WO2006013774A1 - ポリ4-メチル-1-ペンテン樹脂組成物、フィルムおよび電子部品封止体製造用型枠 - Google Patents
ポリ4-メチル-1-ペンテン樹脂組成物、フィルムおよび電子部品封止体製造用型枠 Download PDFInfo
- Publication number
- WO2006013774A1 WO2006013774A1 PCT/JP2005/013827 JP2005013827W WO2006013774A1 WO 2006013774 A1 WO2006013774 A1 WO 2006013774A1 JP 2005013827 W JP2005013827 W JP 2005013827W WO 2006013774 A1 WO2006013774 A1 WO 2006013774A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methyl
- film
- pentene
- resin composition
- polymer
- Prior art date
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 238000007789 sealing Methods 0.000 title abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- 238000000465 moulding Methods 0.000 claims abstract description 32
- 230000000903 blocking effect Effects 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 10
- 239000008393 encapsulating agent Substances 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 38
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 23
- 239000008188 pellet Substances 0.000 description 19
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 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
- RGHIYOCUMCUWAQ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,5-dimethylhexane Chemical compound COCC(COC)(CC(C)C)C(C)C RGHIYOCUMCUWAQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- DYKVLRGFWDMGEM-UHFFFAOYSA-N dec-1-ene 4-methylpent-1-ene Chemical compound CC(C)CC=C.CCCCCCCCC=C DYKVLRGFWDMGEM-UHFFFAOYSA-N 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/02—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/10—Housing; Encapsulation
- H01G2/103—Sealings, e.g. for lead-in wires; Covers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Definitions
- the present invention relates to a poly-4-methyl-1-pentene resin composition having excellent releasability. More specifically, a poly 4-methyl-1-pentene resin composition having a high surface crystallinity when a film having a short semi-crystallization time is formed, a small blocking coefficient of the film and excellent releasability, and Suitable for manufacturing molds for encapsulating electronic components obtained by molding the resin composition, especially molds for encapsulating light emitting diodes (hereinafter abbreviated as LEDs), so-called LED molds and flexible printed boards
- the present invention relates to a release film.
- FPC multilayer flexible printed circuit boards
- the manufacture of a copper-clad laminate performed prior to the manufacture of FPC is to integrate a pre-preda placed on a copper foil by heat and pressure treatment.
- a plurality of copper-clad laminates that are not produced in pairs are press-molded at the same time.
- a release film is sandwiched between the copper-clad laminates, and the molds are released after press-molding.
- the manufacturing method which obtains a copper-clad laminated board one pair at a time by peeling a mold film is performed.
- a release film As a release film, it has excellent heat resistance and releasability after heat and pressure treatment. It has been proposed to use a film made of poly 4_methyl_1 ⁇ Nten. Poly 4-methylolene 1 ⁇ Nten has a high melting point of about 235 ° C, so it has excellent heat resistance and mold release even when forming copper-clad laminates at temperatures from 170 ° C to 180 ° C. In recent years, there has been a tendency for high-quality FPC to be required to increase the wiring speed and improve the reliability, and the copper used in the manufacture of such printed wiring boards. The conditions for heat and pressure treatment during the production of the laminated laminate have become stricter, and the mold release film used is required to have better mold release properties.
- an electronic component sealing body in which an LED, transistor, LSI element, IC element, CCD element or other integrated circuit element, capacitor, resistor, coil, microswitch, dip switch, etc. are sealed
- a sealing material made of a thermosetting resin such as an epoxy resin
- metal molds are expensive and difficult to mass-produce, and resin molds such as polyphenylene sulfide (PPS) are sealed with thermosetting resins.
- PPS polyphenylene sulfide
- Patent Document 1 discloses transparency in which the yield of a solvent-insoluble polymer is improved by polymerizing a 4-methyl-1-pentene polymer in two stages while changing the ⁇ -olefin content. A method for producing a good 4_methyl_1_pentene copolymer is disclosed. However, there is a problem in the releasability when the film made of the copolymer is used as a release film that is insufficient in surface crystallinity.
- Patent Document 2 discloses an electronic component encapsulant for integrated circuits such as LEDs, diodes, transistors, LSI elements, IC elements, and CCD elements that use a thermosetting resin such as an epoxy resin as a sealing material.
