CN1644366A - Embedded shaping articles - Google Patents
Embedded shaping articles Download PDFInfo
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- CN1644366A CN1644366A CNA2004101038040A CN200410103804A CN1644366A CN 1644366 A CN1644366 A CN 1644366A CN A2004101038040 A CNA2004101038040 A CN A2004101038040A CN 200410103804 A CN200410103804 A CN 200410103804A CN 1644366 A CN1644366 A CN 1644366A
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- Prior art keywords
- resin
- embedded shaping
- shaping articles
- sectional shape
- embedded
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/04—Polysulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/0038—Moulds or cores; Details thereof or accessories therefor with sealing means or the like
- B29C33/0044—Moulds or cores; Details thereof or accessories therefor with sealing means or the like for sealing off parts of inserts projecting into the mould cavity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
- B29C43/3642—Bags, bleeder sheets or cauls for isostatic pressing
- B29C2043/3652—Elastic moulds or mould parts, e.g. cores or inserts
Abstract
The present invention provided an insert molded product excellent in high and low temperature impact characteristics and reduced in the occurring amount of a mold deposit at the time of molding. This insert molded product is constituted by the insert molding of a resin composition, which is obtained by compounding 5-200 pts.wt. of a fibrous reinforcing material (B) having a flat cross-sectional shape wherein the ratio of the long diameter (the longest straight line distance of a cross section) and short diameter (the longest straight line distance in the direction right-angled to the long diameter) of a cross section right-angled to a length direction is 1.3-10 and 1-25 pts.wt. of a thermoplastic elastomer (C) with 100 pts.wt. of a polyarylene sulfide resin (A), and a metal or an inorganic solid.
Description
Technical field
The present invention relates to specific resin combination and metal or inoganic solids are carried out that inserts is shaped and the embedded shaping articles that makes relates to the improved embedded shaping articles of high/low-temperature impact particularly.
Background technology
The inserts forming process is effectively to utilize the characteristic of the characteristic of resin and metal or inoganic solids (being designated hereinafter simply as metal etc.) base material to imbed the manufacturing process of metal etc. in resin, it all has application in wide spectrums such as automobile component or electric electronic element, OA machine part, nowadays be one of general forming process.
But, resin is very different with expansion or shrinkage factor (so-called linear expansion coefficient) that metal etc. is caused by variations in temperature, therefore the resin portion wall of formed products is thin, perhaps have the formed products of the big part of the variation of wall thickness and metal etc. and have the formed products of acute angle, ftractureing after just being shaped, perhaps the problem that ftractures because of variations in temperature in the use is more.Therefore, present situation shape of being purposes and formed products etc. is severely limited.And in automotive field, the resinification around the engine has also further developed recently, and embedded shaping articles also becomes important components.Particularly at the igniting associated components, dispenser part, various sensor elements, various transmission components, throttle member, the Power Component parts, the ECU parts, aspects such as various connector components, more research be to wrap up aluminium in poly (arylene sulfide) (Port リ ア リ-レ Application サ Le Off ア イ De) (hereinafter to be referred as PAS) resin of representative with polyphenylene sulfide (Port リ Off エ ニ レ Application サ Le Off ア イ De) (hereinafter to be referred as PPS) resin, copper, iron, brass, the metal parts of various alloys etc., the embedded shaping articles of metal terminal, but, the complex structure of the built in items of these embedded shaping articles, resin wall thickness change part is many, in addition, because the field of employment is near the engine room, therefore high and low temperature changes greatly, so, also high to the desired performance of embedded shaping articles.Therefore, consider above-mentioned factor, recently, tight demand can tolerate the resin that long high and low temperature changes, the i.e. resin of high/low-temperature impact characteristic good.
