JP2006169480A - Heat resistant adhesive tape used for semiconductor - Google Patents
Heat resistant adhesive tape used for semiconductor Download PDFInfo
- Publication number
- JP2006169480A JP2006169480A JP2004367862A JP2004367862A JP2006169480A JP 2006169480 A JP2006169480 A JP 2006169480A JP 2004367862 A JP2004367862 A JP 2004367862A JP 2004367862 A JP2004367862 A JP 2004367862A JP 2006169480 A JP2006169480 A JP 2006169480A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- meth
- heat
- adhesive tape
- ionizing radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 43
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 31
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 66
- 239000010410 layer Substances 0.000 claims description 29
- 239000000853 adhesive Substances 0.000 claims description 26
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 125000000524 functional group Chemical group 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 239000010949 copper Substances 0.000 abstract description 8
- 239000012790 adhesive layer Substances 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 57
- -1 acrylate ester Chemical class 0.000 description 25
- 239000000178 monomer Substances 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- TVYHOTUPISDNFZ-UHFFFAOYSA-N 1,5-dihydroxy-2,4-dimethylpentan-3-one Chemical compound OCC(C)C(=O)C(C)CO TVYHOTUPISDNFZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
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- IFSLSXUHNIVHPB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(C)(C)CO.OCC(C)(C)C(O)=O IFSLSXUHNIVHPB-UHFFFAOYSA-N 0.000 description 1
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- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、半導体用耐熱性粘着テープに関する。さらに詳しくは、本発明は、隣接した複数の開口にそれぞれ配列した端子部を有し、複数の半導体素子の一括樹脂封止が可能なリードフレームの片面全面に貼付され、樹脂封止時の樹脂漏れを防止する粘着テープであって、耐熱性に優れ、封止時の樹脂漏れを十分に防止し得ると共に、樹脂封止後に剥がす際に生じる糊残りを抑制することができる半導体用耐熱性粘着テープに関するものである。 The present invention relates to a heat-resistant adhesive tape for semiconductors. More specifically, the present invention has a terminal portion arranged in each of a plurality of adjacent openings, and is affixed to the entire surface of one side of a lead frame capable of collectively sealing a plurality of semiconductor elements. Adhesive tape that prevents leakage, has excellent heat resistance, can sufficiently prevent resin leakage at the time of sealing, and can suppress adhesive residue that occurs when peeling after resin sealing. It is about tape.
近年、ＬＳＩの実装技術において、半導体素子、半導体素子搭載部、内部リードフレーム等を樹脂で封止した半導体素子の底面部位に外部実装面となる内部リード端子の一部または全部を露出したＳＯＮ（Ｓｍａｌｌ Ｏｕｔｌｉｎｅ Ｎｏｎ−ｌｅａｄｅｄ Ｐａｃｋａｇｅ）やＱＦＮ（Ｑｕａｄ Ｆｌａｔ Ｎｏｎ−ｌｅａｄｅｄ Ｐａｃｋａｇｅ）と呼ばれる半導体装置が提案されている。このような構造の半導体装置の製造方法としては、例えば複数の半導体素子搭載面を持つリードフレームの片面に粘着テープをラミネートする工程と、前記リードフレームの前記粘着テープをラミネートした対面に半導体素子を搭載する工程と、前記半導体素子上の電極と前記リードフレームとを金属細線を用いて接続する工程と、前記半導体素子と、前記金属細線と、前記リードフレームの前記半導体素子を搭載した面とを覆うように樹脂を充填し、樹脂を硬化させる工程と、前記粘着テープを剥離除去する工程と、前記樹脂で封止したリードフレームを前記半導体素子毎に切断する工程を含む製造方法が開示されている（例えば、特許文献１、特許文献２及び特許文献３参照）。
ところが、前記封止樹脂としては、一般にはエポキシ樹脂などの熱硬化性樹脂が用いられている。エポキシ樹脂を充填する際には、通常１７０〜２００℃の加熱が施される。このため、粘着テープの粘着剤層が軟化、変形し、外部露出面にまで封止樹脂が漏出してしまうことがあった。
また、粘着テープを剥離除去した後に、糊残りが生じ、その後の工程に悪影響を与えることがあった。
However, a thermosetting resin such as an epoxy resin is generally used as the sealing resin. When filling the epoxy resin, heating at 170 to 200 ° C. is usually performed. For this reason, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is softened and deformed, and the sealing resin may leak to the externally exposed surface.
Further, after the adhesive tape is peeled and removed, an adhesive residue is generated, which may adversely affect subsequent processes.
本発明は、このような事情のもとで、隣接した複数の開口にそれぞれ配列した端子部を有し、複数の半導体素子の一括樹脂封止が可能なリードフレームの片面全面に貼付され、樹脂封止時の樹脂漏れを防止する粘着テープであって、耐熱性に優れ、封止時の樹脂漏れを十分に防止し得ると共に、樹脂封止後に剥がす際に生じる糊残りを抑制することができる半導体用耐熱性粘着テープを提供することを目的としてなされたものである。 Under such circumstances, the present invention has a terminal portion arranged in each of a plurality of adjacent openings, and is affixed to the entire surface of one side of a lead frame capable of collectively sealing a plurality of semiconductor elements. Adhesive tape that prevents resin leakage at the time of sealing, has excellent heat resistance, can sufficiently prevent resin leakage at the time of sealing, and can suppress adhesive residue generated when peeling after resin sealing It is made for the purpose of providing the heat resistant adhesive tape for semiconductors.
本発明者らは、前記の優れた機能を有する半導体用耐熱性粘着テープを開発すべく鋭意研究を重ねた結果、融点がある値以上の耐熱性基材フィルムの片面に、電離放射線の照射により架橋され、かつゲル分率が特定の値以上であって、銅板に対する温度１８０℃、２時間加熱後の２３℃における粘着力がある値以上の耐熱性粘着剤層を設けてなる粘着テープにより、その目的を達成し得ることを見出し、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、
（１）隣接した複数の開口にそれぞれ配列した端子部を有し、複数の半導体素子の一括樹脂封止が可能なリードフレームの片面全面に貼付され、樹脂封止時の樹脂漏れを防止する粘着テープであって、前記粘着テープが、融点１８０℃以上の耐熱性基材フィルムの片面に、電離放射線の照射により架橋され、かつゲル分率が９５％以上で、銅板に対する温度１８０℃、２時間加熱後の２３℃における粘着力が、ＪＩＳ Ｚ ０２３７に準じた測定法で、０.１〜７Ｎ／２５ｍｍの範囲にある耐熱性粘着剤層を有することを特徴とする半導体用耐熱性粘着テープ、
（２）耐熱性粘着剤層が、電離放射線架橋型アクリル系粘着剤層に、電離放射線を照射することにより形成されたものである上記(１)項に記載の半導体用耐熱性粘着テープ、及び
（３）耐熱性粘着剤層が、活性水素をもつ官能基を少なくとも有する(メタ)アクリル酸エステル系共重合体と、側鎖に電離放射線架橋性の官能基を有する(メタ)アクリル酸エステル系共重合体と、活性水素をもつ官能基と反応し得る架橋剤を含む組成物を、加熱架橋し、かつ電離放射線の照射により架橋したものである上記(１)項に記載の半導体用耐熱性粘着テープ、
を提供するものである。
As a result of intensive research to develop a heat-resistant adhesive tape for semiconductors having the above-mentioned excellent functions, the present inventors have applied ionizing radiation to one side of a heat-resistant substrate film having a melting point of a certain value or more. By a pressure-sensitive adhesive tape that is crosslinked and has a gel fraction that is equal to or higher than a specific value and that has a heat-resistant pressure-sensitive adhesive layer that is equal to or higher than a value having an adhesive strength at 23 ° C. after heating at a temperature of 180 ° C. for 2 hours, It has been found that the object can be achieved, and the present invention has been completed based on this finding.