- a thermosetting resin such as an epoxy resin
- Patent Document 1 JP-A 63-63707
- Patent Document 2 Japanese Patent Laid-Open No. 6-114846
- Patent Document 3 Japanese Patent Laid-Open No. 57_70653
- Patent Document 4 Japanese Patent Laid-Open No. 56-138981
- the present invention solves the above problems, and provides a resin composition having a high surface crystallinity and a small blocking coefficient when formed into a film having a short semi-crystallization time. . It is also desirable to provide a release film having good release properties suitable for the production of FPCs obtained by molding the resin composition. Furthermore, it excels in heat resistance and releasability, and in the manufacture of sealed electronic parts such as LEDs, when the sealing material made of thermosetting resin is cured, the mold is not easily deformed and can be used repeatedly. It is to provide a mold for manufacturing a sealed electronic component that is not easily deformed and an LED mold.
- the semi-crystallization time of a resin composition containing a specific amount of a polymer containing pentene is short.
- the crystallinity of the film surface obtained by molding the resin composition is high and the blocking coefficient is small. The inventors have found that this can be solved, and have completed the present invention.
- the present invention relates to
- a resin composition comprising a polymer (A) having a 4_methyl_1_pentene content of 80% by mass or more, wherein the resin composition has a melting point of 170 to 240 ° C. and a semi-crystallization time.
- a poly-4-methyl-1 ⁇ ene resin composition having a duration of 70 to 220 seconds.
- Polymers (A) containing 95 to 100% by weight of 4_methyl_1_pentene and 5 to 70% by weight of carbon atoms other than 4-methyl-1-pentene and 4-methyl-1-pentene Provided is the poly-4-methyl-1-pentene resin composition according to the above [1], which contains 30 to 95% by mass of the polymer (B) containing olefins of 2 to 20.
- a film comprising the poly-4-methyl-1-pentene resin composition of the present invention has good releasability due to a short semi-crystallization time, a high surface crystallinity and a small blocking coefficient. And can be suitably used as a release film in the production of FPC and the like. In addition, it has excellent heat resistance and releasability, and is difficult to deform when the thermoplastic encapsulant is cured. It can be suitably used as a mold and has an extremely high industrial value.
- the poly-4-methyl-1-pentene resin composition according to the present invention a film obtained by molding the resin composition, and a mold for manufacturing an electronic component encapsulant will be described.
- the polymer (A) of the present invention is a crystalline polymer having a 4-methyl-1 pentene content of 80% by mass or more, and includes 4-methyl-1 pentene and olefins having 2 to 20 carbon atoms other than 4-methyl-1 pentene. Or a homopolymer of 4-methyl-1 pentene.
- Polymer (A) of the present invention 4_ methyl _ 1 _-pentene content of 80 mass% or more, preferably rather 90 mass 0/0 or more, more preferably 95 to 100 mass 0/0, further 99 ⁇ : 100 mass 0/0 a is 4 - methyl one 1 _ pentene principal and the rather most preferably preferred instrument be crystalline polymer is 4 Mechinore one 1 ⁇ pentene homopolymer.
- 4_Methyl_1_Pentene homopolymer is substantially composed of 4_Methyl_1_pentene. Since it does not have any other repeating units, it does not carry out copolymerization by actively adding monomers other than 4_methyl_1 ⁇ nten that can copolymerize with 4_methyl_1 ⁇ ntenene. is there.
- Examples of olefins having 2 to 20 carbon atoms other than 4_methyl_1_pentene that can be used for copolymerization with 4_methyl_1_pentene include ethylene, propylene, 1-butene, 1 One hexene, 1-octene, 1-decene, 1-tetradecene, 1-octa decene, etc., which can be used alone or in combination of two or more S, among these, copolymerized with 4-methyl-1 pentene 1-decene, 1-tetradecene, and 1-octadecene are preferred because they have good toughness and good toughness.
- the production method of the polymer (A) of the present invention is not particularly limited, and can be produced using a well-known catalyst such as a Cidara 'Natta catalyst or a metalocene catalyst.
- the crystal structure may be either isotactic or syndiotactic.
- 4-methyl-1 pentene is homopolymerized in the presence of a catalyst, or 4-methyl-1 pentene and the above-mentioned olefin. Can be obtained as a powder.
- the polymer (A) of the present invention has an intrinsic viscosity [] measured according to ASTM J1601 of 2.5 to 4 dl / g, and more preferably 3 to 3.8 dl / g.
