CN101652430A - Glass fiber reinforced polyamide resin composition - Google Patents
Glass fiber reinforced polyamide resin composition Download PDFInfo
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- CN101652430A CN101652430A CN200880011425A CN200880011425A CN101652430A CN 101652430 A CN101652430 A CN 101652430A CN 200880011425 A CN200880011425 A CN 200880011425A CN 200880011425 A CN200880011425 A CN 200880011425A CN 101652430 A CN101652430 A CN 101652430A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
A polyamide resin composition that simultaneously has mechanical properties, low warpage and weld strength being satisfactory for a resin composition for formation of a thin molding, such as a chassisor housing of electronic equipment. The glass fiber reinforced polyamide resin composition is one obtained by mixing 0.05 to 4.0 parts by mass of organic compound having at least two glycidyl groupsor acid anhydride groups in each molecule with 100 parts by mass of polyamide resin composition consisting of a mixture of 30 to 80 mass% of polyamide resin of 1.5 to 4.0 relative viscosity as measured by means of Ubbelode viscometer using 96 mass% sulfuric acid as a solvent at 25 DEG C and at a concentration of 1 g/dl and 20 to 70 mass% of flat glass fiber with a flat section of 1.5 to 10 major diameter/minor diameter ratio. Further, there is provided a resin molded item obtained by molding the above composition.
Description
Technical field
Can reduce the glass-fiber-reinforced polyamide resin composition of molding warpage when the present invention relates to rigidity height, weld strength excellence and being configured as thin molded article.
Background technology
In recent years, along with the miniaturization of office machine, e-machine, quickened the thin-walled property on shell, chassis.In the past, in order to improve the rerum natura of resin combination, cooperated glass fibre to be strengthened usually with rounded section.But glass fibre has along the character of the flow direction orientation of resin, produces the anisotropic of intensity, causes the generation of warpage.For this is improved, have: cooperate plate-like fillers such as talcum or mica, reduce the method for anisotropic.But, cause the problem that mechanical properties descends although this also exists warpage to improve.
In the patent documentation 1, the method that reduces few reduction thin molded article warpage as mechanical properties has been put down in writing and the glass fibre of flat pattern and the common glass fibre with rounded section mixed and has been coupled to resin combination in the polymeric amide.But even cooperate the glass fibre weld strength of flat pattern low, as the resin combination of shaping thin molded article, the Amilan polyamide resin composition that has sufficient mechanical properties, low warpage properties and weld strength concurrently does not also exist yet.
Patent documentation 1: the spy opens flat 10-219026 communique
Summary of the invention
The problem that invention will solve
The objective of the invention is to: a kind of resin combination that has the Amilan polyamide resin composition of sufficient mechanical properties, low warpage properties and weld strength as the such thin molded article in shell, the chassis of shaping e-machine concurrently is provided.
The means of dealing with problems
The inventor etc. have carried out further investigation repeatedly for solving such problem, found that specific resin combination can address the above problem, thereby have finished the present invention.
That is, main points of the present invention are as follows:
(1) glass-fiber-reinforced polyamide resin composition, it is to be that the ratio of 1.5～4.0 polyamide resin 30～80 quality % and major diameter/minor axis is 1.5～10 and has an Amilan polyamide resin composition that flat glass fiber 20～70 quality % of flat cross section mix with respect to 100 mass parts by relative viscosity, the glass-fiber-reinforced polyamide resin composition that cooperates the organic compound that has 2 above functional groups in 1 molecule of 0.05～4.0 mass parts to form, described relative viscosity is to use Ubbelohde type viscometer, with the sulfuric acid of 96 quality % as solvent, 25 ℃ of temperature, survey periodic viscosity under the condition of concentration 1g/dl, it is characterized in that this organic compound is to be selected from the TriMethylolPropane(TMP) polyglycidyl ether, the Polyglycerine polyglycidyl ether, isocyanuric acid three-glycidyl ester, the organic compound more than a kind in the phenylethylene/maleic anhydride copolymer.
(2) glass-fiber-reinforced polyamide resin composition is characterized in that, the polyamide resin of (1) is a kind the polymeric amide that is selected from nylon 6, nylon 66, the Ni Long11.
