these processes be may be reversed.
That is, after the back side of semiconductor crystal wafer attaches protective film formation composite sheet, by cutting semiconductor crystal wafer and protective film shape
At being divided together with film and semiconductor chip be made.Then, the protective film formation film irradiation energy ray terminated to segmentation, makes
Protective film formation film solidifies and protective film is made.Later, in the same manner as described above by the semiconductor chip with protective film
Separation is from support plate to be picked up, and makes target semiconductor device.
Embodiment
Hereinafter, the present invention will be described in more detail according to specific embodiment.But the present invention is not limited to
Embodiment described below.
Protective film described below forms ingredient used in the preparation with composition.
Energy ray-curable ingredient
(a2) -1: (Nippon Kayaku Co., Ltd. manufacture " KAYARAD to tristane dihydroxymethyl diacrylate
R-684 ", the ultra-violet solidified compound of difunctionality, molecular weight 304)
Polymer without energy ray-curable group
(b) -1: by butyl acrylate (hereinafter, writing a Chinese character in simplified form work " BA ") (10 mass parts), methyl acrylate (hereinafter, writing a Chinese character in simplified form work
" MA ") (70 mass parts), glycidyl methacrylate (hereinafter, writing a Chinese character in simplified form work " GMA ") (5 mass parts) and acrylic acid 2- hydroxyl
Acrylic resin (weight average molecular weight 300000, glass made of ethyl ester (hereinafter, writing a Chinese character in simplified form work " HEA ") (15 mass parts) copolymerization
Change -1 DEG C of transition temperature)
Photoepolymerizationinitiater initiater
(c) -1:2- (dimethylamino) -1- (4- morpholinyl phenyl) -2- benzyl -1- butanone (BASF AG's manufacture
" Irgacure (registered trademark) 369 ")
(c) -2:1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethyl ketone 1- (O- acetyl oxime) (BASF
Company manufactures " Irgacure (registered trademark) OXE02 ")
Packing material
(d) -1: silica filler (vitreous silica filler, 8 μm of average grain diameter)
Coupling agent
(e) -1:3- methacryloxypropyl trimethoxy silane (Shin-Etsu Chemical Co., Ltd. system
Make " KBM-503 ", silane coupling agent)
Colorant
(g) -1: by phthalocyanines blue pigment (Pigment Blue 15:3) 32 mass parts, isoindoline ketone yellow color
Plain (Pigment Yellow 139) 18 mass parts and the mixing of Anthraquinones red pigments (Pigment Red 177) 50 mass parts,
So that the total amount of three kinds of pigments/styrene acrylic resin amount=1/3 (mass ratio) mode carries out pigmentation and obtains
The pigment arrived
[embodiment 1]
<protective film forms the manufacture for using composite sheet>
(protective film forms the preparation for using composition (IV-1))
So that energy ray-curable ingredient (a2) -1, polymer (b) -1, Photoepolymerizationinitiater initiater (c) -1, photopolymerization initiation
Agent (c) -2, packing material (d) -1, coupling agent (e) -1 and colorant (g) -1 content (solid component, mass parts) become table 1
Shown in value mode, they are dissolved or dispersed in methyl ethyl ketone, and is stirred in 23 DEG C, thus prepare solid at
Divide the protective film that concentration is 50 mass % to be formed and uses composition (IV-1).
(preparation of adhesion agent composition (I-4))
Preparation contains acrylic polymer (100 mass parts, solid component) and trifunctional phenylenedimethylidyne diisocyanate
Esters crosslinking agent (" the TAKENATE D110N " of MITSUI CHEMICALS POLYURETHANES, INC. manufacture) (10.7 matter
Measure part, solid component) and further contain methyl ethyl ketone as solvent, solid component concentration for 30 mass % non-energy
Measure the adhesion agent composition (I-4) of ray-curable.The acrylic polymer is 2-EHA (hereinafter, letter
Write " 2EHA ") (36 mass parts), BA (59 mass parts) and HEA (5 mass parts) copolymerization made of weight average molecular weight be 600,
000 acrylic polymer.