That is, the present invention
(1) Adhesives having terminal portions arranged in a plurality of adjacent openings, which are attached to the entire surface of a lead frame capable of collectively sealing a plurality of semiconductor elements, and prevent resin leakage during resin sealing. The adhesive tape is cross-linked by irradiation with ionizing radiation on one side of a heat-resistant substrate film having a melting point of 180 ° C. or higher, has a gel fraction of 95% or higher, and has a temperature of 180 ° C. for a copper plate for 2 hours. A heat-resistant pressure-sensitive adhesive tape for semiconductor, characterized by having a heat-resistant pressure-sensitive adhesive layer having a pressure-sensitive adhesive strength at 23 ° C. after heating in the range of 0.1 to 7 N / 25 mm by a measurement method according to JIS Z 0237;
(2) The heat-resistant pressure-sensitive adhesive tape for semiconductor according to the above item (1), wherein the heat-resistant pressure-sensitive adhesive layer is formed by irradiating an ionizing radiation-crosslinking acrylic pressure-sensitive adhesive layer with ionizing radiation; (3) A (meth) acrylate copolymer having at least a functional group having active hydrogen in the heat-resistant pressure-sensitive adhesive layer, and a (meth) acrylate ester system having an ionizing radiation crosslinkable functional group in the side chain The heat resistance for a semiconductor according to the above item (1), wherein the composition containing a copolymer and a crosslinking agent capable of reacting with a functional group having active hydrogen is crosslinked by heating and irradiation by ionizing radiation. Adhesive tape,
Is to provide.
本発明によれば、複数の半導体素子の一括樹脂封止が可能なリードフレームの片面全面に貼付され、樹脂封止時の樹脂漏れを防止する粘着テープであって、耐熱性に優れ、封止時の樹脂漏れを十分に防止し得ると共に、樹脂封止後に剥がす際に生じる糊残りを抑制することができる半導体用耐熱性粘着テープを提供することができる。 According to the present invention, a pressure-sensitive adhesive tape that is attached to the entire surface of one side of a lead frame capable of encapsulating a plurality of semiconductor elements at once and prevents resin leakage during resin encapsulation, has excellent heat resistance, and is sealed It is possible to provide a heat-resistant pressure-sensitive adhesive tape for semiconductors that can sufficiently prevent resin leakage at the time and can suppress adhesive residue generated when the resin is peeled after sealing.
本発明の半導体用耐熱性粘着テープは、隣接した複数の開口にそれぞれ配列した端子部を有し、複数の半導体素子の一括樹脂封止が可能なリードフレームの片面全面に貼付され、樹脂封止時の樹脂漏れを防止するために用いられる粘着テープである。該粘着テープは、融点１８０℃以上の耐熱性基材フィルムの片面に、電離放射線の照射により架橋され、かつゲル分率が９５％以上であって、銅板に対する温度１８０℃、２時間加熱後の２３℃における粘着力が、ＪＩＳ Ｚ ０２３７に準じた測定法で、０.１〜７Ｎ／２５ｍｍである耐熱性粘着剤層が設けられた構成を有している。
本発明の粘着テープに用いられる耐熱性基材フィルムは、ＪＩＳ Ｋ ７１２１に準拠した測定法で融点が１８０℃以上のものである。なお、本発明における融点が１８０℃以上の耐熱性基材フィルムには、１８０℃以上の温度において溶融しないもの、すなわち、融点をもたないフィルムをも包含する。
このような耐熱性基材フィルムとしては、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリイミドフィルム、ポリエーテルイミドフィルム、アラミド系フィルム、ポリエーテルケトンフィルム、ポリエーテルエーテルケトンフィルム、ポリフェニレンスルフィドフィルム、ポリ(４−メチルペンテン−１)フィルム、液晶ポリマーフィルム、及び上記各フィルムを構成するポリマーを２種以上混合してなる混合ポリマーフィルムなどを例示することができる。これらの中で、特にポリイミドフィルムが好適である。
本発明の耐熱性粘着テープにおいては、これらの耐熱性基材フィルムは、厚さに特に制限はないが、通常１０〜２００μｍ、好ましくは２０〜１００μｍの範囲である。
The heat-resistant adhesive tape for semiconductors of the present invention has terminal portions arranged respectively in a plurality of adjacent openings, and is affixed to the entire surface of one side of a lead frame capable of collectively sealing a plurality of semiconductor elements. It is an adhesive tape used to prevent resin leakage at the time. The pressure-sensitive adhesive tape is cross-linked by irradiation with ionizing radiation on one side of a heat-resistant base film having a melting point of 180 ° C. or higher, and has a gel fraction of 95% or higher, and is heated at a temperature of 180 ° C. for 2 hours against a copper plate. It has a configuration in which a heat-resistant pressure-sensitive adhesive layer having an adhesive strength at 23 ° C. of 0.1 to 7 N / 25 mm is provided by a measurement method according to JIS Z 0237.
The heat-resistant substrate film used for the adhesive tape of the present invention has a melting point of 180 ° C. or higher by a measuring method based on JIS K7121. The heat-resistant substrate film having a melting point of 180 ° C. or higher in the present invention includes a film that does not melt at a temperature of 180 ° C. or higher, that is, a film that does not have a melting point.
Examples of such a heat resistant base film include polyethylene terephthalate film, polyethylene naphthalate film, polyimide film, polyetherimide film, aramid film, polyetherketone film, polyetheretherketone film, polyphenylene sulfide film, poly (4 -Methylpentene-1) A film, a liquid crystal polymer film, and a mixed polymer film formed by mixing two or more kinds of polymers constituting each of the above films can be exemplified. Among these, a polyimide film is particularly preferable.
In the heat-resistant adhesive tape of the present invention, these heat-resistant substrate films are not particularly limited in thickness, but are usually in the range of 10 to 200 μm, preferably 20 to 100 μm.