Pas resin is owing to have high hear resistance, mechanical properties, chemical proofing, dimensional stability, anti-flammability, therefore in electric and electronic component materials, automobile machine part material, chemical machine part material etc., used widely, but pas resin lacking toughness, crisp, the low shortcoming of reliability that exists the withstand prolonged high and low temperature of embedded shaping articles to change.
As the existing method that addresses this problem, having of knowing cooperates various elastomers.For example in Patent Document 1, proposed in the PPS resin to cooperate the scheme of olefin type elastomer, and in Patent Document 2, proposed and with the scheme of specific elastomer and filler.And, in Patent Document 3, proposed to cooperate 2 kinds of elastomeric schemes.In order to obtain desired high/low-temperature impact characteristic, realize by the use level that increases thermoplastic elastomer (TPE), but, because the treatment temperature of pas resin is more than 300 ℃, therefore thermoplastic elastomer (TPE) is easy to generate heat ageing under so high treatment temperature, the shortcoming that exists the metal die deposit when being shaped significantly to increase, thereby, in the method for above-mentioned patent documentation 1-3, all have problems.In patent documentation 4,, proposed and with the scheme of specific elastomer and silicone oil, still, the improvement of high/low-temperature impact characteristic is insufficient as the method that addresses this problem.
On the other hand, improvement under the shaping processing conditions is disclosed in Patent Document 5.This technology is effective method, and still, because form with the low-temperature metal mould, therefore, rerum natura, degree of crystallization in order to improve pas resin need Technology for Heating Processing after shaping, have the problem of process complications.
(patent documentation 1) spy opens flat 10-249876 communique
(patent documentation 2) spy opens the 2000-263586 communique
(patent documentation 3) spy opens the 2002-179914 communique
(patent documentation 4) spy opens the 2003-176410 communique
(patent documentation 5) spy opens the 2001-300977 communique
Summary of the invention
The object of the invention is to solve above-mentioned prior art problems, the pas resin embedded shaping articles that provides the high/low-temperature impact characteristic to obtain improveing.
In view of above-mentioned problem, the inventor concentrates on studies for the embedded shaping articles that obtains the high/low-temperature impact characteristic good, found that, based on pas resin, cooperated flat fibee reinforced dose and the composition of thermoplastic elastomer (TPE) with specific sectional shape to this pas resin, its mechanical properties does not have substantial degradation, and the high/low-temperature impact characteristic is (particularly thin at the resin wall, or metal etc. has under the situation of acute angle) significantly obtain improvement, metal die deposit generation during shaping is also few, thereby finishes the present invention.
Be that the present invention is a kind of embedded shaping articles, by being carried out embedded shaping, following resin combination and metal or inoganic solids obtain, described resin combination is with respect to (A) polyarylene sulfide resin 100 weight portions, cooperate (B) to have fibee reinforced dose 5～200 weight portion with the ratio cross sectional shape between 1.3～10, flat of the major diameter (air line distance that the cross section is the longest) in vertical vertical cross section and minor axis (perpendicular to the longest air line distance of the direction of major diameter), (C) thermoplastic elastomer (TPE) 1～25 weight portion.
The best mode that carries out an invention
Below, the constituent to resin material of the present invention is elaborated successively.The pas resin of (A) of the present invention as being used for composition is mainly to be made of repetitive-(Ar-S)-(wherein Ar is an arlydene).As arlydene, for example, can use p '-diphenylene sulfo group, p, p '-biphenylene, p, p '-diphenylene ether, p, p '-diphenylene carboxyl, naphthyl etc. to phenylene, metaphenylene, adjacent phenylene, substituted phenylene, p.In this case, for the consideration of composition processability, in the arylene sulfide ether that constitutes by above-mentioned arlydene, except the preferred polymer that uses identical repetitive, be the homopolymers, also preferably contain the copolymer of different repeat units sometimes.
