JP2000233448A - Method for thermally welding molten liquid crystal polyester resin molded object and metal - Google Patents
Method for thermally welding molten liquid crystal polyester resin molded object and metalInfo
- Publication number
- JP2000233448A JP2000233448A JP35575899A JP35575899A JP2000233448A JP 2000233448 A JP2000233448 A JP 2000233448A JP 35575899 A JP35575899 A JP 35575899A JP 35575899 A JP35575899 A JP 35575899A JP 2000233448 A JP2000233448 A JP 2000233448A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- molten liquid
- liquid crystalline
- crystalline polyester
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 94
- 239000004645 polyester resin Substances 0.000 title claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims description 53
- 239000004973 liquid crystal related substance Substances 0.000 title abstract 6
- 238000003466 welding Methods 0.000 title 1
- 239000007788 liquid Substances 0.000 claims description 91
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 239000011889 copper foil Substances 0.000 claims description 20
- 230000004927 fusion Effects 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 229910000679 solder Inorganic materials 0.000 claims description 10
- 230000003746 surface roughness Effects 0.000 claims description 8
- 238000007500 overflow downdraw method Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 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
- 238000005259 measurement Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ODSXJQYJADZFJX-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)phenol Chemical compound OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 ODSXJQYJADZFJX-UHFFFAOYSA-N 0.000 description 1
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- -1 and the like Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
-
- 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
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/44—Joining a heated non plastics element to a plastics element
-
- 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
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/56—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using mechanical means or mechanical connections, e.g. form-fits
- B29C65/64—Joining a non-plastics element to a plastics element, e.g. by force
-
- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/303—Particular design of joint configurations the joint involving an anchoring effect
- B29C66/3032—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined
- B29C66/30321—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of protrusions belonging to at least one of the parts to be joined
- B29C66/30322—Particular design of joint configurations the joint involving an anchoring effect making use of protrusions or cavities belonging to at least one of the parts to be joined making use of protrusions belonging to at least one of the parts to be joined in the form of rugosity
-
- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/74—Joining plastics material to non-plastics material
- B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
-
- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/90—Measuring or controlling the joining process
- B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
- B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
- B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
- B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
- B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
- B29C66/91933—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined higher than said fusion temperature
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- 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
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/1403—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
- B29C65/1406—Ultraviolet [UV] radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0079—Liquid crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2305/00—Use of metals, their alloys or their compounds, as reinforcement
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Plasma & Fusion (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、溶融液晶性ポリエ
ステル樹脂成形体と金属とを熱融着する方法および溶融
液晶性ポリエステル樹脂成形体と金属との接合体の製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for heat-sealing a molten liquid crystalline polyester resin molded article and a metal and a method for producing a joined body of the molten liquid crystalline polyester resin molded article and a metal.
【０００２】[0002]
【従来の技術】溶融液晶性ポリエステル樹脂は、耐熱性
が優れ、溶融時の流動性が優れるなどの特徴から精密成
形可能な射出成形用材料として電子材料分野を中心に幅
広く使われるようになっている。そのすぐれた特徴の一
部である耐熱性や低線膨張性などを生かした用途の一つ
に、射出成形によって成形された部品や押出成形によっ
て成形されたフィルムの表面に、金属をメッキあるいは
接着剤により接着させ、機構部品や電気、電子部品とし
て用いるものがある。2. Description of the Related Art Molten liquid crystalline polyester resins have been widely used mainly in the field of electronic materials as injection molding materials capable of precision molding due to their excellent heat resistance and excellent fluidity during melting. I have. One of the applications that takes advantage of some of its outstanding features, such as heat resistance and low linear expansion, is to plate or bond metal to the surface of parts formed by injection molding or the film formed by extrusion. Some are used as mechanical parts, electric or electronic parts by bonding with an agent.
【０００３】このような部品は、実用上は成形体と金属
が十分な強度で接合されていなくてはならないが、溶融
液晶性ポリエステル樹脂成形体は、その分子が成形体表
面の平行方向に強く配向することから金属との接合性が
弱く、ほとんどの薬品に対して不活性であることから、
接着やメッキを施した際に十分な接合強度が得られない
ことがある。[0003] In such a part, the molded body and the metal must be joined with sufficient strength in practical use. However, in the case of the molten liquid crystalline polyester resin molded body, the molecules thereof are strong in the direction parallel to the surface of the molded body. Since it is oriented, it has a weak bond with metals and is inactive against most chemicals,
When bonding or plating is performed, sufficient bonding strength may not be obtained.
【０００４】そこで、溶融液晶性ポリエステル樹脂成形
体と金属との接合強度を改良する種々の方法が検討され
ている。たとえば、特開平１−２１６８２４号公報に
は、溶融液晶性ポリエステル樹脂成形体表面の改質方法
として、紫外線を照射し、塗装、印刷、接着、蒸着、メ
ッキなどを行うために適した表面を得る方法が開示され
ている。また、特開平９−１００３５９号公報には、溶
融液晶性ポリエステル樹脂成形体の表面を部分的に紫外
線照射した後、エッチング液にて粗化することにより、
メッキ等との接合力に優れる成形体表面を得る方法につ
いて開示されている。Therefore, various methods for improving the bonding strength between a molten liquid crystalline polyester resin molded article and a metal have been studied. For example, Japanese Patent Application Laid-Open No. 1-216824 discloses a method for modifying the surface of a molten liquid crystalline polyester resin molded article by irradiating ultraviolet rays to obtain a surface suitable for performing coating, printing, bonding, vapor deposition, plating, and the like. A method is disclosed. In Japanese Patent Application Laid-Open No. Hei 9-100359, the surface of a molten liquid crystalline polyester resin molded article is partially irradiated with ultraviolet rays, and then roughened with an etching solution.
It discloses a method for obtaining a molded body surface having excellent bonding strength with plating or the like.
【０００５】しかし、溶融液晶性ポリエステル樹脂成形
体と金属とを接着剤にて接着させた場合、溶融液晶性ポ
リエステル樹脂が耐熱性や誘電特性などの優れた特性を
有しているにもかかわらず、接着剤の特性が劣るために
その接着された成形体の特性が大きく損なわれる。ま
た、メッキをほどこすにはエッチングなどの煩雑な工程
が必要になる。However, when the molten liquid crystalline polyester resin molded article and the metal are adhered with an adhesive, the molten liquid crystalline polyester resin has excellent properties such as heat resistance and dielectric properties. In addition, since the properties of the adhesive are inferior, the properties of the bonded molded article are greatly impaired. In addition, complicated steps such as etching are required to perform plating.
【０００６】一方、溶融液晶性ポリエステル樹脂成形体
と金属とを、接着やメッキによらず熱融着する方法が種
々検討されている。一例を挙げれば、特開平８−５８０
２４号公報には、溶融液晶性ポリエステル樹脂からなる
フィルムと銅箔とを熱融着させ、回路基板として有用な
積層品を得る方法が記載されている。しかし、このよう
な手法で溶融液晶性ポリエステル樹脂成形体と金属とを
熱融着させたものであっても、溶融液晶性ポリエステル
樹脂成形体と金属との十分な接合強度が得られない場合
があった。[0006] On the other hand, various methods for heat-sealing a molten liquid crystalline polyester resin molded article and a metal without using adhesion or plating have been studied. One example is described in JP-A-8-580.
No. 24 describes a method of heat-sealing a film made of a molten liquid crystalline polyester resin and a copper foil to obtain a laminate useful as a circuit board. However, even when the molten liquid crystalline polyester resin molded article and the metal are heat-sealed by such a method, a sufficient bonding strength between the molten liquid crystalline polyester resin molded article and the metal may not be obtained. there were.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、溶融液晶性
ポリエステル樹脂成形体と金属とを強固に熱融着させる
方法および溶融液晶性ポリエステル樹脂成形体と金属と
が強固に熱融着された接合体の製造方法を提供すること
を目的とするものである。SUMMARY OF THE INVENTION The present invention relates to a method for firmly heat-fusing a molten liquid crystalline polyester resin molded article and a metal, and a method for firmly heat-fusing a molten liquid crystalline polyester resin molded article and a metal. It is an object of the present invention to provide a method for manufacturing a joined body.
