CN101018656A - Exterior molding body comprising a long fiber reinforced thermoplastic resin - Google Patents
Exterior molding body comprising a long fiber reinforced thermoplastic resin Download PDFInfo
- Publication number
- CN101018656A CN101018656A CNA2005800305348A CN200580030534A CN101018656A CN 101018656 A CN101018656 A CN 101018656A CN A2005800305348 A CNA2005800305348 A CN A2005800305348A CN 200580030534 A CN200580030534 A CN 200580030534A CN 101018656 A CN101018656 A CN 101018656A
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- Prior art keywords
- resin
- thermoplastic resin
- formed article
- fiber
- polyamide
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 125
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- 238000000465 moulding Methods 0.000 title claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 223
- 229920005992 thermoplastic resin Polymers 0.000 claims description 44
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- 229920002292 Nylon 6 Polymers 0.000 claims description 27
- 239000004952 Polyamide Substances 0.000 claims description 26
- 229920002647 polyamide Polymers 0.000 claims description 26
- 238000003475 lamination Methods 0.000 claims description 24
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- 229910045601 alloy Inorganic materials 0.000 claims description 10
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- 239000004431 polycarbonate resin Substances 0.000 claims description 10
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- 239000000203 mixture Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Superstructure Of Vehicle (AREA)
- Body Structure For Vehicles (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The object the present invention is to provide an exterior molding body for automobile which is reinforced by a long fiber, is excellent in mechanical properties such as bending elastic modulus and bending strength, chemical resistance and heat resistance, is lightened, has high designability and is reduced in the anisotropy of linear expansion coefficient of molding body caused by the fiber orientation at filling thereof to a mold. In an aspect of the present invention, there is provided an exterior molding body comprising a long fiber reinforced thermoplastic resin having such properties that: the content of long fiber dispersed in the molding body is 30 to 90% by weight, the average fiber length of long fiber is 1.5 to 10 mm, the maximum project area of said molding body is not less than 20000 mm<2>, the molding body has such a shape that the length of narrow resin flow path at the portion having not more than 100 mm<2> of cross sectional area in the mold cavity at the molding is not more than 150 mm, the maximum linear expansion coefficient at a portion of said molding body having a wall thickness of not less than 2 mm is not more than 5 X 10 -5 K<-1> and the ratio of maximum linear expansion coefficient/minimum linear expansion coefficient is not more than 1.8.
Description
Technical field
The present invention relates to the body that is injection molded into of the engineering properties of resistance to impact etc. and mobile good fiber reinforced thermoplastic resin, and, the anisotropic exterior formed article made of long fiber-reinforced thermoplastic resin, particularly automobile exterior formed article that relate to the formed body that the fiber orientation (fiber orientation) when having reduced owing to injection molded produces.
Background technology
At present, with aspect the exterior member, adopt always, the metal outer structure of adorning plate (exterior panel) is installed on metallic structural member at automobile.Yet, in recent years,, the trend of the lightness that needs various automobile components is arranged for the purpose of the fuel consumption rising of automobile, driving performance rising etc., adorn plate outside and support in its tectosome and also used resin gradually.
For example, in patent documentation 1, in order to make automobile with the further lightness of plate, the automobile plate of being made as the FRP of fortifying fibre by the fabric substrate that continuous fiber is made being disclosed, yet, aspect the free degree and production efficiency of design, can't be met.
In addition, in patent documentation 2, from lightness and modular viewpoint, following tail gate has been proposed, its outside plate is made by the polyphenylether/polyamide alloy, and inner panel is made by continuous fiber reinforcing polyamide/polyolefin alloy, yet, because the suction size that PA causes changes, exist the inconvenient and not good problem of streamlined appearance of switch.In order to solve the problem of suction change in size, use Merlon/polybutylene terephthalate (PBT) alloy etc. has also been proposed, yet, because inner panel is a long fibre enhanced polypropylene alkene, need the bonding structure, in addition, the anisotropy that the line that is caused by the fiber of inner panel orientation expands influence outside plate, but the big or small or anisotropic relevant record that does not wherein have line to expand.
In patent documentation 3, as the vehicle exterior member, following carbon fiber reinforced polyamide is disclosed, the linear expansion coefficient of the flow direction during its injection molded and with the mean value of the linear expansion coefficient of the rectangular direction of flow direction be 6 * 10
-5K
-1, still, not about its anisotropic record.When anisotropy was big, the distortion situation that is caused by variations in temperature had influence on exterior quality because of direction is different, have owing to produce member fracture or the crack generation that stress concentrates portion to cause, thereby undesirable.
In addition, in patent documentation 4, disclose, obtain at the fiber-reinforced thermoplastic resin material injection molded that will contain 3～70 weight % fibrous reinforcements, in the thermoplastic resin formed body of (volume)/(surface area)＜2mm, contain the molten resin of fibre reinforced materials flow direction (MD) and with the linear expansion coefficient at 23 ℃～100 ℃ of the rectangular direction of flow direction (TD) be 0.6＜(linear expansion coefficient of TD direction)/(linear expansion coefficient of MD direction)＜2.5.Yet, as automobile with outer assembling structure body, need reduce anisotropy, and if its absolute value is still bigger, just may cause switch, to the influence of circumferential component and because of the expand reduction of the bad or exterior quality that the application be full of cracks causes of the application that causes of line.Even when formed body internal memory during at the little narrow runner of sectional area, the orientation grow of fortifying fibre, it is big that anisotropy becomes, and may all bring bad influence in the formed body because of long the giving of the runner of narrow runner, yet wherein less than the record relevant with the formed body shape.
Patent documentation 1: TOHKEMY 2002-127944 communique
Patent documentation 2: TOHKEMY 2003-118379 communique
Patent documentation 3: TOHKEMY 2002-226703 communique
Patent documentation 4: Japanese kokai publication hei 9-296053 communique
Summary of the invention
Problem to be solved by this invention is, provide a kind of long fibre to strengthen the automobile exterior formed article, it has the mechanical strength of good crooked elastic rate, bending strength etc., good chemical proofing, hear resistance, lightness, the free degree height of product design, and reduced because the anisotropy of the linear expansion coefficient of the formed body that the fiber orientation when filling causes.
The inventor is in order to solve above-mentioned problem, attentively research repeatedly, found that, resin flow channel when being shaped in the mould cavity by limiting, long fibre strengthens automobile being orientated the max line coefficient of expansion that causes, the anisotropy of linear expansion coefficient, maximum moisture absorption size changing rate by fiber and all diminishing, thereby finished the present invention with exterior formed article.
Promptly, main points of the present invention are, a kind of exterior formed article made of long fiber-reinforced thermoplastic resin, its containing ratio that is dispersed in the fortifying fibre in the formed body are 30 weight %～90 weight %, weight average fiber length is 1.5mm～10mm, and the maximal projection area of formed body is 20000mm
2More than, sectional area is at 100mm during shaping
2The runner length of following narrow runner is at 150mm
2Below, and the max line coefficient of expansion of the formed body part of thickness more than 2mm is 5 * 10
-5K
-1Below, and the ratio of the max line coefficient of expansion/minimum line coefficient of expansion is below 1.8.
In exterior formed article made of long fiber-reinforced thermoplastic resin of the present invention, to be 30 weight %～90 weight % and fortifying fibre be dispersed in wherein long-fiber-reinforced resin with the weight average fiber length of 1.5mm～15mm to the containing ratio that has used fortifying fibre, and the sectional area in the mould cavity when being shaped is at 100mm
2The runner length of following narrow runner is below 150mm, thereby, can produce the excellent size stability that causes by linear expansion coefficient and anisotropic reduction thereof, the mechanical strength of crooked elastic rate, bending strength etc. is good, chemical proofing, excellent heat resistance, lightness, product design free degree height is applicable to the large-scale formed body of automobile with exterior formed article.
Description of drawings
Fig. 1 is the plane and the side view of the exterior formed article that obtains of embodiment 1,2,4 and comparative example 1,2,5.
Fig. 2 is the plane and the sectional view of the exterior formed article that obtains of embodiment 3.
Fig. 3 is the plane and the sectional view of the exterior formed article that obtains of comparative example 3.
Fig. 4 is the plane and the sectional view of the exterior formed article that obtains of comparative example 4.
Fig. 5 is the plane and the side view of the exterior formed article that obtains of embodiment 6～8 and comparative example 7,8,11.
Fig. 6 is the plane and the sectional view of the exterior formed article that obtains of embodiment 9.
Fig. 7 is the plane and the schematic section of the exterior formed article that obtains of comparative example 9.
Fig. 8 is the plane and the sectional view of the exterior formed article that obtains of comparative example 10.
The specific embodiment
Describe the present invention below in detail.
Exterior formed article made of long fiber-reinforced thermoplastic resin of the present invention (below, be called for short " formed body of the present invention ") be the significant large-scale formed body of anisotropic influence that is applicable to linear expansion coefficient, the maximal projection area that is this formed body is greater than 20000mm
2Formed body.When using fiber-reinforced resin to be shaped, in general, the superficial layer on the thickness, fiber are along resin flow direction orientation, and central core is then along being orientated with the rectangular direction of flow direction.When fortifying fibre is short fiber,,, often be orientated near the central core along random direction so streamwise is orientated though superficial layer is subjected to from the shearing force of wall because motion (rotation) free degree of fiber improves when being shaped.When fortifying fibre was long fibre, because the influence of its fibre length, the motion of fortifying fibre (rotation) free degree diminished, and we can say that the easy streamwise of superficial layer has clear and definite orientation, and central core has clear and definite orientation along its right angle orientation easily.In addition, the upper limit of maximal projection area 2m normally
2(2,000,000 mm
2).
