CN1131280C - Polyacetal resin composition - Google Patents
Polyacetal resin composition Download PDFInfo
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- CN1131280C CN1131280C CN96197846A CN96197846A CN1131280C CN 1131280 C CN1131280 C CN 1131280C CN 96197846 A CN96197846 A CN 96197846A CN 96197846 A CN96197846 A CN 96197846A CN 1131280 C CN1131280 C CN 1131280C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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Abstract
A polyacetal resin composition improved in hinge characteristics and flowability without impairing the mechanical properties, frictional wear resistances, moldability and tenacity inherent in polyacetals. This composition can be prepared by blending a polyacetal resin with a core-shell polymer composed of a core made of a rubbery polymer and a shell made of a glassy polymer and containing a bisamide of a saturated fatty acid premixed therewith homogeneously as lubricant.
Description
[technical field that the present invention belongs to]
The present invention provides a kind of have the extremely excellent tough mechanicalness and the polyacetal resin composition of shock resistance and good fluidity by polyacetal resin and specific nuclear/shell polymeric blending, and with the polyacetal resin system hinge member of this constituent moulding.
Above-mentioned hinge member as shown in Figure 1, the thin-walled that is applied bending or folding load by one or many in the parts partly is called hinge (among the figure shown in 1).The shape of hinge does not have special restriction, can be sheet, band shape or cord shape.Thickness, length to hinge do not have special stipulation yet.Have the including in the hinge member that the present invention says of folding azido functional in fact.
In this specification sheets, hinge characteristics is defined as the tolerance above-mentioned bending that applies of one or many or the weather resistance of folding load.
Prior art
As everyone knows, polyacetal resin is applied in utmost point extensive fields as the engineering resin with physical property such as excellent mechanical property, electric property or chemical propertys such as resistance to chemical reagents, thermotolerance.Yet along with the expansion of polyacetal resin Application Areas, the character of its material requires singularity sometimes again.As one of such character, require the good material of exploitation flexibility sometimes, i.e. the good material of hinge characteristics.
Especially in recent years, from by reducing the necessity that number of components reduces cost, wish to adopt hinge that the incorporate situation of some parts is increased easily and at an easy rate.And the reason that hinge characteristics is descended is a lot, uses at low temperatures as hinge member, or can not obtain gratifying hinge shape etc. on the structure.Requirement to excellent in fact hinge characteristics is strict more.
In addition, in fields such as general electricapparatus, building, the chance that various combinations of materials use is increased, thereby require further to improve the shock resistance of polyacetal resin according to purpose.
As everybody knows, as the method that satisfies the hinge characteristics requirement, be in polyacetal resin, to add elastomerics such as thermoplastic polyurethane, attempt to improve hinge characteristics or shock resistance.
In this method, it is possible improving hinge characteristics, peels off phenomenon but the blending elastomerics easily causes product surface, exists products appearance badly damaged problem.And thermostability descends, and welding seam of articles intensity and elongation obviously descend.The mobile reduction makes variety of problems such as the degree of freedom of the design of hinge diminishes, and requires to be improved.
In addition in recent years, the function that hinge requires increases, and shape is complicated more simultaneously, the lightweight in order to reduce cost, continuous thin-walled property.And, for improving injection molding productive rate, must shorten shaping cycle, and the goods number that uses multi-mould moulding increasing shot moulding to obtain.For satisfying these requirements, improve the mobile necessary of material.
[content of invention]
Purpose of the present invention is under the condition of not damaging other physicals, provides hinge characteristics than better polyacetal resin composition of past, and polyacetal resin system hinge goods.
The inventor does not lose the original characteristic of polyacetal resin as far as possible to exploitation, address the above problem and make it to have excellent hinge characteristics and keep flexible polyacetal resin material to study with keen determination repeatedly, found that add certain specific saturated fatty acid bisamide and nuclear/shell polymeric in advance the mixture of uniform mixing gained be effective.
Promptly, the polyacetal resin composition that the present invention relates to, form with (B) blending by (A), (A) be 100 weight part polyacetal resins, (B) be 1～100 weight part nuclear/shell polymeric, the latter by the shell of the nuclear of rubbery polymer and glassy polymers form, and evenly be mixed with 0.3～5 weight part (to 100 weight part nuclear/shell polymerics) in advance, by the saturated fatty acid bisamide of following general formula: general formula: R
1-CONH-R
2-NHCO-R
3
In the formula, R
1And R
3Be the alkyl of selecting the aliphatic alkyl, substituted alkyl, aryl, substituted aryl from carbonatoms 10～22, can be the same or different.R
2It is the alkyl of the divalent of carbonatoms 1～12.
As mentioned above, resin combination of the present invention comprises (A) and (B).(B) contain nuclear/shell polymeric and above-mentioned saturated fatty acid bisamide, mix equably.Because it has good hinge characteristics, shock resistance and flowability, very be suitable as the material of hinge with resin, be difficult to reach in the former technology.
As mentioned above, in nuclear/shell polymeric, evenly be mixed with specific lubricant (saturated fatty acid bisamide) in advance, resin combination of the present invention with the polyacetal resin blending demonstrates outstanding effect again, it has not only kept polyacetal equilibrated mechanical and physical performance, and has kept hinge characteristics, good fluidity, good toughness.