- the polymer (B) of the present invention is a crystalline polymer containing 4-methylolene 1 ⁇ -pentene, and has 2-20 carbon atoms other than 4 methyl-1_pentene and 4 methyl-1_pentene, Preferably, it is a copolymer with polyolefin having 7 to 20 carbon atoms, more preferably 8 to 20 carbon atoms.
- examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1_heptene, 1-octene, 1_decene, 1-dodecene, 1-tetradecene, 1_ Hexadecene, 1_heptadecene, 1-octadecene, 1 eicosene, etc., preferably 1-decene, 1-dedecene, 1 Tetradecene, 1_hexadecene, 1_heptadecene, 1-octadecene, which can be used singly or in combination of two or more.
- 1-decene, 1 —Dodecene or 1-tetradecene is preferred.
- the composition of the polymer (B) of the present invention is within the above range, the moldability and rigidity of a film obtained by molding the poly-4-methyl-1 pentene resin composition containing the polymer (B) are excellent.
- the polymer (B) of the present invention can be produced using a well-known catalyst such as a Cidara 'Natta catalyst, a metalocene catalyst, and the crystal structure thereof may be either isotactic or syndiotactic.
- a well-known catalyst such as a Cidara 'Natta catalyst, a metalocene catalyst, and the crystal structure thereof may be either isotactic or syndiotactic.
- powder can be obtained by copolymerizing 4-methylolene 1 pentene and the olefin in the presence of a catalyst.
- the intrinsic viscosity [] measured according to ASTM J1601 is preferably 2.5 to 4 dl / g, more preferably 3 to 3.8 dl / g.
- the poly-4_methyl_1_pentene resin composition of the present invention comprises the polymer (A) of the present invention in an amount of 5 to 70% by mass, preferably 5 to 50% by mass, and the polymer (B) of the present invention.
- a resin composition containing 30 to 95% by mass, preferably 50 to 95% by mass is preferable.
- the total amount of the polymer (A) and the polymer (B) is 100 parts by mass.
- the resin composition has a semi-crystallization time of 70 to 220 seconds, preferably 70 to 165 seconds,
- the film obtained by molding the resin composition has a surface crystallinity of 15 to 60%, preferably 20 to 50%, and a blocking coefficient of 4 to 10 gf / cm 2 , preferably 4 to 7 gf Zcm 2.
- a resin composition having good moldability and good film moldability can be obtained.
- the poly-4-methyl-1 pentene resin composition of the present invention has a A pre-stage polymerization for polymerizing the polymer (A) of the present invention is carried out using a known catalyst such as a sen-based catalyst, and then the polymer (B) of the present invention is added in the presence of the catalyst subjected to the pre-stage polymerization.
- a polymer powder can be obtained by subsequent polymerization.
- the ratio of the polymer (A) to the polymer (B) of the present invention is controlled by adjusting the amount of the polymer obtained by the above-mentioned pre-stage polymerization and post-stage polymerization by the amount of monomer supplied during the polymerization, the polymerization time, etc. This is possible.
- the molecular weight can be adjusted by adding hydrogen to the polymerization temperature and polymerization system.
- the intrinsic viscosity [7] measured according to ASTM J1601 is 2.5-4 dl / g, and further 3-3. / g is preferred.
- the polymer powder obtained is blended with polyolefin such as a heat stabilizer, a weather stabilizer, an anti-fogging agent, a copper damage stabilizer, and an antistatic agent within the range not impairing the object of the present invention.
- polyolefin such as a heat stabilizer, a weather stabilizer, an anti-fogging agent, a copper damage stabilizer, and an antistatic agent within the range not impairing the object of the present invention.
- Various additives known per se can be added, melt-kneaded using a single screw extruder, double screw extruder, kneader, etc. and granulated or pulverized to obtain pellets or pulverized products.
- MFR melt flow rate measured according to the above is 10 to 40 g / 10 min, and further 20 to 30 g / 10 min, the film has good moldability and is preferable.
- the content of olefins having 2 to 20 carbon atoms other than 4-methyl-1 pentene, that is, ethylene or olefins having 3 to 20 carbon atoms is , depending on the kind of monomers used 1: 10 mass 0/0, is preferably preferably from 2 to 7% by weight.
- the poly-4_methyl_1 ⁇ ene resin composition of the present invention is obtained by separately polymerizing a known catalyst such as a Cidara 'Natta catalyst or a metallocene catalyst, respectively.
