CN100577739C - Resin composition, resin molded article and production method thereof - Google Patents
Resin composition, resin molded article and production method thereof Download PDFInfo
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- CN100577739C CN100577739C CN200510104816A CN200510104816A CN100577739C CN 100577739 C CN100577739 C CN 100577739C CN 200510104816 A CN200510104816 A CN 200510104816A CN 200510104816 A CN200510104816 A CN 200510104816A CN 100577739 C CN100577739 C CN 100577739C
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- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 239000011342 resin composition Substances 0.000 title claims description 41
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- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 67
- 239000000446 fuel Substances 0.000 claims abstract description 65
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000005540 biological transmission Effects 0.000 claims abstract description 7
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- 238000001746 injection moulding Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229930182556 Polyacetal Natural products 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
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- 238000000465 moulding Methods 0.000 abstract description 17
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- 230000035939 shock Effects 0.000 description 9
- 239000004734 Polyphenylene sulfide Substances 0.000 description 8
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- 239000003795 chemical substances by application Substances 0.000 description 4
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- 239000000654 additive Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001278264 Fernandoa adenophylla Species 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
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- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 230000000712 assembly Effects 0.000 description 1
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- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)
Abstract
The invention relates to a resin moulding product which realizes the compatibility between the special characters (in particular to fuel barrier performance) of the resin moulding products (in particular to fuel components) and the impact resistance. The resin moulding product is characterized in that fibre (2) with the melting point higher than that of thermoplastic resin or infusibility and the length of 4 to 20mm is dispersed in the matrix of the thermoplastic resin (1). The resin moulding product is molded under the molding temperature that the melting point of which is higher than that of the thermoplastic resin and lower than that of the fibre. The invention is suitable for the fuel components (fuel boxes, etc.) which are exposed in the fuel, under the situation, the thermoplastic resin, the fuel transmission coefficient of which is less than or equal to 10.*10<-11>m<3>.m/m<2>/sec/Mpa under the 65 DEG C , is selected perferably corresponding to CE10.
Description
Technical field
The present invention relates to resin composition and synthetic resin and manufacture method thereof, be specially adapted to be exposed to the fuel system components of fuel container in the fuel etc.
Background technology
In the resinous fuel container that automobile is used, utilize blow molding and integrally formed, also utilize injection moulding, at weld part place be welded between the formed body divided into two parts cutting apart, but anyly all need to have concurrently anti-fuel-barrier and shock-resistance.
(1) the integrally formed fuel container for utilizing blow molding, because can easily realize multi-ply construction by using the multiwalled parison, so studying such multi-layer tectosome, this multi-layer tectosome is laminated by following part: basic unit, its by excellent impact resistance but the high density polyethylene(HDPE) of fuel-barrier difference (HDPE) resin constitute; And barrier layer, it constitutes (patent documentation 1,2) by the good ethylene-vinyl alcohol of fuel-barrier (EVOH) interpolymer resin.But there is following problems in the fuel container that is obtained by blow molding: to compare productivity poor with injection moulding; Freedom shape is restricted; And discontinuous at the privileged sites barrier layer, compare fuel transit dose increase etc. with general place, aforementioned privileged sites are contraction flow regions of pinch off end in blow molding, and for the open holes portion of parts such as valve being installed and processing etc.
(2) on the other hand, for utilizing injection moulding with the fuel container that is welded at the weld part place between the formed body of cutting apart divided into two parts, compare with blow molding and to have following advantage: highly productive, even and privileged sites, compare with general place, the fuel transit dose does not change substantially yet.But,, adopt the fuel-barrier and all good injection moulding material of shock-resistance of individual layer to become important because utilize injection moulding to be difficult to realize multi-ply construction.Up to now, as the injection moulding material, that is studying mainly contains nylon 6, nylon 12 (patent documentation 3), but its existence contains big this problem of transit dose of the fuel of alcohol such as methyl alcohol or ethanol.In addition, studying polyphenylene sulfide (PPS) resin of the good and poor impact resistance of fuel-barrier recently and strengthening the mixture (patent documentation 4) of the vinyl resin of shock-resistance, but having the problem of the illiquidity in the injection moulding.