As homopolymers, preferred especially use with use to phenylene as arlydene to the attach most importance to homopolymers of multiple unit of poly (phenylene sulfide) ether.As copolymer, can use comprising the different combination more than 2 kinds mutually among the arylene sulfide ether of above-mentioned arlydene.Wherein, preferred especially use contains the combination to poly (phenylene sulfide) ether and metaphenylene thioether group.Wherein, on rerum naturas such as hear resistance, formability, mechanical property, it is suitable containing the polymer to the poly (phenylene sulfide) ether that 70 moles of % are above, preferred 80 moles of % are above.
In addition, among these pas resins, can especially preferably use heavy polymer by the straight chain structure in fact that obtains by polycondensation as the monomer of main body with 2 functionality halogenated aromatic compounds, but, except that the pas resin of straight chain structure, use a small amount of monomer such as poly-halogenated aromatic compound more than 3 when also can be applicable to polycondensation, and partly form the polymer of branched structure or cross-linked structure, also can use in the presence of oxygen or oxidant, at high temperature heat the straight chain polymer of lower molecular weight, improve melt viscosity by oxidation cross-linked or heat cross-linking, thus the polymer of improvement shaping processability.
In addition, as the pas resin of (A) composition, also preferably with above-mentioned straight chain shape pas resin (310 ℃, shear rate 1200s
-1The time viscosity be 10～300Pas) for main body, its part (1～30 weight %, preferred 2～25 weight %) is viscosity higher (300～3000Pas, preferred 500～2000Pas) the side chain or the mixed system of crosslinked pas resin.
In addition, the pas resin that uses among the present invention, carry out after the preferred polymeric that pickling is clean, hot water is cleaned, organic solvent clean (the perhaps combination of these washings) to remove by-product impurity etc. the refining resin that obtains.
Secondly, it is different that fibee reinforced dose (B) that uses among the present invention and the general cross section of use always have fibee reinforced dose of approximate circular cross-section shape, it is characterized in that having flat cross sectional shape.In general, being combined with the glass fibre is fibee reinforced dose composition of representative, because fiber is in the flow direction orientation when being shaped, so the difference of the flow direction of the linear expansion coefficient of shaping shrinkage rate and formed products spare and vertical direction (anisotropy) becomes big.Therefore, embedded the formed products of metal etc., the formed products after solidifying of being shaped is inner easily to produce bigger strain, easy to crack, produces such problem.But distinguish: even cooperated the composition of fibrous material, when the cross sectional shape of its this hardening agent is flat situation of the present invention, because the anisotropy of shaping shrinkage rate and linear expansion coefficient is little, also can obtain the very good formed products of high/low-temperature impact characteristic.As the anisotropic method that suppresses shaping shrinkage rate and linear expansion coefficient, known and with the method for laminal filter, still, in this case, because the cohesive of mechanical properties, welding portion reduces, and therefore, can not obtain enough high/low-temperature impact characteristics.
Fibee reinforced dose (B) with flat section that uses among the present invention, be with vertically vertical cross section on, the ratio of major diameter (the longest air line distance in cross section) and minor axis (the longest air line distance of the direction vertical with major diameter) is 1.3～10, preferred 1.5～5.Concrete Long Circle, ellipse, semicircle, cocoon shape (ま ゆ shape), rectangle or their analogous shape of being shaped as especially preferably belongs to cocoon shape, oblong shape.Fibee reinforced dose (B) its specific area with flat cross section becomes big, and the cohesive of fiber and pas resin improves, and bending strength, rigidity etc. also improves, and shows good high/low-temperature impact characteristic.For this point, having at central portion has fibee reinforced dose of cocoon shape cross sectional shape of spill to be more preferably.The ratio of above-mentioned major diameter and minor axis not at the effect of high/low-temperature impact characteristic, in addition, surpasses 10 hardening agent less than 1.3 hardening agent, and the manufacturing of itself is very difficult.