前記耐熱性基材フィルムは、少なくとも粘着剤層が設けられる側の面に、粘着剤層との接着性を向上させる目的で、所望により、酸化法や凹凸化法などにより表面処理を施すことができる。また、プライマー処理を施すこともできる。上記酸化法としては、例えばコロナ放電処理、プラズマ放電処理、クロム酸処理（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理などが用いられ、凹凸化法としては、例えばサンドブラスト法、溶剤処理法などが用いられる。これらの表面処理法は基材フィルムの種類に応じて適宜選ばれるが、一般にはコロナ放電処理法が効果及び操作性などの面から、好ましく用いられる。
本発明の耐熱性粘着テープは、前記の耐熱性基材フィルムの表面処理が施されてなる片面に、電離放射線の照射により架橋され、かつゲル分率が９５％以上であって、銅板に対する温度１８０℃、２時間加熱後の２３℃における粘着力が、ＪＩＳ Ｚ ０２３７に準じた測定法で、０.１〜７Ｎ／２５ｍｍである耐熱性粘着剤層を有するものである。
このような性状を有する耐熱性粘着剤層は、電離放射線架橋型アクリル系粘着剤層に、電離放射線を照射することにより、形成することができる。なお、電離放射線架橋型アクリル系粘着剤層とは、電磁波又は荷電粒子線の中でエネルギー量子を有するもの、すなわち紫外線又は電子線などを照射することにより、架橋するアクリル系粘着剤層を指す。
The heat-resistant substrate film may be subjected to a surface treatment by an oxidation method or a concavo-convex method, if desired, for the purpose of improving the adhesiveness with the pressure-sensitive adhesive layer on at least the surface on which the pressure-sensitive adhesive layer is provided. it can. Moreover, primer treatment can also be performed. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. The law is used. These surface treatment methods are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.
The heat-resistant pressure-sensitive adhesive tape of the present invention is cross-linked by irradiation with ionizing radiation on one surface where the surface treatment of the heat-resistant substrate film is performed, and has a gel fraction of 95% or more, and a temperature relative to the copper plate The adhesive strength at 23 ° C. after heating at 180 ° C. for 2 hours is a measurement method according to JIS Z 0237 and has a heat-resistant pressure-sensitive adhesive layer of 0.1 to 7 N / 25 mm.
The heat-resistant pressure-sensitive adhesive layer having such properties can be formed by irradiating the ionizing radiation-crosslinking acrylic pressure-sensitive adhesive layer with ionizing radiation. The ionizing radiation crosslinkable acrylic pressure-sensitive adhesive layer refers to an acrylic pressure-sensitive adhesive layer that crosslinks by irradiating an electromagnetic wave or a charged particle beam having energy quanta, that is, ultraviolet rays or electron beams.
本発明の粘着テープにおける耐熱性粘着剤層は、ゲル分率が９５％以上であることが必要である。このゲル分率が９５％未満では、リードフレームの片面全面に貼付され、樹脂封止後に剥がす際に糊残りが生じやすい。なお、上記ゲル分率は、下記の方法により測定した値である。
＜ゲル分率の測定方法＞
剥離フィルム上、当該粘着剤を塗工し、本発明の粘着テープ作製時と同一条件で架橋化させたのち、剥離フィルムから架橋化粘着剤（５０ｍｍ×１００ｍｍ）を剥ぎ取る。次いで、上記架橋化粘着剤２枚（合計重量Ａｇ）を１００×１３０ｍｍサイズの２００メッシュの金網で包み込み、これをソックスレー抽出器にセットし、酢酸エチルの還流下で１６時間抽出処理する。次に、抽出処理後、全網上に残存する粘着剤を１００℃で２４時間乾燥させ、２３℃、５０％ＲＨの雰囲気下で３時間以上調湿後、該粘着剤の重量を測定し(Ｂｇ)、次式
ゲル分率（％）＝（Ｂ／Ａ）×１００
により、ゲル分率を算出する。
また、下記の方法で測定した被着体の銅板に対する温度１８０℃、２時間加熱後の２３℃における粘着力が、ＪＩＳ Ｚ ０２３７に準じた測定法で、０.１〜７Ｎ／２５ｍｍの範囲にあることが必要である。該粘着力が上記範囲にあれば、粘着テープの機能を十分に果たすことができると共に、樹脂封止後の剥離も容易である。好ましい粘着力は、０.３〜５Ｎ／２５ｍｍの範囲である。
The heat resistant pressure-sensitive adhesive layer in the pressure-sensitive adhesive tape of the present invention needs to have a gel fraction of 95% or more. When this gel fraction is less than 95%, it is affixed to the entire surface of one side of the lead frame, and adhesive residue is likely to occur when peeling after resin sealing. The gel fraction is a value measured by the following method.
<Method for measuring gel fraction>
The pressure-sensitive adhesive is coated on the release film and crosslinked under the same conditions as in the production of the pressure-sensitive adhesive tape of the present invention, and then the cross-linked pressure-sensitive adhesive (50 mm × 100 mm) is peeled off from the release film. Next, the two cross-linked pressure-sensitive adhesives (total weight Ag) are wrapped in a 200 mesh wire mesh of 100 × 130 mm size, set in a Soxhlet extractor, and extracted for 16 hours under reflux of ethyl acetate. Next, after the extraction treatment, the pressure-sensitive adhesive remaining on the whole net is dried at 100 ° C. for 24 hours, and after conditioning in an atmosphere of 23 ° C. and 50% RH for 3 hours or more, the weight of the pressure-sensitive adhesive is measured ( Bg), the following formula Gel fraction (%) = (B / A) × 100
To calculate the gel fraction.
In addition, the adhesive strength at 23 ° C. after heating at 180 ° C. for 2 hours with respect to the copper plate of the adherend measured by the following method is in the range of 0.1 to 7 N / 25 mm by the measurement method according to JIS Z 0237. It is necessary to be. If the adhesive strength is within the above range, the adhesive tape function can be sufficiently achieved, and peeling after resin sealing is easy. A preferable adhesive force is in the range of 0.3 to 5 N / 25 mm.
前記電離放射線架橋型アクリル系粘着剤層を構成する粘着剤としては、
［１］(メタ)アクリル酸エステル系共重合体を主成分とし、さらに電離放射線重合性オリゴマー及び／又は電離放射線重合性モノマー、並びに所望により電離放射線重合開始剤を含む粘着剤、
［２］側鎖に電離放射線架橋性の官能基を有する(メタ)アクリル酸エステル系共重合体を主成分とし、所望により電離放射線重合開始剤を含む粘着剤、
［３］活性水素をもつ官能基を少なくとも有する(メタ)アクリル酸エステル系共重合体と、側鎖に電離放射線架橋性の官能基を有する(メタ)アクリル酸エステル系共重合体と、活性水素をもつ官能基と反応し得る架橋剤とを含む組成物を主成分とし、所望により電離放射線重合開始剤を含む粘着剤、
などが挙げられる。
前記［１］の粘着剤において、(メタ)アクリル酸エステル系共重合体としては、エステル部分のアルキル基の炭素数が１〜２０の(メタ)アクリル酸エステルと、所望により用いられる他の単量体との重量平均分子量３０万以上の共重合体を好ましく挙げることができる。
ここで、エステル部分のアルキル基の炭素数が１〜２０の(メタ)アクリル酸エステルの例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸２−エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリルなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
また、所望により用いられる他の単量体としては、活性水素をもつ官能基を有する単量体、さらには、ビニルエステル類、オレフィン類、ハロゲン化オレフィン類、スチレン系単量体、ジエン系単量体、ニトリル系単量体、Ｎ,Ｎ−ジアルキル置換アクリルアミド類などと同じものを挙げることができる。
As the pressure-sensitive adhesive constituting the ionizing radiation cross-linking acrylic pressure-sensitive adhesive layer,
[1] A pressure-sensitive adhesive containing a (meth) acrylic acid ester copolymer as a main component, and further containing an ionizing radiation polymerizable oligomer and / or an ionizing radiation polymerizable monomer, and, if desired, an ionizing radiation polymerization initiator,
[2] A pressure-sensitive adhesive mainly comprising a (meth) acrylic ester copolymer having an ionizing radiation crosslinkable functional group in a side chain, and optionally containing an ionizing radiation polymerization initiator,
[3] A (meth) acrylate copolymer having at least a functional group having active hydrogen, a (meth) acrylate copolymer having an ionizing radiation crosslinkable functional group in the side chain, and active hydrogen A pressure-sensitive adhesive comprising, as a main component, a composition containing a crosslinking agent capable of reacting with a functional group having an ionization radiation polymerization initiator, if desired,
Etc.