【０００８】[0008]
【発明を解決するための手段】本発明者らは、鋭意検討
した結果、溶融液晶性ポリエステル樹脂成形体の表面を
あらかじめ活性化し、その表面と金属とを溶融液晶性ポ
リエステル樹脂の流動開始温度以上で熱融着させること
により、上記目的が達成されることを見いだし、本発明
に到達した。Means for Solving the Problems As a result of intensive studies, the present inventors have previously activated the surface of a molten liquid crystalline polyester resin molded article and caused the surface and metal to be heated to a temperature above the flow starting temperature of the molten liquid crystalline polyester resin. It has been found that the above objects can be achieved by heat-sealing with, and the present invention has been achieved.
【０００９】すなわち、本発明は、（１）．溶融液晶性
ポリエステル樹脂成形体の表面を活性化し、その表面と
金属とを溶融液晶性ポリエステル樹脂の流動開始温度以
上で熱融着する溶融液晶性ポリエステル樹脂成形体と金
属との熱融着方法に係るものである。また、本発明は、
（２）．溶融液晶性ポリエステル樹脂成形体の表面に、
２５４ｎｍの波長を含む紫外線を照射し、その表面と金
属とを溶融液晶性ポリエステル樹脂の流動開始温度以上
で熱融着する溶融液晶性ポリエステル樹脂成形体と金属
との熱融着方法に係るものである。さらに、本発明は、
（３）．溶融液晶性ポリエステル樹脂成形体と金属とを
上記（１）または（２）の方法で熱融着する溶融液晶性
ポリエステル成形体と金属との接合体の製造方法に係る
ものである。さらに、本発明は、（４）．溶融液晶性ポ
リエステル樹脂成形体と金属とを上記（１）または
（２）の方法で熱融着する溶融液晶性ポリエステル成形
体と金属との積層体の製造方法に係るものである。That is, the present invention provides (1). A method for activating the surface of a molten liquid crystalline polyester resin molded article and thermally fusing the surface and the metal at a temperature equal to or higher than the flow start temperature of the molten liquid crystalline polyester resin to a method of heat fusion between the molten liquid crystalline polyester resin molded article and the metal. It is related. Also, the present invention
(2). On the surface of the molten liquid crystalline polyester resin molding,
The present invention relates to a method for heat-sealing a molten liquid crystalline polyester resin molded article and a metal, which is irradiated with ultraviolet light having a wavelength of 254 nm and heat-fuses the surface of the metal and the metal at a temperature equal to or higher than the flow start temperature of the molten liquid crystalline polyester resin. is there. Further, the present invention provides
(3). The present invention relates to a method for producing a joined body of a molten liquid crystalline polyester molded article and a metal, wherein the molten liquid crystalline polyester resin molded article and a metal are thermally fused by the method (1) or (2). Further, the present invention provides (4). The present invention relates to a method for producing a laminate of a molten liquid crystalline polyester molded article and a metal, wherein the molten liquid crystalline polyester resin molded article and the metal are thermally fused by the method (1) or (2).
【００１０】[0010]
【発明の実施の形態】本発明で用いられる溶融液晶性ポ
リエステル樹脂成形体は、溶融液晶性ポリエステル樹脂
またはその組成物から射出成形や押し出し成形などによ
って成形されたものである。特にフィルムやシート状成
形体は、銅箔と貼り合わせることにより耐熱性や寸法精
度等に優れた回路基板として使用することができる。BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline polyester resin molded article used in the present invention is formed by injection molding or extrusion molding from a molten liquid crystalline polyester resin or a composition thereof. In particular, a film or a sheet-like molded body can be used as a circuit board having excellent heat resistance, dimensional accuracy, and the like by being bonded to a copper foil.
【００１１】このような成形体を得るための溶融液晶性
ポリエステル樹脂は、芳香族ヒドロキシカルボン酸、芳
香族ジカルボン酸、芳香族ジヒドロキキシ化合物等のモ
ノマー成分を組み合わせて、重縮合反応させることによ
り得ることができる。The molten liquid crystalline polyester resin for obtaining such a molded product is obtained by subjecting a monomer component such as an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, or an aromatic dihydroxy compound to a polycondensation reaction. Can be.
【００１２】モノマー成分の芳香族ヒドロキシカルボン
酸に由来する構造単位としては、The structural units derived from the aromatic hydroxycarboxylic acid of the monomer component include:
【化１】 などが例示される。Embedded image And the like.
【００１３】また、芳香族ジヒドロキシ化合物に由来す
る構造単位としては、The structural units derived from the aromatic dihydroxy compound include:
【化２】 などが例示される。Embedded image And the like.
【００１４】また、芳香族ジカルボン酸に由来する構造
単位としては、Further, as a structural unit derived from an aromatic dicarboxylic acid,
【化３】 などが例示される。Embedded image And the like.
【００１５】ここで、上記構造単位の組み合わせとその
比率は、随意であるが、耐熱性や流動性の点から、下記
構造単位（１）、（２）、（３）および（４）を有し、
それらの合計が全体の９７ｍｏｌ％以上であること、ま
たは下記構造単位（１）および（５）を有し、それらの
合計が全体の９７ｍｏｌ％以上であることが好ましい。Here, the combination of the above structural units and the ratio thereof are optional, but from the viewpoint of heat resistance and fluidity, the following structural units (1), (2), (3) and (4) are available. And
It is preferable that their total is 97 mol% or more of the whole, or that they have the following structural units (1) and (5), and that their total is 97 mol% or more of the whole.
【００１６】[0016]
【化４】 Embedded image
【００１７】中でも、上記構造単位（１）、（２）、
（３）および（４）からなる溶融液晶性ポリエステル樹
脂が、耐熱性の点で、より好ましい。さらに好ましく
は、構造単位（１）が全体の４０〜７０ｍｏｌ％であ
り、構造単位（２）と構造単位（３）の合計が構造単位
（４）と実質上同量で全体の１５〜３０ｍｏｌ％であ
り、かつ、構造単位（２）において主鎖結合位置がパラ
位にあるものが構造単位（２）全体の８０〜１００ｍｏ
ｌ％であり、構造単位（４）において主鎖結合位置がパ
ラ位にあるものが構造単位（４）全体の５０ｍｏｌ％〜
１００ｍｏｌ％である。In particular, the structural units (1), (2),
The molten liquid crystalline polyester resin composed of (3) and (4) is more preferable in terms of heat resistance. More preferably, the structural unit (1) is 40 to 70 mol% of the whole, and the total of the structural unit (2) and the structural unit (3) is substantially the same as the structural unit (4) and is 15 to 30 mol% of the whole. And the main chain bonding position in the structural unit (2) is in the para-position is 80 to 100 mo of the entire structural unit (2).
1%, and the structural unit (4) in which the main chain bonding position is at the para position is 50 mol% or less of the entire structural unit (4).
100 mol%.
【００１８】本発明で用いられる液晶性ポリエステル樹
脂を製造する方法には、特に制限はなく周知の方法を用
いることができる。たとえば、上記モノマー成分からな
る混合物を重合槽中で重縮合反応させることにより得ら
れるが、これらモノマー成分の仕込みは一括方式でも、
分割方式でもよい。反応は不活性気体、たとえば窒素雰
囲気下に常圧、減圧またはそれらの組み合わせで行うこ
とができる。プロセスは回分式、連続式、またはそれら
の組み合わせを採用できる。なお、上記モノマー成分を
より重合し易い化合物に変える反応（たとえば、エステ
ル化反応）を重縮合反応に先立って行った後、引き続き
重縮合反応を行うこともできる。The method for producing the liquid crystalline polyester resin used in the present invention is not particularly limited, and a known method can be used. For example, it is obtained by performing a polycondensation reaction of a mixture of the above monomer components in a polymerization tank.
The division method may be used. The reaction can be carried out under normal pressure, reduced pressure or a combination thereof under an inert gas such as nitrogen atmosphere. The process can be batch, continuous, or a combination thereof. In addition, after performing the reaction (for example, esterification reaction) which changes the said monomer component into the compound which is easy to polymerize before a polycondensation reaction, a polycondensation reaction can also be performed continuously.