Secondly, along with the sectional area change of fibee reinforced dose (B) with flattened that use among the present invention is big, can not get strengthening fully effect, in addition, if it is too little that sectional area becomes, then the manufacturing of himself becomes difficult, and produces the problem on handling.Therefore, fibee reinforced dose sectional area among the present invention is 2 * 10
-5～8 * 10
-3Mm
2, preferred 8 * 10
-5～8 * 10
-4Mm
2
Secondly, the length of fibee reinforced dose (B) with flattened that uses among the present invention is arbitrarily, still, considers the mechanical properties, shaping processability of formed products etc., preferred 50～1000 μ m of average fiber length in the component end item.In addition, for purposes such as reduction resin combination proportions, the fiber that can also use hollow is as fibee reinforced dose (B).
Example as described fibee reinforced dose (B), can enumerate mineral fibres such as glass fibre, carbon fiber, zinc oxide fiber, titanium dioxide fiber, wollastonite, asbestos fibre, boron fibre, Zirconium oxide fibre, silicon dioxide fibre, silica alumina fiber, Zirconium oxide fibre, boron nitride fiber, stainless steel fibre, copper fiber, Fypro, high molecular weight polyethylene fiber, aramid fibre, polyester fiber, fluorine fiber etc., but preferably use glass fibre.And, for the improvement of the improvement of mechanical properties, sliding, give purposes such as electric conductivity, also can mix fibee reinforced dose (B) more than 2 kinds and use.
In the use of these fibee reinforced dose (B), if desired, then preferably use astringent or surface conditioning agent.Enumerating this example, is the functionality compound of epoxy based compound, isocyanates based compound, silane based compound, titanate esters based compound etc.These compounds are implemented surface treatment or convergence process in advance and are used, and perhaps also can add simultaneously in material preparation.
Fibee reinforced dose (B) with described flat cross section for example is under the situation of glass fibre, as the lining ring that uses for the ejection melten glass, the nozzle that has appropriate well shapes such as Long Circle, ellipse, rectangle, slit-shaped by use carries out spinning and prepares.In addition, can prepare by following process: spin melten glass from the contiguous a plurality of nozzles that are provided with various cross sectional shapes (comprising circular cross-section), the spun melten glass that is bonded with each other is made single ultimate fibre.Also available the same therewith method preparation such as carbon fiber.
Fibee reinforced dose (B) that uses among the present invention cooperates 5～200 weight portions, preferred 10～100 weight portions with respect to (A) 100 weight portion polyarylene sulfide resins.If less than 5 weight portions, then can not get the original good mechanical property of filler-reinforced pas resin composition, surpassing under the situation of 200 weight portions, the problem of processabilities such as mobile reduction takes place.
In the present invention, in order further to improve the high/low-temperature impact characteristic, use (C) thermoplastic elastomer (TPE) simultaneously.
As (C) thermoplastic elastomer (TPE), can enumerate polyolefin elastomer, polyester based elastomers, Fuoroelastomer, siloxane-based elastomer, butadiene elastomer, polyamide-based elastomer, polystyrene based elastomers, urethanes based elastomers, center and have various particle based elastomers of cross-linked structure etc., can use more than a kind or 2 kinds.
As (C) thermoplastic elastomer (TPE), the preferred polyolefm based elastomers especially preferably uses with alpha-olefin and α, and the ethylene oxidic ester of beta-unsaturated acid is the olefin copolymer of principal component.In addition, also preferably make various graft copolymers and comprise alpha-olefin and α, the polyolefin elastomer of the principal component copolymerization of the ethylene oxidic ester of beta-unsaturated acid.
As the use level of (C) thermoplastic elastomer (TPE), be 1～25 weight portion, preferred 1～15 weight portion, more preferably 1～8 weight portion with respect to (A) 100 weight portion polyarylene sulfide resins.When less than 1 weight portion, the high/low-temperature impact characteristic to improve effect insufficient, when surpassing 25 weight portions, be created in the mould deposit that adheres on the metal die when being shaped and become many problems.
