SG173298A1 - Liquid crystalline resin composition for injection molding, resin molded article and method for improving blistering resistance - Google Patents
Liquid crystalline resin composition for injection molding, resin molded article and method for improving blistering resistance Download PDFInfo
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- SG173298A1 SG173298A1 SG2011006863A SG2011006863A SG173298A1 SG 173298 A1 SG173298 A1 SG 173298A1 SG 2011006863 A SG2011006863 A SG 2011006863A SG 2011006863 A SG2011006863 A SG 2011006863A SG 173298 A1 SG173298 A1 SG 173298A1
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- Singapore
- Prior art keywords
- liquid crystalline
- resin composition
- molded article
- inorganic filler
- glass beads
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- 229920006038 crystalline resin Polymers 0.000 title claims abstract description 48
- 238000001746 injection moulding Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000011324 bead Substances 0.000 claims abstract description 51
- 239000011521 glass Substances 0.000 claims abstract description 51
- 239000011256 inorganic filler Substances 0.000 claims abstract description 48
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 48
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000003365 glass fiber Substances 0.000 claims abstract description 17
- 238000000465 moulding Methods 0.000 claims description 34
- 239000012792 core layer Substances 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002347 injection Methods 0.000 abstract description 29
- 239000007924 injection Substances 0.000 abstract description 29
- 239000000945 filler Substances 0.000 abstract description 12
- 238000005259 measurement Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 230000001629 suppression Effects 0.000 description 8
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- -1 aromatic diol Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 241000206607 Porphyra umbilicalis Species 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000006872 improvement Effects 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
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- VMXUWOKSQNHOCA-UKTHLTGXSA-N ranitidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-UKTHLTGXSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- CHVRBXDKEMZBAL-UHFFFAOYSA-N (3-amino-4-hydroxyphenyl) acetate Chemical compound CC(=O)OC1=CC=C(O)C(N)=C1 CHVRBXDKEMZBAL-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000812633 Varicus Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
OF THE DISCLOSURE[Problem to be Solved by the Invention] To provide a technique to easily suppress blisters from occurring on a surface of a resin resin molded article, even under conditions in which the injection volume is large.[Means for Solving the Problem] A liquid crystalline resin composition for injection molding is used that contains a liquid crystalline polyester amide resin, and a mixture of fibrous inorganic filler and glass beads, in which a ratio of the fibrous inorganic filler to the glass beads in the mixture (content of fibrous inorganic filler : content of glass beads) is adjusted so as to be from 0.9 : 1.0 to 1.0 : 0.9. It is the most preferable to utilize glass fiber as the fibrousinorganic filler.Figure 1
Description
LIQUID CRYSTALLINE RESIN COMPOSITION FOR INJECTICN MOLDING,
RESIN MOLDED ARTICLE AND METHOD FOR IMPROVING BLISTERING
RESISTANCE
This application 1s based on and claims the benefit of priority from Japanese Patent Application No. 2010-020314, filed on 1 February 2010, the content of which is incorporated herein by reference.
BACKGROUND OF THE TNVENTION
The present invention relates to a liguid crystalline resin composition for injection molding enabling suppression of blistering even when molding under a large injection capacity condition, a resin molded article formed from the composition, and to a method for improving the blister resistance of the resin molded article.
A group of plastics termed “engineering plastics” exhibit high strength, and can be used in substitution for metallic components. Within these plastics, a group of plastics termed “liguid crystalline resins” maintains a crystalline structure when molten, and therefore exhibits advantages such as high strength due to the crystalline structure, low volumetric change in molten or solidifying states due to low change to the crystalline structure when solidifying, and low meld shrinkage.
These types of liguid crystalline resins have superior heat resistance properties and molding properties, and are preferably used as a constituent material of small electronic components. Liquid crystalline resins exhibit low production of gas, excellent hydrolysis resistance, and superior electrical properties, and are therefore suitably applied in electronic components such as connectors. In particular, when a liquid crystalline resin is used as an electronic component material for a connector cor the like, a method of adding glass fiber to improve the deflection temperature under loading is kriown.
In particular, a crystalline polyester amide resin containing glass fibers is extremely preferred as an electronic component material for a connector or the like.