(manufacture of support chip)
Adhesion agent composition obtained above (I-4) is coated on using silicone-treated to polyethylene terephthalate
The single side of film has carried out stripping film (" SP-PET381031 " of Lintec Corporation. manufacture, the thickness of lift-off processing
38 μm) the lift-off processing face on, and in 120 DEG C heat drying 2 minutes, the non-energy ray with a thickness of 10 μm is consequently formed
The adhering agent layer of curability.
Then, the adhering agent layer will be fitted in as the polypropylene film of substrate (Young's modulus 400MPa, 80 μm of thickness)
Exposed surface on, thus obtain the support chip (10) -1 for having the adhering agent layer on the surface of the side of the substrate.
(protective film forms the manufacture for using composite sheet)
Protective film formation obtained above is coated on composition (IV-1) using knife type coater and utilizes silicone-treated
Stripping film (the Lintec Corporation. system of lift-off processing has been carried out to the single side of polyethylene terephthalate film
" SP-PET381031 " made, 38 μm of thickness) the lift-off processing face on, and 2 minutes dry in 100 DEG C, thus production is thick
Degree forms for the protective film of 25 μm of energy ray-curable and uses film (13) -1.
Then, stripping film is removed from the adhering agent layer of support chip (10) -1 obtained above, by guarantor obtained above
Cuticula formation is fitted in the exposed surface of the adhering agent layer with the exposed surface of film (13) -1, is made substrate, adhering agent layer, protection
Film formed film (13) -1 and stripping film along their thickness direction stack gradually made of protective film formation composite sheet.Will
To the composition of protective film formation composite sheet be shown in table 2.
<protective film forms the evaluation for using composite sheet>
For obtained protective film formation composite sheet, ultraviolet lamp (Lintec Corporation. system is used
" RAD2000m/8 " made), with illumination 195mW/cm2, light quantity 170mJ/cm2Condition, from support chip side to solidify before test film
Ultraviolet light is irradiated, thus solidifies protective film formation film (13) -1, test film after being solidified.
Then, for test film after the solidification, substrate and adhering agent layer are removed, and according to JIS Z0237:2010 to making
Rolling Ball Tack value when the exposed surface measurement inclination angle of protective film made of protective film formation film (13) -1 solidifies is 30 °.It will
Measurement result is shown in table 2.
(lid band adhesion is evaluated)
Protective film formation composite sheet obtained above is set to be attached to 6 inches of silicon by its protective film formation film (13) -1
On the #2000 abradant surface of wafer (100 μm of thickness), the piece is further fixed on ring-shaped frame, and stand 30 minutes.
Then, using ultraviolet lamp (" RAD2000m/8 " of Lintec Corporation. manufacture), with illumination
195mW/cm2, light quantity 170mJ/cm2Condition, from (10) -1 side of support chip to protective film formation with composite sheet irradiate ultraviolet light,
Thus solidify protective film formation film (13) -1, make protective film.
Then, using cutting blade, Silicon Wafer is sliced together with protective film, obtains vertical 3mm × horizontal 3mm and protects thickness
Degree is 25 μm, the silicon chip that Si thickness is 350 μm.
Then, using chip engagement machine (the die bonder) (" BESTEM- of Canon Machinery Inc. manufacture
D02 "), pick up 20 silicon chips with protective film.
In vertical 12cm × horizontal 12cm and with a thickness of on the iron plate of 5mm, by 16 silicon chips obtained above with protective film
The latticed position for often indulging the square of 4 × cross 4 is placed in such a way that mutual is divided into equalization, and above
The lid band (CSL-Z7302 of Sumitomo Bakelite Co., Ltd. manufacture) for covering vertical 12cm × horizontal 3.8cm, is placed in
It is heated in 40 DEG C of hot plate, and loads metal plate above, thus so that the pressure applied to the silicon chip with protective film
It is configured, heats one minute for the mode of 350gf.Then, metal plate is removed, peels the lid band, calibration tape protective film off
Silicon chip whether be attached to lid band.Show the result in table 2.