Secondly, in the present invention,, preferably cooperate silicone oil (D) in order further to improve the high/low-temperature impact characteristic.Silicone oil comprises unmodified silicone oil or has introduced the modified silicon oil of functional group.Unmodified silicone oil is representative with dimethyl silicone polymer and PSI, and the latter for example comprises poly dimethyl diphenyl siloxane copolymer, poly dimethyl phenyl methyl silicone copolymers, polymethyl-benzene base diphenyl siloxane copolymer.On the other hand, modified silicon oil is that the part with above-mentioned unmodified silicone oil obtains with functional group modification, preferably list hydroxyl, amino, carboxyl, methanol-based (カ Le レ PVC ノ-Le), epoxy radicals, methacryloxy (メ Network リ ロ キ シ), sulfydryl etc. as its functional group, functional group introduce can be at random at side chain, end, two ends or side chain and two ends.As the object lesson of these modified silicon oils, list terminal silanol dimethyl silicone polymer, terminal silanol poly dimethyl diphenyl siloxane, terminal hydroxyl propyl group dimethyl silicone polymer, poly dimethyl hydroxyl alkylene oxide methylsiloxane, terminal amino group propyl group dimethyl silicone polymer, the T structure dimethyl silicone polymer that contains aminoalkyl, terminal carboxyl group propyl group dimethyl silicone polymer, the T structure dimethyl silicone polymer that contains the carboxyl propyl group, terminal glycidoxy propyl group dimethyl silicone polymer, the T structure dimethyl silicone polymer that contains the glycidoxy propyl group, poly-glycidoxy propyl group methylsiloxane, terminal methyl alcohol dimethyl silicone polymer, terminal acetoxyl group dimethyl silicone polymer, terminal dimethylamino dimethyl silicone polymer, terminal methyl group acryloxy propyl group dimethyl silicone polymer, the T structure dimethyl silicone polymer that contains methacryloxypropyl, the T structure dimethyl silicone polymer that contains the sulfydryl propyl group, poly-sulfydryl propyl group methylsiloxane etc.
The viscosity of silicone oil (D) under 25 ℃ is not particularly limited in the scope of 10～500000cSt (centipoise), and the aspects such as dispersiveness during from operability and mixing are considered, are preferably 100～100000cSt.In addition, the quality aspects such as dispersiveness when handling and mix consider, more preferably support silicone oil on the inorganic micro powder end and use.
The use level of silicone oil (D) is 0.1～15 weight portion with respect to (A) 100 weight portion polyarylene sulfide resins, preferred 0.5～10 weight portion.When less than 0.1 weight portion, can not obtain the improved effect of high/low-temperature impact characteristic, in addition, when surpassing 15 weight portions, become branch to ooze out at the formed products surface oil, therefore not preferred.
In the resin combination of embedded shaping articles of the present invention, for performances such as improved mechanical strength, hear resistance, dimensional stability (anti-distortion, warpage), electrical properties, also can cooperate fibee reinforced dose (B) fibrous and/or non-fibrous inorganic filler (E) in addition with flattened.This is used the filler of fibrous, powder shape, sheet according to purpose.
As fibrous filler, can enumerate the inorganic fibrous material of the fibrous material etc. of metals such as glass fibre, asbestos fibre, carbon fiber, silicon dioxide fibre, silica alumina fiber, Zirconium oxide fibre, boron nitride fiber, boron fibre, potassium titanate fibre and stainless steel, aluminium, titanium, copper, brass.Special representative fibrous filler is glass fibre or carbon fiber.Also can use the organic fiber material of high-melting-points such as polyamide, fluororesin, acrylic resin.