However, when a large injection volume condition is adopted to improve the manufacturing productivity of the electronic components, alr bubbles are generated in an inner portion of the resin molded article since the liguid crystalline resin composition for injection molding that is in a molten state during molding encapsulates air or gas produced by the material. When bubbles are included in an inner portion of the resin molded article, the air or gas in the bubbles expands, and swells the surface of the resin molded article as a result of heating the resin molded article to a high temperature during thermal post-processing or the like. Swelling cof the surface of the resin molded article is a molding defect termed a “blister”, and there is a demand for improvement in this regard.
Approaches for suppressing the generation of such blisters include sufficient degassing from a vent during melt extrusion of the liquid crystalline resin composition, or avoiding a long residence time of the resin composition in the molding apparatus during molding operations. However, sufficient suppression of blistering is not enabled by only varying molding conditions.
Consequently suppression of blistering has been performed by improving the liquid crystalline resin composition for injection molding, or by improving both the liquid crystalline resin composition for injection molding and the molding conditions. For example, Patent Literature 1 discloses a method for manufacturing a resin molded article having a deflection temperature under loading of at least 230°C which is formed by melt-kneading of a specified liguid crystalline resin composition for injection molding that includes a specific amount of an inorganic filler using a kneading machine that includes a release port for removal of volatile components from the kneaded material, and a pair of double- threaded screws. The screw intermeshing ratio of the kneading machine is adjusted to at least 1.60. The technique disclosed in Patent Literature 1 provides a liquid crystalline resin composition for injection molding that exhibits excellent blister resistance while maintaining basic heat resistance performance such as a deflection temperature under loading or the melting point of the liquid crystalline resin composition for injection molding.
However, the method disclosed in Patent Literature 1 is associated with extremely complicated manufacturing conditions for the resin molded article. In addition, a liquid crystalline polyester amide resin tends to generate blisters in comparison to a wholly aromatic polyester resin or the like.
Consequently, there 1s a need for further improvement in relation to suppression of blister generation. [Patent Document 1] Japanese Unexamined Patent Application,
Publication No. 2003-211443
The present invention 1s proposed to solve the above problems, and has the cbject of providing a simple technique for the suppression of blister generation even when under a large injection capacity condition.
The present inventors executed diligent research into solving the above problems. As a result, the invention was completed with the insight that the problem could be solved by use of a liquid crystalline resin composition for injection molding (hereinafter simply referred to as “resin composition”) that contains a liquid crystalline polyester amide resin, and a mixture of a fibrous inorganic filler and glass beads, in which a ratio of the fibrous inorganic filler to the glass beads in the mixture is adjusted so as to be from
0.9 : 1.0 to 1.0 : 0.9. More specifically, the present invention provides the following effects.
(1) A liquid crystalline resin composition for injection molding includes a liquid crystalline polyester amide resin and a mixture of a fibrous inorganic filler and glass beads.
A ratic of the fibrous inorganic filler tc the glass beads in the mixture is from 0.9 : 1.0 tec 1.0 : 0.9.
(2) The liquid crystalline resin composition for injection molding according te (1), in which the fibrous inorganic filler is glass fiber.
(3) The liguid crystalline resin composition for injection molding according to (1) or (2) in which a fiber length of the fibrous inorganic filler is at least 200 um.
(4) The liquid crystalline resin composition for injection molding according to any one of (1) to (3) containing at least 39 parts by mass and no more than 69 parts by mass of the mixture relative to 100 parts by mass of the liguid crystalline polyester amide resin.
(5) A regin molded article made by molding the liquid crystalline resin composition for injection molding according to any one of {1) to (4) in which the liguid crystalline polyester amide resin has a melting point of at least 320°C, and in which a deflection temperature under loading of 1.8 MPa, measured by a method conforming with IS075-1,2, is at least 260°C.
(6) A resin molded article made by melding the liquid crystalline resin composition for injection molding according to any one of (1) to {4} in which a difference between a coefficient of linear thermal expansion of a molded article surface layer (up to 0.2 mm from the molded article surface) and of a molded article core portion (0.2 mm from the molded article center) is no more than 0.7. (7) A method for improving blistering resistance of a resin molded article containing a fibrous inorganic filler and glass beads in a liquid crystalline resin composition including the step of setting a content of the fibrous inorganic filler and a content of the glass beads to be substantially equal.
According to the present invention, the generation of blisters on the surface of a resulting molded article can be suppressed even under a large injection capacity condition by injection molding ¢f an injection-molding liguid crystalline resin composition that contains a fibrous inorganic filler and an amount of glass beads that 1s substantially equal to the amount of fibrous inorganic filler. In other words, according to the present invention, a high quality molded article can be manufactured with high manufacturing productivity.
