TW201941951A - Resin sheet, method for using resin sheet, and method for producing cured sealing body with cured resin layer - Google Patents
Resin sheet, method for using resin sheet, and method for producing cured sealing body with cured resin layer Download PDFInfo
- Publication number
- TW201941951A TW201941951A TW108110933A TW108110933A TW201941951A TW 201941951 A TW201941951 A TW 201941951A TW 108110933 A TW108110933 A TW 108110933A TW 108110933 A TW108110933 A TW 108110933A TW 201941951 A TW201941951 A TW 201941951A
- Authority
- TW
- Taiwan
- Prior art keywords
- resin layer
- hardened
- sealing
- thermosetting resin
- cured
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 38
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- 239000003566 sealing material Substances 0.000 claims abstract description 73
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- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- QDYTUZCWBJRHKK-UHFFFAOYSA-N imidazole-4-methanol Chemical compound OCC1=CNC=N1 QDYTUZCWBJRHKK-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical class [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000000565 sealant Substances 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001629 suppression Effects 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
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-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
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Laminated Bodies (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
本發明係關於樹脂薄片及樹脂薄片的使用方法，以及使用該樹脂薄片的附有硬化樹脂層之硬化密封體的製造方法。The present invention relates to a resin sheet, a method for using the resin sheet, and a method for manufacturing a hardened sealing body with a hardened resin layer using the resin sheet.
近年來，隨著電子裝置之小型化及高功能化，對於半導體封裝的進一步小型化、高功能化，及信賴性之提高等亦被要求著。
對應如此要求的技術之一的晶圓水準封裝(WLP)技術為，於切割成個片化前，於晶片迴路形成面上形成外部電極等，最終使含有晶片的封裝進行切割，可實現小型化至與半導體晶片同程度規模的可進行表面實裝之晶片規模封裝(CSP)的技術。In recent years, with the miniaturization and high functionality of electronic devices, further miniaturization, high functionality of semiconductor packages, and improvement of reliability have been demanded.
The wafer level packaging (WLP) technology, which corresponds to one of the required technologies, is to form external electrodes on the wafer circuit formation surface before dicing, and finally cut the package containing the wafer to achieve miniaturization. A surface-mountable wafer scale package (CSP) technology that is as large as a semiconductor wafer.
WLP分為Fan-In型與Fan-Out型。
在Fan-Out型的WLP中，將密封對象物之半導體晶片，欲成為比該半導體晶片之尺寸更大之區域，以密封材料進行覆蓋，形成半導體晶片密封體後，將再配線層或外部電極，不僅形成於半導體晶片之迴路面上，亦形成於密封材料的表面區域上。WLP is divided into Fan-In type and Fan-Out type.
In the Fan-Out type WLP, a semiconductor wafer to be sealed is to be an area larger than the size of the semiconductor wafer, and is covered with a sealing material to form a semiconductor wafer sealing body, and then a redistribution layer or an external electrode is formed. , Not only on the circuit surface of the semiconductor wafer, but also on the surface area of the sealing material.
例如，於專利文獻1中記載，將自半導體晶圓經個片化的複數個半導體晶片，殘留於該迴路形成面上，使用密封樹脂之模型構件，包圍周圍而形成擴張晶圓，於半導體晶片外的區域使再配線圖型進行延伸而形成的半導體封裝之製造方法。
且，對於專利文獻1所記載的製造方法，矽晶圓為貼著於切割用晶片裝配帶上而提供於切割步驟。其後，排序黏貼於擴展用的晶片裝配帶上，將晶片裝配帶(支持膠帶)展延後，提供於使複數矽晶片之間的距離擴大之磁帶擴展步驟。
[先前技術文獻]
[專利文獻]For example, Patent Document 1 describes that a plurality of semiconductor wafers separated from a semiconductor wafer are left on the circuit formation surface, and a mold member of a sealing resin is used to surround the periphery to form an expansion wafer. A method for manufacturing a semiconductor package in which an outer area is formed by extending a rewiring pattern.
Further, in the manufacturing method described in Patent Document 1, a silicon wafer is provided in a dicing step in order to be attached to a dicing wafer mounting tape. After that, the wafer mounting tape is sequentially pasted and extended, and the wafer mounting tape (supporting tape) is stretched, and a tape expanding step is provided to increase the distance between the plurality of silicon wafers.
[Prior technical literature]
[Patent Literature]
[專利文獻1] 國際公開第2010/058646號[Patent Document 1] International Publication No. 2010/058646
[發明所解決的問題][Problems Solved by the Invention]
然而，對於如專利文獻1所記載的Fan-Out型之WLP的製造，一般為具有以下步驟，該步驟為，將密封對象物之半導體晶片以密封材料進行包覆後，藉由使該密封材料進行加熱而使其熱硬化，經密封後形成硬化密封體者。
然而，將密封材料進行熱硬化而得之硬化密封體，自與支持體經固定的晶片裝配帶等黏著膠帶進行分離時，有時分離後之硬化密封體會藉由熱收縮而產生彎曲。
產生彎曲而表面非平坦的硬化密封體，例如在下個步驟進行硬化密封體之研削時，容易產生割裂等弊害容易發生，又將硬化密封體藉由裝置進行搬送時，藉由支臂進行硬化密封體的轉移時容易產生不佳狀況。However, the production of a Fan-Out type WLP as described in Patent Document 1 generally includes a step of covering a semiconductor wafer to be sealed with a sealing material, and then applying the sealing material. A person who heats and heat-hardens, and forms a hardened seal after sealing.
However, when a hardened sealing body obtained by thermally hardening a sealing material is separated from an adhesive tape such as a wafer mounting tape fixed to a support, the hardened sealed body after separation may be bent by thermal shrinkage.
When a hardened sealing body with a curved and uneven surface is produced, for example, when the hardened sealing body is ground in the next step, defects such as cracking are easy to occur. When the hardened sealing body is transported by the device, the hardened sealing is performed by the arm. Poor conditions are likely to occur when the body is transferred.
又，亦有於硬化密封體的一方表面上進一步設置樹脂膜而成為附有樹脂膜的硬化密封體之情況。
製造如此附有樹脂膜的硬化密封體時，必須經過通常於所形成的硬化密封體之一方表面上，貼合另外準備的樹脂膜形成用片，使樹脂膜形成用片進行硬化而形成樹脂膜的步驟。
另外，硬化密封體係如上述所示，因於製造時容易產生彎曲，有著該硬化密封體之彎曲所造成的貼合於樹脂膜形成用片時的作業性降低，或經硬化而成的樹脂膜與硬化密封體之密著性降低等顧慮。
且，對於所得的附有樹脂膜之硬化密封體，有時彎曲會進一步地擴大，在下個步驟中恐怕造成種種弊害。Moreover, a resin film may be further provided on one surface of a hardened sealing body, and it may become a hardened sealing body with a resin film attached.
When manufacturing a hardened sealed body with a resin film attached in this manner, it is necessary to pass a sheet of a resin film forming sheet which has been separately prepared to one of the surfaces of the hardened sealed body formed, and harden the sheet for forming a resin film to form a resin film. A step of.
In addition, as described above, the hardened sealing system is prone to warping during manufacturing, and the workability during bonding to a sheet for forming a resin film due to the bending of the hardened sealing body is reduced, or the hardened resin film is formed. There is a concern that the adhesion with the hardened sealing body is reduced.
In addition, in the obtained hardened sealed body with a resin film, the bending may be further enlarged, which may cause various disadvantages in the next step.
本發明係以提供一種使用於硬化密封體的製造上之樹脂薄膜為目的，該硬化密封體為抑制彎曲且具有平坦表面之附有硬化樹脂層的硬化密封體，其可提高生產性下製造。
[解決課題的手段]The present invention aims to provide a resin film for use in the manufacture of a hardened sealing body, which is a hardened sealing body with a flat hardened surface and a hardened resin layer which suppresses bending and can be manufactured with improved productivity.
[Means for solving problems]
本發明者們，發現將具有由含有聚合性成分及熱硬化性成分的熱硬化性樹脂組成物所形成的熱硬化性樹脂層之樹脂薄片，使用在於熱硬化性樹脂層之表面上載置密封對象物，以密封材料進行包覆後使其硬化，做成含有密封對象物的硬化密封體之製造上，而解決上述課題。The inventors have found that a resin sheet having a thermosetting resin layer formed of a thermosetting resin composition containing a polymerizable component and a thermosetting component is used to place a sealing object on the surface of the thermosetting resin layer The above problem is solved in the manufacture of a hardened sealing body containing a sealing object after being covered with a sealing material and then cured.
即，本發明係關於以下[1]～[9]。
[1]一種使用於製造硬化密封體之樹脂薄片，其特徵為硬化密封體為，具有由含有聚合性成分(A)及熱硬化性成分(B)之熱硬化性樹脂組成物所形成的熱硬化性樹脂層，於前述熱硬化性樹脂層的表面上載置密封對象物，將前述密封對象物，與該密封對象物的至少周邊部分的前述熱硬化性樹脂層的表面以密封材料進行包覆，使該密封材料進行熱硬化而成為含有前述密封對象物的硬化密封體。
[2]上述[1]所記載的樹脂薄片，其中於硬化前述密封材料時，亦將前述熱硬化性樹脂層進行硬化而可形成硬化樹脂層。
[3]上述[1]或[2]所記載的樹脂薄片，其中前述熱硬化性樹脂組成物中之著色劑的含有量為未達8質量%。
[4]上述[1]～[3]中任一項所記載的樹脂薄片，其中使前述熱硬化性樹脂層進行熱硬化而成的硬化樹脂層在23℃中之貯藏彈性率E’為1.0×107
～1.0×1013
Pa。
[5]上述[1]～[4]中任一項所記載的樹脂薄片樹脂薄片，其中前述熱硬化性樹脂層的厚度為1～500μm。
[6]一種上述[1]～[5]中任一項所記載的樹脂薄片的使用方法，其特徵為於前述熱硬化性樹脂層的表面上載置密封對象物，使前述密封對象物與該密封對象物的至少周邊部分之前述熱硬化性樹脂層的表面上以密封材料進行包覆，使該密封材料進行熱硬化後成為含有前述密封對象物之硬化密封體者。
[7]上述[6]所記載的使用方法，其中於使前述密封材料進行熱硬化時，亦使前述熱硬化性樹脂層進行熱硬化，形成硬化樹脂層，作為附有熱硬化樹脂層的硬化密封體。
[8]一種使用上述[1]～[5]中任一項所記載的樹脂薄片製造附有硬化樹脂層的硬化密封體之方法，其特徵為具有下述步驟(i)～(iii)之附有硬化樹脂層的硬化密封體之製造方法，
･步驟(i)：於前述樹脂薄片所具有的前述熱硬化性樹脂層之表面的一部分上載置密封對象物之步驟，
･步驟(ii)：將前述密封對象物與該密封對象物的至少周邊部分之前述熱硬化性樹脂層的表面上以密封材料進行包覆的步驟，
･步驟(iii)：使前述密封材料進行熱硬化，與形成含有前述密封對象物的硬化密封體之同時，亦使前述熱硬化性樹脂層進行熱硬化，形成硬化樹脂層後得到附有硬化樹脂層的硬化密封體之步驟。
[發明之效果]That is, this invention relates to the following [1]-[9].
[1] A resin sheet for producing a hardened sealing body, characterized in that the hardened sealing body has a heat formed from a thermosetting resin composition containing a polymerizable component (A) and a thermosetting component (B). The curable resin layer places a sealing object on the surface of the thermosetting resin layer, and covers the surface of the thermosetting resin layer with the sealing object and at least a peripheral portion of the sealing object with a sealing material. The sealing material is thermally cured to form a hardened sealing body containing the object to be sealed.
[2] The resin sheet according to the above [1], wherein when the sealing material is cured, the thermosetting resin layer is also cured to form a cured resin layer.
[3] The resin sheet according to the above [1] or [2], wherein the content of the coloring agent in the thermosetting resin composition is less than 8% by mass.
[4] The resin sheet according to any one of the above [1] to [3], wherein the storage elastic modulus E 'of the cured resin layer obtained by thermally curing the thermosetting resin layer at 23 ° C is 1.0 × 10 7 to 1.0 × 10 13 Pa.
[5] The resin sheet resin sheet according to any one of the above [1] to [4], wherein the thickness of the thermosetting resin layer is 1 to 500 μm.
[6] The method for using a resin sheet according to any one of the above [1] to [5], wherein a sealing object is placed on a surface of the thermosetting resin layer, and the sealing object and the The surface of the thermosetting resin layer of at least a peripheral portion of the object to be sealed is covered with a sealing material, and the sealing material is heat cured to become a hardened sealing body containing the object to be sealed.
[7] The method according to the above [6], wherein when the sealing material is thermally cured, the thermally curable resin layer is also thermally cured to form a cured resin layer, and the cured resin layer is cured. Sealing body.
[8] A method for producing a hardened sealed body with a hardened resin layer using the resin sheet according to any one of the above [1] to [5], characterized by having the following steps (i) to (iii) Manufacturing method of hardened sealing body with hardened resin layer,
･ Step (i): a step of placing a sealing object on a part of a surface of the thermosetting resin layer of the resin sheet,
･ Step (ii): a step of covering the surface of the thermosetting resin layer with the sealing object and at least a peripheral portion of the sealing object with a sealing material,
･ Step (iii): The hardening of the sealing material is performed, and at the same time as the hardened sealing body containing the sealing object is formed, the thermosetting resin layer is also heat hardened to form a hardened resin layer to obtain a hardened resin. Step of hardening the seal.
[Effect of the invention]
本發明之樹脂薄片為藉由使用於硬化密封體的製造上，可在提高生產性下製造出抑制彎曲且具有平坦表面之硬化密封體。The resin sheet of the present invention is used for the production of a hardened sealing body, and can improve the productivity to produce a hardened sealing body that suppresses bending and has a flat surface.
[實施發明的型態][Form of Implementing Invention]
本說明書中，所謂「有效成分」表示含於作為對象的組成物之成分中，除去稀釋溶劑之成分。
本說明書中，質量平均分子量(Mw)為藉由凝膠滲透層析法(GPC)法所測定的標準聚苯乙烯換算之值，具體為依據實施例所記載的方法而測定之值。
本說明書中，例如所謂「(甲基)丙烯酸」表示「丙烯酸」與「甲基丙烯酸」之雙方，其他類似用語亦相同。
本說明書中，對於較佳數值範圍(例如含有量等範圍)，以段階式記載的下限值及上限值可各獨立下進行組合。例如，由「以10～90為佳為佳，較佳為30～60」的記載，可組合成「以下限值(10)為佳」與「較佳上限值(60)」，而成為「10～60」。In the present specification, the "active ingredient" means a component contained in a target composition and a component excluding a diluent solvent.