As determination method, by 16 silicon chips with protective film, even have one be attached to lid band the case where judgement
For " A ", it will be determined as " B " in 16 silicon chips with protective film, the case where none is attached to lid band.
[embodiment 2]
<protective film forms the manufacture and evaluation for using composite sheet>
In addition to the content (blended amount) of 20 mass parts of energy ray-curable ingredient (a2) -1 is replaced as shown in table 1
Other than 30 mass parts, in the same manner as in Example 1, protective film formation composition (IV-1) is prepared.
Other than using protective film formation composition (IV-1) this point obtained above, with same as Example 1
Method, make the protective film formation film (13) -25 with a thickness of 25 μm of energy ray-curable.
Then, in addition to by protective film formation film (13) -1 replace with (13) -25 this point of protective film formation film with
Outside, in the same manner as in Example 1, composite sheet is used in the formation of production protective film.By obtained protective film formation composite sheet
Composition is shown in table 2.
Using protective film formation composite sheet obtained above, in the same manner as in Example 1, Rolling Ball Tack value is carried out
Measurement and lid band adhesion evaluate.Show the result in table 2.
[embodiment 3]
<protective film forms the manufacture and evaluation for using composite sheet>
In addition to the content (blended amount) of 0.3 mass parts of Photoepolymerizationinitiater initiater (c) -1 is replaced with 1.0 as shown in table 1
Mass parts simultaneously replace with the content (blended amount) of 0.3 mass parts of Photoepolymerizationinitiater initiater (c) -2 other than 1.0 mass parts, with
The identical method of embodiment 1, prepares protective film formation composition (IV-1).
Other than using protective film formation composition (IV-1) obtained above, in the same manner as in Example 1,
Make the protective film formation film (13) -26 of the energy ray-curable with a thickness of 25 μm.
Then, other than protective film formation film (13) -1 is replaced with the protective film formation film (13) -26, with
Composite sheet is used in the identical method of embodiment 1, production protective film formation.The composition of obtained protective film formation composite sheet is shown in
Table 2.
Using protective film formation composite sheet obtained above, in the same manner as in Example 1, Rolling Ball Tack value is carried out
Measurement and lid band adhesion evaluate.Show the result in table 2.
[comparative example 1]
<protective film forms the manufacture and evaluation for using composite sheet>
In addition to the content (blended amount) of 20 mass parts of energy ray-curable ingredient (a2) -1 is replaced as shown in table 1
Other than 5 mass parts, in the same manner as in Example 1, protective film formation composition (IV-1) is prepared.
Other than using protective film formation composition (IV-1) obtained above, in the same manner as in Example 1,
Make the protective film formation film (13) -27 of the energy ray-curable with a thickness of 25 μm.
Then, other than protective film formation film (13) -1 is replaced with the protective film formation film (13) -27, with
Composite sheet is used in the identical method of embodiment 1, production protective film formation.The composition of obtained protective film formation composite sheet is shown in
Table 2.
Using protective film formation composite sheet obtained above, in the same manner as in Example 1, Rolling Ball Tack value is carried out
Measurement and lid band adhesion evaluate.Show the result in table 2.
[comparative example 2]
<protective film forms the manufacture and evaluation for using composite sheet>
In addition to the content (blended amount) of 0.3 mass parts of Photoepolymerizationinitiater initiater (c) -1 is replaced with 0.1 as shown in table 1
Mass parts simultaneously replace with the content (blended amount) of 0.3 mass parts of Photoepolymerizationinitiater initiater (c) -2 other than 0.1 mass parts, with reality
The identical method of example 1 is applied, protective film formation composition (IV-1) is prepared.