Fig. 1 shows a sectional view of a test piece prepared in conformance with IS01l/3277.
Fig. 2 shows the connection of a runner, a sprue and a nozzle.
The embodiments of the present invention will be described in detail below. However the present invention is not limited in any way by the following embodiments, and the present invention may be worked by addition of suitable modification within the scope of the object of the invention. [Liguid Crystalline Resin Composition for Injection Molding]
The liquid crystalline resin composition for injection molding according to the present invention is characterized by including a liquid crystalline polyester amide resin, a fibrous inorganic filler, and glass beads. Firstly, these materials will be described below. [Liquid Crystalline Polyester Amide Resin]
Blister tends to generate on a molded article when a liguid crystalline polyester amide resin is selected for use from liguid crystalline resins. One characteristic feature of the present invention is that blister generation can be sufficiently suppressed even during use cof a liquid crystalline polyester amide resin that exhibits a tendency to generate blisters. Preferred liguid crystalline polyester amide resins in the following examples are resins that are preferred due to increasing the physical properties of the resulting molded article. When the preferred resins described below are used, the present invention is also characterized by suppression of blistering while maintaining the physical properties of the molded article (almost no reduction), even under a large injection capacity condition.
The liquid crystalline polyester amide resin used in the present invention may be a conventionally known resin without particular limitation thereon. However a melt-fabricable polyester is preferred that has a melting point in a range of 270 - 370°C, and that has properties that enable formation of an optical anisotropic melt phase. The properties of the anisotropic melt phase may be confirmed by a normal polarized light scanning method that employs an orthogonal polarizer.
More specifically, the confirmation of the anisotropic melt phase uses a Leitz polarization microscope, and 1s performed by observation of a molten test substance mounted on a Leitz hot stage at a 40x magnification under a nitrogen atmosphere.
When the liquid crystalline polyester amide resin used in the present invention is scanned between the orthogonal polarizers, pelarized light is normally transmitted and exhibits optical anisotropy even in a molten stationary state for example.
The liguid crystalline polyester amide resin used in the present invention is preferred to the property of forming a optical anisotropic melt phase as described above, and to the fact the resin has specific constituent units.
The monomers that constitute the liquid crystalline polyester amide resin include an aromatic hydroxycarboxylic acid, an arcmatic carboxylic acid, an aromatic diol, or the like. In addition to these monomers, it is preferred that the resin includes one, or two or more of 4-aminophenol, 1,4- phenvlenediamine, 4-amincbenzoic acid, and derivatives thereof.
It is preferred that the amide component is contained in a ratio of 2-35 mole% in all bonds. It is still more preferred that the amide ccmponent is contained in a ratio of 4-25 mole% in all bonds.
The aromatic hydroxycarboxylic acid includes 4- hydroxybenzolc acid, 6~hydroxy-2-naphthoic acid, or the like.
The aromatic carboxylic acid includes terephthalic acid, isophthalic acid, 4, 4’-diphenyl dicarboxylic acid, 2,6~ naphthalenedicarboxylic acid, or the like. The aromatic diol includes 2, 6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroguinone, resorcin, or the like. Derivatives of the above compounds include monomers.
A monomer for making the amide component be included in a ratio of 2 - 3% mole% include 4-aminophenol, 1,4- phenylenediamine, 4-aminobenzoic acid, and derivatives thereof as described above, and for example, includes 4-acetoxy- aminophenol, or the like.
More specifically, a wholly aromatic polyester amide resin is preferred in which a liguid crystalline polyester amide resin copolymerizes the monomers (i) - (iii) below within the following ranges. (1} é6~hydroxy-2-naphthoic acid; 30 - 90 mole% (11) 4-aminophencl; 15 — 35 mole% (1ii} terephthalic acid; 15 - 35 mole} furthermcre a wholly aromatic polyester amide resin is preferred in which a liquid crystalline polyester amide resin copolymerizes the monomers (i) - (v) below within the fellowing ranges.
(1) 6-hydroxy-2-naphthoic acid (iv) 4d-hydroxybenzolic acid the amount (i) + {iv} is 30 — 90 mole% (ii) 4-aminophenol: 2 — 35 mole% (iii) terephthalic acid; 5 - 35 mole% (v} bisphenol:2 - 35 mole% [Fibrous Inorganic Filler]
The fibrous inorganic filler used in the present invention may be a conventionally known filler without particular limitation thereon. One of the principal objects of inclusion of a fibrecus inorganic filler is to suppress blistering by combination with glass beads as described below. A further ohiject is to impart the molded article that constitutes the final product with physical properties such as sufficient deflection temperature under loading.