(patent documentation 1) spy opens flat 6-340033 communique
(patent documentation 2) spy opens flat 6-191296 communique
(patent documentation 3) real microfilm of being willing to clear 61-89188 number (opening clear 62-20922 number in fact)
(patent documentation 4) spy opens the 2002-226707 communique
Summary of the invention
In addition, if the mixture of PPS resin and alkene family macromolecule is observed for a long time, might as among Fig. 6 from solid line to shown in the variation of two dot chain line, be stored in the alkene family macromolecule 52 in the PPS resin 51 and the swelling that produces causes dimensional change by fuel.This be because, because alkene family macromolecule fuel oil resistance is poor, so usually can dissolving or swelling in fuel.
The objective of the invention is to solve above-mentioned problem, a kind of resin composition and synthetic resin (particularly fuel system components) are provided, this resin composition and synthetic resin be the good and thermoplastic resin of poor impact resistance for specific character (particularly fuel-barrier), by improving its shock-resistance, make that it can realize specific character (particularly fuel-barrier) and shock-resistance and deposit.
(1) resin composition of the present invention is characterized in that: in thermoplastic resin the fusing point height of this thermoplastic resin of ratio of mixture or infusibility, length is the organic fibre of 4～20mm.
(2) synthetic resin of the present invention is characterized in that: in the matrix of thermoplastic resin, be scattered here and there than the fusing point height of this thermoplastic resin or infusibility, length is the organic fibre of 4～20mm.
(3) manufacture method of synthetic resin of the present invention, it is characterized in that: in thermoplastic resin, the fusing point height of this thermoplastic resin of ratio of mixture or infusibility, length is the organic fibre of 4～20mm, higher than the fusing point of aforementioned thermoplastic resin and than the low-melting mold temperature compacted under of aforementioned organic fibre.
A: thermoplastic resin
As thermoplastic resin, be not particularly limited, but as preferably can illustration as follows.
(1) under the situation of the moulding that is applicable to fuel system components described later, preferred thermoplastic resin is the high thermoplastic resin of fuel-barrier, specifically, than the test fuel (hereinafter referred to as " CE10 ") that is 45/45/10 composition, the fuel transmission coefficient under 65 ℃ is less than or equal to 1.0 * 10 for toluene/octane-iso/alcoholic acid mixed volume
-11m
3M/m
2/ sec/MPa.
(2) preferred thermoplastic resin is the good thermoplastic resin of fuel oil resistance, and specifically, the saturated swelling amount of the CE10 under 65 ℃ is less than or equal to 10 quality %.
(3) preferred thermoplastic resin is mobile high thermoplastic resin, specifically, according to melt mass flow rate (MFR) (5000g load) that ASTM-D1238 measured more than or equal to 15g/10 minute.
(4) as kind, preferred a kind (monomer) or the mixture of from the group of polyacetal, vibrin, ketone resin, polyamide resin and fluorine-type resin, selecting more than 2 kinds and 2 kinds.
(5) more preferably satisfy in aforementioned (1) (2) (3) thermoplastic resin of the kind of aforementioned (4) of 1 or 2 and 2 above condition arbitrarily, expression several examples wherein in table 1.
