TW202307129A - Liquid-crystalline polyester-based resin composition, liquid-crystalline polyester-based film using said composition, metal laminated film using said film, and circuit board - Google Patents
Liquid-crystalline polyester-based resin composition, liquid-crystalline polyester-based film using said composition, metal laminated film using said film, and circuit board Download PDFInfo
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- TW202307129A TW202307129A TW111113968A TW111113968A TW202307129A TW 202307129 A TW202307129 A TW 202307129A TW 111113968 A TW111113968 A TW 111113968A TW 111113968 A TW111113968 A TW 111113968A TW 202307129 A TW202307129 A TW 202307129A
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- liquid crystal
- crystal polyester
- thermoplastic liquid
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- 229920000728 polyester Polymers 0.000 title claims abstract description 147
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 42
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims description 29
- 239000002184 metal Substances 0.000 title claims description 29
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 142
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 142
- 238000002844 melting Methods 0.000 claims abstract description 95
- 230000008018 melting Effects 0.000 claims abstract description 95
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000001125 extrusion Methods 0.000 claims abstract description 41
- 239000004645 polyester resin Substances 0.000 claims abstract description 36
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 16
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims abstract description 15
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 197
- 239000000155 melt Substances 0.000 claims description 72
- 229920006267 polyester film Polymers 0.000 claims description 40
- 239000000470 constituent Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 5
- 239000010408 film Substances 0.000 description 68
- 239000000178 monomer Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 27
- 239000010410 layer Substances 0.000 description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920000106 Liquid crystal polymer Polymers 0.000 description 12
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 12
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 238000007664 blowing Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 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 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical group C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BYEMVXMBTJJKGV-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid;naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21.C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 BYEMVXMBTJJKGV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
Abstract
Description
本發明係關於將可形成光學各向異性的熔融相之熱塑性液晶聚酯作為主成分之液晶聚酯系樹脂組成物。又，關於使用該樹脂組成物之液晶聚酯系薄膜，及使用該薄膜之金屬層合薄膜、電路基板。The present invention relates to a liquid crystal polyester resin composition mainly composed of a thermoplastic liquid crystal polyester capable of forming an optically anisotropic molten phase. Also, it relates to a liquid crystal polyester film using the resin composition, a metal laminate film and a circuit board using the film.
近年來，於電子•電氣領域，對於機器的小型化•輕量化的要求變強，正尋求電氣特性或機械特性等優異之絕緣用薄膜。惟，於以往之絕緣用薄膜的原料之聚醯亞胺或聚對苯二甲酸乙二酯等，有起因於於高頻率區域之電氣特性並不充足，並且吸濕性高，導致電氣特性惡化或產生大幅尺寸變化的問題，滿足上述的要求之薄膜的實現困難。In recent years, in the field of electronics and electrics, the demand for miniaturization and weight reduction of equipment has become stronger, and insulating films with excellent electrical and mechanical properties are being sought. However, polyimide, polyethylene terephthalate, etc., which are used as raw materials for conventional insulating films, have insufficient electrical properties in the high-frequency region and high moisture absorption, resulting in deterioration of electrical properties. Or there is a problem that a large dimensional change occurs, and it is difficult to realize a thin film that satisfies the above-mentioned requirements.
對於此，熱塑性液晶聚酯由於顯示優異之機械特性或電氣特性、低尺寸變化率、高耐熱性及化學的安定性等，故在電子•電氣領域為有用。尤其是熔點為300℃以上之熱塑性液晶聚酯，由於無鉛焊接的回流焊亦可能，故對印刷電路基板用途為有用。然而，熱塑性液晶聚酯由於具有即使於熔融狀態，剛直之分子鏈亦整齊排列，分子鏈不會糾纏如順暢流動的特性，故分子鏈容易往樹脂的流動方向配向，僅單純薄膜化，無法達到可使用的水準。In contrast, thermoplastic liquid crystal polyesters are useful in the fields of electronics and electricity because they exhibit excellent mechanical and electrical properties, low dimensional change rate, high heat resistance, and chemical stability. In particular, thermoplastic liquid crystal polyester having a melting point of 300°C or higher is useful for printed circuit board applications because reflow soldering of lead-free soldering is also possible. However, the thermoplastic liquid crystal polyester has the characteristic that even in the molten state, the rigid and straight molecular chains are arranged neatly, and the molecular chains are not entangled, so that the molecular chains are easy to align in the flow direction of the resin. usable level.
作為製造由熱塑性液晶聚酯所構成之薄膜之方法，已知有利用充氣擠出成形等之擠出成形法之製造方法。(參照專利文獻1)為充氣擠出成形時，藉由適當調整吹氣比，可某種程度控制分子鏈的配向。As a method for producing a film composed of thermoplastic liquid crystal polyester, a production method using an extrusion molding method such as pneumatic extrusion molding is known. (Refer to Patent Document 1) In the case of pneumatic extrusion molding, the alignment of molecular chains can be controlled to some extent by properly adjusting the blowing ratio.
然而，熱塑性液晶聚酯具有熔融黏度大幅依賴切斷應力，藉由切斷應力的些微上昇，顯著降低熔融黏度的特徵。因此，藉由充氣擠出成形法，熔融擠出熱塑性液晶聚酯時，有藉由於模具(Dice)部分發生之切斷應力，急遽降低熔融黏度，保持氣泡的形狀變困難的情況，有安定地製膜薄膜困難的問題。However, the thermoplastic liquid crystal polyester has a characteristic that the melt viscosity is greatly dependent on the shear stress, and the melt viscosity is significantly lowered by a slight increase of the shear stress. Therefore, when the thermoplastic liquid crystal polyester is melt-extruded by the pneumatic extrusion molding method, the shear stress generated in the die (Dice) part may suddenly reduce the melt viscosity, and it may become difficult to maintain the shape of the bubbles. Difficulty in making thin films.
又，熱塑性液晶聚酯具有熔融黏度大幅依賴溫度，在熔點附近，藉由些微的溫度上昇，顯著降低熔融黏度的特徵。熔點越高之熱塑性液晶聚酯，此傾向越顯著，尤其是熔點為300℃以上之熱塑性液晶聚酯由於熔點附近的熔融黏度低，故藉由充氣擠出成形，製膜薄膜時，於從模具擠出之氣泡容易發生孔洞，安定地製膜薄膜困難。In addition, thermoplastic liquid crystal polyester has a characteristic that its melt viscosity is greatly dependent on temperature, and the melt viscosity is significantly lowered by a slight temperature rise near the melting point. The higher the melting point of the thermoplastic liquid crystal polyester, the more pronounced this tendency is, especially the thermoplastic liquid crystal polyester with a melting point above 300°C has a low melt viscosity near the melting point, so when forming a film by air-inflated extrusion, the film is formed from the mold. The extruded air bubbles are prone to holes, and it is difficult to form a stable film.
另一方面，專利文獻2係關於一種液晶聚酯組成物之發明，其特徵為由於250℃以上的溫度，為光學性形成各向異性的熔融相之聚酯及於200℃以下的溫度，為光學性形成各向異性的熔融相之聚酯所構成，記載藉由混合於200℃以下的溫度，為光學性形成各向異性的熔融相之液晶聚酯，降低熔融黏度，提昇低溫成型性。On the other hand, Patent Document 2 relates to an invention of a liquid crystal polyester composition, which is characterized in that it is a polyester that optically forms an anisotropic melt phase at a temperature above 250°C and that at a temperature below 200°C, it is: Composed of polyester that optically forms an anisotropic melt phase, it is described that by mixing at a temperature below 200°C, it is a liquid crystal polyester that optically forms an anisotropic melt phase, which reduces melt viscosity and improves low-temperature moldability.
專利文獻3係關於一種液晶聚合物混合物之發明，其特徵為由拉伸彈性率為20～32GPa，熔點為250℃以上330℃以下之液晶聚合物(A)及熔點為190℃以上且未滿250℃之液晶聚合物(B)所構成，記載有藉由摻合顯示低熔點之液晶聚合物，提昇成形時之流動性及低溫加工性。Patent Document 3 is an invention of a liquid crystal polymer mixture, which is characterized by a liquid crystal polymer (A) with a tensile modulus of 20 to 32 GPa, a melting point of 250°C to 330°C, and a melting point of 190°C or higher and less than Composed of a liquid crystal polymer (B) at 250°C, it is described that fluidity during molding and low-temperature processability are improved by blending a liquid crystal polymer exhibiting a low melting point.
然而，於專利文獻2及專利文獻3之實施例，僅揭示將該組成物藉由射出成型，以作為試驗片，針對藉由充氣擠出成形，連續性製膜薄膜並未有任何揭示。 [先前技術文獻] [專利文獻] However, in the examples of Patent Document 2 and Patent Document 3, it is only disclosed that the composition is injection molded as a test piece, and there is no disclosure about continuous film formation by pneumatic extrusion molding. [Prior Art Literature] [Patent Document]
[專利文獻1]日本特開2005-1376 [專利文獻2]日本特開平5-186671 [專利文獻3]日本特開2007-119639 [Patent Document 1] Japanese Patent Laid-Open No. 2005-1376 [Patent Document 2] Japanese Patent Laid-Open No. 5-186671 [Patent Document 3] Japanese Patent Laid-Open No. 2007-119639
[發明欲解決之課題][Problem to be solved by the invention]
本發明係鑑於這般的問題而完成者，以提供一種在充氣擠出成形，可安定地製膜薄膜之機械特性、電氣特性、耐熱性優異之液晶聚酯系樹脂組成物作為目的。 [用以解決課題之手段] The present invention was made in view of such problems, and an object of the present invention is to provide a liquid crystal polyester resin composition which is excellent in mechanical properties, electrical properties, and heat resistance, and which can be stably formed into a film by pneumatic extrusion molding. [Means to solve the problem]
本發明者們針對維持熔點高之熱塑性液晶聚酯(例如熔點300℃以上)所具有之優異之機械特性或電氣特性、耐熱性，並且在充氣擠出成形，安定地薄膜的製膜成為可能之樹脂組成物，進行努力研究的結果，發現藉由對熔點高且耐熱性優異之熱塑性液晶聚酯，摻合相對性熔點低之熱塑性液晶聚酯，對於熔融黏度的溫度或切斷應力之依賴度縮小，在充氣擠出成形，變成可安定地製膜，而終至完成本發明。The present inventors aimed to maintain the excellent mechanical properties, electrical properties, and heat resistance of thermoplastic liquid crystal polyester with a high melting point (for example, a melting point of 300° C. or higher), and make it possible to stably form a film by pneumatic extrusion molding. As a result of intensive research on the resin composition, it was found that by blending a thermoplastic liquid crystal polyester with a relatively low melting point with a thermoplastic liquid crystal polyester with a high melting point and excellent heat resistance, the dependence of the melt viscosity on temperature or shear stress Shrinkage, inflated extrusion molding, become a stable film, and finally complete the present invention.