In the pressure-sensitive adhesive of [1], the (meth) acrylic acid ester-based copolymer includes (meth) acrylic acid ester having 1 to 20 carbon atoms in the alkyl group of the ester moiety and other units used as desired. Preferred is a copolymer having a weight average molecular weight of 300,000 or more.
Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
Other monomers used as desired include monomers having a functional group having active hydrogen, vinyl esters, olefins, halogenated olefins, styrene monomers, diene monomers. Examples thereof include the same as the monomer, nitrile monomer, N, N-dialkyl-substituted acrylamides and the like.
ここで、活性水素をもつ官能基を有する単量体の例としては、(メタ)アクリル酸２−ヒドロキシエチル、(メタ)アクリル酸２−ヒドロキシプロピル、(メタ)アクリル酸３−ヒドロキシプロピル、(メタ)アクリル酸２−ヒドロキシブチル、(メタ)アクリル酸３−ヒドロキシブチル、(メタ)アクリル酸４−ヒドロキシブチルなどの(メタ)アクリル酸ヒドロキシアルキルエステル；(メタ)アクリル酸モノメチルアミノエチル、(メタ)アクリル酸モノエチルアミノエチル、(メタ)アクリル酸モノメチルアミノプロピル、(メタ)アクリル酸モノエチルアミノプロピルなどの(メタ)アクリル酸モノアルキルアミノアルキル；アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸などのエチレン性不飽和カルボン酸などが挙げられる。
また、ビニルエステル類としては、酢酸ビニル、プロピオン酸ビニルなどが、オレフィン類としては、エチレン、プロピレン、イソブチレンなどが、ハロゲン化オレフィン類としては、塩化ビニル、ビニリデンクロリドなどが、スチレン系単量体としては、スチレン、α−メチルスチレンなどが、ジエン系単量体としては、ブタジエン、イソプレン、クロロプレンなどが、ニトリル系単量体としては、アクリロニトリル、メタクリロニトリルなどが、Ｎ,Ｎ−ジアルキル置換アクリルアミド類としては、Ｎ,Ｎ−ジメチルアクリルアミド、Ｎ,Ｎ−ジエチルアクリルアミドなどが挙げられる。
これらの所望により用いられる他の単量体は単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Here, examples of the monomer having a functional group having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; monomethylaminoethyl (meth) acrylate, (meta ) Monoethylaminoethyl acrylate, monomethylaminopropyl (meth) acrylate, monoalkylaminoalkyl (meth) acrylate such as monoethylaminopropyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, maleic acid, And ethylenically unsaturated carboxylic acids such as itaconic acid and citraconic acid.
Vinyl esters include vinyl acetate and vinyl propionate, olefins include ethylene, propylene, and isobutylene, and halogenated olefins include vinyl chloride and vinylidene chloride. Styrene, α-methyl styrene, etc., diene monomers are butadiene, isoprene, chloroprene, etc., and nitrile monomers are acrylonitrile, methacrylonitrile, etc., N, N-dialkyl-substituted. Examples of acrylamides include N, N-dimethylacrylamide and N, N-diethylacrylamide.
These other monomers used as desired may be used alone or in combination of two or more.
また、電離放射線重合性オリゴマーとしては、例えばポリエステルアクリレート系、エポキシアクリレート系、ウレタンアクリレート系、ポリエーテルアクリレート系、ポリブタジエンアクリレート系、シリコーンアクリレート系などが挙げられる。ここで、ポリエステルアクリレート系オリゴマーとしては、例えば多価カルボン酸と多価アルコールの縮合によって得られる両末端に水酸基を有するポリエステルオリゴマーの水酸基を(メタ)アクリル酸でエステル化することにより、あるいは、多価カルボン酸にアルキレンオキシドを付加して得られるオリゴマーの末端の水酸基を(メタ)アクリル酸でエステル化することにより得ることができる。エポキシアクリレート系オリゴマーは、例えば、比較的低分子量のビスフェノール型エポキシ樹脂やノボラック型エポキシ樹脂のオキシラン環に、(メタ)アクリル酸を反応しエステル化することにより得ることができる。また、このエポキシアクリレート系オリゴマーを部分的に二塩基性カルボン酸無水物で変性したカルボキシル変性型のエポキシアクリレートオリゴマーも用いることができる。ウレタンアクリレート系オリゴマーは、例えば、ポリエーテルポリオールやポリエステルポリオールとポリイソシアナートの反応によって得られるポリウレタンオリゴマーを、(メタ)アクリル酸でエステル化することにより得ることができ、ポリオールアクリレート系オリゴマーは、ポリエーテルポリオールの水酸基を(メタ)アクリル酸でエステル化することにより得ることができる。
さらに、電離放射線重合性オリゴマーとして、一般式［１］
で表されるイミド(メタ)アクリレート０.１〜３０重量％及びエチレン性不飽和基含有単量体７０〜９９.９重量％を構成単位とする共重合オリゴマーも使用することができる。
上記電離放射線重合性オリゴマーの重量平均分子量は、ＧＰＣ法で測定した標準ポリメチルメタクリレート換算の値で、好ましくは５００〜１００,０００、より好ましくは１,０００〜７０,０００さらに好ましくは３,０００〜４０,０００の範囲で選定される。
この電離放射線重合性オリゴマーは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
Examples of the ionizing radiation polymerizable oligomer include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, and silicone acrylate. Here, as the polyester acrylate oligomer, for example, by esterifying hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol with polyisocyanate with (meth) acrylic acid. It can be obtained by esterifying the hydroxyl group of ether polyol with (meth) acrylic acid.
Further, as an ionizing radiation polymerizable oligomer, the general formula [1]
A copolymer oligomer having 0.1 to 30% by weight of imide (meth) acrylate and 70 to 99.9% by weight of an ethylenically unsaturated group-containing monomer as structural units can also be used.