With the hinge member of this polyacetal resin composition machine-shaping, its purposes for example has automobile, electric and electronic, building materials, the various hinge portion product in the fields such as sundry goods.Have particularly automobile with joint, electrical equipment with joint etc., polyacetal resin composite is applicable to these purposes.
The simple declaration of accompanying drawing
Fig. 1 is the test piece sketch that is used to measure hinge characteristics.(a) (b) (c) represents the expanded view of orthographic plan, side elevational view and hinge member respectively.The unit of numerical value is mm among the figure.
The working of an invention scheme
Below constituent of the present invention is elaborated.
At first, used (A) polyacetal resin of the present invention is with carboxaldehyde radicals (CH
2O-) be the unitary macromolecular compound of main composition.Can be polyacetal homopolymer, except that carboxaldehyde radicals, also contain a small amount of other and constitute unitary multipolymer, terpolymer, segmented copolymer.Molecule can be a linear chain, also can have side chain or crosslinking structure.The present invention is according to the ASTMD1238-89E method, is that the melt index of 190 ℃ of mensuration is 0.1～30g/10min at barrel temperature, is more preferably 0.5～15g/10min.
(B) nuclear/shell polymeric that the present invention uses, be in the nuclear/shell polymeric of the shell of nuclear with rubbery polymer and glassy polymers, evenly be mixed with 0.3～5 weight part (per relatively 100 weight part nuclear/shell polymerics) in advance, by the nuclear/shell polymeric of the saturated fatty acid bisamide of following general formula.
General formula: R
1-CONH-R
2-NHCO-R
3
In the formula, R
1And R
3Be the alkyl of selecting the aliphatic alkyl, substituted alkyl, aryl, substituted aryl from carbonatoms 10～22, can be the same or different.R
2It is the alkyl of the divalent of carbonatoms 1～12.
Evenly being mixed with the nuclear/shell polymeric (B) of the saturated fatty acid bisamide that the present invention uses in advance, is to have the nuclear of rubbery polymer and the compound of glassy polymers shell as the nuclear/shell polymeric of its parent.Available on record method preparation, also available commercially available product, its typical case has Rohm﹠amp; ア Network リ ロ イ De KM330 and KM653 that Haas Co.Ltd (rom Haars Co., Ltd) produces, the パ テ リ ロ イ De KCA-102 and the KCA-301 of Wu Yu chemistry (strain), the ス Off イ ロ イ De PO-0143 and the PO-0148 of military field pharmaceutical industries (strain).The カ ネ エ-ス FM of clock deep pool chemical industry (strain), mitsubishi rayon's's (strain) ト Block レ Application C-102, E-901, W-800, S-2001.Among such nuclear/shell polymeric, preferably have elastomeric nuclear and methyl methacrylate and be the polymkeric substance of shell of the glassy polymers of major ingredient.Especially preferably can not detect anionic nuclear/shell polymeric in fact.When use can detect anionic nuclear/shell polymeric, when melting mixing and injection molding, may promote the decomposition of polyacetal, can not obtain desirable hinge characteristics, and decompose too much, sometimes can not melting mixing.What is called can not detect anionic nuclear/shell polymeric in fact among the present invention, is meant with conventional negatively charged ion qualitative test not detect negatively charged ion.For example its measuring method is to take by weighing 5g sample (nuclear/shell polymeric) in the 50ml erlenmeyer flask, adds the water of 20ml through ion-exchange, uses magnetic stirrer 3 hours, then the filtrate with the No.5C filter paper filtering is divided into two parts.1 part adds 1% barium chloride solution 0.5ml, the muddiness (qualitative test of sulfate ion) that paired observation produces.1 part is carried out same processing in addition, adds the 0.1N silver nitrate aqueous solution and replaces 1% barium chloride solution.By contrast muddy method (halogen ionic qualitative test) taking place can confirm anionic existence.Preferably use and do not have anionic nuclear/shell polymeric fully.
Ideal nuclear/the shell polymeric that the present invention uses is preferably to carry out letex polymerization in the presence of nonionic surface active agent and the polymerization starter that can produce neutral free radical to obtain such nuclear/shell polymeric.For example can adopt the spy to open emulsion polymerization technology production among the flat 3-14856.Letex polymerization, for example available surfactant down and polymerization starter carry out.As nonionic surface active agent, can use nearly all widely used nonionic surface active agent.Comprise: the ether type, as polyoxyethylene nonylplenyl ether, polyoxyethylene stearyl acyl ether, polyoxyethylene lauryl ether etc.; The ester type is as polyoxyethylene stearic acid ester etc.; The sorbitan ester type is as polyoxyethylene sorbitan list lauryl etc.; The block polymer type is as polyoxyethylene polyoxypropylene block copolymer etc.Its addition is suitably selected according to the stabilizing power of surfactant particles.The polymerization starter that can be used alone or in combination of two or more comprises azo class polymerization starter, as Diisopropyl azodicarboxylate, 2,2 '-azo-two isopropylformic acid dimethyl ester, 2,2 '-azo two (2-aminopropane) dihydrochloride etc.The peroxide polymerization starter is as isopropyl benzene hydroperoxide, diisopropylbenzenehydroperoxide, hydrogen peroxide etc.If in the reaction system that does not contain aniorfic surfactant and non-persulphate, carry out letex polymerization, can not conformed to anionicly in fact, or only contain few anionic nuclear/shell polymeric.Using so in fact not, the polyacetal resin composition of anion-containing nuclear/shell polymeric becomes the hinge characteristics excellent material.