Other than using protective film formation composition (IV-1) obtained above, in the same manner as in Example 1,
Make the protective film formation film (13) -28 of the energy ray-curable with a thickness of 25 μm.
Then, other than protective film formation film (13) -1 is replaced with the protective film formation film (13) -28, with
Composite sheet is used in the identical method of embodiment 1, production protective film formation.The composition of obtained protective film formation composite sheet is shown in
Table 2.
Using protective film formation composite sheet obtained above, in the same manner as in Example 1, Rolling Ball Tack value is carried out
Measurement and lid band adhesion evaluate.Show the result in table 2.
[table 1]
[table 2]
By the above results it will be apparent that, in the case where the protective film formation composite sheet using Examples 1 to 3, protective film
, according to JIS Z0237:2010 with the Rolling Ball Tack value of 30 ° of inclination angle measurement for 2 or less, it is suppressed that partly leading with protective film
Body chip is attached to lid band.
In contrast, in the case where the protective film formation composite sheet for having used comparative example 1~2, protective film, according to
JIS Z0237:2010 is with the Rolling Ball Tack value of the 30 ° of measurements in inclination angle for 3~4, thus it is speculated that is easy to be attached to lid and takes.
In addition, protective film, which is formed, uses composition (IV-1) in the case where protective film formation composite sheet using comparative example 1
In, the ratio of the content of total content relative to the ingredient in addition to solvent, described energy ray-curable ingredient (a) is as little as
5.8 mass %, therefore supposition is energy ray curing and insufficient, and the Rolling Ball Tack value is caused to become larger.On the other hand, using than
In the case where protective film formation composite sheet compared with example 2, relative to 100 mass parts of energy ray-curable ingredient (a), protective film
Content as little as 1 mass parts with the Photoepolymerizationinitiater initiater (c) in film are formed, therefore speculate that protective film forms the solidification for using composite sheet
And it is insufficient, cause the Rolling Ball Tack value to become larger.
Industrial applicibility
The present invention can be used for the manufacture of semiconductor device, therefore be industrially useful.
Description of symbols
1A, 1B, 1C, 1D, 1E: composite sheet is used in protective film formation；2F: piece is used in protective film formation；10: support chip, 10a: branch
The surface of blade；11: substrate；11a: the surface of substrate；12: adhering agent layer；12a: the surface of adhering agent layer；13,23: protective film
Formation film；13a, 23a: protective film forms the surface for using film；15: stripping film；15 ': the first stripping film；15 ": the second removing
Film；16: fixture adhesive phase；16a: the surface of fixture adhesive phase；101: the semiconductor chip with protective film；102: pressure
Line carrier band；102a: the pocket of embossed carrier tape；103: lid band.
Claims (5)
- It is the protective film formation film of energy ray-curable 1. a kind of protective film, which is formed, uses film,Wherein, the protective film formation film irradiation energy ray to protective film is made when, with the protective film, press According to JIS Z0237:2010 with the Rolling Ball Tack value of the 30 ° of measurements in inclination angle for 2 characteristics below.
- 2. protective film according to claim 1, which is formed, uses film, wherein the protective film formation film is solid comprising energy-ray The property changed ingredient (a).
- 3. protective film according to claim 2, which is formed, uses film, the protective film formation further includes photopolymerization with film and draws It sends out agent (c).
- 4. protective film according to claim 3, which is formed, uses film, wherein relative to 100 matter of energy ray-curable ingredient (a) Part is measured, the content of the Photoepolymerizationinitiater initiater (c) is 2.0~12.0 mass parts.