In this specification, the mass average molecular weight (Mw) is a value converted into a standard polystyrene measured by a gel permeation chromatography (GPC) method, and is specifically a value measured according to a method described in Examples.
In this specification, for example, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are the same.
In the present specification, the lower limit value and the upper limit value described in the step formula can be combined independently for each of the preferable numerical ranges (for example, the range of the content). For example, the description of "It is better to be 10 to 90, and preferably 30 to 60" can be combined into "the lower limit (10) is better" and "preferably the upper limit (60)" to become "10 to 60".
[樹脂薄片之構成]
本發明之樹脂薄片為具有由含有聚合性成分(A)及熱硬化性成分(B)的熱硬化性樹脂組成物所形成的熱硬化性樹脂層。
本發明之一態樣的樹脂薄片為，可僅由熱硬化性樹脂層所成的單層構成之薄片，但亦可為與熱硬化性樹脂層同時具有熱硬化性樹脂層以外之層的複層構成之薄片。[Composition of resin sheet]
The resin sheet of the present invention is a thermosetting resin layer having a thermosetting resin composition containing a polymerizable component (A) and a thermosetting component (B).
A resin sheet according to one aspect of the present invention is a sheet composed of only a single layer made of a thermosetting resin layer, but may be a layer having a layer other than the thermosetting resin layer at the same time as the thermosetting resin layer. Layers of flakes.
圖1表示本發明之一態樣的樹脂薄片之構成的該樹脂薄片之截面模式圖。
作為本發明之一態樣的樹脂薄片，可舉出如圖1(a)所示，具有基材20與熱硬化性樹脂層10之樹脂薄片1a。如樹脂薄片1a，可藉由具有基材的樹脂薄片，使自身支持性變良好，且可提高處理性。FIG. 1 is a schematic cross-sectional view of a resin sheet composed of a resin sheet according to an aspect of the present invention.
As one aspect of the present invention, a resin sheet 1a having a substrate 20 and a thermosetting resin layer 10 as shown in FIG. 1 (a) is mentioned. For example, the resin sheet 1a can improve the self-supporting property by using a resin sheet having a base material, and can improve handling properties.
又，欲提高基材20與熱硬化性樹脂層10的密著性，如圖1(b)所示的樹脂薄片1b，亦可為將基材20、黏著劑層30，及熱硬化性樹脂層10以此順序進行層合的樹脂薄片。
且，樹脂薄片1b亦可作為於黏著劑層30的黏著表面上，進一步層合剝離材的構成。In order to improve the adhesion between the substrate 20 and the thermosetting resin layer 10, the resin sheet 1b shown in FIG. 1 (b) may be a substrate 20, an adhesive layer 30, and a thermosetting resin. The layer 10 is a resin sheet laminated in this order.
In addition, the resin sheet 1b may have a configuration in which a release material is further laminated on the adhesive surface of the adhesive layer 30.
又，作為本發明之其他態樣的樹脂薄片，可舉出如圖1(c)所示，具有熱硬化性樹脂層10與黏著劑層30之樹脂薄片1c。
因具有如樹脂薄片1c的黏著劑層30，可使樹脂薄片於支持體等上充分地固定，且可使在密封步驟的作業性變的良好。In addition, as another aspect of the resin sheet of the present invention, as shown in FIG. 1 (c), a resin sheet 1 c having a thermosetting resin layer 10 and an adhesive layer 30 is mentioned.
With the adhesive layer 30 such as the resin sheet 1c, the resin sheet can be sufficiently fixed on a support or the like, and the workability in the sealing step can be improved.
且，如圖1(d)所示的樹脂薄片1d，可為將第2黏著劑層32、基材20、第1黏著劑層31，及熱硬化性樹脂層10以此順序進行層合的樹脂薄片。
藉由成為如樹脂薄片1d的構成，可使樹脂薄片於支持體等進行充分固定的同時，亦可提高基材20與熱硬化性樹脂層10之密著性，故可使在密封步驟的作業性變的更良好。
且，樹脂薄片1d亦可作為於第2黏著劑層32的黏著表面上，進一步層合剝離材之構成。The resin sheet 1d shown in FIG. 1 (d) may be a laminate of the second adhesive layer 32, the substrate 20, the first adhesive layer 31, and the thermosetting resin layer 10 in this order. Resin flakes.
With the configuration such as the resin sheet 1d, the resin sheet can be sufficiently fixed to the support and the like, and the adhesion between the base material 20 and the thermosetting resin layer 10 can be improved, so that the work in the sealing step can be performed. Sex becomes better.
In addition, the resin sheet 1d may have a configuration in which a release material is further laminated on the adhesive surface of the second adhesive layer 32.
本發明之一態樣的樹脂薄片，由保護熱硬化性樹脂層之表面的觀點來看，亦可作為於熱硬化性樹脂層的表面上，進一步具有剝離材的構成。
例如，本發明之一態樣的樹脂薄片可為，熱硬化性樹脂層藉由2個剝離材進行夾持之構成，亦可為圖1所示露出具有樹脂薄片1a、1b、1c、1d之熱硬化性樹脂層10的表面上，進一步層合剝離材之構成。
且，該剝離材為欲保護熱硬化性樹脂層之表面而設置者，於使用樹脂薄片時被除去者。From the viewpoint of protecting the surface of the thermosetting resin layer, the resin sheet according to one aspect of the present invention may further have a constitution of a release material on the surface of the thermosetting resin layer.
For example, a resin sheet according to one aspect of the present invention may be a structure in which a thermosetting resin layer is sandwiched between two release materials, or a resin sheet 1a, 1b, 1c, 1d may be exposed as shown in FIG. 1. The surface of the thermosetting resin layer 10 is further laminated with a release material.
The release material is provided for protecting the surface of the thermosetting resin layer, and is removed when a resin sheet is used.
[樹脂薄片之用途]
本發明之樹脂薄片為使用於下述硬化密封體之製造上者，該硬化密封體之製造為，於前述熱硬化性樹脂層的表面上載置密封對象物，將前述密封對象物，與該密封對象物的至少周邊部分之前述熱硬化性樹脂層的表面以密封材料進行包覆，使該密封材料進行熱硬化後，成為含有前述密封對象物之硬化密封體。
且對於有關使用本發明之樹脂薄片的硬化密封體之製造的具體態樣，如後述。[Use of resin sheet]
The resin sheet of the present invention is used in the manufacture of a hardened sealing body, which is manufactured by placing a sealing object on the surface of the thermosetting resin layer, and sealing the sealing object with the sealing material. The surface of the thermosetting resin layer of at least a peripheral portion of the object is covered with a sealing material, and the sealing material is thermally cured to form a hardened sealing body containing the object to be sealed.
The specific aspect of the production of the hardened and sealed body using the resin sheet of the present invention will be described later.
例如，可考慮為如在專利文獻1所記載的製造方法所使用的一般晶片裝配帶等黏著薄片之黏著表面上，載置密封對象物後，將密封對象物及其周邊部分的黏著表面以密封材料進行包覆，使密封材料進行熱硬化後，製造硬化密封體之情況。
使密封材料進行熱硬化時，雖使密封材料收縮的應力會啟動，但因黏著薄片固定於支持體，故密封材料的應力受到抑制。
然而，支持體及自黏著薄片經分離而得之硬化密封體，對欲要收縮的應力之抑制變的困難。分離後的硬化密封體為，在存在密封對象物的側之表面側，與該相反的表面側，因密封材料的存在量相異，於收縮應力上容易產生差。該收縮應力之差成為造成於硬化密封體產生彎曲之原因。
又，由生產性之觀點來看，加熱後之硬化密封體在某程度之加熱狀態下，自支持體及黏著薄片進行分離者為一般。因此，亦在分離後，進行密封材料之硬化的同時，亦產生因自然冷卻造成的收縮，故成為更容易產生於硬化密封體的彎曲之狀態。For example, it is conceivable to place an object to be sealed on the adhesive surface of an adhesive sheet such as a general wafer mounting tape used in the manufacturing method described in Patent Document 1, and then seal the adhered surface of the object to be sealed and its peripheral portion to seal the object. When the material is covered and the sealing material is thermally hardened, a hardened sealing body is produced.
When the sealing material is thermally hardened, although the stress causing the sealing material to shrink is activated, the adhesive sheet is fixed to the support, so the stress of the sealing material is suppressed.
However, the hardened sealing body obtained by separating the support and the self-adhesive sheet makes it difficult to suppress the stress to be shrunk. The separated hardened sealing body is on the surface side of the side where the object to be sealed is located, and the opposite surface side is different in the amount of the sealing material, which is liable to cause a difference in shrinkage stress. This difference in shrinkage stress is a cause of bending in the hardened sealing body.
From the viewpoint of productivity, it is common that the hardened sealing body after heating is separated from the support and the adhesive sheet under a certain degree of heating. Therefore, after the sealing material is hardened after separation, shrinkage due to natural cooling also occurs, so that it is more likely to occur in a bent state of the hardened sealing body.
另一方面，使用本發明之樹脂薄片時，由以下理由而可得到可效率地抑制彎曲的硬化密封體。
換言之，於本發明之樹脂薄片的熱硬化性樹脂層之表面上載置密封對象物，以密封材料進行包覆，使密封材料進行熱硬化，同時亦使熱硬化性樹脂層進行熱硬化。此時，密封材料的存在量為少，被認為因為密封材料之硬化而導致收縮應力變小的密封對象物所存在的側之表面側上，因設有熱硬化性樹脂層，故會啟動藉由熱硬化性樹脂層之熱硬化的收縮應力。
其結果，考慮到可得到可使硬化密封體之2個表面間的收縮應力之差變小，可有效果地抑制彎曲的硬化密封體。On the other hand, when the resin sheet of the present invention is used, a cured seal body that can effectively suppress bending can be obtained for the following reasons.
In other words, a sealing object is placed on the surface of the thermosetting resin layer of the resin sheet of the present invention, covered with a sealing material, the sealing material is thermally cured, and the thermosetting resin layer is also thermally cured. At this time, since the amount of the sealing material is small, it is considered that the shrinkage stress is reduced due to the hardening of the sealing material. The surface of the sealing object on the side where the sealing object exists is provided with a thermosetting resin layer, so it will start Shrinkage stress due to thermal curing of the thermosetting resin layer.
As a result, it is considered that a hardened sealing body can be obtained in which the difference in shrinkage stress between the two surfaces of the hardened sealing body can be made small, and bending can be effectively suppressed.
另外，賦予硬化密封體的彎曲之抑制的熱硬化性樹脂層，可藉由熱硬化而成為硬化樹脂層。該硬化樹脂層為可具有作為保護膜之功能。
換言之，使用本發明之樹脂薄片，因經由上述密封步驟，可同時於硬化密封體之一方表面上形成硬化樹脂層，故可省略欲形成硬化樹脂層的步驟，而亦賦予提高生產性。Moreover, the thermosetting resin layer which gives the suppression of the bending of a hardened sealing body can be made into a hardened resin layer by thermosetting. This hardened resin layer can have a function as a protective film.
In other words, by using the resin sheet of the present invention, a hardened resin layer can be simultaneously formed on one surface of the hardened sealing body through the above-mentioned sealing step, so that the step of forming a hardened resin layer can be omitted, and productivity can be improved.
以下對於本發明之一態樣的具有樹脂薄片之各層做說明。Hereinafter, each layer having a resin sheet according to one aspect of the present invention will be described.
＜熱硬化性樹脂層＞
本發明之樹脂薄片為具有：由含有聚合性成分(A)及熱硬化性成分(B)的熱硬化性樹脂組成物所形成的熱硬化性樹脂層。
熱硬化性樹脂層為，於使密封材料進行熱硬化時，與密封材料同時熱硬化，使硬化密封體的2個表面間之收縮應力的差縮小，賦予對於所得之硬化密封體產生的彎曲之抑制。
又，熱硬化性樹脂層為經熱硬化後成為硬化樹脂層。該硬化樹脂層為，於所得的硬化密封體之一方表面上形成，具有作為保護膜之功能者。<Thermosetting resin layer>
The resin sheet of the present invention has a thermosetting resin layer formed of a thermosetting resin composition containing a polymerizable component (A) and a thermosetting component (B).
The thermosetting resin layer is configured to thermally harden the sealing material at the same time as the sealing material, thereby reducing the difference in shrinkage stress between the two surfaces of the hardened sealing body and imparting a bending effect to the obtained hardened sealing body. inhibition.
The thermosetting resin layer is a layer that becomes a cured resin after being thermally cured. This cured resin layer is formed on one surface of the obtained cured sealing body, and has a function as a protective film.
由作為可製造出彎曲受到抑制且具有平坦表面之硬化密封體的樹脂薄片之觀點來看，使熱硬化性樹脂層進行熱硬化而成的硬化樹脂層於23℃中之貯藏彈性率E’，以1.0×107
Pa以上為佳，較佳為1.0×108
Pa以上，更佳為1.0×109
Pa以上，更較佳為5.0×109
Pa以上，又以1.0×1013
Pa以下為佳為佳，較佳為1.0×1012
Pa以下，更佳為5.0×1011
Pa以下，更較佳為1.0×1011
Pa以下。
且，對於本說明書，貯藏彈性率E’表示依據實施例所記載的方法而測定的值。From the viewpoint that a resin sheet capable of producing a hardened sealed body having a flat surface with suppressed warping is used, the hardened resin layer obtained by thermally hardening the thermosetting resin layer at 23 ° C has a storage elastic modulus E ', It is preferably 1.0 × 10 7 Pa or more, more preferably 1.0 × 10 8 Pa or more, more preferably 1.0 × 10 9 Pa or more, still more preferably 5.0 × 10 9 Pa or more, and 1.0 × 10 13 Pa or less. Preferably, it is preferably 1.0 × 10 12 Pa or less, more preferably 5.0 × 10 11 Pa or less, and still more preferably 1.0 × 10 11 Pa or less.
In addition, in this specification, storage elasticity E 'shows the value measured according to the method as described in an Example.