The another one feature of formed body of the present invention is preferably, in the relation of the sectional area of narrow runner and its flow channel length, to have 100mm when being shaped
2The flow channel length of the narrow runner of following sectional area is below the 150mm, more preferably has 80mm
2The flow channel length of the narrow runner of following sectional area is below the 100mm.If have 100mm when being shaped
2When the flow channel length of the narrow runner of following sectional area surpasses 150mm, the differently-oriented directivity of fortifying fibre is many along the change of the filling direction orientation of molten resin, thereby becomes big in the effect that reduces linear expansion coefficient of filling direction, but its effect in right angle orientation reduces, thus, anisotropy just becomes big.Anisotropy is in case become big, may cause influencing as the needed switch of exterior member, with the coupling and the pore volume of circumferential component, and further bring because of the expand reduction of the bad and exterior quality that the application be full of cracks is caused of the application that causes of line.
In addition, another feature of formed body of the present invention is: about the fortifying fibre that disperses in the formed body, the containing ratio of fortifying fibre is 30 weight %～90 weight %, and is that the weight average fiber length of 1.5mm～10mm is disperseed wherein with fortifying fibre length; And being, is the optional position (many places) of the formed body part more than the 2mm at thickness, measures 23 ℃～80 ℃ linear expansion coefficient, and the maximum of these measured values (the max line coefficient of expansion) is 5 * 10
-5K
-1Below, and calculate ratio with the minimum of a value (the minimum line coefficient of expansion) of these measured values, the ratio of the max line coefficient of expansion/minimum line coefficient of expansion is below 1.8.
Then, the containing ratio of above-mentioned fortifying fibre is discontented with 30 weight %, perhaps during the discontented 1.5mm of weight average fiber length, is that the mechanical strength and the dimensional stability of representative can reduce with the crooked elastic rate bending strength, thereby not preferred.In addition, when the containing ratio of above-mentioned fortifying fibre surpassed 90 weight %, when perhaps weight average fiber length surpassed 10mm, formability reduced, thereby not preferred.And, at above-mentioned linear expansion coefficient greater than 5 * 10
-5K
-1The time and the ratio of the max line coefficient of expansion/minimum line coefficient of expansion greater than 1.8 o'clock, the distortion quantitative change all with respect to the formed body of variations in temperature is big, may cause to as the needed switch of exterior member, with the coupling of circumferential component and the influence of pore volume, the generation of the fragmentation that causes because of distortion, the deformation of outward appearance, application be full of cracks, even the expand reduction of the bad and exterior quality that the application be full of cracks is caused of the application that causes of the line when bringing by the formed body application, thus not preferred.
The fortifying fibre that constitutes formed body of the present invention is, weight average fiber length is the long fibre of 1.5mm～10mm, in order to make anterior construction body with better mechanical strength and dimensional stability, be preferably the long fibre of 2mm～7mm, as long as and can in this formed body, disperse, just have no particular limits.Usually, can use glass fibre, carbon fiber, metallic fiber, synthetic fibers of the enhancing that is used for resin etc., but glass fibre and carbon fiber are practical.The diameter of carbon fiber is preferably 5 μ m～15 μ m.In addition, in order to improve the interface adhesiveness with thermoplastic resin, fortifying fibre preferably carries out surface treatment with astringent or surface conditioning agent (for example, the functional compound of epoxy compounds, acrylic compounds, isocyanate ester compound, silane compound, titanate ester compound etc.).
When the fortifying fibre that constitutes formed body of the present invention was glass fibre, from the viewpoint with the rerum natura balance lost of further raising glass fibre, preferred diameter was 10 μ m～20 μ m.The actual glass fibre that uses is made of glass ingredients such as A glass, C glass, E glass, brings the viewpoint of bad influence to set out never for the heat endurance of thermoplastic resin, preferred especially E glass (alkali-free glass).The manufacture method of glass fibre for example, is adopted in the following method.At first, with the forming of glass of dissolving is the glass marble that is known as the prescribed level of hoodle (marble), in the fiber drawing furnace that is known as propelling movement type (pushing), make its thermoplastic, a plurality of nozzles from this table flow down it, when this matrix material is at full speed extended, coat size (sizing material) by dipping in the size applying device in being arranged on its way and make it boundling, dry then, in rotary drum (rotating drum), twine.The nozzle diameter size of regulating this moment, hauling speed and traction atmosphere temperature etc. make the size of the average diameter of glass fibre for regulation.
When the fortifying fibre that constitutes formed body of the present invention was carbon fiber, from the viewpoint with the rerum natura balance lost of further raising carbon fiber, preferred diameter was 5 μ m～15 μ m.
The actual carbon fiber that uses is that the raw material sintering manufactures with acrylic fiber, oil or the special pitch of carbon class, cellulose fibre, lignin etc. generally, has fire-resistant, carbonaceous, graphite matter etc. various types of, is not restricted to specific type.
The good viewpoint of impact strength, fatigue properties, creep properties when having change in size that mechanical strength, oil resistivity, chemical proofing, hear resistance, durability, formability, suction cause, high temperature, as the particularly preferred example of thermoplastic resin that constitutes formed body of the present invention, be selected from the alloy of mylar, aromatic polycarbonate resin and these resins of polybutylene terephthalate (PBT), PETG etc., for example, the alloy of mylar/aromatic polycarbonate resin.And, as mylar, the reduction of the engineering properties that causes from losing of fortifying fibre and the viewpoint of hydrolytic resistance, mylar is, 30 ℃ of inherent viscosities of measuring in the mixed solution of 1 to 1 (weight ratio) of phenol and tetrachloroethanes are the polybutylene terephthalate (PBT) of 0.30dl/g～1.20dl/g, and the titanium amount, according to the weight basis of the titanium in the resin, be preferably below the 50ppm, more preferably below the 33ppm.If the inherent viscosity of polybutylene terephthalate (PBT) is discontented with 0.30dl/g, the mechanical performance of the basic resin (base resin) of the matrix (matrix) of formation long-fiber-reinforced resin will reduce, and can't satisfy the performance that strengthens the needed machinery of exterior formed article as long fibre.In addition, surpass 1.20dl/g if constitute the inherent viscosity of the polybutylene terephthalate (PBT) of formed body, the basic resin that constitutes the matrix of long-fiber-reinforced resin will become high viscosity, formability reduces, losing of forming process medium-length fibre becomes big, and mechanical strength takes place to be reduced, thereby not preferred.Moreover the intensity that causes for the hydrolysis of the polybutylene terephthalate (PBT) that suppresses to constitute long fiber material reduces, and preferred titanium amount is below the 33ppm.
As particularly preferred another example of thermoplastic resin that constitutes formed body of the present invention is polyamide.Polyamide is an excellent characteristic of utilizing hear resistance, toughness, oil resistivity, petrol-resistance, rub resistance, formability etc., is being the resin that uses in a lot of fields of representative with automotive field and electric and electronic field.Particularly at automotive field, effectively utilize its hear resistance, oil resistivity, having with the parts of engine periphery is a lot of actual use achievement of representative.
As polyamide, the various polymer and the copolymer that can use the polycondensation of polymerization (polycondensation) by omega-amino acid or its lactams and/or diamine and dicarboxylic acids to obtain.Specifically have, alpha-pyrrolidone, α-piperidones (α-piperidon), epsilon-caprolactams, aminocaproic acid, oenantholcatam (oenantholactam), the 7-aminoheptylic acid, the 8-aminocaprylic acid, 9 aminononanoic acid, the 11-aminoundecanoic acid, the polymer of 12 etc., by making hexamethylene diamine, nine methylene diamine, 11 methylene diamine, ten dimethylene diamines, the diamine and the terephthalic acid (TPA) of m-xylylenediamine (m-xylylenediamine) etc., M-phthalic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, polymer that the dicarboxylic acids polycondensation of dodecanedioic acid etc. obtains or their copolymer, for example, can enumerate polyamide 4, polyamide 6, polyamide 7, polyamide 8, polyamide 11, polyamide 12, polyamide 6-6, polyamide 6-9, polyamide 6-10, polyamide 6-11, polyamide 6-12, polyamide 6 T, copolymer polyamide 6/6-6, copolymer polyamide 6/12, copolymer polyamide 6/6T, copolymer polyamide 6 I/6T etc.Preferably can enumerate polyamide 6, polyamide 6-6 and copolymer polyamide 6/6-6, special preferred polyamide 6.In addition, the polyamide that also preferably obtains with the polycondensation reaction by aromatic diamine and aliphatic dicarboxylic acid is the aromatic polyamide resin of main component.As aromatic diamine, can enumerate p dimethylamine and m-xylene diamine etc., preferably use the mixing diamine of p dimethylamine and m-xylene diamine.Reason for exterior formed article material selection continuous fiber reinforcing polyamide resin of the present invention is, because compare with other fiber reinforced thermoplastic resins such as polyester, the continuous fiber reinforcing polyamide resin is the material with good mechanical strength, oil resistivity, chemical proofing, hear resistance, durability, formability, the impact strength when especially having excellent high-temperature, fatigue properties, creep properties.
