JP2017100397A - Release film for processing, application thereof and manufacturing method of resin encapsulated semiconductor using the same - Google Patents
Release film for processing, application thereof and manufacturing method of resin encapsulated semiconductor using the same Download PDFInfo
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- JP2017100397A JP2017100397A JP2015236639A JP2015236639A JP2017100397A JP 2017100397 A JP2017100397 A JP 2017100397A JP 2015236639 A JP2015236639 A JP 2015236639A JP 2015236639 A JP2015236639 A JP 2015236639A JP 2017100397 A JP2017100397 A JP 2017100397A
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- 239000011347 resin Substances 0.000 title claims abstract description 129
- 239000004065 semiconductor Substances 0.000 title claims description 102
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 238000000034 method Methods 0.000 claims abstract description 176
- 230000008569 process Effects 0.000 claims abstract description 150
- 238000007789 sealing Methods 0.000 claims abstract description 79
- 230000008859 change Effects 0.000 claims abstract description 78
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 63
- 238000000465 moulding Methods 0.000 claims description 59
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- 238000010438 heat treatment Methods 0.000 claims description 13
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- 238000000113 differential scanning calorimetry Methods 0.000 claims description 6
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- 229920002430 Fibre-reinforced plastic Polymers 0.000 claims description 5
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- 238000009820 dry lamination Methods 0.000 description 5
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
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- 239000007788 liquid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 229920002302 Nylon 6,6 Polymers 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- 239000003381 stabilizer Substances 0.000 description 3
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- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
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- 239000004830 Super Glue Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Landscapes
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Laminated Bodies (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
【課題】樹脂封止後の成形品を、金型構造や離型剤量によることなく容易に離型でき、かつ皺や欠け等の外観不良のない成形品を得ることができるプロセス用離型フィルムを提供する。【解決手段】離型層Ａと、耐熱樹脂層Ｂと、所望により離型層Ａ’と、を含む積層フィルムであるプロセス用離型フィルムであって、前記離型層Ａ（及び存在する場合離型層Ａ’）の水に対する接触角が、９０°から１３０°であり、前記積層フィルムの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下であるか、又は前記積層フィルムの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が４％以下である、上記プロセス用離型フィルム。【選択図】 図１[PROBLEMS] To release a molded product after resin sealing easily without depending on the mold structure or the amount of release agent, and to obtain a molded product having no appearance defects such as wrinkles and chips. Provide film. A process release film which is a laminated film including a release layer A, a heat-resistant resin layer B, and optionally a release layer A ′, wherein the release layer A (and when present) The contact angle of the release layer A ′) with respect to water is 90 ° to 130 °, and the rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the laminated film is 3% or less, Alternatively, the release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less. [Selection] Figure 1
Description
本発明は、プロセス用離型フィルム、好適には半導体封止プロセス用離型フィルムに関し、特に金型内に半導体チップ等を配置して樹脂を注入成形する際に、半導体チップ等と金型内面との間に配置されるプロセス用離型フィルム、及びそれを用いた樹脂封止半導体の製造方法に関する。 The present invention relates to a release film for a process, preferably a release film for a semiconductor sealing process, and in particular, when a semiconductor chip is placed in a mold and a resin is injected and molded, the semiconductor chip and the inner surface of the mold And a process for producing a resin-encapsulated semiconductor using the same.
近年、半導体パッケージ等の小型軽量化に伴い、封止樹脂の使用量を減らすことが検討されている。そして、封止樹脂の使用量を減らしても、半導体チップ等と樹脂との界面を強固に接着できるようにするため、封止樹脂に含まれる離型剤の量を減らすことが望まれている。このため、硬化成形後の封止樹脂と金型との離型性を得る方法として、金型内面と半導体チップ等との間に離型フィルムを配置する方法が採られている。 In recent years, with the reduction in size and weight of semiconductor packages and the like, it has been studied to reduce the amount of sealing resin used. And even if it reduces the usage-amount of sealing resin, in order to be able to adhere | attach the interface of a semiconductor chip etc. and resin firmly, reducing the quantity of the mold release agent contained in sealing resin is desired. . For this reason, as a method for obtaining the releasability between the sealing resin and the mold after the curing molding, a method in which a release film is disposed between the inner surface of the mold and the semiconductor chip or the like is employed.
このような離型フィルムとして、離型性および耐熱性に優れる、フッ素系樹脂フィルム（例えば、特許文献１〜２）、ポリ４−メチル−１−ペンテン樹脂フィルム（例えば、特許文献３）等が提案されている。しかしながら、これらの離型フィルムは、金型内面に装着された際に皺が発生し易く、この皺が成形品の表面に転写されて外観不良を生じるという問題があった。 As such a release film, a fluorine-based resin film (for example, Patent Documents 1 and 2), a poly-4-methyl-1-pentene resin film (for example, Patent Document 3), etc. that are excellent in releasability and heat resistance. Proposed. However, these release films have a problem that wrinkles are easily generated when they are mounted on the inner surface of the mold, and the wrinkles are transferred to the surface of the molded product, resulting in poor appearance.
これに対して、離型層と、耐熱層とを有する積層離型フィルムが提案されている。これらの離型フィルムは、離型層で離型性を得るとともに、耐熱層で皺を抑制しようとするものである。これらの提案の代表的なものは、離型層と、耐熱層との貯蔵弾性率の関係に着目したものである（例えば、特許文献４及び５ご参照。）。例えば、特許文献４には、離型層の貯蔵弾性率が比較的低く、耐熱層の貯蔵弾性率が比較的高い構成の積層離型フィルム、より具体的には、離型層の１７５℃における貯蔵弾性率Ｅ’が、４５ＭＰａ以上１０５ＭＰａ以下であり、耐熱層の１７５℃における貯蔵弾性率Ｅ’が１００ＭＰａ以上２５０ＭＰａ以下である、半導体封止プロセス用離型フィルムが記載されている。 On the other hand, a laminated release film having a release layer and a heat-resistant layer has been proposed. These release films are intended to obtain mold release properties in the release layer and to suppress wrinkles in the heat resistant layer. A representative of these proposals is a technique that focuses on the relationship between the storage elastic modulus of the release layer and the heat-resistant layer (see, for example, Patent Documents 4 and 5). For example, Patent Document 4 discloses a laminated release film having a configuration in which the storage elastic modulus of the release layer is relatively low and the storage elastic modulus of the heat-resistant layer is relatively high, more specifically, the release layer at 175 ° C. A release film for a semiconductor encapsulation process is described in which the storage elastic modulus E ′ is 45 MPa or more and 105 MPa or less, and the storage elastic modulus E ′ of the heat resistant layer at 175 ° C. is 100 MPa or more and 250 MPa or less.
しかしながら、当該技術分野の発展に伴い半導体封止プロセス用離型フィルム等のプロセス用離型フィルムに対する要求水準は年々高まっており、より過酷なプロセス条件においても皺の発生が抑制されたプロセス用離型フィルムが求められており、特に、離型性、皺の抑制、及び金型追従性が更に高いレベルでバランスしたプロセス用離型フィルムが強く求められている。 However, with the development of this technical field, the level of requirements for process release films such as semiconductor encapsulation process release films has been increasing year by year, and process release with reduced generation of wrinkles even under more severe process conditions. There is a need for mold films, and in particular, there is a strong demand for process release films that balance mold release, suppression of wrinkles, and mold followability at a higher level.
本発明は、このような事情を鑑みてなされたものであり、樹脂封止後の成形品を、金型構造や離型剤量によることなく容易に離型でき、かつ皺や欠け等の外観不良のない成形品を得ることができるプロセス用離型フィルムを提供することを目的とする。 The present invention has been made in view of such circumstances, and the molded product after resin sealing can be easily released without depending on the mold structure or the amount of the release agent, and has an appearance such as wrinkles and chips. It aims at providing the release film for processes which can obtain the molded product without a defect.
本発明者らは上記課題を解決するために鋭意検討を重ねた結果、プロセス用離型フィルムの特定の温度における熱寸法変化率、とりわけプロセス用離型フィルムを構成する積層フィルムのＴＤ方向（フィルムの面内であって、フィルムの製造時の長手方向に対して直行する方向。以下、「横方向」ともいう。）の熱寸法変化率を適切に制御することが、金型内面に装着された際の皺の抑制に重要であることを見出し、本発明を完成するに至った。
すなわち本発明及びその各態様は、下記［１］から［１９］に記載のとおりである。
As a result of intensive studies to solve the above problems, the present inventors have determined that the rate of thermal dimensional change at a specific temperature of the process release film, particularly the TD direction of the laminated film constituting the process release film (film Is a direction perpendicular to the longitudinal direction when the film is manufactured (hereinafter also referred to as “lateral direction”). As a result, the present invention has been completed.
That is, the present invention and each aspect thereof are as described in the following [1] to [19].
［１］
離型層Ａと、耐熱樹脂層Ｂと、を含む積層フィルムであるプロセス用離型フィルムであって、
前記離型層Ａの水に対する接触角（以下、「水に対する接触角」を「水接触角」と表記することがある。）が、９０°から１３０°であり、
前記耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下である、上記プロセス用離型フィルム。
［２］
前記積層フィルムの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１２０℃までの熱寸法変化率の和が６％以下である、［１］に記載のプロセス用離型フィルム。
［３］
離型層Ａと、耐熱樹脂層Ｂと、を含むを含む積層フィルムであるプロセス用離型フィルムであって、
前記離型層Ａの水に対する接触角が、９０°から１３０°であり、
前記耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が４％以下である、上記プロセス用離型フィルム。
［４］
前記積層フィルムの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１７０℃までの熱寸法変化率の和が７％以下である、［３］に記載のプロセス用離型フィルム。
［５］
前記耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下である、［１］から［４］のいずれかに記載のプロセス用離型フィルム。
［６］
前記耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１２０℃までの熱寸法変化率の和が６％以下である、［５］に記載のプロセス用離型フィルム。
［７］
前記耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が３％以下である、［１］から［４］のいずれかに記載のプロセス用離型フィルム。
［８］
前記耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１２０℃までの熱寸法変化率の和が４％以下である、［７］に記載のプロセス用離型フィルム。
［９］
前記離型層Ａが、フッ素樹脂、４−メチル−１−ペンテン（共）重合体、及びポリスチレン系樹脂からなる群より選ばれる樹脂を含む、［１］から［８］のいずれか一項に記載のプロセス用離型フィルム。
［１０］
前記耐熱樹脂層Ｂが、延伸フィルムを含んでなる、［１］から［９］のいずれか一項に記載のプロセス用離型フィルム。
［１１］
前記延伸フィルムが、延伸ポリエステルフィルム、延伸ポリアミドフィルム、及び延伸ポリプロピレンフィルムからなる群より選ばれる、［１０］に記載のプロセス用離型フィルム。
［１２］
前記耐熱樹脂層ＢのＪＩＳＫ７２２１に準じて示差走査熱量測定（ＤＳＣ）によって測定した第１回昇温工程での結晶融解熱量が１５Ｊ／ｇ以上、６０Ｊ／ｇ以下である、［１］から［１１］のいずれか一項に記載のプロセス用離型フィルム。
［１３］
前記積層フィルムが、更に離型層Ａ’を有し、かつ、該離型層Ａと、前記耐熱樹脂層Ｂと、前記離型層Ａ’と、をこの順で含み、
該離型層Ａ’の水に対する接触角が、９０°から１３０°である、［１］から［１２］のいずれか一項に記載のプロセス用離型フィルム。
［１４］
前記離型層Ａ及び前記離型層Ａ’の少なくとも一方が、フッ素樹脂、４−メチル−１−ペンテン（共）重合体、及びポリスチレン系樹脂からなる群より選ばれる樹脂を含む、［１３］に記載のプロセス用離型フィルム。
［１５］
熱硬化性樹脂による封止プロセスに用いる、［１］から［１４］のいずれか一項に記載のプロセス用離型フィルム
［１６］
半導体封止プロセスに用いる、［１］から［１５］のいずれか一項に記載のプロセス用離型フィルム。
［１７］
繊維強化プラスチック成形プロセス、またはプラスチックレンズ成形プロセスに用いる、［１］から［１５］のいずれか一項に記載のプロセス用離型フィルム。
［１８］
樹脂封止半導体の製造方法であって、
成形金型内の所定位置に、樹脂封止される半導体装置を配置する工程と、
前記成形金型内面に、［１］から［１４］のいずれか一項に記載の半導体封止プロセス用離型フィルムを、前記離型層Ａが前記半導体装置と対向するように配置する工程と、
前記成形金型を型締めした後、前記半導体装置と、前記半導体封止プロセス用離型フィルムとの間に封止樹脂を注入成形する工程と、
を有する、上記樹脂封止半導体の製造方法。
［１９］
樹脂封止半導体の製造方法であって、
成形金型内の所定位置に、樹脂封止される半導体装置を配置する工程と、
前記成形金型内面に、［１３］又は［１４］に記載の半導体封止プロセス用離型フィルムを、前記離型層Ａ’が前記半導体装置と対向するように配置する工程と、
前記成形金型を型締めした後、前記半導体装置と、前記半導体封止プロセス用離型フィルムとの間に封止樹脂を注入成形する工程と、
を有する、上記樹脂封止半導体の製造方法。
[1]
A release film for a process which is a laminated film including a release layer A and a heat resistant resin layer B,
The contact angle of the release layer A with water (hereinafter, “contact angle with water” may be referred to as “water contact angle”) is 90 ° to 130 °,
The release film for a process as described above, wherein the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer B is 3% or less.
[2]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less, [1 ] The release film for processes as described in any one of Claims 1-3.
[3]
A release film for process which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer B is 4% or less.
[4]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the laminated film is 7% or less, [3 ] The release film for processes as described in any one of Claims 1-3.
[5]
The process release film according to any one of [1] to [4], wherein a rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is 3% or less.
[6]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction is 6% or less. [5] The release film for a process according to [5].
[7]
The release film for process according to any one of [1] to [4], wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is 3% or less.
[8]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer B and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction is 4% or less. [7] The process release film according to [7].
[9]
In any one of [1] to [8], the release layer A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. The release film for process as described.
[10]
The release film for process according to any one of [1] to [9], wherein the heat-resistant resin layer B includes a stretched film.
[11]
The release film for process according to [10], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
[12]
[1] to [11], wherein the heat-resisting resin layer B has a heat of crystal melting of 15 J / g or more and 60 J / g or less in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221. The release film for processes as described in any one of these.
[13]
The laminated film further has a release layer A ′, and includes the release layer A, the heat-resistant resin layer B, and the release layer A ′ in this order,
The release film for process according to any one of [1] to [12], wherein a contact angle of the release layer A ′ with respect to water is 90 ° to 130 °.
[14]
At least one of the release layer A and the release layer A ′ includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin [13]. Release film for process as described in 2.
[15]
The process release film [16] according to any one of [1] to [14], which is used for a sealing process with a thermosetting resin.