Nuclear/the shell polymeric that is used as parent among the present invention has the nuclear of rubbery polymer and the shell of glassy polymers.Emulsion polymer adopts the continuous multi-stage emulsion polymerization in the seed emulsion polymerization to make usually.The polymkeric substance of polymer overmold generation the last period of back in order one section generation.When nuclear/shell polymeric has intermediate phase described later, the intermediate phase that has the multistage emulsion polymerization to generate, promptly back one section polymkeric substance infiltrates in the polymkeric substance of the last period.
During particle generation polymerization, preferably monomer, tensio-active agent and water are added in the reactor, and then the polyaddition initiator begins emulsion polymerization.The polymerization of fs is the reaction that forms rubbery polymer, comprise as conjugated diene or alkyl acrylate as the monomer that constitutes rubbery polymer, wherein the carbonatoms of alkyl is 2～8 or both mixture, and these monomer polymerizations form the rubbery polymer below second-order transition temperatures-30 ℃.As such conjugated diolefine, comprise as divinyl, isoprene, chloroprene etc.And be the alkyl acrylate of 2-8 as the alkyl carbon atoms number, ethyl propenoate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, ethyl acrylate etc. are arranged.
In the fs polymerization, can with the monomer of copolymerization such as conjugated diolefine and alkyl acrylate, for example aromatic ethenyl, aromatic series vinylidenes such as vinylbenzene, Vinyl toluene, alpha-methyl styrene; Vinyl cyanide, as vinyl cyanide and methacrylonitrile vinylidene cyanide; And alkyl methacrylate, as methyl methacrylate and butyl methacrylate etc.
In the fs polymerization, when not containing conjugated diolefine, or the amount of contained conjugated diolefine is 20 weight % of used monomer total amount of fs when following, can obtain having the polymkeric substance of high impact properties by using a spot of cross-linking monomer or grafted monomer.Cross-linking monomer comprises aromatic diethylene base monomer such as Vinylstyrene; Many acrylate of alkane polyol or the many methacrylic esters of alkane polyol are as ethylene glycol diacrylate, Ethylene glycol dimethacrylate, diacrylate butanediol ester, hexanediol diacrylate, dimethacrylate hexylene glycol ester, the low macrogol ester of diacrylate, the low macrogol ester of dimethacrylate, diacrylate trihydroxymethylpropanyl ester, dimethacrylate trihydroxymethylpropanyl ester, trimethyol propane triacrylate, trihydroxy methyl propane trimethyl acrylate.Preferably use diacrylate butanediol ester, hexanediol diacrylate.As grafted monomer, comprise the unsaturated carboxylic acid allyl ester, as vinylformic acid allyl ester, allyl methacrylate, toxilic acid diallyl ester, fumaric acid diallyl ester, methylene-succinic acid diallyl ester etc.Preferably use allyl methacrylate.The consumption of these cross-linking monomers and grafted monomer generally is equivalent to 0～5 weight % of used monomer total amount of the 1st stage, preferably 0.1～2 weight %.
The nuclear of this rubbery polymer accounts for the scope of 50～90 weight % of nuclear/shell polymeric total amount.This weight range of little what or when exceeding this weight range with the molten resin combination of making that mixes of institute's product nucleus/shell polymeric, under some occasion, can not provide gratifying effect aspect the shock resistance improving.And, when the second-order transition temperature of nuclear compares-30 ℃ high, under some occasion, can not be satisfied with to the effect of improving the low-temperature impact resistance aspect.
Outermost shell (shell phase) is a glassy polymers.The monomer that constitutes glassy polymers comprises methyl methacrylate.And a kind of can with the monomeric mixture of methyl methacrylate copolymer.The second-order transition temperature of the glassy polymers that generates is 60 ℃ or higher.As can with the monomer of methylmethacrylate copolymer, comprise the polymerisable monomer of vinyl, as alkyl methacrylate, as Jia Jibingxisuanyizhi, butyl methacrylate; Alkyl acrylate is as ethyl propenoate, butyl acrylate, aromatic ethenyl compound, as vinylbenzene, Vinyl toluene, alpha-methyl styrene; The aromatic series vinylidene compound; Vinyl cyanide is as vinyl cyanide, methacrylonitrile and vinylidene cyanide.Especially preferably use ethyl propenoate, vinylbenzene and vinyl cyanide.
Outermost shell (shell phase) preferably accounts for 10～50 weight % of nuclear/shell polymeric gross weight.If the low mutually what of shell or when surpassing this weight range uses the molten resin combination that mixes system of the nuclear/shell polymeric that is generated under some occasion, can not be satisfactory in the effect of improving aspect the shock resistance.
In addition, be preferably in first section with polymerization mutually that final stage generates between may have intermediate phase.This intermediate phase generates with the inoculation letex polymerization, for example, have polymerisable monomers such as the polymerisable monomer of functional group such as glycidyl methacrylate, methacrylic acid, methacrylic acid hydroxyethyl ester, form the polymerization single polymerization monomer of the glassy polymers of methyl methacrylate etc. and so on, form the polymerization single polymerization monomer of rubbery polymer such as methyl acrylate.This intermediate phase can be selected according to the character of desirable nuclear/shell polymeric.Its polymerization ratio can suitably be selected according to the monomer that uses.For example, when glassy polymers was used as intermediate phase, a part that can be used as shell was calculated polymerization ratio.Under the occasion of rubbery polymer, a part that then can be used as nuclear is calculated its polymerization ratio.