【００１９】重縮合反応の温度は、２７０〜３８０℃が
好ましい。温度が２７０℃より低いと重合反応の進行が
遅く、３８０℃を超えると分解等の副反応が起こり易
い。多段階の反応温度を採用しても構わないし、場合に
より昇温途中で、あるいは最高温度に達したらすぐに反
応生成物である溶融液晶性ポリエステル樹脂を溶融状態
で抜出し、回収することもできる。回収された溶融液晶
性ポリエステル樹脂は固化、粉砕によりパウダー状にさ
れるか、重合槽より直接押出機へ導入して、造粒し、ペ
レット状にすることができる。また、取出した溶融液晶
性ポリエステル樹脂の分子量をさらに上げるため、不活
性ガス雰囲気下、加温により固相重合等の後処理を施す
こともできる。The temperature of the polycondensation reaction is preferably from 270 to 380 ° C. If the temperature is lower than 270 ° C., the progress of the polymerization reaction is slow, and if it exceeds 380 ° C., side reactions such as decomposition are likely to occur. A multi-stage reaction temperature may be employed, and depending on the case, a molten liquid crystalline polyester resin as a reaction product may be extracted in a molten state and recovered during the heating or as soon as the maximum temperature is reached. The recovered molten liquid crystalline polyester resin can be powdered by solidification and pulverization, or can be directly introduced into an extruder from a polymerization tank, granulated, and pelletized. Further, in order to further increase the molecular weight of the extracted molten liquid crystalline polyester resin, post-treatment such as solid phase polymerization can be performed by heating under an inert gas atmosphere.
【００２０】得られた溶融液晶性ポリエステル樹脂がパ
ウダーの場合、溶融押出機でペレット形状とした後、射
出成形機や押し出し成形機へ投入し成形する方が、取扱
いの点で好ましい。When the obtained molten liquid crystalline polyester resin is a powder, it is preferable in terms of handling that the melted liquid crystalline polyester resin be pelletized by a melt extruder and then injected into an injection molding machine or an extrusion molding machine and molded.
【００２１】また、本発明の目的を阻害しない範囲にお
いて無機充填材、有機充填材、酸化防止剤、熱安定剤、
光安定剤、難燃剤、滑剤、帯電防止剤、防錆剤、蛍光
剤、表面平滑剤、表面改良剤または離型剤等の各種添加
剤を添加することができる。特に、射出成形用材料とし
て用いるにあたっては、成形された部品の弾性率を向上
させたり、異方性を緩和させたりする目的で、ガラス繊
維、タルクなどの充填材を溶融液晶性ポリエステル樹脂
１００重量部に対して４０〜７０重量部充填したものが
好ましく用いられる。In addition, as long as the object of the present invention is not impaired, an inorganic filler, an organic filler, an antioxidant, a heat stabilizer,
Various additives such as a light stabilizer, a flame retardant, a lubricant, an antistatic agent, a rust inhibitor, a fluorescent agent, a surface smoothing agent, a surface improving agent or a release agent can be added. In particular, when used as an injection molding material, a filler such as glass fiber, talc or the like is added to a molten liquid crystalline polyester resin in an amount of 100% by weight in order to improve the modulus of elasticity of a molded part or to reduce anisotropy. Those charged to 40 to 70 parts by weight per part are preferably used.
【００２２】本発明に用いられる溶融液晶性ポリエステ
ル樹脂は、流動開始温度（異方性溶融相を形成し始める
温度）にて剪断速度１０００ｓｅｃ-1で測定した溶融粘
度（粘度１ａ）と、流動開始温度＋２０℃にて剪断速度
１０００ｓｅｃ-1で測定した溶融粘度（粘度２ａ）との
比率［（粘度２ａ）／（粘度１ａ）］、または、流動開
始温度にて剪断速度１００ｓｅｃ-1で測定した溶融粘度
（粘度１ｂ）と、流動開始温度＋２０℃にて剪断速度１
００ｓｅｃ-1で測定した溶融粘度（粘度２ｂ）との比率
［（粘度２ｂ）／（粘度１ｂ）］の少なくとも一方が
０．１０〜０．７０であることが好ましく、さらに好ま
しくは前者が０．１０〜０．７０、さらに好ましくは前
者が０．１０〜０．５０である。ここで言う流動開始温
度とは、４℃／ｍｉｎの昇温速度で加熱された樹脂を荷
重１００Ｋｇｆ／ｃｍ2のもとで、内径１ｍｍ、長さ１
０ｍｍのノズルから押出したときに、溶融粘度が４８０
００ポイズを示す温度を言う。溶融粘度比が上記の範囲
外であると、特に押出し成形加工でフィルムやシートを
成形するに際して、フィルム引き取り性などの加工性が
低下したり、得られた加工品の異方性が強くなることが
ある。The molten liquid crystalline polyester resin used in the present invention has a melt viscosity (viscosity 1a) measured at a flow start temperature (a temperature at which an anisotropic molten phase starts to form) at a shear rate of 1000 sec -1 and a flow start temperature. ratio of melt viscosity measured at a shear rate of 1,000 sec -1 at a temperature of + 20 ° C. (viscosity 2a) [(viscosity 2a) / (viscosity 1a)], or, melted measured at a shear rate of 100 sec -1 at flow temperature Viscosity (viscosity 1b), shear rate 1 at flow start temperature + 20 ° C
It is preferable that at least one of the ratio [(viscosity 2b) / (viscosity 1b)] to the melt viscosity (viscosity 2b) measured at 00 sec -1 is 0.10 to 0.70, more preferably 0.1 to 0.70. 10 to 0.70, more preferably the former is 0.10 to 0.50. The flow start temperature referred to herein means that the resin heated at a temperature rising rate of 4 ° C./min has an inner diameter of 1 mm and a length of 1 under a load of 100 kgf / cm 2.
When extruded from a 0 mm nozzle, the melt viscosity is 480.
It refers to a temperature that indicates 00 poise. If the melt viscosity ratio is out of the above range, especially when forming a film or sheet by extrusion molding, the processability such as film take-off property is reduced, or the obtained product has an increased anisotropy. There is.
【００２３】本発明に用いられる溶融液晶性ポリエステ
ル樹脂は、耐熱性の点で、そのハンダ耐熱温度が２５０
℃以上あることが好ましい。ここでハンダ耐熱温度と
は、厚みが１．２ｍｍのＪＩＳ１（１／２）号ダンベル
を成形し、錫６０％、鉛４０％からなる２４０℃のハン
ダ浴に浸漬し、同温度に６０ｓｅｃ間保持した後取出
し、外観を観察する。その後、該ハンダ浴を１０℃ずつ
昇温させては同様の実験を行い、同試験片が発泡または
変形しない最高温度を言う。ハンダ耐熱温度が２５０℃
未満の場合、本発明によって得られる金属と融着された
部品のハンダリフロー炉での使用などに制限が多くな
る。The molten liquid crystalline polyester resin used in the present invention has a solder heat resistance temperature of 250 from the viewpoint of heat resistance.
It is preferable that the temperature is not lower than ° C. Here, the solder heat-resistant temperature means that a JIS 1 (1/2) dumbbell having a thickness of 1.2 mm is formed, immersed in a 240 ° C. solder bath composed of 60% tin and 40% lead, and maintained at the same temperature for 60 seconds. After taking out, observe the appearance. Thereafter, the same experiment is performed by raising the temperature of the solder bath by 10 ° C., and the maximum temperature at which the test piece does not foam or deform. Solder heat resistance temperature is 250 ℃
If the amount is less than the above range, the use of a metal-fused part obtained by the present invention in a solder reflow furnace is limited.
【００２４】本発明に用いられる溶融液晶性ポリエステ
ル樹脂の溶融張力は１０ｇ以上であることが好ましい。
ここで言う溶融張力とは、該樹脂の流動開始温度より３
０℃高い温度に設定された長さ８．０ｍｍ×２．１ｍｍ
φのダイス中で樹脂を溶融させ、ピストン速度２ｍｍ／
ｍｉｎでこれを押出し、テンションプーリーを通した後
引き取りローラーでモノフィラメント状に引き取り、引
き取り速度を上げていったときに糸が破断する時のテン
ションプーリーにかかる力を表したものである。溶融張
力が１０ｇより低い場合、特に溶融押し出しによるフィ
ルムやシートの成形においては成膜時の伸びが不十分と
なり、本発明に供する溶融液晶性ポリエステル樹脂成形
体を得るための加工が困難となる場合がある。The melt tension of the liquid crystalline polyester resin used in the present invention is preferably 10 g or more.
The melt tension referred to here is 3 degrees from the flow start temperature of the resin.
8.0 mm x 2.1 mm length set at 0 ° C higher temperature
The resin is melted in a dice of φ and the piston speed is 2mm /
min, extruded, passed through a tension pulley, taken up in a monofilament shape by a take-off roller, and expressed the force applied to the tension pulley when the yarn was broken when the take-up speed was increased. When the melt tension is lower than 10 g, especially when forming a film or sheet by melt extrusion, the elongation at the time of film formation becomes insufficient, and processing for obtaining a molten liquid crystalline polyester resin molded article to be used in the present invention becomes difficult. There is.