In addition, constitute the polyamide of formed body of the present invention, preferred, have the degree of polymerization in the certain limit, promptly have the relative viscosity in the particular range.The value that preferred relative viscosity, polyamide 6 are measured in 23 ℃, 98% sulfuric acid, during concentration 1% is 1.5～2.5, and the value that aromatic polyamide is measured in 23 ℃, 96% sulfuric acid, during concentration 1% is 1.5～2.5, more preferably 1.7～2.4.When relative viscosity was discontented with 1.5, mechanical strength was low; When surpassing 2.5, the mobile reduction, long stapled losing becomes big during shaping, and mechanical strength takes place to be reduced, thereby not preferred.
And by the formed body of the present invention that polyamide constitutes, except above-mentioned feature, the maximum moisture absorption size changing rate that can also have the above formed body part of thickness 2mm is this feature below 0.3%.The change in size on the formed body surface that produces is handled in the suction of measuring in the optional position (many places) of the formed body more than thickness 2mm part when carrying out saturated suction for 50% time in 23 ℃ of temperature, relative humidity, calculate the moisture absorption size changing rate of following formula respectively by these measured values, confirm the maximum (maximum moisture absorption size changing rate) of these values of calculating, can easily judge whether to possess above-mentioned character thus.
[formula 1]
Moisture absorption size changing rate=[size before (size before suction back size-suction)/suction] * 100
The maximum of above-mentioned maximum moisture absorption size changing rate is greater than 0.3% o'clock, and there is the change in size that causes by suction and causes switch inconvenience, influence, the not good problem of streamlined appearance bringing with the coupling and the gap of circumferential component, thereby not preferred.By the way, in the above-mentioned prior art not about the record of moisture absorption change in size.
As the thermoplastic resin that constitutes formed body of the present invention, so long as can be shaped, just there is no particular limitation, except above-mentioned thermoplastic resin, for example, can also use olefine kind resins such as polyethylene, polypropylene, vinyl resins such as polyvinyl chloride, polystyrene, acrylonitrile/styrene/butadiene copolymers, polyacetal resin (polyacetal resin), polymethacrylate resin, polysulfone resin, polyphenylene oxide resin etc.These thermoplastic resins both can use separately, and use also can two or morely combine.
Formed body of the present invention by use fiber reinforced thermoplastic resin (A), or uses the mixture that cooperates recycled resin described later (B) to form in (A) as required to be shaped as moulding material.Its method can be enumerated, forming process about the general use of thermoplastic resin, be various forming processes such as injection molded, ejection compress moulding, hollow forming, extrusion molding, plate shaping, hot forming, rotary forming, laminating molding, drawing, but, viewpoint from the minimizing of the free degree of formed products outward appearance and design, manufacturing process preferably is shaped with the injection molded method.When fiber reinforced thermoplastic resin (A) is shaped, usually, in the cylinder of forming machine during melting mixing, when mould is filled, there is fortifying fibre to be broken, the danger that the length of fiber shortens, but, adjust the length of pellet (pellet), the shape of the cylinder inner wall of forming machine and the shape of screw rod, molding condition (for example, resin temperature during shaping, injection moulding speed), the mold shape etc. that comprises the aspect of above-mentioned narrow runner helps the weight average fiber length of the fortifying fibre that will disperse in the formed body of the present invention to remain in the scope of 1.5mm～10mm.In addition, lug boss (boss) and muscle (rib) structure etc. are set, also can access high rigidity, high-intensity front structure of vehicle body body.And, also can in muscle and lug boss, inject gas-pressurized.In addition, in order further to improve rigidity intensity, moving part is set in mould, to injecting gas-pressurized by the mobile capacity enlarged that causes of moving part, also can form hollow thus, form the high section configuration of section rigidity, to hollow bulb filling foaming body that forms and low-melting-point metal etc., also can strengthen, further improve rigidity intensity.
In addition, in the fiber reinforced thermoplastic resin (A) of the moulding material of formed body of the present invention, as required, can add other composition.As other composition, for example, can enumerate intermiscibility modifying agent, stabilizing agent, fire retardant, against weather modifying agent, blowing agent, lubricant, fluidity amendment, resistance to impact modifying agent, charged preventor, dyestuff, pigment, dispersant, inorganic strengthening agent, mould release, antioxidant, against weather modifying agent, basic soap, metallic soap, hydrotalcite, plasticizer, nucleator, dripping inhibitor etc.As shock-resistant modifying agent, can list, vistanexes such as polyethylene and polypropylene, alpha-olefin are that rubber, vinyl benzene rubber, acrylic rubber, silicon are rubber, MBS and core-shell polymer etc.As the concrete example of inorganic strengthening agent, can list glass fibre beyond the long fibre, carbon fiber, aromatic polyamide fibre, mica, talcum, wollastonite, potassium titanate, calcium carbonate, silica etc.
As the method for making of the fiber reinforced thermoplastic resin (A) of the moulding material of formed body of the present invention, preferred drawing.Drawing, basically be while drawing the method for continuous enhancing with the fibre bundle impregnating resin, known have: the method that fiber is passed through and flood in the dipping bath that is added with the emulsion of resin, suspension or solution, toner is sprayed on the fiber or with fiber by in the groove that powder is housed, the method that makes toner be attached to fiber, then the resin fusion be flooded, while making fiber pass through the method for supplying with molten resin and flooding to crosshead from extruder in the crosshead, any can utilize.As moulding material, preferred especially, Yi Bian fiber is passed through among the crosshead, Yi Bian supply with the molten thermoplastic resin to crosshead from extruder, after dipping, the cooling, be cut into length in 3.0～50mm, preferred length method at particle (pellet) shape of 4.0～30mm.Fortifying fibre in the pellet that obtains like this, since parallel substantially with pellet, so the length of the length pellet of fortifying fibre.The length of pellet is during less than 3.0mm, and the length of fortifying fibre shortens, and it is little to strengthen effect, and is opposite, when the length of pellet surpasses 50mm, have such situation, promptly bulk density becomes big, shaping adds interior bridging of hopper in man-hour, and the variation that is absorbed in to screw rod can't stably be shaped.
Use has cooperated recycled resin (B) in fiber reinforced thermoplastic resin (A) mixture is during as the moulding material of formed body of the present invention, and preferably its ratio of components is represented with the weight basis of this mixture, is in
(A): 30 weight %～100 weight %
(B): 0 weight %～70 weight %
Scope in.When fiber reinforced thermoplastic resin (A) was discontented with 30 weight %, it is big that the decline of its mechanical strength, dimensional stability, outward appearance etc. becomes, thereby not preferred.In addition, in order to prevent the classification phenomenon in the forming process, the shape of preferred fiber reinforced thermoplastic resin (A) and recycled resin (B) and size are approximate as far as possible.
As the moulding material of formed body of the present invention, the recycled resin (B) that cooperates with fiber reinforced thermoplastic resin (A), not special restriction from the intermiscibility aspect, can be used the recirculation goods of thermoplastic resin (A), but the combination that is preferably as follows.
When (1) thermoplastic resin of fiber reinforced thermoplastic resin (A) is the alloy of mylar, aromatic polycarbonate resin or these resins, if recycled resin (B) is a viscosity-average molecular weight at the recirculation product of 10000～17000 aromatic polycarbonate resin, just has good flowability, it is less that long stapled in the forming process lost, and eliminate because the shaping shrinkage rate that the alloying with crystalline resin causes and the reduction effect of linear expansion coefficient are well suited for the moulding material use as large-scale formed body.This situation as required, also can be used the intermiscibility modifying agent.
When (2) thermoplastic resin of fiber reinforced thermoplastic resin (A) is polyamide, if recycled resin (B) is the recirculation product that are selected from least a thermoplastic resin in polypropylene, polyethylene, polystyrene and the acrylonitrile styrene-butadiene-copolymer, just have good flowability, the moulding material that is well suited for using as large-scale formed body uses.This situation as required, can be used the intermiscibility modifying agent.
As this recycled resin (B), can enumerate, cleaning resin (purgeresin) during shaping, in the cast gate (sprue), in the running channel (runner), when being shaped, during secondary operations, the substandard products that produce of the in-process in when installation etc., be used for formed products that is recovered after the purpose purposes etc., from the recirculation product in each stage.Certainly, the shape of formed products is also unrestricted, specifically, also can use the recirculation product after outside plate, mechanism components and the pulverizing of other formed products of automobile, electric and electronic OA equipment etc.Yet, the formed products that the attachment of solvent, grease class etc. is many, owing to can become mechanical strength, heat endurance, outward appearance reduction, thereby not preferred.
In addition, the fitting method of recycled resin (B) and fiber reinforced thermoplastic resin (A), not special the qualification, can use known various hybrid machine, for example, Henschel mixer, ribbon mixer, V-type blender, extruder, banbury mixers, Laboplastomill mixing roll (Brabender mixer), kneader (kneader) etc.