A fibrous incrganic filler that is capable of application includes glass fiber, asbestos fiber, silica fiber, silica and alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, wollastonite, and further includes metallic fibrous materials such as stainless steel, aluminum, titanium, copper, brass, or the like. Of the above materials, the use of glass fiber is particularly preferred.
Although there is no particular limitation on the length of the fibrous inorganic filler, a length of at least 200 um to no more than 700 um is preferred, and in particular at least 400 um to no more than 650 um is preferred in order to impart physical properties such as sufficient deflection temperature under loading to the molded article, and to maintain superior flow characteristics. “Fiber length” denctes the fiber length in the kneaded pellet of the liquid crystalline resin compesition prior to injection molding. A fiber length is adopted that is measured using a method as described hereafter. {Measurement Method)
A LUZEX AP image processing and analysis equipment (Nireco
Corporation) is used for measurements. The measurements are performed in the order (1) to (6) below. (1) Heat and incinerate a kneaded pellet approximately of 2g of the liquid crystalline resin composition at 600°C for 3 hours. (2) 3 mg of ash of the kneaded pellet of liquid crystalline resin composition is weighed, and dissolved in a 5% polyethylene glycol agusous solution. (3) 5 ml of the dispersion is injected uniformly into a dish. (4) Imaging (n=9} is performed using a stereoscopic microscope (x10 magnification). (5) The respectively captured images are binarized, and the size of the filler is measured using the above image processing and analysis eguipment. Values less than 100 pm are discarded to avoid an effect from the size of the glass beads. (6) A weight average of the measured values is taken as the fiber length of the fibrous inorganic filler.
In particular, when molding an electronic component such as a connector, a sufficient deflection temperature under loading must be imparted to the molded article. In this case, a glass fiber that has a fiber length within the preferred range is used as the fibrous incrganic filler, and it is preferred that the content amount of the glass fiber is at least 10 parts by mass to no more than 100 parts by mass relative to 100 parts by mass of the liquid crystalline polyester amide resin. [Glass Beads]
The glass beads used in the present invention may be a conventionally known glass beads without particular limitation thereon. For example, glass beads having an average particle diameter of at least 5 pm to no more than 50 pm are preferably used.
The preferred content of glass beads contained in the resin composition according to the present invention is determined from the preferred content amount of the fibrous inorganic filler above and the content ratio of glass beads and the fibrous inorganic filler as described hereafter. [Mixture]
The mixture is a mixture of the fibrous inorganic filer and the glass beads. A principal characteristic feature of the invention according to this application is the formation of an injection-molded resin composition including a mixture of a fibrous incrganic filler and glass beads.
In the specification of the present application, the description of the liquid crystalline resin composition for injection molding according to the present invention has provided a separate description of the liquid crystalline polyester amide resin and the mixture of fibrous inorganic filler and glass beads. However such description does not intentionally create a limitation on the resin composition according to the present invention to a resin composition that is obtained by forming a mixture in advance by mixing the fibrous inorganic filler and the glass beads, and then mixing a liquid crystalline polyester amide resin into this mixture.
In other words, the resin compcsition according to the invention in the present application includes a liquid crystalline polyester amide resin, a fibrous inorganic filler, and glass beads with the content ratio of the fibrous inorganic filler and glass beads being in a specified range.
The content ratio of the fibrous inorganic filler and glass beads contained in the mixture (fibrous inorganic filler: glass beads} is from 0.2 : 1.0 to 1.0 : 0.9. This ratio is a mass ratic.
Blistering during manufacturing of the molded article is suppressed by a configuration of a resin composition in which the content ratio of the fibrous inorganic filler and thes glass beads in the mixture is adjusted tc the above range and that 1s a combination with a liquid crystalline polyester amide resin. Consequently, the difference in the coefficient of linear expansion of a skin layer and the coefficient of linear expansion of a core layer can be reduced by adjusting the content ratio of the fibrous inorganic filler and the glass beads in the mixture to the above range. A principal characteristic feature of the invention according to the present application is that the emphasis is on an inorganic filler such as a fibrous inorganic filler or glass beads, and furthermore that the content ratio thereof is adjusted to a specified range to thereby reduce the difference between the above coefficients of linear expansion. In other words, the characteristic feature resides in the insight that the difference in the above coefficients of linear expansion can be reduced by selecting a specific filler, and adjusting the content ratio of the specific filler to a specific range.