【００２５】また、本発明に用いられる溶融液晶性ポリ
エステル樹脂の固有粘度［η］は、５．５以上であるこ
とが望ましい。［η］が５．５未満の場合、上述の好ま
しい溶融粘度特性、溶融張力を得ることが困難となる。Further, the intrinsic viscosity [η] of the molten liquid crystalline polyester resin used in the present invention is desirably 5.5 or more. When [η] is less than 5.5, it is difficult to obtain the above-mentioned preferable melt viscosity characteristics and melt tension.
【００２６】このようにして得られた溶融液晶性ポリエ
ステル樹脂は、射出成形機や押出し成形機に投入され賦
形される。特に、金属との熱融着によって回路基板を形
成する目的のためには、その取り扱い性等の点でフィル
ムまたはシート状成形体であることが好ましく、フィル
ムで有ることがより好ましい。また、シートやフィルム
は、実質的に溶融液晶性ポリエステル樹脂のみからなる
のが好ましい。The molten liquid crystalline polyester resin thus obtained is put into an injection molding machine or an extrusion molding machine and shaped. In particular, for the purpose of forming a circuit board by heat fusion with a metal, it is preferably a film or a sheet-like molded body from the viewpoint of handleability and the like, and more preferably a film. Further, it is preferable that the sheet or the film is substantially composed only of the molten liquid crystalline polyester resin.
【００２７】特に、フィルムを成形する場合の成形法と
しては、溶融した樹脂をＴダイと呼ばれるスリット状の
加工機から所定の幅、厚みに押出し、冷却してそのまま
フィルムとするキャスト法、また押出し後、製膜方向、
およびその直角方向に逐次延伸する延伸法、環状ダイか
ら円筒状に樹脂を押出し、ガスによって巻き取り方向と
それに直角方向に同時に延伸させるインフレ−ション法
等が挙げられる。溶融液晶性ポリエステル樹脂の場合、
異方性のコントロールのし易さの点でインフレ−ション
法が好ましく用いられる。In particular, as a molding method for forming a film, a molten resin is extruded to a predetermined width and thickness from a slit-shaped processing machine called a T-die, and then cast into a film as it is after cooling. Later, the film forming direction,
And an inflation method in which a resin is extruded into a cylindrical shape from an annular die and stretched simultaneously in a winding direction and a direction perpendicular thereto with a gas. In the case of molten liquid crystalline polyester resin,
The inflation method is preferably used from the viewpoint of easy control of anisotropy.
【００２８】次に、本発明の溶融液晶性ポリエステル樹
脂成形体と金属との熱融着方法と、接合体や積層体の製
造方法について説明する。本発明の溶融液晶性ポリエス
テル樹脂成形体と金属との熱融着方法は、溶融液晶性ポ
リエステル樹脂成形体の表面を活性化し、その表面と金
属とを溶融液晶性ポリエステル樹脂の流動開始温度以上
で熱融着することを特徴とする。溶融液晶性ポリエステ
ル樹脂成形体の表面を活性化する方法としては、紫外線
を照射することや、コロナ放電をすることやプラズマ処
理をすることが挙げられる。特に、溶融液晶性ポリエス
テル樹脂成形体の表面に、２５４ｎｍの波長を含む紫外
線を照射することが好ましい。Next, a method for heat-sealing the molten liquid crystalline polyester resin molded article of the present invention to a metal and a method for producing a joined body or a laminate will be described. The method of heat fusion between a molten liquid crystalline polyester resin molded article and a metal of the present invention activates the surface of the molten liquid crystalline polyester resin molded article, and the surface and the metal are heated at a flow starting temperature of the molten liquid crystalline polyester resin or higher. It is characterized by heat fusion. Examples of a method for activating the surface of the molten liquid crystalline polyester resin molded body include irradiating ultraviolet rays, performing corona discharge, and performing plasma treatment. In particular, it is preferable to irradiate the surface of the molten liquid crystalline polyester resin molded body with ultraviolet light having a wavelength of 254 nm.
【００２９】ここで、溶融液晶性ポリエステル樹脂成形
体の表面が活性化された状態とは、紫外線、コロナ放
電、プラズマ照射などのエネルギー照射によって、成形
体表面が酸化された状態、あるいは官能基が形成された
状態、等をいう。成形体表面の酸化される程度として
は、本願の効果を発現する程度であれば特に限定される
ものではないが、例えば表面を構成する元素中の、酸素
原子が活性化以前の状態に比べて５％以上、好ましくは
２０％以上増加することが挙げられる。表面に形成され
る官能基としては、例えば水酸基、カルボニル基などが
挙げられるが、これに限定されるものではない。また、
その官能基の密度も、本願の効果を発現する程度であれ
ば特に限定されるものではない。Here, the activated state of the surface of the molten liquid crystalline polyester resin molded body refers to a state in which the molded body surface is oxidized by irradiation of energy such as ultraviolet rays, corona discharge, or plasma irradiation, or a state in which a functional group is present. It refers to the formed state, and the like. The degree of oxidation of the surface of the molded body is not particularly limited as long as the effect of the present application is exhibited, but, for example, in the elements constituting the surface, oxygen atoms are compared with the state before activation. The increase is 5% or more, preferably 20% or more. Examples of the functional group formed on the surface include a hydroxyl group and a carbonyl group, but are not limited thereto. Also,
The density of the functional group is not particularly limited as long as the effect of the present invention is exhibited.
【００３０】このような活性化は、Ｘ線電子分光分析に
より表面元素構成を測定することで確認される。また、
表面に水酸基、カルボニル基など親水性の官能基が形成
されている場合、その表面に対する水の接触角が低下す
ることからも確認される。Such activation is confirmed by measuring the surface element composition by X-ray electron spectroscopy. Also,
When a hydrophilic functional group such as a hydroxyl group or a carbonyl group is formed on the surface, it is confirmed from the fact that the contact angle of water with the surface is reduced.
【００３１】また、上記の熱融着方法を適用することに
より、溶融液晶性ポリエステル樹脂成形体と金属との接
合体が得られる。特に、溶融液晶性ポリエステルフィル
ムまたはシートと金属箔とに、上記の熱融着方法を適用
することにより、溶融液晶性ポリエステル樹脂成形体と
金属との薄い積層体が得られる。以下、熱融着方法につ
いて主として記載するが、同方法をそのまま適用するこ
とにより、溶融液晶性ポリエステル樹脂成形体と金属と
の接合体や積層体が製造されることは明らかである。By applying the above-mentioned heat fusion method, a joined body of a molten liquid crystalline polyester resin molded article and a metal can be obtained. In particular, a thin laminate of a molten liquid crystalline polyester resin molded article and a metal can be obtained by applying the above-mentioned heat fusion method to a molten liquid crystalline polyester film or sheet and a metal foil. Hereinafter, the heat fusion method will be mainly described, but it is apparent that a joint or a laminate of a molten liquid crystalline polyester resin molded product and a metal is manufactured by applying the method as it is.
【００３２】本発明において、溶融液晶性ポリエステル
樹脂成形体と金属とを熱融着するには、その融着温度が
溶融液晶性ポリエステル樹脂の流動開始温度＋１０℃〜
流動開始温度＋６０℃であることが好ましく、さらに好
ましくは流動開始温度＋３０℃〜流動開始温度＋６０℃
である。熱融着温度が溶融液晶性ポリエステル樹脂の流
動開始温度＋１０℃より小さいと、成形体と金属との接
合強度が十分ではないことがあり、流動開始温度＋６０
℃より大きい場合、成形体の形状変形が著しくなること
がある。In the present invention, in order to heat-fuse the molten liquid crystalline polyester resin molded body and the metal, the fusion temperature is set to the flow starting temperature of the molten liquid crystalline polyester resin + 10 ° C.
It is preferable that the flow start temperature is + 60 ° C, more preferably the flow start temperature + 30 ° C to the flow start temperature + 60 ° C.
It is. If the heat fusion temperature is lower than the flow start temperature of the molten liquid crystalline polyester resin + 10 ° C, the bonding strength between the molded body and the metal may not be sufficient, and the flow start temperature +60
If it is higher than ℃, the shape deformation of the molded body may be remarkable.