Structure with nuclear/shell polymeric of this intermediate phase, be included in the multilayered structure that also has another layer between nuclear and the shell, intermediate phase becomes the Sa Lami structure of particulate for loosing in nuclear, in nuclear/shell polymeric with Sa Lami structure, under extreme occasion, should the dispersive intermediate phase, form new nuclear at the middle part of nuclear sometimes.Nuclear/shell polymeric with this structure constitutes under the monomeric occasion as intermediate phase and may produce using with the monomer of vinylbenzene as representative.Have in use under the occasion of nuclear/shell polymeric of intermediate phase, might improve shock resistance, improve counter-bending Young's modulus, improve heat-drawn wire, improve outward appearance (inhibition of sur-face peeling and pearly-lustre color and luster is because the tonal variation that variations in refractive index produces).
As the method for giving the polyacetal resin shock resistance, except adding rubber, people know, add the method for nuclear/shell polymeric at polyacetal resin, though can satisfy hinge characteristics condition in addition really with this method, but a shortcoming is arranged, that is: add nuclear/shell polymeric in the bad polyacetal resin of inherent tough mechanical property, tough mechanical property is further reduced, the polyacetal resin composition that not only keeps mobile, non-separability but also can satisfy tough machinery can not be provided.
Like this, add the conventional nuclear/shell polymeric that is mixed in polyacetal resin, though can not reduce the mechanical property of polyacetal resin excellence, and can improve its toughness, hinge characteristics is poor, can not make the hinge member purposes uses.
Feature of the present invention, be in above-mentioned nuclear/shell polymeric, be mixed in advance specific lubricant (saturated fatty acid bisamide) (B) with (A) polyacetal resin is mixing.In this way, with (A) and (B) two kinds of compositions be mixed, can under the condition of not damaging the original equalization characteristic of polyacetal resin, improve the hinge characteristics of polyacetal resin effectively.
As three kinds of composition blended methods, comprise promptly that with 2 kinds of compositions adding all the other a kind of compositions after mixing again continues mixingly, comprises that also three kinds of compositions are simultaneously mixing with polyacetal resin, nuclear/shell polymeric and lubricant etc.
For example, polyacetal resin and nuclear/shell polymeric add lubricant again after mixing and carry out mixing method.Under the influence of lubricant, the polyacetal resin composition lack of homogeneity that the dispersiveness of mixing state difference, lubricant is also poor, make.The result is unsuitable for moulding with the gained polyacetal resin composition and makes hinge member, because its hinge characteristics is poor.
As other method, after let us is investigated polyacetal resin and the mixed chain of lubricant, add nuclear/shell polymeric polymkeric substance again and carry out mixing method, but because it is mixing to contain the polyacetal resin and the nuclear/shell polymeric of lubricant, nuclear/shell polymeric is difficult to homodisperse, hinge member is made in polyacetal resin composition moulding with gained, and its hinge characteristics is also bad.
In addition, same as above, even three kinds of compositions are simultaneously mixing, with the hinge member of gained polyacetal resin composition moulding, owing to the function difference of making hinge is not suitable for using.
Even with above-mentioned either party's method, three kinds of compositions are mixing, in the gained polyacetal resin composition, nuclear/shell polymeric, lubricant bad dispersibility.Homogeneity is bad.Therefore with the polyacetal resin composition moulding hinge member that makes like this, be not suitable for using because of making the hinge function difference.
But present inventors find, behind the saturated fatty acid bisamide that evenly is mixed in nuclear/shell polymeric in advance, it are added to the method in the polyacetal resin again, and it is effective being used for hinge member.
Among the present invention, with the polymkeric substance of polyacetal resin blending be the nuclear/shell polymeric that contains lubricant, the latter is nuclear/shell polymeric and should be blended into the even blending gained of full dose lubricant in the polyacetal resin composition.Method is that the saturated fatty acid bisamide is dissolved in a kind of solvent, and gained solution mixes with the Henschel high-speed mixer with commercially available nuclear/shell polymeric, removes then and desolvates; Another kind method is to add the saturated fatty acid bisamide in the drying process of the letex polymerization of nuclear/shell polymeric; With these two kinds of methods, can in advance the saturated fatty acid bisamide be evenly dispersed in nuclear/shell polymeric.
The present invention uses the saturated fatty acid bisamide of following general formula for this purpose:
General formula: R
1-CONH-R
2-NHCO-R
3
In the formula, R
1And R
3Be the group of selecting the aliphatic alkyl, substituted alkyl, aryl, substituted aryl from carbonatoms 10～22, can be the same or different.R
2It is the divalent alkyl of carbonatoms 1～12.It is made by specific Alkylenediamine and specific saturated fatty acid.
The saturated fatty acid composition of saturated fatty acid bisamide is that carbonatoms is 11～23 compound, comprise 11 (alkane) acid, 12 (alkane) acid, 13 (alkane) acid, 14 (alkane) acid, 15 (alkane) acid, 16 (alkane) acid, 17 (alkane) acid, 18 (alkane) acid, 19 (alkane) acid, twenty (carbon) alkanoic acid and 22 (carbon) alkanoic acid, wherein preferably 18 (alkane) acid.