The weight average molecular weight of the ionizing radiation polymerizable oligomer is a value in terms of standard polymethyl methacrylate measured by the GPC method, preferably 500 to 100,000, more preferably 1,000 to 70,000, still more preferably 3,000. It is selected in the range of ~ 40,000.
This ionizing radiation polymerizable oligomer may be used individually by 1 type, and may be used in combination of 2 or more type.
一方、電離放射線重合性モノマーとしては、例えばシクロヘキシル(メタ)アクリレート、２−エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソボニル(メタ)アクリレートなどの単官能性アクリレート類、１,４−ブタンジオールジ(メタ)アクリレート、１,６−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールアジペートジ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、ジシクロペンタニルジ(メタ)アクリレート、カプロラクトン変性ジシクロペンテニルジ(メタ)アクリレート、エチレンオキシド変性リン酸ジ(メタ)アクリレート、アリル化シクロヘキシルジ(メタ)アクリレート、イソシアヌレートジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレート、プロピオン酸変性ジペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、プロピレンオキシド変性トリメチロールプロパントリ(メタ)アクリレート、トリス（アクリロキシエチル）イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ(メタ)アクリレートなどが挙げられる。これらの電離放射線重合性モノマーは１種用いてもよいし、２種以上を組み合わせて用いてもよい。
これらの電離放射線重合性オリゴマーや電離放射線重合性モノマーの使用量は、電離放射線の照射により、前述の性状を有するアクリル系耐熱性粘着剤層が得られるように選定される。
On the other hand, examples of the ionizing radiation polymerizable monomer include monofunctional acrylates such as cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate Hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate phosphate, Cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified di Examples include pentaerythritol hexa (meth) acrylate. These ionizing radiation polymerizable monomers may be used alone or in combination of two or more.
The amount of the ionizing radiation polymerizable oligomer or ionizing radiation polymerizable monomer used is selected so that an acrylic heat-resistant pressure-sensitive adhesive layer having the above-mentioned properties can be obtained by irradiation with ionizing radiation.
また、所望により用いられる電離放射線重合開始剤としては、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２,２−ジメトキシ−２−フェニルアセトフェノン、２,２−ジエトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−[４−(メチルチオ)フェニル]−２−モルフォリノ−プロパン−１−オン、４−(２−ヒドロキシエトキシ)フェニル−２(ヒドロキシ−２−プロプル)ケトン、ベンゾフェノン、ｐ−フェニルベンゾフェノン、４,４'−ジエチルアミノベンゾフェノン、ジクロロベンゾフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリ−ブチルアントラキノン、２−アミノアントラキノン、２−メチルチオキサントン、２−エチルチオキサントン、２−クロロチオキサントン、２,４−ジメチルチオキサントン、２,４−ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、ｐ−ジメチルアミン安息香酸エステルなどが挙げられる。これらは１種を用いてもよいし、２種以上を組み合わせて用いてもよく、また、その配合量は、前記電離放射線重合性オリゴマー及び／又は電離放射線重合性モノマー１００重量部に対して、通常０.２〜２０重量部の範囲で選ばれる。
この電離放射線架橋型アクリル系粘着剤には、所望により、架橋剤を用いることができる。この架橋剤としては特に制限はなく、従来アクリル系粘着剤において架橋剤として慣用されているものの中から、任意のものを適宜選択して用いることができる。このような架橋剤としては、例えばポリイソシアネート化合物、エポキシ樹脂、メラミン樹脂、尿素樹脂、ジアルデヒド類、メチロールポリマー、アジリジン系化合物、金属キレート化合物、金属アルコキシド、金属塩などが挙げられるが、ポリイソシアネート化合物が好ましく用いられる。
ここで、ポリイソシアネート化合物の例としては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート、ヘキサメチレンジイソシアネートなどの脂肪族ポリイソシアネート、イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどの脂環式ポリイソシアネートなど、及びそれらのビウレット体、イソシアヌレート体、さらにはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油などの低分子活性水素含有化合物との反応物であるアダクト体などを挙げることができる。
Examples of the ionizing radiation polymerization initiator used as desired include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, and 2,2-dimethoxy. 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4 ′ Diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, Examples include 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, and p-dimethylamine benzoate. These may be used alone, or may be used in combination of two or more, and the blending amount thereof is 100 parts by weight of the ionizing radiation polymerizable oligomer and / or ionizing radiation polymerizable monomer. Usually selected in the range of 0.2 to 20 parts by weight.
If desired, a crosslinking agent can be used for the ionizing radiation crosslinking acrylic pressure-sensitive adhesive. There is no restriction | limiting in particular as this crosslinking agent, Arbitrary things can be suitably selected and used from what was conventionally used as a crosslinking agent in an acrylic adhesive. Examples of such crosslinking agents include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, and metal salts. A compound is preferably used.
Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Polyisocyanates, etc., and biurets, isocyanurates, and adducts that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. Can be mentioned.
本発明においては、この架橋剤は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、その使用量は、架橋剤の種類にもよるが、前記(メタ)アクリル酸エステル系共重合体１００重量部に対し、通常０.０１〜２０重量部、好ましくは、０.１〜１０重量部の範囲で、前記性状を有するアクリル系粘着剤層が得られるように選定される。
次に、前記［２］の粘着剤において、側鎖に電離放射線架橋性の官能基を有する(メタ)アクリル酸エステル系共重合体としては、例えば前述の［１］の粘着剤において説明した(メタ)アクリル酸エステル系共重合体のポリマー鎖に−ＣＯＯＨ、−ＮＣＯ、エポキシ基、−ＯＨ、−ＮＨ2などの活性点を導入し、この活性点と電離放射線架橋性の官能基を有する化合物と反応させて、該(メタ)アクリル酸エステル系共重合体の側鎖に電離放射線架橋性の官能基を導入してなる粘着剤を挙げることができる。
(メタ)アクリル酸エステル系共重合体に前記活性点を導入するには、該(メタ)アクリル酸エステル系共重合体を重合する際に、−ＣＯＯＨ、−ＮＣＯ、エポキシ基、−ＯＨ、−ＮＨ2などの官能基を有する単量体を共存させればよい。
具体的には、−ＣＯＯＨ基を導入する場合には(メタ)アクリル酸などを、−ＮＣＯ基を導入する場合には(メタ)アクリロイルオキシエチルイソシアネートなどを、エポキシ基を導入する場合にはグリシジル(メタ)アクリレートなどを、−ＯＨ基を導入する場合には２−ヒドロキシエチル(メタ)アクリレートなどを、−ＮＨ2基を導入する場合にはＮ−メチル(メタ)アクリルアミドなどを用いればよい。
これら活性点と反応させる電離放射線架橋性の官能基を有する化合物としては、例えば(メタ)アクリロイルオキシエチルイソシアネート、グリシジル(メタ)アクリレート、ペンタエリスリトールモノ(メタ)アクリレート、ジペンタエリスリトールモノ(メタ)アクリレート、トリメチロールプロパンモノ(メタ)アクリレートなどの重合性二重結合を有する化合物の中から、活性点の種類に応じて、適宜選択して用いることができる。
このようにして、側鎖に電離放射線架橋性の官能基を有する(メタ)アクリル酸エステル系共重合体が得られる。
次に、前記［３］の粘着剤において、活性水素をもつ官能基を少なくとも有する(メタ)アクリル酸エステル系共重合体としては、例えば前述の［１］の粘着剤において説明した(メタ)アクリル酸エステルと、活性水素をもつ官能基を有する単量体とを用いて共重合させればよい。
側鎖に電離放射線架橋性の官能基を有する(メタ)アクリル酸エステル系共重合体としては、前記［２］の粘着剤において述べたものを用いることができる。また、その使用量は、前記活性水素をもつ官能基を少なくとも有する(メタ)アクリル酸エステル系共重合体１００重量部に対し、通常５〜１００重量部、好ましくは１０〜５０重量部の範囲で選ばれる。
活性水素をもつ官能基と反応し得る架橋剤としては、前記［１］の粘着剤において述べた架橋剤を用いることができる。