【００３３】前記のようにして得られた溶融液晶性ポリ
エステル樹脂成形体の、金属と熱融着されようとする表
面は、その表面粗さがＲａ(中心線平均粗さ)で１〜５０
μｍの範囲であることが好ましい。このような範囲の表
面粗さへ調整する方法としては、射出成形に用いる金型
のキャビティー表面の粗さを調整して成形体へその表面
を転写する方法、エンボスを付したロールへフィルムを
加圧、加熱と共に連続的に通し、そのエンボスを転写す
る方法、エンボスを付した型を成形体へ押し当ててその
エンボスを転写する方法などがあるが、これらに限られ
るものではない。The surface of the molten liquid crystalline polyester resin molded product obtained as described above, which is to be thermally fused with a metal, has a surface roughness Ra (center line average roughness) of 1 to 50.
It is preferably in the range of μm. As a method of adjusting the surface roughness to such a range, a method of transferring the surface to a molded body by adjusting the roughness of a cavity surface of a mold used for injection molding, and a method of transferring a film to an embossed roll There is a method in which the emboss is transferred by continuously passing the material under pressure and heat, and a method in which the embossed mold is pressed against the molded body to transfer the emboss, but the method is not limited thereto.
【００３４】本発明で用いられる溶融液晶性ポリエステ
ル樹脂成形体と熱融着される金属としては、銅、銀、
金、鉄、亜鉛、マグネシウム、ニッケルなど、またはそ
の合金類が挙げられる。これらは、単独であるものや複
合されたものであってもかまわない。さらに、本発明を
妨げない範囲の表面処理、例えばアミノシラン剤などに
よる処理が施された金属であってもかまわない。The metal to be heat-fused with the molten liquid crystalline polyester resin molded article used in the present invention includes copper, silver,
Gold, iron, zinc, magnesium, nickel, and the like, or alloys thereof are included. These may be used alone or in combination. Furthermore, a metal that has been subjected to a surface treatment that does not impair the present invention, for example, a treatment with an aminosilane agent or the like, may be used.
【００３５】金属の形状としては、構造部品としての形
状の他、電気、電子回路を形成するための細線やエッチ
ング処理にて回路を形成するための箔状などが挙げられ
る。特に複雑で微細な回路形成のためには銅箔であるこ
とが好ましい。銅箔を用いた場合、それを溶融液晶性ポ
リエステル樹脂成形体と融着した後、エッチングによっ
て回路が形成される。As the shape of the metal, in addition to the shape as a structural component, a thin wire for forming an electric or electronic circuit, a foil for forming a circuit by etching, and the like can be mentioned. In particular, copper foil is preferable for forming complicated and fine circuits. When a copper foil is used, a circuit is formed by fusing it to a molten liquid crystalline polyester resin molded article and then etching.
【００３６】この銅箔とは、電解銅箔と称されるもので
あり、厚さが２〜２００μｍ、片側の表面には微細な銅
粒子が析出されており、亜鉛やニッケルによってコート
されたのち、表面処理をなされたものが一般的である。
しかし、本発明はこれに限られるものではない。This copper foil is referred to as an electrolytic copper foil, has a thickness of 2 to 200 μm, and has fine copper particles deposited on one surface, and after being coated with zinc or nickel, In general, those subjected to surface treatment are used.
However, the present invention is not limited to this.
【００３７】溶融液晶性ポリエステル樹脂成形体と金属
とを熱融着するためには、前記の融着温度に設定された
プレス装置にて成形体と金属とを加圧する方法、予め上
記の融着温度に熱せられた金属を成形体に圧着する方
法、上記の融着温度に設定された熱ロールにてフィルム
やシート形状の成形体と金属箔とを連続的に加圧する方
法などが挙げられる。また、各々の成形体と金属は、成
形体と金属の片側同士が接合されても良いし、片方また
は各々の両面が接合される形態であってもかまわない。
これは、目的とする部品に要求される形状によって選択
されるものである。In order to thermally fuse the molten liquid crystalline polyester resin molded body and the metal, a method in which the molded body and the metal are pressurized by a press apparatus set at the above-mentioned fusion temperature is performed by the above-mentioned method. Examples of the method include a method in which a metal heated to a temperature is press-bonded to a molded body, and a method in which a film or a sheet-shaped molded body and a metal foil are continuously pressed by a hot roll set at the above-mentioned fusing temperature. Further, each of the molded body and the metal may be joined to one side of the molded body and the metal, or may be a form in which one or both sides are joined.
This is selected according to the shape required for the target part.
【００３８】また、例えばプレス装置にて加圧される成
形体と金属は、一度の融着操作につき一個の熱融着され
た成形体を得てもよいし、剥離用フィルムなどによって
複数組の融着させる金属と成形体を分離し、一度の融着
操作にて複数個の融着された成形体を得てもよい。これ
は、融着された成形体を得るために求められる生産性に
よって選択されるものである。For example, a compact and a metal which are pressed by a press device may be obtained as one heat-fused compact per fusion operation, or a plurality of sets may be formed by a release film or the like. The metal to be fused and the compact may be separated, and a plurality of fused compacts may be obtained by a single fusing operation. This is selected according to the productivity required to obtain a fused molded body.
【００３９】[0039]
【実施例】以下、実施例により本発明をさらに詳しく説
明するが、本発明はこれらによって限定されるものでは
ない。物性の測定法は、次のとおりである。 剥離強度：金属箔と成形体が融着された試験片から、幅
１０ｍｍ、長さ６４ｍｍの試験片を切り取り、島津製作
所製オートグラフＡＧ−５０００Ｄを用いて、金属箔の
９０℃引き剥がし試験（引き取り速度：５０ｍｍ／分）
にて剥離強度（ピール強度ともいう）を測定した。 表面粗さ：熱融着させる成形体の表面粗さは、非接触表
面粗さ計 Ｆｅｉｎｐｒｕｆ Ｐｅｒｔｈｅｎ Ｇｍｂ
Ｈ製 Ｆｏｃｏｄｙｎ、およびペルトメーターＣ５Ｄを
用いて計測した。 流動開始温度：島津製高化式フローテスターＣＦＴ−５
００型で測定した。すなわち、４℃／ｍｉｎの昇温速度
で加熱された樹脂を荷重１００Ｋｇｆ／ｃｍ2のもと
で、内径１ｍｍ、長さ１０ｍｍのノズルから押出したと
きに、溶融粘度が４８０００ポイズを示す温度を測定
し、これを流動開始温度とした。 溶融粘度：東洋精機社製キャピログラフ１Ｂで、所定温
度下、キャピラリー径０．５ｍｍ、キャピラリー長１０
ｍｍ、剪断速度１０００ｓｅｃ-1で測定を行った。 溶融張力：東洋精機キャピログラフ１Ｂを用い、所定温
度に設定された長さ８．０ｍｍ×２．１ｍｍφのダイス
中で樹脂を溶融させ、ピストン速度２ｍｍ／ｍｉｎでこ
れを押出し、テンションプーリーを通した後巻き取る装
置において、巻き取りスピードを上げていきながら引き
取り、糸が破断する時のテンションプーリーにかかる力
をグラム単位で求めた。 固有粘度［η］：樹脂を３，５−ビストリフロロメチル
フェノールに溶解させ、ウベローデ粘度計を用いて６０
℃で測定した。 ハンダ耐熱温度：射出成形機を用いて厚みが１．２ｍｍ
のＪＩＳ１（１／２）号ダンベルを成形し、錫６０％、
鉛４０％からなる２３０℃のハンダ浴に浸漬し、同温度
に６０ｓｅｃ間保持した後取出し、外観を観察する。そ
の後、該ハンダ浴を１０℃ずつ昇温させ同様の実験を行
い、同試験片が発泡または変形しない最高温度を求め
た。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The measuring method of the physical properties is as follows. Peel strength: A test piece having a width of 10 mm and a length of 64 mm was cut out from a test piece in which a metal foil and a molded body were fused, and a 90 ° C peeling test of the metal foil was performed using an Autograph AG-5000D manufactured by Shimadzu Corporation ( (Pickup speed: 50 mm / min)
The peel strength (also referred to as peel strength) was measured. Surface roughness: The surface roughness of the heat-sealed molded body is measured by a non-contact surface roughness meter Feinpruf Perthen Gmb.