Divalent alkyl as the saturated fatty acid bisamide preferably includes alkylidene groups such as single methylene radical, dimethylene, trimethylene, tetramethylene, pentamethylene and hexa-methylene, wherein, and especially preferably single methylene radical, dimethylene.
In the above saturated fatty acid bisamide, particularly preferably be ethylenebisstearamide (C
17H
35-CONH-CH
2-CH
2-NHCO-C
17H
35) and methylene-bis stearylamide (C
17H
35-CONH-CH
2-NHCO-C
17H
35).
The addition of saturated fatty acid bisamide to the nuclear/shell polymeric of 100 weight parts, is advisable with 0.3～5 weight part.Preferably 1～5 weight part, 2～4 weight parts especially preferably.During few what 0.3 weight part, it is little that hinge characteristics improves effect, during big what 5 weight parts, improves effect and reach capacity.The original characteristic of polyacetal resin is produced detrimentally affect.
Though this unsaturated fatty acid amide can obtain having the polyacetal resin composition of excellent toughness with (A) polyacetal resin and nuclear/shell polymeric blending.But can not obtain giving the hinge profiled part of excellent hinge characteristics.To examine/shell polymeric in advance with the blending of saturated fatty acid bisamide, have the significant effect of improving, find to have the effect of excellent hinge characteristics.
In the prepared moulded products of blending nuclear/shell polymeric, nuclear/shell polymeric disperses in its surface with the particle shape in polyacetal resin, and during with the moulded products bending, its nuclear/shell polymeric just becomes the starting point of destroying or rupturing.Therefore, the nuclear/shell polymeric and (A) blend of polyacetal resin, hinge characteristics reduces significantly.But,, just can observe the significant effect of improving effect and the hinge characteristics of excellence being provided in advance with saturated fatty acid bisamide and nuclear/shell polymeric blending.
This by inference effect and effect although be because the granularity of nuclear/shell polymeric primary particle has only several μ, can be condensed into the secondary particle caking of tens of μ usually, only become primary particle with the mixing nuclear/shell polymeric homodisperse that can not allow of polyacetal resin.But, by in advance with the saturated fatty acid bisamide with after nuclear/shell polymeric mixes, again with polyacetal resin when mixing, nuclear/shell polymeric just can be dispersed into primary particle equably.The saturated fatty acid bisamide is because the affinity of the shell component of saturated fatty acid bisamide and nuclear/shell polymeric is big as the huge effect of lubricant according to estimates, can improve the dispersive ability of nuclear/shell polymeric.Above-mentioned effect and effect are still not fully aware of, and therefore, the present invention is not limited.
According to the present invention, with the addition of the nuclear/shell polymeric (B) of saturated fatty acid bisamide blending, be 1～100 weight part to the polyacetal resin of 100 weight parts, 5～50 weight parts preferably.Nuclear/shell polymeric addition is very little the time, and high hinge characteristics and shock resistance can not get gratifying performance.And addition is when excessive, and mechanical property, especially rigidity reduce significantly, and can produce bad influence to thermostability.
Furtherly, preferably in constituent of the present invention, add well-known various stablizers, to strengthen its thermostability.For this purpose, preferably use or be used in combination known oxidation inhibitor separately, nitrogenous compound, basic metal or alkaline earth metal compound.
According to the purpose requirement, furtherly, for desired characteristic being provided for constituent of the present invention, also can add known additives more than a kind or 2 kinds, for example the lubricant except that the saturated fatty acid bisamide, nucleator, release agent, static inhibitor, other tensio-active agent, organic polymer material, inorganic, organically fibrous, powder shape, flaky weighting agent etc.
Constituent of the present invention, the preparation equipment of available generally acknowledged synthetic resins constituent and method preparation.That is, can single screw rod or twin screw extruder is mixing with essential component, carry out moulding again behind the extruding pelletization.Perhaps the preparation of constituent and moulding also can be carried out in shaper simultaneously.In addition, for making the blending of relevant component homodisperse, also can adopt a part of resin or all resins are pulverized, mixed fusion and extrusion moulding process for granulating.Any of aforesaid method all can use.
In addition, also can add aforementioned stablizer, additive in the stage in office, also can before being about to make the final molding goods, add and blending certainly.
Resin combination of the present invention can adopt arbitrary method of extrusion moulding, injection molding, compressed moulding, vacuum forming, blow molding, foaming to be carried out to type.[embodiment]
Below enumerate embodiment and comparative example explanation the present invention.But the present invention is not subjected to the restriction of these embodiment. " part " in embodiment, the comparative example all represents weight part. embodiment, the abbreviation of using in the comparative example is as follows: ethyl acrylate EA methyl methacrylate MMA acrylic acid-BDO ester BGA allyl methacrylate AIMA Methacrylamide MAM acrylic acid-2-ethyl caproite EHA butadiene BD nonionic surfactant (flower king エ マ processed Le グ Application 950) E950 oligomeric anionic surfactant surfactant A
(open among the clear 53-10682 embodiment 13 methods according to the spy and synthesize, after being adjusted to pH and being 7.5 with ammoniacal liquor, solids content is 10% in pure water).Dodecyl
(in the formula, a: b=7: 3, a+b=about 13.6)
(composition) methacrylic acid 155g methyl methacrylate 360g n-dodecyl mercaptan 109g azodiisobutyronitrile 4.4g isopropyl alcohol 314g molecular weight 1310 deionized water DIW2,2 '-two (2-aminopropane) the dihydrochloride V50 ethylenebisstearamide EBSC of azo17H
35-CONH-CH
2-CH
2-NHCO-C
17H
35Methylene-bis stearylamide MBSC
17H
35-CONH-CH
2-NHCO-C
17H
35The preparation of pentaerythritol tetrastearate PETS polyacetal resin POM resin＜nuclear/shell polymeric B-1 and B '-1 〉
In 5 liters have the polymeric kettle of reflux exchanger, add deionized water (DIW) 1200g, 25% ammoniacal liquor 1.68g, surfactant A 7g, Methacrylamide (MAM) 0.14g, under the nitrogen gas stream protection, be warmed up to 70 ℃ while stirring.Add the seed monomer mixture 27.86g of following composition, after disperseing with 10 minutes, add 10% aqueous solution 21g of V50, carry out the seed particles polymerization.