- the polymer (A) and the polymer (B) are blended in the above-mentioned quantitative ratio of the present invention, and mixed with a mixer such as a Banbury mixer or a Henschel mixer, a single screw extruder, a double screw extruder, a kneader, etc. It can also be obtained by melt-kneading and granulating or pulverizing.
- a film obtained by molding the poly 4_methyl_1_pentene resin composition of the present invention is obtained by pressing the above poly 4_methyl_1_pentene resin composition using a press molding method, an extrusion molding method, an inflation method,
- the film can be formed by a known method such as a calendar method. You may extend
- the thickness of the film comprising the poly 4 methyl 1 ⁇ nten resin composition of the present invention is usually 5 to 1000 xm when used as a force-releasing film depending on the intended use. When the thickness is from 50 to 100 ⁇ m, the productivity of the film is excellent, and pinholes are not generated during film formation, which is preferable.
- the film obtained by molding the poly-4-methyl-1 pentene resin composition of the present invention is suitably used for food wrap films, medical bag protection films, liquid crystal display reflector films, etc., in addition to release films. can do.
- the mold release film which is a film made of the poly-4-methyl-11-pentene resin composition of the present invention can be suitably used for a release film for printed circuit boards, a release film for thermosetting resins, and the like.
- the release film, which is a film made of the poly-4-methyl-1-pentene resin composition of the present invention has a high surface crystallinity and a small blocking coefficient, and therefore has good release properties, particularly for FPC production. It can be suitably used as a release film.
- the mold for producing an electronic component encapsulant comprising the poly-4_methyl_1_pentene resin composition of the present invention is a mold for producing an encapsulated electronic component having excellent releasability and high heat resistance and rigidity. It can be used suitably.
- the LED mold so-called mold for LED sealing This is a mold used for LED sealing.
- the LED mold comprising the poly 4_methyl_1_pentene resin composition of the present invention has high heat resistance and rigidity, and excellent releasability. Furthermore, since the mold is difficult to deform when the sealing material made of a thermosetting resin is cured, and it is excellent in durability in repeated use, it can be suitably used as an LED mold.
- a differential run type calorimeter (DSC-7 type, manufactured by Perkin Elma Co., Ltd.) was used, and 10 mg of sampnole cut out from the press-formed sheet was heat-treated at 280 ° C for 10 minutes in a nitrogen atmosphere, and the temperature was lowered In the crystallization curve observed when cooling to 220 ° C at a rate of 320 ° CZ and constant temperature at 220 ° C, the time to reach half of the integrated value of the exothermic peak (t 1/2 (Seconds)).
- the intensity of the diffracted X-rays was scintillated. Measure with the counter. 2 Perform ⁇ scanning at 5 to 35 ° to obtain a wide-angle X-ray diffraction profile of the sample.
- an amorphous sample of the same material is prepared, and the X-ray diffraction profile (amorphous halo) of the amorphous sample obtained by performing the same measurement is used to convert the X-ray diffraction profile of the actual sample to an amorphous halo.
- crystal peak The crystallinity of the actual sample is determined as follows. First, the baseline is cut off, and the ratio of the total crystal peak area to the total area is obtained as a percentage.
- a cast film molding machine with a T-die was molded at a cylinder temperature of 310 ° C and a chill roll temperature of 20 ° C.
- a film with a thickness of 50 zm was cut from a 6cm x 12cm film and an epoxy resin.
- the sheets were stacked, sandwiched between two mirror-finished metal plates, and heated and pressurized at 180 ° C for 30 minutes under a 5 MPa load.
- a cast film molding machine with a T-die was molded at a cylinder temperature of 310 ° C and a chill roll temperature of 20 ° C.
- a film force of 50 zm in thickness was cut out from a 6 cm x 12 cm film and a polyimide resin.
- the sheets were stacked, sandwiched between two mirror-finished metal plates, and heated and pressurized at 180 ° C for 30 minutes under a 5 MPa load.
- the peelability when peeling the film from the copper foil with the edge of the film is: ⁇ : Easy peeling without adhesion to the polyimide resin.
- X Evaluated as having high adhesive strength and impossible to peel by hand.
- Anhydrous magnesium chloride (750 g), decane (2800 g), and 2-ethylhexyl alcohol (3,080 g) were heated at 130 ° C for 3 hours to form a homogeneous solution, and this solution was then mixed with 2-isobutynol 2-isopropinolol 1, 220 ml of 3-dimethoxypropane was added, and further stirred and mixed at 100 ° C. for 1 hour. After cooling the homogeneous solution thus obtained to room temperature, 3000 ml of this homogeneous solution was all added dropwise into 800 ml of titanium tetrachloride maintained at ⁇ 20 ° C. over 45 minutes with stirring.