因於熱硬化性樹脂層的表面上，載置密封對象物，故由使與密封對象物之密著性變的良好之觀點來看，熱硬化性樹脂層的表面具有黏著性者為佳。
又，對於與載置熱硬化性樹脂層的密封對象物之側為相反側的表面上，亦由與支持體等的密著性，及作為設置基材的樹脂薄片之情況時，使與基材的密著性變的良好之觀點來看，以具有黏著性者為佳。Since the sealing object is placed on the surface of the thermosetting resin layer, from the viewpoint of improving the adhesion with the sealing object, it is preferable that the surface of the thermosetting resin layer has adhesion.
In addition, on the surface opposite to the side of the object to be sealed on which the thermosetting resin layer is placed, the adhesiveness with the support or the like and the case of the resin sheet as the base material are used. From the viewpoint that the adhesiveness of the material is improved, it is preferable that the material has adhesiveness.
在室溫(23℃)下於熱硬化性樹脂層的表面中之黏著力，以0.01～5N/25mm為佳為佳，較佳為0.05～4N/25mm，更佳為0.1～3N/25mm。
且，對於本說明書，於熱硬化性樹脂層的表面中之黏著力表示，藉由實施例所記載的方法而測定的值。The adhesive force on the surface of the thermosetting resin layer at room temperature (23 ° C) is preferably 0.01 to 5 N / 25 mm, more preferably 0.05 to 4 N / 25 mm, and still more preferably 0.1 to 3 N / 25 mm.
In addition, in this specification, the adhesive force on the surface of a thermosetting resin layer shows the value measured by the method as described in an Example.
對於本發明之一態樣的樹脂薄片，熱硬化性樹脂層之厚度，以1～500μm為佳，較佳為5～300μm，更佳為10～200μm，更較佳為15～100μm。For the resin sheet according to one aspect of the present invention, the thickness of the thermosetting resin layer is preferably 1 to 500 μm, more preferably 5 to 300 μm, more preferably 10 to 200 μm, and still more preferably 15 to 100 μm.
對於本發明，熱硬化性樹脂層係由含有聚合物成分(A)及熱硬化性成分(B)之熱硬化性樹脂組成物所形成的層。
但，熱硬化性樹脂組成物亦可進一步含有選自著色劑(C)、偶合劑(D)及無機填充材(E)的1種以上，但由欲作為可製造出彎曲受到抑制且具有平坦表面之硬化密封體的樹脂薄片之觀點來看，至少含有無機填充材(E)者為佳。In the present invention, the thermosetting resin layer is a layer formed of a thermosetting resin composition containing a polymer component (A) and a thermosetting component (B).
However, the thermosetting resin composition may further contain one or more selected from the group consisting of a coloring agent (C), a coupling agent (D), and an inorganic filler (E). From the viewpoint of the resin sheet of the hardened sealing body on the surface, one containing at least the inorganic filler (E) is preferred.
(聚合物成分(A))
於熱硬化性樹脂組成物所含的聚合物成分(A)表示，質量平均分子量為2萬以上，具有至少1種重複單位之化合物。
熱硬化性樹脂組成物可藉由含有聚合性成分(A)，可對所形成的熱硬化性樹脂層賦予可撓性及造膜性，使薄片性狀維持性變良好。
聚合物成分(A)的質量平均分子量(Mw)，以2萬以上為佳，較佳為2萬～300萬，更佳為5萬～200萬，更較佳為10萬～150萬，更較佳為20萬～100萬。(Polymer component (A))
The polymer component (A) contained in the thermosetting resin composition shows a compound having a mass average molecular weight of 20,000 or more and having at least one repeating unit.
When the thermosetting resin composition contains a polymerizable component (A), flexibility and film forming properties can be imparted to the formed thermosetting resin layer, and the sheet property maintenance property can be improved.
The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, preferably 20,000 to 3 million, more preferably 50,000 to 2 million, more preferably 100,000 to 1.5 million, and more It is preferably 200,000 to 1 million.
聚合物成分(A)之含有量對於熱硬化性樹脂組成物的有效成分之全量(100質量%)而言，以5～50質量%為佳，較佳為8～40質量%，更佳為10～30質量%。The content of the polymer component (A) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and even more preferably the entire amount (100% by mass) of the effective component of the thermosetting resin composition. 10 to 30% by mass.
作為聚合物成分(A)，例如可舉出丙烯酸系聚合物、聚酯、苯氧基系樹脂、聚碳酸酯、聚醚、聚胺基甲酸酯、聚矽氧烷、橡膠系聚合物等。
這些聚合物成分(A)可單獨下使用，亦可併用2種以上。
且，對於本說明書，具有環氧基的丙烯酸系聚合物，或具有環氧基之苯氧基樹脂雖具有熱硬化性，但此等的質量平均分子量為2萬以上，若為具有至少1種重複單位的化合物，作為含於聚合物成分(A)之概念者。Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, and rubber-based polymers. .
These polymer components (A) may be used alone or in combination of two or more.
In this specification, although an acrylic polymer having an epoxy group or a phenoxy resin having an epoxy group has thermosetting properties, the mass average molecular weight thereof is 20,000 or more, and if it has at least one kind A compound of a repeating unit is a concept contained in a polymer component (A).
此等中，亦以聚合物成分(A)含有丙烯酸系聚合物(A1)者為佳。
聚合物成分(A)中之丙烯酸系聚合物(A1)的含有比例，對於含於熱硬化性樹脂組成物的聚合物成分(A)之全量(100質量%)而言，以60～100質量%為佳，較佳為70～100質量%，更佳為80～100質量%，更較佳為90～100質量%。Among these, it is also preferable that the polymer component (A) contains an acrylic polymer (A1).
The content ratio of the acrylic polymer (A1) in the polymer component (A) is 60 to 100 mass for the total amount (100% by mass) of the polymer component (A) contained in the thermosetting resin composition. % Is preferably, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.
(丙烯酸系聚合物(A1))
丙烯酸系聚合物(A1)的質量平均分子量(Mw)，由對於所形成的熱硬化性樹脂層可賦予可撓性及造膜性之觀點來看，以2萬～300萬為佳，較佳為10萬～150萬，更佳為15萬～120萬，更較佳為25萬～100萬。(Acrylic polymer (A1))
The mass average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3 million from the viewpoint of imparting flexibility and film-forming properties to the formed thermosetting resin layer. It is 100,000 to 1.5 million, more preferably 150,000 to 1.2 million, and still more preferably 250,000 to 1 million.
丙烯酸系聚合物(A1)的玻璃轉移溫度(Tg)，由於所形成的熱硬化性樹脂層之表面上賦予良好黏著性的觀點，及將使用樹脂薄片而製造出的附有硬化樹脂層的硬化密封體之信賴性提高的觀點來看，以-60～50℃為佳，較佳為-50～30℃，更佳為-40～10℃，更較佳為-35～5℃。The glass transition temperature (Tg) of the acrylic polymer (A1) is based on the viewpoint of imparting good adhesion to the surface of the formed thermosetting resin layer, and the hardening of the cured resin layer produced by using a resin sheet. From the viewpoint of improving the reliability of the sealing body, -60 to 50 ° C is preferable, -50 to 30 ° C is more preferable, -40 to 10 ° C is more preferable, and -35 to 5 ° C is more preferable.
作為丙烯酸系聚合物(A1)，可舉出將烷基(甲基)丙烯酸酯作為主成分的聚合物，具體以含有來自具有碳數1～18的烷基之烷基(甲基)丙烯酸酯(a1’)(以下亦稱為「單體(a1’)」)的構成單位(a1)之丙烯酸系聚合物為佳，同時具有構成單位(a1)與來自含官能基的單體(a2’)(以下亦稱為「單體(a2’)」)的構成單位(a2)之丙烯酸系共聚物為較佳。
丙烯酸系聚合物(A1)可單獨下使用，亦可併用2種以上。
且，丙烯酸系聚合物(A1)為共聚物時，該共聚物之型態可為嵌段共聚物、無規共聚物、交互共聚物、接枝共聚物中任一種。Examples of the acrylic polymer (A1) include a polymer containing an alkyl (meth) acrylate as a main component, and specifically an alkyl (meth) acrylate containing an alkyl group having 1 to 18 carbon atoms (a1 ') (hereinafter also referred to as "monomer (a1')") is preferably an acrylic polymer having a constituent unit (a1), and has both a constituent unit (a1) and a functional group-containing monomer (a2 ' ) (Hereinafter also referred to as "monomer (a2 ')") is preferably an acrylic copolymer having a constituent unit (a2).
The acrylic polymer (A1) may be used alone or in combination of two or more kinds.
When the acrylic polymer (A1) is a copolymer, the type of the copolymer may be any of a block copolymer, a random copolymer, an interpolymer, and a graft copolymer.
具有單體(a1’)的烷基之碳數，由對所形成的熱硬化性樹脂層賦予可撓性及造膜性之觀點來看，以1～18為佳，較佳為1～12，更佳為1～8。該烷基可為直鏈烷基，亦可為分支鏈烷基。
這些單體(a1’)可單獨下使用，亦可併用2種以上。The carbon number of the alkyl group having the monomer (a1 ') is preferably from 1 to 18, and more preferably from 1 to 12 in terms of imparting flexibility and film-forming properties to the formed thermosetting resin layer. , More preferably 1 to 8. The alkyl group may be a linear alkyl group or a branched alkyl group.
These monomers (a1 ') may be used alone or in combination of two or more kinds.
欲提高使用樹脂薄片所製造的附有硬化樹脂層的硬化密封體之信賴性的觀點來看，單體(a1’)以含有具有碳數1～3的烷基之烷基(甲基)丙烯酸酯者為佳，以含有甲基(甲基)丙烯酸酯者為較佳。
由上述觀點來看，來自具有碳數1～3的烷基之烷基(甲基)丙烯酸酯的構成單位(a11)之含有量，對於丙烯酸系聚合物(A1)之全構成單位(100質量%)而言，以1～80質量%為佳，較佳為5～80質量%，更佳為10～80質量%。From the viewpoint of improving the reliability of a hardened sealing body with a hardened resin layer produced using a resin sheet, the monomer (a1 ') is an alkyl (meth) acrylic acid having an alkyl group having 1 to 3 carbon atoms. Ester is preferred, and meth (meth) acrylate is more preferred.
From the viewpoint described above, the content of the constituent unit (a11) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms is 100 mass based on the total constituent unit of the acrylic polymer (A1). %), Preferably 1 to 80% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 80% by mass.
又，由提高使所形成的熱硬化性樹脂層進行熱硬化而成的硬化樹脂層之總價值，且提高雷射標識適性之觀點來看，單體(a1’)以含有具有碳數4以上的烷基之烷基(甲基)丙烯酸酯者為佳，以含有具有碳數4～6的烷基之烷基(甲基)丙烯酸酯者為較佳，以含有丁基(甲基)丙烯酸酯者為更佳。
由上述觀點來看，來自具有碳數4以上(以4～6為佳，更佳為4)的烷基之烷基(甲基)丙烯酸酯的構成單位(a12)之含有量，對於丙烯酸系聚合物(A1)的全構成單位(100質量%)而言，以1～70質量%為佳，較佳為5～65質量%，更佳為10～60質量%。From the viewpoint of increasing the total value of the cured resin layer obtained by thermally curing the formed thermosetting resin layer and improving the suitability of the laser marking, the monomer (a1 ') contains a carbon number of 4 or more. Alkyl (meth) acrylates are preferred, and alkyl (meth) acrylates containing alkyl groups having 4 to 6 carbon atoms are preferred, and butyl (meth) acrylates are preferred. Ester is more preferred.
From the viewpoint described above, the content of the constitutional unit (a12) of an alkyl (meth) acrylate derived from an alkyl group having a carbon number of 4 or more (preferably 4 to 6, and more preferably 4) is for acrylics. The total constituent unit (100% by mass) of the polymer (A1) is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and even more preferably 10 to 60% by mass.
構成單位(a1)的含有量對於丙烯酸系聚合物(A1)之全構成單位(100質量%)，以50質量%以上為佳，較佳為50～99質量%，更佳為55～90質量%，更佳為60～90質量%。The content of the constituent unit (a1) is preferably 50% by mass or more with respect to the total constituent unit (100% by mass) of the acrylic polymer (A1), more preferably 50 to 99% by mass, and more preferably 55 to 90% %, More preferably 60 to 90% by mass.
單體(a2’)以選自含羥基的單體及含環氧基的單體的1種以上者為佳。
且，單體(a2’)可單獨下使用，亦可併用2種以上。The monomer (a2 ') is preferably one or more selected from a hydroxyl-containing monomer and an epoxy-containing monomer.
The monomer (a2 ') may be used alone or in combination of two or more kinds.
作為含羥基的單體，例如可舉出2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、3-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、3-羥基丁基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯等羥基烷基(甲基)丙烯酸酯類；乙烯基醇、烯丙基醇等不飽和醇類等。
此等中，含羥基的單體亦以羥基烷基(甲基)丙烯酸酯為佳，以2-羥基乙基(甲基)丙烯酸酯者為較佳。Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy Hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; vinyl alcohol, allyl Unsaturated alcohols such as alcohols.
Among these, the hydroxy-containing monomer is also preferably a hydroxyalkyl (meth) acrylate, and more preferably a 2-hydroxyethyl (meth) acrylate.
作為含環氧基的單體，例如可舉出縮水甘油基(甲基)丙烯酸酯、β-甲基縮水甘油基(甲基)丙烯酸酯、(3,4-環氧環己基)甲基(甲基)丙烯酸酯、3-環氧環-2-羥基丙基(甲基)丙烯酸酯等環氧基含有(甲基)丙烯酸酯；縮水甘油基巴豆酸酯、烯丙基縮水甘油基醚等。
此等中，含環氧基的單體亦以含環氧基的(甲基)丙烯酸酯為佳，以縮水甘油基(甲基)丙烯酸酯者為較佳。Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl ( (Meth) acrylate, 3-epoxycyclo-2-hydroxypropyl (meth) acrylate and other epoxy groups containing (meth) acrylate; glycidyl crotonate, allyl glycidyl ether, etc. .
Among these, the epoxy group-containing monomer is also preferably an epoxy group-containing (meth) acrylate, and a glycidyl (meth) acrylate is more preferable.