Seed monomer ethyl propenoate (EA) 27.664g allyl methacrylate(AMA) (AIMA) 0.14g vinylformic acid-1,4-butanediol ester (BGA) 0.056g
Then, add Methacrylamide (MAM) 7g, in the nuclear partial monosomy mixture of the following composition of 1500g, add surfactant A 210g, deionized water (DIW) 900g, 25% ammoniacal liquor 2.80g and mixed monomer emulsion, and the mixed solution of the ammoniacal liquor 0.63g of 10%V50 aqueous solution 21.0g and 1%, in 180 minutes time, send into continuously, carry out seeding polymerization.
Nuclear partial monosomy mixture ethyl acrylate (EHA) 1040.2g divinyl (BD) 450.0g vinylformic acid-1,4-butanediol ester (BGA) 2.8g allyl methacrylate(AMA) (AIMA) 7.0g
Be warmed up to 80 ℃, after 1 hour maturation, be cooled to 70 ℃.
Then, add 10% aqueous solution 9g of V50,1% ammoniacal liquor 0.27g, with the shell partial monosomy emulsion of following composition and 10% aqueous solution 12g of V50,1% ammoniacal liquor 0.36g carries out letex polymerization with 60 minutes time continuously feeding.
Shell partial monosomy emulsion methyl methacrylate (MMA) 438.8g ethyl acrylate (EA) 60.0g surfactant A 30.0g deionized water (DIW) 500.0g25% ammoniacal liquor 0.72g acrylic acid-BDO ester (BGA) 1.2g Methacrylamide (MAM) 3.0g
Be warmed up to 80 ℃, after 1 hour maturation, the cooling,, can make nuclear/shell polymeric latex with 300 order Stainless Steel Wire net filtrations.At-15 ℃ this latex is freezed, after filtering with glass filter,, can make nuclear/shell polymeric B '-1 at the dry diel of 60 ℃ of katabatic winds.
To examine/shell polymeric and 60g ethylenebisstearamide [trade(brand)name ア-モ ワ Star Network ス that the lion AKZO N. V produces] solution that is dissolved in the 100ml dimethyl formamide (DMF), after the mixing of Henschel high-speed mixer, having reduced pressure, obtain nuclear/shell polymeric B-1 except that desolvating.The preparation of＜nuclear/shell polymeric B-2～5, B '-2～3 〉
Except that the monomer that adopts composition as shown in table 1, other equally carries out polymerization with B-1, makes nuclear/shell polymeric B-2～5 and B '-2～3.(nuclear/shell polymeric B '-4 preparation)
Monomer with forming shown in the table 1 does not add outside the lubricant, and other equally carries out polymerization with B-1, makes nuclear/shell polymeric B '-4.
Table 1
[qualitative test of sulfate ion]
| Monomer is formed (weight part) | Nuclear/shell polymeric | |||||||
| B-2 | B-3 | B-4 | B-5 | B′-2 | B′-3 | B′-4 | ||
| Nuclear | EHA BD BGA AIMA | 1040.2 450.0 2.8 7.0 | 1110.2 480.0 2.8 7.0 | 1110.2 480.0 2.8 7.0 | 1040.2 450.0 2.8 7.0 | 1040.2 450.0 2.8 7.0 | 1040.2 450.0 2.8 7.0 | 1110.2 480.0 2.8 7.0 |
| Shell | MMA EA BGA | 438.8 60.0 1.2 | 338.8 60.0 1.2 | 338.8 60.0 1.2 | 438.8 60.0 1.2 | 438.8 60.0 1.2 | 438.8 60.0 1.2 | 338.8 60.0 1.2 |
| Lubricant | EBS MBS PETS | - 60.0 - | 60.0 - - | - 60.0 - | 30.0 - - | 2.0 - - | - - 60.0 | - - - |
Measure contained sulfate ion among nuclear/shell polymeric-B-1～5 and the B '-1～4.
That is, take by weighing the 5g test portion and be added in the 5ml erlenmeyer flask, add the 20ml ion exchanged water, use magnetic stirrer 3 hours.
Then, use the No.5C filter paper filtering, filtrate is divided into two parts, in 1 part, add 1% barium chloride solution 0.5ml, the generation of paired observation muddiness.
In this qualitative test, from nuclear/shell polymeric B-1～5 and B '-1～4, do not measure sulfate ion.