The process release film according to any one of [1] to [15], which is used in a semiconductor sealing process.
[17]
The release film for a process according to any one of [1] to [15], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
[18]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for semiconductor encapsulation process according to any one of [1] to [14] on the inner surface of the molding die so that the release layer A faces the semiconductor device; ,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
[19]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing the release film for semiconductor sealing process according to [13] or [14] on the inner surface of the molding die so that the release layer A ′ faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
本発明のプロセス用離型フィルムは、従来技術では実現できなかった高いレベルの離型性、皺の抑制、及び金型追従性を兼ね備えるので、これを用いることで、半導体チップ等を樹脂封止等して得られる成形品を容易に離型できるとともに、皺や欠けなどの外観不良のない成形品を、高い生産性で製造することができる。 The process release film of the present invention combines a high level of mold release, suppression of wrinkles, and mold followability that could not be realized with the prior art. By using this, a semiconductor chip or the like is sealed with resin. In addition, it is possible to easily release a molded product obtained by the above method, and it is possible to manufacture a molded product having no appearance defects such as wrinkles and chips with high productivity.
プロセス用離型フィルム
本発明のプロセス用離型フィルムは、以下の４態様を含む。
（第１態様）
離型層Ａと、耐熱樹脂層Ｂと、を含む積層フィルムであるプロセス用離型フィルムであって、
前記離型層Ａの水に対する接触角が、９０°から１３０°であり、
前記積層フィルムの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下である、上記プロセス用離型フィルム。
（第２態様）
離型層Ａと、耐熱樹脂層Ｂと、を含む積層フィルムであるプロセス用離型フィルムであって、
前記離型層Ａの水に対する接触角が、９０°から１３０°であり、
前記積層フィルムの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が４％以下である、上記プロセス用離型フィルム。
（第３態様）
離型層Ａと、耐熱樹脂層Ｂと、離型層Ａ’と、をこの順で含む積層フィルムであるプロセス用離型フィルムであって、
前記離型層Ａ、及び前記離型層Ａ’の水に対する接触角が、９０°から１３０°であり、
前記積層フィルムの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下である、上記プロセス用離型フィルム。
（第４態様）
離型層Ａと、耐熱樹脂層Ｂと、離型層Ａ’と、をこの順で含む積層フィルムであるプロセス用離型フィルムであって、
前記離型層Ａ、及び前記離型層Ａ’の水に対する接触角が、９０°から１３０°であり、
前記積層フィルムの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が４％以下である、上記プロセス用離型フィルム。
Process Release Film The process release film of the present invention includes the following four embodiments.
(First aspect)
A release film for a process which is a laminated film including a release layer A and a heat resistant resin layer B,
The contact angle of the release layer A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
(Second aspect)
A release film for a process which is a laminated film including a release layer A and a heat resistant resin layer B,
The contact angle of the release layer A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
(Third aspect)
A release film for process which is a laminated film including a release layer A, a heat-resistant resin layer B, and a release layer A ′ in this order,
The contact angle of the release layer A and the release layer A ′ with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
(4th aspect)
A release film for process which is a laminated film including a release layer A, a heat-resistant resin layer B, and a release layer A ′ in this order,
The contact angle of the release layer A and the release layer A ′ with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
上記各態様から明らかな様に、本発明のプロセス用離型フィルム（以下、単に「離型フィルム」ともいう）は、成形品や金型に対する離型性を有する離型層Ａ、及び所望により離型層Ａ’、並びに該離型層を支持する耐熱樹脂層Ｂ、を含む積層フィルムである。 As is clear from the above embodiments, the process release film of the present invention (hereinafter also simply referred to as “release film”) includes a release layer A having release properties for molded products and molds, and, if desired, It is a laminated film including a release layer A ′ and a heat-resistant resin layer B that supports the release layer.
本発明のプロセス用離型フィルムは、成形金型の内部で半導体素子等を樹脂封止するときに、成形金型の内面に配置される。このとき、離型フィルムの離型層Ａ（離型層Ａ’が存在する場合には離型層Ａ’であってもよい）を、樹脂封止される半導体素子等（成形品）側に配置することが好ましい。本発明の離型フィルムを配置することで、樹脂封止された半導体素子等を、金型から容易に離型することができる。
離型層Ａの水に対する接触角は、９０°から１３０°であり、この様な接触角を有することにより離型層Ａは濡れ性が低く、硬化した封止樹脂や金型表面に固着することなく、成形品を容易に離型することができる。
離型層Ａの水に対する接触角は、好ましくは９５°から１２０°であり、より好ましくは９８°から１１５°、更に好ましくは１００°から１１０°である。
The process release film of the present invention is disposed on the inner surface of a molding die when a semiconductor element or the like is resin-sealed inside the molding die. At this time, the release layer A of the release film (or the release layer A ′ when the release layer A ′ is present) may be placed on the resin-encapsulated semiconductor element or the like (molded product) side. It is preferable to arrange. By disposing the release film of the present invention, a resin-sealed semiconductor element or the like can be easily released from the mold.
The contact angle of the release layer A with respect to water is 90 ° to 130 °. By having such a contact angle, the release layer A has low wettability and adheres to the cured sealing resin or the mold surface. Without this, the molded product can be easily released.
The contact angle of the release layer A with respect to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.
前記の通り、離型層Ａ（場合によっては離型層Ａ’）は成形品側に配置されるので、樹脂封止工程における離型層Ａ（場合によっては離型層Ａ’）での皺の発生を抑制することが好ましい。発生した皺が成形品に転写されて、成形品の外観不良が生じる可能性が高いためである。 As described above, since the release layer A (in some cases, the release layer A ′) is disposed on the molded product side, the mold in the release layer A (in some cases, the release layer A ′) in the resin sealing step. It is preferable to suppress the occurrence of. This is because the generated wrinkles are transferred to the molded product and the appearance defect of the molded product is highly likely to occur.
本発明においては、上記目的を達成するために、プロセス用離型フィルムを構成する積層フィルムとして、離型層Ａ（及び所望により離型層Ａ’）、並びに該離型層を支持する耐熱樹脂層Ｂ、を含む積層フィルムであって、その横（ＴＤ）方向の熱寸法変化率が特定の値を示す積層フィルムを用いる。
すなわち、離型層Ａ（及び所望により離型層Ａ’）、並びに該離型層を支持する耐熱樹脂層Ｂ、を含む積層フィルムは、そのＴＤ方向（横方向）の２３℃から１２０℃までの熱寸法変化率が３％以下であるか、又は、そのＴＤ方向（横方向）の２３℃から１７０℃までの熱寸法変化率が４％以下である。さらに、前記積層フィルムは、ＴＤ方向（横方向）の２３℃から１２０℃までの熱寸法変化率が３％以下であってかつＴＤ方向（横方向）の２３℃から１７０℃までの熱寸法変化率が４％以下であることがより好ましい。
上記積層フィルムのＴＤ方向（横方向）の２３℃から１２０℃までの熱寸法変化率が３％以下であるか、又は、そのＴＤ方向（横方向）の２３℃から１７０℃までの熱寸法変化率が４％以下であることにより、樹脂封止工程等における離型層の皺の発生を有効に抑制することができる。プロセス用離型フィルムを構成する積層フィルムとして横（ＴＤ）方向の熱寸法変化率が上記の特定の値を示すもの用いることで、離型層の皺の発生が抑制されるメカニズムは必ずしも明らかではないが、比較的熱膨張／収縮の小さい積層フィルムを用いることにより、プロセス時の加熱／冷却による離型層Ａ（又は離型層Ａ’）の熱膨張／収縮が抑制されることと関連があるものと推測される。
In the present invention, in order to achieve the above object, as the laminated film constituting the process release film, the release layer A (and the release layer A ′ if necessary) and the heat-resistant resin that supports the release layer A laminated film including the layer B, which has a specific value in the rate of thermal dimensional change in the transverse (TD) direction is used.
That is, the laminated film including the release layer A (and the release layer A ′ if necessary) and the heat-resistant resin layer B that supports the release layer is from 23 ° C. to 120 ° C. in the TD direction (lateral direction). The rate of thermal dimensional change in the TD direction (lateral direction) from 23 ° C. to 170 ° C. is 4% or less. Further, the laminated film has a thermal dimensional change rate of 23% to 120 ° C. in the TD direction (lateral direction) of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The rate is more preferably 4% or less.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of the laminated film is 3% or less, or the thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). When the rate is 4% or less, generation of wrinkles in the release layer in the resin sealing step or the like can be effectively suppressed. The mechanism that suppresses the occurrence of wrinkles in the release layer is not always clear by using a film having a specific rate of thermal dimensional change in the transverse (TD) direction as a laminated film constituting the release film for the process. However, there is a relation with the fact that the thermal expansion / contraction of the release layer A (or the release layer A ′) due to heating / cooling during the process is suppressed by using a laminated film having relatively small thermal expansion / shrinkage. Presumed to be.
本発明のプロセス用離型フィルムを構成する積層フィルムは、そのＴＤ方向（横方向）の２３℃から１２０℃までの熱寸法変化率が２．５％以下であることが好ましく、２．０％以下であることより好ましく、１．５％以下であることが更に好ましくい。一方、積層フィルムは、そのＴＤ方向（横方向）の２３℃から１２０℃までの熱寸法変化率が−５．０％以上であることが好ましい。
本発明のプロセス用離型フィルムを構成する積層フィルムは、そのＴＤ方向（横方向）の２３℃から１７０℃までの熱寸法変化率が３．５％以下であることが好ましく、３．０％以下であることがより好ましく、２．０％以下であることが更に好ましくい。一方、積層フィルムは、そのＴＤ方向（横方向）の２３℃から１７０℃までの熱寸法変化率が−５．０％以上であることが好ましい。
In the laminated film constituting the process release film of the present invention, the thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) is preferably 2.5% or less, and 2.0% Or less, and more preferably 1.5% or less. On the other hand, the laminated film preferably has a thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of −5.0% or more.
In the laminated film constituting the process release film of the present invention, the thermal dimensional change rate from 23 ° C. to 170 ° C. in the TD direction (lateral direction) is preferably 3.5% or less, 3.0% More preferably, it is more preferably 2.0% or less. On the other hand, the laminated film preferably has a thermal dimensional change rate from 23 ° C. to 170 ° C. in the TD direction (lateral direction) of −5.0% or more.
耐熱樹脂層Ｂとして、横（ＴＤ）方向の熱寸法変化率が上記の特定の値を示す樹脂層を用いることで、より効果的に離型層の皺の発生が抑制されるメカニズムは必ずしも明らかではないが、比較的熱膨張／収縮の小さい耐熱樹脂層Ｂを用いることにより、プロセス時の加熱／冷却による離型層Ａ（又は離型層Ａ’）の熱膨張／収縮が抑制されることと関連があるものと推測される。 The mechanism by which the generation of wrinkles in the release layer is more effectively suppressed by using a resin layer in which the thermal dimensional change rate in the transverse (TD) direction exhibits the above specific value as the heat resistant resin layer B is not necessarily clear. However, the thermal expansion / contraction of the release layer A (or release layer A ′) due to heating / cooling during the process is suppressed by using the heat-resistant resin layer B having relatively small thermal expansion / contraction. It is presumed to be related.
離型層Ａ（及び所望により離型層Ａ’）、並びに該離型層を支持する耐熱樹脂層Ｂ、を含む積層フィルムである本発明のプロセス用離型フィルムは、そのＴＤ方向（横方向）の熱寸法変化率とＭＤ方向（フィルムの製造時の長手方向。以下、「縦方向」ともいう）の熱寸法変化率の和が特定の値以下であることが好ましい。
すなわち、上記積層フィルムの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１２０℃までの熱寸法変化率の和は、６％以下であることが好ましく、一方、前記積層フィルムは、そのＴＤ方向（横方向）の２３℃から１２０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１２０℃までの熱寸法変化率の和が−５．０％以上であることが好ましい。
離型層Ａ（及び所望により離型層Ａ’）、並びに耐熱樹脂層Ｂ、を含む積層フィルムの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１２０℃までの熱寸法変化率の和が６％以下であることにより、金型内面に装着された際の皺の発生を一層有効に抑制することができる。
The process release film of the present invention, which is a laminated film including the release layer A (and release layer A ′ if necessary) and the heat-resistant resin layer B that supports the release layer, has a TD direction (lateral direction). ) And the dimensional change rate in the MD direction (longitudinal direction during production of the film; hereinafter referred to as “longitudinal direction”) are preferably not more than a specific value.
That is, the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less. On the other hand, the laminated film is the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the vertical (MD) direction. Is preferably −5.0% or more.
The rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction and the longitudinal (MD) direction of the laminated film including the release layer A (and release layer A ′ if necessary) and the heat-resistant resin layer B. When the sum of the thermal dimensional change rates from 23 ° C. to 120 ° C. is 6% or less, generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.
また、離型層Ａ（及び所望により離型層Ａ’）、並びに耐熱樹脂層Ｂ、を含む積層フィルムの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１７０℃までの熱寸法変化率の和は、７％以下であることが好ましく、一方、前記積層フィルムは、そのＴＤ方向（横方向）の２３℃から１７０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１７０℃までの熱寸法変化率の和が−５．０％以上であることが好ましい。
上記積層フィルムの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率と縦（ＭＤ）方向の２３℃から１７０℃までの熱寸法変化率の和が７％以下であることにより、金型内面に装着された際の皺の発生を更に有効に抑制することができる。
Further, the thermal dimensional change rate and longitudinal (MD) from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film including the release layer A (and release layer A ′ if necessary) and the heat-resistant resin layer B. The sum of the thermal dimensional change rates from 23 ° C. to 170 ° C. in the direction is preferably 7% or less, while the laminated film has a thermal dimension from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The sum of the rate of change and the rate of change in thermal dimension from 23 ° C. to 170 ° C. in the machine direction (MD) is preferably −5.0% or more.
By the sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction being 7% or less, Generation of wrinkles when mounted on the inner surface of the mold can be further effectively suppressed.
離型層Ａ
本発明のプロセス用離型フィルムを構成する離型層Ａは、水に対する接触角が、９０°から１３０°であり、好ましくは９５°から１２０°であり、より好ましくは９８°から１１５°、更に好ましくは１００°から１１０°である。成形品の離型性に優れること、入手の容易さなどから、フッ素樹脂、４−メチル−１−ペンテン（共）重合体、及びポリスチレン系樹脂からなる群より選ばれる樹脂を含むことが好ましい。
Release layer A
The release layer A constituting the process release film of the present invention has a water contact angle of 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115 °, More preferably, the angle is 100 ° to 110 °. It is preferable that the resin contains a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene-based resin because of excellent mold releasability and availability.