Table 1
| Material category | The material name | Fusing point (℃) | Material transmission coefficient (m 3·m/m 2/sec/MPa〕 | Remarks |
| Polyacetal | ?homoPOM ?co-POM | ?190 ?165 | 1.7×10 -126.3×10 -12 | |
| Polyester | ?PBT ?PEN ?PBN | ?220 | 1.4×10 -124.9×10 -124.7×10 -12 | PET also can |
| Ketone resin | Aliphatics PEEK | 5.5×10 -131.3×10 -13 | ||
| Polymeric amide | ?PA11 ?PA12 ?PA6 ?PA66 ?MXD6 | ?185 ?175 ?215 ?265 ?240 | 6.0×10 -122.0×10 -123.1×10 -123.9×10 -131.2×10 -13 | All PA are all passable |
| The fluorine class | ?ETFE | ?200 | 6.0×10 -13 | Other PTFE, PVdF, FEP, PFA etc. are arranged |
| Other | ?EVOH ?PPS ?PEI | ?190 ?280 ?- | 6.6×10 -145.7×10 -148.9×10 -15 |
In addition, the fuel transmission coefficient in the table 1 uses commercially available differential pressure type gas permeation rate determination test machine (GTR テ Star Network Co., Ltd. system: model GTR-30XVT) measure.As shown in Figure 3, in the thermostatic bath 31 of this trier, on the sintering metal 38 that is set at the test portion platform 32 under the steady temperature, experimental film S is set, is bolted on the test portion platform 32 with anchor clamps 33 pushing down experimental film S fluid-tight on every side.Then, will close the loam cake 34 of fluid-tight as the upper surface of the CE10 injection test film S of test fuel F with anchor clamps 33.Like this, the upper surface of experimental film S is exposed among the test fuel F, utilizes vacuum pump 35 to reduce the pressure of experimental film S below, keep this state under steady temperature, to place, make experimental film S stable.After stable,, collect the test fuel F that sees through experimental film S, be injected in the gas chromatograph 37 detection peak, qualitative, quantitative by gauge line 36 every the constant time.Quantitative methods is, in advance with in each composition inject gas chromatograph 37 among the CE10 of specified amount, detection peak is obtained the lubber-line that expression respectively becomes the relation of component and peak area, obtains the peak value that is produced that sees through by every above-mentioned constant time by this lubber-line.
B: organic fibre
As organic fibre, as previously mentioned, be than the fusing point height of thermoplastic resin or infusibility, length is the organic fibre of 4～20mm.Employing is to keep fibre shape for the fusion of relatively hot plastic resin than the fusing point height of thermoplastic resin or the organic fibre of infusibility.In addition, employing length is that the organic fibre of 4～20mm is because if less than 4mm, then reduction improves the effect of shock-resistance, as if surpassing 20mm, the tendency of the external form variation of moulding product is arranged then.More preferably length is the organic fibre of 6～10mm.
For organic fibre, in addition there is no particular limitation, but as preferably can illustration as follows.
As the kind of organic fibre, preferably a kind (monomer) or the mixing of from cellulosic fibre, tynex, polyester fiber, polyvinyl alcohol fibrid, polyvinyl chloride fiber, polyvinylidene dichloride fibrid, polyolefins fiber, polyurethane kind fiber, the group of poly-alkylene, selecting more than 2 kinds and 2 kinds to oxybenzoic acid fat (polyalkylenepara oxybenzoate) fiber and polytetrafluoroethylene fiber.Wherein several examples and carbon fiber are illustrated in the table 2 together.
Table 2
C: the combination of thermoplastic resin and fiber
(1) fiber of infusibility can be mixed in any thermoplastic resin.
(2) fiber of hot melt property can be mixed in the higher any thermoplastic resin of fusing point.
(3) as concrete combination, but the combination of the fiber on the thermoplastic resin on the left hurdle of illustration table 3 and right hurdle.
Table 3
| Resin | Fiber |
| PBT | PET, PA66, vinylon, Mierocrystalline cellulose, fluorine class, diphenyl sulfide, aromatic poly, carbon |
| POM | PET, PBT, PA6, PA66, vinylon, Mierocrystalline cellulose, fluorine class, diphenyl sulfide, aromatic poly, carbon |
| Nylon 6 | Regenerated fiber, nylon 66, aromatic poly, diphenyl sulfide |
D: other additive
In thermoplastic resin, also can add fiber other additives in addition, but illustration is as follows.
(1) antioxidant
(2) modifying agent: can the mixed coupling agent, common modifying agent such as plasticizer, crystallization nucleating agent, metallic soap, parting agent, anti-coloring agent, lubricant, ultraviolet screener, tinting material, fire retardant, whipping agent.
(3) packing material
E: the blending ratio of resin composition
The blending ratio optimum fiber of resin composition is 5～50 quality %, and thermoplastic resin and other additive are rest part.If fiber less than 5 quality % then can reduce the effect that improves shock-resistance,, then has the tendency that forming process (outward appearance weldability) reduces if fiber surpasses 50 quality %.More preferably fiber is 20～40 quality %.