Polyacetal
The POM copolymer resin that polymer plastic company produces, trade(brand)name ジ ュ ラ コ Application
A-1 melt index (190 ℃) 2.5 (g/10min)
A-2 melt index (190 ℃) 9.0 (g/10min)
Press the composition shown in the table 2, POM copolymer resin ジ ラ コ Application with the production of polymer plastic company, nuclear/shell polymeric B-1～5 with the aforesaid way preparation, be dried to water content below 0.3% after, with the twin screw extruder PCM-30 of pond shellfish ironworker corporate system, melting mixing granulation under the condition of 190 ℃ of barrel zone temperatures, 200 ℃ of head temperatures.This pellet more than 3 hours, is machined to test piece with injection molding 80 ℃ of dryings, carries out following evaluation, the results are shown in table 2.Comparative example 1～11
Press shown in the table 3 and form, POM copolymer resin ジ ュ ラ コ Application with the production of polymer plastic company, nuclear/shell polymeric B '-1～4 with the aforesaid way preparation, be dried to water content below 0.3% after, with the twin screw extruder PCM-30 that Bei Tiegong company in pond makes, melting mixing, granulation under the condition of 190 ℃ of barrel zone temperatures, 200 ℃ of head temperatures.Same with embodiment, be made into test piece with this pellet, carry out following evaluation.The results are shown in table 3.
In addition, the evaluating characteristics in embodiment, the comparative example carries out by the following method.
(1) evaluation of hinge characteristics
Make the test piece of shape shown in Figure 1, estimate by standard shown below.
Sample number: n=10
Testing method: with sample after placing more than 24 hours under-10 ℃, the environment of 50%RH, under the same conditions, with hinge fraction by the bending 100 times repeatedly of the angles of 180 degree.
Estimate A: among the bending 100 times, hinge fraction destructive number.
(numerical value is healed better little)
Estimate B:, represent with average mark with the state of hinge fraction after the following judging criterion evaluation bending 100 times.
(numerical value more better)
5: almost do not have unusual result.
4: the surface of hinge fraction produces micro-fractures.
3: the slight crack on hinge fraction surface increases.
2: further to the center expansion, hinge fraction becomes as thin as a wafer the slight crack of hinge portion.
1: the hinge fraction of attenuation has the crack near fracture.
0: sample fracture
(2) Ai Zuode resistance to impact shock
With the series connection injection moulding machine, the resin granular material of embodiment and comparative example system is processed into test with sample (wide 12.7mm, thick 6.4mm, the rectangular parallelepiped of long 64mm), make breach by the method for ASTM D256, measure the Ai Zuode impact value.Ai Zuode impact value height shows that performance is good.
Among the embodiment, it is as follows that hinge characteristics, mechanical and physical performance are estimated the forming method of used test piece.
*Shaper: the system IS80 of Toshiba's (strain)
*Condition of molding
Nozzle C
1C
2C
3Barrel zone temperature (℃) 200 190 180 160 injection pressures, 650 (kg/cm
2) injection speed 1.0 (m/min) die temperature 70 (℃)
(3) assay method of mobile (thin slice length of flow)
Adopt the shaper of setting following condition, be processed into thin test piece (wide 5mm * thick 0.5mm), estimate mobile by its length of flow (length of potting resin).
*Shaper; Day smart (strain) system PS20E
*Condition of molding
Nozzle C
1C
2C
3Barrel zone temperature (℃) 200 190 180 160 injection pressures, 1000 (kg/cm
2) injection speed 4.0 (m/min) die temperature 70 (℃)
Table 2
| | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |||
| Form | Polyacetal resin | Kind | A-1 | A-2 | A-2 | A-2 | A-2 | A-2 | A-2 | A-2 |
| Weight part | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | ||
| Nuclear/shell polymeric | Kind | B-1 | B-1 | B-1 | B-1 | B-2 | B-3 | B-4 | B-5 | |
| Weight part | 30 | 30 | 10 | 50 | 30 | 30 | 30 | 30 | ||
| Performance | Hinge characteristics | Estimate A | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| -10℃，50％RH | Estimate B | 5.1 | 4.1 | 3.8 | 5.0 | 4.0 | 5.0 | 5.0 | 4.0 | |
| Shock strength (kgcm/cm) | 25.1 | 18.6 | 12.2 | 36.3 | 17.9 | 21.9 | 20.5 | 18.8 | ||
| Mobile (mm) P=1000kgf/cm 2 | 26.2 | 43.0 | ＞50 | 31.3 | 42.0 | 43.6 | 42.5 | 42.6 | ||
Table 3
| Comparative example | |||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | |||
| Form | Poly-methyl esters resin | Kind | A-1 | A-1 | A-2 | A-2 | A-2 | A-2 | A-2 | A-2 | A-2 | A-2 | A-2 |
| Weight part | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | ||
| Nuclear/shell polymeric | Kind | B′-1 | B′-1 | B′-1 | B′-1 | B′-2 | B′-3 | B′-1 | B′-1 | B′-1 | B′-4 | B′-4 | |
| Weight part | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Lubricant | Kind | - | EBS | - | EBS | - | - | MBS | EBS | EBS | - | EBS | |
| Weight part | - | 0.9 | - | 0.9 | - | - | 0.9 | 0.3 | 1.5 | - | 0.9 | ||
| Hinge characteristics-10 ℃, 50%RH | Estimate A | 10 | 6 | 10 | 6 | 10 | 10 | 8 | 10 | 8 | 10 | 8 | |
| | 0 | 2.1 | 0 | 1.9 | 0 | 0 | 0.7 | 0 | 0.9 | 0 | 0.6 | ||
| Shock strength (kgcm/cm) | 20.6 | 19.9 | 17.2 | 16.3 | 17.5 | 16.2 | 15.1 | 9.2 | 32.5 | 15.7 | 15.5 | ||
| Mobile (mm) P=1000kgf/cm 2 | 22.2 | 23.4 | 38.0 | 38.7 | 38.5 | 38.9 | 38.5 | ＞50 | 28.9 | 37.5 | 38.1 | ||
Claims (8)
1. polyacetal resin composition, this constituent contains (A) 100 weight part polyacetal resins, (B) 1～100 weight part nuclear/shell polymeric, this nuclear/shell polymeric is made up of the nuclear of rubbery polymer and the shell of glassy polymers, and for 100 weight part nuclear/shell polymerics, evenly mixed the saturated fatty acid bisamide that 0.3～5 weight part is represented with following general formula in advance.