Since the glass beads are isotropic inorganic fillers, it can be predicated that the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer will decrease as the content of glass beads in the mixture increases. However, the difference in the coefficients of linear expansion is reduced when the content ratio of the fibrous inorganic filler and the glass beads 1s in the above range near to a value of one. This insight is also a characteristic feature of the present invention. “A small difference between the coefficient of linear expansion of a skin layer and the coefficient of linear expansion cof a core layer” means that the difference between the coefficients of linear expansion measured by the method described in the embodiments is no more than 0.7.
Use of a glass fiber as the fibrous inorganic filler is preferred. The combination of the glass fiber and the glass beads enhances the effect of suppressing blistering. In other words, the combination of glass fiber and the glass beads exhibits a tendency to reduce the difference between the coefficients of linear expansion.
The content amount of the mixture in the liguid crystalline resin composition for injection melding according to the present invention is preferably at least 39% parts by mass to no more than 69 parts by mass relative to 100 parts by mass of the liguid crystalline polyester amide resin. The molded article can be imparted with sufficient physical properties by including a sufficient amount of filler in the resin composition according to the present invention. [Ofher Components]
The liquid crystalline resin composition for injection molding of the invention according to the present application may be a polymer blend with another thermcplastic resin within a range that does not have an adverse effect on the operation of the present invention. Two or more thermoplastic resins may be used as a mixture. Varicus types of additives cr toughening agents may be added as reguired to these resins in order to improve various properties such as mechanical, electrical, chemical properties, fire retardant properties, or the like.
The liquid crystalline resin composition used in the present invention may include a composition imparted with a required characteristic by additicn of a nucleating agent,
pigment such as carbon black and an inorganic firing pigment, a filler other than the fillers that have been described above such as glass beads, or an added agent such as an antioxidant, a stabilizer, a plasticizer, a lubricant, a mold release agent, a fire retardant, or the like, within a range that does not have an adverse effect on the operation of the present invention.
As described above, other components may be added within a range that does not have an adverse effect on the cperation of the present invention. However the content amount of other components 1s preferably within 10 parts by mass relative to 100 parts by mass of the liquid crystalline polyester amide resin. [Molded Article]
The molded article according to the present invention is a molded article that forms the liquid crystalline resin composition for injection molding according to the present invention according to a method of injection molding. One characteristic feature of the present invention is that blistering can be suppressed even when using an extremely large injection capacity. Firstly, the molding conditions of the molded article will be described, and then the molded article will be described. [Molding Conditions for Molded Article]
As described above, the molded article according to the present invention is a molded article that is melded using the liguid crystalline resin composition for injection molding according to the present invention, and there is no particular limitation on the molding conditions. Suitable and preferred molding conditions may be determined in accordance with the raw material such as the resin or the like that is employed, or the shape of the manufactured molded article. However, the invention according to the present application is characterized in that manufacture is enabled as described above under a large injection capacity. Next, conditions related to a large injection capacity will be described.
Normally, there is a tendency for blistering toe cccur on the surface of the molded article when molding under a large injection capacity condition. However, in the present invention, the difference between the coefficient cof linear expansion of the skin layer and the coefficient of linear expansion of the core layer is adjusted to a value not exceeding 0.7 by including a fibrous inorganic filler and glass beads in the liquid crystalline polyester amide resin in a specified proportion. As a result, blistering on the surface of the molded article can be suppressed under a large capacity molding condition. Therefore, high-efficiency manufacture of a high-quality molded article that enables suppression of blistering is enabled by the present invention.
A “large injection capacity” resulting in the generation of blistering on the surface of a molded article when using a conventional technigue is a value of at least 150 cm/sec.
The generation of blisters that is the problem to be solved by the present invention thereby becomes a problem of the flow speed of the molten resin composition that flows in the mold. The flow speed of the molten resin composition in the mold is increased by increasing the injection capacity.