構成單位(a2)的含有量，對於丙烯酸系聚合物(A1)的全構成單位(100質量%)而言，以1～50質量%為佳，較佳為5～45質量%，更佳為10～40質量%，更較佳為10～30質量%。The content of the constituent unit (a2) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, and even more preferably all the constituent units (100% by mass) of the acrylic polymer (A1). 10 to 40% by mass, and more preferably 10 to 30% by mass.
且，丙烯酸系聚合物(A1)對於不損害本發明之效果的範圍，亦可具有來自上述構成單位(a1)及(a2)以外的其他單體之構成單位。
作為其他單體，例如可舉出乙酸乙烯基、苯乙烯、乙烯、α-烯烴等。In addition, the acrylic polymer (A1) may have a constitutional unit derived from monomers other than the constitutional units (a1) and (a2) as far as the effect of the present invention is not impaired.
Examples of other monomers include vinyl acetate, styrene, ethylene, and α-olefin.
＜熱硬化性成分(B)＞
熱硬化性成分(B)為擔任使所形成的熱硬化性樹脂層進行熱硬化，成為硬質的硬化樹脂層之角色者，其為質量平均分子量未達2萬的化合物。
硬化性成分(B)的質量平均分子量(Mw)，以10,000以下為佳，較佳為100～10,000。<Thermosetting component (B)>
The thermosetting component (B) is a compound that functions to thermally harden the formed thermosetting resin layer to become a hard cured resin layer, and has a mass average molecular weight of less than 20,000.
The mass average molecular weight (Mw) of the curable component (B) is preferably 10,000 or less, and more preferably 100 to 10,000.
熱硬化性成分(B)由可製造出彎曲受到抑制且具有平坦表面的硬化密封體之樹脂薄片的觀點來看，以含有具有環氧基的化合物之環氧化合物(B1)及熱硬化劑(B2)者為佳，同時含有環氧化合物(B1)及熱硬化劑(B2)下，更含有硬化促進劑(B3)者為佳。The thermosetting component (B) is an epoxy compound (B1) containing a compound having an epoxy group and a thermosetting agent ( B2) is more preferred, and if it contains both an epoxy compound (B1) and a thermosetting agent (B2), it is more preferred to contain a hardening accelerator (B3).
作為環氧化合物(B1)，例如可舉出多官能系環氧樹脂、雙酚A二縮水甘油基醚及其氫化物、鄰甲酚酚醛清漆環氧樹脂、二環戊二烯型環氧樹脂、聯苯基型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、伸苯基骨架型環氧樹脂等於分子中具有2官能以上，且質量平均分子量未達2萬的環氧化合物等。
環氧化合物(B1)可單獨下使用，亦可併用2種以上。Examples of the epoxy compound (B1) include a polyfunctional epoxy resin, a bisphenol A diglycidyl ether and a hydrogenated product thereof, an o-cresol novolac epoxy resin, and a dicyclopentadiene type epoxy resin. , Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin are equal to those having more than two functions in the molecule and the mass average molecular weight is less than 20,000 Epoxy compounds, etc.
The epoxy compound (B1) may be used alone or in combination of two or more kinds.
環氧化合物(B1)的含有量，由可製造抑制彎曲且具有平坦表面的硬化密封體的樹脂薄片之觀點來看，對於含於熱硬化性樹脂組成物的聚合物成分(A)100質量份而言，以1～500質量份為佳，較佳為3～300質量份，更佳為10～150質量份，更較佳為20～120質量份。The content of the epoxy compound (B1) is 100 parts by mass of the polymer component (A) contained in the thermosetting resin composition from the viewpoint that a resin sheet capable of producing a hardened sealing body having a flat surface while suppressing bending can be produced. Specifically, it is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, more preferably 10 to 150 parts by mass, and still more preferably 20 to 120 parts by mass.
熱硬化劑(B2)為作為對環氧化合物(B1)的硬化劑而發揮其功能。
熱硬化劑(B2)以於1分子中具有可與環氧基進行反應的2個以上官能基之化合物者為佳。
作為該官能基，可舉出酚性羥基、醇性羥基、胺基、羧基及酸酐等。此等中亦以由可製造可抑制彎曲且具有平坦表面的附有硬化樹脂層的硬化密封體之黏著性層合體的觀點來看，以酚性羥基、胺基或酸酐為佳，以酚性羥基或胺基為較佳，以胺基為更佳。The thermosetting agent (B2) functions as a curing agent for the epoxy compound (B1).
The thermosetting agent (B2) is preferably a compound having two or more functional groups capable of reacting with an epoxy group in one molecule.
Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acid anhydride. Among these, from the viewpoint of producing an adhesive laminate of a hardened sealing body with a hardened resin layer having a flat surface that can suppress bending, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferred, and a phenolic property is preferred. Hydroxyl or amine groups are preferred, and amine groups are more preferred.
作為具有酚基的酚系熱硬化劑，例如可舉出多官能系酚樹脂、雙酚、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、聚酚醚(Xyloc)型酚樹脂、芳烷基酚樹脂等。
作為具有胺基的胺系熱硬化劑，例如可舉出二氰二胺(DICY)等。
這些熱硬化劑(B2)可單獨下使用，亦可併用2種以上。Examples of the phenol-based thermosetting agent having a phenol group include polyfunctional phenol resins, bisphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, polyphenol ether (Xyloc) -type phenol resins, and aromatic compounds. Alkyl phenol resin and the like.
Examples of the amine-based thermosetting agent having an amine group include dicyandiamine (DICY).
These thermosetting agents (B2) may be used alone or in combination of two or more kinds.
熱硬化劑(B2)的含有量由可製造出可抑制彎曲且具有平坦表面的附有硬化樹脂層的硬化密封體之黏著性層合體的觀點來看，對於環氧化合物(B1)100質量份而言，以0.1～500質量份為佳，較佳為1～200質量份。The content of the thermosetting agent (B2) is 100 parts by mass of the epoxy compound (B1) from the viewpoint that an adhesive laminated body having a hardened resin layer with a hardened resin layer and a flat surface can be suppressed from being bent. In particular, it is preferably from 0.1 to 500 parts by mass, and more preferably from 1 to 200 parts by mass.
硬化促進劑(B3)為，於使所形成的熱硬化性樹脂層進行熱硬化時，具有可提高熱硬化的速度之功能的化合物。
作為硬化促進劑(B3)，例如可舉出三乙二胺、苯甲基二甲基胺、三乙醇胺、二甲基胺基乙醇、參(二甲基胺基甲基)酚等3級胺類；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等咪唑類；三丁基膦、二苯基膦、三苯基膦等有機膦類；四苯基鏻四苯基硼酸鹽、三苯基膦四苯基硼酸鹽等四苯基硼鹽等。
這些硬化促進劑(B3)可單獨下使用，亦可併用2種以上。The hardening accelerator (B3) is a compound having a function of increasing the rate of thermal curing when the formed thermosetting resin layer is thermally cured.
Examples of the hardening accelerator (B3) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and gins (dimethylaminomethyl) phenol. Class; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl- Imidazoles such as 5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc. Phenyl boron salt and the like.
These hardening accelerators (B3) may be used alone or in combination of two or more.
硬化促進劑(B3)的含有量由可製造可抑制彎曲且具有平坦表面的硬化密封體之樹脂薄片的觀點來看，對於環氧化合物(B1)及熱硬化劑(B2)的合計量100質量份而言，以0.01～10質量份為佳，較佳為0.1～6質量份，更佳為0.3～4質量份。The content of the hardening accelerator (B3) is 100 mass based on the total amount of the epoxy compound (B1) and the thermosetting agent (B2) from the viewpoint that a resin sheet capable of suppressing bending and having a flat surface can be produced. In terms of parts, it is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and even more preferably 0.3 to 4 parts by mass.
＜著色劑(C)＞
在本發明之一態樣所使用的熱硬化性樹脂組成物可進一步含有著色劑(C)。
由含有著色劑(C)的熱硬化性樹脂組成物所形成的熱硬化性樹脂層在進行熱硬化使其成為硬化樹脂層時，該硬化樹脂層可遮蔽由周圍的裝置所產生的紅外線等，可防止密封對象物(半導體晶片等)之錯誤操作。<Colorant (C)>
The thermosetting resin composition used in one aspect of the present invention may further contain a colorant (C).
When a thermosetting resin layer formed of a thermosetting resin composition containing a colorant (C) is thermally cured to become a cured resin layer, the cured resin layer can shield infrared rays and the like generated by surrounding devices. Prevents erroneous operation of sealed objects (semiconductor wafers, etc.).
作為著色劑(C)，可使用有機或無機的顏料及染料。
作為染料，例如亦可使用於酸性染料、反應染料、直接染料、分散染料、陽離子染料等任一染料。
又，對於顏料，並無特別限制，可適宜地選自公知顏料者。
這些中，由電磁波或紅外線的遮蔽性良好，且藉由雷射標識法可使識別性更提高的觀點來看，以黑色顏料為佳。
作為黑色顏料，例如可舉出碳黑、氧化鐵、二氧化錳、苯胺黑、活性碳等，但由提高半導體晶片之信賴性的觀點來看以碳黑為佳。
且，這些著色劑(C)可單獨下使用，亦可併用2種以上。As the colorant (C), organic or inorganic pigments and dyes can be used.
As the dye, for example, an acid dye, a reactive dye, a direct dye, a disperse dye, or a cationic dye can be used.
The pigment is not particularly limited, and may be appropriately selected from known pigments.
Among these, a black pigment is preferable from the viewpoint that the shielding property by electromagnetic waves or infrared rays is good, and the visibility can be further improved by the laser marking method.
Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but carbon black is preferred from the viewpoint of improving the reliability of semiconductor wafers.
These colorants (C) may be used alone or in combination of two or more.
但，對於在本發明之一態樣所使用的熱硬化性樹脂組成物，著色劑(C)的含有量，對於熱硬化性樹脂組成物之有效成分的全量(100質量%)而言，以未達8質量%者為佳。
著色劑(C)的含有量僅未達8質量%，可成為該晶片表面之裂紋有無或碎裂(Chipping)可藉由目視確認的樹脂薄片。
由上述觀點來看，在本發明之一態樣使用的熱硬化性樹脂組成物中，著色劑(C)的含有量對於熱硬化性樹脂組成物的有效成分全量(100質量%)而言，以未達5質量%為佳，較佳為未達2質量%，更佳為未達1質量%，更較佳為未達0.5質量%。However, in the thermosetting resin composition used in one aspect of the present invention, the content of the colorant (C) is based on the total amount (100% by mass) of the effective components of the thermosetting resin composition. It is preferably less than 8% by mass.
The content of the colorant (C) is less than 8% by mass, and it can be a resin sheet on which the presence or absence of cracks or chipping of the wafer surface can be visually confirmed.
From the viewpoint described above, in the thermosetting resin composition used in one aspect of the present invention, the content of the colorant (C) is based on the total amount (100% by mass) of the active ingredient of the thermosetting resin composition. It is preferably less than 5 mass%, more preferably less than 2 mass%, more preferably less than 1 mass%, and even more preferably less than 0.5 mass%.
又，由將所形成的熱硬化性樹脂層進行熱硬化而成的硬化樹脂層上可表現紅外線等遮蔽效果之觀點來看，著色劑(C)的含有量對於熱硬化性樹脂組成物之有效成分的全量(100質量%)而言，以0.01質量%以上為佳，較佳為0.05質量%以上，更佳為0.10質量%以上，更較佳為0.15質量%以上。In addition, the content of the colorant (C) is effective for the thermosetting resin composition from the viewpoint that a shielding effect such as infrared rays can be exhibited on the cured resin layer formed by thermosetting the formed thermosetting resin layer. In terms of the total amount (100% by mass) of the component, 0.01% by mass or more is preferable, 0.05% by mass or more is more preferable, 0.10% by mass or more is more preferable, and 0.15% by mass or more is more preferable.
＜偶合劑(D)＞
在本發明之一態樣所使用的熱硬化性樹脂組成物可進一步含有偶合劑(D)。
由含有偶合劑(D)的熱硬化性樹脂組成物所形成的熱硬化性樹脂層，可提高載置密封對象物時與密封對象物之接著性。又，使熱硬化性樹脂層進行熱硬化而成的硬化樹脂層，不會損害其耐熱性且亦可提高耐水性。＜ Coupling agent (D) ＞
The thermosetting resin composition used in one aspect of the present invention may further contain a coupling agent (D).
The thermosetting resin layer formed of the thermosetting resin composition containing the coupling agent (D) can improve the adhesion to the sealing target when the sealing target is placed. In addition, a cured resin layer obtained by thermosetting a thermosetting resin layer can also improve water resistance without impairing its heat resistance.
偶合劑(D)係以可與聚合性成分(A)或熱硬化性成分(B)所具有的官能基進行反應的化合物為佳，具體為以矽烷偶合劑為佳。
作為矽烷偶合劑，例如可舉出3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-(甲基丙烯醯氧基丙基)三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-3-胺基丙基甲基二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、3-脲丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽基丙基)四硫烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基乙醯氧基矽烷、咪唑矽烷等。
這些偶合劑(D)可單獨下使用，亦可併用2種以上。The coupling agent (D) is preferably a compound capable of reacting with a functional group of the polymerizable component (A) or the thermosetting component (B), and more preferably a silane coupling agent.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldioxane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (methacryloxypropyl) trimethoxysilane, 3-aminopropyltrimethoxy Silane, N-6- (aminoethyl) -3-aminopropyltrimethoxysilane, N-6- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N -Phenyl-3-aminopropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-Triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, imidazolesilane, and the like.
These coupling agents (D) may be used alone or in combination of two or more.
偶合劑(D)的分子量，以100～15,000為佳，較佳為125～10,000為佳，較佳為150～5,000，更佳為175～3,000，更較佳為200～2,000。The molecular weight of the coupling agent (D) is preferably 100 to 15,000, more preferably 125 to 10,000, more preferably 150 to 5,000, more preferably 175 to 3,000, and still more preferably 200 to 2,000.
偶合劑(D)的含有量對於熱硬化性樹脂組成物之有效成分的全量(100質量%)而言，以0.01～10質量%為佳，較佳為0.05～7質量%，更佳為0.10～4質量%，更較佳為0.15～2質量%。The content of the coupling agent (D) is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, and more preferably 0.10% with respect to the entire amount (100% by mass) of the effective component of the thermosetting resin composition. 4 mass%, more preferably 0.15 to 2 mass%.