General formula: R
1-CONH-R
2-NHCOR
3
In the formula, R
1And R
3Be the group of selecting the aliphatic alkyl, substituted alkyl, aryl, substituted aryl from carbonatoms 10～22, can be the same or different.R
2It is the divalent alkyl of carbonatoms 1～12.
2. the polyacetal resin composition described in claim 1, wherein, nuclear/shell polymeric (B) is can not detect anionic nuclear/shell polymeric in fact.
3. the polyacetal resin composition described in claim 1 or claim 2, wherein, nuclear/shell polymeric (B) is that free radical in nonionic surface active agent and generation carries out nuclear/shell polymeric that letex polymerization makes in the presence of for the neutral polymerization starter.
4. polyacetal constituent as claimed in claim 1 or 2, wherein, it is the polymkeric substance of main component that the shell of nuclear/shell polymeric (B) comprises with the methyl methacrylate.
5. polyacetal resin composition as claimed in claim 1 or 2, wherein, the saturated fatty acid composition of saturated fatty acid bisamide is selected from undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, margaric acid, octadecanoic acid, nondecylic acid, eicosanoic acid and docosanoic acid.
6. polyacetal resin composition as claimed in claim 1 or 2, wherein, the divalent alkyl of saturated fatty acid bisamide is selected from single methylene radical, dimethylene, trimethylene, tetramethylene, pentamethylene and hexa-methylene.
7. polyacetal resin composition as claimed in claim 1 or 2, wherein, the saturated fatty acid bisamide is ethylenebisstearamide (C
17H
35-CONH-CH
2-CH
2-NHCO-C
17H
35) and/or methylene-bis stearylamide (C
17H
35-CONH-CH
2-NHCOC
17H
35).
8. by a kind of polyacetal resin hinge member of any one described polyacetal resin composition moulding in the claim 1～7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP275490/95 | 1995-10-24 | ||
| JP27549095A JP3255567B2 (en) | 1995-10-24 | 1995-10-24 | Polyacetal resin composition |
| JP275490/1995 | 1995-10-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1200752A CN1200752A (en) | 1998-12-02 |
| CN1131280C true CN1131280C (en) | 2003-12-17 |
Family
ID=17556244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96197846A Expired - Lifetime CN1131280C (en) | 1995-10-24 | 1996-10-22 | Polyacetal resin composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3255567B2 (en) |
| KR (1) | KR100475401B1 (en) |
| CN (1) | CN1131280C (en) |
| CA (1) | CA2230632A1 (en) |
| WO (1) | WO1997015625A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4563004B2 (en) * | 2003-07-08 | 2010-10-13 | ポリプラスチックス株式会社 | Sliding parts made of polyacetal resin |
| WO2021002314A1 (en) * | 2019-07-03 | 2021-01-07 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition and molded article |
| JPWO2021002315A1 (en) * | 2019-07-03 | 2021-01-07 | ||
| WO2021002316A1 (en) * | 2019-07-03 | 2021-01-07 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition and molded article |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3187917B2 (en) * | 1992-03-16 | 2001-07-16 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JPH06100759A (en) * | 1992-09-16 | 1994-04-12 | Polyplastics Co | Resin composition for clip |
| JPH0718157A (en) * | 1993-07-06 | 1995-01-20 | Polyplastics Co | Polyacetal resin composition |
-
1995
- 1995-10-24 JP JP27549095A patent/JP3255567B2/en not_active Expired - Lifetime
-
1996
- 1996-10-22 KR KR10-1998-0702938A patent/KR100475401B1/en not_active IP Right Cessation
- 1996-10-22 WO PCT/JP1996/003065 patent/WO1997015625A1/en active IP Right Grant
- 1996-10-22 CA CA002230632A patent/CA2230632A1/en not_active Abandoned
- 1996-10-22 CN CN96197846A patent/CN1131280C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09118805A (en) | 1997-05-06 |
| JP3255567B2 (en) | 2002-02-12 |
| CA2230632A1 (en) | 1997-05-01 |
| KR19990067002A (en) | 1999-08-16 |
| CN1200752A (en) | 1998-12-02 |
| KR100475401B1 (en) | 2005-05-16 |
| WO1997015625A1 (en) | 1997-05-01 |
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