藉由本發明時， (1)提供一種液晶聚酯系樹脂組成物，其係包含熱塑性液晶聚酯(A)與熱塑性液晶聚酯(B)之液晶聚酯系樹脂組成物，其特徵為前述熱塑性液晶聚酯(A)與前述熱塑性液晶聚酯(B)的熔點之差為5℃以上95℃以下，前述熱塑性液晶聚酯(A)包含源自p-羥基苯甲酸之構成單位與源自6-羥基-2-萘甲酸之構成單位，前述熱塑性液晶聚酯(B)為包含源自p-羥基苯甲酸之構成單位與源自6-羥基-2-萘甲酸之構成單位，或者包含源自p-羥基苯甲酸之構成單位與源自4,4’-二羥基聯苯之構成單位之任一者，前述熱塑性液晶聚酯(A)與前述熱塑性液晶聚酯(B)的摻合比例為(A)：(B)=40～98重量%：2～60重量%，使用在充氣擠出成形、 (2)提供一種如(1)所記載之液晶聚酯系樹脂組成物，其特徵為於剪切速度122sec -1的條件下測定之在前述熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與於剪切速度122sec -1的條件下測定之在前述熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R 122(μ Tm/μ Tm+10)為未滿3.4、 (3)提供一種如(1)所記載之液晶聚酯系樹脂組成物，其特徵為於剪切速度122sec -1的條件下測定之在前述熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與於剪切速度122sec -1的條件下測定之在前述熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R 122(μ Tm/μ Tm+10)，相對於在剪切速度1216sec -1的條件下測定之在前述熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與於剪切速度1216sec -1的條件下測定之在前述熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R 1216(μ Tm/μ Tm+10)之比(R 122/R 1216)之值為1.5以下、 (4)提供一種如(1)所記載之液晶聚酯系樹脂組成物，其特徵為在剪切速度122～2430sec -1的範圍內，以個別之剪切速度的條件下測定之在前述熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與在前述熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度R(μ Tm+10)的熔融黏度比(μ Tm/μ Tm+10)之最大值與最小值的差(不均)為未滿1.2、 (5)提供一種如(1)所記載之液晶聚酯系樹脂組成物，其特徵為在剪切速度6～2430sec -1的範圍內，以個別之剪切速度的條件下測定之在前述熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與在前述熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R(μ Tm/μ Tm+10)之最大值與最小值的差(不均)為未滿3.4、 (6)提供一種如(1)所記載之液晶聚酯系樹脂組成物，其特徵為前述熱塑性液晶聚酯(A)的熔點為300℃以上，前述熱塑性液晶聚酯(B)的熔點未滿300℃、 (7)提供一種如請求項1所記載之液晶聚酯系樹脂組成物，其特徵為前述熱塑性液晶聚酯(A)與前述熱塑性液晶聚酯(B)的摻合比例為(A)：(B)=60～96重量%：4～40重量%、 (8)提供一種液晶聚酯系薄膜，其特徵為由如(1)至(7)中任一項所記載之樹脂組成物所構成、 (9)提供一種如(8)所記載之液晶聚酯系薄膜，其特徵為將薄膜之流動方向的拉伸強度定為F(MD)，將薄膜寬度方向的拉伸強度定為F(TD)時，為0.75≦F(TD)/F(MD)≦1.25、 (10)提供一種如(9)所記載之液晶聚酯系薄膜之製造方法，其特徵為藉由充氣擠出成形法製膜、 (11)提供一種金屬層合薄膜，其特徵為於如(10)所記載之液晶聚酯系薄膜的單面或兩面層合金屬層、 (12)提供一種電路基板，其係具備：至少一個導體層、與如(11)所記載之熱塑性液晶聚酯系薄膜。 [發明效果] According to the present invention, (1) there is provided a liquid crystal polyester resin composition, which is a liquid crystal polyester resin composition comprising thermoplastic liquid crystal polyester (A) and thermoplastic liquid crystal polyester (B), characterized in that the aforementioned thermoplastic The difference between the melting points of the liquid crystalline polyester (A) and the thermoplastic liquid crystalline polyester (B) is 5°C to 95°C, and the thermoplastic liquid crystalline polyester (A) contains constituent units derived from p-hydroxybenzoic acid and 6 -Constituent units of hydroxy-2-naphthoic acid, the aforementioned thermoplastic liquid crystalline polyester (B) contains structural units derived from p-hydroxybenzoic acid and structural units derived from 6-hydroxy-2-naphthoic acid, or contains structural units derived from Either the constituent unit of p-hydroxybenzoic acid or the constituent unit derived from 4,4'-dihydroxybiphenyl, the blend ratio of the thermoplastic liquid crystal polyester (A) to the thermoplastic liquid crystal polyester (B) is: (A): (B) = 40-98% by weight: 2-60% by weight, used in pneumatic extrusion molding, (2) Provide a liquid crystal polyester resin composition as described in (1), characterized by The melt viscosity (μ Tm ) at the melting point of the aforementioned thermoplastic liquid crystal polyester (A) measured under the condition of a shear rate of 122 sec -1 is the same as that measured under the condition of a shear rate of 122 sec -1 in the aforementioned thermoplastic liquid crystal polyester ( A) The melt viscosity ratio R 122 (μ Tm /μ Tm +10 ) of the melting point + 10°C melt viscosity (μ Tm + 10 ) is less than 3.4. (3) Provide a liquid crystal polymer as described in (1). The ester resin composition is characterized in that the melt viscosity (μ Tm ) at the melting point of the aforementioned thermoplastic liquid crystal polyester (A) measured under the condition of a shear rate of 122 sec -1 is the same as that measured under the condition of a shear rate of 122 sec -1 The melt viscosity ratio R 122 (μ Tm /μ Tm +10 ) of the melt viscosity (μ Tm+10 ) measured at the melting point of the aforementioned thermoplastic liquid crystal polyester (A) + 10°C, relative to that at a shear rate of 1216sec -1 The melt viscosity (μ Tm ) at the melting point of the aforementioned thermoplastic liquid crystal polyester (A) measured under the condition of 1216sec -1 and the melting point of the aforementioned thermoplastic liquid crystal polyester (A) + 10°C The value of the ratio (R 122 /R 1216 ) of the melt viscosity (μ Tm +10 ) to the melt viscosity ratio R 1216 (μ Tm /μ Tm+10 ) is 1.5 or less. (4) Provide a method as described in (1) A liquid crystal polyester resin composition characterized in that the melt viscosity at the melting point of the aforementioned thermoplastic liquid crystal polyester (A) is measured under individual shear speed conditions within a shear speed range of 122 to 2430 sec -1 The difference between the maximum value and the minimum value of the melt viscosity ratio ( μ Tm / μ Tm+10 ) of (μ Tm ) and the melt viscosity R (μ Tm+ 10 ) at the melting point of the thermoplastic liquid crystal polyester (A) + 10°C (uneven) provide one for less than 1.2, (5) A kind of liquid crystal polyester resin composition as described in (1), is characterized in that in the range of shear rate 6～2430sec -1 , under the condition of individual shear rate, measure under the condition of individual shear rate in above-mentioned thermoplastic liquid crystal polyester ( The ratio R(μ Tm /μ Tm+10 ) of the melt viscosity (μ Tm ) at the melting point of A) to the melt viscosity (μ Tm+10 ) at the melting point of the thermoplastic liquid crystal polyester (A) + 10°C The difference (unevenness) between the maximum value and the minimum value is less than 3.4. (6) Provide a liquid crystal polyester resin composition as described in (1), characterized in that the melting point of the aforementioned thermoplastic liquid crystal polyester (A) is 300°C or higher, and the melting point of the thermoplastic liquid crystal polyester (B) is less than 300°C. (7) Provide a liquid crystal polyester resin composition as described in claim 1, wherein the thermoplastic liquid crystal polyester (A) The blending ratio with the aforementioned thermoplastic liquid crystal polyester (B) is (A): (B) = 60 to 96% by weight: 4 to 40% by weight. (8) Provide a liquid crystal polyester film, which is characterized by the following: (9) Provide a liquid crystal polyester film as described in (8), characterized in that the tensile strength in the flow direction of the film is Defined as F(MD), when the tensile strength in the width direction of the film is defined as F(TD), it is 0.75≦F(TD)/F(MD)≦1.25. (10) Provide a method as described in (9) A method for producing a liquid crystal polyester film, which is characterized in that the film is formed by an inflated extrusion molding method. Or laminated metal layers on both sides. (12) Provide a circuit board comprising: at least one conductor layer, and the thermoplastic liquid crystal polyester film as described in (11). [Invention effect]
本發明之液晶聚酯系樹脂組成物藉由對熔點高且耐熱性優異之熱塑性液晶聚酯，摻合相對性熔點低之熱塑性液晶聚酯，在充氣擠出成形，製膜薄膜時，可抑制於從模具擠出之氣泡發生孔洞，且可安定地製膜薄膜，並且可維持熔點高之熱塑性液晶聚酯所具有之優異之機械特性或電氣特性、耐熱性。因此，貼合由本發明之液晶聚酯系樹脂組成物所構成之液晶聚酯系薄膜及液晶聚酯系薄膜與金屬層所得之金屬層合薄膜，具備優異之機械特性、電氣特性、焊接回流性，且可適合使用在適合高速通訊用途之電路基板用之層合板等之用途。The liquid crystal polyester-based resin composition of the present invention is blended with a thermoplastic liquid crystal polyester with a relatively low melting point and a thermoplastic liquid crystal polyester with a high melting point and excellent heat resistance. Holes are formed in the air bubbles extruded from the die, and films can be stably formed, and the excellent mechanical properties, electrical properties, and heat resistance of thermoplastic liquid crystal polyesters with high melting points can be maintained. Therefore, the metal laminated film obtained by laminating the liquid crystal polyester film composed of the liquid crystal polyester resin composition of the present invention and the liquid crystal polyester film and the metal layer has excellent mechanical properties, electrical properties, and solder reflow properties. , and can be suitable for use in laminated boards for circuit substrates suitable for high-speed communication purposes.