＜無機填充材(E)＞
在本發明之一態樣所使用的熱硬化性樹脂組成物，由可製造可抑制彎曲且具有平坦表面的硬化密封體之樹脂薄片的觀點來看，進一步含有無機填充材(E)者為佳。
作為由含有無機填充材(E)的熱硬化性樹脂組成物所形成的熱硬化性樹脂層，在使密封材料進行熱硬化時，欲使硬化密封體的2個表面間之收縮應力的差變小，可調整該熱硬化性樹脂層的熱硬化之程度。其結果，可製造出可抑制彎曲且具有平坦表面的硬化密封體。
又，可使將所形成的熱硬化性樹脂層進行熱硬化而成的硬化樹脂層的熱膨張係數調整至適度範圍，可提高密封對象物的信賴性。又，亦可減低該硬化樹脂層之吸濕率。<Inorganic Filler (E)>
In the thermosetting resin composition used in one aspect of the present invention, it is preferable that the inorganic filler (E) is further contained from the viewpoint that a resin sheet capable of suppressing warpage and having a flat surface can be produced. .
As a thermosetting resin layer formed of a thermosetting resin composition containing an inorganic filler (E), when the sealing material is thermally cured, a difference in shrinkage stress between two surfaces of the cured sealing body is intended to be changed. It is small, and the degree of thermosetting of this thermosetting resin layer can be adjusted. As a result, a hardened sealed body having a flat surface that can suppress bending can be manufactured.
In addition, the thermal expansion coefficient of the cured resin layer obtained by thermally curing the formed thermosetting resin layer can be adjusted to an appropriate range, and the reliability of the object to be sealed can be improved. In addition, the moisture absorption of the cured resin layer can be reduced.
作為無機填充材(E)，例如可出二氧化矽、氧化鋁、滑石、碳酸鈣、氧化鈦、氧化鐵、碳化矽、氮化硼等粉末、將這些經球形化的珠子、單結晶纖維及玻璃纖維等非熱膨張性粒子。
這些無機填充材(E)可單獨下使用，亦可併用2種以上。
這些中，亦以可製造可抑制彎曲且具有平坦表面的硬化密封體的樹脂薄片之觀點來看，以二氧化矽或氧化鋁為佳。As the inorganic filler (E), for example, powders such as silicon dioxide, aluminum oxide, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, and the like, which are spheroidized beads, single crystal fibers, and Non-thermally expandable particles such as glass fibers.
These inorganic fillers (E) may be used individually or in combination of 2 or more types.
Among these, silicon dioxide or aluminum oxide is preferred from the viewpoint that a resin sheet capable of suppressing bending and having a flat sealing surface can be produced.
無機填充材(E)的平均粒子徑由可提高將所形成的熱硬化性樹脂層進行熱硬化而成的硬化樹脂膜之總價值的觀點來看，以0.3～50μm為佳，較佳為0.5～30μm，更佳為0.7～10μm。The average particle diameter of the inorganic filler (E) is preferably 0.3 to 50 μm, and more preferably 0.5 from the viewpoint of increasing the total value of the cured resin film obtained by thermally curing the formed thermosetting resin layer. -30 μm, more preferably 0.7-10 μm.
無機填充材(E)的含有量，由可製造可抑制彎曲且具有平坦表面的硬化密封體的樹脂薄片之觀點來看，對於熱硬化性樹脂組成物的有效成分之全量(100質量%)而言，以25～80質量%為佳，較佳為30～70質量%，更佳為40～65質量%，更較佳為45～60質量%。The content of the inorganic filler (E) is the total amount (100% by mass) of the effective components of the thermosetting resin composition from the viewpoint that a resin sheet capable of suppressing bending and having a flat surface can be produced. In other words, it is preferably 25 to 80% by mass, more preferably 30 to 70% by mass, more preferably 40 to 65% by mass, and still more preferably 45 to 60% by mass.
＜其他添加劑＞
在本發明之一態樣所使用的熱硬化性樹脂組成物，在不損害本發明之效果的範圍下，進一步可含有除上述聚合性成分(A)、熱硬化性成分(B)、著色劑(C)、偶合劑(D)及無機填充材(E)(以下稱為成分(A)～(E))以外的其他添加劑。
作為成分(A)～(E)以外的其他添加劑，例如可舉出交聯劑、塗平劑、可塑劑、帶電防止劑、抗氧化劑、離子捕捉劑、吸除劑、連鎖移動劑等。
成分(A)～(E)以外的其他添加劑之合計含有量對於熱硬化性樹脂組成物的有效成分全量(100質量%)而言，以0～20質量%為佳，較佳為0～10質量%，更佳為0～5質量%。＜ Other additives ＞
The thermosetting resin composition used in one aspect of the present invention may further contain the polymerizable component (A), the thermosetting component (B), and a colorant in addition to the effects of the present invention. (C), a coupling agent (D), and other additives other than the inorganic filler (E) (hereinafter referred to as components (A) to (E)).
Examples of the additives other than the components (A) to (E) include a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion trapping agent, a getter, and a chain transfer agent.
The total content of the additives other than the components (A) to (E) is preferably from 0 to 20% by mass, and more preferably from 0 to 10, based on the total amount (100% by mass) of the effective component of the thermosetting resin composition. Mass%, more preferably 0 to 5 mass%.
＜基材＞
本發明之一態樣的樹脂薄片可與熱硬化性樹脂層同時具有基材。
在本發明之一態樣所使用的基材之厚度，以10～500μm為佳，較佳為15～300μm，更佳為20～200μm。＜ Base material ＞
The resin sheet according to one aspect of the present invention may have a substrate simultaneously with the thermosetting resin layer.
The thickness of the substrate used in one aspect of the present invention is preferably 10 to 500 μm, more preferably 15 to 300 μm, and even more preferably 20 to 200 μm.
作為在本發明之一態樣所使用的基材，例如可舉出由選自紙材、樹脂、金屬等的1種以上所構成的薄片狀物，但以含有樹脂的樹脂基材為佳。
作為紙材，例如可舉出薄葉紙、中質紙、上質紙、含浸紙、塗布紙、藝術紙、硫酸紙、玻璃紙等。
作為構成樹脂基材的樹脂，例如可舉出聚乙烯、聚丙烯等聚烯烴樹脂；聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯基醇共聚物等乙烯基系樹脂；聚乙烯對苯二甲酸乙二醇酯、聚丁烯對苯二甲酸乙二醇酯、聚乙烯萘二甲酸酯等聚酯系樹脂；聚苯乙烯；丙烯腈-丁二烯-苯乙烯共聚物；三乙酸纖維素；聚碳酸酯；聚胺基甲酸酯、丙烯酸改性聚胺基甲酸酯等胺基甲酸酯樹脂；聚甲基戊烯；聚碸；聚醚醚酮；聚迷碸；聚伸苯基硫化物；聚醚醯亞胺、聚醯亞胺等聚醯亞胺系樹脂；聚醯胺系樹脂；丙烯酸樹脂；氟系樹脂等。
作為金屬，例如可舉出鋁、錫、鉻、鈦等。Examples of the substrate used in one aspect of the present invention include a sheet-like material composed of one or more selected from the group consisting of paper, resin, and metal, but a resin-containing resin substrate is preferred.
Examples of the paper material include thin-leaf paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, and cellophane.
Examples of the resin constituting the resin substrate include polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymerization Products such as vinyl resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polystyrene; acrylonitrile- Butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane resins such as polyurethane and acrylic-modified polyurethane; polymethylpentene; polyfluorene Polyether ether ketone; polymetamidine; polyphenylene sulfide; polyetherimide, polyimide, and other polyimide-based resins; polyimide-based resins; acrylic resins; fluorine-based resins.
Examples of the metal include aluminum, tin, chromium, and titanium.
且，樹脂基材可與上述樹脂同時含有紫外線吸收劑、光安定劑、抗氧化劑、帶電防止劑、滑劑、防密封劑、著色劑等基材用添加劑。In addition, the resin substrate may contain additives for the substrate such as an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, a sealant, and a colorant together with the resin.
在本發明所使用的基材可為由1種所成的材料而形成者，亦可由2種以上的材料所形成者。
作為由2種以上材料所形成的基材，例如可舉出將紙材以聚乙烯等熱可塑性樹脂進行層合者，或於含有樹脂之樹脂基材的表面上形成金屬膜者等。
且，作為金屬層的形成方法，例如可舉出藉由上述金屬的真空蒸鍍、濺射、離子鍍敷等PVD法進行蒸鍍之方法，或將由上述金屬所成的金屬箔使用一般黏著劑進行貼合的方法等。The substrate used in the present invention may be formed of one type of material, or may be formed of two or more types of materials.
Examples of the base material formed of two or more materials include a paper material laminated with a thermoplastic resin such as polyethylene, and a metal film formed on the surface of a resin-containing resin base material.
In addition, as a method for forming the metal layer, for example, a method in which the above-mentioned metal is vapor-deposited by a PVD method such as vacuum evaporation, sputtering, or ion plating, or a general adhesive using a metal foil made of the above-mentioned metal is used. The method of bonding.
又，如圖1(a)所示樹脂薄片1a，於基材上層合熱硬化性樹脂層的構成時，由使基材與熱硬化性樹脂層的密著性變的良好之觀點來看，對於基材之表面而言，可施予藉由氧化法或凹凸化法等表面處理、易接著處理或者底漆處理。In addition, when the resin sheet 1a shown in FIG. 1 (a) is laminated with a thermosetting resin layer on a substrate, from the viewpoint of improving the adhesion between the substrate and the thermosetting resin layer, The surface of the base material may be subjected to a surface treatment such as an oxidation method or an embossing method, an easy adhesion treatment, or a primer treatment.
＜黏著劑層＞
本發明之一態樣的樹脂薄片可進一步具有黏著劑層。
對於本發明之一態樣，黏著劑層的黏著力以0.10～10.0N/25mm為佳，較佳為0.15～8.0N/25mm，更佳為0.20～6.0N/25mm，更較佳為0.25～4.0N/25mm。
且，對於本說明書，黏著力表示藉由實施例所記載的方法所測定之值。
又，例如如圖1(d)所示樹脂薄片1d，具有第1黏著劑層及第2黏著劑層時，以第1黏著劑層及第2黏著劑層的各黏著力在上述範圍內者為佳。＜ Adhesive layer ＞
One aspect of the present invention may further include an adhesive layer.
For one aspect of the present invention, the adhesive force of the adhesive layer is preferably from 0.10 to 10.0 N / 25 mm, more preferably from 0.15 to 8.0 N / 25 mm, more preferably from 0.20 to 6.0 N / 25 mm, and even more preferably from 0.25 to 4.0N / 25mm.
In addition, in this specification, an adhesive force shows the value measured by the method as described in an Example.
For example, if the resin sheet 1d shown in FIG. 1 (d) has the first adhesive layer and the second adhesive layer, the adhesive force of the first adhesive layer and the second adhesive layer is within the above range. Better.
對於本發明之一態樣，黏著劑層的厚度以1～100μm為佳，較佳為3～50μm，更佳為5～25μm。In one aspect of the present invention, the thickness of the adhesive layer is preferably 1 to 100 μm, more preferably 3 to 50 μm, and even more preferably 5 to 25 μm.
黏著劑層可為由含有黏著性樹脂的黏著劑組成物所形成。
在本發明之一態樣所使用的黏著性樹脂為該樹脂單獨下具有黏著性，質量平均分子量(Mw)若為1萬以上的聚合物即可。作為黏著性樹脂，例如可舉出丙烯酸系樹脂、胺基甲酸酯系樹脂、聚異丁烯系樹脂等橡膠系樹脂、聚酯系樹脂、烯烴系樹脂、聚矽氧系樹脂、聚乙烯醚系樹脂等。
這些黏著性樹脂可單獨下使用，亦可併用2種以上。The adhesive layer may be formed of an adhesive composition containing an adhesive resin.
The adhesive resin used in one aspect of the present invention is a polymer having adhesiveness under the resin alone, and a polymer having a mass average molecular weight (Mw) of 10,000 or more may be used. Examples of the adhesive resin include rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. Wait.
These adhesive resins may be used alone or in combination of two or more.
在本發明之一態樣所使用的黏著性樹脂之質量平均分子量(Mw)，由提高黏著力的觀點來看，以1萬～200萬為佳，較佳為2萬～150萬，更佳為3萬～100萬。From the viewpoint of improving the adhesive force, the mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention is preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, and more preferably It is 30,000 to 1 million.
又，黏著劑組成物可配合所使用的黏著性樹脂之種類，進一步含有黏著劑用添加劑。
作為如此黏著劑用添加劑，例如可舉出交聯劑、黏著賦予劑、聚合性化合物、聚合起始劑、抗氧化劑、軟化劑(可塑劑)、防鏽劑、顏料、染料、遲延劑、反應促進劑(觸媒)、紫外線吸收劑、帶電防止劑等。In addition, the adhesive composition may further contain an additive for an adhesive in accordance with the type of the adhesive resin to be used.
Examples of such an adhesive additive include a cross-linking agent, an adhesion-imparting agent, a polymerizable compound, a polymerization initiator, an antioxidant, a softener (plasticizer), a rust inhibitor, a pigment, a dye, a retarder, and a reaction. Accelerator (catalyst), ultraviolet absorber, antistatic agent, etc.
黏著性樹脂的含有量對於黏著劑組成物的有效成分全量(100質量%)而言，以35質量%以上為佳，較佳為50質量%以上，更佳為60質量%以上，更較佳為70質量%以上。The content of the adhesive resin is preferably 35% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total amount (100% by mass) of the active ingredient of the adhesive composition. It is 70 mass% or more.
且，具有如圖1的樹脂薄片1b、1c、1d之構成的樹脂薄片之黏著劑層，可為由含有能量線硬化型的黏著性樹脂及光聚合起始劑之能量線硬化型黏著劑組成物所形成的層。
藉由作為由如此能量線硬化型黏著劑組成物所形成的黏著劑層，形成硬化樹脂層及硬化密封體後，藉由照射能量線，可降低黏著力，可在黏著劑層與硬化樹脂層之間容易地分離。
且，作為能量線，可舉出紫外線或電子線，以紫外線為佳。In addition, the adhesive layer of the resin sheet having the resin sheets 1b, 1c, and 1d as shown in FIG. 1 may be an energy ray-curable adhesive containing an energy ray-curable adhesive resin and a photopolymerization initiator. The layer formed by the object.