The measurement was performed using Focodyn manufactured by H. Co. and Pertometer C5D. Flow initiation temperature: Shimadzu Koka type flow tester CFT-5
It was measured with type 00. That is, when a resin heated at a heating rate of 4 ° C./min is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 100 kgf / cm 2 , the temperature at which the melt viscosity shows 48,000 poise is measured. This was taken as the flow start temperature. Melt viscosity: Capillograph 1B manufactured by Toyo Seiki Co., Ltd., at a predetermined temperature, capillary diameter 0.5 mm, capillary length 10
mm and a shear rate of 1000 sec -1 . Melt tension: Using Toyo Seiki Capillograph 1B, the resin is melted in a 8.0 mm × 2.1 mmφ die set at a predetermined temperature, extruded at a piston speed of 2 mm / min, and passed through a tension pulley. In the winding device, the yarn was taken up while increasing the winding speed, and the force applied to the tension pulley when the yarn was broken was obtained in grams. Intrinsic viscosity [η]: The resin was dissolved in 3,5-bistrifluoromethylphenol, and the resin was dissolved in
Measured in ° C. Solder heat resistant temperature: 1.2mm thick using an injection molding machine
Of JIS1 (1/2) No. dumbbell, tin 60%,
It is immersed in a 230 ° C. solder bath made of 40% lead, kept at the same temperature for 60 seconds, taken out, and observed for appearance. Thereafter, the temperature of the solder bath was increased by 10 ° C. at a time, and the same experiment was performed to determine the maximum temperature at which the test piece did not foam or deform.
【００４０】参考例１ （溶融液晶性ポリエステル樹脂、溶融液晶性ポリエステ
ル樹脂成形体の調製）ｐ−アセトキシ安息香酸１０．８
Ｋｇ（６０モル）、テレフタル酸２．４９Ｋｇ（１５モ
ル）、イソフタル酸０．８３Ｋｇ（５モル）、および、
４，４’−ジアセトキシジフェニル５．４５Ｋｇ（２
０．２モル）を櫛形攪拌翼を持つ重合槽に仕込み、窒素
ガス雰囲気下で攪拌しながら昇温し、３３０℃で１時間
重合させた。この間に副生する酢酸を除去しながら、強
力な攪拌下で重合させた。その後、系を徐々に冷却し、
２００℃で得られたポリマーを系外に取出した。得られ
たポリマーを細川ミクロン（株）製のハンマーミルで粉
砕し、２．５ｍｍ以下の粒子とした。Reference Example 1 (Preparation of a molten liquid crystalline polyester resin and a molded product of a molten liquid crystalline polyester resin) p-acetoxybenzoic acid 10.8
Kg (60 mol), terephthalic acid 2.49 Kg (15 mol), isophthalic acid 0.83 Kg (5 mol), and
5.45 Kg of 4,4′-diacetoxydiphenyl (2
(0.2 mol) was charged into a polymerization tank having a comb-shaped stirring blade, and the temperature was increased while stirring under a nitrogen gas atmosphere, and polymerization was performed at 330 ° C. for 1 hour. The polymerization was carried out under strong stirring while removing acetic acid produced as a by-product during this time. After that, the system is gradually cooled,
The polymer obtained at 200 ° C. was taken out of the system. The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less.
【００４１】これをさらにロータリーキルン中で窒素雰
囲気下に２９０℃、３時間処理することにより、流動開
始温度が３４１℃の粒子状の下記の繰り返し単位からな
る全芳香族の溶融液晶性ポリエステル樹脂を得た。This is further treated in a rotary kiln under a nitrogen atmosphere at 290 ° C. for 3 hours to obtain a wholly aromatic molten liquid crystalline polyester resin having the following recurring units in the form of particles having a flow start temperature of 341 ° C. Was.
【化５】 ＝６０：２０：１５：５（モル比）Embedded image = 60: 20: 15: 5 (molar ratio)
【００４２】この溶融液晶性ポリエステル樹脂を、二軸
押出機（池貝鉄工（株）製ＰＣＭ−３０）を用いてシリ
ンダー温度３５０℃で造粒しペレットを得た。得られた
ペレットを用いて、上記方法によって樹脂の物性を測定
した。その結果は以下の通りである。 流動開始温度：３３２℃、固有粘度［η］：６．８ 溶融粘度： （剪断速度：１０００ｓｅｃ-1、３３２℃で測定） ９５００ｐｏｉｓｅ （剪断速度：１０００ｓｅｃ-1、３５２℃で測定） １４００ｐｏｉｓｅ （溶融粘度比） ０．１５ 溶融張力：２５ｇ、ハンダ耐熱温度：２９０℃This molten liquid crystalline polyester resin was granulated at a cylinder temperature of 350 ° C. using a twin-screw extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) to obtain pellets. Using the obtained pellets, the physical properties of the resin were measured by the above method. The results are as follows. Flow initiation temperature: 332 ° C., intrinsic viscosity [η]: 6.8 Melt viscosity: (shear rate: 1000 sec −1 , measured at 332 ° C.) 9500 poise (shear rate: 1000 sec −1 , measured at 352 ° C.) 1400 poise (melt viscosity) Ratio) 0.15 Melt tension: 25 g, Solder heat resistant temperature: 290 ° C
【００４３】上記ペレットを、射出成形機（日精樹脂工
業（株）製ＰＳ４０Ｅ５ＡＳＥ）を用いてシリンダー温
度３６０℃、金型温度１３０℃で、６４×６４×１ｍｍ
ｔの平板を成形し、以下の実施例に用いた。Using an injection molding machine (PS40E5ASE, manufactured by Nissei Plastics Industry Co., Ltd.), the pellets were prepared at a cylinder temperature of 360 ° C. and a mold temperature of 130 ° C. at 64 × 64 × 1 mm.
A flat plate of t was formed and used in the following Examples.
【００４４】比較例１ 参考例１にて成形した平板と、銅箔（厚さ１８μｍ）を
以下に示す方法で張り合わせた。平板は、エタノールで
表面を払拭した後１２０℃で８時間以上乾燥して使用し
た。銅箔はマット面（銅の微粒子が析出している面）を
熱融着させ、上記のように成形品のＭＤに沿って幅１０
ｍｍに切断して、そのピール強度を測定した。さらに剥
離界面の状態を観察し、樹脂側で破壊が進行している状
態を材料破壊、樹脂と銅箔の界面で剥離している状態を
界面剥離、と判定した。 熱融着方法：平板（表面粗さ：０．８μｍ）と銅箔とを
重ね合せ、その上下を０．１ｍｍｔアルミ板ではさみ、
さらにその上下を３ｍｍｔＳＵＳ板ではさみ、あらかじ
め３５０℃に設定したプレス機のプラテン間にはさむ。
直ちに平板に対して４０ｋｇ／ｃｍ2の圧力で加圧し２
分間保持した後、冷プレス機へ移して３分間冷却する。
ＳＵＳ板、アルミ板を外して溶融液晶性ポリエステル樹
脂と銅箔の熱融着された成形体を得る。その結果は以下
の通りである。 ピール強度：０．６ｋｇ／ｃｍ、剥離状態：界面剥離Comparative Example 1 The flat plate formed in Reference Example 1 and a copper foil (thickness: 18 μm) were bonded by the following method. The plate was wiped with ethanol and then dried at 120 ° C. for 8 hours or more before use. As for the copper foil, the mat surface (the surface where the copper fine particles are deposited) is heat-sealed, and a width of 10 mm along the MD of the molded product as described above.
mm, and the peel strength was measured. Furthermore, the state of the delamination interface was observed, and a state in which the destruction was progressing on the resin side was determined as material destruction, and a state in which delamination was occurring at the interface between the resin and the copper foil was determined as interfacial delamination. Thermal fusion method: Laminate a flat plate (surface roughness: 0.8 μm) and copper foil, sandwich the top and bottom with a 0.1 mmt aluminum plate,
Further, the upper and lower portions are sandwiched between 3 mmt SUS plates, and sandwiched between platens of a press machine previously set to 350 ° C.
Immediately press the plate with a pressure of 40 kg / cm 2 ,
After holding for 1 minute, it is transferred to a cold press and cooled for 3 minutes.
The SUS plate and the aluminum plate are removed to obtain a heat-fused molded body of the molten liquid crystalline polyester resin and the copper foil. The results are as follows. Peel strength: 0.6 kg / cm, peeling state: interfacial peeling
【００４５】実施例１ エタノールで表面を払拭した後１２０℃で８時間以上乾
燥した平板に対して、低圧水銀灯（セン特殊光源（株）
製表面改質装置）を用いて１７ｍＷ／ｃｍ2（測定波長
２５４ｎｍ）で紫外線を１０分間照射して、紫外線を照
射した平板の面と銅箔とを張り合わせること以外は、比
較例１と同様にして銅箔を張り合わせ、そのピール強度
を測定し、剥離状態を観察した。その結果は以下の通り
である。 ピール強度：０．９ｋｇ／ｃｍ、剥離状態：材料破壊Example 1 A flat plate dried at 120 ° C. for 8 hours or more after wiping the surface with ethanol was applied to a low-pressure mercury lamp (Sen Special Light Source Co., Ltd.).