F: the manufacture method of resin composition
The manufacture method of resin composition (blending means of thermoplastic resin and fiber) does not limit especially, but is preferably as follows illustrative method.Shown in Fig. 1 (a), in the pinblock 8 that is installed in resin extruded machine end, supply with fused thermoplastic resin 1, supply with many successive fiber 2 simultaneously.The supply of this fiber 2 can be carried out like this: 2a twists on the coil bobbin 9 with the many fibrous bundles of being made up of monofilament (line), from this coil bobbin 9 plurality of fibers bundle 2a is sent etc.Extrude longitudinal bodies 3 from pinblock 8, this longitudinal bodies 3 is the state of coated thermoplastic on the plurality of fibers of together pulling out, and this longitudinal bodies 3 is cut into specified length, and (this length is the length of fiber.) particle 4, can obtain granular resin composition thus.In addition, carry out fusion and mixing, then can obtain the resin composition of molten by the mixing machine that this particle 4 is utilized injection moulding machine etc.
G: the dispersion state of fiber
Fig. 1 (b) is the resin composition of schematically illustration molten or by the enlarged view of the microtexture in the synthetic resin of its moulding, be illustrated in the matrix of thermoplastic resin 1, fiber 2 is that units separate dispersive state (partly twine mutually by the part that also can be monofilament with the monofilament.)。Preferred this dispersion state.Because fiber 2 is than the fusing point height of thermoplastic resin 1 or the material of infusibility, so even thermoplastic resin 1 fusion also keeps this fibre shape.In addition, as previously mentioned, if the staple length of fiber 2 is more than or equal to 4mm, then as shown in the drawing, winding increases.If fiber 2 is disperseed, then when synthetic resin was applied surging force, impact energy was absorbed by the matrix and the friction between the fiber 2 of thermoplastic resin 1, infers that with this shock-resistance should improve.Particularly when the staple length of fiber 2 is the macrofiber of 4～20mm, consider that its friction increases, and winding increases mutually, correspondingly shock-resistance can improve more.
H: synthetic resin
Synthetic resin is not limited to the article of specific end use, can be in the parts of automobile implements in the synthetic resin of parts shell, the indoor various uses such as main body cover that product are set of parts shell, mechanism of ornaments, electric appliance and electronic device.Particularly, because have fuel-barrier and shock-resistance concurrently, so can be advantageously applied to the fuel system components that is exposed in the fuel by blend fiber in the good thermoplastic resin of fuel-barrier.The based part that acts as a fuel, but illustration fuel container, valve, fuel tube, fuel tube joint, petrolift, petrolift shell, jar etc. are specially adapted to fuel container.
I: forming method
Do not limit especially as the forming method of synthetic resin, but can illustration melt molding (injection moulding, injection moulding extrusion molding etc.), blow molding, extrusion molding, impact briquetting, vacuum forming, the empty moulding of pressure, roll forming, compressed moulding etc.Particularly under the situation of fuel system components, the preferred molten moulding.
J: mold temperature
The mold temperature of synthetic resin as mentioned above, be higher and than the low-melting temperature of aforementioned fibers than the fusing point of aforementioned thermoplastic resin, but preferred higher 10～50 ℃, and than fusing point low 20～30 ℃ or the above temperature of aforementioned fibers than the fusing point of aforementioned thermoplastic resin.Its objective is to make the abundant fusion of thermoplastic resin, prevent the fusion of fiber simultaneously reliably.
The effect of invention
By resin composition of the present invention and synthetic resin and manufacture method thereof, by the thermoplastic resin of poor impact resistance improves its shock-resistance to specific character is good, can realize special properties and shock-resistance and deposit.Especially, by the resin composition and the fuel system components that have used the good thermoplastic resin of fuel-barrier, by to the good and thermoplastic resin of poor impact resistance of fuel-barrier, improve its shock-resistance, can realize fuel-barrier and shock-resistance and deposit, thereby can realize utilizing the fuel system components of the individual layer of melt molding (injection moulding, injection moulding extrusion molding etc.).
Description of drawings
Fig. 1 represents resin composition of the present invention, (a) is the sketch chart of expression particulate manufacture method, (b) is the enlarged view of resin composition.
Fig. 2 is the sectional view of the fuel container that relates to of embodiment.