When the flow speed cf the resin composition flowing in the mold exceeds 7000 mm/sec, use of a conventional technique results in a tendency for blister generation on the surface of the melded article. When the flow speed of the resin composition flowing in the mold exceeds 12000 mm/sec, the tendency for blister generation on the surface of the molded article is further promoted. Normally, a condition under which the injection capacity is at least 150 cm’/sec means that the flow speed at least exceeds 7000 mm/sec. As described above, the molded article according to the present invention as described above includes a fibrous inorganic filler and glassbeads in the liquid crystalline polyester amide resin in a specific proportion, and is adjusted so that the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer is no more than 0.7. In this manner, blister generation on the surface of the molded article can be suppressed even when the flow speed of the molten resin composition in the mold is increased as described above since it is possible to perform an adjustment to reduce the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer. [Molded Article]
As described above, the molded article according to the present invention is characterized in that the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer is no more than 0.7, even when manufacturing under a large injection capacity condition. The difference between the coefficients of linear expansion can be adjusted for example with reference to the content ratio of the fibrous inorganic filler and the glass beads.
The coefficient cof linear expansion of the skin layer and the coefficient of linear expansion of the core layer will be described below. The object used for measurement of the coefficients of linear expansion, and the method of measurement will be described below. A test piece for measurement of the coefficient cof linear expansion is a test plece manufactured according to ISOL/32''. Fig. 1 is a sectional view of the test piece. The surface layer is the skin layer, and the inner portion is the core layer.
Measurement of the coefficient of linear expansion of the skin layer is performed by cutting a 0.2 mm range from the surface of the skin layer (the range shown in Fig. 1) to thereby cut out a test plece. Measurement of the coefficient of linear expansion of the core layer is performed by cutting a 0.2 mm width from the center of a core layer {the range shown in Fig. 1} to thereby cut out a test piece. These test pieces are processed by heating to 250°C for one hour, and then taking the expansion coefficient at 240°C with reference to the dimensions at 30°C as the coefficient of linear expansion.
When a molded article is manufactured by molding the liguid crystalline resin composition for injection molding according to the present invention, blistering is not produced even when manufacturing is executed under a large injection capacity condition since the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer 1s no more than 0.7.
When a molded article is manufactured under a large injection capacity condition using a conventional and known resin compositicn, the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer increases, and produces blistering. However, use of the resin composition according to the present invention enables suppression of an increase in the difference in the coefficient of linear expansion even when setting a large injection capacity condition condition,
As a result, blistering can be suppressed, even when manufacturing a molded article under a large injection capacity. [Method of Improving Blister Resistance]
A method of improving the blister resistance according to the present invention improves the blister resistance of a resin molded article by mixing an fibrous incrganic filler and glass beads with a liquid crystalline resin composition containing a liguid crystalline polyester amide resin, and making the content amcunt of the fibrous inorganic filler substantially egual to the content amount of the glass beads. “Substantially equal” as used herein means that the content amount of the fibrous inorganic filler apprcaches the content amount of the glass beads in the resin composition so that the difference between the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer is no more than 0.7.
One principal characteristic feature of the invention according to the present application resides in the insight that the difference between the coefficient of linear expansion cf the skin layer and the coefficient of linear expansion of the core is not increased even when manufacturing a molded article under a large injection capacity condition by including an fibrous inorganic filler (particularly, a glass fiber) and glass beads in a liquid crystalline polyester amide resin, and making the content amount ratio (mass ratio) of the fibrous inorganic filler and the glass beads take approximately a value of one. According to the method of the present invention, a high-quality molded article can be manufactured with highly efficient productivity.
The present invention will be described in further detail below making reference to the examples. However the present invention is not limited by these embodiments.
Materials]
A liguid crystalline polyester amide resin (liquid crystalline resin): Vectra E9501 (manufactured by Polyplastics
Co., Ltd.), melting viscosity 20Parsec, Chopped strand glass fibers (glass fibers): ECS03T~786H {Nippon Electric Glass Co.,
Ltd.), fiber diameter 10 um, fiber length 3 mm (refer to the results measured using the above method as shown in Table 1 for fiber length in the kneaded pellet), Glass beads: EGB731 (Potters-Balletini Cec, . Ltd}, average particle diameter 18 um.
After executing a dry blending process with the materials shown above using the ratio shown in Table 1, a kneaded pellet is prepared using a twin screw extruder (“TEX30a” manufactured by Japan Steel Works Ltd.). A liquid crystalline resin composition (kneaded pellet} in the examples and comparative examples was used to perform the measurement of the deflection temperature under loading, the measurement of the coefficient of linear expansion, the measurement of the blister-resistant injection capacity as described below. [Measurement of Deflection Temperature under Loading]
A measurement test plece (4 mm x 10 mm x 80 mm) was formed under the following molding conditions using the kneaded pellet of the examples and comparative examples, and an injection molding device (manufactured by Sumitomo Heavy
Industries Limited, “SE100DU (screw diameter &36)7).