(3) glass-fiber-reinforced polyamide resin composition, wherein, (1) flat glass fiber is the glass fibre with the arbitrary special crosssection shape in Pear-Shaped, cocoon shape, Long Circle, ellipse, the rectangle, and it is that coupling agent, zirconium white are that the coupling agent more than a kind selected the coupling agent carries out surface treatment and forms that glass fibre adopts from silane coupling agent, titanium.
(4) resin forming product that the glass-fiber-reinforced polyamide resin composition of (1)～(3) is shaped and forms.
The effect of invention
Amilan polyamide resin composition of the present invention is when being configured as the such thin molded article of the shell of e-machine, chassis, have sufficient mechanical properties, low warpage properties and weld strength concurrently, so can obtain excellent in dimensional stability, firm resin forming product, the utility value on the industry is high.
Embodiment
Below, describe the present invention in detail.
The polyamide resin that the present invention uses is that the polymkeric substance that has amido linkage in the main chain gets final product, and is poly-epsilon-caproamide (nylon 6), nylon 46 (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (NYLON610), nylon 612 (nylon 612), poly hexamethylene adipamide undecane diamines (Ni Long11 6), nylon 11 (Ni Long11), poly-lauramide (nylon 12), poly-6I hexamethylene isoterephalamide (nylon 6I), poly-hexamethylene terephthalamide (nylon 6T), poly-paraphenylene terephthalamide's nonamethylene diamine (nylon 9 T), poly hexamethylene adipamide metaxylylene diamine (nylon MXD 6) and comprise the polyamide copolymer of at least 2 kinds of different polyamide compositions in the middle of these, perhaps their mixture etc.Preferred polyamide resin can be enumerated nylon 6, nylon 66, Ni Long11, nylon 12, nylon 6T etc., most preferably is nylon 6, nylon 66, Ni Long11.
The molecular weight (relative viscosity) of the polyamide resin that the present invention uses is to use Ubbelohde type viscometer, with the sulfuric acid of 96 quality % as solvent, the relative viscosity of measuring under the condition of 25 ℃ of temperature, concentration 1g/dl is preferably 1.5～4.0, and more preferably 1.8～3.5.Relative viscosity is 1.8～3.5 o'clock, can guarantee the resin flow of appropriateness, and resin can obtain the good molding of outward appearance to the transfer printing excellence of metal pattern.And can also obtain suitable weld strength.There was the trend of the mechanical properties deterioration of molding in relative viscosity less than 1.5 o'clock.Relative viscosity is big more, and flowability is poor more, produces resin and is full of degradation problem under the time lengthening of metal pattern and the metal pattern transfer printing, and be difficult to obtain the excellent appearance of molding.During relative viscosity superelevation 4.0, there are plasticity, the remarkable downward trend of weld strength.Relative viscosity is big more, and the resin temperature of flow front reduces more, and promptly there is the weld strength downward trend in the joint variation of the resin of weld seam part.
Herein, so-called weld seam is meant the endemism that particularly takes place when resin injection is shaped, and is the undesirable condition of the part generation fine rule of molten resin flow interflow welding in the metal pattern.Grade in order in molding, to form hollow bulb, pin or core are set in metal pattern, then after molten resin makes a circulation to flow through above-mentioned part, collaborate once more, thereby produce welding line.In addition, in the situation that must establish the cast gate more than 2, the generation of welding line is inevitable.
This weld seam disfeatures owing to welding is bad, perhaps can significantly reduce mechanical characteristics.In order to improve this undesirable condition, must manage (1) and improve molten resin and metal pattern temperature, (2) change the position, number, size of cast gate etc. improving injection pressure and injection speed, etc.So-called weld strength is meant the mechanical characteristics (for example bending elastic modulus etc.) at weld seam position.
Glass fibre of the present invention can be according to the manufacture method manufacturing of known glass fibre, for improving and the adaptation of matrix resin, uniformly dispersed, can adopt that to be suitable for containing silane coupling agent, titanium be that coupling agent, zirconium white are that the known collecting agent of the allotment resin of in the coupling agent such as coupling agent at least a kind and film forming agent etc. carries out boundling, can adopt the glass fiber bundle set of boundling, the form that cuts into the chopped strand of certain-length are used.
In the present invention, the cross-sectional shape of described glass fibre uses flat flat glass fiber.So-called flat cross section is meant that the shape with the tangent plane of glass fibre long axis direction vertical direction is not circular, but special-shaped shape.Finger has the major diameter that defines with the maximum length by central point, the shape of using the minor axis of the minimum length definition of passing through central point.But flat cross section illustration Pear-Shaped, cocoon shape, Long Circle, ellipse, the rectangle of such shape or be similar to these shape, for example, Pear-Shaped, according to above-mentioned definition, major diameter is the distance that is equivalent to the protuberance direction of cucurbit two statures, and minor axis is the distance that is equivalent to the recess direction of the thin part in cucurbit centre.