以下，詳細說明本發明。尚，本發明並非被限定於以下的形態者，在發揮本發明之效果的範圍，可成為各種形態。Hereinafter, the present invention will be described in detail. Still, the present invention is not limited to the following forms, and various forms can be adopted within the scope of exerting the effects of the present invention.
[液晶聚酯系樹脂組成物] 本發明之液晶聚酯系樹脂組成物係由包含熔點高且耐熱性優異之熱塑性液晶聚酯(A)與較熱塑性液晶聚酯(A)熔點更低之熱塑性液晶聚酯(B)的樹脂組成物所構成者，熱塑性液晶聚酯(A)與熱塑性液晶聚酯(B)係熔點之差為5℃以上95℃以下。本發明之液晶聚酯系樹脂組成物藉由混合熱塑性液晶聚酯(A)與熱塑性液晶聚酯(B)，由於可縮小對於熔融黏度的溫度或切斷應力之依賴度，故可適合使用在充氣擠出成形用途。熱塑性液晶聚酯(A)與熱塑性液晶聚酯(B)的熔點之差較佳為10℃以上80℃以下，更佳為20℃以上60℃以下，特佳為25℃以上55℃以下。 [Liquid Crystal Polyester Resin Composition] The liquid crystal polyester resin composition of the present invention is composed of a thermoplastic liquid crystal polyester (A) with a high melting point and excellent heat resistance and a thermoplastic liquid crystal polyester (B) with a lower melting point than the thermoplastic liquid crystal polyester (A) In the composition, the difference between the melting points of the thermoplastic liquid crystalline polyester (A) and the thermoplastic liquid crystalline polyester (B) is 5°C or more and 95°C or less. The liquid crystal polyester-based resin composition of the present invention can be suitably used in the present invention because it can reduce the dependence on the temperature or the breaking stress of the melt viscosity by mixing the thermoplastic liquid crystal polyester (A) and the thermoplastic liquid crystal polyester (B). Inflatable extrusion molding application. The melting point difference between the thermoplastic liquid crystal polyester (A) and the thermoplastic liquid crystal polyester (B) is preferably 10°C to 80°C, more preferably 20°C to 60°C, particularly preferably 25°C to 55°C.
熱塑性液晶聚酯(A)及熱塑性液晶聚酯(B)為顯示熔融各向異性之液晶聚酯(可形成光學性各向異性的熔融相之聚酯)。熔融各向異性的性質可藉由利用正交偏光子之慣用之偏光檢査方法確認。具體而言，熔融各向異性可藉由使用偏光顯微鏡(奧林巴斯(股)製等)，熔融放置在熱載台(Linkam公司製等)的試料，並於氮環境下以150倍的倍率觀察來確認。於熔融時顯示光學性各向異性之液晶性的樹脂，為光學性各向異性，於正交偏光子間插入時，透過光。試料為光學性各向異性時，例如即使為熔融靜止液狀態，亦透過偏光。The thermoplastic liquid crystal polyester (A) and the thermoplastic liquid crystal polyester (B) are liquid crystal polyesters exhibiting melt anisotropy (polyesters capable of forming an optically anisotropic melt phase). The nature of the melting anisotropy can be confirmed by conventional polarization inspection methods using crossed polarized photons. Specifically, melting anisotropy can be determined by melting a sample placed on a thermal stage (manufactured by Linkam, etc.) using a polarizing microscope (manufactured by Olympus Co., Ltd., etc.), and measuring it at 150 times under nitrogen atmosphere Magnification observation to confirm. A liquid crystalline resin that exhibits optical anisotropy when melted is optically anisotropic, and transmits light when interposed between crossed polarizers. When the sample is optically anisotropic, for example, it transmits polarized light even in a state of molten still liquid.
[熱塑性液晶聚酯(A)] 使用在本發明之樹脂組成物之熱塑性液晶聚酯(A)，將源自p-羥基苯甲酸之構成單位(有時亦稱為單體成分A)、與源自6-羥基-2-萘甲酸之構成單位(有時亦稱為單體成分B)作為必須單位包含。熱塑性液晶聚酯(A)可包含單體成分A及單體成分B以外之其他單體成分C，作為單體成分C，可列舉芳香族或脂肪族二羧酸；芳香族或脂肪族二羥基化合物；芳香族羥基羧酸；芳香族二胺、芳香族羥基胺或芳香族胺基羧酸；等，可組合此等之1種或者2種以上使用。 [thermoplastic liquid crystal polyester (A)] The thermoplastic liquid crystal polyester (A) used in the resin composition of the present invention is composed of constituent units derived from p-hydroxybenzoic acid (sometimes referred to as monomer component A) and derived from 6-hydroxy-2-naphthalene The constituent unit of formic acid (sometimes also referred to as monomer component B) is included as an essential unit. The thermoplastic liquid crystal polyester (A) may contain other monomer components C other than monomer component A and monomer component B. Examples of monomer component C include aromatic or aliphatic dicarboxylic acids; aromatic or aliphatic dihydroxy acids; Compounds; aromatic hydroxycarboxylic acids; aromatic diamines, aromatic hydroxyamines, or aromatic aminocarboxylic acids; etc., may be used in combination of one or more of these.
使用在本發明之樹脂組成物之熱塑性液晶聚酯(A)，較佳為熔點為300℃以上之樹脂。熔點低於300℃時，由於焊接回流性劣化，使用在印刷電路基板等之用途時，變成限制加工方法。熱塑性液晶聚酯(A)的熔點雖並非被特別限制，但從耐熱性或成形加工性等之觀點來看，例如較佳為300℃以上400℃以下，更佳為305℃以上370℃以下，再更佳為310℃以上360℃以下，特佳為315℃以上345℃以下。尚，熱塑性液晶聚酯(A)的熔點係將使用差示掃瞄熱量計(DSC)，將樣品以10℃/分鐘的速度昇溫，使其完全熔融後，再將熔融物以10℃/分鐘的速度冷卻至30℃，再次以10℃/分鐘的速度昇溫時所出現之吸熱峰值的位置定為熔點。The thermoplastic liquid crystal polyester (A) used in the resin composition of the present invention is preferably a resin with a melting point of 300°C or higher. When the melting point is lower than 300°C, the solder reflow property deteriorates, and when it is used for applications such as printed circuit boards, it becomes a limited processing method. The melting point of the thermoplastic liquid crystalline polyester (A) is not particularly limited, but from the viewpoint of heat resistance and moldability, for example, it is preferably from 300°C to 400°C, more preferably from 305°C to 370°C, Still more preferably, it is not less than 310°C and not more than 360°C, particularly preferably not less than 315°C and not more than 345°C. Still, the melting point of the thermoplastic liquid crystal polyester (A) will use a differential scanning calorimeter (DSC), heat up the sample at a rate of 10°C/min, make it completely melted, and then melt the melt at 10°C/min The temperature is cooled to 30°C at a speed of 10°C/min, and the position of the endothermic peak that appears when the temperature is raised again at a speed of 10°C/min is defined as the melting point.
作為熔點為300℃以上之熱塑性液晶聚酯(A)之具體例，例如可列舉p-羥基苯甲酸(單體成分A)、與6-羥基-2-萘甲酸(單體成分B)的二元系縮聚物；p-羥基苯甲酸(單體成分A)、與6-羥基-2-萘甲酸(單體成分B)、與對苯二甲酸(單體成分C)的三元系縮聚物；由p-羥基苯甲酸(單體成分A)、與6-羥基-2-萘甲酸(單體成分B)、與選自由對苯二甲酸、間苯二甲酸、2,6-萘二甲酸(Naphthalenedicarboxylic acid)、4,4’-二羥基聯苯、雙酚A、對苯二酚、對苯二甲酸乙二酯所成之群組中之1種以上(單體成分C)所構成之三元系以上之縮聚物；等。Specific examples of the thermoplastic liquid crystalline polyester (A) having a melting point of 300° C. or higher include, for example, dihydrogen benzoic acid (monomer component A) and 6-hydroxy-2-naphthoic acid (monomer component B). Elementary condensation polymer; ternary condensation polymer of p-hydroxybenzoic acid (monomer component A), 6-hydroxy-2-naphthoic acid (monomer component B), and terephthalic acid (monomer component C) ; from p-hydroxybenzoic acid (monomer component A), and 6-hydroxy-2-naphthoic acid (monomer component B), and selected from terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid (Naphthalenedicarboxylic acid), 4,4'-dihydroxybiphenyl, bisphenol A, hydroquinone, and ethylene terephthalate, consisting of one or more (monomer component C) Condensation polymers of ternary or higher systems; etc.