On the other hand, can enumerate the metal sulfate of the metal carbonate, calcium sulfate, barium sulfate and so on of the metal oxide, calcium carbonate, magnesium carbonate and so on of the silicate, iron oxide, titanium oxide, zinc oxide, aluminium oxide and so on of carbon black, silica, quartz powder, bead, glass dust, calcium silicates, alumina silicate, kaolin, talcum, clay, diatomite, wollastonite and so on as powder shape filler, other can also enumerate carborundum, silicon nitride, boron nitride, various metal dust.
List mica, glass flake, various metal forming as the sheet filler.These inorganic fillers can use a kind of or and with two or more.
In the use of these fillers, if necessary, preferably use astringent or surface conditioning agent.Enumerating example is functionality compounds such as epoxy based compound, isocyanates based compound, silane based compound, titanate esters based compound.These compounds are implemented surface treatment or convergence process in advance and are used, and perhaps, also can add simultaneously in material preparation.
The use amount of inorganic filler (E) is not particularly limited, and usually pas resin 100 weight portions with respect to (A) composition are 20～250 weight portions.Than 20 weight portions under the littler situation, bad mechanical strength, under excessive situation, the forming operation difficulty that becomes, in addition, the mechanical strength of formed products also goes wrong.
In addition, in the resin combination of embedded shaping articles of the present invention,, also can cooperate the higher amorphous resin (F) of hear resistance of 5～50 weight portions with respect to pas resin 100 weight portions of (A) composition for the purpose of further improving the high/low-temperature impact characteristic.Such amorphous resin (F) can be enumerated the copolymer of polyphenylene ether, polyarylate, polysulfones, polyether sulfone, PEI, Merlon, annular ethylene series resin and these amorphous resins or the copolymer of functional group modification etc.
In addition, in the resin combination of embedded shaping articles of the present invention, in the scope of not damaging effect of the present invention, the purpose for improvement burr etc. can cooperate silane compound.Comprise all kinds such as vinyl silanes, methacryloxy silane, epoxy silane, amino silane, hydrosulphonyl silane as silane compound, for example exemplify out vinyl trichlorosilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-An Jibingjisanyiyangjiguiwan, γ-sulfydryl trimethoxy silane etc., but be not limited to these.
In addition, in the resin combination of the embedded shaping articles that uses among the present invention, according to its purpose, except mentioned component, also can assist ground a small amount of and with other thermoplastic resin composition.As other thermoplastic resins as used herein, if at high temperature stabilized resins then can be any thermoplastic resin.
In addition, in the resin combination of the embedded shaping articles that uses among the present invention, in order to give the desired characteristic that adapts with its purpose, performance cooperates the known material that generally adds, i.e. colouring agents such as fire retardant, dyestuff and pigment, lubricant, crystallization promoter, nucleus agent, various antioxidant, heat stabilizer, against weather stabilizing agent etc. in thermoplastic resin and thermosetting resin as requested.
The preparation of the resin combination of the embedded shaping articles that uses among the present invention can utilize equipment and the method generally used in the preparation of compound resin composition to prepare.In general, mix neccessary composition after, use single screw rod or double screw extruder to carry out melting mixing, push and can make the pill of shaping usefulness.In addition, the melt extruded resinous principle, the method for adding the fibrous inorganic filler of cooperation in this process also is one of preferable methods.
Embedded shaping articles is that metal etc. is installed in forming metal mould in advance, fills above-mentioned resin composition containing in its outside and forms the combined shaping product.Be used for injection moulding, extruding compression forming method etc. being arranged, but be generally the injection molded method in the method for metal die potting resin.The blank that in resin, embeds for effectively utilize its characteristic and remedy resin shortcoming purpose and use, therefore, use when being shaped the material of shape invarianceization when contacting or fusion with resin.Therefore, the main insert that is configured as rod, pin, bolt etc. by the inoganic solids class of the metal species of aluminium, magnesium, copper, iron, brass and their alloy etc. and glass, pottery and so in advance that uses.
[embodiment]
Below, the present invention will be described in more detail with embodiment, but the present invention is not limited to these embodiment.