- 5. a kind of protective film, which is formed, uses composite sheet, by having guarantor according to any one of claims 1 to 4 on support chip Cuticula formation is formed with film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-092013 | 2016-04-28 | ||
| JP2016092013 | 2016-04-28 | ||
| PCT/JP2017/016335 WO2017188231A1 (en) | 2016-04-28 | 2017-04-25 | Film for forming protective coat and composite sheet for forming protective coat |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109071845A true CN109071845A (en) | 2018-12-21 |
Family
ID=60161658
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780025032.9A Pending CN109071845A (en) | 2016-04-28 | 2017-04-25 | Protective film formation film and protective film formation composite sheet |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6971977B2 (en) |
| KR (1) | KR102407322B1 (en) |
| CN (1) | CN109071845A (en) |
| TW (1) | TWI781099B (en) |
| WO (1) | WO2017188231A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111951694A (en) * | 2019-05-16 | 2020-11-17 | 三星显示有限公司 | Polymer resin, window module comprising polymer resin and display device comprising window module |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102519799B1 (en) * | 2018-03-30 | 2023-04-10 | 린텍 가부시키가이샤 | Composite sheet for forming support sheet and protective film |
| JP7288200B2 (en) * | 2020-07-30 | 2023-06-07 | 日亜化学工業株式会社 | Light emitting device and package |
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| JPS5144433B1 (en) | 1970-02-02 | 1976-11-29 | ||
| KR100815383B1 (en) * | 2006-12-28 | 2008-03-20 | 제일모직주식회사 | Photocuring composition for pressure sensitive adhesive layer and dicing die bonding film comprising the same |
| JP2010031183A (en) | 2008-07-30 | 2010-02-12 | Furukawa Electric Co Ltd:The | Energy ray hardening type chip protecting film |
| JP5144433B2 (en) * | 2008-08-28 | 2013-02-13 | 古河電気工業株式会社 | Chip protection film |
| JP5048815B2 (en) * | 2010-07-20 | 2012-10-17 | 日東電工株式会社 | Flip chip type semiconductor back film and dicing tape integrated semiconductor back film |
| CN104837942B (en) * | 2012-12-14 | 2017-04-26 | 琳得科株式会社 | Holding membrane forming film |
| KR102368140B1 (en) * | 2014-08-22 | 2022-02-25 | 린텍 가부시키가이샤 | Protective-coating-forming sheet and method for manufacturing semiconductor chip provided with protective coating |
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2017
- 2017-04-25 CN CN201780025032.9A patent/CN109071845A/en active Pending
- 2017-04-25 KR KR1020187030754A patent/KR102407322B1/en active IP Right Grant
- 2017-04-25 JP JP2018514615A patent/JP6971977B2/en active Active
- 2017-04-25 WO PCT/JP2017/016335 patent/WO2017188231A1/en active Application Filing
- 2017-04-26 TW TW106113974A patent/TWI781099B/en active
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| JP2007297591A (en) * | 2006-04-06 | 2007-11-15 | Lintec Corp | Adhesive sheet |
| CN101831253A (en) * | 2009-03-11 | 2010-09-15 | 日东电工株式会社 | No base material pressure sensitive adhesion sheet, its production method and use its Ginding process |
| JP2010212474A (en) * | 2009-03-11 | 2010-09-24 | Nitto Denko Corp | Substrateless adhesive sheet for semiconductor wafer protection, semiconductor wafer backside grinding method using the adhesive sheet, and production method of the adhesive sheet |
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| CN104937712A (en) * | 2013-03-22 | 2015-09-23 | 琳得科株式会社 | Protective film-forming film and protective film-forming composite sheet |
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| CN111951694A (en) * | 2019-05-16 | 2020-11-17 | 三星显示有限公司 | Polymer resin, window module comprising polymer resin and display device comprising window module |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6971977B2 (en) | 2021-11-24 |
| KR102407322B1 (en) | 2022-06-10 |
| TW201806767A (en) | 2018-03-01 |
| KR20190002471A (en) | 2019-01-08 |
| WO2017188231A1 (en) | 2017-11-02 |
| JPWO2017188231A1 (en) | 2019-03-07 |
| TWI781099B (en) | 2022-10-21 |
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