In the present invention, the ratio of the major diameter/minor axis of use flat pattern is 1.5～10, preferred 2.0～6.0 flat glass fiber.The ratio of major diameter/minor axis is by being that major diameter, the minor axis that benchmark is measured calculated according to the vertical direction in cut-out cross section above-mentioned definition, that adopt the microscopic examination flat glass fiber and with the micron order, and it uses 10 mean value.The ratio of major diameter/minor axis is less than 1.5 o'clock, and making the cross section is that the effect of flat pattern is little, surpasses at 10 o'clock, the manufacturing difficulty of glass fibre self.
In addition, in the present invention, the use mean length is the flat glass fiber of 1～15mm, preferred 2～10mm.Herein, so-called mean length is meant and adopts the microscopic examination flat glass fiber and be 20 the mean value that benchmark is measured with the micron order.The mean length of fiber is during greater than 15mm, during ester moulding, and the resin flow variation, the operation deterioration, and during less than 1mm, can not guarantee sufficient mechanical.
The use level of polyamide resin (A) and flats glass fibre (B) is (A)/(B)=25/75～80/20 (quality %), preferred (A)/(B)=30/70～75/25 (quality %), more preferably (A)/(B)=30/70～70/30 (quality %).The use level of flats glass fibre (B) is when 20 quality % are following, and warpage increases, thereby not preferred.And the use level of flats glass fibre (B) is when surpassing 75 quality %, and the flow characteristics variation can't be carried out the traction of tow during the resin melting mixing, the manufacturing difficulty of glass-fiber-reinforced polyamide resin composition.
But the compound that the organic compound illustration functional group that has 2 above functional groups in 1 molecule has a plurality of epoxy group(ing), anhydride group, oxazolinyl, carboxylic acid group, amino, isocyanate group.The organic compound that preferably has epoxy group(ing), acid anhydrides.Wherein, be particularly suitable for using TriMethylolPropane(TMP) (single, two, three) glycidyl ether, preferred TriMethylolPropane(TMP) polyglycidyl ether, TriMethylolPropane(TMP) (two or three) glycidyl ether for example, more preferably TriMethylolPropane(TMP) (three) glycidyl ether, perhaps Polyglycerine polyglycidyl ether glycidyl ether compounds such as (oxirane values 100～300), the compound that tricarbimide glycidyl esters such as isocyanuric acid three-glycidyl ester are such with epoxy group(ing), phenylethylene/maleic anhydride copolymer (has number-average molecular weight 1000～5000, the anhydride group of acid number 100～600 is as the compound of side group).
The use level that has the organic compound of 2 above functional groups in 1 molecule is 0.05～4.0 mass parts with respect to the Amilan polyamide resin composition of 100 mass parts, preferred 0.1～3.5 mass parts.This use level is when 0.05 mass parts is following, and the raising of thermoplastic resin composition's weld strength is insufficient, thereby not preferred.And this use level exists thermoplastic resin composition's flowability to descend when surpassing 4.0 mass parts, and shaping processability worsens, the trend that mechanical properties is reduced, thereby not preferred.
In addition, glass-fiber-reinforced polyamide resin composition of the present invention can obtain being more suitable for the molding of its purposes by cooperating other inorganic filler as required.Described inorganic filler can be enumerated: various powder such as silicon-dioxide, glass micropowder, kaolin, talcum, titanium oxide, lime carbonate, aluminum oxide.In addition, also can add known static inhibitor, tinting material, lubricant, releasing agent, nucleator, fire retardant, shock-resistance modifying agent etc.