Fig. 3 is the sketch chart of the measuring method of expression fuel transit dose.
Fig. 4 is the sketch chart of other measuring methods of expression fuel transit dose.
Fig. 5 is the mensuration that ruptures in the izod impact test of embodiment 2 microphotograph that splits section with test film.
Fig. 6 is the sketch chart of the resin composition of conventional example.
Embodiment
Fig. 2 represents to use the fuel container of following resin composition manufacturing, and this resin composition forms for the fusing point height or the infusibility fiber of this thermoplastic resin of ratio of mixture in fuel-barrier and mobile high thermoplastic resin.From microcosmic, shown in Fig. 1 (b), in the matrix of thermoplastic resin, fiber is that units separate is disperseed with the monofilament as the aforementioned.This fuel container is at weld part 30 places, will utilize injection moulding and upper casing 10 and the lower casing 20 of cutting apart formed body divided into two parts is welded, and this upper casing 10 is for the handstand of lower openings has end cup-shaped, and this lower casing 20 has an end cup-shaped for upper opening.The wall thickness of the general portion of upper casing 10 and lower casing 20 is approximately 4mm, and interior dimensions is wide about 400mm * be about 600mm.The degree of depth from the lower openings of upper casing 10 to inner top surface is about 150mm, and the degree of depth from the upper opening of lower casing 20 to inner bottom surface is about 150mm.Weld part 30 is positions that the lower surface 11 of upper casing 10 (having the flange 12 that makes periphery outwards outstanding in the illustrated example) is docked with the upper surface 21 (having flange 22 equally) of lower casing 20.Upper surface (general portion) at upper casing 10 is gone up formation open holes 13, posts the mounting plate 14a of pump assembly 14 on this open holes 13, utilizes lock ring 15 to be locked in the inside by packing ring (not shown).
This fuel container is with following operation manufacturing.
(1) under fusing point height and low-melting mold temperature than aforementioned fibers than aforementioned thermoplastic resin, the aforementioned resin synthetics is injected the forming mould that upper casing is used, injection moulding upper casing 10, the aforementioned resin synthetics is injected the forming mould that lower casing is used, injection moulding lower casing 20 (Fig. 2 (a)).
(2) lower surface 11 of upper casing 10 is carried out docking (hot plate welding) after hot plate heats with the upper surface 21 of lower casing 20, form weld part 30 (Fig. 2 (b) (c)).
(3) on the open holes 13 of upper casing 10 (form during in injection moulding, but also can be), the mounting plate 14a (Fig. 2 (b)) of pump assemblies 14 is installed by lock ring 15 in this moulding aft opening processing.
By the fuel container of present embodiment, can obtain following action effect.
(A) because use aforementioned resin synthetics injection moulding upper casing 10 and lower casing 20, so the productivity height.In addition,, use mobile high thermoplastic resin,, can not produce lack of fill, can guarantee impact characteristics and tensile strength simultaneously so formability is good because as previously mentioned.
(B) because use high thermoplastic resin injection moulding upper casing 10 and the lower casing 20 of the fuel-barrier barrier of gasoline, alcohol (particularly to), see through so can suppress the fuel of general portion.In addition, because also be the structure that merges between this thermoplastic resin,, can suppress fuel and see through so the fuel-barrier of weld part 30 is identical with general portion at weld part 30 places.
(C) because utilizing length is that the fiber dispersion of 4～20mm increases shock-resistance, so can obtain the fuel container of excellent impact resistance.
Embodiment
Shown in following table 4, utilize each resin composition of embodiment 1～8 and comparative example 1～4, moulding is as the fuel container of synthetic resin, and detection is also compared performance.
Table 4
If with embodiment 1 and embodiment 2 is that example illustrates its detailed content, then according to the method shown in the earlier figures 1 (a), make the particle of resin composition, this resin composition is in the POM resin of the high thermoplastic resin of the barrier that acts as a fuel, and the length as fiber of mixing quality 30% is that the PET fiber of 6mm forms.More particularly, the fiber shown in Fig. 1 (a) is supplied with, and is that 12 fibrous bundles of being made up of 192 monofilament (line) 2a (1670dTEX) are sent into pinblock 8.Utilize the mixing machine of injection moulding machine (diagram slightly), will this particle fusion and mix the back and inject to mould, thus be shaped to the upper casing and the lower casing of aforementioned fuel container.Mold temperature is higher and than low-melting about 200 ℃ of PET than the fusing point of POM.