In order to make formed body of the present invention become the automobile exterior formed article, consider the dimensional accuracy this point of requirement, be preferably hood (bonnet), roof (roof), hood (hood), panel (front panel), top (canopy), luggage-boot lid (trunk lid), door-plate (doorpanel), post (pillar) and and outer plate or its tectosomes adorned of these similar automobiles.
In the present invention, exterior formed article made of long fiber-reinforced thermoplastic resin, lamination its outer surface, have the bed thickness ratio of at least 1 layer of non-enhancing resin bed and the long fibre enhancement layer on the section vertical/non-enhancing resin bed to be preferably more than 1.0, more preferably more than 1.2 with this lamination face.If the bed thickness of long fibre enhancement layer/non-enhancing resin bed is than less than 1.0, when long fibre is enhanced to the shaping of body and/or because temperature environment changes, the bending that the line differential expansion because of long fibre enhancement layer and non-enhancing resin bed causes may take place.In addition, the non-enhancing resin that uses in above-mentioned lamination though not special restriction from the adhesiveness aspect, is preferably the resin of the same race with this fiber reinforced thermoplastic resin, perhaps is the alloy of main component with this resin.In addition, in above-mentioned lamination, also can be enhanced to and enclose the ornamental portion that comprises literal, symbol and/or mark between body and this non-enhancing resin bed at this long fibre.Such formed body as the automobile exterior formed article with good appearance characteristics and design, design durability, is useful.
In the present invention, as the outer surface lamination that is formed on exterior formed article made of long fiber-reinforced thermoplastic resin, the method of at least 1 layer of non-enhancing resin bed, can enumerate, for the general processing method of using of thermoplastic resin, promptly with for example non-enhancing resin molding of non-enhancing resin bed of at least 1 layer of injection molded while lamination or the method for plate, duplicate shaping, double-colored shaping, two shapings and hot plate are deposited, vibrate deposited, the deposited method of laser cladding etc., but outward appearance and design freedom from formed products, the viewpoint that manufacturing process reduces, the method for preferred especially and injection molded while this film of lamination and thin plate.
In the present invention, with injection molded simultaneously when this film of lamination or thin plate, the heat of the resin combination in order to promote with the fusion injection moulding fuses, and makes lamination integrated more reliable, also can implement bottom and be coated with (primer coating) on this film or thin plate.As the resin that is used for the bottom coating, select melt viscosity to be higher than thermoplastic resin that constitutes formed body and the resin that bonds well with this film or thin plate.For example, with this thermoplastic resin with kind and have the resin of HMW more or as the resin of main body, by heat or UV cured resin.
Formed body of the present invention, as required, can single face give be selected from hard conating, antifog, prevent charged, prevent the reflection and shield ultrared at least a functional layer, maybe can give the incrustation that forms by application or duplicate etc.In order to form functional layer, use the known the whole bag of tricks of prior art.For the formation of hard conating, can use following method, be provided with as required after the bottom, hard coating agents such as coating epoxy system, acrylic acid series, amino resins system, polysiloxane series, silica gel system, the method by heat or ultraviolet ray etc. makes it sclerosis again.For the formation of anti-fog layer, can use coating to contain water-soluble or hydrophilic resin and interfacial agent as anti-fog coating that must composition and the method that makes it to harden.In addition, charged layer, antireflection layer, the infrared ray shielding layer etc. of preventing also can have the coating of these functions and make it sclerosis and form by coating, or form the thin layer with these functions by the method for vacuum vapour deposition etc.In addition, also these functional layers can be formed composite bed, form the layer that possesses two or more functions simultaneously.And, except these functional layer, or on this functional layer, also can form and give the layer of design by implementing attractive in appearancely to handle the method that makes it to have design etc. in advance with application.
Embodiment
Below, with reference to accompanying drawing,, describe the present invention in detail, but the present invention is not limited to these scopes according to preferred embodiment.Among the following embodiment, short of other appointment, % refers to weight %.
[evaluation]
Estimate 1. fiber containing ratios, weight average fiber length
Downcut test film arbitrarily from the optional position of the exterior formed article made of long fiber-reinforced thermoplastic resin that is shaped, in 500 ℃ electric furnace, only burn behind the moldable resin composition, measure the weight and the length of remaining fiber, will be with respect to the ratio of weight of the test film before the burning as containing ratio, with the weighed average of fibre length as weight average fiber length.
Estimate 2. inherent viscosities, viscosity-average molecular weight
The sample that use is downcut arbitrarily from the optional position of the exterior formed article made of long fiber-reinforced thermoplastic resin of shaping, with regard to the polybutylene terephthalate (PBT) resin, represent with the inherent viscosity of under 30 ℃, in phenol and tetrachloroethanes weight ratio are 1: 1 mixed solvent, measuring.With regard to polycarbonate resin, based under 25 ℃, the value (dl/g of unit) of the inherent viscosity ([η]) in carrene, measured, obtain viscosity-average molecular weight (Mv).
Estimate 3. engineering properties
Optional position more than the thickness 2mm of the exterior formed article made of long fiber-reinforced thermoplastic resin that is shaped is downcut the rectangle test film of 80mm * 10mm arbitrarily, crooked elastic rate, bending strength are measured according to ISO 178, and card is finished notched Izod impact strength (Charpy notched impactstrength) and measured according to ISO 179.And, when implementing to measure, the quantity n=10 of test film.
Estimate 4. linear expansion coefficients
Optional position more than the thickness 2mm of the exterior formed article made of long fiber-reinforced thermoplastic resin that is shaped is downcut the rectangle test film of 30mm * 10mm arbitrarily, is determined at 23 ℃～80 ℃ the interior linear expansion coefficient of temperature range.And, measure according to the quantity n=10 enforcement of test film, and on each test film, mutually perpendicular both direction is implemented to measure, the max line coefficient of expansion divided by the minimum line coefficient of expansion, is calculated ratio.This ratio is more little, is evaluated as anisotropy and reduces more.
Estimate 5. maximum moisture absorption size changing rates
Saturated suction state to 23 ℃ of temperature, relative humidity 50% is handled in the continuous fiber reinforcing polyamide resin exterior formed article made suction that is shaped, shown in Fig. 5～8, use is illustrated in the mark of position at four angles that draw, at least 5 squares (length on one side is about 25～50mm), optional position on the surface of the above formed body part of the thickness 2mm of this formed body, measure the size in length and breadth of suction front and back, calculate the suction size changing rate (%) of following formula, represent with their maximum.
[formula 2]
Moisture absorption size changing rate=[size before (size before suction back size-suction)/suction] * 100
Moreover, in embodiment 10 and comparative example 12, carry out mark as shown in Figure 5 on the surface of the formed body that obtains, be used to calculate maximum moisture absorption size changing rate.
[embodiment 1]
The preparation of long glass fiber reinforced polyester resin granular material
Use and draw forming process, promptly, continuous glass fiber bundle (rove) is opened fine and traction on one side, in dipping former, pass through on one side, after making the molten resin dipping of supplying with dipping former, figuration, cooling are cut off, thereby produce the long glass fiber reinforced polyester resin granular material of fiber containing ratio 30%, length 10mm.As resin, will use after polybutylene terephthalate (PBT) resin (Mitsubishi's engineering plastics corporate system, ProductName NOVADURAN (ノ バ デ ュ ラ Application) 5008, inherent viscosity 0.85dl/g, the titanium amount 30ppm) fusion.In the pellet that obtains, glass fiber diameter 16 μ m have the length identical with pellet, are arranged in parallel on the length direction of pellet in fact.