得られた活性水素をもつ官能基を少なくとも有する(メタ)アクリル酸エステル系共重合体と、側鎖に電離放射線架橋性の官能基を有する(メタ)アクリル酸エステル系共重合体と、活性水素をもつ官能基と反応し得る架橋剤とを含む組成物は、加熱架橋および電離放射線架橋の両方を行うことができるので、耐熱性を飛躍的に向上させることができる。
この電離放射線架橋型アクリル系粘着剤には、本発明の目的が損なわれない範囲で、所望によりアクリル系粘着剤に通常使用されている各種添加剤、例えば粘着付与剤、酸化防止剤、紫外線吸収剤、光安定剤、軟化剤、充填剤などを添加することができる。
電離放射線としては、例えば紫外線や電子線などが挙げられる。上記紫外線は、高圧水銀ランプ、ヒュージョンＨランプ、キセノンランプなどで得られ、一方、電子線は電子線加速器などによって得られる。この電離放射線の中では、特に紫外線が好適である。なお、電子線を使用する場合は、重合開始剤を添加することなく、架橋化粘着剤層を形成することができる。
この電離放射線架橋型アクリル系粘着剤層に対する電離放射線の照射量としては、前述の性状を有する架橋化耐熱性粘着剤層が得られるように、適宜選定される。
このようにして、各成分の種類や量、照射条件、加熱架橋条件などを適宜選ぶことにより、架橋化度が制御され、前述の性状を有するアクリル系耐熱性粘着剤層を形成することができる。
In this invention, this crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. The amount used depends on the type of the crosslinking agent, but is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester copolymer. The acrylic pressure-sensitive adhesive layer having the above properties is selected in the range of parts by weight.
Next, in the adhesive of [2], the (meth) acrylic acid ester copolymer having an ionizing radiation crosslinkable functional group in the side chain has been described in, for example, the above-mentioned adhesive of [1] ( A compound having an active site such as —COOH, —NCO, epoxy group, —OH, —NH 2, etc. introduced into the polymer chain of the (meth) acrylic acid ester copolymer and having this active site and ionizing radiation crosslinkable functional group And a pressure-sensitive adhesive obtained by introducing an ionizing radiation crosslinkable functional group into the side chain of the (meth) acrylic acid ester copolymer.
In order to introduce the active site into the (meth) acrylic acid ester copolymer, when the (meth) acrylic acid ester copolymer is polymerized, -COOH, -NCO, epoxy group, -OH,- A monomer having a functional group such as NH 2 may be allowed to coexist.
Specifically, (meth) acrylic acid or the like is introduced when a -COOH group is introduced, (meth) acryloyloxyethyl isocyanate is introduced when an -NCO group is introduced, and glycidyl is introduced when an epoxy group is introduced. For example, 2-hydroxyethyl (meth) acrylate may be used for introducing (meth) acrylate or the like, and N-methyl (meth) acrylamide or the like may be used for introducing -NH 2 group.
Examples of the compound having an ionizing radiation crosslinkable functional group to be reacted with these active sites include (meth) acryloyloxyethyl isocyanate, glycidyl (meth) acrylate, pentaerythritol mono (meth) acrylate, and dipentaerythritol mono (meth) acrylate. From among compounds having a polymerizable double bond such as trimethylolpropane mono (meth) acrylate, it can be appropriately selected and used depending on the type of active site.
In this way, a (meth) acrylic acid ester copolymer having an ionizing radiation crosslinkable functional group in the side chain is obtained.
Next, as the (meth) acrylic acid ester copolymer having at least a functional group having active hydrogen in the pressure-sensitive adhesive of [3], for example, the (meth) acrylic described in the pressure-sensitive adhesive of [1] described above is used. What is necessary is just to copolymerize using acid ester and the monomer which has a functional group which has active hydrogen.
As the (meth) acrylic acid ester-based copolymer having an ionizing radiation crosslinkable functional group in the side chain, those described in the above [2] pressure-sensitive adhesive can be used. The amount used is usually in the range of 5 to 100 parts by weight, preferably 10 to 50 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer having at least the functional group having active hydrogen. To be elected.
As the crosslinking agent capable of reacting with a functional group having active hydrogen, the crosslinking agent described in the pressure-sensitive adhesive of [1] can be used.
The obtained (meth) acrylate copolymer having at least a functional group having active hydrogen, a (meth) acrylate copolymer having an ionizing radiation crosslinkable functional group in the side chain, and active hydrogen Since the composition containing a crosslinking agent capable of reacting with a functional group having an ability to perform both thermal crosslinking and ionizing radiation crosslinking, the heat resistance can be drastically improved.
This ionizing radiation crosslinkable acrylic pressure-sensitive adhesive has various additives that are usually used in acrylic pressure-sensitive adhesives as desired, for example, tackifiers, antioxidants, UV absorbers, as long as the object of the present invention is not impaired. Agents, light stabilizers, softeners, fillers and the like can be added.
Examples of the ionizing radiation include ultraviolet rays and electron beams. The ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like, while the electron beam is obtained with an electron beam accelerator or the like. Among these ionizing radiations, ultraviolet rays are particularly preferable. In addition, when using an electron beam, a crosslinked adhesive layer can be formed, without adding a polymerization initiator.
The amount of ionizing radiation applied to the ionizing radiation cross-linking acrylic pressure-sensitive adhesive layer is appropriately selected so that a cross-linked heat-resistant pressure-sensitive adhesive layer having the above-described properties can be obtained.
Thus, by appropriately selecting the type and amount of each component, irradiation conditions, heating crosslinking conditions, etc., the degree of crosslinking can be controlled, and an acrylic heat-resistant pressure-sensitive adhesive layer having the aforementioned properties can be formed. .