Manufacture method as glass-fiber-reinforced polyamide resin composition of the present invention, for example obtain: adopt twin screw extruder with following method, supply with the polyamide resin of specified amount from the feed port (its top feed) that is positioned at upstream side, reach moment of molten state at this polyamide resin, use liquid to inject meter is supplied with specified amount from the liquid filling orifice organic compound.Then, supply with the flats glass fibre from the side opening for feed of specified amount, after being installed in the spinning the place, hole and be configured as the tow shape of forcing machine downstream side front end, cooling cuts into particulate state.The relative viscosity of the Amilan polyamide resin composition that obtains be sulfuric acid with 96 quality % as solvent, the relative viscosity of measuring under the condition of 25 ℃ of temperature, concentration 1g/dl is preferably in 1.8～4.5 scope, more preferably in 2.0～4.5 scope.Relative viscosity is less than 1.8 o'clock, the weld strength variation, thereby not preferred.And surpassing at 4.5 o'clock, mobile extreme decline the when having the glass-fiber-reinforced polyamide resin composition fusion brings the trend of obstruction to plasticity, thereby not preferred.Should illustrate, the fiber that the glass fibre with flat cross section that the present invention uses uses the general like that glass fibre of E glass to form, but so long as can make glass fibre, whatsoever the composition of sample all can use, no particular restriction.
Resin combination manufacturing process of the present invention is in the process that the Amilan polyamide resin composition heating and melting is shaped, can use various moulding methodes such as injection forming, extrusion molding, but, be fit to use injection molding method in order to use Amilan polyamide resin composition of the present invention to obtain thin molded article.
When using injection molding method to be shaped, for the plasticising Amilan polyamide resin composition, the cylinder temperature of injection machine preferably sets in fusing point+20 ℃～fusing point+70 ℃, and in order to make the deterioration equilibrium of resin flow and resin, more preferably fusing point+30 ℃～fusing point+60 ℃.
In addition, the metal pattern temperature preferably sets higher slightly than the glass transformation temperature of Amilan polyamide resin composition, this heats in cylinder, plastifying resin injection and being filled to when the metal pattern internal cooling, rapid cooling, the crystalline that suppresses resin carried out, make the transfer printing good (outward appearance attractive in appearance) of metal pattern, the dimensional precision (contraction of the molding that the inhibition crystallization causes) that improves the molding that obtains is useful.
In addition, metal pattern temperature controlling (setting for higher slightly than the glass transformation temperature of Amilan polyamide resin composition) is also useful to suppressing to produce welding line in the molding.Same with the transfer printing of metal pattern, by the cooling of the resin that slows down, can fully guarantee resin flow, the resin temperature that suppresses the resin flows front end descends, and carries out the joint of the resin at weld seam position more fully.
Embodiment
Below, be described more specifically the present invention by embodiment, as long as but the present invention is no more than its main points, then be not limited to following examples.In addition, raw material that uses in embodiment and the comparative example and physical property measurement method are as follows.
Raw material
(A) polyamide resin
Polymeric amide A: nylon 6 (but You Niji corporate system A1030BRL relative viscosity 2.6)
Polymeric amide B: nylon 6 (but You Niji corporate system A1030BRT relative viscosity 3.4)
Polymeric amide C: nylon 66 (but You Niji corporate system A125 relative viscosity 2.8)
Polymeric amide D: Ni Long11 (the system BMNO TLD of Arkema relative viscosity 1.8)
(B) glass fibre
Glass fibre A: the ratio of the line of apsides is 2 the flat glass fiber with long round section (mean length 3mm)
(corporate system CSH3PA870 is spun in day east, through the silicane surface treatment)
Glass fibre B: the ratio of the line of apsides is 4 the flat glass fiber with long round section (mean length 3mm)
(corporate system CSG3PA820 is spun in day east, through the silicane surface treatment)
Glass fibre C: diameter is that 10 μ m, mean length are the glass fibre with rounded section of 3mm
(corporate system CS3J-451 is spun in day east, through the silicane surface treatment)
(C) organic compound
Organic compound A: TriMethylolPropane(TMP) polyglycidyl ether (this drug company of slope system SR-TMP)
Organic compound B: phenylethylene/maleic anhydride copolymer (Herucules corporate system)
Organic compound C: Polyglycerine polyglycidyl ether (this drug company of slope system SR-4GL)
Organic compound D: isocyanuric acid three-glycidyl ester (the system TEPIC of daily output chemical company)
Measuring method
(1) relative viscosity of polyamide resin and Amilan polyamide resin composition
Be dissolved in the sulfuric acid of 96 quality %, the concentration that makes the dried particles of polyamide resin is 1g/dl, remove by filter composition beyond the polymeric amide with the G-3 glass filter after, for measuring.Measure and adopt Ubbelohde type viscometer, under 25 ℃, carry out.Amilan polyamide resin composition also is after having replenished glass fiber component, measures equally.