Embodiment 5 mixes the resin composition that obtains behind the nylon 66 fiber in the PBT resin, mold temperature is that the fusing point than PBT is high and than low-melting about 240 ℃ of nylon 66.
Embodiment 6 mixes the resin composition that obtains behind the Kevlar in the PBT resin, mold temperature is that the fusing point than PBT is high and than low-melting about 240 ℃ of aromatic poly.
Embodiment 7 mixes the resin composition that obtains behind the Kevlar in Nylon 6, mold temperature is that the fusing point than nylon 6 is high and than low-melting about 240 ℃ of aromatic poly.
Comparative example 1 is the POM resin monomer of unmixed fiber, and mold temperature is 200 ℃.
Comparative example 2 be in the PPS resin, mix total amount 30% quality as the resin composition that obtains behind the epoxy modifying polyethylene of alkene class rubber and the ethylene-alpha-olefin interpolymer, mold temperature is 300 ℃.
Comparative example 3 is the resin compositions that obtain behind the hybrid PET fiber in the PBT resin, and mold temperature is higher and than high about 250 ℃ of the fusing point of PET than the fusing point of PBT.
Comparative example 4 is the resin compositions that mix nylon 66 fiber in Nylon 6, and mold temperature is that the fusing point than nylon 6 is high and than high about 260 ℃ of the fusing point of nylon 66.
And embodiment 3,4,5 and the forming method of staple length, fibre weight, particle making method and the housing of comparative example 2,3 identical with embodiment 1, the forming method of the housing in the comparative example 1 is also identical with embodiment 1.
In addition, utilize each resin composition and each mold temperature of embodiment 1～8 and comparative example 1～4, the mensuration of shaped fuel transit dose is measured fuel transit dose and Emhorn shock strength with the mensuration test film of test film and Emhorn (Izod) shock strength.Size changing rate when in addition, measuring saturated swelling to fuel.These measuring methods as hereinafter described.These measurement results are illustrated in the above-mentioned table 4.
(mensuration of Emhorn shock strength)
The sample that injection moulding is obtained carries out post-treatment makes it have otch, according to ASTM-D256, under temperature environment-40 ℃, measures nicked Emhorn shock strength.
(mensuration of fuel transit dose (cup modulus method))
So-called cup modulus method is meant following method: pour 17ml test fuel F into flanged cup (internal diameter: 34mm shown in Figure 4, cup inner height: 25mm) in 40, on flange part 41, carry test film S, and,, utilize pressure coil 43 to exert pressure by wire cloth 42, fixing with bolt 44, then, make the upset of this cup part, measure the dissipation amount of test fuel F between on time.Test fuel F is CE10, measures down at 65 ℃.Numerical value is scaled the value of 1mm when thick.
(mensuration of the size changing rate during saturated swelling)
Be determined among the CE10 that is impregnated into 65 ℃ 2000 hours preceding and after, the size of the width of sample (many purposes of defined test film type A central part among the ISO3167) is tried to achieve size changing rate.
As shown in table 4, the good and poor impact resistance of comparative example 1 fuel-barrier, comparative example 2 is big by the dimensional change that saturated swelling causes, and is relative with it, and embodiment 1～8 is good aspect any one of fuel-barrier, shock-resistance and anti-saturated swelling.In addition, comparative example 3, though 4 mixed the fiber higher than the fusing point of thermoplastic resin, injection moulding under than the high mold temperature of the fusing point of fiber is so the result is a poor impact resistance.In case be considered to because the fiber fusion does not then have fibre shape to retain, and merge, so can not realize improving the effect of shock-resistance with matrix.