The injection molded of exterior formed article
The toshiba machine system of use IS-150 injection molding machine, shaping thickness 3mm, 150mm * 150mm, maximal projection area 22500mm as shown in Figure 1
2The tabular exterior formed article.That is, supply with the long fibre reinforced polyester resin granular material of preparation as mentioned above in being heated to 270 ℃ the heating cylinder of injection molding machine, and carrying out plasticising, fusion is measured.And, when the metering pressure with injection molding machine applies the back pressure of 5MPa, implement plasticising, measurement.After the measurement, the resin injection mouth injection molding process by as shown in the figure is in the die cavity of mould.Be 2 seconds inject time, adds that 20 seconds the metering pressure according to injection molding machine is the packing pressure of 100MPa, after 25 seconds cool time, opens mould, takes out exterior formed article made of long fiber-reinforced thermoplastic resin, finishes shaping.The temperature of the mould of this moment is 70 ℃.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high rigidity sense.In addition, for the test film that cuts out from this formed body, the result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is estimated in expression in aftermentioned table-1.Engineering properties in the evaluation result is all very high, and the anisotropy that linear expansion coefficient, line expand is all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 2]
In embodiment 1, fiber reinforced thermoplastic resin pellet preparation time, fiber containing ratio 30% is replaced with 50%, in addition, strengthen exterior formed article with embodiment 1 long fibre that equally is shaped.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high rigidity sense.In addition, for the test film that cuts out from this formed body, the result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is estimated in expression in aftermentioned table-1.Engineering properties in the evaluation result is all very high, and the anisotropy that linear expansion coefficient, line expand is all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 3]
In embodiment 2, in the time of the injection molded of exterior formed article, with the tabular formed body shown in the accompanying drawing 1 replace with thickness 3mm, 150mm * 200mm shown in Figure 2, have a part of notch part, the maximal projection area is 27300mm
2, have a sectional area 90mm
2, the long 45mm of runner the exterior formed article of narrow runner, in addition, strengthen exterior formed article with embodiment 2 long fibre that equally is shaped.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is represented in aftermentioned table-1.Engineering properties in the evaluation result is all very high, and the anisotropy that linear expansion coefficient, line expand is all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 4]
In embodiment 2, in the time of the injection molded of exterior formed article, as moulding material, replace long fibre reinforced polyester resin granular material, and use identical long fibre reinforced polyester resin (A) pellet with respect to 80 weight % to cooperate the mixture (fiber containing ratio 40%) of aromatic polycarbonate resin (B) of the viscosity-average molecular weight 14000 of 20 weight %, this aromatic polycarbonate resin (B) is to separate design film and functional membrane from recording medium (CD) in the tepidarium of having added chemical treatments, and the recirculation product that its pulverizing is obtained.In addition, strengthen exterior formed article with embodiment 2 long fibre that equally is shaped.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high stiffness sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity, viscosity-average molecular weight is represented in aftermentioned table-1.Engineering properties in the evaluation result is all very high, and the anisotropy that linear expansion coefficient, line expand is all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 5]
In embodiment 2, when exterior formed article is injection molding, the size of the die cavity of mould is become thick 4mm, 150mm * 150mm, on two die cavity faces, load onto in advance the thin plate (Mitsubishi's engineering plastics corporate system, ProductName Iupilon Sheet (ュ one ピ ロ Application シ one ト) CFI-5) that the thick surface of 0.5mm that is shaped has the Merlon system of hard conating functional layer.In addition, similarly to Example 2, be formed in exterior formed article (the maximal projection area: 22500mm of the non-enhancing resin bed of two sides lamination of long-fiber-reinforced resin layer
2).The thickness ratio of the long-fiber-reinforced resin layer in the tabular exterior formed article of this lamination/non-enhancing resin bed is 3.Merlon sheeting, one side is a hard conating, another side is printed on cross mark, installs in the mode (enclosing tag) that hard conating is contacted with die face, is shaped.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with good surface smoothing and high stiffness sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is represented in aftermentioned table-1.Engineering properties in the evaluation result is all very high, and the anisotropy that linear expansion coefficient, line expand is all very little, can satisfy as the function of automobile with exterior formed article.
[table 1]
| Embodiment | |||||||
| 1 | 2 | 3 | 4 | 5 | |||
| Raw material | The resin kind | PBT | PBT | PBT | PBT/ recycles PC | PBT | |
| Inherent viscosity | [dl/g] | 0.85 | 0.85 | 0.85 | 0.85 | 0.85 | |
| Viscosity-average molecular weight | - | - | - | 14000 | - | ||
| GF | Containing ratio | [weight %] | 30.5 | 49.6 | 50.4 | 40.5 | 37.9 |
| Weight average fiber length | [mm] | 2.97 | 2.65 | 3 | 1.96 | 2.88 | |
| Diameter | [μm] | 16 | 16 | 16 | 16 | 16 | |
| Formed body | The maximal projection area | [mm 2] | 22500 | 22500 | 27300 | 22600 | 22500 |
| Inherent viscosity | [sl/g] | 1.10 | 1.15 | 1.12 | 1.16 | 1.10 | |
| Viscosity-average molecular weight | - | - | - | 13500 | - | ||
| Narrow runner | Sectional area | [mm 2] | - | - | 90 | - | - |
| Runner is long | [mm] | - | - | 45 | - | - | |
| Lamination | Enhancement layer/non-enhancement layer | - | - | - | - | 3 | |
| Crooked | Spring rate | [GPa] | 10.2 | 12.3 | 12.5 | 10.6 | 8.9 |
| Intensity | [MPa] | 230 | 250 | 242 | 200 | 196 | |
| Card is finished impact strength | [kJ/mm 2] | 28 | 42 | 39 | 35 | 48 | |
| Linear expansion coefficient | Maximum | [×10 -5K -1] | 4.8 | 4.6 | 4.2 | 4.4 | 4.7 |
| Minimum | [×10 -5K -1] | 4.1 | 3.4 | 3.5 | 3.2 | 3.6 | |
| Maximum/minimum is than (anisotropy) | 1.2 | 1.4 | 1.2 | 1.4 | 1.3 | ||
[comparative example 1]
In embodiment 1, in preparation long glass fiber reinforced polyester resin granular material, fiber containing ratio 30% is replaced with 15%, in addition similarly to Example 1, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, becomes the lower formed body of rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is represented in aftermentioned table-2.Though the result of the weight average fiber length of formed body for long 2.6mm arranged, but the engineering properties in the evaluation result is all lower, though the anisotropy of linear expansion coefficient (ratio of the max line coefficient of expansion/minimum line coefficient of expansion) is low to 1.5, the max line coefficient of expansion is greatly to 7.1 * 10
-5K
-1, do not satisfy as the function of automobile with exterior formed article.
[comparative example 2]
At embodiment 1, replace the preparation of long glass fiber reinforced polyester resin granular material, and the polybutylene terephthalate (PBT) (Mitsubishi's engineering plastics corporate system, trade name NOVADURAN (ノ バ デ ュ ラ Application) 5010G45, inherent viscosity 0.10dl/g) of use fiber containing ratio 30%.In addition, similarly to Example 1, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is represented in aftermentioned table-2, because the weight average fiber length of formed body is as short as 0.35mm, impact strength in the evaluation result is low, and the max line coefficient of expansion is 6.2 * 10
-5K
-1, anisotropy is 1.9, and is all very big, do not satisfy as the function of automobile with exterior formed article.
[comparative example 3]
In embodiment 2, in the time of the injection molded of exterior formed article, with the tabular formed body shown in the accompanying drawing 1 replace with thickness 3mm shown in Figure 3 (a part of 4mm), 150mm * 200mm, have a part of notch part, maximal projection area 20400mm
2, and have sectional area 40mm
2, the long 160mm of runner the exterior formed article of narrow runner, same with embodiment 2 in addition, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high stiffness sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is represented in aftermentioned table-2.The max line coefficient of expansion in the evaluation result is 5.6 * 10
-5K
-1, anisotropy is 2.7, and is all very big, do not satisfy as the function of automobile with exterior formed article.
[comparative example 4]
In embodiment 2, in the time of the injection molded of exterior formed article, with the tabular formed body shown in the accompanying drawing 1 replace with thickness 3mm, 150mm * 200mm shown in Figure 4, have a part of notch part, maximal projection area 20400mm
2, and have sectional area 90mm
2, the long 160mm of runner the exterior formed article of narrow runner, same with embodiment 2 in addition, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, relative viscosity is represented in aftermentioned table-2.The max line coefficient of expansion in the evaluation result is 6.4 * 10
-5K
-1, anisotropy is 3.4, and is all bigger, do not satisfy as the function of automobile with exterior formed article.
[comparative example 5]
In embodiment 2, when carrying out the preparation of long glass fiber reinforced polyester resin granular material, use polybutylene terephthalate (PBT) (Mitsubishi's engineering plastics corporate system, trade name NOVADURAN (ノ バ デ ュ ラ Application) 5020, inherent viscosity 1.20dl/g) replaces polybutylene terephthalate (PBT) (Mitsubishi's engineering plastics corporate system, trade name NOVADURAN (ノ バ デ ュ ラ Application) 5008, inherent viscosity 0.85dl/g, titanium amount 30ppm), in addition, the long fibre that is shaped similarly to Example 2 strengthens exterior formed article.
The long fibre that obtains like this is enhanced to body, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is represented in aftermentioned table-2, because the weight average fiber length of formed body is as short as 0.94mm, thereby the impact strength in the evaluation result is low, and the max line coefficient of expansion is greatly to 5.2 * 10
-5K
-1, do not satisfy as the function of automobile with exterior formed article.
[comparative example 6]
In embodiment 5, when exterior formed article is injection molding, on two die cavity faces of mould, load onto the thin plate that the thick surface of 1.1mm has the Merlon system of hard conating functional layer, replace the thick surface of 0.5mm to have thin plate (Mitsubishi's engineering plastics corporate system of the Merlon system of hard conating functional layer, ProductName Iupilon Sheet (ュ one ピ ロ Application シ one ト) CFI-5), in addition, similarly to Example 5, shaping exterior formed article, this exterior formed article lamination on the two sides of long-fiber-reinforced resin layer has non-enhancing resin bed.Thickness ratio in the tabular exterior formed article of this lamination, long-fiber-reinforced resin layer/non-enhancing resin bed is 0.82.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with good surface flatness.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, inherent viscosity is represented in aftermentioned table-2.Impact strength height in the evaluation result, but the engineering properties of rigidity, intensity etc. is all very low, and also the maximum and the minimum of a value of linear expansion coefficient are 5 * 10
-5K
-1More than, can't satisfy as the function of automobile with exterior formed article.