[熱塑性液晶聚酯(B)] 使用在本發明之樹脂組成物之熱塑性液晶聚酯(B)，將源自p-羥基苯甲酸之構成單位(有時稱為單體成分A’)、與源自6-羥基-2-萘甲酸之構成單位(有時稱為單體成分B’)作為必須單位包含，或者將源自p-羥基苯甲酸之構成單位(有時稱為單體成分A’)、與源自4,4’-二羥基聯苯之構成單位(有時稱為單體成分B’)作為必須單位包含。熱塑性聚酯(B)可包含單體成分A’及單體成分B’以外之其他單體成分C’，作為單體成分C’，可列舉芳香族或脂肪族二羧酸；芳香族或脂肪族二羥基化合物；芳香族羥基羧酸；芳香族二胺、芳香族羥基胺或芳香族胺基羧酸；等，可組合此等之1種或者2種以上使用。 [thermoplastic liquid crystal polyester (B)] The thermoplastic liquid crystal polyester (B) used in the resin composition of the present invention is composed of constituent units derived from p-hydroxybenzoic acid (sometimes referred to as monomer component A') and derived from 6-hydroxy-2-naphthalene The constituent unit of formic acid (sometimes called monomer component B') is included as an essential unit, or the constituent unit derived from p-hydroxybenzoic acid (sometimes called monomer component A') and derived from 4,4 A constituent unit of '-dihydroxybiphenyl (sometimes referred to as monomer component B') is included as an essential unit. The thermoplastic polyester (B) may contain monomer component C' other than monomer component A' and monomer component B', and examples of monomer component C' include aromatic or aliphatic dicarboxylic acids; aromatic or aliphatic dicarboxylic acids; Aromatic dihydroxy compounds; aromatic hydroxycarboxylic acids; aromatic diamines, aromatic hydroxyamines, or aromatic aminocarboxylic acids;
使用在本發明之樹脂組成物之熱塑性液晶聚酯(B)，較佳為熔點未滿300℃。熱塑性液晶聚酯(B)的熔點雖並非被特別限制，但從維持耐熱性優異之熱塑性液晶聚酯(A)的耐熱性，並且縮小對於熔融黏度的溫度及切斷應力之依賴度的觀點來看，例如較佳為230℃以上且未滿300℃，更佳為250℃以上295℃以下，再更佳為260℃以上290℃以下，特佳為265℃以上285℃以下。尚，熱塑性液晶聚酯(B)的熔點藉由與在上述之熱塑性液晶聚酯(A)的熔點的測定方法相同之方法測定即可。The thermoplastic liquid crystal polyester (B) used in the resin composition of the present invention preferably has a melting point of less than 300°C. The melting point of the thermoplastic liquid crystalline polyester (B) is not particularly limited, but from the viewpoint of maintaining the heat resistance of the thermoplastic liquid crystalline polyester (A) which is excellent in heat resistance, and reducing the dependence of the melt viscosity on temperature and breaking stress See, for example, it is preferably 230°C or more and less than 300°C, more preferably 250°C or more and 295°C or less, still more preferably 260°C or more and 290°C or less, particularly preferably 265°C or more and 285°C or less. Furthermore, the melting point of the thermoplastic liquid crystalline polyester (B) may be measured by the same method as the method for measuring the melting point of the above-mentioned thermoplastic liquid crystalline polyester (A).
作為熔點未滿300℃之熱塑性液晶聚酯(B)之具體例，例如可列舉p-羥基苯甲酸(單體成分A’)、與6-羥基-2-萘甲酸(單體成分B’)的二元系縮聚物；p-羥基苯甲酸(單體成分A’)、與6-羥基-2-萘甲酸(單體成分B’)、與對苯二甲酸(單體成分C’)、與對苯二酚(單體成分C’)的三元系以上ˊ縮聚物；p-羥基苯甲酸(單體成分A’)、與4,4’-二羥基聯苯(單體成分B’)、與對苯二甲酸(單體成分C’)的三元系縮聚物；等。Specific examples of the thermoplastic liquid crystal polyester (B) having a melting point of less than 300°C include p-hydroxybenzoic acid (monomer component A'), and 6-hydroxy-2-naphthoic acid (monomer component B'). Binary condensation polymer of p-hydroxybenzoic acid (monomer component A'), and 6-hydroxy-2-naphthoic acid (monomer component B'), and terephthalic acid (monomer component C'), Ternary or higher polycondensate with hydroquinone (monomer component C'); p-hydroxybenzoic acid (monomer component A'), and 4,4'-dihydroxybiphenyl (monomer component B' ), the ternary polycondensate with terephthalic acid (monomer component C'); etc.
本發明之液晶聚酯系樹脂組成物係將上述之熱塑性液晶聚酯(A)、與熱塑性液晶聚酯(B)，以(A)：(B)=40～98重量%：2～60重量%的比例包含。較佳為(A)：(B)=50～97重量%：3～50重量%，更佳為(A)：(B)=60～96重量%：4～40重量%，再更佳為(A)：(B)=65～95重量%：5～35重量%，特佳為(A)：(B)=70～95重量%：5～30重量%。熱塑性液晶聚酯(B)的摻合比例較上述範圍更少時，無法改善藉由液晶聚酯系樹脂組成物的充氣擠出成形之薄膜的製膜加工性，進行安定之製膜變困難。又，熱塑性液晶聚酯(B)的摻合比例較上述範圍更多時，無法改善藉由液晶聚酯系樹脂組成物的充氣擠出成形之薄膜的製膜加工性，進行安定之製膜變困難，並且降低由液晶聚酯系樹脂組成物所構成之液晶聚酯系薄膜的耐熱性或機械性物性。The liquid crystal polyester resin composition of the present invention is the above-mentioned thermoplastic liquid crystal polyester (A) and thermoplastic liquid crystal polyester (B), with (A): (B) = 40-98% by weight: 2-60% by weight % ratio inclusive. Preferably (A): (B)=50-97% by weight: 3-50% by weight, more preferably (A): (B)=60-96% by weight: 4-40% by weight, more preferably (A): (B) = 65 to 95% by weight: 5 to 35% by weight, particularly preferably (A): (B) = 70 to 95% by weight: 5 to 30% by weight. When the blending ratio of the thermoplastic liquid crystalline polyester (B) is less than the above range, the film forming processability of the film formed by pneumatic extrusion of the liquid crystalline polyester resin composition cannot be improved, and stable film forming becomes difficult. In addition, when the blending ratio of the thermoplastic liquid crystal polyester (B) is larger than the above range, the film forming processability of the film formed by the pneumatic extrusion molding of the liquid crystal polyester resin composition cannot be improved, and a stable film forming process is performed. It is difficult and reduces the heat resistance or mechanical properties of the liquid crystal polyester film composed of the liquid crystal polyester resin composition.
本發明之液晶聚酯系樹脂組成物，較佳為於剪切速度122sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與於剪切速度122sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R 122(μ Tm/μ Tm+10)未滿3.4。於剪切速度122 sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與於剪切速度122sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比若未滿上述數值，在充氣擠出成形之擠出溫度附近的熔融黏度的變化小，改善藉由充氣擠出形成之薄膜的製膜加工性。熔融黏度比R 122(μ Tm/μ Tm+10)更佳為未滿3.3，再更佳為未滿3.0，特佳為未滿2.5。尚，熔融黏度比(μ Tm/μ Tm+10)的下限值雖並非被特別限制者，但通常為1.0以上。 The liquid crystal polyester resin composition of the present invention is preferably the melt viscosity (μ Tm ) measured at the melting point of the thermoplastic liquid crystal polyester (A) at a shear rate of 122 sec -1 and at a shear rate of 122 sec -1 The melt viscosity ratio R 122 (μ Tm /μ Tm+10 ) of the melt viscosity (μ Tm+10 ) at the melting point of the thermoplastic liquid crystal polyester (A) + 10°C measured under the condition of 1 is less than 3.4. The melt viscosity (μ Tm ) at the melting point of the thermoplastic liquid crystal polyester (A) measured under the condition of a shear rate of 122 sec -1 is the same as the melt viscosity (μ Tm ) measured under the condition of a shear rate of 122 sec -1 in the thermoplastic liquid crystal polyester (A) ) melting point + 10 ° C melt viscosity (μ Tm + 10 ) if the melt viscosity ratio is less than the above value, the change of the melt viscosity near the extrusion temperature of inflatable extrusion molding is small, and the process formed by inflatable extrusion is improved. Film processability of thin film. The melt viscosity ratio R 122 (μ Tm /μ Tm+10 ) is more preferably less than 3.3, still more preferably less than 3.0, and most preferably less than 2.5. Also, the lower limit of the melt viscosity ratio (μ Tm /μ Tm+10 ) is not particularly limited, but is usually 1.0 or more.