Below, make the resin composition that the PET fibre weight of the resin composition (POM numerical value (copoly type)+PET fiber) of embodiment 2 is changed into 20,30,40 quality %, measure at the about 200 ℃ of compacted unders of mold temperature and use test film, mensuration Emhorn shock strength.Its measurement result is illustrated in the following table 5.In the PET fibre weight is under any situation of 20～40 quality %, can both obtain high impulse strength, can obtain high impact under the situation of 30 quality %.Mensuration under this 30 quality % situation shows as shown in Figure 5 with the microphotograph of the surface of fracture of test film.
Table 5
| Fibre weight (quality %) | 20 | ?30 | ?40 |
| -40 ℃ of Emhorn shock strengths (J/m) | 380 | ?540 | ?450 |
Below, make that PET staple length with the resin composition (POM resin (copoly type)+PET fiber) of embodiment 2 changes 3,6 into, the resin composition of 9mm, measure at the about 200 ℃ of compacted unders of mold temperature and use test film, mensuration Emhorn shock strength.Its measurement result is illustrated in the following table 6, is can obtain high impulse strength under any situation of 3～6mm in PET length, particularly can obtain high shock strength under more than or equal to the situation of 6mm.
Table 6
| Fiber long (mm) | 3 | ?6 | ?9 |
| -40 ℃ of Emhorn shock strengths (J/m) | 250 | ?540 | ?530 |
In addition, the present invention is not limited among the aforementioned embodiments embodiment, for example, also can be as described below, suitably change realizes in the scope that does not break away from inventive concept.
(1) situation of injection moulding extrusion forming upper casing 10 and lower casing 20.
(2) use resin composition of the present invention, the situation of the synthetic resin of the various uses beyond the melt molding fuel container.
(3) use resin composition of the present invention, melt molding does not have the situation of the synthetic resin of weld part.
Claims (5)
1. resin composition,
Its for fusing point height of this thermoplastic resin of ratio of mixture in thermoplastic resin or infusibility, length is that the organic fibre of 4～20mm forms,
Described thermoplastic resin be with respect to toluene/octane-iso/alcoholic acid mixed volume than the test fuel that is 45/45/10 composition, the fuel transmission coefficient under 65 ℃ is less than or equal to 1.0 * 10
-11m
3M/m
2The thermoplastic resin of/sec/MPa,
Wherein, described thermoplastic resin is the polyacetal resin of copoly type, and described organic fibre is a trevira.
2. resin composition as claimed in claim 1,
The length of described organic fibre is 6～10mm.
3. synthetic resin,
It is in the thermoplastic resin matrix, be scattered here and there than the fusing point height of this thermoplastic resin or infusibility, length is the organic fibre of 4～20mm,
Described thermoplastic resin be with respect to toluene/octane-iso/alcoholic acid mixed volume than the test fuel that is 45/45/10 composition, the fuel transmission coefficient under 65 ℃ is less than or equal to 1.0 * 10
-11m
3M/m
2The thermoplastic resin of/sec/MPa,
Wherein, described thermoplastic resin is the polyacetal resin of copoly type, and described organic fibre is a trevira.
4. synthetic resin as claimed in claim 3,
Synthetic resin is the fuel system components that is exposed in the fuel.
5. the manufacture method of a synthetic resin,
In thermoplastic resin, the fusing point height of this thermoplastic resin of ratio of mixture or infusibility, length is the organic fibre of 4～20mm, higher than the fusing point of aforementioned thermoplastic resin and than the low-melting mold temperature of aforementioned organic fibre under injection moulding,
Described thermoplastic resin be with respect to toluene/octane-iso/alcoholic acid mixed volume than the test fuel that is 45/45/10 composition, the fuel transmission coefficient under 65 ℃ is less than or equal to 1.0 * 10
-11m
3M/m
2The thermoplastic resin of/sec/MPa,
Wherein, described thermoplastic resin is the polyacetal resin of copoly type, and described organic fibre is a trevira.
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| JP2004286264 | 2004-09-30 | ||
| JP2004286264 | 2004-09-30 | ||
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| US20120108136A1 (en) * | 2010-10-29 | 2012-05-03 | E.I. Du Pont De Nemours And Company | Overmolded polyamide composite structures and processes for their preparation |
| CN110172231A (en) * | 2019-05-08 | 2019-08-27 | 南通开普乐工程塑料有限公司 | A kind of refrigerant PBT resin composition and preparation method thereof |
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