[table 2]
| Comparative example | ||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | |||
| Raw material | The resin kind | PBT | PBT | PBT | PBT | PBT | PBT | |
| Inherent viscosity | [dl/g] | 0.85 | 0.85 | 0.85 | 0.85 | 1.20 | 0.85 | |
| GF | Containing ratio | [weight %] | 15.4 | 45.6 | 50.3 | 50.2 | 49.9 | 24.7 |
| Weight average fiber length | [mm] | 2.64 | 0.35 | 2.65 | 2.39 | 0.94 | 2.44 | |
| Diameter | [μm] | 16 | 16 | 16 | 16 | 16 | 16 | |
| Formed body | The maximal projection area | [mm 2] | 22500 | 22500 | 20400 | 20400 | 22500 | 22500 |
| Inherent viscosity | [dl/g] | 1.10 | 0.85 | 1.13 | 1.08 | 1.56 | 1.09 | |
| Narrow runner | Sectional area | [mm 2] | - | - | 40 | 90 | - | - |
| Runner is long | [mm] | - | - | 160 | 160 | - | - | |
| Lamination | Enhancement layer/non-enhancement layer | - | - | - | - | - | 0.82 | |
| Crooked | Spring rate | [GPa] | 5.7 | 12.9 | 12.4 | 12.4 | 12.8 | 5.2 |
| Intensity | [MPa] | 143 | 238 | 246 | 251 | 245 | 196 | |
| Card is finished impact strength | [kJ/mm 2] | 13 | 10 | 40 | 42 | 12 | 60 | |
| Linear expansion coefficient | Maximum | [×10 -5K -1] | 7.1 | 6.2 | 5.6 | 6.4 | 6.2 | 6 |
| Minimum | [×10 -5K -1] | 4.9 | 3.3 | 2.1 | 1.9 | 2.9 | 5.2 | |
| Maximum/minimum is than (anisotropy) | 1.5 | 1.9 | 2.7 | 3.4 | 1.8 | 1.2 | ||
[embodiment 6]
The preparation of long glass fiber reinforced polyamide resin granular material
Use and draw forming process, promptly, continuous glass fiber bundle (rove) is opened fine and traction on one side, pass through dipping former on one side, make after the infiltration of dipping former molten resin supplied, figuration, cooling are cut off, thereby produce fiber containing ratio 30%, the glass fiber reinforced polyamide pellet of length 10mm.As resin, will use after polyamide 6 (Mitsubishi's engineering plastics corporate system, ProductName NOVAMID (ノ バ ミ Star De) 1007J, the relative viscosity 2.2) fusion.In the pellet that obtains, glass fiber diameter 16 μ m have the length identical with pellet, are arranged in parallel on the length direction of pellet in fact.
The injection molded of exterior formed article
The IS-150 injection molding machine of the toshiba machine system of use, shaping thickness 3mm, 150mm * 150mm, maximal projection area 22500mm as shown in Figure 5
2The tabular exterior formed article.That is, supply with the continuous fiber reinforcing polyamide resin granular material of preparation as mentioned above in being heated to 270 ℃ the heating cylinder of injection molding machine, carry out plasticising, fusion is measured.And, when pressing the back pressure that applies 5MPa, implement plasticising, measurement with the metering of injection molding machine.After the measurement, the resin injection mouth injection molding process by as shown in the figure is in the chamber of mould.Be 2 seconds inject time, adds the packing pressure of 20 seconds 100MPa with the metering pressure of injection molding machine, after 25 seconds cool time, opens mould, takes out continuous fiber reinforcing polyamide resin exterior formed article made, finishes shaping.In addition, Ci Shi mold temperature is 70 ℃.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table-3.Engineering properties in the evaluation result is all very high, and anisotropy, moisture absorption change in size that linear expansion coefficient, line expand are all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 7]
In embodiment 6, continuous fiber reinforcing polyamide resin granular material preparation time, fiber containing ratio 30% is replaced with 50%, strengthen exterior formed article with embodiment 6 long fibre that equally is shaped.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table-3.Engineering properties in the evaluation result is all very high, and anisotropy, moisture absorption size changing rate that linear expansion coefficient, line expand are all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 8]
In embodiment 7, in the time of the preparation of continuous fiber reinforcing polyamide resin granular material, use aromatic polyamide (Mitsubishi's engineering plastics corporate system, ProductName Reny (レ ニ one) 6002, relative viscosity 2.1 abbreviates MXD6-PA as) to replace polyamide 6; During injection molded, the heating cylinder temperature of injection molding machine replaces 270 ℃ with 280 ℃, and the temperature of mould replaces 70 ℃ with 135 ℃; In addition, the same with embodiment 7, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate is represented in aftermentioned table-3.Engineering properties in the evaluation result is all very high, and anisotropy, moisture absorption size changing rate that linear expansion coefficient, line expand are all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 9]
In embodiment 7, in the time of the injection molded of exterior formed article, with the tabular formed body shown in the accompanying drawing 5 replace with thickness 3mm, 150mm * 200mm shown in Figure 6, have a part of notch part, maximal projection area 27300mm
2, and have sectional area 90mm
2, the long 45mm of runner the exterior formed article of narrow runner, the same with embodiment 7 in addition, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the tectosome with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table-3.Engineering properties in the evaluation result is all very high, and anisotropy, moisture absorption size changing rate that linear expansion coefficient, line expand are all very little, can satisfy as the function of automobile with exterior formed article.
[embodiment 10]
In embodiment 7, when exterior formed article is injection molding, the size of mould cavity is become thick 4mm, 150mm * 150mm, on two die cavity faces, load onto in advance the film of the thick polyamide 6 system of the 0.5mm that is shaped, in addition, similarly to Example 7, the two sides lamination that is formed in the long-fiber-reinforced resin layer has exterior formed article (the maximal projection area: 22500mm of non-enhancing resin bed
2).The thickness ratio of the long-fiber-reinforced resin layer in the tabular exterior formed article of this lamination/non-enhancing resin bed is 3.Be used to estimate the cross mark of position skew etc. in the one side of polyamide 6 made membrane by the silk screen print method printing, be shaped with the form of enclosing printing surface.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with good surface smoothing and high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table-3.Engineering properties in the evaluation result is all very high, and anisotropy, moisture absorption size changing rate that linear expansion coefficient, line expand are all very little, can satisfy as the function of automobile with exterior formed article.
[table 3]
| Embodiment | |||||||
| 6 | 7 | 8 | 9 | 10 | |||
| Resin | PA6 | PA6 | MXD6 -PA | PA6 | PA6 | ||
| GF | Containing ratio | [weight %] | 30.2 | 50.3 | 50.1 | 49.8 | 40.5 |
| Weight average fiber length | [mm] | 2.99 | 2.78 | 2.58 | 2.23 | 2.65 | |
| Diameter | [μm] | 16 | 16 | 16 | 16 | 16 | |
| Formed body | The maximal projection area | [mm 2] | 22500 | 22500 | 22500 | 27300 | 22500 |
| Inherent viscosity | [dl/g] | 2.2 | 2.2 | 2.1 | 2.2 | 2.2 | |
| Narrow runner | Sectional area | [mm 2] | - | - | - | 90 | - |
| Runner is long | [mm] | - | - | - | 45 | - | |
| Lamination | Enhancement layer/non-enhancement layer | - | - | - | - | 3 | |
| Crooked | Spring rate | [GPa] | 6.9 | 12.5 | 15.1 | 12.9 | 11.8 |
| Intensity | [MPa] | 239 | 265 | 318 | 270 | 240 | |
| Card is finished impact strength | [kJ/mm 2] | 24 | 31 | 29 | 34 | 26 | |
| Linear expansion coefficient | Maximum | [×10 -5K -1] | 4.8 | 4.2 | 3.0 | 4.8 | 4.6 |
| Minimum | [×10 -5K -1] | 3.3 | 3.3 | 2.4 | 3.0 | 3.0 | |
| Maximum/minimum is than (anisotropy) | 1.5 | 1.3 | 1.3 | 1.6 | 1.5 | ||
| Maximum moisture absorption size changing rate | [％] | 0.22 | 0.16 | 0.11 | 0.28 | 0.26 | |
[comparative example 7]
In embodiment 6, in the time of preparation long glass fiber reinforced polyamide resin granular material, fiber containing ratio 30% is replaced with 10%, in addition similarly to Example 6, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the lower formed body of rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, relative viscosity is represented in aftermentioned table-4.The result is that the weight average fiber length of formed body reaches 2.8mm, but the engineering properties in the evaluation result is all lower, and the max line coefficient of expansion is 7.0 * 10
-5K
-1, anisotropy (the max line coefficient of expansion/minimum line coefficient of expansion) has increased to 1.9, and maximum moisture absorption size changing rate is to 0.65%, and is all very big, do not satisfy as the function of automobile with exterior formed article.
[comparative example 8]
In embodiment 6, replace preparation long glass fiber reinforced polyamide resin granular material, and polyamide 6 (Mitsubishi's engineering plastics corporate system of use fiber containing ratio 30%, trade name NOVAMID (ノ バ ミ Star De) 1013GH30), in addition, similarly to Example 6, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, relative viscosity is represented in aftermentioned table-4, because the weight average fiber length of formed body is as short as 0.41mm, impact strength in the evaluation result is low, and the max line coefficient of expansion is 7.1 * 10
-5K
-1, anisotropy is 2.2, maximum moisture absorption size changing rate is 0.32%, and is all bigger, do not satisfy as the function of automobile with exterior formed article.