離型層Ａに用いることができるフッ素樹脂は、テトラフルオロエチレンに由来する構成単位を含む樹脂であってもよい。テトラフルオロエチレンの単独重合体であってもよいが、他のオレフィンとの共重合体であってもよい。他のオレフィンの例には、エチレンが含まれる。モノマー構成単位としてテトラフルオロエチレンとエチレンとを含む共重合体は好ましい一例であり、この様な共重合体においては、テトラフルオロエチレンに由来する構成単位の割合が５５〜１００質量％であり、エチレンに由来する構成単位の割合が０〜４５質量％であることが好ましい。 The fluororesin that can be used for the release layer A may be a resin containing a structural unit derived from tetrafluoroethylene. Although it may be a homopolymer of tetrafluoroethylene, it may be a copolymer with other olefins. Examples of other olefins include ethylene. A copolymer containing tetrafluoroethylene and ethylene as monomer constitutional units is a preferred example. In such a copolymer, the proportion of constitutional units derived from tetrafluoroethylene is 55 to 100% by mass, and ethylene The proportion of the structural unit derived from is preferably 0 to 45% by mass.
離型層Ａに用いることができる４−メチル−１−ペンテン（共）重合体は、４−メチル−１−ペンテンの単独重合体であってもよく、また４−メチル−１−ペンテンと、それ以外の炭素原子数２〜２０のオレフィン（以下「炭素原子数２〜２０のオレフィン」という）との共重合体であってもよい。 The 4-methyl-1-pentene (co) polymer that can be used for the release layer A may be a homopolymer of 4-methyl-1-pentene, and 4-methyl-1-pentene, It may be a copolymer with other olefins having 2 to 20 carbon atoms (hereinafter referred to as “olefins having 2 to 20 carbon atoms”).
４−メチル−１−ペンテンと、炭素原子数２〜２０のオレフィンとの共重合体の場合、４−メチル−１−ペンテンと共重合される炭素原子数２〜２０のオレフィンは、４−メ
チル−１−ペンテンに可とう性を付与し得る。炭素原子数２〜２０のオレフィンの例には、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−テトラデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−エイコセン等が含まれる。これらのオレフィンは、１種のみを用いてもよいし、２種以上を組み合せて用いてもよい。
In the case of a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, the olefin having 2 to 20 carbon atoms copolymerized with 4-methyl-1-pentene is 4-methyl -1-Pentene can be given flexibility. Examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, -Octadecene, 1-eicosene and the like are included. These olefins may be used alone or in combination of two or more.
４−メチル−１−ペンテンと、炭素原子数２〜２０のオレフィンとの共重合体の場合、４−メチル−１−ペンテンに由来する構成単位の割合が９６〜９９質量％であり、それ以外の炭素原子数２〜２０のオレフィンに由来する構成単位の割合が１〜４質量％であることが好ましい。炭素原子数２〜２０のオレフィン由来の構成単位の含有量が少なくすることで、共重合体を硬く、すなわち貯蔵弾性率Ｅ’が高くすることができ、封止工程等における皺が発生の抑制に有利である。一方、炭素原子数２〜２０のオレフィン由来の構成単位の含有量が多くすることで、共重合体を軟らかく、すなわち貯蔵弾性率Ｅ’を低くすることができ、金型追従性を向上させるのに有利である。 In the case of a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, the proportion of structural units derived from 4-methyl-1-pentene is 96 to 99% by mass, otherwise It is preferable that the ratio of the structural unit derived from the olefin of 2-20 carbon atoms is 1-4 mass%. By reducing the content of structural units derived from olefins having 2 to 20 carbon atoms, the copolymer can be hardened, that is, the storage elastic modulus E ′ can be increased, and the occurrence of wrinkles in the sealing process and the like can be suppressed. Is advantageous. On the other hand, by increasing the content of structural units derived from olefins having 2 to 20 carbon atoms, the copolymer can be softened, that is, the storage elastic modulus E ′ can be lowered, and the mold followability can be improved. Is advantageous.
４−メチル−１−ペンテン（共）重合体は、当業者において公知の方法で製造されうる。例えば、チーグラ・ナッタ触媒、メタロセン系触媒等の公知の触媒を用いた方法により製造されうる。４−メチル−１−ペンテン（共）重合体は、結晶性の高い（共）重合体であることが好ましい。結晶性の共重合体としては、アイソタクチック構造を有する共重合体、シンジオタクチック構造を有する共重合体のいずれであってもよいが、特にアイソタクチック構造を有する共重合体であることが物性の点からも好ましく、また入手も容易である。さらに、４−メチル−１−ペンテン（共）重合体は、フィルム状に成形でき、金型成形時の温度や圧力等に耐える強度を有していれば、立体規則性や分子量も、特に制限されない。４−メチル−１−ペンテン共重合体は、例えば、三井化学株式会社製ＴＰＸ（登録商標）等、市販の共重合体であってもよい。 4-Methyl-1-pentene (co) polymer can be prepared by methods known to those skilled in the art. For example, it can be produced by a method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. The 4-methyl-1-pentene (co) polymer is preferably a (co) polymer with high crystallinity. The crystalline copolymer may be either a copolymer having an isotactic structure or a copolymer having a syndiotactic structure, but in particular a copolymer having an isotactic structure. Is preferable from the viewpoint of physical properties and is easily available. Furthermore, if 4-methyl-1-pentene (co) polymer can be formed into a film and has the strength to withstand the temperature and pressure during molding, the stereoregularity and molecular weight are also particularly limited. Not. The 4-methyl-1-pentene copolymer may be a commercially available copolymer such as TPX (registered trademark) manufactured by Mitsui Chemicals, Inc.
離型層Ａに用いることができるポリスチレン系樹脂には、スチレンの単独重合体及び共重合体が包含され、その重合体中に含まれるスチレン由来の構造単位は少なくとも６０重量％以上であることが好ましく、より好ましくは８０重量％以上である。
ポリスチレン系樹脂は、アイソタクチックポリスチレンであってもシンジオタクチックポリスチレンであってもよいが、透明性、入手の容易さなどの観点からはアイソタクチックポリスチレンが好ましく、離型性、耐熱性などの観点からは、シンジオタクチックポリスチレンが好ましい。ポリスチレンは、１種を単独で用いてもよく、２種以上を併用してもよい。
Polystyrene resins that can be used for the release layer A include styrene homopolymers and copolymers, and the structural unit derived from styrene contained in the polymer is at least 60% by weight or more. Preferably, it is 80% by weight or more.
The polystyrene resin may be isotactic polystyrene or syndiotactic polystyrene, but is preferably isotactic polystyrene from the viewpoint of transparency, availability, release properties, heat resistance, etc. From this point of view, syndiotactic polystyrene is preferable. Polystyrene may be used alone or in combination of two or more.
離型層Ａは、成形時の金型の温度（典型的には１２０〜１８０℃）に絶え得る耐熱性を有することが好ましい。かかる観点から、離型層Ａとしては、結晶成分を有する結晶性樹脂を含むことが好ましく、当該結晶性樹脂の融点は１９０℃以上であることが好ましく、２００℃以上３００℃以下がより好ましい。
離型層Ａに結晶性をもたらすため、例えばフッ素樹脂においてはテトラフルオロエチレンから導かれる構成単位を少なくとも含むことが好ましく、４−メチル−１−ペンテン（共）重合体においては４−メチル−１−ペンテンから導かれる構成単位を少なくとも含むことが好ましく、ポリスチレン系樹脂においてはシンジオタクチックポリスチレンを少なくとも含むことが好ましい。離型層Ａを構成する樹脂に結晶成分が含まれることにより、樹脂封止工程等において皺が発生し難く、皺が成形品に転写されて外観不良を生じることを抑制するのに好適である。
It is preferable that the release layer A has heat resistance that can withstand the temperature of the mold during molding (typically 120 to 180 ° C.). From this point of view, the release layer A preferably contains a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 190 ° C. or higher, more preferably 200 ° C. or higher and 300 ° C. or lower.
In order to bring the crystallinity to the release layer A, for example, a fluororesin preferably contains at least a structural unit derived from tetrafluoroethylene, and a 4-methyl-1-pentene (co) polymer has 4-methyl-1 -It is preferable to contain at least the structural unit derived from pentene, and it is preferable to contain at least syndiotactic polystyrene in the polystyrene-based resin. By including a crystal component in the resin constituting the release layer A, it is difficult for wrinkles to occur in the resin sealing process and the like, and it is suitable for suppressing wrinkles from being transferred to a molded product to cause poor appearance. .
離型層Ａを構成する上記結晶性成分を含む樹脂は、ＪＩＳＫ７２２１に準じて示差走査熱量測定（ＤＳＣ）によって測定した第１回昇温工程での結晶融解熱量が１５Ｊ／ｇ以上、６０Ｊ／ｇ以下であることが好ましく、２０Ｊ／ｇ以上、５０Ｊ／ｇ以下であることがより好ましい。１５Ｊ／ｇ以上であると、樹脂封止工程等での熱プレス成形に耐え得る耐熱性及び離型性をより効果的に発現することが可能であることに加え、寸法変化率も抑制することができるため、皺の発生も防止することができる。一方、前記結晶融解熱量が６０Ｊ／ｇ以下であると、離型層Ａが適切な硬度となるため、樹脂封止工程等においてフィルムの金型への十分な追随性を得ることができるため、フィルムの破損のおそれもない。 The resin containing the crystalline component constituting the release layer A has a heat of crystal melting in the first heating step measured by differential scanning calorimetry (DSC) according to JIS K7221 and is from 15 J / g to 60 J / g. It is preferable that it is 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, in addition to being able to more effectively express heat resistance and releasability that can withstand hot press molding in the resin sealing step, etc., it also suppresses the dimensional change rate. Therefore, generation of wrinkles can be prevented. On the other hand, if the heat of crystal fusion is 60 J / g or less, the release layer A has an appropriate hardness, so that sufficient followability to the mold of the film can be obtained in the resin sealing step or the like. There is no risk of film damage.
離型層Ａは、フッ素樹脂、４−メチル−１−ペンテン共重合体、及び／又はポリスチレン系樹脂の他に、さらに他の樹脂を含んでもよい。この場合、他の樹脂の硬度が比較的高いことが好ましい。他の樹脂の例には、ポリアミド−６、ポリアミド−６６、ポリブチレンテレフタレート、ポリエチレンテレフタレートが含まれる。このように、離型層Ａが、例えば柔らかい樹脂を多く含む場合（例えば、４−メチル−１−ペンテン共重合体において炭素原子数２〜２０のオレフィンを多く含む場合）でも、硬度の比較的高い樹脂をさらに含むことで、離型層Ａを硬くすることができ、封止工程等における皺が発生の抑制に有利である。 The release layer A may further contain other resin in addition to the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin. In this case, it is preferable that the hardness of the other resin is relatively high. Examples of other resins include polyamide-6, polyamide-66, polybutylene terephthalate, and polyethylene terephthalate. Thus, even when the release layer A contains a lot of soft resin (for example, when the 4-methyl-1-pentene copolymer contains a lot of olefins having 2 to 20 carbon atoms), the hardness of the release layer A is relatively high. By further including a high resin, the release layer A can be hardened, which is advantageous in suppressing wrinkles in the sealing process and the like.
これらの他の樹脂の含有量は、離型層Ａを構成する樹脂成分に対して例えば３〜３０質量％であることが好ましい。他の樹脂の含有量を３質量以上とすることで、添加による効果を実質的なものとすることができ、３０質量％以下とすることで、金型や成形品に対する離型性を維持することができる。 It is preferable that content of these other resin is 3-30 mass% with respect to the resin component which comprises the mold release layer A, for example. By setting the content of other resins to 3 mass or more, the effect of addition can be made substantial, and by setting the content to 30 mass% or less, the releasability for a mold or a molded product is maintained. be able to.
また離型層Ａは、フッ素樹脂、４−メチル−１−ペンテン（共）重合体、及び／又はポリスチレン系樹脂に加えて、本発明の目的を損なわない範囲で、耐熱安定剤、耐候安定剤、発錆防止剤、耐銅害安定剤、帯電防止剤等、フィルム用樹脂に一般的に配合される公知の添加剤を含んでもよい。これらの添加剤の含有量は、フッ素樹脂、４−メチル−１−ペンテン共重合体、及び／又はポリスチレン系樹脂１００重量部に対して、例えば０．０００１〜１０重量部とすることができる。 In addition to the fluororesin, 4-methyl-1-pentene (co) polymer, and / or polystyrene resin, the release layer A is a heat-resistant stabilizer and a weather-resistant stabilizer as long as the object of the present invention is not impaired. Further, known additives generally blended in a resin for a film, such as a rust inhibitor, a copper damage resistance stabilizer, and an antistatic agent, may be included. The content of these additives can be, for example, 0.0001 to 10 parts by weight with respect to 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.
離型層Ａの厚みは、成形品に対する離型性が十分であれば、特に制限はないが、通常１〜５０μｍであり、好ましくは５〜３０μｍである。 Although there will be no restriction | limiting in particular if the release property with respect to a molded article is enough, the thickness of the mold release layer A is 1-50 micrometers normally, Preferably it is 5-30 micrometers.
離型層Ａの表面は、必要に応じて凹凸形状を有していてもよく、それにより離型性を向
上させることができる。離型層Ａの表面に凹凸を付与する方法は、特に制限はないが、エ
ンボス加工等の一般的な方法が採用できる。
The surface of the release layer A may have a concavo-convex shape as necessary, thereby improving the releasability. The method for imparting irregularities to the surface of the release layer A is not particularly limited, but a general method such as embossing can be employed.
離型層Ａ’
本発明のプロセス用離型フィルムは、離型層Ａ及び耐熱樹脂層Ｂに加えて、更に離型層Ａ’を有していてもよい。すなわち、本発明のプロセス用離型フィルムは、離型層Ａと、耐熱樹脂層Ｂと、離型層Ａ’とをこの順で含む積層フィルムであるプロセス用離型フィルムであってもよい。
本発明のプロセス用離型フィルムを構成してもよい離型層Ａ’の水に対する接触角は、９０°から１３０°であり、好ましくは９５°から１２０°であり、より好ましくは９８°から１１５°、更に好ましくは１００°から１１０°である。そして、離型層Ａ’の好ましい材質、構成、物性等は、上記において離型層Ａについて説明したものと同様である。
Release layer A '
In addition to the release layer A and the heat-resistant resin layer B, the process release film of the present invention may further have a release layer A ′. That is, the process release film of the present invention may be a process release film that is a laminated film including the release layer A, the heat-resistant resin layer B, and the release layer A ′ in this order.
The contact angle with respect to water of the release layer A ′ that may constitute the process release film of the present invention is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 °. 115 °, more preferably 100 ° to 110 °. The preferable material, configuration, physical properties, and the like of the release layer A ′ are the same as those described for the release layer A above.