- the solid titanium catalyst component prepared by the above operation was stored as a decane slurry, but a part of this was dried for the purpose of examining the catalyst composition.
- the composition of the catalyst component obtained by titanium 3.0 mass 0 I magnesium 17.0 mass 0 I chlorine 57 mass 0 I 2_ Isobuchinore _2_ iso Puropinore - 1, 3-dimethoxypropane 18.8 mass 0 / 0 and 2_ethylhexyl alcohol 1.3 mass 0 /. Met. [0037] (Production of polymer (A))
- the yield of the polymer obtained was 26 kg, the limiting viscosity [] was 3.5 dl / g, and the mass ratio of the prepolymerization amount and the postpolymerization amount, that is, the mass ratio of the polymer (A) and the polymer (B) was The ratio of polymer (A) / polymer (B) was 20/80. Further, the decene 1 content of the resin composition measured by NMR and the mass specific force of the pre-polymerization amount and the post-polymerization amount were determined. The decene 1 content in the polymer (B) of the present invention was 3.3% by mass. Met.
- Polymerization was conducted in the same manner, and the obtained powder was melt-kneaded to obtain pellets.
- the MFR of the obtained pellet was 25 gZlO. Table 1 shows the results of film formation and evaluation of the physical properties of the film.
- the polymer (A) 10% by mass obtained by polymerization separately, 90% by mass of the polymer) and a conventionally known neutralizing agent and phenolic antioxidant were mixed in a Henschel mixer. Using an extruder, the mixture was melt-kneaded at 290 ° C. to obtain poly 4_methyl_1_pentene resin composition pellets. The MFR of the obtained pellet was 25 g / l0 min.
- a cast film with a thickness of 50 ⁇ was obtained by forming the film at a cylinder temperature of 310 ° C. and a chill roll temperature of 20 ° C. using a cast film molding machine with a T die.
- Table 2 shows the physical property evaluation results of the obtained film.
- Pellets were obtained in the same manner as in Example 4 except that the polymer ( ⁇ ) was 30% by mass and the polymer ( ⁇ ) was 70% by mass.
- the MFR of the obtained pellet was 25 g / 10 min.
- Table 2 shows the results of film formation performed at the next stage and the film physical properties evaluated.
- Pellets were obtained in the same manner as in Example 4 except that the polymer (A) was 50% by mass and the polymer (B) was 50% by mass.
- the MFR of the obtained pellet was 25 g / 10 min.
- Table 2 shows the results of film formation performed at the next stage and the film physical properties evaluated.
- Pellets were obtained in the same manner as in Example 4 except that the polymer (A) was 70% by mass and the polymer (B) was 30% by mass.
- the MFR of the obtained pellet was 25 g / l0 min.
- Table 2 shows the results of film formation performed at the next stage and the film physical properties evaluated.
- Example 2 In a SUS polymerization tank with an internal volume of 150 liters and equipped with a stirrer, decane 100 liters, 26 kg of 4 methylolates _ 1 _pentene, 230 g of decene 1, hydrogen 6.75 liters of triethylaluminum, 67.5 mmol Then, the solid titanium catalyst component obtained in Example 1 was calcined with 0.27 monolayer in terms of Ti atom, and the polymerization tank was kept at 60 ° C to obtain 4-methyl-1 pentene. And decene_1 polymerization was carried out for 5 hours. The powder was taken out from the polymerization tank, filtered and washed, and then dried to obtain a powdery polymer (A). The yield of the obtained polymer powder was 26 kg , and the intrinsic viscosity [ ⁇ ] was 3.5 dl / g. Further, the content of decene 11 measured by NMR was 1.0 mass. /. Met.
- 30% by mass of the polymer (8) obtained by the above polymerization, 70% by mass of the polymer (8), and a conventionally known neutralizing agent and phenolic antioxidant were mixed with a hensil mixer, and an extruder was used. Using 290. The mixture was melt-kneaded in C to obtain pellets. The MFR of the obtained pellet was 25 g / 10 minutes.
- Table 2 shows the physical property evaluation results of the obtained film.