By forming the hardened resin layer and hardened sealing body as an adhesive layer formed of such an energy ray-curable adhesive composition, the energy can be reduced by irradiating the energy ray, and the adhesive layer and the hardened resin layer can be reduced. Easily separated between.
In addition, examples of the energy rays include ultraviolet rays and electron rays, and ultraviolet rays are preferred.
能量線硬化型黏著劑組成物可為含有於上述黏著性樹脂的側鏈導入(甲基)丙烯醯基、乙烯基等聚合性官能基的能量線硬化型之黏著性樹脂的組成物，亦可為含有具有聚合性官能基的單體或寡聚物之組成物。
且，這些組成物以進一步含有光聚合起始劑者為佳。The energy ray-curable adhesive composition may be a composition of an energy ray-curable adhesive resin containing polymerizable functional groups such as (meth) acrylfluorene and vinyl groups in the side chain of the adhesive resin, or it may be It is a composition containing a monomer or oligomer having a polymerizable functional group.
In addition, those compositions preferably contain a photopolymerization initiator.
作為光聚合起始劑，例如可舉出1-羥基-環己基-苯基-酮、安息香、安息香甲基醚、安息香乙基醚、安息香丙基醚、苯甲基苯基硫化物、四甲基秋蘭姆單硫化物、偶氮二異丁腈、二苯甲基、二乙醯、8-氯蒽醌等。
這些光聚合起始劑可單獨下使用，亦可併用2種以上。
光聚合起始劑的含有量對於能量線硬化型黏著性樹脂100質量份或者具有聚合性官能基的單體或寡聚物100質量份而言，以0.01～10質量份為佳，較佳為0.03～5質量份，更佳為0.05～2質量份。Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, and tetramethyl Kitiulam monosulfide, azobisisobutyronitrile, diphenylmethyl, diethylpyrene, 8-chloroanthraquinone, etc.
These photopolymerization initiators may be used alone or in combination of two or more.
The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the energy ray-curable adhesive resin or 100 parts by mass of the monomer or oligomer having a polymerizable functional group, and more preferably 0.03 to 5 parts by mass, more preferably 0.05 to 2 parts by mass.
[黏著性層合體之使用方法]
本發明之樹脂薄片藉由使用於硬化密封體之製造上，可將抑制彎曲且具有平坦表面的硬化密封體在提高生產性下製造。
因此，本發明亦提供下述[I]所示樹脂薄片之使用方法。
[I]上述本發明之樹脂薄片的使用方法中，
於前述熱硬化性樹脂層之表面上載置密封對象物，
前述密封對象物，與該密封對象物的至少周邊部分之前述熱硬化性樹脂層的表面以密封材料進行包覆，
使該密封材料進行熱硬化，使其成為含有前述密封對象物之硬化密封體的樹脂薄片之使用方法。[How to use the adhesive laminate]
The resin sheet of the present invention is used for the production of a hardened sealing body, so that a hardened sealing body having a flat surface while suppressing bending can be manufactured with improved productivity.
Therefore, the present invention also provides a method for using the resin sheet shown in the following [I].
[I] In the method of using the resin sheet of the present invention,
Placing a sealing object on the surface of the thermosetting resin layer,
The object to be sealed is coated with a sealing material on a surface of the thermosetting resin layer and at least a peripheral portion of the object to be sealed,
This sealing material is a method of using a resin sheet including a hardened sealing body containing the object to be sealed by thermally curing the sealing material.
且，對於上述[I]所記載的使用方法，在使前述密封材料進行熱硬化時，亦使前述熱硬化性樹脂層進行熱硬化，形成硬化樹脂層，做成熱附有硬化樹脂層的硬化密封體者為佳。
藉由使用上述本發明之樹脂薄片，可將抑制彎曲且具有平坦表面的硬化密封體(附有硬化樹脂層的硬化密封體)在提高生產性下製造。
且，對於上述[I〕所記載的使用方法，樹脂薄片的較佳構成係如上述，對於密封材料的種類，或密封材料的包覆方法、熱硬化的各條件等，如以下所示的「附有硬化樹脂層的硬化密封體之製造方法」的項目所記載的。In addition, in the use method described in the above [I], when the sealing material is thermally cured, the thermally curable resin layer is also thermally cured to form a cured resin layer, and it is cured by thermally attaching the cured resin layer. Sealed body is preferred.
By using the resin sheet of the present invention as described above, it is possible to manufacture a hardened sealing body (a hardened sealing body with a hardened resin layer) having a flat surface while suppressing bending, with improved productivity.
In addition, with regard to the method of use described in [I], the preferred composition of the resin sheet is as described above. Regarding the type of sealing material, the method of coating the sealing material, and the conditions of thermal curing, etc. "Production method of hardened sealing body with hardened resin layer" described in the item.
[硬化附有樹脂膜之硬化密封體的製造方法]
作為使用本發明之樹脂薄片，製造硬化附有樹脂膜之硬化密封體的方法，可舉出具有下述步驟(i)～(iii)的方法。
･步驟(i)：使於具有前述樹脂薄片的熱硬化性樹脂層之表面的一部分載置密封對象物之步驟。
･步驟(ii)：將前述密封對象物，與該密封對象物的至少周邊部分之前述熱硬化性樹脂層的表面以密封材料進行包覆的步驟。
･步驟(iii)：使前述密封材料進行熱硬化，使含有前述密封對象物的硬化密封體形成之同時，亦使前述熱硬化性樹脂層進行熱硬化，形成硬化樹脂層，得到附有硬化樹脂層的硬化密封體之步驟。
圖2表示使用如圖1(d)所示樹脂薄片1d而製造附有硬化樹脂層的硬化密封體之步驟的截面模式圖。以下一邊適宜地參照圖2下，對於上述各步驟進行說明。[Manufacturing method of hardened sealed body with resin film]
As a method of manufacturing the hardened sealing body with a resin film using the resin sheet of this invention, the method which has the following steps (i)-(iii) is mentioned.
･ Step (i): A step of placing a sealing object on a part of the surface of the thermosetting resin layer having the resin sheet.
(Ii) Step (ii): a step of covering the surface of the thermosetting resin layer with the sealing object and at least a peripheral portion of the sealing object with a sealing material.
･ Step (iii): The sealing material is thermally cured to form a cured sealing body containing the sealing object, and the thermosetting resin layer is also thermally cured to form a cured resin layer to obtain a cured resin. Step of hardening the seal.
FIG. 2 is a schematic cross-sectional view showing a step of manufacturing a hardened sealing body with a hardened resin layer using the resin sheet 1d shown in FIG. 1 (d). Each of the above steps will be described below with reference to FIG. 2 as appropriate.
＜步驟(i)＞
步驟(i)為使於具有前述樹脂薄片的熱硬化性樹脂層之表面的一部份載置密封對象物的步驟。
圖2(a)表示將樹脂薄片1d的第2黏著劑層32之黏著表面貼合於支持體100，使於熱硬化性樹脂層10的表面之一部分載置密封對象物60的狀態。
且，圖2(a)為表示使用圖1(d)所是的樹脂薄片1d的例子，對於使用具有其他構成的本發明之樹脂薄片的情況，如圖2(a)所示，以支持體、樹脂薄片及密封對象物的順序進行層合或載置。<Step (i)>
Step (i) is a step of placing a sealing object on a part of the surface of the thermosetting resin layer having the resin sheet.
FIG. 2 (a) shows a state where the adhesive surface of the second adhesive layer 32 of the resin sheet 1 d is adhered to the support 100 and a sealing object 60 is placed on a part of the surface of the thermosetting resin layer 10.
2 (a) shows an example of using the resin sheet 1d shown in FIG. 1 (d). When a resin sheet of the present invention having another structure is used, as shown in FIG. 2 (a), a support is used. , The resin sheet and the sealing object are laminated or placed in this order.
且，步驟(i)中，熱硬化性樹脂層在不會進行熱硬化的溫度下進行者為佳，步驟(i)的具體溫度條件通常為10～80℃。In addition, in the step (i), it is preferable that the thermosetting resin layer is performed at a temperature at which the thermosetting is not performed, and the specific temperature condition of the step (i) is usually 10 to 80 ° C.
且，如圖1(d)之樹脂薄片1d，使用於支持體側具有第2黏著劑層的樹脂薄片時，以該樹脂薄片的第2黏著劑層之黏著表面的全面與支持體進行貼合者為佳。
因此，支持體以板狀者為佳。
又，此時，與第2黏著劑層的黏著表面貼合之側的支持體表面之面積如圖2所示，以第2黏著劑層的黏著表面之面積以上者為佳。In addition, when the resin sheet 1d shown in FIG. 1 (d) is used for a resin sheet having a second adhesive layer on the support side, the entire surface of the adhesive surface of the second adhesive layer of the resin sheet is adhered to the support. Those are better.
Therefore, the support is preferably a plate.
At this time, as shown in FIG. 2, the area of the surface of the support on the side which is in contact with the adhesive surface of the second adhesive layer is preferably greater than the area of the adhesive surface of the second adhesive layer.
構成前述支持體的材質，配合密封對象物之種類或在步驟(ii)所使用的密封材料之種類等，考慮到機械強度或耐熱性等所要求的特性下可適宜地選擇。
作為具體的構成支持體之材質，例如可舉出SUS等金屬材料；玻璃、矽晶圓等非金屬無機材料；環氧樹脂、ABS樹脂、丙烯酸樹脂、工程塑質、超級工程塑質、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂等樹脂材料；玻璃環氧樹脂等複合材料等，此等中亦以SUS、玻璃及矽晶圓等為佳。
且，作為工程塑質，可舉出尼龍、聚碳酸酯(PC)及聚乙烯對苯二甲酸乙二醇酯(PET)等。
作為超級工程塑質，可舉出聚伸苯基硫化物(PPS)、聚醚碸(PES)、及聚醚醚酮(PEEK)等。The material constituting the support may be appropriately selected in consideration of required characteristics such as mechanical strength and heat resistance in accordance with the type of the sealing object or the type of the sealing material used in step (ii).
Examples of the material constituting the support include metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resin, ABS resin, acrylic resin, engineering plastics, super engineering plastics, and polyfluorene Resin materials such as imine resin and polyimide resin; composite materials such as glass epoxy resin, etc. Among these, SUS, glass, and silicon wafers are also preferred.
Examples of the engineering plastic include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).
Examples of the super engineering plastic include polyphenylene sulfide (PPS), polyether fluorene (PES), and polyether ether ketone (PEEK).
前述支持體的厚度可配合密封對象物之種類，或在步驟(ii)所使用的密封材料之種類等而適宜地選擇，但以20μm以上50mm以下者為佳，較佳為60μm以上20mm以下。The thickness of the support can be appropriately selected in accordance with the type of the object to be sealed, the type of the sealing material used in step (ii), and the like, but preferably 20 μm to 50 mm, and more preferably 60 μm to 20 mm.
另一方面，作為於熱硬化性樹脂層表面的一部份經載置的密封對象物，例如可舉出半導體晶片、半導體晶圓、化合物半導體、半導體封裝、電子零件、藍寶石(sapphire)基板、顯示器、面板用基板等。On the other hand, examples of the sealing object placed on the surface of the thermosetting resin layer include semiconductor wafers, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, Display, panel substrate, etc.
例如在密封對象物為半導體晶片之情況時，藉由使用本發明之樹脂薄片，可製造出附有硬化樹脂層的半導體晶片。
半導體晶片可使用過去公知者，於該迴路面可形成由電晶體、電阻、凝結器等迴路元件所構成的集成電路。
而，半導體晶片可載置於與迴路面為相反側的裏面，形成如藉由熱硬化性樹脂層的表面進行包覆一般者為佳。此時，載置後半導體晶片的迴路面會成為露出的狀態。
於半導體晶片的載置中，可使用倒裝晶片焊接機、貼片機等公知裝置。
半導體晶片的配置之佈置、配置數等可配合作為目的之封裝的型態、生產數等做適宜地決定即可。For example, when the sealing object is a semiconductor wafer, a semiconductor wafer with a cured resin layer can be manufactured by using the resin sheet of the present invention.
As the semiconductor wafer, a conventionally known one can be used, and an integrated circuit composed of circuit elements such as a transistor, a resistor, and a condenser can be formed on the circuit surface.
The semiconductor wafer may be placed on the inside opposite to the circuit surface, and it is generally preferable to form the semiconductor wafer by coating the surface with a thermosetting resin layer. At this time, the circuit surface of the semiconductor wafer is exposed after mounting.
For mounting the semiconductor wafer, a known device such as a flip chip soldering machine or a chip mounter can be used.
The arrangement and number of semiconductor wafers may be appropriately determined according to the type and production number of the intended package.
其中，如FOWLP、FOPLP等，將半導體晶片的比晶片尺寸更大的區域以密封材料進行包覆，不僅為半導體晶片的迴路面，對於密封材料的表面區域，亦適用於形成再配線層的封裝者為佳。
因此，半導體晶片為載置於熱硬化性樹脂層的表面之一部分者，複數的半導體晶片在以空出一定間隔之經整列的狀態下，於該表面進行載持者為佳，複數的半導體晶片在以空出一定間隔之經整列成複數行且複數列的矩陣狀之狀態下，於該表面進行載置者為較佳。
半導體晶片彼此的間隔為配合作為目的之封裝的型態等而做適宜決定即可。Among them, such as FOWLP, FOPLP, etc., the area larger than the wafer size of the semiconductor wafer is covered with a sealing material, which is not only the circuit surface of the semiconductor wafer, but also the surface area of the sealing material. Those are better.
Therefore, the semiconductor wafer is a part of the surface of the thermosetting resin layer, and a plurality of semiconductor wafers are preferably carried on the surface in a state of being aligned at a certain interval. In a state where a plurality of rows are arranged in a matrix and a plurality of rows are arranged at a certain interval, it is better to mount on the surface.
The interval between the semiconductor wafers may be appropriately determined in accordance with the type and the like of the intended package.
＜步驟(ii)＞
步驟(ii)為將前述密封對象物，與該密封對象物的至少周邊部分之前述熱硬化性樹脂層的表面，以密封材料進行包覆的步驟。
密封材料雖使密封對象物所露出的面全體進行包覆，但對於複數的半導體晶片彼此之間隙亦進行填充。
圖2(b)表示，欲使密封對象物60與熱硬化性樹脂層10的表面皆被包覆，以密封材料70進行包覆的狀態。
對於本步驟，如圖2(b)所示，欲使熱硬化性樹脂層10的表面皆被包覆，可藉由密封材料70進行包覆，亦可將成為密封對象物60的周邊部分之熱硬化性樹脂層10的表面之一部分以密封材料70進行包覆。<Step (ii)>
Step (ii) is a step of coating the sealing object with a surface of the thermosetting resin layer on at least a peripheral portion of the sealing object with a sealing material.