プロセス用離型フィルムが、離型層Ａと、耐熱樹脂層Ｂと、離型層Ａ’とをこの順で含む積層フィルムである場合の離型層Ａと離型層Ａ’とは同一の構成の層であってもよいし、異なる構成の層であってもよい。
反りの防止や、いずれの面も同様の離型性を有することによる取り扱いの容易さ等の観点からは、離型層Ａと離型層Ａ’とは同一または略同一の構成であることが好ましく、離型層Ａと離型層Ａ’とを使用するプロセスとの関係でそれぞれ最適に設計する観点、例えば、離型層Ａを金型からの離型性に優れたものとし、離型層Ａ’を成形物からの剥離性に優れたものとする等の観点からは、離型層Ａと離型層Ａ’とを異なる構成のものとすることが好ましい。
離型層Ａと離型層Ａ’とを異なる構成のものとする場合には、離型層Ａと離型層Ａ’とを同一の材料であって厚み等の構成が異なるものとしてもよいし、材料もそれ以外の構成も異なるものとしてもよい。
The release layer A and the release layer A ′ are the same when the release film for the process is a laminated film including the release layer A, the heat-resistant resin layer B, and the release layer A ′ in this order. It may be a layer having a different structure or a layer having a different structure.
From the standpoints of warpage prevention and ease of handling due to the same release properties on both surfaces, the release layer A and the release layer A ′ may have the same or substantially the same configuration. Preferably, from the viewpoint of optimal design in relation to the process of using the release layer A and the release layer A ′, for example, the release layer A has excellent release properties from the mold. From the viewpoint of making the layer A ′ excellent in releasability from the molded product, it is preferable that the release layer A and the release layer A ′ have different structures.
When the release layer A and the release layer A ′ have different configurations, the release layer A and the release layer A ′ may be made of the same material and have different configurations such as thickness. However, the materials and other configurations may be different.
耐熱樹脂層Ｂ
本発明のプロセス用離型フィルムを構成する耐熱樹脂層Ｂは、離型層Ａ（及び場合により離型層Ａ’）を支持し、かつ金型温度等による皺発生を抑制する機能を有する。
本発明のプロセス用離型フィルムにおいては、耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下であるか、又は耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が３％以下であることが好ましい。さらに、耐熱樹脂層Ｂは、その横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下であってかつ横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が３％以下であることがより好ましい。
耐熱樹脂層Ｂには、無延伸フィルムも含め任意の樹脂層を用いることができるが、延伸フィルムを含んでなることが特に好ましい。
延伸フィルムは、製造のプロセスにおける延伸の影響で、熱膨張率が低いか又は負となる傾向があり、横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下であるか、又は耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が３％以下であるという特性を実現することが比較的容易であるので、耐熱樹脂層Ｂとして好適に使用することができる。
耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率は、２％以下であることが好ましく、１．５％以下であることがより好ましく、１％以下であることが更に好ましく、一方、−１０％以上であることが好ましい。
耐熱樹脂層Ｂの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率は、２％以下であることが好ましく、１．５％以下であることがより好ましく、１％以下であることが更に好ましく、一方、−１０％以上であることが好ましい。
Heat resistant resin layer B
The heat-resistant resin layer B constituting the process release film of the present invention has a function of supporting the release layer A (and possibly the release layer A ′) and suppressing wrinkle generation due to mold temperature and the like.
In the release film for a process of the present invention, the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is 3% or less, or the transverse (TD It is preferable that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the) direction is 3% or less. Further, the heat resistant resin layer B has a thermal dimensional change rate of 23% to 120 ° C. in the transverse (TD) direction of 3% or less and a thermal dimensional change of 23 ° C. to 170 ° C. in the transverse (TD) direction. The rate is more preferably 3% or less.
Although any resin layer including an unstretched film can be used for the heat resistant resin layer B, it is particularly preferable that the heat resistant resin layer B comprises a stretched film.
The stretched film tends to have a low or negative coefficient of thermal expansion due to the influence of stretching in the manufacturing process, and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction is 3% or less. Alternatively, it is relatively easy to realize the characteristic that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer B is 3% or less. It can be preferably used.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.
The rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.
上記延伸フィルムは、一軸延伸フィルムであってもよく、二軸延伸フィルムであってもよい。一軸延伸フィルムである場合には、縦延伸、横延伸のいずれであっても良いが、少なくとも横（ＴＤ）方向に延伸が行われたものであることが望ましい。
上記延伸フィルムを得るための方法、装置にも特に限定は無く、当業界において公知の方法で延伸を行えばよい。例えば、加熱ロールやテンター式延伸機で延伸することができる。
The stretched film may be a uniaxially stretched film or a biaxially stretched film. In the case of a uniaxially stretched film, either longitudinal stretching or lateral stretching may be used, but it is desirable that stretching is performed at least in the transverse (TD) direction.
The method and apparatus for obtaining the stretched film are not particularly limited, and stretching may be performed by a method known in the art. For example, it can be stretched with a heating roll or a tenter stretching machine.
上記延伸フィルムとしては、延伸ポリエステルフィルム、延伸ポリアミドフィルム、及び延伸ポリプロピレンフィルムからなる群より選ばれる延伸フィルムを使用することが好ましい。これらの延伸フィルムは、延伸により、横（ＴＤ）方向の熱膨張率を低下させ、又は負とすることが比較的容易であり、機械的物性が本発明の用途に適したものであり、また低コストで入手が比較的容易であるため、耐熱樹脂層Ｂにおける延伸フィルムとして特に好適である。 As the stretched film, it is preferable to use a stretched film selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film. These stretched films are relatively easy to reduce the thermal expansion coefficient in the transverse (TD) direction or to be negative by stretching, and the mechanical properties are suitable for the use of the present invention. Since it is inexpensive and relatively easy to obtain, it is particularly suitable as a stretched film in the heat-resistant resin layer B.
延伸ポリエステルフィルムとしては、延伸ポリエチレンテレフタレート（ＰＥＴ）フィルム、延伸ポリブチレンテレフタレート（ＰＢＴ）フィルムが好ましく、二軸延伸ポリエチレンテレフタレート（ＰＥＴ）フィルムが特に好ましい。
延伸ポリアミドフィルムを構成するポリアミドには特に限定は無いが、ポリアミド−６、ポリアミド−６６等を好ましく用いることができる。
延伸ポリプロピレンフィルムとしては、一軸延伸ポリプロピレンフィルム、二軸延伸ポリプロピレンフィルム等を好ましく用いることができる。
延伸倍率には特に限定はなく、熱寸法変化率を適切に制御し、好適な機械的性質を実現するために適切な値を適宜設定すれば良いが、例えば延伸ポリエステルフィルムの場合は、縦方向、横方向ともに２．７〜８．０倍の範囲であることが好ましく、延伸ポリアミドフィルムの場合は、縦方向、横方向ともに２．７〜５．０倍の範囲であることが好ましく、延伸ポリプロピレンフィルムの場合は、二軸延伸ポリプロピレンフィルムの場合は、縦方向、横方向ともに５．０〜１０．０倍の範囲であることが好ましく、一軸延伸ポリプロピレンフィルムの場合は、縦方向に１．５〜１０．０倍の範囲であることが好ましい。
As the stretched polyester film, a stretched polyethylene terephthalate (PET) film and a stretched polybutylene terephthalate (PBT) film are preferable, and a biaxially stretched polyethylene terephthalate (PET) film is particularly preferable.
Although there is no limitation in particular in the polyamide which comprises a stretched polyamide film, Polyamide-6, polyamide-66, etc. can be used preferably.
As the stretched polypropylene film, a uniaxially stretched polypropylene film, a biaxially stretched polypropylene film, or the like can be preferably used.
There is no particular limitation on the draw ratio, and the thermal dimensional change rate can be appropriately controlled, and an appropriate value may be set as appropriate in order to achieve suitable mechanical properties. For example, in the case of a stretched polyester film, the machine direction In the case of a stretched polyamide film, it is preferably in the range of 2.7 to 5.0 times in both the longitudinal direction and the transverse direction. In the case of a polypropylene film, in the case of a biaxially stretched polypropylene film, it is preferably in the range of 5.0 to 10.0 times in both the machine direction and the transverse direction. The range is preferably 5 to 10.0 times.
耐熱樹脂層Ｂは、フィルムの強度や、その熱寸法変化率を適切な範囲に制御する観点から、成形時の金型の温度（典型的には１２０〜１８０℃）に絶え得る耐熱性を有することが好ましい。かかる観点から、耐熱樹脂層Ｂは、結晶成分を有する結晶性樹脂を含むことが好ましく、当該結晶性樹脂の融点は１２５℃以上であることが好ましく、融点が１５５℃以上３００℃以下であることがより好ましく、１８５以上２１０℃以下であることが更に好ましく、１８５以上２０５℃以下であることが特に好ましい。 The heat-resistant resin layer B has heat resistance that can withstand the mold temperature (typically 120 to 180 ° C.) at the time of molding from the viewpoint of controlling the strength of the film and the thermal dimensional change rate to an appropriate range. It is preferable. From this viewpoint, the heat-resistant resin layer B preferably contains a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 125 ° C. or higher, and the melting point is 155 ° C. or higher and 300 ° C. or lower. Is more preferably 185 to 210 ° C., and particularly preferably 185 to 205 ° C.
上述の様に、耐熱樹脂層Ｂは結晶成分を有する結晶性樹脂を含むことが好ましい。耐熱樹脂層Ｂに含有させる結晶性樹脂として、例えばポリエステル樹脂、ポリアミド樹脂、ポリプロピレン樹脂等の結晶性樹脂をその一部または全部に用いることができる。具体的にはポリエステル樹脂においてはポリエチレンテレフタレートまたはポリブチレンテレフタレート、ポリアミド樹脂においてはポリアミド６やポリアミド６６、ポリプロピレン樹脂においてはアイソタクチックポリプロピレンを用いることが好ましい。 As described above, the heat resistant resin layer B preferably contains a crystalline resin having a crystalline component. As the crystalline resin to be contained in the heat-resistant resin layer B, for example, a crystalline resin such as a polyester resin, a polyamide resin, or a polypropylene resin can be used for a part or all thereof. Specifically, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 or polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.
耐熱樹脂層Ｂに前記結晶性樹脂の結晶成分を含ませることにより、樹脂封止工程等において皺が発生し難く、皺が成形品に転写されて外観不良を生じることを抑制するのにより有利となる。
耐熱樹脂層Ｂを構成する樹脂は、ＪＩＳＫ７２２１に準じて示差走査熱量測定（ＤＳＣ）によって測定した第１回昇温工程での結晶融解熱量が２０Ｊ／ｇ以上、１００Ｊ／ｇ以下であることが好ましく、２５Ｊ／ｇ以上、６５Ｊ／ｇ以下であることがより好ましく、２５Ｊ／ｇ以上、５５Ｊ／ｇ以下であることがより好ましく、２８Ｊ／ｇ以上、５０Ｊ／ｇ以下であることがより好ましく、２８Ｊ／ｇ以上、４０Ｊ／ｇ以下であることがより好ましく、２８Ｊ／ｇ以上、３５Ｊ／ｇ以下であることがさらに好ましい。２０Ｊ／ｇ以上であると、樹脂封止工程等での熱プレス成形に耐え得る耐熱性及び離型性を効果的に発現させることができ、また寸法変化率も僅少に抑制することができるため、皺の発生も防止することができる。一方、前記結晶融解熱量が１００Ｊ／ｇ以下であることにより、耐熱樹脂層Ｂに適度な硬度を付与することができるため樹脂封止工程等においてフィルムの十分な金型への追随性が確保することができることに加えフィルムが破損しやすくなるおそれもない。なお、本実施形態において、結晶融解熱量とは、ＪＩＳＫ７２２１に準じて示差走査熱量測定（ＤＳＣ）による測定での第１回昇温工程で得られた縦軸の熱量（Ｊ／ｇ）と横軸の温度（℃）との関係を示すチャート図において、１２０℃以上でピークを有するピーク面積の和によって求められる数値をいう。
耐熱樹脂層Ｂの結晶融解熱量は、フィルム製造時の加熱、冷却の条件や、延伸の条件を適宜設定することで調節することができる。
By including a crystalline component of the crystalline resin in the heat-resistant resin layer B, it is more advantageous to suppress the occurrence of defects in the resin sealing process and the like, and to suppress the appearance of defects due to the transfer of defects to the molded product. Become.
The resin constituting the heat-resistant resin layer B preferably has a heat of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) in accordance with JISK7221 being 20 J / g or more and 100 J / g or less. It is more preferably 25 J / g or more and 65 J / g or less, more preferably 25 J / g or more and 55 J / g or less, more preferably 28 J / g or more and 50 J / g or less, and more preferably 28 J / g g or more and 40 J / g or less is more preferable, and 28 J / g or more and 35 J / g or less is more preferable. When it is 20 J / g or more, it is possible to effectively exhibit heat resistance and releasability that can withstand hot press molding in a resin sealing process and the like, and the dimensional change rate can be slightly suppressed. The occurrence of wrinkles can also be prevented. On the other hand, since the heat of crystal fusion is 100 J / g or less, the heat resistant resin layer B can be provided with an appropriate hardness, so that sufficient followability of the film to the mold is ensured in the resin sealing step and the like. In addition to being able to do so, there is no risk of the film being easily damaged. In the present embodiment, the crystal melting calorie is the calorific value (J / g) on the vertical axis obtained in the first heating step in the differential scanning calorimetry (DSC) measurement according to JISK7221 and the horizontal axis. In the chart showing the relationship with temperature (° C.), it is a numerical value obtained by the sum of peak areas having a peak at 120 ° C. or higher.
The heat of crystal fusion of the heat-resistant resin layer B can be adjusted by appropriately setting the heating and cooling conditions and the stretching conditions during film production.
耐熱樹脂層Ｂの厚みは、フィルム強度を確保できれば、特に制限はないが、通常１〜１
００μｍ、好ましくは５〜５０μｍである。
The thickness of the heat-resistant resin layer B is not particularly limited as long as the film strength can be secured, but usually 1-1.
It is 00 μm, preferably 5 to 50 μm.
それ以外の層
本発明のプロセス用離型フィルムは、本発明の目的に反しない限りにおいて、離型層Ａ、耐熱樹脂層Ｂ及び離型層Ａ’以外の層を有していてもよい。例えば、離型層Ａ（又は離型層Ａ’）と耐熱樹脂層Ｂとの間に、必要に応じて接着層を有してもよい。接着層に用いる材料は、離型層Ａと耐熱樹脂層Ｂとを強固に接着でき、樹脂封止工程や離型工程においても剥離しないものであれば、特に制限されない。
Other layers The release film for a process of the present invention may have a layer other than the release layer A, the heat-resistant resin layer B, and the release layer A ′ as long as the object of the present invention is not violated. For example, an adhesive layer may be provided between the release layer A (or release layer A ′) and the heat resistant resin layer B as necessary. The material used for the adhesive layer is not particularly limited as long as it can firmly bond the release layer A and the heat-resistant resin layer B and does not peel in the resin sealing step or the release step.