(2) bending elastic modulus
Use the test film of 1 long 150mm of cast gate injection forming, wide 10mm, thick 3mm, measure at 23 ℃ according to ASTM D790.
Bending elastic modulus is the yardstick of the degree that bends of expression counter stress, its value is high more preferred more, the viewpoint of the distortion that external force causes when making thin molded article is considered, when the use level of glass fibre is 30 quality %, is required it at 5GPa, preferably more than 8GPa.
(3) bending elastic modulus of weld seam part
Use 2 long 150mm of cast gate injection forming at two ends, the test film of wide 10mm, thick 3mm, same to weld seam part and (2) bending elastic modulus that middle body forms, measure at 23 ℃ according to ASTM D790.In addition, when making test film, the cylinder temperature of injection machine is 230 ℃ in the situation of polymeric amide 11, the situation of polyamide 6 is 250 ℃, the situation of polyamide 66 is 280 ℃, and the metal pattern temperature is 60 ℃ in the situation of polymeric amide 11, and the situation of polyamide 6 is 80 ℃, the situation of polyamide 66 is 100 ℃, and be 1 minute cooling time.Welding line traverses test film ground in the centre of experiment slice and is wire, but outward appearance has unusual test film not test, but is excluded.
The yardstick of the bending elastic modulus of the weld seam part degree that to be expression bend to the stress of weld seam part particularly.If the bending elastic modulus of weld seam part is enough high, then as molding when practical, because mechanical load repeatedly causes rupturing from the welding seam part branch.Not only wish the problem of outward appearance, wish that also the bending elastic modulus of weld seam part is fully high.
According to following formula, get the ratio of the bending elastic modulus of (2) bending elastic modulus and (3) weld seam part, the conservation rate of calculating bending elastic modulus.
The conservation rate of bending elastic modulus (%)={ (bending elastic modulus of weld seam part)/(bending elastic modulus) } * 100
The conservation rate of bending elastic modulus is 100% under the situation that does not have bending elastic modulus decline fully.Usually the decline of bending elastic modulus to a certain degree can take place, but the conservation rate of wishing bending elastic modulus is more than 70%, preferably more than 75%.
(4) amount of warpage
The cylinder temperature of injection machine is 230 ℃ in the situation of polymeric amide 11, the situation of polyamide 6 is 250 ℃, the situation of polyamide 66 is 280 ℃, the metal pattern temperature is 60 ℃ in the situation of polymeric amide 11, the situation of polyamide 6 is 80 ℃, the situation of polyamide 66 is 100 ℃, is set at 1 minute cooling time, by the plectane of side gate (1) injection forming diameter 100mm, thick 1.6mm.
Put into moisture eliminator immediately from the molding that metal pattern takes out, be cooled to room temperature (23 ℃), in moisture eliminator, carry out state damping in 24 hours simultaneously, to keep absolute dry condition.
After 24 hours, take out molding in the self-desiccation device, on horizontal plate, leave standstill molding, measure following 4 distances, calculate amount of warpage by this measured value apart from horizontal plate.
Determine following (with reference to Fig. 1, Fig. 2) at 4 that measure.The position of the side gate of plectane is defined as a, along the circumferential direction is rotated counterclockwise, become 90 ° position to be defined as b with a, 180 ° position is defined as c, and 270 ° position is defined as d.
Warpage is normally with the ac (perhaps bd) with respect to subtend, and the state of bd (perhaps ac) rise (perhaps descending) takes place.On horizontal plate, the warpage of molding is left standstill to lower convexity, instrumentation with respect to reference plane to top offset what.
Calculate amount of warpage according to following formula.
Amount of warpage (mm)=(b+d)/2-(a+c)/2
Should illustrate that this formula is the ac (reference line) with respect to subtend, bd rises the formula of situation, when reference line changes, suitably changes reference line in the above-mentioned formula (ac=＞bd), obtain the displacement (the rise height of bd=＞ac) with respect to it for example.
More little preferred more according to the amount of warpage that aforesaid method is obtained, in practicality, being that 1.0mm is following gets final product.