本發明之液晶聚酯系樹脂組成物，較佳為於剪切速度122sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與於剪切速度122sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R 12 2(μ Tm/μ Tm+10)，相對於在剪切速度1216sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與於剪切速度1216sec -1的條件下測定之在熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R 12 16(μ Tm/μ Tm+10)之比(R 122(μ Tm/μ Tm+10)/R 1216(μ Tm/ μ Tm+10))之值(以下，有時稱為R 122/R 1216)為1.50以下。比(R 122/R 1216)之值若為上述數值以下，由於對於熔融黏度的溫度或切斷應力之依賴度小，在充氣擠出成形之擠出溫度附近的熔融黏度的變化小，改善藉由充氣擠出形成之薄膜的製膜加工性。比(R 122/R 1216)之值，更佳為1.45以下，再更佳為1.40以下，特佳為1.35以下。尚，下限值雖並非被特別限制者，但例如為0.5以上，較佳為0.7以上，更佳為0.85以上。 The liquid crystal polyester resin composition of the present invention is preferably the melt viscosity (μ Tm ) measured at the melting point of the thermoplastic liquid crystal polyester (A) at a shear rate of 122 sec -1 and at a shear rate of 122 sec -1 The melt viscosity ratio R 12 2 (μ Tm /μ Tm +10 ) of the melt viscosity (μ Tm+10 ) measured at the melting point of thermoplastic liquid crystal polyester (A) + 10°C under the condition of 1 , relative to the The melt viscosity (μ Tm ) at the melting point of thermoplastic liquid crystal polyester ( A ) measured under the condition of speed 1216sec -1 and the melting point of thermoplastic liquid crystal polyester (A) measured under the condition of shear speed 1216sec -1+ The ratio of the melt viscosity (μ Tm+10 ) to the melt viscosity ratio R 12 16 (μ Tm /μ Tm+10 ) at 10°C (R 122 (μ Tm /μ Tm+10 )/R 1216 (μ Tm / μ Tm The value of +10 )) (hereinafter, sometimes referred to as R 122 /R 1216 ) is 1.50 or less. If the value of the ratio (R 122 /R 1216 ) is below the above value, since the dependence on the temperature or shear stress of the melt viscosity is small, the change of the melt viscosity near the extrusion temperature of the inflatable extrusion molding is small, and the improvement is improved. Film processability of films formed by pneumatic extrusion. The value of the ratio (R 122 /R 1216 ) is more preferably at most 1.45, still more preferably at most 1.40, and most preferably at most 1.35. Furthermore, although the lower limit is not particularly limited, it is, for example, 0.5 or more, preferably 0.7 or more, more preferably 0.85 or more.
本發明之液晶聚酯系樹脂組成物，較佳為在剪切速度122～2430sec -1的範圍內，以個別之剪切速度的條件下測定之在熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與在熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R(μ Tm/μ Tm+10)之最大值與最小值的差(不均)為未滿1.1，若為上述範圍，由於對於熔融黏度的溫度或切斷應力之依賴度小，在充氣擠出成形之擠出溫度附近的熔融黏度的變化小，改善藉由充氣擠出形成之薄膜的製膜加工性。在剪切速度122～2430sec -1的範圍內之不均更佳為未滿1.1，再更佳為未滿1.0，特佳為未滿0.8。尚，下限值雖並非被特別限制者，但例如為0.1以上。 The liquid crystal polyester resin composition of the present invention is preferably melted at the melting point of the thermoplastic liquid crystal polyester (A) in the range of a shear rate of 122 to 2430 sec -1 and measured under individual shear rate conditions. The difference between the maximum value and the minimum value of the melt viscosity ratio R(μ Tm /μ Tm+10 ) of the viscosity (μ Tm ) and the melt viscosity (μ Tm+10 ) at the melting point of thermoplastic liquid crystal polyester (A) +10°C (Unevenness) is less than 1.1. If it is in the above range, since the dependence on the temperature or shear stress of the melt viscosity is small, the change of the melt viscosity near the extrusion temperature of the inflation extrusion molding is small, and the improvement by inflation Processability of films formed by extrusion. The unevenness within the range of the shear rate of 122 to 2430 sec -1 is more preferably less than 1.1, still more preferably less than 1.0, and most preferably less than 0.8. Furthermore, although the lower limit is not particularly limited, it is, for example, 0.1 or more.
本發明之液晶聚酯系樹脂組成物，較佳為在剪切速度6～2430sec -1的範圍內，以個別之剪切速度的條件下測定之在熱塑性液晶聚酯(A)的熔點之熔融黏度(μ Tm)與在熱塑性液晶聚酯(A)的熔點+10℃之熔融黏度(μ Tm+10)的熔融黏度比R(μ Tm/μ Tm+10)之最大值與最小值的差(不均)為未滿3.4，若為上述範圍，由於對於熔融黏度的溫度或切斷應力之依賴度小，在充氣擠出成形之擠出溫度附近的熔融黏度的變化小，改善藉由充氣擠出形成之薄膜的製膜加工性。在剪切速度6～2430sec -1的範圍內之不均更佳為未滿3.2，再更佳為未滿3.0，特佳為未滿2.5、未滿2.0、未滿1.5。尚，下限值雖並非被特別限制者，但例如為0.1以上。 The liquid crystal polyester resin composition of the present invention is preferably melted at the melting point of the thermoplastic liquid crystal polyester (A) at a shear rate of 6 to 2430 sec -1 , measured under individual shear rate conditions. The difference between the maximum value and the minimum value of the melt viscosity ratio R(μ Tm /μ Tm+10 ) of the viscosity (μ Tm ) and the melt viscosity (μ Tm+10 ) at the melting point of thermoplastic liquid crystal polyester (A) +10°C (Unevenness) is less than 3.4. If it is within the above range, since the dependence on the temperature or shear stress of the melt viscosity is small, the change of the melt viscosity near the extrusion temperature of the inflatable extrusion molding is small, and the improvement by inflating is improved. Processability of films formed by extrusion. The unevenness within the range of the shear rate of 6 to 2430 sec -1 is more preferably less than 3.2, still more preferably less than 3.0, and most preferably less than 2.5, less than 2.0, and less than 1.5. Furthermore, although the lower limit is not particularly limited, it is, for example, 0.1 or more.
本發明之液晶聚酯系樹脂組成物在不阻礙本發明之效果的範圍，可包含上述之熱塑性液晶聚酯(A)與熱塑性液晶聚酯(B)以外之其他樹脂成分。作為其他樹脂成分，可列舉聚芳酯、聚苯硫醚(Polyphenylene sulfide)、聚苯醚、聚醚醚酮、聚醚醯亞胺、環烯烴聚合物、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、含有環氧基之烯烴系共聚物、苯乙烯系樹脂等之熱塑性樹脂。又，本發明之液晶聚酯系樹脂組成物可包含潤滑劑、抗氧化劑、填充劑等之添加劑。尚，本發明之液晶聚酯系樹脂組成物包含其他成分時，較佳為將熱塑性液晶聚酯(A)與熱塑性液晶聚酯(B)的合計量作為主成分包含。於此，所謂主成分，係意指構成樹脂組成物之成分當中，構成比率為50重量%以上者，較佳為60重量%以上，更佳為80重量%以上，再更佳為90重量%以上，特佳為95重量%以上。The liquid crystal polyester resin composition of the present invention may contain other resin components other than the above-mentioned thermoplastic liquid crystal polyester (A) and thermoplastic liquid crystal polyester (B) within the range that does not hinder the effect of the present invention. Examples of other resin components include polyarylate, polyphenylene sulfide, polyphenylene ether, polyetheretherketone, polyetherimide, cycloolefin polymer, polyamide, polyamideimide , Polyimide, olefin-based copolymers containing epoxy groups, styrene-based resins and other thermoplastic resins. In addition, the liquid crystal polyester resin composition of the present invention may contain additives such as lubricants, antioxidants, and fillers. Furthermore, when the liquid crystal polyester resin composition of the present invention contains other components, it is preferable to contain the total amount of the thermoplastic liquid crystal polyester (A) and the thermoplastic liquid crystal polyester (B) as the main component. Here, the so-called main component means that among the components constituting the resin composition, the constituent ratio is 50% by weight or more, preferably 60% by weight or more, more preferably 80% by weight or more, and more preferably 90% by weight Above, especially preferably 95% by weight or more.
[液晶聚酯系薄膜之製造方法] 於本發明亦提案由上述之樹脂組成物所構成之薄膜，及該薄膜之製造方法。本發明之液晶聚酯系薄膜係藉由將上述之熱塑性液晶聚酯(A)與熱塑性液晶聚酯(B)，藉由公知之方法混合並進行製膜而獲得。尚，本發明之樹脂組成物減少熱塑性液晶聚酯(B)的摻合比例時，由於提供經安定之混煉狀態，故較佳為在製膜前，先進行熔融混煉•造粒。 [Manufacturing method of liquid crystal polyester film] The present invention also proposes a film composed of the above-mentioned resin composition, and a method for producing the film. The liquid crystal polyester film of the present invention is obtained by mixing the above-mentioned thermoplastic liquid crystal polyester (A) and thermoplastic liquid crystal polyester (B) by a known method and forming a film. Furthermore, when the blending ratio of the thermoplastic liquid crystal polyester (B) is reduced, the resin composition of the present invention provides a stable kneaded state, so it is preferable to perform melt kneading and granulation before film formation.
作為用以熔融混煉之設備，雖並非被特別限制，但例如可列舉批式混煉機、捏合機、揉捏機(co-kneader)、班伯里攪拌機、輥磨機、單軸或雙軸擠出機等、公知之各種擠出機。此等當中，從混煉能力或生產性優異的點來看，較佳為使用單軸擠出機或雙軸擠出機。The equipment used for melt kneading is not particularly limited, but examples include batch kneaders, kneaders, co-kneaders, Banbury mixers, roll mills, single-shaft or double-shaft kneaders, etc. Various well-known extruders, such as a shaft extruder. Among these, it is preferable to use a single-screw extruder or a twin-screw extruder from the viewpoint of being excellent in kneading ability and productivity.
本發明之樹脂組成物藉由摻合熱塑性液晶聚酯(B)，可抑制對於溫度或切斷應力等之樹脂組成物的熔融黏度的急遽降低或者變化，使得改善藉由充氣擠出成形之薄膜的製膜加工性變可能。The resin composition of the present invention can suppress a sharp drop or change in the melt viscosity of the resin composition with respect to temperature, shear stress, etc. by blending the thermoplastic liquid crystal polyester (B), making it possible to improve the film formed by pneumatic extrusion The film forming processability becomes possible.