[comparative example 9]
In embodiment 7, in the time of the injection molded of exterior formed article, with the tabular formed body shown in the accompanying drawing 5 replace with thickness 3mm, 150mm * 200mm shown in Figure 7, have a part of notch part, maximal projection area 23600mm
2, and have sectional area 100mm
2, the long 160mm of runner the exterior formed article of narrow runner, same with embodiment 7 in addition, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table 4.The max line coefficient of expansion in the evaluation result is 6.0 * 10
-5K
-1, anisotropy is 2.3, maximum moisture absorption size changing rate is 0.36%, and is all bigger, do not satisfy as the function of automobile with exterior formed article.
[comparative example 10]
In embodiment 7, in the time of the injection molded of exterior formed article, with the tabular formed body shown in the accompanying drawing 5 replace with thickness 3mm, 150mm * 200mm shown in Figure 8, have a part of notch part, the maximal projection area is 20400mm
2, and have sectional area 90mm
2, the long 160mm of runner the exterior formed article of narrow runner, same with embodiment 7 in addition, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table-4.The max line coefficient of expansion in the evaluation result is 6.5 * 10
-5K
-1, anisotropy is 3.0, maximum moisture absorption size changing rate is 0.41%, and is all bigger, do not satisfy as the function of automobile with exterior formed article.
[comparative example 11]
In embodiment 7, when carrying out the preparation of long glass fiber reinforced polyamide resin granular material, use polyamide 6 (Mitsubishi's engineering plastics corporate system, ProductName NOVAMID (ノ バ ミ Star De) 1030J, relative viscosity 4.5) replacement polyamide 6 (Mitsubishi's engineering plastics corporate system, ProductName NOVAMID (ノ バ ミ Star De) 1007J, relative viscosity 2.2), in addition, similarly to Example 7, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table-4, because the weight average fiber length of formed body is as short as 0.91mm, thereby the impact strength in the evaluation result is low, and the max line coefficient of expansion has reached 6.5 * 10
-5K
-1, anisotropy to 2.0, maximum moisture absorption size changing rate is to 0.32%, and is all bigger, do not satisfy as the function of automobile with exterior formed article.
[comparative example 12]
In embodiment 10, when exterior formed article is injection molding, on two die cavity faces of mould, load onto the thick polyamide 6 film of 1.1mm, replace the thick polyamide 6 film of 0.5mm.In addition, similarly to Example 10, shaping exterior formed article, this exterior formed article lamination on the two sides of long-fiber-reinforced resin layer has non-enhancing resin bed.The thickness ratio of the long-fiber-reinforced resin layer in the tabular exterior formed article of this lamination/non-enhancing resin bed is 0.82.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with good surface flatness.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, moisture absorption size changing rate, relative viscosity is represented in aftermentioned table-4.Engineering properties such as the rigidity in the evaluation result, intensity are all very low, and linear expansion coefficient is to 7.0 * 10
-5K
-1, anisotropy to 2.1, maximum moisture absorption size changing rate is to 0.37%, and is all very big, can't satisfy as the function of automobile with exterior formed article.
[comparative example 13]
In comparative example 8, use aromatic polyamide (gas chemical company of the Mitsubishi system of fiber containing ratio 50%, trade name MX nylon S6121, relative viscosity 3.65, abbreviation MX) polyamide 6 (Mitsubishi's engineering plastics corporate system, trade name NOVAMID (ノ バ ミ Star De) 1030GH30) of replacement fiber containing ratio 30%, in addition, same with comparative example 8, the shaping long fibre strengthens exterior formed article.
The long fibre that obtains like this strengthens exterior formed article, is the formed body with high rigidity sense.In addition, for the test film that cuts out from this formed body, the evaluation result of fiber containing ratio, weight average fiber length, engineering properties, linear expansion coefficient, relative viscosity is represented in aftermentioned table-4, because the weight average fiber length of formed body is as short as 0.55mm, thereby the impact strength in the evaluation result significantly reduces, and do not satisfy as the function of automobile with exterior formed article.
[table 4]
| Comparative example | |||||||||
| 7 | 8 | 9 | 10 | 11 | 12 | 13 | |||
| Raw material | The resin kind | PA6 | PA6 | PA6 | PA6 | PA6 | PA6 | MX | |
| GF | Containing ratio | [weight %] | 10.6 | 29.8 | 49.7 | 50.4 | 50.1 | 25.3 | 49.5 |
| Weight average fiber length | [mm] | 2.76 | 0.41 | 2.32 | 2.41 | 0.91 | 2.22 | 0.55 | |
| Diameter | [μm] | 16 | 16 | 16 | 16 | 16 | 16 | 16 | |
| Formed body | The maximal projection area | [mm 2] | 22500 | 22500 | 20400 | 20400 | 22500 | 22500 | 22500 |
| Inherent viscosity | [dl/g] | 2.2 | 2.2 | 2.2 | 2.2 | 4.5 | 2.2 | 3.65 | |
| Narrow runner | Sectional area | [mm 2] | - | - | 100 | 90 | - | - | - |
| Runner is long | [mm] | - | - | 160 | 160 | - | - | - | |
| Lamination | Enhancement layer/non-enhancement layer | - | - | - | - | - | 0.82 | - | |
| Crooked | Spring rate | [GPa] | 2.6 | 7.2 | 12.6 | 12.3 | 12.2 | 6.2 | 15.6 |
| Intensity | [MPa] | 102 | 250 | 260 | 270 | 250 | 231 | 320 | |
| Card is finished impact strength | [kJ/mm 2] | 10 | 10 | 33 | 30 | 16 | 10 | 7 | |
| Linear expansion coefficient | Maximum | [×10 -5K -1] | 7.0 | 7.1 | 6.0 | 6.5 | 6.5 | 7.0 | 4.2 |
| Minimum | [×10 -5K -1] | 3.7 | 3.3 | 2.6 | 2.2 | 3.2 | 3.3 | 2.8 | |
| Maximum/minimum is than (anisotropy) | 1.9 | 2.2 | 2.3 | 3.0 | 2.0 | 2.1 | 1.5 | ||
| Maximum moisture absorption size changing rate | [％] | 0.65 | 0.32 | 0.36 | 0.41 | 0.32 | 0.37 | 0.12 | |
Claims (16)
1. exterior formed article made of long fiber-reinforced thermoplastic resin is characterized in that:
The containing ratio that is dispersed in the fortifying fibre in the formed body is 30 weight %～90 weight %, and the weight average fiber length that is dispersed in the fortifying fibre in the formed body is 1.5mm～10mm, and the maximal projection area of formed body is 20000mm
2More than, sectional area 100mm during shaping
2The runner of following narrow runner is long for below the 150mm, and the max line coefficient of expansion of the formed body part that thickness 2mm is above is 5 * 10
-5K
-1Below, and the ratio of the max line coefficient of expansion/minimum line coefficient of expansion of the part of the formed body more than the thickness 2mm is below 1.8.
2. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 1 is characterized in that:
Thermoplastic resin is to be selected from the alloy of mylar, aromatic polycarbonate resin, these resins and the resin of polyamide.
3. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 1 is characterized in that:
Thermoplastic resin is a polyamide, and the above formed body maximum moisture absorption size changing rate partly of thickness 2mm is below 0.3%.
4. fiber reinforced thermoplastic resin as claimed in claim 2 is made body, it is characterized in that:
Thermoplastic resin is the polybutylene terephthalate (PBT) resin, the inherent viscosity that this polybutylene terephthalate (PBT) resin is measured in 1 to 1 (weight ratio) mixed liquor of 30 ℃ of phenol and tetrachloroethanes is 0.30dl/g～1.20dl/g, and the titanium amount is below the 33ppm.
5. as claim 2 or 3 described continuous fiber reinforcing polyamide resin exterior formed article mades, it is characterized in that:
Polyamide is that to measure the relative viscosity that obtains with concentration 1% in 23 ℃, 98% sulfuric acid be 1.5～2.5 polyamide 6.
6. as claim 2 or 3 described continuous fiber reinforcing polyamide resin exterior formed article mades, it is characterized in that:
Polyamide is that to measure the relative viscosity that obtains with concentration 1% in 23 ℃, 96% sulfuric acid be 1.5～2.5 aromatic polyamide.
7. as claim 2 or 3 described continuous fiber reinforcing polyamide resin exterior formed article mades, it is characterized in that:
Polyamide is to be the aromatic polyamide resin of main component with the polyamide that the polycondensation reaction by aromatic diamine and aliphatic dicarboxylic acid obtains.
8. as each described exterior formed article made of long fiber-reinforced thermoplastic resin of claim 1～7, it is characterized in that:
Use has cooperated mixture that recycled resin (B) forms as moulding material in fiber reinforced thermoplastic resin (A), its ratio of components, according to the weight basis of this mixture, in following scope:
(A): 30 weight %～100 weight %;
(B): 0 weight %～70 weight %.
9. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 8 is characterized in that:
The thermoplastic resin of fiber reinforced thermoplastic resin (A) is the alloy of mylar, aromatic polycarbonate resin or these resins, and recycled resin (B) is the recirculation product of the aromatic polycarbonate resin of viscosity-average molecular weight 10000～17000.
10. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 8 is characterized in that:
The thermoplastic resin of fiber reinforced thermoplastic resin (A) is a polyamide, and recycled resin (B) is the recirculation product that are selected from least a thermoplastic resin in polypropylene, polyethylene, polystyrene and the acrylonitrile styrene-butadiene-copolymer.
11. each the described exterior formed article made of long fiber-reinforced thermoplastic resin as claim 1～10 is characterized in that:
Fortifying fibre is the glass fibre of diameter 10 μ m～20 μ m.
12. each the described exterior formed article made of long fiber-reinforced thermoplastic resin as claim 1～11 is characterized in that:
Formed body is the formed body that obtains by injection molded.
13. each the described exterior formed article made of long fiber-reinforced thermoplastic resin as claim 1～12 is characterized in that:
As be selected from hood (bonnet), roof (roof), hood (hood), panel (front panel), top (canopy), luggage-boot lid (trunk lid), door-plate (doorpanel), post (pillar), with these similar automobiles with any the automobile exterior formed article in outer dress plate and the tectosome thereof.
14. exterior formed article made of long fiber-reinforced thermoplastic resin as claimed in claim 13 is characterized in that:
Have the non-enhancing resin bed of lamination one deck at least on the outer surface, and the bed thickness ratio of the long fibre enhancement layer on the cross section vertical with this lamination face/non-enhancing resin bed is more than 1.0.
15. automobile exterior formed article as claimed in claim 14 is characterized in that:
Non-enhancing resin is and the congener resin of this fiber reinforced thermoplastic resin, or is the alloy of main component with this resin.
16., it is characterized in that as claim 14 or 15 described automobile exterior formed articles:
When lamination, being enhanced between body and this non-enhancing resin bed to enclose at this long fibre has the ornamental portion that comprises literal, symbol and/or mark.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004267154A JP4439361B2 (en) | 2004-09-14 | 2004-09-14 | Long fiber reinforced thermoplastic resin exterior molding |
| JP267155/2004 | 2004-09-14 | ||
| JP267154/2004 | 2004-09-14 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910171775 Division CN101665121B (en) | 2004-09-14 | 2005-09-07 | Exterior formed article made of long fiber-reinforced thermoplastic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101018656A true CN101018656A (en) | 2007-08-15 |
| CN100592976C CN100592976C (en) | 2010-03-03 |
Family
ID=36161173
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200580030534A Active CN100592976C (en) | 2004-09-14 | 2005-09-07 | Exterior molding body comprising a long fiber reinforced thermoplastic resin |
| CN 200910171775 Active CN101665121B (en) | 2004-09-14 | 2005-09-07 | Exterior formed article made of long fiber-reinforced thermoplastic resin |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910171775 Active CN101665121B (en) | 2004-09-14 | 2005-09-07 | Exterior formed article made of long fiber-reinforced thermoplastic resin |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4439361B2 (en) |
| CN (2) | CN100592976C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452147A (en) * | 2010-10-22 | 2012-05-16 | 住友化学株式会社 | Process for producing resin molded article |
| CN109228408A (en) * | 2013-01-21 | 2019-01-18 | 株式会社日本制钢所 | Method for producing fiber-reinforced resin base material or resin molded article, and plasticizing ejector used in the production method |
| CN112453401A (en) * | 2020-12-04 | 2021-03-09 | 西安交通大学 | Method for reducing anisotropy of rare earth molybdenum alloy material |
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| JP2006083227A (en) * | 2004-09-14 | 2006-03-30 | Mitsubishi Engineering Plastics Corp | Exterior molded article made of long fiber reinforced polyamide resin |
| JP2008095066A (en) * | 2006-05-25 | 2008-04-24 | Mitsubishi Engineering Plastics Corp | Molded article from fiber-reinforced thermoplastic resin |
| WO2007138966A1 (en) | 2006-05-25 | 2007-12-06 | Mitsubishi Engineering-Plastics Corporation | Moldings of fiber-reinforced thermoplastic resin |
| JP2008202013A (en) | 2007-02-23 | 2008-09-04 | Daicel Polymer Ltd | Automotive exterior resin part |
| JP4978234B2 (en) * | 2007-02-23 | 2012-07-18 | 豊田合成株式会社 | Manufacturing method of resin exterior products for automobiles |
| EP2639037A4 (en) | 2010-11-08 | 2016-02-17 | Mitsubishi Heavy Ind Plastic Technology Co Ltd | Resin molded product for vehicle structural member or aircraft structural member |
| JP2012148443A (en) * | 2011-01-18 | 2012-08-09 | Toyota Motor Corp | Fiber-reinforced resin material of structure with rib, and method for manufacturing the same |
| JP2012206721A (en) * | 2012-07-17 | 2012-10-25 | Mitsubishi Engineering Plastics Corp | Panel structure having window |
| JP6176532B2 (en) * | 2012-09-06 | 2017-08-09 | 東レ株式会社 | Shock absorbing member |
| JP5738374B2 (en) * | 2013-09-27 | 2015-06-24 | 住友理工株式会社 | Glass fiber reinforced thermoplastic resin molded article and method for producing the same |
| WO2015072373A1 (en) * | 2013-11-18 | 2015-05-21 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing resin molded article |
| CN104494162B (en) * | 2014-12-11 | 2017-06-16 | 厦门传晟德新材料科技有限公司 | Continuous fiber once strengthens environment-protecting thermoplastic resin composite materials product processes |
| JP6875271B2 (en) * | 2015-04-16 | 2021-05-19 | 三菱瓦斯化学株式会社 | Method for manufacturing a molded product by press molding a thermoplastic resin sheet or film |
| JP6567866B2 (en) * | 2015-05-14 | 2019-08-28 | 三菱エンジニアリングプラスチックス株式会社 | Laser welding resin composition and welded body thereof |
| KR101794844B1 (en) * | 2016-01-05 | 2017-11-08 | 현대자동차주식회사 | Carbon Fiber Reinforced Plastic Roof-Panel |
| CN106828612B (en) * | 2016-12-29 | 2019-09-06 | 重庆理工大学 | The electric car bonnet of integrated injection molding forming |
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| US5213889B1 (en) * | 1981-01-21 | 1996-10-29 | Kawasaki Chem Holding | Fibre-reinforced compositions and methods for producing such compositions |
| JPH06143331A (en) * | 1992-11-12 | 1994-05-24 | Mitsubishi Gas Chem Co Inc | Synthetic resin molded article and manufacture thereof |
| JPH08132478A (en) * | 1994-11-04 | 1996-05-28 | Aisin Seiki Co Ltd | Resin exterior product |
| JP2002105343A (en) * | 2000-10-03 | 2002-04-10 | Mitsubishi Engineering Plastics Corp | Thermoplastic resin composition, method for producing the same and automobile molded product for automobile |
| JP2002326331A (en) * | 2001-02-19 | 2002-11-12 | Teijin Chem Ltd | Synthetic resin molding suitable for sheathing material of vehicle and sheet-like molding for insert molding |
| JP2002240566A (en) * | 2001-02-21 | 2002-08-28 | Nissan Motor Co Ltd | Resin panel for vehicle and manufacturing method for the same |
| DE10143564A1 (en) * | 2001-09-05 | 2003-03-20 | Basf Ag | Composite hollow profile product for vehicle body construction comprises a ribbed component connected to a plastic layer injected onto the rear side of a film layer |
| JP2004209773A (en) * | 2002-12-27 | 2004-07-29 | Daicel Degussa Ltd | Composite molded article and its production method |
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2004
- 2004-09-14 JP JP2004267154A patent/JP4439361B2/en not_active Expired - Lifetime
-
2005
- 2005-09-07 CN CN200580030534A patent/CN100592976C/en active Active
- 2005-09-07 CN CN 200910171775 patent/CN101665121B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452147A (en) * | 2010-10-22 | 2012-05-16 | 住友化学株式会社 | Process for producing resin molded article |
| CN109228408A (en) * | 2013-01-21 | 2019-01-18 | 株式会社日本制钢所 | Method for producing fiber-reinforced resin base material or resin molded article, and plasticizing ejector used in the production method |
| CN109228408B (en) * | 2013-01-21 | 2021-04-16 | 株式会社日本制钢所 | Method for producing fiber-reinforced resin base material or resin molded article, and plasticizing ejector used in the production method |
| CN112453401A (en) * | 2020-12-04 | 2021-03-09 | 西安交通大学 | Method for reducing anisotropy of rare earth molybdenum alloy material |
| CN112453401B (en) * | 2020-12-04 | 2021-12-28 | 西安交通大学 | Method for reducing anisotropy of rare earth molybdenum alloy material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006082275A (en) | 2006-03-30 |
| CN101665121A (en) | 2010-03-10 |
| CN101665121B (en) | 2013-08-07 |
| JP4439361B2 (en) | 2010-03-24 |
| CN100592976C (en) | 2010-03-03 |
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Effective date of registration: 20231219 Address after: Tokyo, Japan Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Tokyo, Japan Patentee before: MITSUBISHI ENGINEERING-PLASTICS Corp. |