Embodiment 1
Polyamide resin A uses Kubo field system weight-loss type continuous and quantitative feedway CE-W-1 to measure, to the main supplying opening supply of the equidirectional twin screw extruder (the system TEM37BS of Toshiba Machine Co. Ltd) of screw diameter 37mmL/D40.And, being set in 230 ℃～270 ℃, screw rod rotation number at the barrel temperature of forcing machine is that 250rpm, output are to carry out melting mixing under the condition of 35kg/h, after treating the abundant fusion of polymeric amide, from liquid injection port,, inject the organic compound A of 1.0 mass parts with respect to the resin combination of 100 mass parts, after fully mixing, supply with glass fibre A from the side opening for feed,, make polyamide resin A/ glass fibre A=70/30 (quality %) carry out mixing as resin combination.At last, will lead to the tank cooling curing, and adopt tablets press that it is cut off, obtain resin composition pellet from the resin combination of metal pattern drawing and filament forming pencil.
Then, use injection machine (the system EC100 of Toshiba Machine Co. Ltd), under the condition of 250 ℃ of cylinder temperatures, 80 ℃ of metal pattern temperature,, make rerum natura determination test sheet, carry out various evaluation tests the resin composition pellet injection forming that obtains.Its result is as shown in table 1.
Embodiment 2～6 and comparative example 1～9
Except being made as the component ratio shown in the table 1, other and embodiment 1 operate equally, make test film, carry out various evaluation tests.Its result is as shown in table 1.In addition, the barrel temperature of forcing machine is made as 210 ℃～250 ℃ when being polymeric amide 11, is made as 230 ℃～270 ℃ when being polyamide 6, is made as 250 ℃～290 ℃ when being polyamide 66.In addition, the cylinder temperature of extrusion shaper is made as 230 ℃ when being polymeric amide 11, is made as 250 ℃ when being polyamide 6, be made as 280 ℃ when being polyamide 66, the metal pattern temperature is made as 60 ℃ when being polymeric amide 11, be made as 80 ℃ when being polyamide 6, is made as 100 ℃ when being polyamide 66.
In an embodiment, by the glass fibre and the organic compound coupling that will have long round section, obtained the glass-fiber-reinforced polyamide resin composition of the excellent rigidity of low warpage and rigidity and weld seam part.
Comparative example 1 is because the use level of flat glass fiber is few, so amount of warpage is big.Comparative example 2 is because the use level of flat glass fiber is many, thus mobile poor during melting mixing, can not carry out the traction of tow, so can not obtain the particle of Amilan polyamide resin composition.Comparative example 3 since the organic compound that cooperates below specified amount, so a little less than the physical strength of weld seam part, the conservation rate of bending elastic modulus is low.Comparative example 4 is because the organic compound that cooperates more than specified amount, so flowability is poor, can not obtain the particle of Amilan polyamide resin composition.Comparative example 5, comparative example 7 be not owing to be combined with organic compounds at all, so a little less than the physical strength of weld seam part, the conservation rate of bending elastic modulus is low.Comparative example 6, comparative example 8 are owing to using the glass fibre with long round section shape, so amount of warpage is big.
Description of drawings
The stereographic map (before the state damping) of the molding during [Fig. 1] amount of warpage of the present invention is estimated.
The stereographic map (after the state damping) of the molding during [Fig. 2] amount of warpage of the present invention is estimated.
Nomenclature
A, b, c, d: measure the position
Claims (5)
1. glass-fiber-reinforced polyamide resin composition, wherein, is that the ratio of 1.5～4.0 polyamide resin 30～80 quality % and major diameter/minor axis is 1.5～10 and has an Amilan polyamide resin composition that flat glass fiber 20～70 quality % of flat cross section mix with respect to 100 mass parts by relative viscosity, the organic compound that has 2 above glycidyls or anhydride group in 1 molecule of cooperation 0.05～4.0 mass parts, described relative viscosity is to use Ubbelohde type viscometer, with the sulfuric acid of 96 quality % as solvent, 25 ℃ of temperature, survey periodic viscosity under the condition of concentration 1g/dl.
2. the described glass-fiber-reinforced polyamide resin composition of claim 1, it is characterized in that the organic compound that has 2 above glycidyls or anhydride group in 1 molecule is the organic compound more than a kind that is selected from TriMethylolPropane(TMP) polyglycidyl ether, Polyglycerine polyglycidyl ether, isocyanuric acid three-glycidyl ester, the phenylethylene/maleic anhydride copolymer.
3. each described glass-fiber-reinforced polyamide resin composition of claim 1～2 is characterized in that, polyamide resin is a kind the polymeric amide that is selected from nylon 6, nylon 66, the Ni Long11.