作為充氣擠出成形，例如可列舉藉由將上述之樹脂組成物供給至具備環狀狹縫的模具(Die)之熔融擠出機，從擠出機的環狀狹縫，將熔融狀態的樹脂組成物往上方或下方擠出成氣泡狀，從由熔融狀態的樹脂組成物所構成之氣泡的內側，吹入空氣或惰性氣體，於與流動方向(MD方向)直角的方向(TD方向)使氣泡膨脹拉伸，而得到薄膜之方法。熔融擠出機的料筒溫度通常為280～400℃，較佳為320～380℃。環狀狹縫的間隔通常為0.1～5mm，較佳為0.2～2mm。環狀狹縫的直徑通常為20～1000mm，較佳為25～600mm。As pneumatic extrusion molding, for example, by supplying the above-mentioned resin composition to a melt extruder having a die (Die) having an annular slit, the resin in a molten state is melted from the annular slit of the extruder. The composition is extruded upwards or downwards in the form of bubbles, and air or inert gas is blown from the inner side of the bubbles formed by the molten resin composition in a direction (TD direction) at right angles to the flow direction (MD direction). The method of obtaining a film by expanding and stretching air bubbles. The barrel temperature of the melt extruder is usually 280-400°C, preferably 320-380°C. The interval of the annular slits is usually 0.1-5 mm, preferably 0.2-2 mm. The diameter of the annular slit is usually 20-1000 mm, preferably 25-600 mm.
在充氣擠出成形，吹氣比較佳為1.5以上，更佳為2.0以上，再更佳為4.0以上，特佳為4.5以上。吹氣比的上限雖並非被特別限制者，但例如吹氣比為10以下。又，牽伸比較佳為1.5以上20以下，更佳為1.5以上10以下。於此，吹氣比為TD方向的拉伸倍率，牽伸比為MD方向之拉伸倍率。吹氣比及牽伸比為上述範圍時，可改善所得之薄膜的拉伸彈性率或拉伸強度的各向異性(MD方向與TD方向之差)。然而，在充氣擠出成形，為了改善薄膜的各向異性，提高吹氣比，由於由熔融狀態的樹脂組成物所構成之氣泡的形狀保持往成為不安定的方向行動，變容易發生氣泡的波動或孔洞等。尤其是藉由充氣擠出成形，將熔點超過300℃之液晶聚酯以吹氣比成為4.0以上的方式，膨脹拉伸氣泡時，於氣泡多發孔洞，進行薄膜製膜困難。對此，由於本發明之樹脂組成物藉由摻合熱塑性液晶聚酯(B)，可抑制因溫度或切斷應力等導致之樹脂組成物的熔融黏度的急遽降低或者變化，故即使吹氣比為4.0以上，亦可抑制於氣泡發生孔洞，並可改善薄膜的各向異性，可安定地製膜薄膜。In pneumatic extrusion molding, the blowing ratio is preferably at least 1.5, more preferably at least 2.0, even more preferably at least 4.0, and most preferably at least 4.5. Although the upper limit of the blowing ratio is not particularly limited, the blowing ratio is, for example, 10 or less. Also, the draft ratio is preferably from 1.5 to 20, more preferably from 1.5 to 10. Here, the air blow ratio is the draw ratio in the TD direction, and the draft ratio is the draw ratio in the MD direction. When the air blow ratio and the draw ratio are in the above ranges, the tensile modulus of elasticity and the anisotropy of tensile strength (the difference between the MD direction and the TD direction) of the obtained film can be improved. However, in pneumatic extrusion molding, in order to improve the anisotropy of the film and increase the blowing ratio, since the shape of the bubbles made of the molten resin composition keeps moving in an unstable direction, fluctuations in the bubbles tend to occur or holes etc. In particular, liquid crystal polyester having a melting point of more than 300°C is formed by air extrusion molding so that the blowing ratio becomes 4.0 or more. When the air bubbles are expanded and stretched, many holes are formed in the air bubbles, making it difficult to form a film. On the other hand, since the resin composition of the present invention is blended with thermoplastic liquid crystal polyester (B), it can suppress the sharp decrease or change of the melt viscosity of the resin composition caused by temperature or shear stress, so even if the blowing ratio When it is 4.0 or more, it is also possible to suppress the occurrence of cavities in air bubbles, improve the anisotropy of the film, and form a film stably.
本發明之液晶聚酯系薄膜的厚度雖並非被特別限制，但例如為0.5μm以上1000μm以下，考量熔融擠出時之操作性或生產性等時，較佳為5μm以上500μm以下，更佳為10μm以上300μm以下，再更佳為20μm以上200μm以下。Although the thickness of the liquid crystal polyester film of the present invention is not particularly limited, it is, for example, from 0.5 μm to 1000 μm, and in consideration of operability and productivity during melt extrusion, it is preferably from 5 μm to 500 μm, more preferably 10 μm to 300 μm, more preferably 20 μm to 200 μm.
本發明之液晶聚酯系薄膜較佳為流動方向(MD方向)與寬度方向(TD方向)的拉伸強度為200MPa以上。拉伸強度更佳為220MPa以上，再更佳為240MPa以上。拉伸強度的上限雖並非被特別限制者，但例如較佳為500MPa以下，更佳為400MPa以下，再更佳為350MPa以下。拉伸強度若為上述範圍，於適合在高速通訊用途之電路基板用之層合板等進行加工時之操作性優異，可抑制於薄膜的端部產生之缺陷和裂紋等。The liquid crystal polyester film of the present invention preferably has a tensile strength of 200 MPa or more in the flow direction (MD direction) and the width direction (TD direction). The tensile strength is more preferably at least 220 MPa, still more preferably at least 240 MPa. Although the upper limit of the tensile strength is not particularly limited, for example, it is preferably at most 500 MPa, more preferably at most 400 MPa, and even more preferably at most 350 MPa. When the tensile strength is in the above range, it is excellent in workability when processing laminated boards suitable for circuit boards for high-speed communication applications, and it is possible to suppress defects, cracks, etc. that occur at the ends of the film.
本發明之液晶聚酯系薄膜較佳為流動方向(MD方向)與寬度方向(TD方向)之各向異性低者。詳細而言，相對於薄膜流動方向的拉伸強度F(MD)之薄膜寬度方向的拉伸強度F(TD)(亦即F(TD)/F(MD))以較佳為0.5以上1.5以下，更佳為0.75以上1.25以下，再更佳為0.85以上1.15以下較佳，特佳為0.90以上1.10以下。相對於薄膜流動方向的拉伸強度F(MD)之薄膜寬度方向的拉伸強度F(TD)若為上述範圍，可適合使用在薄膜的機械特性或電氣特性之各向異性小，適合在高速通訊用途之電路基板用之層合板等之用途。The liquid crystal polyester film of the present invention preferably has low anisotropy in the flow direction (MD direction) and width direction (TD direction). Specifically, the tensile strength F(TD) in the width direction of the film relative to the tensile strength F(MD) in the flow direction of the film (that is, F(TD)/F(MD)) is preferably 0.5 to 1.5 , more preferably not less than 0.75 and not more than 1.25, more preferably not less than 0.85 and not more than 1.15, particularly preferably not less than 0.90 and not more than 1.10. If the tensile strength F(TD) in the width direction of the film relative to the tensile strength F(MD) in the flow direction of the film is within the above range, it is suitable for use when the anisotropy of the mechanical or electrical properties of the film is small, and it is suitable for high-speed applications. Uses such as laminated boards for circuit substrates for communication purposes.
本發明之液晶聚酯系薄膜藉由進一步實施熱處理，成為可緩和分子鏈的配向性，並提昇薄膜尺寸安定性者。熱處理可使用以往公知之方法，例如可列舉接觸式之熱處理、非接觸式之熱處理等，其種類並未被特別限制。The liquid crystal polyester film of the present invention can relax the alignment of molecular chains and improve the dimensional stability of the film by further performing heat treatment. Conventionally known methods can be used for heat treatment, for example, contact heat treatment, non-contact heat treatment, etc. are mentioned, and the type is not specifically limited.
[金屬層合薄膜] 本發明之液晶聚酯系薄膜可於此層合金屬層，作為金屬層合薄膜使用。在層合金屬層，於層合液晶聚酯系薄膜之金屬層的面，為了提高接著力，可實施電暈放電處理、紫外線照射處理或電漿處理。 [Metal Laminated Film] The liquid crystal polyester film of the present invention can be used as a metal laminated film by laminating a metal layer thereon. In the laminated metal layer, corona discharge treatment, ultraviolet irradiation treatment or plasma treatment may be performed on the surface of the metal layer on which the liquid crystal polyester film is laminated to improve adhesion.
作為於本發明之液晶聚酯系薄膜層合金屬層之方法，可列舉例如(1)將液晶聚酯系薄膜藉由加熱壓接貼附在金屬箔之方法、(2)將液晶聚酯系薄膜與金屬箔藉由接著劑貼附之方法、(3)於液晶聚酯系薄膜，將金屬層藉由蒸鍍形成之方法。其中，(1)之層合方法為使用沖壓機或加熱輥，於液晶聚酯薄膜的流動起始溫度附近，與金屬箔壓接之方法，由於可輕易實施故推薦。作為在(2)之層合方法使用之接著劑，例如可列舉熱熔接著劑、聚胺基甲酸酯接著劑。其中，較佳為使用含有環氧基之乙烯共聚物作為接著劑。作為(3)之層合方法，例如可列舉離子束濺鍍法、高頻率濺鍍法、直流磁控管濺鍍法、輝光放電法。其中，較佳為使用高頻率濺鍍法。As a method of laminating a metal layer on the liquid crystal polyester film of the present invention, for example, (1) a method of attaching a liquid crystal polyester film to a metal foil by thermocompression bonding, (2) a method of bonding a liquid crystal polyester film A method of attaching a film and a metal foil with an adhesive, (3) a method of forming a metal layer on a liquid crystal polyester film by vapor deposition. Among them, the lamination method of (1) is to use a punching machine or a heating roll to press-bond the metal foil with a liquid crystal polyester film near the flow start temperature, and it is recommended because it can be easily implemented. As an adhesive used in the lamination method of (2), a hot melt adhesive and a polyurethane adhesive are mentioned, for example. Among them, it is preferable to use an epoxy group-containing ethylene copolymer as an adhesive. As the lamination method of (3), an ion beam sputtering method, a high frequency sputtering method, a DC magnetron sputtering method, and a glow discharge method are mentioned, for example. Among them, it is preferable to use a high-frequency sputtering method.