The assay method of the evaluation of physical property shown in the following example carries out according to following.
(1) high/low-temperature impact characteristic
At 320 ℃ of resin temperatures, 150 ℃ of metal die temperature, injection time 40s, cool time 60s condition under, (the embedded injection molded of 14mm * 14mm * 24mm), and make the minimum wall thickness (MINI W.) of resin portion reach 1mm has been made embedded shaping articles to metallic pin with resin pellet.
About resulting embedded shaping articles, descend heating after 2 hours with the cold shock testing machine at 180 ℃, cooling is after 2 hours after cooling to-40 ℃, be warmed up to 180 ℃ again, with this process as 1 cycle, carry out high and low temperature impact test, measure the periodicity till in formed products, cracking, estimate high/low-temperature impact.
The mold deposit amount is estimated when (2) being shaped
Carry out the shaping of specific formed products under the following conditions with injection molding machine, behind the solids number of the regulation that is shaped, by visual, mold deposit surperficial to metal die with following 3 ranks and the outlet periphery adheres to be estimated.
Zero: adhesion amount is few
△: have and adhere to, but in the permission level
*: adhesion amount is many, reaches the level that can not be shaped in a large number and produce
(molding condition)
Injection moulding machine: the IS30FRA-1A of Toshiba
Cylinder temperature: 340 ℃
Injection time: 2 seconds
Cool time: 5 seconds
Metal die temperature: 60 ℃
Shaping solids number: 500 solids
Embodiment 1～6, comparative example 1～9
Shown in table 1～2, each material composition ((A), (C), (D), (E), (F) composition) was mixed 5 minutes with Henschel (ヘ Application シ エ Le) mixer, it is in 320 ℃ the twin (double) screw extruder that mixture is put into temperature cylinder, (B) composition adds separately from extruder side-fed portion, in twin (double) screw extruder, under 350 ℃ of resin temperatures, carry out melting mixing, make the resin combination pill, carry out the evaluation of above-mentioned rerum natura.The results are shown in table 1～2.
The concrete material of each composition that uses in embodiment and the comparative example is as follows.
(A) polyphenylene sulfide (PPS) resin
Wu Yu chemical industry (strain) is made, Off オ-ト ロ Application KPS (310 ℃, shear rate 1200s
-1The time viscosity 30Pas)
(B) glass fibre
Glass fibre with flat cross sectional shape
(B-abnormity 1)
Cross sectional shape: cocoon shape, major diameter 24 μ m, minor axis 12 μ m, the ratio of major diameter/minor axis are 2 ((strain) manufacturing, CSH-3PA are spun in day east)
(B-abnormity 2)
Cross sectional shape: Long Circle, major diameter 24 μ m, minor axis 6 μ m, the ratio of major diameter/minor axis are 4 ((strain) manufacturing, CS-3PF are spun in day east)
Glass fibre with circular section shape
(B-circle 1)
Major diameter 17 μ m, the ratio of major diameter/minor axis are 1 ((strain) manufacturing, CS-3QL are spun in day east)
(B-circle 2)
Major diameter 13 μ m, the ratio of major diameter/minor axis are 1 (NEC glass (strain) manufacturing, ECS03-717)
(C) thermoplastic elastomer (TPE)
The copolymer that makes ethylene/methacrylic acid glycidyl ester copolymer and methyl methacrylate/butyl acrylate cores copolymer carry out grafting and obtain (Japanese grease (strain) is made, モ デ イ パ-A4300)
(D) silicone oil
Polydimethyl siloxane oil, viscosity 5000cSt (eastern beautiful ダ ウ コ-ニ Application ゲ シ リ コ-Application (strain) is made, SH200 oil)
(E) inorganic filler
Calcium carbonate (Japan's Off ア イ Application ケ ミ カ Le (strain) is made, ホ ワ イ ト Application P-30)
(F) amorphous resin
(Ticona company makes annular ethylene series resin, TOPAS6017)