17mW / cm 2 (measurement wavelength)
254 nm), and the copper foil was adhered in the same manner as in Comparative Example 1 except that the surface of the flat plate irradiated with the ultraviolet light was adhered to the copper foil, and the peel strength was measured. Was observed. The results are as follows. Peel strength: 0.9kg / cm, peeling state: material destruction
【００４６】参考例２ 比較例１で使用した熱融着前の平板表面、および実施例
１で使用した紫外線照射後の平板表面の元素構成を、Ｘ
線光電子分光測定装置(Surface Science Instruments
社製 SSX-100)で測定した。また、それぞれの表面に対
する水の接触角を接触角測定装置(協和界面科学株式会
社製 CA-A)を用いて測定した。その結果を表１に示
す。Reference Example 2 The elemental structures of the flat plate surface before heat fusion used in Comparative Example 1 and the flat plate surface used in Example 1 after ultraviolet irradiation were X
Line Photoelectron Spectrometer (Surface Science Instruments
(SSX-100). The contact angle of water on each surface was measured using a contact angle measuring device (CA-A manufactured by Kyowa Interface Science Co., Ltd.). Table 1 shows the results.
【００４７】[0047]
【表１】 [Table 1]
【００４８】実施例２〜３、比較例２ 熱融着の際、プラテンの温度を以下に示す温度に設定す
る他は実施例１と同様にして銅箔を貼り合わせ、そのピ
ール強度を測定し剥離状態を観察した。その結果は以下
の通りである。Examples 2 to 3 and Comparative Example 2 At the time of heat fusion, a copper foil was adhered in the same manner as in Example 1 except that the temperature of the platen was set to the following temperature, and the peel strength was measured. The peeled state was observed. The results are as follows.
【００４９】[0049]
【表２】 [Table 2]
【００５０】比較例３ 熱融着の際、プラテンの温度を３９０℃に設定する他は
比較例１と同様にして銅箔を貼り合わせ、そのピール強
度を測定し剥離状態を観察した。その結果は以下の通り
である。 ピール強度：０．８ｋｇ／ｃｍ、剥離状態：界面剥離Comparative Example 3 A copper foil was adhered in the same manner as in Comparative Example 1 except that the temperature of the platen was set to 390 ° C. during heat fusion, and the peel strength was measured to observe the peeled state. The results are as follows. Peel strength: 0.8 kg / cm, peeling state: interfacial peeling
【００５１】実施例４、５ 銅箔と融着させる平板として、以下に示す方法で表面を
粗化されたものを使用する他は、実施例１と同様にして
表面払拭、紫外線照射を行い、銅箔を貼り合わせ、その
ピール強度を測定し剥離状態を観察した。 表面粗化方法：エタノールで表面を払拭した平板と＃３
２０または＃６００のサンドペーパーを、間に０．０５
ｍｍｔフッ素樹脂フィルムを介して重ね合せ、その上下
を０．１ｍｍｔアルミ板、１ｍｍｔシリコーンシート、
３ｍｍｔＳＵＳ板の順ではさんで組み合わせ、あらかじ
め２５０℃に設定したプレス機のプラテン間にはさむ。
直ちに平板に対して１０ｋｇ／ｃｍ2の圧力で加圧し５
分間保持した後、冷プレス機へ移して３分間冷却する。
ＳＵＳ板、アルミ板、シリコーンシート、サンドペーパ
ー及びフッ素樹脂フィルムを外して、表面を粗化処理さ
れた平板を得る。得られた結果は次の通りである。Examples 4 and 5 Surface wiping and ultraviolet irradiation were carried out in the same manner as in Example 1 except that a plate whose surface was roughened by the following method was used as a flat plate to be fused with a copper foil. The copper foil was bonded, the peel strength was measured, and the peeled state was observed. Surface roughening method: flat plate whose surface has been wiped with ethanol and # 3
20 or # 600 sandpaper with 0.05 in between
The upper and lower sides are laminated by a 0.1 mmt aluminum plate, 1 mmt silicone sheet,
Combine them in the order of 3 mmt SUS plate and sandwich them between the platens of the press set at 250 ° C. in advance.
Immediately press the plate with a pressure of 10 kg / cm 2 for 5 minutes.
After holding for 1 minute, it is transferred to a cold press and cooled for 3 minutes.
The SUS plate, the aluminum plate, the silicone sheet, the sandpaper and the fluororesin film are removed to obtain a flat plate whose surface is roughened. The results obtained are as follows.
【００５２】[0052]
【表３】 [Table 3]
【００５３】比較例４ 銅箔と融着させる平板として、上記の方法で表面を粗化
し、表面粗さを４μｍとされたものを使用する他は、比
較例１と同様にして銅箔を貼り合わせ、そのピール強度
を測定し剥離状態を観察した。使用したサンドペーパー
は、＃３２０であった。得られた結果は、以下の通りで
ある。 ピール強度：０．７ｋｇ／ｃｍ、剥離状態：界面剥離Comparative Example 4 A copper foil was adhered in the same manner as in Comparative Example 1, except that the surface was roughened by the above method and the surface roughness was set to 4 μm as a flat plate to be fused with the copper foil. The peel strength was measured by measuring the peel strength. The used sandpaper was # 320. The results obtained are as follows. Peel strength: 0.7 kg / cm, peeling state: interfacial peeling
【００５４】[0054]
【発明の効果】本発明の方法によれば、溶融液晶性ポリ
エステル樹脂成形体と金属とを強固に熱融着させること
ができる。また、本発明の製造方法によれば、溶融液晶
性ポリエステル樹脂成形体と金属とが強固に熱融着され
た接合体や積層体を得ることができる。この方法によっ
て得られる溶融液晶性ポリエステル樹脂と金属の熱融着
された接合体や積層体は、電気、電子回路基板や産業用
機器、家電製品、ＯＡ機器、電気、電子部品などの用途
にきわめて有用なものである。According to the method of the present invention, a molten liquid crystalline polyester resin molded article and a metal can be firmly thermally fused. Further, according to the production method of the present invention, it is possible to obtain a joined body or a laminated body in which a molten liquid crystalline polyester resin molded body and a metal are firmly thermally fused. A bonded body or a laminate obtained by heat-fusing a molten liquid crystalline polyester resin and a metal obtained by this method is extremely useful for applications such as electricity, electronic circuit boards, industrial equipment, home appliances, OA equipment, electricity, and electronic components. It is useful.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 67/03 Ｃ０８Ｌ 67/03 // Ｂ２９Ｋ 67:00 Ｂ２９Ｌ 9:00 Ｆターム(参考） 4F073 AA04 AA28 BA23 BA25 BB01 BB07 CA45 GA01 HA02 HA04 HA06 4F100 AB01B AB17B AB33B AK41A BA02 BA10A BA10B DD07A EC032 EH361 EJ202 EJ422 EJ541 GB41 GB48 JA04A JA06A JA11A JK06 YY00A 4F211 AA24 AD03 AD08 AD29 AG01 AG03 AH33 AK01 AK03 TA01 TC02 TD11 TH02 TH06 TH10 TN26 TQ01 TQ04 4J002 CF061 CF181 FD010 GF00 GQ00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C08L 67/03 C08L 67/03 // B29K 67:00 B29L 9:00 F term (Reference) 4F073 AA04 AA28 BA23 BA25 BB01 BB07 CA45 GA01 HA02 HA04 HA06 4F100 AB01B AB17B AB33B AK41A BA02 BA10A BA10B DD07A EC032 EH361 EJ202 EJ422 EJ541 GB41 GB48 JA04A JA06A JA11A JK06 YY00A 4F211 AA24 AD03 T08 012 CF181 FD010 GF00 GQ00
Claims (9)
を活性化し、その表面と金属とを溶融液晶性ポリエステ
ル樹脂の流動開始温度以上で熱融着することを特徴とす
る溶融液晶性ポリエステル樹脂成形体と金属との熱融着
方法。1. A molten liquid crystalline polyester resin molding characterized by activating the surface of a molten liquid crystalline polyester resin molded article and thermally fusing the surface to a metal at a temperature equal to or higher than the flow start temperature of the molten liquid crystalline polyester resin. Heat fusion method between body and metal.