例えば、離型層Ａ（又は離型層Ａ’）が４−メチル−１−ペンテン共重合体を含む場合は、接着層は、不飽和カルボン酸等によりグラフト変性された変性４−メチル−１−ペンテン系共重合体樹脂、４−メチル−１−ペンテン系共重合体とα−オレフィン系共重合体とからなるオレフィン系接着樹脂等であることが好ましい。離型層Ａ（又は離型層Ａ’）がフッ素樹脂を含む場合は、接着層は、ポリエステル系、アクリル系、フッ素ゴム系等の粘着剤であることが好ましい。接着層の厚みは、離型層Ａ（又は離型層Ａ’）と耐熱樹脂層Ｂとの接着性を向上できれば、特に制限はないが、例えば０．５〜１０μｍである。 For example, when the release layer A (or release layer A ′) contains 4-methyl-1-pentene copolymer, the adhesive layer is modified 4-methyl-1 graft-modified with an unsaturated carboxylic acid or the like. A pentene copolymer resin, an olefin adhesive resin composed of a 4-methyl-1-pentene copolymer and an α-olefin copolymer is preferable. When the release layer A (or release layer A ′) contains a fluororesin, the adhesive layer is preferably a pressure-sensitive adhesive such as polyester, acrylic or fluororubber. The thickness of the adhesive layer is not particularly limited as long as the adhesiveness between the release layer A (or release layer A ′) and the heat-resistant resin layer B can be improved, but is 0.5 to 10 μm, for example.
本発明のプロセス用離型フィルムの総厚みには特に制限は無いが、例えば１０〜３００μｍであることが好ましく、３０〜１５０μｍであることがより好ましい。離型フィルムの総厚みが上記範囲にあると、巻物として使用する際のハンドリング性が良好であるとともに、フィルムの廃棄量が少ないため好ましい。 Although there is no restriction | limiting in particular in the total thickness of the release film for processes of this invention, For example, it is preferable that it is 10-300 micrometers, and it is more preferable that it is 30-150 micrometers. When the total thickness of the release film is in the above range, it is preferable because the handling property when used as a roll is good and the amount of discarded film is small.
以下、本発明のプロセス用離型フィルムの好ましい実施形態について更に具体的に説明する。図１は、３層構造のプロセス用離型フィルムの一例を示す模式図である。図１に示されるように、離型フィルム１０は、耐熱樹脂層１２と、その片面に接着層１４を介して形成された離型層１６とを有する。 Hereinafter, the preferred embodiment of the release film for process of the present invention will be described more specifically. FIG. 1 is a schematic diagram showing an example of a three-layer process release film. As shown in FIG. 1, the release film 10 has a heat-resistant resin layer 12 and a release layer 16 formed on one surface of the release film 16 with an adhesive layer 14 interposed therebetween.
離型層１６は前述の離型層Ａであり、耐熱樹脂層１２は前述の耐熱樹脂層Ｂであり、接着層１４は前述の接着層である。離型層１６は、封止プロセスにおいて封止樹脂と接する側に配置されることが好ましく；耐熱樹脂層１２は、封止プロセスにおいて金型の内面と接する側に配置されることが好ましい。 The release layer 16 is the aforementioned release layer A, the heat resistant resin layer 12 is the aforementioned heat resistant resin layer B, and the adhesive layer 14 is the aforementioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing process; the heat-resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the mold in the sealing process.
図２は、５層構造のプロセス用離型フィルムの一例を示す模式図である。図１と同一の機能を有する部材には同一の符号を付する。図２に示されるように、離型フィルム２０は、耐熱性樹脂層１２と、その両面に接着層１４を介して形成された離型層１６Ａおよび離型層１６Ｂとを有する。離型層１６Ａは前述の離型層Ａであり、耐熱樹脂層１２は前述の耐熱樹脂層Ｂであり、離型層１６Ｂは前述の離型層Ａ’であり、接着層１４はそれぞれ前述の接着層である。 FIG. 2 is a schematic view showing an example of a five-layer process release film. Members having the same functions as those in FIG. 1 are denoted by the same reference numerals. As shown in FIG. 2, the release film 20 includes a heat resistant resin layer 12 and a release layer 16 </ b> A and a release layer 16 </ b> B formed on both surfaces of the release film 16 via an adhesive layer 14. The release layer 16A is the aforementioned release layer A, the heat-resistant resin layer 12 is the aforementioned heat-resistant resin layer B, the release layer 16B is the aforementioned release layer A ′, and the adhesive layer 14 is the above-described release layer A ′. It is an adhesive layer.
離型層１６Ａおよび１６Ｂの組成は、互いに同一でも異なってもよい。離型層１６Ａおよび１６Ｂの厚みも、互いに同一でも異なってもよい。ただし、離型層１６Ａおよび１６Ｂが互いに同一の組成および厚みを有すると、対称な構造となり、離型フィルム自体の反りが生じ難くなるため好ましい。特に、本発明の離型フィルムには、封止プロセスにおける加熱により応力が生じることがあるので、反りを抑制することが好ましい。このように、離型層１６Ａおよび１６Ｂが、耐熱樹脂層１２の両面に形成されていると、成形品および金型内面のいずれおいても、良好な離型性が得られるため好ましい。 The compositions of the release layers 16A and 16B may be the same or different from each other. The thicknesses of the release layers 16A and 16B may be the same as or different from each other. However, it is preferable that the release layers 16A and 16B have the same composition and thickness as each other because a symmetric structure is obtained and the release film itself is hardly warped. In particular, since the release film of the present invention may be stressed by heating in the sealing process, it is preferable to suppress warpage. As described above, it is preferable that the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12 because good release properties can be obtained on both the molded product and the inner surface of the mold.
プロセス用離型フィルムの製造方法
本発明のプロセス用離型フィルムは、任意の方法で製造されうる。例えば、１）離型層Ａと耐熱樹脂層Ｂを共押出成形して積層することにより、プロセス用離型フィルムを製造する方法（共押出し形成法）、２）耐熱樹脂層Ｂとなるフィルム上に、離型層Ａや接着層となる樹脂の溶融樹脂を塗布・乾燥したり、または離型層Ａや接着層となる樹脂を溶剤に溶解させた樹脂溶液を塗布・乾燥したりして、プロセス用離型フィルムを製造する方法（塗布法）、３）予め離型層Ａとなるフィルムと、耐熱樹脂層Ｂとなるフィルムとを製造しておき、これらのフィルムを積層（ラミネート）することにより、プロセス用離型フィルムを製造する方法（ラミネート法）などがある。
Process Release Film Production Method The process release film of the present invention can be produced by any method. For example, 1) A method for producing a release film for a process by co-extrusion molding of a release layer A and a heat-resistant resin layer B (co-extrusion forming method), 2) On a film to be a heat-resistant resin layer B In addition, by applying and drying a molten resin of the resin to be the release layer A and the adhesive layer, or applying and drying a resin solution in which the resin to be the release layer A and the adhesive layer is dissolved in a solvent, Process for producing a release film for process (coating method), 3) Production of a film to be the release layer A and a film to be the heat-resistant resin layer B in advance, and laminating these films Thus, there is a method for producing a release film for a process (lamination method).
３）の方法において、各樹脂フィルムを積層する方法としては、公知の種々のラミネート方法が採用でき、例えば押出ラミネート法、ドライラミネート法、熱ラミネート法等が挙げられる。
ドライラミネート法では、接着剤を用いて各樹脂フィルムを積層する。接着剤としては、ドライラミネート用の接着剤として公知のものを使用できる。例えばポリ酢酸ビニル系接着剤；アクリル酸エステル（アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシルエステル等）の単独重合体もしくは共重合体、またはアクリル酸エステルと他の単量体（メタクリル酸メチル、アクリロニトリル、スチレン等）との共重合体等からなるポリアクリル酸エステル系接着剤；シアノアクリレ−ト系接着剤；エチレンと他の単量体（酢酸ビニル、アクリル酸エチル、アクリル酸、メタクリル酸等）との共重合体等からなるエチレン共重合体系接着剤；セルロ−ス系接着剤；ポリエステル系接着剤；ポリアミド系接着剤；ポリイミド系接着剤；尿素樹脂またはメラミン樹脂等からなるアミノ樹脂系接着剤；フェノ−ル樹脂系接着剤；エポキシ系接着剤；ポリオール（ポリエーテルポリオール、ポリエステルポリオール等）とイソシアネートおよび／またはイソシアヌレートと架橋させるポリウレタン系接着剤；反応型（メタ）アクリル系接着剤；クロロプレンゴム、ニトリルゴム、スチレン−ブタジエンゴム等からなるゴム系接着剤；シリコーン系接着剤；アルカリ金属シリケ−ト、低融点ガラス等からなる無機系接着剤；その他等の接着剤を使用できる。３）の方法で積層する樹脂フィルムは、市販のものを用いてもよく、公
知の製造方法により製造したものを用いてもよい。樹脂フィルムには、コロナ処理、大気圧プラズマ処理、真空プラズマ処理、プライマー塗工処理等の表面処理が施されてもよい。樹脂フィルムの製造方法としては、特に限定されず、公知の製造方法を利用できる。
In the method 3), as a method for laminating the resin films, various known laminating methods can be employed, and examples thereof include an extrusion laminating method, a dry laminating method, and a thermal laminating method.
In the dry laminating method, each resin film is laminated using an adhesive. As the adhesive, known adhesives for dry lamination can be used. For example, polyvinyl acetate adhesive; homopolymer or copolymer of acrylic acid ester (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or acrylic acid ester and other monomers (methacrylic acid) Polyacrylate adhesives consisting of copolymers with methyl, acrylonitrile, styrene, etc .; Cyanoacrylate adhesives; Ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid) Etc.) Ethylene copolymer adhesives made of copolymers, etc .; Cellulose adhesives; Polyester adhesives; Polyamide adhesives; Polyimide adhesives; Amino resin systems made of urea resins or melamine resins Adhesive; phenolic resin adhesive; epoxy adhesive; polyol (polyether polyol) , Polyester polyols, etc.) and isocyanate and / or isocyanurate crosslinkable polyurethane adhesives; reactive (meth) acrylic adhesives; chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc. rubber adhesives; silicone Adhesives; inorganic adhesives made of alkali metal silicate, low-melting glass, etc .; other adhesives can be used. As the resin film laminated by the method 3), a commercially available one may be used, or one produced by a known production method may be used. The resin film may be subjected to surface treatment such as corona treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, and primer coating treatment. It does not specifically limit as a manufacturing method of a resin film, A well-known manufacturing method can be utilized.
１）共押出し成形法は、離型層Ａとなる樹脂層と耐熱樹脂層Ｂとなる樹脂層との間に、異物が噛み込む等による欠陥や、離型フィルムの反りが生じ難い点で好ましい。３）ラミネート法は、耐熱樹脂層Ｂに延伸フィルムを用いる場合に好適な製造方法である。この場合は、必要に応じてフィルム同士の界面に適切な接着層を形成することが好ましい。フィルム同士の接着性を高める上で、フィルム同士の界面に、必要に応じてコロナ放電処理等の表面処理を施してもよい。 1) The co-extrusion molding method is preferable in that a defect due to a foreign matter biting between the resin layer to be the release layer A and the resin layer to be the heat-resistant resin layer B, and the release film are not easily warped. . 3) The laminating method is a manufacturing method suitable when a stretched film is used for the heat resistant resin layer B. In this case, it is preferable to form an appropriate adhesive layer at the interface between the films as necessary. In order to improve the adhesiveness between the films, a surface treatment such as a corona discharge treatment may be applied to the interface between the films as necessary.
プロセス用離型フィルムは、必要に応じて１軸または２軸延伸されていてもよく、それによりフィルムの膜強度を高めることができる。 The process release film may be uniaxially or biaxially stretched as necessary, thereby increasing the film strength of the film.
上記２）塗布法における塗布手段は、特に限定されないが、例えばロールコータ、ダイコータ、スプレーコータ等の各種コータが用いられる。溶融押出手段は、特に限定されないが、例えばＴ型ダイやインフレーション型ダイを有する押出機などが用いられる。 The coating means in the above 2) coating method is not particularly limited, but various coaters such as a roll coater, a die coater, and a spray coater are used. The melt extrusion means is not particularly limited. For example, an extruder having a T-type die or an inflation type die is used.
製造プロセス
本発明のプロセス用離型フィルムは、金型内に半導体チップ等を配置して樹脂を注入成形する際に、半導体チップ等と金型内面との間に配置して使用することができる。本発明のプロセス用離型フィルムを用いることで、金型からの離型不良、バリの発生等を効果的に防止することができる。
上記製造プロセスに用いる樹脂は、熱可塑性樹脂、熱硬化性樹脂のいずれであってもよいが、当該技術分野においては熱硬化性樹脂が広く用いられており、特にエポキシ系の熱硬化性樹脂を用いることが好ましい。
上記製造プロセスとしては、半導体チップの封止が最も代表的であるが、これに限定されるものではなく、本発明は、繊維強化プラスチック成形プロセス、プラスチックレンズ成形プロセス等にも適用することができる。
Manufacturing Process The release film for process of the present invention can be used by placing a semiconductor chip or the like in the mold and injecting and molding the resin between the semiconductor chip and the inner surface of the mold. . By using the release film for a process of the present invention, it is possible to effectively prevent a release failure from the mold, the occurrence of burrs, and the like.
The resin used in the manufacturing process may be either a thermoplastic resin or a thermosetting resin. However, thermosetting resins are widely used in the technical field, and in particular, epoxy-based thermosetting resins are used. It is preferable to use it.
As the above manufacturing process, semiconductor chip sealing is the most representative, but the present invention is not limited to this, and the present invention can also be applied to a fiber reinforced plastic molding process, a plastic lens molding process, and the like. .
図３、図４Ａおよび図４Ｂは、本発明の離型フィルムを用いた樹脂封止半導体の製造方法の一例を示す模式図である。
図３ａに示すように、本発明の離型フィルム１を、ロール状の巻物からロール１−２およびロール１−３により、成形金型２内に供給する。次いで、離型フィルム１を上型２の内面に配置する。必要に応じて、上型２内面を真空引きして、離型フィルム１を上型２内面に密着させてもよい。モールディング成形装置の下金型５に、基板上に配置した半導体チップ６が配置されており、その半導体チップ６上に封止樹脂を配するか、又は半導体チップ６を覆うように液状封止樹脂を注入することで、排気吸引され密着された離型フィルム１を配置した上金型２と下金５型との間に封止樹脂４が収容される。次に図３ｂに示すように、上金型２と下金型５とを、本発明の離型フィルム１を介して型閉じし、封止樹脂４を硬化させる。
3, 4A and 4B are schematic views showing an example of a method for producing a resin-encapsulated semiconductor using the release film of the present invention.