Although the sealing material covers the entire exposed surface of the sealing object, the gaps between the plurality of semiconductor wafers are also filled.
FIG. 2 (b) shows a state in which both the surfaces of the sealing object 60 and the surface of the thermosetting resin layer 10 are to be covered, and the sealing material 70 is to be covered.
In this step, as shown in FIG. 2 (b), if the surface of the thermosetting resin layer 10 is to be covered, it may be covered with a sealing material 70, or it may be a peripheral portion of the object 60 to be sealed. A part of the surface of the thermosetting resin layer 10 is covered with a sealing material 70.
密封材料為具有對密封對象物及伴隨其的要素由外部環境進行保護的功能者。
在本發明之製造方法所使用的密封材料為含有熱硬化性樹脂的熱硬化性之密封材料。
又，密封材料可為在室溫為顆粒狀、顆粒狀、薄膜狀等固體者，亦可為成為組成物型態的液狀者，由作業性的觀點來看，以薄膜狀密封材料的密封樹脂薄膜為佳。The sealing material has a function of protecting the object to be sealed and the elements accompanying it from the external environment.
The sealing material used in the manufacturing method of this invention is a thermosetting sealing material containing a thermosetting resin.
In addition, the sealing material may be a solid such as granular, granular, or thin film at room temperature, or may be a liquid in the form of a composition. From the viewpoint of workability, sealing with a thin film sealing material A resin film is preferred.
作為包覆方法，可由過去適用於密封步驟的方法之中，配合密封材料的種類而做適宜選擇而適用，例如可適用輥層合法、真空加壓法、真空層合法、旋轉塗布法、模塗法、轉移成型法、壓縮成形模型法等。As the coating method, among the methods that have been applied to the sealing step in the past, it can be appropriately selected and applied according to the type of sealing material. For example, roll coating method, vacuum pressure method, vacuum layer method, spin coating method, and die coating can be applied. Method, transfer molding method, compression molding model method, etc.
＜步驟(iii)＞
步驟(iii)為，使密封材料進行熱硬化，使含有密封對象物的硬化密封體形成之同時，熱硬化性樹脂層亦進行熱硬化，形成硬化樹脂層，得到附有硬化樹脂層的硬化密封體之步驟。
且，步驟(iii)可與前步驟(ii)個別實施，亦可同時實施。
例如，對於前步驟(ii)，於加熱密封材料之情況時，可藉由該加熱而進行本步驟，亦可直接對密封材料進行熱硬化。<Step (iii)>
Step (iii) is to heat harden the sealing material to form a hardened sealing body containing the sealing object, and also heat harden the thermosetting resin layer to form a hardened resin layer to obtain a hardened seal with a hardened resin layer. Body steps.
Moreover, step (iii) may be implemented separately from the previous step (ii), or may be performed simultaneously.
For example, in the case of the previous step (ii), in the case of heating the sealing material, this step may be performed by the heating, or the sealing material may be directly thermally hardened.
如圖2(c)所示，在本步驟中，使密封材料進行熱硬化，使含有密封對象物60的硬化密封體71形成之同時，亦使熱硬化性樹脂層進行熱硬化後形成硬化樹脂層11。
在本步驟中，欲亦使密封材料與熱硬化性樹脂層同時進行熱硬化，可使硬化密封體的2個表面間之收縮應力的差變小，被認為可有效果地抑制於硬化密封體所生成的彎曲。As shown in FIG. 2 (c), in this step, the sealing material is thermally cured to form a cured sealing body 71 containing the object 60 to be sealed, and a thermosetting resin layer is also thermally cured to form a cured resin. Layer 11.
In this step, if the sealing material and the thermosetting resin layer are also heat-cured at the same time, the difference in shrinkage stress between the two surfaces of the hardened sealing body can be reduced, and it is considered that it can effectively suppress the hardened sealing body. The resulting bend.
且，於步驟(iii)中之溫度條件若為可使密封材料及熱硬化性樹脂層進行熱硬化之溫度以上即可，可藉由密封材料的種類或構成熱硬化性樹脂層的成分之種類而適宜地設定，通常為120～220℃。In addition, if the temperature condition in step (iii) is equal to or higher than the temperature at which the sealing material and the thermosetting resin layer can be thermally cured, the type of the sealing material or the type of the components constituting the thermosetting resin layer may be used. Instead, it is suitably set to 120 to 220 ° C.
此後，如圖2(d)所示，藉由以使熱硬化性樹脂層進行熱硬化而成的硬化樹脂層，與第1黏著劑層31的界面進行分離，可得到具有硬化樹脂層11，與含有密封對象物60的硬化密封體71之附有硬化樹脂層的硬化密封體80。
其中，第1黏著劑層31若為由能量線硬化型的黏著劑組成物所形成的層之情況時，可藉由照射能量線而可容易地分離。Thereafter, as shown in FIG. 2 (d), the hardened resin layer formed by thermally hardening the thermosetting resin layer is separated from the interface of the first adhesive layer 31 to obtain the hardened resin layer 11. A hardened sealing body 80 with a hardened resin layer is attached to the hardened sealing body 71 containing the sealing object 60.
However, when the first adhesive layer 31 is a layer formed of an energy ray-curable adhesive composition, the first adhesive layer 31 can be easily separated by irradiating the energy ray.
且，由支持體進行分離後，使用一般的黏著薄片時，有時會於硬化密封體產生彎曲。但，使用本發明之樹脂薄片而得之附有硬化樹脂層的硬化密封體因具有硬化樹脂層，故可有效果地抑制於硬化密封體所產生的彎曲。In addition, when a general adhesive sheet is used after separation from the support, the hardened seal may be warped. However, since the hardened sealing body with a hardened resin layer obtained by using the resin sheet of the present invention has a hardened resin layer, it is possible to effectively suppress bending caused by the hardened sealing body.
對於如此所得的附有硬化樹脂層的硬化密封體，其後將硬化密封體進行研削至半導體晶片的迴路面露出為止，亦可經由對於迴路面進行再配線之步驟，或形成外部電極墊，連接外部電極墊與外部端子電極之步驟等。
又，於硬化密封體連接外部端子電極後，使硬化密封體進行個片化後亦可製造出半導體裝置。
[實施例]The hardened sealing body with the hardened resin layer obtained in this way can be ground after the hardened sealing body is exposed until the circuit surface of the semiconductor wafer is exposed. Alternatively, the circuit surface can be rewired or an external electrode pad can be formed and connected. Steps for external electrode pads and external terminal electrodes.
In addition, after the hardened sealing body is connected to the external terminal electrodes, the hardened sealing body is singulated into pieces, and a semiconductor device can also be manufactured.
[Example]
對於本發明，雖對於以下實施例做更具體的說明，但本發明並未受限於以下實施例者。且，對於以下製造例及實施例中之物性值為藉由以下方法所測定的值。Regarding the present invention, although the following embodiments are described in more detail, the present invention is not limited to the following embodiments. The physical property values in the following production examples and examples are values measured by the following methods.
＜質量平均分子量(Mw)＞
使用凝膠滲透層析法裝置(Tosoh公司股份有限公司製之製品名「HLC-8020」)，以下述條件下進行測定，以標準聚苯乙烯換算而測定的值。
(測定條件)
･管柱：將「TSK guard column HXL-L」「TSK gel
G2500HXL」「TSK gel G2000HXL」「TSK gel
G1000HXL」(皆為Tosoh公司股份有限公司製)依序地連結者
･管柱溫度：40℃
･展開溶劑：四氫呋喃
･流速：1.0mL/min<Mass average molecular weight (Mw)>
A gel permeation chromatography device (product name "HLC-8020" manufactured by Tosoh Corporation, Ltd.) was used to measure under the following conditions, and the value was measured in terms of standard polystyrene conversion.
(Measurement conditions)
･ Column: "TSK guard column HXL-L""TSK gel
G2500HXL "" TSK gel "" G2000HXL "" TSK gel
"G1000HXL" (all manufactured by Tosoh Co., Ltd.) sequentially connected, column temperature: 40 ° C
･ Developing solvent: Tetrahydrofuran ･ Flow rate: 1.0mL / min
＜各層厚度之測定＞
使用Techlock股份有限公司製之定壓厚度測定器(型號：「PG-02J」，依據標準規格：JIS K6783、Z1702、
Z1709)而測定。＜ Measurement of thickness of each layer ＞
Using a constant pressure thickness measuring device (model: "PG-02J", manufactured by Techlock Co., Ltd., based on standard specifications: JIS K6783, Z1702
Z1709).
＜熱硬化性樹脂層的熱硬化後之硬化樹脂層的貯藏彈性率E’＞
將熱硬化性樹脂層進行層合至厚度200μm後，在大氣環境下放入烤箱內，在130℃進行2小時加熱，將厚度200μm的熱硬化性樹脂層進行熱硬化後作為硬化樹脂層。
使用動態黏彈性測定裝置(TAInstruments Company製的製品名「DMAQ800」)，在試驗開始溫度0℃，試驗終了溫度300℃，昇溫速度3℃/分鐘，振動數11Hz，振幅20μm之條件下，測定在23℃中之所形成的硬化樹脂層之貯藏彈性率E’。<Storage elasticity E 'of the cured resin layer after thermal curing of the thermosetting resin layer>
The thermosetting resin layer was laminated to a thickness of 200 μm, then placed in an oven in an atmospheric environment, and heated at 130 ° C. for 2 hours, and the thermosetting resin layer having a thickness of 200 μm was thermally cured as a cured resin layer.
Using a dynamic viscoelasticity measuring device (product name "DMAQ800" manufactured by TA Instruments Corporation), the test was performed under the conditions of a test start temperature of 0 ° C, a test end temperature of 300 ° C, a heating rate of 3 ° C / min, a vibration frequency of 11 Hz, and an amplitude of 20 μm The storage elasticity E 'of the cured resin layer formed at 23 ° C.
＜黏著力之測定＞
對於剝離薄膜上所形成的黏著劑層或熱硬化性樹脂層之表面上，層合厚度50μm之PET薄膜(東洋紡股份有限公司製，製品名「Cosmo ShineA4100」)。
除去剝離薄膜，將露出的黏著劑層或熱硬化性樹脂層之表面，貼合於被著體之不鏽鋼鋼板(SUS304 360號研磨)，在23℃，50%RH(相對濕度)之環境下，靜置24小時後，於相同環境下，依據JIS Z0237:2000，藉由180°拉剝法以拉伸速度300mm/分鐘下測定在23℃中之黏著力。＜ Measurement of adhesion ＞
A PET film (manufactured by Toyobo Co., Ltd., product name "Cosmo Shine A4100") was laminated on the surface of the adhesive layer or the thermosetting resin layer formed on the release film.
After removing the release film, the exposed surface of the adhesive layer or the thermosetting resin layer is bonded to the stainless steel plate (SUS304 360 No. grinding) of the object to be adhered, at 23 ° C, 50% RH (relative humidity), After standing for 24 hours, the adhesive force at 23 ° C. was measured at a tensile speed of 300 mm / minute by a 180 ° pull-peel method in the same environment according to JIS Z0237: 2000.
且，在以下製造例所使用的剝離材如以下所示。
＜剝離材＞
･重剝離薄膜：Lintec股份有限公司製，製品名「SP-PET382150」，於聚乙烯對苯二甲酸乙二醇酯(PET)薄膜的單面上，設置由聚矽氧系剝離劑所形成的剝離劑層者，厚度：38μm。
･輕剝離薄膜：Lintec股份有限公司製，製品名「SP-PET381031」，於PET薄膜的單面上，設置由聚矽氧系剝離劑所形成的剝離劑層者，厚度：38μm。The release materials used in the following production examples are shown below.
＜ Peeling material ＞
Heavy-duty release film: Lintec Co., Ltd., product name "SP-PET382150", a polyethylene terephthalate (PET) film is provided on one side with a silicone release agent For a release agent layer, thickness: 38 μm.
･ Light release film: Lintec Co., Ltd., product name "SP-PET381031", a release agent layer formed of a silicone release agent on one side of the PET film, thickness: 38 μm.
製造例1
(1)熱硬化性樹脂組成物之調製
調配出下述所種類及配合量(皆為「有效成分比」)之各成分，再以甲基乙基酮進行稀釋，經均勻攪拌後，調製出固體成分濃度(有效成分濃度)61質量%的熱硬化性樹脂組成物之溶液。
･丙烯酸系聚合物：配合量=26.07質量份
使n-丁基丙烯酸酯10質量份、甲基丙烯酸酯70質量份、縮水甘油基甲基丙烯酸酯5質量份及2-羥基乙基丙烯酸酯15質量份進行共聚合而成的丙烯酸系聚合物(質量平均分子量：40萬，玻璃轉移溫度：-1℃)，相當於上述成分(A1)。
･環氧化合物(1)：配合量=10.4質量份
雙酚A型環氧樹脂(三菱化學股份有限公司製之製品名「jER828」，環氧當量=184～194g/eq)，相當於上述成分(B1)。
･環氧化合物(2)：配合量=5.2質量份
二環戊二烯型環氧樹脂(DIC股份有限公司製之製品名「EPICLONHP-7200HH」，環氧當量=255～260g/eq)，相當於上述成分(B1)。
･環氧化合物(3)：配合量=1.7質量份
雙酚A型環氧樹脂(三菱化學股份有限公司製之製品名「jER1055」、環氧當量=800～900g/eq)，相當於上述成分(B1)。
･熱硬化劑：配合量=0.42質量份
二氰二胺(ADEKA公司製之製品名「Adeka
HardnerEH-3636AS」，活性氫量=21g/eq)，相當於上述成分(B2)。
･硬化促進劑：配合量=0.42質量份
2-苯基-4,5-二羥基甲基咪唑(四國化成工業股份有限公司製之製品名「CUREZOL2PHZ」)，相當於上述成分(B3)。
･著色劑：配合量=0.20質量份
碳黑(三菱化學股份有限公司製之製品名
「#MA650」，平均粒子徑=28nm)，相當於上述成分(C)。
･矽烷偶合劑：配合量=0.09質量份
3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業股份有限公司製之製品名「KBM403」)，分子量=236.64，相當於上述成分(D)。
･無機填充材：配合量=55.5質量份
二氧化矽填充物(Admatechs公司製之製品名
「SC2050MA」，平均粒子徑=0.5μm)，相當於上述成分(E)。Manufacturing example 1
(1) Preparation of thermosetting resin composition. Each component of the following types and blending amounts (all "active ingredient ratio") is prepared, and then diluted with methyl ethyl ketone. A solution of a thermosetting resin composition having a solid content concentration (effective component concentration) of 61% by mass.