作為金屬層所使用之金屬，例如可列舉金、銀、銅、銅合金、鎳、鎳合金、鋁、鋁合金、鐵、鐵合金等。於標籤膠帶、電路基板用途，較佳為銅，於電容器用途，較佳為鋁。作為如此進行所得之金屬層合薄膜的構造，例如可列舉液晶聚酯系薄膜與金屬層的二層構造、於液晶聚酯系薄膜兩面層合金屬層之三層構造、交互層合液晶聚酯系薄膜與金屬層之五層構造。尚，層合體中以高強度表現的目的，如有必要可進行熱處理。金屬層的厚度雖並非被特別限制，但例如較佳為1.5～1000μm，更佳為2～500μm，再更佳為5～150μm，特佳為7～100μm。較該範圍更薄時，機械性強度劣化，較上述範圍更厚時，操作性或加工性劣化。As the metal used for the metal layer, gold, silver, copper, copper alloy, nickel, nickel alloy, aluminum, aluminum alloy, iron, iron alloy, etc. are mentioned, for example. Copper is preferred for label tapes and circuit substrates, and aluminum is preferred for capacitors. As the structure of the metal laminated film obtained in this way, for example, a two-layer structure of a liquid crystal polyester film and a metal layer, a three-layer structure of laminating a metal layer on both sides of a liquid crystal polyester film, alternately laminated liquid crystal polyester It is a five-layer structure of thin film and metal layer. Also, for the purpose of expressing high strength in the laminate, heat treatment may be performed if necessary. Although the thickness of the metal layer is not particularly limited, for example, it is preferably 1.5-1000 μm, more preferably 2-500 μm, even more preferably 5-150 μm, particularly preferably 7-100 μm. When it is thinner than this range, mechanical strength will deteriorate, and when it is thicker than the said range, handleability or processability will deteriorate.
[電路基板] 本發明之電路基板已包含至少一個導體層、與至少一個絕緣體(或電介質)層，只要能將本發明之液晶聚酯系薄膜作為絕緣體(或電介質)使用，該形態並未特別限定，藉由公知或慣用之手段，可作為各種高頻率電路基板使用。又，電路基板可為搭載半導體元件(例如IC晶片)之電路基板(或半導體元件實裝基板)。 [circuit substrate] The circuit substrate of the present invention already includes at least one conductor layer and at least one insulator (or dielectric) layer, as long as the liquid crystal polyester film of the present invention can be used as an insulator (or dielectric), the form is not particularly limited, by Known or commonly used methods can be used as various high-frequency circuit boards. Also, the circuit board may be a circuit board (or a semiconductor device mounting substrate) on which a semiconductor device (such as an IC chip) is mounted.
本發明之電路基板所使用之導體層，例如，由至少具有導電性之金屬形成，於此導體層使用公知之電路加工方法，形成電路圖型。作為形成導體層之導體，可為具有導電性之各種金屬，例如可為金、銀、銅、鐵、鎳、鋁或此等之合金金屬等。又，可於上述之金屬層合薄膜的金屬層部分形成電路圖型。 [實施例] The conductive layer used in the circuit board of the present invention is, for example, formed of at least conductive metal, and a circuit pattern is formed on the conductive layer using a known circuit processing method. As the conductor forming the conductor layer, various metals having conductivity can be used, for example, gold, silver, copper, iron, nickel, aluminum or alloy metals thereof can be used. In addition, a circuit pattern can be formed on the metal layer portion of the above-mentioned metal laminated film. [Example]
以下，雖藉由實施例，進一步詳細說明本發明，但本發明並非被限定於以下之實施例者。Hereinafter, although the present invention will be described in further detail through examples, the present invention is not limited to the following examples.
作為在實施例、比較例使用之樹脂，使用下述者。 LCP(1)：由源自p-羥基苯甲酸之構成單位、與源自6-羥基-2-萘甲酸之構成單位、與源自對苯二甲酸之構成單位所構成之熱塑性液晶聚酯(Polyplastics股份有限公司製LAPEROS(註冊商標)C950RX、熔點：320℃) LCP(2)：由源自p-羥基苯甲酸之構成單位、與源自6-羥基-2-萘甲酸之構成單位所構成之熱塑性液晶聚酯(Polyplastics股份有限公司製LAPEROS(註冊商標)A950RX、熔點：280℃) LCP(3)：由源自p-羥基苯甲酸之構成單位、與源自4,4’-二羥基聯苯之構成單位、與源自對苯二甲酸之構成單位所構成之熱塑性液晶聚酯(ENEOS液晶股份有限公司製XYDAR(註冊商標)CX-2199、熔點：280℃) LCP(4)：熱塑性液晶聚酯(上野製藥股份有限公司製UENO LCP(註冊商標)A8100、熔點：220℃) As resins used in Examples and Comparative Examples, the following were used. LCP (1): thermoplastic liquid crystal polyester composed of constituent units derived from p-hydroxybenzoic acid, constituent units derived from 6-hydroxy-2-naphthoic acid, and constituent units derived from terephthalic acid ( Polyplastics Co., Ltd. LAPEROS (registered trademark) C950RX, melting point: 320°C) LCP (2): Thermoplastic liquid crystal polyester composed of constituent units derived from p-hydroxybenzoic acid and constituent units derived from 6-hydroxy-2-naphthoic acid (LAPEROS (registered trademark) A950RX manufactured by Polyplastics Co., Ltd. , Melting point: 280°C) LCP(3): Thermoplastic liquid crystal polyester composed of constituent units derived from p-hydroxybenzoic acid, constituent units derived from 4,4'-dihydroxybiphenyl, and constituent units derived from terephthalic acid (XYDAR (registered trademark) CX-2199 manufactured by ENEOS Liquid Crystal Co., Ltd., melting point: 280°C) LCP (4): thermoplastic liquid crystal polyester (UENO LCP (registered trademark) A8100, manufactured by Ueno Pharmaceutical Co., Ltd., melting point: 220° C.)
(1)樹脂組成物之製造 將熱塑性液晶聚酯以表1所記載之比例預備混合後，使用雙軸擠出機(東芝機械股份有限公司製、型式：TEM-18SS―12/2V)，並以料筒溫度330℃、擠出速度10kg/h造粒，得到液晶聚酯系樹脂組成物的顆粒，使用在以下的測定。 (1) Manufacture of resin composition After preliminarily mixing the thermoplastic liquid crystal polyester in the proportions listed in Table 1, use a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., type: TEM-18SS-12/2V), and extrude at a barrel temperature of 330°C. The pellets were granulated at a discharge rate of 10 kg/h to obtain pellets of the liquid crystal polyester resin composition, which were used in the following measurements.
(2)熔融黏度比的測定 使用毛細管流變儀(東洋精機股份有限公司製、型式：Capillograph F1)，在噴嘴徑.1mm、噴嘴長10mm的模具進行測定。在剪切速度6～2430sec -1的條件下，分別測定熱塑性液晶聚酯(A)的熔點的熔融黏度(μ Tm)與熱塑性液晶聚酯(A)的熔點+10℃的熔融黏度(μ Tm+10)之值，藉由下述式算出熔融黏度比。將熔融黏度比的測定結果示於表1。 熔融黏度比=熱塑性液晶聚酯(A)的熔點的熔融黏度(μ Tm)/熱塑性液晶聚酯(A)的熔點+10℃的熔融黏度(μ Tm+10) 尚，除了於上述所得之液晶聚酯系樹脂組成物，將於實施例、比較例使用之熱塑性液晶聚酯樹脂單體(參考例)的熔融黏度比以LCP(1)的熔點作為基準來測定。 (2) Measurement of melt viscosity ratio Using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd., model: Capillograph F1), measurement was performed on a die having a nozzle diameter of 1 mm and a nozzle length of 10 mm. Under the condition of shear rate of 6～2430sec -1 , the melting viscosity (μ Tm ) of the melting point of thermoplastic liquid crystal polyester (A) and the melting viscosity (μ Tm ) of melting point of thermoplastic liquid crystal polyester (A)+10°C were measured respectively. +10 ), the melt viscosity ratio was calculated by the following formula. Table 1 shows the measurement results of the melt viscosity ratio. Melt viscosity ratio=melt viscosity (μ Tm ) of melting point of thermoplastic liquid crystal polyester (A)/melt viscosity (μ Tm+10 ) of melting point of thermoplastic liquid crystal polyester (A)+10°C, except for the liquid crystal obtained above For the polyester-based resin composition, the melt viscosity ratio of the thermoplastic liquid crystal polyester resin monomer (reference example) used in Examples and Comparative Examples was measured based on the melting point of LCP (1).
(3)藉由充氣擠出成形之薄膜之製造 將於上述所得之液晶聚酯系樹脂組成物及各熱塑性液晶聚酯以單軸擠出機加熱混煉，從環狀充氣模具(Die)(直徑25mm)，以排放量3kg/h熔融擠出，並以牽伸比=2、吹氣比=5的條件拉伸，藉由充氣擠出成形法，而得到厚度50μm的液晶聚酯系薄膜。將藉由以下之評估方法所得之薄膜的製膜性、拉伸強度示於表2。 (3) Manufacture of film formed by pneumatic extrusion Heat and knead the liquid crystal polyester resin composition obtained above and each thermoplastic liquid crystal polyester with a single-screw extruder, and melt and extrude it from a ring-shaped inflatable die (Die) (25 mm in diameter) at a discharge rate of 3 kg/h , and stretched under the conditions of draft ratio = 2, blow ratio = 5, and a liquid crystal polyester film with a thickness of 50 μm was obtained by an inflated extrusion molding method. Table 2 shows the film formability and tensile strength of the films obtained by the following evaluation methods.