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| ??(A)PPS | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| (B) glass fibre | B-abnormity 1 45 | B-abnormity 2 45 | B-abnormity 1 45 | B-abnormity 1 100 | B-abnormity 1 45 | B-abnormity 1 45 |
| (C) thermoplastic elastomer (TPE) | ??3 | ??3 | ??3 | ??5 | ??3 | ??10 |
| (D) silicone oil | ??1 | |||||
| (E) inorganic filler | ??100 | |||||
| (F) amorphous resin | ??10 | ??10 | ||||
| High/low-temperature impact (cycle) | ??121 | ??124 | ??168 | ??119 | ??153 | ??226 |
| Mold deposit amount during shaping | ??○ | ??○ | ??○ | ??○ | ??○ | ??△ |
The unit of the addition in the table is a weight portion
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | |
| (A)PPS | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| (B) glass fibre | B-abnormity 1 45 | B-circle 2 45 | B-circle 1 45 | B-circle 2 100 | B-circle 2 45 | B-circle 2 100 | B-circle 2 45 | B-circle 2 45 | B-circle 2 45 |
| (C) thermoplastic elastomer (TPE) | 3 | 3 | 3 | 5 | 3 | 10 | 30 | ||
| (D) silicone oil | 2 | ||||||||
| (E) inorganic filler | 100 | ||||||||
| (F) amorphous resin | 10 | ||||||||
| High/low-temperature impact (cycle) | 67 | 33 | 78 | 68 | 95 | 59 | 80 | 103 | 251 |
| Mold deposit amount during shaping | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | × |
The unit of the addition in the table is a weight portion.
Claims (7)
1. embedded shaping articles, following resin combination and metal or inoganic solids embedded shaping are formed, described resin combination is with respect to (A) polyarylene sulfide resin 100 weight portions, has cooperated (B) to have and fibee reinforced dose 5～200 weight portion of the flat cross sectional shape of ratio between 1.3～10 of the major diameter (air line distance that the cross section is the longest) in vertically vertical cross section and minor axis (perpendicular to the longest air line distance of the direction of major diameter), the resin combination of (C) thermoplastic elastomer (TPE) 1～25 weight portion.
2. as the embedded shaping articles of claim 1 record, fibee reinforced dose (B) wherein having flat cross sectional shape is glass fibre.
3. as the embedded shaping articles of claim 1 or 2 records, the cross sectional shape that wherein has fibee reinforced dose (B) of flat cross sectional shape is Long Circle, ellipse, semicircle, cocoon shape, rectangle or these shape analogous shapes.
4. as the embedded shaping articles of claim 1 or 2 records, wherein thermoplastic elastomer (TPE) (C) is with alpha-olefin and α, and the ethylene oxidic ester of beta-unsaturated acid is the olefin copolymer of principal component.
5. as the embedded shaping articles of claim 1 or 2 records,, further cooperated the silicone oil (D) of 0.1～15 weight portion wherein with respect to polyarylene sulfide resin (A) 100 weight portions.
6. as the embedded shaping articles of claim 1 or 2 records, wherein further cooperated fibee reinforced dose (B) fibrous and/or non-fibrous inorganic filler (E) in addition with flat cross sectional shape.
7. as the embedded shaping articles of claim 1 or 2 records, wherein further cooperated amorphous resin (F).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003404122A JP2005161693A (en) | 2003-12-03 | 2003-12-03 | Insert molded product |
| JP404122/2003 | 2003-12-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1644366A true CN1644366A (en) | 2005-07-27 |
Family
ID=34727185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004101038040A Pending CN1644366A (en) | 2003-12-03 | 2004-12-03 | Embedded shaping articles |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2005161693A (en) |
| KR (1) | KR20050053510A (en) |
| CN (1) | CN1644366A (en) |
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| KR20050053510A (en) | 2005-06-08 |
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