Thereafter, the deflection temperature under loading was measured using a method that conforms with ISO 75-1,2. The measurement results for the deflection temperature under loading are shown in Table 1.
[Molding Conditions]
Cylinder temperature 350°C
Mold temperature: 90°C
Back pressure: 1.0 MPa
Injection speed: 33 m/sec [Measurement of Coefficient of Linear Expansion]
An ISOL/32'' combustion test piece was molded under the following molding conditions using the kneading pellets according to the examples and the comparative examples and an injecting molding device {manufactured by Fanuc Corporation, “ROBOSHOT ob50C molding device (screw diameter ®26)7). {Molding Conditions]
Cylinder temperature 340°C
Mold temperature: 80°C
Injection speed: 300 mm/sec
A 0.2 mm portion from the surface, and a 0. 2 mm portion of the central portion of the resulting test piece were respectively cut to form a test sample. The measurement of the coefficient of linear expansion of the respective test samples formed by cutting was performed using a coefficient of linear expansion measuring device manufactured by TA Instruments Co.
Ltd. (TMAzZ940}. The test sample 1s heat processed for one hour at 250°C, and the coefficient of linear expansion is taken to be the expansion coefficient at 240°C with reference to the dimensions at 30°C. The results in relation to the coefficient of linear expansion, and the difference in the coefficients of linear expansion (the coefficient of linear expansion of the skin layer - the coefficient of linear expansion of the core layer) are shown in Table 1. [Measurement of Blister-Resistant Injection Capacity]
An I301/32'" combustion test piece was molded using the kneading pellets according to the examples and an injecting molding device (“o~50-C” manufactured by Fanuc Corporation).
Thereafter, injection molding was performed by fixing the nozzle discharge port diameter at 1.5 mm, fixing the ratio of the sprue discharge port diameter and the nozzle discharge port diameter (sprue discharge port diameter/nozzle discharge port diameter) to 2, and adapting other molding conditions to the molding conditions described below. The nozzle position and the sprue position are shown in Fig. 2. The nozzle discharge port diameter is the nozzle inner diameter of the nozzle distal discharge port as shown in Fig. 2, and the sprue discharge port diameter is the inner diameter of the sprue distal discharge port. The injection capacity is defined as 26.5 (cm’/sec), 39.8 (cm’/sec), 53.1 (cm®/sec), 66.3 (cm’/sec), 79.6 (cm’/sec), 92.9 (cm’/sec), 106.1 (cm/sec), 119.4 (cm’/sec), 132.7 (cm’/sec), 145.9 (cm®/sec), 159.2 (cm®/sec), and a S5-shot molding process is performed in relation to each molding capacity in order from the lowest capacity. Then, a reflow process (described in detail below) with a peak temperature of 280°C is executed. In the event that blistering cannot be confirmed on the basis of visual observation with reference to the 5 molded articles, a 5-shot molding process is performed in relation to the next largest molding capacity. The same reflow process iz executed, and visual evaluation of blister generation is performed. Thereby, the maximum injection capacity {blister-resistant injection capacity) that does not produce blistering {not at all capable of visual cbservation) is obtained. [Molding Conditions]
Screw Diameter: ®26 mm
Screw Rotation Speed: 100 rpm
Back Pressure : 3 MPa
Dwelling Pressure: 50 MPa
Dwelling Time: 1 sec
Cooling Time: 5 sec
Suck Back: 3 mm
Cycle Time: 15 sec
Cylinder Temperature: 340°C - 340°C = 330°C - 320°C
Mold Temperature: 80°C
Reflow Conditions]
Device: Infrared Reflow Oven {“RE-300”, Japan Pulse
Laboratories Inc.).
Preheat Zone Temperature Setting: 150°C x 3 minutes
Healt Zone Temperature Setting: 218°C x 2 minutes
Heating Cven Heating Time: 5 min
Molded Article Surface Peak Temperature: 280°C {The peak temperature of the surface of the molded article 1s the highest temperature that is measured by mounting a thermocouple on the molded article surface under the reflow heating conditions).