As shown in FIG. 3a, the release film 1 of the present invention is supplied into the molding die 2 from a roll-shaped roll by a roll 1-2 and a roll 1-3. Next, the release film 1 is disposed on the inner surface of the upper mold 2. If necessary, the inner surface of the upper mold 2 may be evacuated to bring the release film 1 into close contact with the inner surface of the upper mold 2. A semiconductor chip 6 disposed on a substrate is disposed in a lower mold 5 of the molding apparatus, and a sealing resin is disposed on the semiconductor chip 6 or a liquid sealing resin so as to cover the semiconductor chip 6. The sealing resin 4 is accommodated between the upper mold 2 and the lower mold 5 on which the release film 1 that has been sucked and adhered is exhausted. Next, as shown in FIG. 3b, the upper mold 2 and the lower mold 5 are closed via the release film 1 of the present invention, and the sealing resin 4 is cured.
型閉め硬化により、図３ｃに示すように封止樹脂４ が金型内に流動化し、封止樹脂４ が空間部に流入し半導体チップ６の側面周囲を囲むようにして充填され、封止された半導体チップ６を上金型２と下金型５とが型開きして取り出す。型開きし、成形品を取り出した後、離型フィルム１を複数回繰り返して利用するか、新たな離型フィルムを供給し、次の、樹脂モールディング成形に付される。 As shown in FIG. 3c, the sealing resin 4 is fluidized in the mold by the mold closing and curing, and the sealing resin 4 flows into the space portion and is filled so as to surround the side surface of the semiconductor chip 6 to be sealed. The chip 6 is taken out by the upper mold 2 and the lower mold 5 being opened. After the mold is opened and the molded product is taken out, the release film 1 is repeatedly used for a plurality of times or a new release film is supplied and subjected to the next resin molding.
本発明の離型フィルムを上金型に密着させ、金型と封止樹脂との間に介在させ、樹脂モ
ールドすることにより金型への樹脂の付着を防ぎ、金型の樹脂モールド面を汚さず、かつ
成形品を容易に離型させることができる。
なお、離型フィルムは一回の樹脂モールド操作ごとに新たに供給して樹脂モールドする
こともできるし複数回の樹脂モールド操作ごとに新たに供給して樹脂モールドすることも
できる。
The mold release film of the present invention is closely attached to the upper mold, interposed between the mold and the sealing resin, and resin molding prevents the resin from adhering to the mold and stains the resin mold surface of the mold. In addition, the molded product can be easily released.
The release film can be newly supplied and resin-molded for each resin molding operation, or can be newly supplied and resin-molded for each of a plurality of resin molding operations.
封止樹脂としては、液状樹脂であっても、常温で固体状の樹脂であってもよいが、樹脂封止時液状となるものなどの封止材を適宜採用できる。封止樹脂材料として、具体的には、主としてエポキシ系（ビフェニル型エポキシ樹脂、ビスフェノールエポキシ樹脂、ｏ−クレゾールノボラック型エポキシ樹脂など）が用いられ、エポキシ樹脂以外の封止樹脂として、ポリイミド系樹脂（ビスマレイミド系）、シリコーン系樹脂（熱硬化付加型）など封止樹脂として通常使用されているものを用いることができる。また、樹脂封止条件としては、使用する封止樹脂により異なるが、例えば硬化温度１２０℃〜１８０℃、成形圧力１０〜５０ｋｇ／ｃｍ２、硬化時間１〜６０分の範囲で適宜設定することができる。 The sealing resin may be a liquid resin or a resin that is solid at room temperature, but a sealing material such as a liquid that is liquid at the time of resin sealing can be appropriately employed. Specifically, as the sealing resin material, epoxy type (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolac type epoxy resin, etc.) is mainly used, and polyimide type resin ( Bismaleimide-based), silicone-based resin (thermosetting addition type), or the like that is usually used as a sealing resin can be used. The resin sealing conditions vary depending on the sealing resin to be used, but may be set appropriately within a range of, for example, a curing temperature of 120 ° C. to 180 ° C., a molding pressure of 10 to 50 kg / cm 2 , and a curing time of 1 to 60 minutes. it can.
離型フィルム１を成形金型８の内面に配置する工程と、半導体チップ６を成形金型８内に配置する工程の前後は、特に限定されず、同時に行ってもよいし、半導体チップ６を配置した後、離型フィルム１を配置してもよいし、離型フィルム１を配置した後、半導体チップ６を配置してもよい。 Before and after the step of placing the release film 1 on the inner surface of the molding die 8 and the step of placing the semiconductor chip 6 in the molding die 8 are not particularly limited and may be performed simultaneously. After the placement, the release film 1 may be placed, or after the release film 1 is placed, the semiconductor chip 6 may be placed.
このように、離型フィルム１は、離型性の高い離型層Ａ（及び所望により離型層Ａ’）を有するため、半導体パッケージ４−２を容易に離型することができる。また、離型フィルム１は、適度な柔軟性を有するので、金型形状に対する追従性に優れながらも、成形金型８の熱によって皺になり難い。このため、封止された半導体パッケージ４−２の樹脂封止面に皺が転写されたり、樹脂が充填されない部分（樹脂欠け）が生じたりすることなく、外観の良好な封止された半導体パッケージ４−２を得ることができる。 Thus, since the release film 1 has the release layer A (and release layer A ′ if desired) having a high release property, the semiconductor package 4-2 can be easily released. Moreover, since the release film 1 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 8 while having excellent followability to the mold shape. For this reason, a sealed semiconductor package having a good appearance without causing wrinkles to be transferred to the resin sealing surface of the sealed semiconductor package 4-2 or a portion not filled with resin (resin lack). 4-2 can be obtained.
また、図３で示したような、固体の封止樹脂材料４を加圧加熱する圧縮成型法に限らず、後述の様に流動状態の封止樹脂材料を注入するトランスファーモールド法を採用してもよい。 Further, not only the compression molding method in which the solid sealing resin material 4 is pressurized and heated as shown in FIG. 3, but also a transfer molding method in which a sealing resin material in a fluid state is injected as described later. Also good.
図４Ａおよび図４Ｂは、本発明の離型フィルムを用いた樹脂封止半導体の製造方法の一例であるトランスファーモールド法を示す模式図である。 4A and 4B are schematic views showing a transfer mold method which is an example of a method for producing a resin-encapsulated semiconductor using the release film of the present invention.
図４Ａに示されるように、本発明の離型フィルム２２を、ロール状の巻物からロール２４およびロール２６により、成形金型２８内に供給する（工程ａ）。次いで、離型フィルム２２を上型３０の内面３０Ａに配置する（工程ｂ）。必要に応じて、上型内面３０Ａを真空引きして、離型フィルム２２を上型内面３０Ａに密着させてもよい。次いで、成形金型２８内に、樹脂封止すべき半導体チップ３４（基板３４Ａに固定された半導体チップ３４）を配置するとともに、封止樹脂材料３６をセットし（工程ｃ）、型締めする（工程ｄ）。 As shown in FIG. 4A, the release film 22 of the present invention is supplied from a roll-shaped roll into the molding die 28 by a roll 24 and a roll 26 (step a). Next, the release film 22 is disposed on the inner surface 30A of the upper mold 30 (step b). If necessary, the upper mold inner surface 30A may be evacuated to bring the release film 22 into close contact with the upper mold inner surface 30A. Next, the semiconductor chip 34 to be resin-sealed (semiconductor chip 34 fixed to the substrate 34A) is placed in the molding die 28, and the sealing resin material 36 is set (step c), and the mold is clamped ( Step d).
次いで、図４Ｂに示されるように、所定の加熱および加圧条件下、成形金型２８内に封止樹脂材料３６を注入する（工程ｅ）。このときの成形金型２８の温度（成形温度）は、例えば１６５〜１８５℃であり、成形圧力は、例えば７〜１２ＭＰａであり、成形時間は、例えば９０秒程度である。そして、一定時間保持した後、上型３０と下型３２を開き、樹脂封止された半導体パッケージ４０や離型フィルム２２、を同時にまたは順次離型する（工程ｆ）。 Next, as shown in FIG. 4B, a sealing resin material 36 is injected into the molding die 28 under predetermined heating and pressing conditions (step e). The temperature (molding temperature) of the molding die 28 at this time is, for example, 165 to 185 ° C., the molding pressure is, for example, 7 to 12 MPa, and the molding time is, for example, about 90 seconds. And after hold | maintaining for a fixed time, the upper mold | type 30 and the lower mold | type 32 are opened, and the semiconductor package 40 and the release film 22 which were resin-sealed are released simultaneously or sequentially (process f).
そして、図５に示されるように、得られた半導体パッケージ４０のうち、余分な樹脂部分４２を除去することで、所望の半導体パッケージ４４を得ることができる。離型フィルム２２は、そのまま他の半導体チップの樹脂封止に使用してもよいが、成形が１回終了するごとにロールを操作してフィルムを送り、新たに離型フィルム２２を成形金型２８に供給することが好ましい。 Then, as shown in FIG. 5, a desired semiconductor package 44 can be obtained by removing the excess resin portion 42 from the obtained semiconductor package 40. The release film 22 may be used as it is for resin sealing of other semiconductor chips as it is, but each time molding is completed, the roll is operated to feed the film, and a new release film 22 is formed as a molding die. 28 is preferably supplied.
離型フィルム２２を成形金型２８の内面に配置する工程と、半導体チップ３４を成形金型２８内に配置する工程の前後は、特に限定されず、同時に行ってもよいし、半導体チップ３４を配置した後、離型フィルム２２を配置してもよいし、離型フィルム２２を配置した後、半導体チップ３４を配置してもよい。 Before and after the step of disposing the release film 22 on the inner surface of the molding die 28 and the step of disposing the semiconductor chip 34 in the molding die 28 are not particularly limited and may be performed simultaneously. After the placement, the release film 22 may be placed, or after the release film 22 is placed, the semiconductor chip 34 may be placed.
このように、離型フィルム２２は、離型性の高い離型層Ａ（及び所望により離型層Ａ’）を有するため、半導体パッケージ４０を容易に離型することができる。また、離型フィルム２２は、適度な柔軟性を有するので、金型形状に対する追従性に優れながらも、成形金型２８の熱によって皺になり難い。このため、半導体パッケージ４０の樹脂封止面に皺が転写されたり、樹脂が充填されない部分（樹脂欠け）が生じたりすることなく、外観の良好な半導体パッケージ４０を得ることができる。 Thus, since the release film 22 has the release layer A (and release layer A ′ if necessary) having a high release property, the semiconductor package 40 can be easily released. Moreover, since the release film 22 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 28 while having excellent followability to the die shape. Therefore, it is possible to obtain the semiconductor package 40 having a good appearance without transferring wrinkles on the resin sealing surface of the semiconductor package 40 or generating a portion not filled with resin (resin chipping).
本発明の離型フィルムは、半導体素子を樹脂封止する工程に限らず、成型金型を用いて
各種成形品を成形および離型する工程、例えば繊維強化プラスチック成形および離型工程、プラスチックレンズ成形および離型工程等においても好ましく使用できる。
The release film of the present invention is not limited to the step of resin-sealing a semiconductor element, but the step of molding and releasing various molded products using a molding die, for example, fiber reinforced plastic molding and release step, plastic lens molding In addition, it can be preferably used also in a mold release step.
以下、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、これにより何ら限定
されるものではない。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by this.
以下の実施例／比較例において、物性／特性の評価は下記の方法で行った。
（熱寸法変化率）
フィルムサンプルをフィルムの長手方向および幅方向にそれぞれ長さ２０ｍｍ、幅４ｍｍに切り出し、ＴＡインスツルメンツ社製ＴＭＡ（熱機械分析装置、製品名：Ｑ４００）を用い、チャック間距離８ｍｍにて０．００５Ｎの荷重をかけた状態で２３℃５分間保持後、２３℃から１２０℃まで１０℃／分の昇温速度で昇温させ、それぞれの方向の寸法変化を測定し、下記式（１）により寸法変化率を算出した。
熱寸法変化率（％）（２３→１２０℃） ＝ ｛［（Ｌ２−Ｌ１）／Ｌ１］×１００｝
・・・（１）
Ｌ１：２３℃時のサンプル長（ｍｍ）
Ｌ２：１２０℃時のサンプル長（ｍｍ）
同様に、２３℃から１７０℃まで１０℃／分の昇温速度で昇温させ、それぞれの方向の寸法変化を測定し、下記式（２）により寸法変化率を算出した。
熱寸法変化率（％）（２３→１７０℃） ＝ ｛［（Ｌ３−Ｌ１）／Ｌ１］×１００｝
・・・（２）
Ｌ１：２３℃時のサンプル長（ｍｍ）
Ｌ３：１７０℃時のサンプル長（ｍｍ）
In the following examples / comparative examples, physical properties / characteristics were evaluated by the following methods.
(Thermal dimensional change rate)
A film sample was cut into a length of 20 mm and a width of 4 mm in the longitudinal direction and the width direction of the film, respectively, and a TA instrument TMA (thermomechanical analyzer, product name: Q400) was used to obtain 0.005 N at a chuck distance of 8 mm. After holding at 23 ° C. for 5 minutes under a load, the temperature is increased from 23 ° C. to 120 ° C. at a rate of 10 ° C./min, the dimensional change in each direction is measured, and the dimensional change according to the following formula (1) The rate was calculated.
Thermal dimensional change rate (%) (23 → 120 ° C.) = {[(L 2 −L 1 ) / L 1 ] × 100}
... (1)
L 1 : Sample length at 23 ° C. (mm)
L 2 : Sample length at 120 ° C. (mm)
Similarly, the temperature was raised from 23 ° C. to 170 ° C. at a rate of 10 ° C./min, the dimensional change in each direction was measured, and the dimensional change rate was calculated by the following formula (2).
Thermal dimensional change rate (%) (23 → 170 ° C.) = {[(L 3 −L 1 ) / L 1 ] × 100}
... (2)
L 1 : Sample length at 23 ° C. (mm)
L 3 : Sample length at 170 ° C. (mm)
水に対する接触角（水接触角）
ＪＩＳ Ｒ ３ ２ ５ ７ に準拠して、接触角測定器（Ｋｙｏｗａ Ｉｎｔｅｒ ｆａｃｅ Ｓｃｉｅｎｃｅ社製、ＦＡＣＥＣＡ−Ｗ）を用いて離型層Ａの表面の水接触角を測定した。
Water contact angle (water contact angle)
Based on JIS R 3 2 5 7, the water contact angle on the surface of the release layer A was measured using a contact angle measuring device (manufactured by Kyowa Interface Science, FACECA-W).
（融点（Ｔｍ）、結晶融解熱量）
示差走査熱量計（ＤＳＣ）としてティー・エイ・インスツルメント社製Ｑ１００を用い、重合体試料約５ｍｇを精秤し、ＪＩＳＫ７１２１に準拠し、窒素ガス流入量：５０ｍｌ／分の条件下で、２５℃から加熱速度：１０℃／分で２８０℃まで昇温して熱融解曲線を測定し、得られた熱融解曲線から、試料の融点（Ｔｍ）及び結晶融解熱量を求めた。
(Melting point (Tm), heat of crystal melting)
Using a Q100 manufactured by TA Instruments Inc. as a differential scanning calorimeter (DSC), about 5 mg of a polymer sample is precisely weighed, and in accordance with JISK7121, a nitrogen gas inflow rate of 50 ml / min is 25. The heat melting curve was measured by heating from ℃ to 280 ° C. at a heating rate of 10 ° C./min, and the melting point (Tm) and the crystal melting heat amount of the sample were determined from the obtained heat melting curve.