4. each described glass-fiber-reinforced polyamide resin composition of claim 1～3, wherein, flat glass fiber is the glass fibre with the arbitrary special crosssection shape in Pear-Shaped, cocoon shape, Long Circle, ellipse, the rectangle, and it is that coupling agent, zirconium white are that the coupling agent more than a kind selected the coupling agent carries out surface treatment and forms that glass fibre adopts from silane coupling agent, titanium.
5. the resin forming product that each described glass-fiber-reinforced polyamide resin composition of claim 1～4 is shaped and forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP097403/2007 | 2007-04-03 | ||
| JP2007097403 | 2007-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101652430A true CN101652430A (en) | 2010-02-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880011425A Pending CN101652430A (en) | 2007-04-03 | 2008-03-28 | Glass fiber reinforced polyamide resin composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5500986B2 (en) |
| KR (1) | KR20090127905A (en) |
| CN (1) | CN101652430A (en) |
| TW (1) | TW200904898A (en) |
| WO (1) | WO2008120703A1 (en) |
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| CN102675863A (en) * | 2012-05-11 | 2012-09-19 | 金发科技股份有限公司 | Low warpage polyamide composite material |
| CN102675870A (en) * | 2012-05-22 | 2012-09-19 | 苏州新区华士达工程塑胶有限公司 | Formula of reinforced polycaprolactam GF30HB |
| WO2015089720A1 (en) * | 2013-12-17 | 2015-06-25 | Rhodia Operations | Polyamide molding compositions, molded parts obtained therefrom, and use thereof |
| CN107033588A (en) * | 2017-05-17 | 2017-08-11 | 江苏金发科技新材料有限公司 | Laser welding is modified light-coloured polyamide composite with flat fiber |
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| JP5279415B2 (en) * | 2007-09-03 | 2013-09-04 | ユニチカ株式会社 | Resin composition and molded body using the same |
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Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925823B2 (en) * | 1976-03-31 | 1984-06-21 | 旭化成株式会社 | polyamide composition |
| JPH01311146A (en) * | 1988-06-09 | 1989-12-15 | Tonen Sekiyukagaku Kk | Thermoplastic resin composition |
| JP3057753B2 (en) * | 1990-11-19 | 2000-07-04 | ジェイエスアール株式会社 | Oil resistant resin composition |
| JPH09157335A (en) * | 1995-12-08 | 1997-06-17 | Kanegafuchi Chem Ind Co Ltd | Graft modified polyolefin resin and thermoplastic resin composition containing the same |
| JPH10219026A (en) * | 1997-01-31 | 1998-08-18 | Nitto Boseki Co Ltd | Glass fiber-reinforced resin composition |
| JP2000204240A (en) * | 1999-01-08 | 2000-07-25 | Ube Ind Ltd | Polyamide resin composition having excellent weld strength |
| JP2003082228A (en) * | 2001-09-14 | 2003-03-19 | Kuraray Co Ltd | Polyamide composition |
| JP2004107488A (en) * | 2002-09-18 | 2004-04-08 | Asahi Kasei Chemicals Corp | Thermoplastic resin composition |
| JP4876377B2 (en) * | 2004-08-05 | 2012-02-15 | 日東紡績株式会社 | Method for producing flat glass fiber-containing pellets |
| JP2006131832A (en) * | 2004-11-09 | 2006-05-25 | Unitika Ltd | Polyamide resin composition |
| JP2007302866A (en) * | 2006-01-13 | 2007-11-22 | Mitsubishi Engineering Plastics Corp | Polyamide resin composition for portable electronic device and molding for portable electronic device |
-
2008
- 2008-03-28 KR KR1020097020525A patent/KR20090127905A/en not_active Application Discontinuation
- 2008-03-28 JP JP2009507506A patent/JP5500986B2/en not_active Expired - Fee Related
- 2008-03-28 CN CN200880011425A patent/CN101652430A/en active Pending
- 2008-03-28 WO PCT/JP2008/056045 patent/WO2008120703A1/en active Application Filing
- 2008-04-01 TW TW097111824A patent/TW200904898A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5500986B2 (en) | 2014-05-21 |
| KR20090127905A (en) | 2009-12-14 |
| TW200904898A (en) | 2009-02-01 |
| JPWO2008120703A1 (en) | 2010-07-15 |
| WO2008120703A1 (en) | 2008-10-09 |
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