･ Acrylic polymer: Compounding amount = 26.07 parts by mass to make 10 parts by mass of n-butyl acrylate, 70 parts by mass of methacrylate, 5 parts by mass of glycidyl methacrylate, and 15 of 2-hydroxyethyl acrylate The acrylic polymer (mass average molecular weight: 400,000, glass transition temperature: -1 ° C) obtained by copolymerizing parts by mass corresponds to the aforementioned component (A1).
･ Epoxy compound (1): blending amount = 10.4 parts by mass of bisphenol A type epoxy resin (product name "jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight = 184 to 194 g / eq), equivalent to the above components (B1).
･ Epoxy compound (2): Compounding amount = 5.2 parts by mass of dicyclopentadiene epoxy resin (product name "EPICLONHP-7200HH" manufactured by DIC Corporation, epoxy equivalent = 255 to 260 g / eq), equivalent To the above-mentioned component (B1).
･ Epoxy compound (3): blending amount = 1.7 parts by mass of bisphenol A type epoxy resin (product name "jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight = 800 to 900 g / eq), equivalent to the above components (B1).
･ Heat hardener: blending amount = 0.42 parts by mass of dicyandiamine (product name "Adeka" manufactured by ADEKA Corporation)
HardnerEH-3636AS ", active hydrogen content = 21 g / eq), equivalent to the above-mentioned component (B2).
･ Hardening accelerator: blending amount = 0.42 parts by mass
2-phenyl-4,5-dihydroxymethylimidazole (product name "CUREZOL2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.) corresponds to the above-mentioned component (B3).
･ Colorant: Blending amount = 0.20 parts by mass of carbon black (product name "# MA650" manufactured by Mitsubishi Chemical Corporation, average particle diameter = 28 nm), which is equivalent to the aforementioned component (C).
･ Silane coupling agent: blending amount = 0.09 parts by mass
3-Glycidoxypropyltrimethoxysilane (product name "KBM403" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), molecular weight = 236.64, equivalent to the above-mentioned component (D).
･ Inorganic filler: Compounding amount = 55.5 parts by mass of silica filler (product name "SC2050MA" manufactured by Admatechs, average particle diameter = 0.5 μm), which is equivalent to the aforementioned component (E).
(2)熱硬化性樹脂層之形成
於上述輕剝離薄膜的剝離處理面上，將在上述(1)所調製的熱硬化性樹脂組成物之溶液進行塗布後形成塗膜，將該塗膜在120℃進行2分鐘乾燥，形成厚度25μm的熱硬化性樹脂層。
且，所形成的熱硬化性樹脂層之黏著力為0.5 N/25mm。
又，將熱硬化性樹脂層進行熱硬化而成的硬化樹脂層之在23℃的貯藏彈性率E’為6.5×109
Pa。(2) The thermosetting resin layer is formed on the release-treated surface of the light release film, and a coating film is formed by applying the solution of the thermosetting resin composition prepared in (1) above, and the coating film is formed on Drying was performed at 120 ° C for 2 minutes to form a thermosetting resin layer having a thickness of 25 µm.
The adhesive force of the formed thermosetting resin layer was 0.5 N / 25 mm.
Moreover, the storage elastic modulus E 'at 23 degreeC of the hardening resin layer which heat-hardened the thermosetting resin layer was 6.5 * 10 <9> Pa.
製造例2
(1)黏著劑組成物之調製
於黏著性樹脂的下述丙烯酸系共聚物(i)之固體成分100質量份中，添加下述異氰酸酯系交聯劑(i)5.0質量份(固體成分比)，以甲苯進行稀釋後均勻地攪拌，調製出固體成分濃度(有效成分濃度)25質量%之黏著劑組成物。
･丙烯酸系共聚物(i)：具有來自由2-乙基己基丙烯酸酯(2EHA)/2-羥基乙基丙烯酸酯(HEA)=80.0/20.0(質量比)所成的原料單體之構成單位，質量平均分子量60萬的丙烯酸系共聚物。
･異氰酸酯交聯劑(i)：Tosoh公司股份有限公司製之製品名「Coronate L」，固體成分濃度：75質量%。Manufacturing example 2
(1) Preparation of Adhesive Composition To 100 parts by mass of the solid content of the following acrylic copolymer (i) of the adhesive resin, 5.0 parts by mass of the following isocyanate-based crosslinking agent (i) (solid content ratio) were added. After diluting with toluene, the mixture was stirred uniformly to prepare an adhesive composition having a solid content concentration (effective component concentration) of 25% by mass.
･ Acrylic copolymer (i): It has a constituent unit derived from a raw material monomer formed from 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio) Acrylic copolymer with a mass average molecular weight of 600,000.
･ Isocyanate crosslinking agent (i): Product name "Coronate L" manufactured by Tosoh Corporation, Ltd., solid content concentration: 75% by mass.
(2)黏著劑層之形成
於上述輕剝離薄膜的剝離劑層之表面上，將在上述(1)所調製的黏著劑組成物進行塗布而形成塗膜，將該塗膜在100℃進行60秒乾燥後，形成厚度5μm之第1黏著劑層。
又，於上述重剝離薄膜的剝離劑層之表面上，同樣地形成厚度5μm的第2黏著劑層。
且，依據上述方法所測定的第1黏著劑層及第2黏著劑層之黏著力皆為0.3N/25mm。(2) The adhesive layer is formed on the surface of the release agent layer of the light release film, and the adhesive composition prepared in the above (1) is applied to form a coating film, and the coating film is subjected to 60 ° C at 100 ° C. After drying for a second, a first adhesive layer having a thickness of 5 μm was formed.
A second adhesive layer having a thickness of 5 μm was similarly formed on the surface of the release agent layer of the heavy release film.
In addition, the adhesion force of the first adhesive layer and the second adhesive layer measured according to the above-mentioned methods was 0.3 N / 25 mm.
實施例1
於基材的厚度50μm之聚乙烯對苯二甲酸乙二醇酯(PET)薄膜(東洋紡股份有限公司製，製品名「Cosmo ShineA4100」)之兩面上，各貼合在製造例2所形成的第1黏著劑層及第2黏著劑層。
然後使層合於第1黏著劑層上的輕剝離薄膜除去，將露出的第1黏著劑層之黏著表面，與在製造例1所形成的熱硬化性樹脂層之表面進行貼合，得到以重剝離薄膜/第2黏著劑層/基材/第1黏著劑層/熱硬化性樹脂層/輕剝離薄膜的順序進行層合的樹脂薄片。Example 1
On both sides of a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "Cosmo Shine A4100") with a thickness of 50 μm on the substrate, each was bonded to the first surface formed in Production Example 2. 1 adhesive layer and 2 adhesive layer.
Then, the light release film laminated on the first adhesive layer was removed, and the exposed adhesive surface of the first adhesive layer was bonded to the surface of the thermosetting resin layer formed in Production Example 1 to obtain A resin sheet laminated in the order of a heavy release film / second adhesive layer / base material / first adhesive layer / thermosetting resin layer / light release film.
實施例2
藉由以下程序，製作出附有硬化樹脂層的硬化密封體。
(1)半導體晶片之載置
將在實施例1所製作的樹脂薄片之重剝離薄膜除去，將露出的第2黏著劑層之黏著表面與支持體(玻璃)進行貼合。
然後亦除去該樹脂薄片之輕剝離薄膜，於露出的熱硬化性樹脂層之表面上，將9個半導體晶片(各晶片尺寸為6.4mm×6.4mm，晶片厚度為200μm(#2000))以空出必要間隔下載置成，使各半導體晶片的迴路面之相反側的裏面與該表面進行銜接。Example 2
A hardened sealing body with a hardened resin layer was produced by the following procedure.
(1) Mounting of semiconductor wafer The heavy release film of the resin sheet produced in Example 1 was removed, and the exposed adhesive surface of the second adhesive layer was bonded to a support (glass).
Then, the light release film of the resin sheet was also removed. On the surface of the exposed thermosetting resin layer, 9 semiconductor wafers (each wafer size was 6.4 mm × 6.4 mm, and the wafer thickness was 200 μm (# 2000)) were vacant. It is installed at a necessary interval so that the inner surface on the opposite side of the circuit surface of each semiconductor wafer is connected to the surface.
(2)硬化密封體及硬化樹脂層之形成
將9個前述半導體晶片，與該半導體晶片的至少周邊部分之熱硬化性樹脂層的表面，藉由密封材料之熱硬化性的密封樹脂薄膜進行包覆，使用真空加熱加壓層合體(ROHM and HAAS公司製之「7024HP5」)，使密封樹脂薄膜進行熱硬化，製作出硬化密封體。
且，密封條件如下述所示。
･預熱溫度：台和隔膜同為100℃
･真空拉出：60秒
･動態加壓模式：30秒
･靜態加壓模式：10秒
･密封溫度：180℃
･密封時間：60分鐘
且，與該密封樹脂薄膜之熱硬化同時下，對熱硬化性樹脂層亦在上述環境下進行硬化而成為硬化樹脂層。(2) Formation of hardened sealing body and hardened resin layer The surface of the nine semiconductor wafers and at least the peripheral part of the thermosetting resin layer of the semiconductor wafer is covered with a thermosetting sealing resin film of a sealing material. Then, the laminated resin (“7024HP5” manufactured by ROHM and HAAS Co., Ltd.) was vacuum-heated, and the sealing resin film was thermally hardened to produce a hardened sealing body.
The sealing conditions are as follows.
･ Preheating temperature: 100 ° C for both stage and diaphragm
･ Vacuum pull-out: 60 seconds ･ Dynamic pressure mode: 30 seconds ･ Static pressure mode: 10 seconds ･ Sealing temperature: 180 ° C
･ Sealing time: 60 minutes. Simultaneously with the thermal curing of the sealing resin film, the thermosetting resin layer is cured under the above-mentioned environment to become a cured resin layer.
(3)硬化樹脂層與第1黏著劑層之分離
上述(2)後，熱硬化性樹脂層在進行熱硬化而成硬化樹脂層，與第1黏著劑層之界面進分離，得到附有硬化樹脂層的硬化密封體。
將所得之附有硬化樹脂層的硬化密封體冷卻至室溫(25℃)，但未見到彎曲。
[產業上可利用性](3) Separation of the hardened resin layer and the first adhesive layer After the above (2), the thermosetting resin layer is thermally hardened to form a hardened resin layer, and the interface with the first adhesive layer is separated to obtain hardening. Resin hardened seal.
The obtained hardened sealing body with a hardened resin layer was cooled to room temperature (25 ° C), but no warpage was observed.
[Industrial availability]
本發明之樹脂薄片為可使用於含有：於熱硬化性樹脂層的表面上，載置半導體晶片等密封對象物，以密封材料進行包覆並使其硬化，成為含有密封對象物之硬化密封體的製造上。然後將可抑制彎曲且具有平坦表面的附有硬化樹脂層的硬化密封體可在提高生產性下製造。The resin sheet of the present invention can be used to contain a sealing object such as a semiconductor wafer on the surface of a thermosetting resin layer, cover and harden it with a sealing material, and form a cured sealing body containing the sealing object. Manufacturing. Then, the hardened sealing body with a hardened resin layer having a flat surface that can suppress bending and can be manufactured with improved productivity.
1a、1b、1c、1d‧‧‧樹脂薄片1a, 1b, 1c, 1d ‧‧‧ resin sheet
10‧‧‧熱硬化性樹脂層 10‧‧‧ thermosetting resin layer
11‧‧‧硬化樹脂層 11‧‧‧hardened resin layer
20‧‧‧基材 20‧‧‧ substrate
30、31、32‧‧‧黏著劑層 30, 31, 32‧‧‧ Adhesive layer
60‧‧‧密封對象物 60‧‧‧ Sealed Object
70‧‧‧密封材料 70‧‧‧sealing material
71‧‧‧硬化密封體 71‧‧‧hardened seal
80‧‧‧附有硬化樹脂層的硬化密封體 80‧‧‧ Hardened sealing body with hardened resin layer
100‧‧‧支持體 100‧‧‧ support
[圖1] 表示本發明之一態樣的樹脂薄片之構成的該樹脂薄片之截面模式圖。[Fig. 1] A schematic cross-sectional view of the resin sheet showing the configuration of the resin sheet according to an aspect of the present invention.
[圖2] 表示使用圖1(d)所示樹脂薄片1d製造附有硬化樹脂層之硬化密封體的步驟之截面模式圖。 [Fig. 2] A schematic cross-sectional view showing a step of manufacturing a hardened sealing body with a hardened resin layer using the resin sheet 1d shown in Fig. 1 (d).
Claims (8)
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|---|---|---|---|
| JP2018068732 | 2018-03-30 | ||
| JP2018-068732 | 2018-03-30 |
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| Country | Link |
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| JP (2) | JP7280242B2 (en) |
| KR (1) | KR20200138193A (en) |
| CN (1) | CN111902468A (en) |
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| JP4846406B2 (en) * | 2006-03-28 | 2011-12-28 | リンテック株式会社 | Chip protection film forming sheet |
| JP5435685B2 (en) * | 2007-02-28 | 2014-03-05 | ナミックス株式会社 | Resin film for sealing |
| TWI433545B (en) | 2007-10-30 | 2014-04-01 | Nippon Telegraph & Telephone | Image encoding apparatuses and decoding apparatuses |
| WO2014021450A1 (en) * | 2012-08-02 | 2014-02-06 | リンテック株式会社 | Film-like adhesive, adhesive sheet for semiconductor junction, and method for producing semiconductor device |
| JP6735270B2 (en) * | 2015-02-24 | 2020-08-05 | リンテック株式会社 | Film adhesive, adhesive sheet, and method for manufacturing semiconductor device |
| JP2017092335A (en) * | 2015-11-13 | 2017-05-25 | 日東電工株式会社 | Method of manufacturing semiconductor package |
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| JPWO2019189541A1 (en) | 2021-04-22 |
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