本発明の粘着テープを作製する具体的な方法としては、まず、所望によりコロナ放電処理などの表面処理された基材フィルムの該表面処理面に、直接電離放射線架橋型粘着剤層を形成するか、又は剥離シート上に上記粘着剤を塗布して粘着剤層を設けたのち、これを基材フィルムの表面処理面に貼着し、転写する。次いで、該粘着剤層に電離放射線を照射して架橋処理を行い、前記性状を有する架橋化アクリル系耐熱性粘着剤層を形成させる。この粘着剤層の厚さは、通常５〜１００μｍ、好ましくは１０〜５０μｍ程度である。
次に、このようにして得られた本発明の半導体用耐熱性粘着テープを用いた半導体装置の製造方法の１例について説明する。
（１）リードフレームとしては、ダイパット及びインナーリードを有するパターンが複数形成されたリードフレームを用い、このリードフレームの片面に、本発明の粘着テープを、０〜２００℃で貼着する工程、（２）次いで、リードフレームの露出面（本発明の粘着テープを貼着した面と反対の面）上のダイパッドに銀ペースト等の接着剤を用いて半導体素子を接着し、１４０〜２００℃程度で、３０分〜２時間程度の加熱を行うことにより銀ペースト等の接着剤を硬化する工程、（３）その後、１５０〜２５０℃程度で加熱して、リードフレームのインナーリードと半導体素子とを金線等のワイヤボンドを行って接続する工程、（４）１５０〜２００℃程度で、リードフレームの露出面、複数の半導体素子及び複数のワイヤを封止材で一括封止する工程、（５）１５０〜２００℃程度で４〜６時間程度の加熱を行うことにより封止材樹脂を硬化する工程、（６）０〜５０℃程度で半導体用粘着テープをリードフレーム及び封止材から剥離する工程、（７）封止したリードフレームを分割することにより、各々１個の半導体素子を有する複数の半導体装置を得る工程の各工程を施すことにより、目的の半導体装置を製造することができる。なお、（６）の工程は、（５）の工程の前に行うこともできる。
前記半導体装置の製造工程に、本発明の粘着テープを用いた場合、該テープは耐熱性に優れているので、封止時の樹脂漏れを十分に防止し得ると共に、樹脂封止後に剥がした際に、糊残りが少ない。
As a specific method for producing the pressure-sensitive adhesive tape of the present invention, first, an ionizing radiation cross-linking pressure-sensitive adhesive layer is directly formed on the surface-treated surface of a surface-treated substrate film such as corona discharge treatment, if desired. Or after apply | coating the said adhesive on a peeling sheet and providing an adhesive layer, this is stuck on the surface treatment surface of a base film, and is transcribe | transferred. Next, the pressure-sensitive adhesive layer is subjected to a crosslinking treatment by irradiating with ionizing radiation to form a crosslinked acrylic heat-resistant pressure-sensitive adhesive layer having the above properties. The thickness of this pressure-sensitive adhesive layer is usually about 5 to 100 μm, preferably about 10 to 50 μm.
Next, an example of a method for producing a semiconductor device using the thus obtained heat-resistant adhesive tape for semiconductors of the present invention will be described.
(1) Using a lead frame in which a plurality of patterns having die pads and inner leads are formed as the lead frame, the adhesive tape of the present invention is attached to one side of the lead frame at 0 to 200 ° C. ( 2) Next, a semiconductor element is bonded to the die pad on the exposed surface of the lead frame (the surface opposite to the surface on which the adhesive tape of the present invention is adhered) using an adhesive such as silver paste, and the temperature is about 140 to 200 ° C. A step of curing an adhesive such as a silver paste by heating for about 30 minutes to 2 hours, (3) Thereafter, heating is performed at about 150 to 250 ° C., and the inner lead of the lead frame and the semiconductor element are made of gold (4) at about 150 to 200 ° C., the exposed surface of the lead frame, the plurality of semiconductor elements, and the plurality of wires are all sealed with a sealing material. A step of sealing, (5) a step of curing the encapsulant resin by heating at about 150 to 200 ° C. for about 4 to 6 hours, and (6) a lead frame for the semiconductor adhesive tape at about 0 to 50 ° C. And a step of separating from the sealing material, and (7) dividing the sealed lead frame to obtain a plurality of semiconductor devices each having one semiconductor element, thereby performing a target semiconductor device. Can be manufactured. The step (6) can also be performed before the step (5).
When the pressure-sensitive adhesive tape of the present invention is used in the manufacturing process of the semiconductor device, the tape is excellent in heat resistance, so that it can sufficiently prevent resin leakage at the time of sealing and is peeled off after resin sealing. There is little glue residue.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
実施例１
厚さ２５μｍのポリイミドフィルム［デュポン社製、商品名「カプトン１００Ｈ」、融点なし］に、アクリル系マレイミド樹脂を含む粘着剤［東亜合成社製、商品名「ＵＶＡ３３００」］を、乾燥厚さが２５μｍになるように塗布し、ベルトコンベア式ＵＶ照射機「アイグラフィックス社製、商品名「ＵＢ０４２−５ＡＭ／Ｗ」、照度２００ｍＷ／ｃｍ2、高圧水銀ランプ２灯］にて、積算光量２０００ｍＪ／ｃｍ2照射し、硬化させ、紫外線架橋型粘着テープを作製した。
実施例２
実施例１におけるポリイミドフィルムの代わりに、厚さ２５μｍのポリエチレンテレフタレートフィルム［東レ社製、商品名「ルミラー」、融点２６０℃］を用いた以外は、実施例１と同様にして、紫外線架橋型粘着テープを作製した。
実施例３
実施例１におけるポリイミドフィルムの代わりに、厚さ２５μｍのポリフェニレンスルフィドフィルム［東レ社製、商品名「トレリナ」、融点２８５℃］を用いた以外は、実施例１と同様にして、紫外線架橋型粘着テープを作製した。
実施例４
アクリル酸２−エチルヘキシル８０重量部、アクリル酸ヒドロキシエチル２０重量部から得られた共重合体１００重量部と、アクリル酸２−エチルヘキシル８０重量部、アクリル酸ヒドロキシエチル２０重量部から得られた共重合体に２−メタクリロイルオキシエチルイソシアネート２０重量部を付加したもの２０重量部、電離放射線重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン［長瀬産業社製、商品名「イルガキュア１８４」］０.７重量部、多価イソシアネート化合物［日本ポリウレタン社製、商品名「コロネートＬ」］０.８重量部を混合したものを、厚さ２５μｍのポリイミドフィルム［デュポン社製、商品名「カプトン１００Ｈ」、融点なし］に乾燥厚さが２０μｍになるように塗布し、１００℃で２分間加熱架橋させたのち、ベルトコンベア式ＵＶ照射機［アイグラフィックス社製、商品名「ＵＢ０４２−５ＡＭ／Ｗ」、照度３００ｍＷ／ｃｍ2、高圧水銀ランプ２灯］にて、積算光量５００ｍＪ／ｃｍ2照射し、硬化させ、加熱架橋・紫外線架橋併用型粘着テープを作製した。
比較例１
実施例１におけるポリイミドフィルムの代わりに、厚さ５０μｍのポリプロピレンフィルム（融点１７０℃）を用いた以外は、実施例１と同様にして、紫外線架橋型粘着テープを作製した。
比較例２
アクリル酸ブチル６０重量部、メタクリル酸メチル２０重量部、アクリル酸ヒドロキシエチル２０重量部から得られた共重合体１００重量部及び多価イソシアネート化合物［日本ポリウレタン社製、商品名「コロネートＬ」］１.０重量部を混合したものを、厚さ２５μｍのポリイミドフィルム［デュポン社製、商品名「カプトン１００Ｈ」、融点なし］に、乾燥厚さが２０μｍになるように塗布し、１００℃で２分間加熱架橋させ、加熱架橋型粘着テープを作製した。
実施例１〜４及び比較例１、２で得られた粘着テープについて、下記の試験を行った。結果を第１表に示す。
（１）粘着力
２５ｍｍ幅の評価サンプルを銅被着体に２ｋｇのゴムロールで一往復させ貼り付け、２０分後テンシロン引張試験機［(株)オリエンテック製、ＲＴＡ−Ｔ−２Ｍ］にて剥離角度１８０°、ＪＩＳ Ｚ ０２３７に準じて剥離速度３００ｍｍ／ｍｉｎで粘着力を測定した。
（２）熱後粘着力
測定条件は上記と同様で、サンプルを貼り付け後１８０℃で２時間処理した後、測定した。
（３）粘着剤層のゲル分率
明細書本文記載の方法に従って測定した。
（４）糊残り
粘着テープを銅被着体に貼付後１８０℃で２時間処理し、剥離した際の銅被着体への糊残りの有無を目視で確認した。
（５）樹脂漏れ
粘着テープを、リードフレームに貼付し、トランスファー成型機により１７５℃の温度下でエポキシ樹脂を用いて樹脂封止を行った。その後、粘着テープを剥離し、樹脂漏れの有無を目視で確認した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
A 25 μm thick polyimide film [DuPont, trade name “Kapton 100H”, no melting point] and an adhesive containing acrylic maleimide resin [Toa Gosei Co., Ltd., trade name “UVA3300”] are dried to a thickness of 25 μm. With a belt conveyor type UV irradiator “trade name“ UB042-5AM / W ”, illuminance 200 mW / cm 2 , two high-pressure mercury lamps], a cumulative amount of light 2000 mJ / cm 2 Irradiation and curing were carried out to produce a UV cross-linked adhesive tape.