(製膜性：氣泡的孔洞) 藉由充氣擠出成形法製膜薄膜時，將從模具擠出之熔融狀態的由樹脂所構成之氣泡的外觀以目視並以下述基準評估。 ○：於氣泡無孔洞 △：於氣泡發生小的孔洞(由於氣泡內部的空氣滲出，氣泡形狀不安定) ×：於氣泡發生孔洞，無法安定的製膜薄膜 (拉伸強度) 依據ASTMD882，將切斷成190mm×15mm的大小之樣品使用Autograph AGS-500NX(島津製作所股份有限公司製)，將拉伸速度12.5mm/分鐘、夾具(Chuck)間距離作為125mm測定。測定溫度為23℃。尚，測定薄膜的流動方向(MD方向)與寬度方向(TD方向)雙方。 (Membrane-forming properties: pores of air bubbles) When a film is produced by the pneumatic extrusion molding method, the appearance of bubbles made of resin in a molten state extruded from a die is visually evaluated by the following criteria. ○: There are no holes in the air bubbles △: A small hole occurs in the bubble (the shape of the bubble is unstable due to the leakage of the air inside the bubble) ×: Holes are generated in air bubbles, making it impossible to form a stable film (Tensile Strength) According to ASTM D882, a sample cut into a size of 190 mm×15 mm was measured using Autograph AGS-500NX (manufactured by Shimadzu Corporation), with a tensile speed of 12.5 mm/min and a distance between chucks of 125 mm. The measurement temperature was 23°C. Furthermore, both the flow direction (MD direction) and the width direction (TD direction) of the film were measured.
由於由源自熔點為320℃之p-羥基苯甲酸之構成單位、與源自6-羥基-2-萘甲酸之構成單位、與源自對苯二甲酸之構成單位所構成之熱塑性液晶聚酯(A)，摻合3、5、10、20、30、50重量%之由源自熔點為280℃之p-羥基苯甲酸之構成單位、與源自6-羥基-2-萘甲酸之構成單位所構成之熱塑性液晶聚酯(B)的樹脂組成物所構成之實施例1至6的液晶聚酯系薄膜，顯示該樹脂組成物對於溫度或剪切速度之熔融黏度的依賴度低的結果，即使在吹氣比超過4.0之拉伸倍率，亦顯示改善藉由充氣擠出成形之薄膜的製膜加工性的結果。尤其是於由實施例2至5之液晶聚酯系樹脂組成物所構成之液晶聚酯系薄膜，於從模具(Die)擠出之熔融樹脂的氣泡無孔洞且安定之製膜為可能。又，實施例1至6之液晶聚酯系薄膜維持熔點為300℃以上之熱塑性液晶聚酯所具有之優異之機械特性或電氣特性、耐熱性，並且顯示拉伸強度的各向異性小的結果。Thermoplastic liquid crystal polyester composed of constituent units derived from p-hydroxybenzoic acid with a melting point of 320°C, constituent units derived from 6-hydroxy-2-naphthoic acid, and constituent units derived from terephthalic acid (A), blending 3, 5, 10, 20, 30, 50% by weight of constituent units derived from p-hydroxybenzoic acid with a melting point of 280°C, and constituents derived from 6-hydroxy-2-naphthoic acid The liquid crystal polyester films of Examples 1 to 6 composed of the resin composition of the thermoplastic liquid crystal polyester (B) composed of units showed that the melt viscosity of the resin composition has a low dependence on temperature or shear rate. , even at a stretching ratio exceeding 4.0, it shows the result of improving the film-making processability of a film formed by pneumatic extrusion. In particular, in the liquid crystal polyester film composed of the liquid crystal polyester resin composition of Examples 2 to 5, it is possible to form a stable film without voids in the bubbles of the molten resin extruded from the die. In addition, the liquid crystal polyester films of Examples 1 to 6 maintained the excellent mechanical properties, electrical properties, and heat resistance of thermoplastic liquid crystal polyesters with a melting point of 300° C. or higher, and showed a result that the anisotropy of tensile strength was small. .
由對由源自熔點為320℃之p-羥基苯甲酸之構成單位、與源自6-羥基-2-萘甲酸之構成單位、與源自對苯二甲酸之構成單位所構成之熱塑性液晶聚酯(A)，摻合10重量%之由源自熔點為280℃之p-羥基苯甲酸之構成單位、與源自4,4’-二羥基聯苯之構成單位、與源自對苯二甲酸之構成單位所構成之熱塑性液晶聚酯(B)的樹脂組成物所構成之實施例7之液晶聚酯系薄膜，顯示該樹脂組成物對於溫度或剪切速度之熔融黏度的依賴度低的結果，即使在吹氣比超過4.0之拉伸倍率，亦顯示改善藉由充氣擠出成形之薄膜的製膜加工性的結果，於從模具(Die)擠出之熔融樹脂的氣泡無孔洞且安定之製膜為可能。又，實施例7之液晶聚酯系薄膜維持熔點為300℃以上之熱塑性液晶聚酯所具有之優異之機械特性或電氣特性、耐熱性，並且顯示拉伸強度的各向異性小的結果。Thermoplastic liquid crystal polymer composed of constituent units derived from p-hydroxybenzoic acid with a melting point of 320°C, constituent units derived from 6-hydroxy-2-naphthoic acid, and constituent units derived from terephthalic acid Esters (A), blending 10% by weight of constituent units derived from p-hydroxybenzoic acid with a melting point of 280°C, constituent units derived from 4,4'-dihydroxybiphenyl, and terephthalic acid The liquid crystal polyester film of Example 7 composed of the resin composition of the thermoplastic liquid crystal polyester (B) composed of formic acid constituent units shows that the resin composition has a low dependence on the melt viscosity of the temperature or the shear rate. As a result, even at a stretching ratio exceeding 4.0, it shows that the processability of the film formed by pneumatic extrusion is improved, and the bubbles in the molten resin extruded from the die (Die) have no holes and are stable. It is possible to make a film. Also, the liquid crystal polyester film of Example 7 maintained the excellent mechanical properties, electrical properties, and heat resistance of thermoplastic liquid crystal polyesters having a melting point of 300° C. or higher, and exhibited small anisotropy in tensile strength.
由於熔點為320℃之熱塑性液晶聚酯(A)，摻合5重量%熔點為220℃之熱塑性液晶聚酯(B)的樹脂組成物所構成之比較例1之液晶聚酯系薄膜，顯示該樹脂組成物對於溫度或剪切速度之熔融黏度的依賴度高的結果，在吹氣比超過4.0之拉伸倍率，於從模具(Die)擠出之熔融樹脂的氣泡發生孔洞，無法安定地薄膜製膜的結果。又，比較例1之液晶聚酯系薄膜雖為吹氣比超過4.0之拉伸倍率，但顯示拉伸強度的各向異性大的結果。The liquid crystal polyester film of Comparative Example 1 composed of a thermoplastic liquid crystal polyester (A) having a melting point of 320°C and a resin composition blended with 5% by weight of a thermoplastic liquid crystal polyester (B) having a melting point of 220°C shows that As a result of the high dependence of the melt viscosity of the resin composition on temperature or shear rate, at a stretching ratio exceeding 4.0, holes will be formed in the bubbles of the molten resin extruded from the die (Die), and a stable film cannot be produced. The result of film making. Moreover, although the liquid crystal polyester film of Comparative Example 1 had a draw ratio of more than 4.0 at the blowing ratio, it showed the result that the anisotropy of the tensile strength was large.
僅由熔點為320℃之熱塑性液晶聚酯所構成之參考例1之液晶聚酯系薄膜，顯示對於溫度或剪切速度之熔融黏度的依賴度高之結果，並顯示在吹氣比超過4.0之拉伸倍率，發生從模具(Die)擠出之熔融樹脂的氣泡孔洞，氣泡形狀變不安定，無法安定地薄膜製膜的結果。The liquid crystal polyester film of Reference Example 1 composed only of thermoplastic liquid crystal polyester having a melting point of 320°C showed a high degree of dependence on the melt viscosity of temperature or shear rate, and showed that the blowing ratio exceeded 4.0. As a result of stretching ratio, bubble holes in the molten resin extruded from the die (Die) occur, and the shape of the bubbles becomes unstable, making it impossible to stably form a film.
僅由熔點為280℃之熱塑性液晶聚酯所構成之參考例2之液晶聚酯系薄膜，顯示在吹氣比超過4.0之拉伸倍率，於從模具(Die)擠出之熔融樹脂的氣泡無孔洞可安定之製膜，但顯示熔點低，且焊接回流性劣化之結果。 [產業上之可利用性] The liquid crystal polyester film of Reference Example 2 composed only of thermoplastic liquid crystal polyester having a melting point of 280°C showed no air bubbles in the molten resin extruded from the die (Die) at a stretching ratio exceeding 4.0. Holes can be used for stable film formation, but the result is low melting point and poor soldering reflow performance. [Industrial availability]
如以上，藉由本發明所得之液晶聚酯系薄膜，活化其優異之電氣特性、尺寸安定性或耐熱性等，亦被利用在電機變壓器之電氣絕緣用途、可撓性太陽能電池之元件形成膜用途等。又，亦可在表面保護薄膜或振動板等之音響領域利用。 本發明之金屬層合薄膜亦可使用在電路基板或電容器、電磁波屏蔽材等。本發明之電路基板可使用在各種傳送線路或天線(例如微波或毫米波用天線)，又，亦可使用在天線與傳送線路一體化之天線裝置。 As above, the liquid crystal polyester film obtained by the present invention activates its excellent electrical properties, dimensional stability, heat resistance, etc., and is also used in the electrical insulation of motor transformers and the element formation film of flexible solar cells wait. In addition, it can also be used in the field of acoustics such as surface protection films and diaphragms. The metal laminated film of the present invention can also be used in circuit boards, capacitors, electromagnetic wave shielding materials, and the like. The circuit board of the present invention can be used in various transmission lines or antennas (such as microwave or millimeter wave antennas), and can also be used in an antenna device in which the antenna and the transmission line are integrated.
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