[Table 1]
Exampl | Exampl | Compar | Compar | Compar e 1 e 2 ative [ative |ative
Exampl | Exampl | Exampl e 1 e 2 e 3
Liguid Crystalline Resin | 70 70 70 70 {% by mass) cr sent oman [5 fo Jo [0 Jo ove [0 fo 266 267 280 273 259
Under Loading (°C)
Of Linear
Expansion (® | oove raver [1.56 [0.97 [1.68 [1.14 [1.31 }
Coefficient of Linear
Expansion of Skin Laver 0.55 0.62 1.05 0.71 - Coefficient of Linear
Expansion of Core Layer
Blister-Resistant
Injection 159.2 [159.2 [53.1 79.6 66.3
Capacity (cm’/sec) *The expansion ratio at 240°C when 30°C is used as a reference value is taken to be the coefficient of linear expansion.
As clearly shown in Table 1, when the content amount of the glass fiber 1s the same as the content amount of the glass beads, the difference between the coefficient of linear expansion of the skin layer and the coefficient of linear expansion of the core layer is not more than 0.7, and the blister-resistant injection capacity exceeds 150 cm’/sec.
As clearly shown by Example 2 and Comparative Example 3, the content amount of glass beads in Example 2 1s the same as the content amount of glass fiber and enables a greater reduction in the difference between the coefficient of linear expansion of the skin laver and the coefficient of linear expansion of the core layer Than Comparative Example 2 in which there is a higher content amount of glass beads.
Claims (7)
1. A liquid crystalline resin composition for injection molding comprising a liguid crystalline polyester amide resin and a mixture of a fibrous inorganic filler and glass beads, wherein a ratio of the fibrous inorganic filler to the glass beads in the mixture is from 0.9 : 1.0 to 1.0 : 0.9.
2. The liquid crystalline resin composition for injection molding according to claim 1, wherein the fibrous inorganic filler is glass fiber.
3. The liquid crystalline resin composition for injection molding according to claim 1 or 2, wherein a fiber length of the fibrous inorganic filler is at least 200 pm.
4. The liquid crystalline resin composition for injection molding according to any one of claims 1 to 3, comprising at least 39 parts by mass and no more than 69 parts by mass of the mixture relative to 100 parts by mass of the liquid crystalline polyester amide resin.
5. A resin molded article made by molding the liguid crystalline resin composition for injection molding according to any one of claims 1 to 4, wherein the liguid crystalline polyester amide resin has a melting pecint of at least 320°C, and wherein deflection temperature under loading of 1.8 MPa, measured by a method conforming with I8075-1,2, is at least 260°C.
6. A resin molded article made by molding the liquid crystalline resin composition for injection molding according to any one of claims 1 to 4, wherein a difference between a coefficient of linear thermal expansion cf a skin layer and a coefficient of linear thermal expansion of a core layer is no more than 0.7.
7. A method for improving blistering resistance of a resin molded article containing a fibrous inorganic filler and glass beads in a liquid crystalline resin composition, by setting a content of the fibrous inorganic filler and a content of the glass beads to be substantially equal.
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| JP2010020314A JP5717347B2 (en) | 2010-02-01 | 2010-02-01 | Liquid crystalline resin composition for injection molding, molded product and method for improving blister resistance |
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| KR (1) | KR101658621B1 (en) |
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| KR101945912B1 (en) * | 2016-04-15 | 2019-02-08 | 포리프라스틱 가부시키가이샤 | Liquid crystalline resin composition |
| WO2018074155A1 (en) * | 2016-10-21 | 2018-04-26 | ポリプラスチックス株式会社 | Composite resin composition, and electronic component formed from said composite resin composition |
| US20220243038A1 (en) * | 2019-05-14 | 2022-08-04 | Basf Se | Black-coloured polyamide composition with high laser transmittance for laser welding application |
| JP6796165B1 (en) * | 2019-07-09 | 2020-12-02 | ポリプラスチックス株式会社 | Molded article, composite molded article, and method for manufacturing the composite molded article |
| JP6773930B1 (en) * | 2019-08-09 | 2020-10-21 | 住友化学株式会社 | Manufacturing method of liquid crystal polyester resin molded product, liquid crystal polyester resin pellet, and liquid crystal polyester resin pellet |
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| JP4118425B2 (en) * | 1998-12-18 | 2008-07-16 | ポリプラスチックス株式会社 | Liquid crystalline polymer composition for connector and connector |
| JP3848880B2 (en) | 2002-01-25 | 2006-11-22 | 新日本石油化学株式会社 | Method for producing blister-resistant liquid crystal polyester composition |
| JP5271479B2 (en) * | 2005-12-14 | 2013-08-21 | 上野製薬株式会社 | Liquid crystalline polyester resin composition |
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| CN102140248B (en) | 2014-08-20 |
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