Example 2
In place of the polyimide film in Example 1, a 25 μm-thick polyethylene terephthalate film [trade name “Lumirror”, melting point 260 ° C., manufactured by Toray Industries, Inc.] was used in the same manner as in Example 1 to cure the UV-crosslinked adhesive. A tape was prepared.
Example 3
In place of the polyimide film in Example 1, a 25 μm-thick polyphenylene sulfide film [trade name “Torellina”, melting point 285 ° C., manufactured by Toray Industries, Inc.] was used in the same manner as in Example 1, except that an ultraviolet crosslinking adhesive was used. A tape was prepared.
Example 4
Copolymer obtained from 80 parts by weight of 2-ethylhexyl acrylate and 100 parts by weight of a copolymer obtained from 20 parts by weight of hydroxyethyl acrylate, 80 parts by weight of 2-ethylhexyl acrylate and 20 parts by weight of hydroxyethyl acrylate 20 parts by weight of 20-part by weight of 2-methacryloyloxyethyl isocyanate added to the coal, 0.7 parts by weight of 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 184” manufactured by Nagase Sangyo Co., Ltd.] as an ionizing radiation polymerization initiator, A polyisocyanate compound [manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate L”] mixed with 0.8 part by weight is added to a 25 μm-thick polyimide film [manufactured by DuPont, trade name “Kapton 100H”, no melting point]. Apply to a dry thickness of 20μm and crosslink by heating at 100 ° C for 2 minutes Mixture was allowed, belt conveyor type UV irradiation machine [Eye Graphics Co., Ltd. under the trade name "UB042-5AM / W", illuminance of 300mW / cm 2, a high-pressure mercury lamp 2-lamp] in, integrated quantity of light 500mJ / cm 2 was irradiated And cured to produce a heat-crosslinking / ultraviolet-crosslinking pressure-sensitive adhesive tape.
Comparative Example 1
In place of the polyimide film in Example 1, a 50 μm-thick polypropylene film (melting point: 170 ° C.) was used, and an ultraviolet-crosslinked adhesive tape was produced in the same manner as in Example 1.
Comparative Example 2
100 parts by weight of a copolymer obtained from 60 parts by weight of butyl acrylate, 20 parts by weight of methyl methacrylate and 20 parts by weight of hydroxyethyl acrylate and a polyisocyanate compound [trade name “Coronate L” manufactured by Nippon Polyurethane Co., Ltd.] 1 A mixture of 0.0 part by weight was applied to a polyimide film having a thickness of 25 μm [manufactured by DuPont, trade name “Kapton 100H”, no melting point] to a dry thickness of 20 μm, and at 100 ° C. for 2 minutes. Heat-crosslinking was carried out to produce a heat-crosslinking pressure-sensitive adhesive tape.
The following test was done about the adhesive tape obtained in Examples 1-4 and Comparative Examples 1 and 2. The results are shown in Table 1.
(1) Adhesive strength An evaluation sample with a width of 25 mm was attached to a copper adherence by reciprocating with a 2 kg rubber roll, and after 20 minutes, peeled off using a Tensilon tensile tester [Orientec Co., Ltd., RTA-T-2M]. The adhesive strength was measured at an angle of 180 ° and a peeling speed of 300 mm / min according to JIS Z 0237.
(2) Adhesive force after heating The measurement conditions were the same as described above, and the sample was attached and then treated at 180 ° C. for 2 hours and then measured.
(3) Gel fraction of adhesive layer It measured according to the method of description text.
(4) Adhesive residue After sticking the adhesive tape on the copper adherend, it was treated at 180 ° C for 2 hours, and the presence or absence of adhesive residue on the copper adherend when peeled was visually confirmed.
(5) Resin leakage Adhesive tape was affixed to the lead frame, and resin sealing was performed using an epoxy resin at a temperature of 175 ° C. using a transfer molding machine. Then, the adhesive tape was peeled off and the presence or absence of resin leakage was confirmed visually.
本発明の半導体用耐熱性粘着テープは、隣接した複数の開口にそれぞれ配列した端子部を有し、複数の半導体素子の一括樹脂封止が可能なリードフレームの片面全面に貼付され、樹脂封止時の樹脂漏れを効果的に防止すると共に、樹脂封止後剥がした場合、糊残りが少ない。 The heat-resistant adhesive tape for semiconductors of the present invention has terminal portions arranged respectively in a plurality of adjacent openings, and is affixed to the entire surface of one side of a lead frame capable of collectively sealing a plurality of semiconductor elements. While effectively preventing resin leakage at the time, there is little glue residue when peeled off after resin sealing.
Claims (3)
The (meth) acrylate copolymer having at least a functional group having active hydrogen in the heat-resistant pressure-sensitive adhesive layer and the (meth) acrylate copolymer having an ionizing radiation crosslinkable functional group in the side chain The heat-resistant pressure-sensitive adhesive tape for semiconductor according to claim 1, wherein the composition containing a crosslinking agent capable of reacting with a functional group having active hydrogen is crosslinked by heating and by irradiation with ionizing radiation.
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