- the film obtained by molding the poly 4-methyl- 1-pentene resin composition of the present invention has a high surface crystallinity and a small blocking coefficient, and therefore has good releasability, a printed wiring board, In particular, it can be suitably used in the production of a multilayer flexible wiring board.
- the mold for producing an electronic component sealing material body obtained by molding the poly-4-methyl-11-pentene resin composition of the present invention is excellent in releasability and has high heat resistance and rigidity.
- the sealing material made of a thermosetting resin is cured, the mold frame is not easily deformed, and is excellent in durability in repeated use. In particular, it can be suitably used as an LED mold.
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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05767102A EP1775320A4 (en) | 2004-08-03 | 2005-07-28 | POLY-4-METHYL-1-PENTENE RESIN COMPOSITION, FILM AND MOLD FOR MANUFACTURING ELECTRONIC COMPONENT SEAL BODIES |
CN2005800263044A CN1993418B (zh) | 2004-08-03 | 2005-07-28 | 聚4-甲基-1-戊烯树脂组合物、薄膜和电子部件密封体制造用模具 |
US11/658,992 US20080315066A1 (en) | 2004-08-03 | 2005-07-28 | Poly 4-Methyl-1-Pentene Resin Composition, Film and Mold for Production of Sealed Electronic Element Product |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004227209 | 2004-08-03 | ||
JP2004-227209 | 2004-08-03 |
Publications (1)
Publication Number | Publication Date |
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WO2006013774A1 true WO2006013774A1 (ja) | 2006-02-09 |
Family
ID=35787062
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/013827 WO2006013774A1 (ja) | 2004-08-03 | 2005-07-28 | ポリ4-メチル-1-ペンテン樹脂組成物、フィルムおよび電子部品封止体製造用型枠 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080315066A1 (ja) |
EP (1) | EP1775320A4 (ja) |
KR (1) | KR20070047274A (ja) |
CN (1) | CN1993418B (ja) |
TW (1) | TWI305791B (ja) |
WO (1) | WO2006013774A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008144155A (ja) * | 2006-11-14 | 2008-06-26 | Mitsui Chemicals Inc | 4−メチル−1−ペンテン系ランダム共重合体およびその製造方法ならびに該共重合体を含む組成物 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US8058379B2 (en) | 2007-07-10 | 2011-11-15 | Mitsui Chemicals, Inc. | 4-methyl-1-pentene polymer, process for producing the same and use thereof |
WO2010013993A1 (en) * | 2008-08-01 | 2010-02-04 | Titan Petchem (M) Sdn Bhd | Halal polymer resins and process for making the same |
CN102089379B (zh) * | 2008-08-01 | 2013-05-01 | 三井化学株式会社 | 聚4-甲基-1-戊烯树脂组合物、含其的膜、微多孔膜、电池用隔膜及锂离子电池 |
KR20170023432A (ko) * | 2015-08-24 | 2017-03-06 | 주식회사 덴티스 | 3d 프린터용 이형 수조 |
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JP2790330B2 (ja) * | 1989-08-15 | 1998-08-27 | 三井化学株式会社 | プリント配線板製造用の離型フィルムおよびその製造方法 |
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2005
- 2005-07-28 WO PCT/JP2005/013827 patent/WO2006013774A1/ja active Application Filing
- 2005-07-28 US US11/658,992 patent/US20080315066A1/en not_active Abandoned
- 2005-07-28 KR KR1020077000092A patent/KR20070047274A/ko not_active Application Discontinuation
- 2005-07-28 EP EP05767102A patent/EP1775320A4/en not_active Withdrawn
- 2005-07-28 CN CN2005800263044A patent/CN1993418B/zh active Active
- 2005-08-02 TW TW094126176A patent/TWI305791B/zh active
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JPS56138981A (en) | 1980-03-31 | 1981-10-29 | Hitachi Chemical Co Ltd | Method of producing adhesive coated laminate |
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JPS62209153A (ja) * | 1986-03-11 | 1987-09-14 | Mitsui Petrochem Ind Ltd | 樹脂組成物 |
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Also Published As
Publication number | Publication date |
---|---|
CN1993418B (zh) | 2010-05-26 |
KR20070047274A (ko) | 2007-05-04 |
TWI305791B (en) | 2009-02-01 |
EP1775320A1 (en) | 2007-04-18 |
US20080315066A1 (en) | 2008-12-25 |
TW200617092A (en) | 2006-06-01 |
EP1775320A4 (en) | 2009-03-18 |
CN1993418A (zh) | 2007-07-04 |
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