（離型性）
各実施例／比較例で作製したプロセス用離型フィルムを、図３に示されるように、上型と下型との間に１０Ｎの張力を印加した状態で配置した後、上型のパーティング面に真空吸着させた。次いで、半導体チップを覆うように基板上に封止樹脂を充填後、基板に固定された半導体チップを下型に配置し、型締めした。このとき、成形金型の温度（成形温度）を１２０℃、成形圧力を１０ＭＰａ、成形時間を４００秒とした。そして、図３ｃに示されるように、半導体チップを封止樹脂で封止した後、樹脂封止された半導体チップ（半導体パッケージ）を離型フィルムから離型した。
離型フィルムの離型性を、以下の基準で評価した。
○：離型フィルムが、金型の開放と同時に自然に剥がれる。
△：離型フィルムは自然には剥がれないが、手で引っ張ると（張力を加えると）簡単に剥がれる。
×：離型フィルムが、半導体パッケージの樹脂封止面に密着しており、手では剥がせない。
(Releasability)
As shown in FIG. 3, the process release film produced in each example / comparative example was placed with a 10 N tension applied between the upper mold and the lower mold, and then the upper mold parting. The surface was vacuum-adsorbed. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 120 ° C., the molding pressure was 10 MPa, and the molding time was 400 seconds. Then, as shown in FIG. 3c, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film.
The releasability of the release film was evaluated according to the following criteria.
○: The release film is naturally peeled off at the same time as the mold is opened.
(Triangle | delta): Although a release film does not peel naturally, when it pulls by hand (when tension is added), it peels easily.
X: The release film is in close contact with the resin sealing surface of the semiconductor package and cannot be peeled off by hand.
（皺）
上記工程で離型を行った後の、離型フィルム、および半導体パッケージの樹脂封止面の皺の状態を、以下の基準で評価した。
○：離型フィルムおよび半導体パッケージのいずれにも皺が全くない。
△：離型フィルムにはわずかに皺があるが、半導体パッケージへの皺の転写はない。
×：離型フィルムはもちろん、半導体パッケージにも多数の皺あり。
(wrinkle)
The state of wrinkles on the release film and the resin sealing surface of the semiconductor package after release in the above process was evaluated according to the following criteria.
○: There is no wrinkle in both the release film and the semiconductor package.
Δ: The release film has slight wrinkles, but there is no transfer of wrinkles to the semiconductor package.
X: There are many defects in the semiconductor package as well as the release film.
（金型追従性）
上記工程で離型を行った際の離型フィルムの金型追従性を、以下の基準で評価した。
○：半導体パッケージに、樹脂欠け（樹脂が充填されない部分）が全くない。
△：半導体パッケージの端部に、樹脂欠けが僅かにある（ただし皺による欠けは除く） ×：半導体パッケージの端部に、樹脂欠けが多くある（ただし皺による欠けは除く）
(Mold followability)
The mold following property of the release film at the time of releasing in the above process was evaluated according to the following criteria.
○: There is no resin deficiency (portion where resin is not filled) in the semiconductor package.
△: Slight resin chipping at the edge of the semiconductor package (excluding chipping due to defects) ×: Many resin chipping at the edge of the semiconductor package (excluding chipping due to defects)
［実施例１］
耐熱樹脂層Ｂとして、膜厚１６μｍの二軸延伸ＰＥＴ（ポリエチレンテレフタレート）フィルム（東レ株式会社製、製品名：ルミラーＦ８６５）を使用した。当該二軸延伸ＰＥＴフィルムの２３℃から１２０℃までの熱寸法変化率は、縦（ＭＤ）方向で−１．６％、横（ＴＤ）方向で−１．２％であった。また、当該二軸延伸ＰＥＴフィルムの融点は、１８７℃であり、結晶融解熱量は、３０．６Ｊ／ｇであった。
[Example 1]
As the heat resistant resin layer B, a biaxially stretched PET (polyethylene terephthalate) film (product name: Lumirror F865 manufactured by Toray Industries, Inc.) having a film thickness of 16 μm was used. The thermal dimensional change rate from 23 ° C. to 120 ° C. of the biaxially stretched PET film was −1.6% in the machine direction (MD) and −1.2% in the transverse (TD) direction. Moreover, the melting point of the biaxially stretched PET film was 187 ° C., and the heat of crystal fusion was 30.6 J / g.
離型層Ａ及びＡ’として、無延伸の４−メチル−１−ペンテン共重合樹脂フィルムを使用した。具体的には、三井化学株式会社製４−メチル−１−ペンテン共重合樹脂（製品名：ＴＰＸ、銘柄名：ＭＸ０２２）」を２７０℃で溶融押出して、Ｔ型ダイのスリット幅を調整することにより、厚み１５μｍの無延伸フィルムを成膜したものを使用した。
無延伸の４−メチル−１−ペンテン共重合樹脂フィルムは、一方のフィルム表面が、ＪＩＳ Ｒ３２５７に基づく水接触角が３０°以上の場合、３０以下となるように、接着剤による接着性向上の観点からコロナ処理を施した。
当該４−メチル−１−ペンテン共重合樹脂フィルムの２３℃から１２０℃までの熱寸法変化率は、縦（ＭＤ）方向で６．５％、横（ＴＤ）方向で３．１％であった。
As the release layers A and A ′, unstretched 4-methyl-1-pentene copolymer resin films were used. Specifically, a 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. is melt extruded at 270 ° C. to adjust the slit width of the T-die. Thus, a non-stretched film having a thickness of 15 μm was used.
The non-stretched 4-methyl-1-pentene copolymer resin film is improved in adhesiveness by an adhesive so that one film surface has a water contact angle of 30 ° or more based on JIS R3257 to 30 or less. Corona treatment was applied from the viewpoint.
The thermal dimensional change rate from 23 ° C. to 120 ° C. of the 4-methyl-1-pentene copolymer resin film was 6.5% in the longitudinal (MD) direction and 3.1% in the transverse (TD) direction. .
(接着剤)
各フィルムを貼り合せるドライラミ工程で使用する接着剤としては、以下のウレタン系接着剤Ａを用いた。
［ウレタン系接着剤Ａ］
主剤：タケラックＡ−６１６（三井化学社製）。硬化剤：タケネートＡ−６５（三井化学社製）。主剤と硬化剤とを、質量比（主剤：硬化剤）が１６：１となるように混合し、希釈剤として酢酸エチルを用いた。
(adhesive)
The following urethane-based adhesive A was used as the adhesive used in the dry lamination process for bonding each film.
[Urethane adhesive A]
Main agent: Takelac A-616 (manufactured by Mitsui Chemicals). Curing agent: Takenate A-65 (Mitsui Chemicals). The main agent and the curing agent were mixed so that the mass ratio (main agent: curing agent) was 16: 1, and ethyl acetate was used as a diluent.
（離型フィルムの製造）
二軸延伸ＰＥＴ（ポリエチレンテレフタレート）フィルムの一方の面に、グラビアコートでウレタン系接着剤Ａを１．５ｇ／ｍ２で塗工し、無延伸の４−メチル−１−ペンテン共重合樹脂フィルムのコロナ処理面をドライラミネートにて貼り合わせ後、続いてこのラミネートフィルムの二軸延伸ＰＥＴ（ポリエチレンテレフタレート）フィルム面の側に、ウレタン系接着剤Ａを１．５ｇ／ｍ２で塗工し、無延伸の４−メチル−１−ペンテン共重合樹脂フィルムのコロナ処理面をドライラミネートにて貼り合わせて、５層構造（離型層Ａ／接着層／耐熱樹脂層Ｂ／接着層／離型層Ａ’）のプロセス用離型フィルムを得た。
ドライラミネート条件は、基材幅９００ｍｍ、搬送速度３０ｍ／分、乾燥温度５０〜６０℃、ラミネートロール温度５０℃、ロール圧力３．０ＭＰａとした。
(Manufacture of release film)
One side of a biaxially stretched PET (polyethylene terephthalate) film was coated with urethane adhesive A at 1.5 g / m 2 by gravure coating, and an unstretched 4-methyl-1-pentene copolymer resin film After laminating the corona-treated surfaces by dry lamination, urethane adhesive A was applied at 1.5 g / m 2 on the side of the biaxially stretched PET (polyethylene terephthalate) film surface of the laminate film. The corona-treated surface of the stretched 4-methyl-1-pentene copolymer resin film is bonded by dry lamination, and a five-layer structure (release layer A / adhesive layer / heat-resistant resin layer B / adhesive layer / release layer A) ') A release film for the process was obtained.
The dry lamination conditions were a substrate width of 900 mm, a conveyance speed of 30 m / min, a drying temperature of 50 to 60 ° C., a laminate roll temperature of 50 ° C., and a roll pressure of 3.0 MPa.
当該プロセス用離型フィルムの２３℃から１２０℃までの熱寸法変化率は、縦（ＭＤ）方向で２．１％、横（ＴＤ）方向で１．５％であった。
離型性、皺、及び金型追従性の評価結果を表１に示す。離型フィルムが、金型の開放と同時に自然に剥がれる良好な離型性を示し、離型フィルムおよび半導体パッケージのいずれにも皺が全くなく、すなわち皺が十分に抑制され、半導体パッケージに樹脂欠けが全くない良好な金型追従性を示した。すなわち、実施例１のプロセス用離型フィルムは、離型性、皺の抑制、及び金型追従性が良好なプロセス用離型フィルムであった。
The thermal dimensional change rate from 23 ° C. to 120 ° C. of the release film for the process was 2.1% in the machine direction (MD) and 1.5% in the transverse (TD) direction.
Table 1 shows the evaluation results of releasability, wrinkles, and mold followability. The release film exhibits good release properties that peel off spontaneously at the same time as the mold is opened, and there is no wrinkle in both the release film and the semiconductor package, that is, wrinkles are sufficiently suppressed, and the semiconductor package lacks resin. The mold following ability was excellent without any. That is, the process release film of Example 1 was a process release film having good release characteristics, suppression of wrinkles, and mold followability.
［実施例２〜１２］
表１に示す組み合わせで表１記載の各フィルムを離型層Ａ及びＡ’並びに耐熱樹脂層Ｂとして用いた他は、実施例１と同様にしてプロセス用離型フィルムを作製し、封止、離型を行い、特性を評価した。結果を表１に示す。
一部に皺の抑制、又は金型追従性が実施例１には及ばないものもあったが、いずれの実施例も離型性、皺の抑制、及び金型追従性が高いレベルでバランスした良好なプロセス用離型フィルムであった
[Examples 2 to 12]
A process release film was prepared in the same manner as in Example 1 except that each film shown in Table 1 was used as the release layers A and A ′ and the heat-resistant resin layer B in the combinations shown in Table 1. The mold was released and the characteristics were evaluated. The results are shown in Table 1.
In some cases, the suppression of wrinkles or mold followability did not reach that of Example 1, but all the examples were balanced at a high level of mold release, wrinkle suppression, and mold followability. It was a good release film for process
なお、表に記載の各フィルムの詳細は、以下のとおりである。
（Ａ１）無延伸４ＭＰ−１（ＴＰＸ）フィルム
三井化学株式会社製４−メチル−１−ペンテン共重合樹脂（製品名：ＴＰＸ、銘柄名：ＭＸ０２２）を用いて厚み１５μｍの無延伸フィルムを成膜したもの。（融点：２２９℃、結晶融解熱量：２１．７Ｊ／ｇ）
（Ａ２）無延伸４ＭＰ−１（ＴＰＸ）フィルム
三井化学株式会社製４−メチル−１−ペンテン共重合樹脂（製品名：ＴＰＸ、銘柄名：ＤＸ８１８）を用いて厚み１５μｍの無延伸フィルムを成膜したもの。（融点：２３５℃、結晶融解熱量：２８．１Ｊ／ｇ）
（Ａ３）無延伸４ＭＰ−１（ＴＰＸ）フィルム
三井化学株式会社製４−メチル−１−ペンテン共重合樹脂（製品名：ＴＰＸ、銘柄名：ＭＸ０２２）を用いて厚み５０μｍの無延伸フィルムを成膜したもの。（融点：２２９℃、結晶融解熱量：２１．７Ｊ／ｇ）
（Ａ４）無延伸４ＭＰ−１（ＴＰＸ）フィルム
三井化学株式会社製４−メチル−１−ペンテン共重合樹脂（製品名：ＴＰＸ、銘柄名：ＤＸ８１８）を用いて厚み５０μｍの無延伸フィルムを成膜したもの。（融点：２３５℃、結晶融解熱量：２８．１Ｊ／ｇ）
（Ａ５）フッ素樹脂フィルム
膜厚２５μｍのＥＴＦＥ（エチレン-テトラフルオロエチレン）フィルム（旭硝子株式会社製、製品名：アフレックス２５Ｎ）（融点：２５６℃、結晶融解熱量：３３．７Ｊ／ｇ）
（Ａ６）ポリスチレン系樹脂フィルム
膜厚５０μｍのポリスチレン系フィルム（倉敷紡績株式会社製、製品名：オイディスＣＡ-Ｆ）（融点：２５３℃、結晶融解熱量：１９．２Ｊ／ｇ）
（Ｂ１）２軸延伸ＰＥＴフィルム
膜厚１６μｍの二軸延伸ＰＥＴ（ポリエチレンテレフタレート）フィルム（東レ株式会社製、製品名：ルミラーＦ８６５）（融点：１８７℃、結晶融解熱量：３０．６Ｊ／ｇ）
（Ｂ２）２軸延伸ＰＥＴフィルム
膜厚１２μｍの二軸延伸ＰＥＴ（ポリエチレンテレフタレート）フィルム（東レ株式会社製、製品名：ルミラーＳ１０）（融点：２５８℃、結晶融解熱量：３９．４Ｊ／ｇ）
（Ｂ３）２軸延伸ナイロンフィルム
膜厚１５μｍの二軸延伸ナイロンフィルム（興人フィルム&ケミカルズ株式会社製、製品名：ボニールＲＸ）（融点：２１２℃、結晶融解熱量：５３．１Ｊ／ｇ）
（Ｂ４）２軸延伸ナイロンフィルム
膜厚１５μｍの二軸延伸ナイロンフィルム（出光ユニテック株式会社製、製品名：ユニロンＳ３３０）（融点：２２１℃、結晶融解熱量：６０．３Ｊ／ｇ）
（Ｂ５）２軸延伸ポリプロピレンフィルム
膜厚２０μｍの二軸延伸ポリプロピレンフィルム（三井化学東セロ株式会社製、製品名：Ｕ−２）（融点：１６０℃、結晶融解熱量：９３．３Ｊ／ｇ）
（Ｂ６）無延伸ナイロンフィルム
膜厚２０μｍの無延伸ナイロンフィルム（三菱樹脂株式会社製、製品名：ダイナミロンＣ）（融点：２２０℃、結晶融解熱量：３９．４Ｊ／ｇ）
（Ｂ７）２軸延伸ＰＥＴフィルム
膜厚２５μｍの２軸延伸ＰＥＴフィルム（帝人デュポンフィルム株式会社製、製品名：ＦＴ３ＰＥ）（融点：２１４℃、結晶融解熱量：４０．３Ｊ／ｇ）
（Ｂ８）無延伸ポリブチレンテレフタレートフィルム
三菱エンジニアリングプラスチックス株式会社製のポリブチレンテレフタレート樹脂（銘柄名：５０２０）を用いて厚み２０μｍの無延伸フィルムを成膜したもの。（融点：２２３℃、結晶融解熱量：４９．８Ｊ／ｇ）
（Ｂ９）無延伸ポリブチレンテレフタレートフィルム
三菱エンジニアリングプラスチックス株式会社製のポリブチレンテレフタレート樹脂（銘柄名：５５０５Ｓ）を用いて厚み２０μｍの無延伸フィルムを成膜したもの。（融点：２１９℃、結晶融解熱量：４８．３Ｊ／ｇ）
（Ｂ１０）無延伸ポリブチレンテレフタレートフィルム
三菱エンジニアリングプラスチックス株式会社製のポリブチレンテレフタレート樹脂（銘柄名：５０２０）を用いて厚み５０μｍの無延伸フィルムを成膜したもの。（融点：２２３℃、結晶融解熱量：４９．８Ｊ／ｇ）
（Ｂ１１）無延伸ポリブチレンテレフタレートフィルム
三菱エンジニアリングプラスチックス株式会社製のポリブチレンテレフタレート樹脂（銘柄名：５５０５Ｓ）を用いて厚み５０μｍの無延伸フィルムを成膜したもの。（融点：２１９℃、結晶融解熱量：４８．３Ｊ／ｇ）
In addition, the detail of each film as described in a table | surface is as follows.