に２５４ｎｍの波長を含む紫外線を照射し、その表面と
金属とを溶融液晶性ポリエステル樹脂の流動開始温度以
上で熱融着することを特徴とする溶融液晶性ポリエステ
ル樹脂成形体と金属との熱融着方法。2. A method of irradiating an ultraviolet ray having a wavelength of 254 nm to a surface of a molten liquid crystalline polyester resin molded article, and thermally fusing the surface to a metal at a temperature equal to or higher than a flow starting temperature of the molten liquid crystalline polyester resin. Fusion method between a molten liquid crystalline polyester resin molded article and a metal.
ル樹脂の流動開始温度＋１０℃〜流動開始温度＋６０℃
の範囲である請求項１または２に記載の溶融液晶性ポリ
エステル樹脂成形体と金属との熱融着方法。3. The temperature at which heat fusion is carried out, the flow start temperature of the molten liquid crystalline polyester resin + 10 ° C. to the flow start temperature + 60 ° C.
3. The method for thermally fusing a molten liquid crystalline polyester resin molded product according to claim 1 or 2 with a metal.
属と熱融着される面の表面粗さが、Ｒａで１〜５０μｍ
の範囲である請求項１、２または３記載の溶融液晶性ポ
リエステル樹脂成形体と金属との熱融着方法。4. The molten liquid crystalline polyester resin molded body has a surface roughness Ra of 1 to 50 μm which is thermally fused to a metal.
4. The method for heat-sealing a molten liquid crystalline polyester resin molded article and a metal according to claim 1, 2 or 3, wherein
質的に溶融液晶性ポリエステル樹脂のみからなるフィル
ムまたはシートである請求項１〜４のいずれかに記載の
溶融液晶性ポリエステル樹脂成形体と金属との熱融着方
法。5. The molten liquid crystalline polyester resin molded product according to claim 1, wherein the molten liquid crystalline polyester resin molded product is a film or a sheet consisting essentially of the molten liquid crystalline polyester resin alone. And heat fusion method.
温度にて剪断速度１０００ｓｅｃ-1で測定した溶融粘度
（粘度１）と、流動開始温度＋２０℃にて剪断速度１０
００ｓｅｃ-1で測定した溶融粘度（粘度２）との比率
［（粘度２）／（粘度１）］が０．１０〜０．７０の範
囲であり、かつハンダ耐熱温度が２５０℃以上である請
求項１〜５のいずれかに記載の溶融液晶性ポリエステル
樹脂成形体と金属との熱融着方法。6. A melt viscosity (viscosity 1) of a molten liquid crystalline polyester resin measured at a flow start temperature at a shear rate of 1000 sec -1 and a shear rate of 10 at a flow start temperature of + 20 ° C.
The ratio [(viscosity 2) / (viscosity 1)] to the melt viscosity (viscosity 2) measured at 00 sec -1 is in the range of 0.10 to 0.70, and the solder heat resistance temperature is 250 ° C. or higher. Item 6. A method for thermally fusing a molten liquid crystalline polyester resin molded article according to any one of Items 1 to 5 to a metal.
れかに記載の溶融液晶性ポリエステル樹脂成形体と金属
との熱融着方法。7. The method according to claim 1, wherein the metal is an electrolytic copper foil.
とを請求項１〜７のいずれかに記載の方法で熱融着する
ことを特徴とする溶融液晶性ポリエステル樹脂成形体と
金属との接合体の製造方法。8. A joint between a molten liquid crystalline polyester resin molded article and a metal, wherein the molten liquid crystalline polyester resin molded article and the metal are thermally fused by the method according to claim 1. How to make the body.
とを請求項１〜７のいずれかに記載の方法で熱融着する
ことを特徴とする溶融液晶性ポリエステル樹脂成形体と
金属との積層体の製造方法。9. A lamination of a molten liquid crystalline polyester resin molded article and a metal, wherein the molten liquid crystalline polyester resin molded article and the metal are thermally fused by the method according to any one of claims 1 to 7. How to make the body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35575899A JP2000233448A (en) | 1998-12-16 | 1999-12-15 | Method for thermally welding molten liquid crystal polyester resin molded object and metal |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-357548 | 1998-12-16 | ||
| JP35754898 | 1998-12-16 | ||
| JP35575899A JP2000233448A (en) | 1998-12-16 | 1999-12-15 | Method for thermally welding molten liquid crystal polyester resin molded object and metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000233448A true JP2000233448A (en) | 2000-08-29 |
Family
ID=26580325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35575899A Pending JP2000233448A (en) | 1998-12-16 | 1999-12-15 | Method for thermally welding molten liquid crystal polyester resin molded object and metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000233448A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005320478A (en) * | 2004-05-11 | 2005-11-17 | Ueno Seiyaku Oyo Kenkyusho:Kk | Joining method of liquid crystal polyester resin composition and joined product of liquid crystal resin composition |
| EP1645662A1 (en) | 2004-10-06 | 2006-04-12 | Furukawa Circuit Foil Co., Ltd. | Surface treated copper foil and circuit board |
| WO2007029440A1 (en) * | 2005-09-01 | 2007-03-15 | Osaka University | Method for joining metal and resin and metal-resin composite, method for joining glass and resin and glass-resin composite, and method for joining ceramic and resin and ceramic-resin composite |
| US7381475B2 (en) | 2004-02-06 | 2008-06-03 | Furukawa Circuit Foil Co., Ltd. | Treated copper foil and circuit board |
| WO2008102585A1 (en) * | 2007-02-22 | 2008-08-28 | Rohm Co., Ltd. | Substrate bonding method, microchip manufacturing method and microchip |
| JP2010103269A (en) * | 2008-10-23 | 2010-05-06 | Kuraray Co Ltd | Multilayer circuit board and manufacturing method thereof |
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1999
- 1999-12-15 JP JP35575899A patent/JP2000233448A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7381475B2 (en) | 2004-02-06 | 2008-06-03 | Furukawa Circuit Foil Co., Ltd. | Treated copper foil and circuit board |
| JP2005320478A (en) * | 2004-05-11 | 2005-11-17 | Ueno Seiyaku Oyo Kenkyusho:Kk | Joining method of liquid crystal polyester resin composition and joined product of liquid crystal resin composition |
| JP4558374B2 (en) * | 2004-05-11 | 2010-10-06 | 上野製薬株式会社 | Bonding method of liquid crystal polyester resin composition and liquid crystal polyester resin composition joined body |
| US7238769B2 (en) * | 2004-05-11 | 2007-07-03 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Method for joining liquid-crystalline polyester resin composition parts and jointed article made of liquid-crystalline polyester resin composition |
| EP1645662A1 (en) | 2004-10-06 | 2006-04-12 | Furukawa Circuit Foil Co., Ltd. | Surface treated copper foil and circuit board |
| JPWO2007029440A1 (en) * | 2005-09-01 | 2009-03-26 | 国立大学法人大阪大学 | Metal resin bonding method and metal resin composite, glass resin bonding method and glass resin composite, ceramic resin bonding method and ceramic resin composite |
| WO2007029440A1 (en) * | 2005-09-01 | 2007-03-15 | Osaka University | Method for joining metal and resin and metal-resin composite, method for joining glass and resin and glass-resin composite, and method for joining ceramic and resin and ceramic-resin composite |
| US8168031B2 (en) | 2005-09-01 | 2012-05-01 | Osaka University | Method for metal-resin joining and a metal-resin composite, a method for glass-resin joining and a glass-resin composite, and a method for ceramic-resin joining and a ceramic-resin composite |
| WO2008102585A1 (en) * | 2007-02-22 | 2008-08-28 | Rohm Co., Ltd. | Substrate bonding method, microchip manufacturing method and microchip |
| JP2010103269A (en) * | 2008-10-23 | 2010-05-06 | Kuraray Co Ltd | Multilayer circuit board and manufacturing method thereof |
| JP2014042043A (en) * | 2013-10-01 | 2014-03-06 | Kuraray Co Ltd | Evaluation method of thermoplastic liquid crystal polymer film |
| JP2016062954A (en) * | 2014-09-16 | 2016-04-25 | 株式会社プライマテック | Laminate for electronic circuit board and electronic circuit board |
| JP2017222089A (en) * | 2016-06-15 | 2017-12-21 | 株式会社新技術研究所 | Copper alloy article containing polyester resin and method for producing the same |
| WO2017217467A1 (en) * | 2016-06-15 | 2017-12-21 | 株式会社新技術研究所 | Copper alloy article including polyester-based resin, and method for manufacturing same |
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