(A1) Unstretched 4MP-1 (TPX) film A 15 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(A2) Unstretched 4MP-1 (TPX) film A 15 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: DX818) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 235 ° C., heat of crystal melting: 28.1 J / g)
(A3) Unstretched 4MP-1 (TPX) film An unstretched film having a thickness of 50 μm is formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(A4) Unstretched 4MP-1 (TPX) film A non-stretched film having a thickness of 50 μm was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: DX818) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 235 ° C., heat of crystal melting: 28.1 J / g)
(A5) Fluororesin film 25 μm thick ETFE (ethylene-tetrafluoroethylene) film (Asahi Glass Co., Ltd., product name: Aflex 25N) (melting point: 256 ° C., heat of crystal melting: 33.7 J / g)
(A6) Polystyrene resin film Polystyrene film with a film thickness of 50 μm (manufactured by Kurashiki Boseki Co., Ltd., product name: Eudis CA-F) (melting point: 253 ° C., heat of crystal melting: 19.2 J / g)
(B1) Biaxially stretched PET film Biaxially stretched PET (polyethylene terephthalate) film with a film thickness of 16 μm (product name: Lumirror F865 manufactured by Toray Industries, Inc.) (melting point: 187 ° C., heat of crystal melting: 30.6 J / g)
(B2) Biaxially stretched PET film Biaxially stretched PET (polyethylene terephthalate) film with a film thickness of 12 μm (manufactured by Toray Industries, Inc., product name: Lumirror S10) (melting point: 258 ° C., heat of crystal melting: 39.4 J / g)
(B3) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (manufactured by Kojin Film & Chemicals Co., Ltd., product name: Bonile RX) (melting point: 212 ° C., heat of crystal melting: 53.1 J / g)
(B4) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (product name: Unilon S330, manufactured by Idemitsu Unitech Co., Ltd.) (melting point: 221 ° C., heat of crystal melting: 60.3 J / g)
(B5) Biaxially stretched polypropylene film Biaxially stretched polypropylene film with a film thickness of 20 μm (Mitsui Chemicals Tosero Co., Ltd., product name: U-2) (melting point: 160 ° C., heat of crystal melting: 93.3 J / g)
(B6) Unstretched nylon film Unstretched nylon film having a film thickness of 20 μm (product name: Dynamilon C, manufactured by Mitsubishi Plastics, Inc.) (melting point: 220 ° C., heat of crystal melting: 39.4 J / g)
(B7) Biaxially stretched PET film Biaxially stretched PET film with a thickness of 25 μm (manufactured by Teijin DuPont Films, product name: FT3PE) (melting point: 214 ° C., heat of crystal melting: 40.3 J / g)
(B8) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm formed using a polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)
(B9) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)
(B10) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm is formed using a polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)
(B11) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)
［比較例１〜４］
表１に示すフィルムＡ３、Ａ４、Ｂ１０、及びＢ１１を、それぞれ単独でプロセス用離型フィルムとして使用して、実施例１と同様にして封止、離型を行い、プロセス用離型フィルムの特性を評価した。
いずれの比較例も、総合的に実施例には及ばない性能に留まり、特に皺の発生を抑制することができなかった。
[Comparative Examples 1-4]
Using the films A3, A4, B10, and B11 shown in Table 1 independently as a process release film, sealing and release were performed in the same manner as in Example 1, and characteristics of the process release film were obtained. Evaluated.
In any of the comparative examples, the performance generally did not reach that of the examples, and the generation of wrinkles could not be particularly suppressed.
［実施例１３〜２０］
表２に示す組み合わせで表２記載の各フィルムを離型層Ａ及びＡ’並びに耐熱樹脂層Ｂとした離型フィルムを用いて、実施例１と同様にしてプロセス用離型フィルムを作製し、封止、離型を行い、特性を評価した。
図４に示されるように、離型フィルムを上型と下型との間に２０Ｎの張力を印加した状態で配置した後、上型のパーティング面に真空吸着させた。次いで、半導体チップを覆うように基板上に封止樹脂を充填後、基板に固定された半導体チップを下型に配置し、型締めした。このとき、成形金型の温度（成形温度）を１７０℃、成形圧力を１０ＭＰａ、成形時間を１００秒とした。そして、図３ｃに示されるように、半導体チップを封止樹脂で封止した後、樹脂封止された半導体チップ（半導体パッケージ）を離型フィルムから離型した。結果を表２に示す。
一部に金型追従性が実施例１には及ばないものもあったが、いずれの実施例も離型性、皺の抑制、及び金型追従性が高いレベルでバランスした良好なプロセス用離型フィルムであり、特に実施例１１、及び実施例１３から１５は、離型性、皺の抑制、及び金型追従性が良好なプロセス用離型フィルムであった。
[Examples 13 to 20]
A release film for a process was prepared in the same manner as in Example 1, using a release film in which the films shown in Table 2 were used as the release layers A and A ′ and the heat-resistant resin layer B in the combinations shown in Table 2. Sealing and mold release were performed to evaluate the characteristics.
As shown in FIG. 4, the release film was placed in a state where a tension of 20 N was applied between the upper mold and the lower mold, and then vacuum-adsorbed on the upper parting surface. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 170 ° C., the molding pressure was 10 MPa, and the molding time was 100 seconds. Then, as shown in FIG. 3c, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film. The results are shown in Table 2.
Although some of the mold followability did not reach that of Example 1, each example had good process separation with a good balance between mold release, suppression of wrinkles, and mold followability. In particular, Example 11 and Examples 13 to 15 were process release films having good release properties, suppression of wrinkles, and mold followability.
［比較例５〜７］
表２に示す組み合わせで表２記載の各フィルムを離型層Ａ及びＡ’並びに耐熱樹脂層Ｂとして用いたこと以外は、実施例１１から１６と同様にしてプロセス用離型フィルムを作製し、封止、離型を行い、特性を評価した。結果を表２に示す。
離型性、及び金型追従性は実施例と同様に良好であったが、皺の発生を抑制することができなかった。
[Comparative Examples 5 to 7]
Except having used each film of Table 2 by the combination shown in Table 2 as mold release layer A and A 'and the heat-resistant resin layer B, the mold release film for processes was produced like Example 11-16, Sealing and mold release were performed to evaluate the characteristics. The results are shown in Table 2.
Although mold release property and mold followability were good as in the examples, the generation of wrinkles could not be suppressed.
［比較例８〜１１］
表２に示すフィルムＡ１、Ａ２、Ｂ１０、及びＢ１１を、それぞれ単独でプロセス用離型フィルムとして使用して、実施例１１から１６と同様にして封止、離型を行い、プロセス用離型フィルムの特性を評価した。
いずれの比較例も、総合的に各実施例には及ばない性能に留まり、特に皺の発生を抑制することができなかった。
[Comparative Examples 8 to 11]
Using the films A1, A2, B10, and B11 shown in Table 2 alone as a process release film, sealing and release were performed in the same manner as in Examples 11 to 16, and the process release film was used. The characteristics were evaluated.
All of the comparative examples generally had performances that did not reach the respective examples, and in particular, generation of wrinkles could not be suppressed.
本発明のプロセス用離型フィルムは、従来技術では実現できなかった高いレベルの離型性、皺の抑制、及び金型追従性を兼ね備えるので、これを用いることで、半導体チップ等を樹脂封止等して得られる成形品を容易に離型できるとともに、皺や欠けなどの外観不良のない成形品を、高い生産性で製造することができるという実用上高い価値を有する技術的効果をもたらすものであり、半導体プロセス産業をはじめとする産業の各分野において、高い利用可能性を有する。
また、本発明のプロセス用離型フィルムは、半導体パッケージに限らず、繊維強化プラスチック成形プロセス、プラスチックレンズ成形プロセス等における種々の金型成形にも用いることができるので、半導体産業以外の金型成形を行う産業の各分野においても、高い利用可能性を有する。
The process release film of the present invention combines a high level of mold release, suppression of wrinkles, and mold followability that could not be realized with the prior art. By using this, a semiconductor chip or the like is sealed with resin. That can be easily released from molded products, and that can produce molded products that do not have defects in appearance such as wrinkles and chips with high productivity. It has high applicability in various fields of industries including the semiconductor process industry.
The process release film of the present invention can be used not only for semiconductor packages but also for various mold moldings in fiber reinforced plastic molding processes, plastic lens molding processes, etc. It has high applicability in each field of the industry that conducts.
１、１−２、１−３： 離型フィルム
２： 上金型
３： 吸引口
４： 封止樹脂
４−２：半導体パッケージ
５： 下金型
６： 半導体チップ
７： 基板
８： 成形金型
１０、２０、２２： 離型フィルム
１２： 耐熱樹脂層Ｂ
１４： 接着層
１６、１６Ａ：離型層Ａ
１６Ｂ： 離型層Ａ´
２４、２６： ロール
２８： 成形金型
３０： 上型
３２： 下型
３４： 半導体チップ
３４Ａ： 基板
３６： 封止樹脂
４０、４４： 半導体パッケージ
1, 1-2, 1-3: Release film 2: Upper mold 3: Suction port 4: Sealing resin 4-2: Semiconductor package 5: Lower mold 6: Semiconductor chip 7: Substrate 8: Mold 10, 20, 22: Release film 12: Heat-resistant resin layer B
14: Adhesive layers 16, 16A: Release layer A
16B: Release layer A ′
24, 26: Roll 28: Mold 30: Upper mold 32: Lower mold 34: Semiconductor chip 34A: Substrate 36: Sealing resin 40, 44: Semiconductor package
Claims (19)
前記離型層Ａの水に対する接触角が、９０°から１３０°であり、
前記積層フィルムの横（ＴＤ）方向の２３℃から１２０℃までの熱寸法変化率が３％以下である、上記プロセス用離型フィルム。 A release film for a process which is a laminated film including a release layer A and a heat resistant resin layer B,
The contact angle of the release layer A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
前記離型層Ａの水に対する接触角が、９０°から１３０°であり、
前記積層フィルムの横（ＴＤ）方向の２３℃から１７０℃までの熱寸法変化率が４％以下である、上記プロセス用離型フィルム。 A release film for a process which is a laminated film including a release layer A and a heat resistant resin layer B,
The contact angle of the release layer A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
該離型層Ａ’の水に対する接触角が、９０°から１３０°である、請求項１から１２のいずれか一項に記載のプロセス用離型フィルム。 The laminated film further has a release layer A ′, and includes the release layer A, the heat-resistant resin layer B, and the release layer A ′ in this order,
The process release film according to any one of claims 1 to 12, wherein a contact angle of the release layer A 'with water is 90 ° to 130 °.
成形金型内の所定位置に、樹脂封止される半導体装置を配置する工程と、
前記成形金型内面に、請求項１から１４のいずれか一項に記載の半導体封止プロセス用離型フィルムを、前記離型層Ａが前記半導体装置と対向するように配置する工程と、
前記成形金型を型締めした後、前記半導体装置と、前記半導体封止プロセス用離型フィルムとの間に封止樹脂を注入成形する工程と、
を有する、上記樹脂封止半導体の製造方法。 A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for semiconductor sealing process according to any one of claims 1 to 14 on the inner surface of the molding die so that the release layer A faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
成形金型内の所定位置に、樹脂封止される半導体装置を配置する工程と、
前記成形金型内面に、請求項１３又は１４に記載の半導体封止プロセス用離型フィルムを、前記離型層Ａ’が前記半導体装置と対向するように配置する工程と、
前記成形金型を型締めした後、前記半導体装置と、前記半導体封止プロセス用離型フィルムとの間に封止樹脂を注入成形する工程と、
を有する、上記樹脂封止半導体の製造方法。
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
The step of disposing the release film for semiconductor sealing process according to claim 13 or 14 on the inner surface of the molding die so that the release layer A ′ faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
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| JP2015236639A JP6818406B2 (en) | 2015-12-03 | 2015-12-03 | Release film for process, its application, and manufacturing method of resin-sealed semiconductor using it |
| KR1020187012541A KR102172867B1 (en) | 2015-12-03 | 2016-12-02 | Process release film, its use, and manufacturing method of resin-encapsulated semiconductor using the same |
| TW105139939A TWI723093B (en) | 2015-12-03 | 2016-12-02 | Mold release film for manufacturing process, applications thereof and method of manufacturing resin-sealed semiconductor using the same |
| CN201680065928.5A CN108349122B (en) | 2015-12-03 | 2016-12-02 | Release film for process, use thereof, and method for producing resin-sealed semiconductor using same |
| PCT/JP2016/085859 WO2017094871A1 (en) | 2015-12-03 | 2016-12-02 | Process release film, use thereof, and method of producing resin-sealed semiconductor using same |
| JP2020197012A JP7461281B2 (en) | 2015-12-03 | 2020-11-27 | Process release film, its uses, and method for manufacturing resin-encapsulated semiconductors using the same |
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