CN1195676A - Polyacetal resin composition - Google Patents
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Abstract
The invention relates to a polyacetal resin composition whose molding processability is improved, which has excellent sliding property, the invention comprises (A) polyacetal resin which is 100 parts (weight), (B) modified silicon oil with at least two hydroxyl groups which is 0.01-20 parts (weight) and (C) boracic acid compound which is 0.001-3 parts (weight), in addition, the invention also comprises (E) lubricating oil which keeps liquid state under the molding processability temperature of the polyacetal resin and is 0.05-20 parts (weight).
Description
The invention relates to and in polyacetal resin, allocate modified silicon oil and boronic acid compounds polyacetal resin composite that constitute, that have good sliding, the remarkable improvement of shaping processability into hydroxyl.
Polyacetal resin has the rerum natura of various overall equilbriums, in addition, has excellent sliding capability as resin, thereby is widely used for the slide unit as automobile, motor electronic goods, office machine, building materials etc.But, follow the expansion of Application Areas, its sliding capability is had higher requirement, require sliding capability further to improve and have persistence.
According to this requirement, in order to improve sliding, have the people once to attempt in polyacetal resin, allocating into lubricating oil in the past, particularly allocate into have good thermotolerance, lubricating oil---the silicone oil of cold property, chemical/physical stability.
But, in general, consistency and the non-constant of affinity with lubricating oil headed by the silicone oil and polyacetal resin, thereby allocate very difficulty of silicone oil into, promptly enable to make such composition, when forming, oil is exuded to resin surface easily, slide owing to lubrication makes resin produce to each other or between resin and screw rod, thereby cause in forming mill wedging bad or plastify badly etc., can't process when serious.In addition, the molding that obtains like this, near the oil major part its top layer is oozed out in the extremely short time easily and is consumed, and therefore, though the slip initial stage demonstrates good sliding properties, can not keep permanent.And, slimy owing to oil is exuded on the molding surface easily, thereby commodity value reduces.
In order to overcome above-mentioned shortcoming, have into once proposed with lubricating oil particularly silicone oil add the 3rd kind of material as keeping material, and carried out various researchs.For example, the maintenance material of mineral-type has gac, graphite etc., and the organic polymer class keeps material that High molecular weight polyethylene etc. is arranged.But absorption such as gac and graphite keeps the ability of silicone oil less, and High molecular weight polyethylene etc. are poor with the avidity of silicone oil, and is less equally to the confining force of silicone oil, can not be met the practical effect that requires.
In addition, as the maintenance material that has good affinity with silicone oil, the spy opens among the clear 50-121344 and has proposed silicon rubber.Described silicon rubber is to have and the straight chain of silicone oil similar structures or the polymkeric substance of part side chain, and just the polymerization degree (or viscosity) is higher a little, and is therefore fine with the consistency of silicone oil, extrude when waiting shaping processibility be improved significantly.
But the silicone oil confining force of such silicon rubber under sliding condition neither be good especially, and after sliding after a while, sliding properties reduces.In addition, be material as the silicon rubber itself that keeps material with superelevation viscosity, sliding properties may not be fine, thereby make the good slip effect of silicone oil weakened.In addition, such silicone oil demonstrates flowability through heating, and the same with silicone oil, and is very poor with the consistency of polyacetal resin, thereby rubber condenses upon the resin surface layer of molding, formation thin layer epithelium.This epithelium externally is easy to peel off under the stress.
As mentioned above, usefulness known method in the past can not obtain the polyacetal resin composite that processibility is good, have good short-term and long-term sliding properties, presses for and is improved.
In order to obtain to adapt to the polyacetal resin composite of above-mentioned needs, the inventor studies repeatedly, found that, by in polyacetal resin, allocating modified silicon oil and boronic acid compounds into hydroxyl, can obtain plasticity etc. and significantly improve, be all good polyacetal resin composites of short-term or secular sliding capability, thereby finish the present invention.
That is, the invention relates to the improved polyacetal resin composites of processibility such as plasticity, it is characterized in that, with respect to
(A) 100 parts of (weight) polyacetal resins are allocated into
(B) 0.01-20 part (weight) have at least 2 hydroxyls modified silicon oil and
(C) 0.001-3 part (weight) boronic acid compounds.
Composition of the present invention contains above-mentioned (A), (B) and (C).In addition, can also contain (E) 0.05-20 part (weight) keeps liquid state under the shaping processing temperature of polyacetal resin lubricating oil.(E) lubricating oil of composition is preferentially selected silicon system oil, polyalkylene glycol, alpha-olefin low polymers, paraffin oil, the phenyl ether of alkyl replacement or the ester of senior aliphat alcohol for use.
Copolyacetal preferably, for example, with the comonomer copolymerization of 0.5-30% (weight) or 1-30% (weight), particularly 0.5-5% (weight) or 1-5% (weight) and the Copolyacetal that forms.
The present invention can provide that frictional coefficient reduces, wear resistance is good, have the polyacetal resin composite that good sliding and shaping processability greatly improve.
The following describes constituent of the present invention.
The polyacetal resin that uses among the present invention (A) is with inferior methoxyl group (CH
2O) be the unitary macromolecular compound of main composition, can be polyacetal homopolymer, also have a small amount of other to constitute in unitary Copolyacetal (comprising segmented copolymer), the terpolymer any except that inferior methoxyl group, also can be the compound that molecule not only has wire but also has the side chain crosslinking structure.In the present invention, polyacetal resin can use blending more than 2 kinds as required, but considers from the plasticity angle, preferably uses Copolyacetal.For example, the Copolyacetal that the comonomer copolymerization of 1-30% (weight), particularly 1-5% (weight) is formed can keep good thermostability, thereby is preferentially selected for use.The comonomer composition of making the Copolyacetal use has no particular limits, the general comonomer with following general formula that uses.
In the formula, R
1, R
2, R
3And R
4Expression hydrogen atom or alkyl, can be identical also can be different, generally be hydrogen atom.R
5Methylene radical that expression methylene radical, inferior methoxyl group, alkyl replace or inferior methoxyl group (in this case, p represents the integer of 0-3) or by molecular formula-(CH
2)
q-OCH
2-or-(O-CH
2-CH
2)
q-OCH
2The divalent radical (in this case, p represents 1, and q represents the integer of 1-4) of-expression.
Above-mentioned comonomer for example can be enumerated oxyethane, epoxy chloropropane, 1,3-dioxolane, glycol ether formal, 1,4-butanediol formal, 1,3-dioxan, propylene oxide etc.
Secondly, the modified silicon oil with hydroxyl (B) that uses as (B) composition among the present invention, can enumerate by the hold silicone oil and have the silicone oil of silanol base of following general formula (1) expression by the molecular chain two ends that following general formula (2) is represented with alcoholic hydroxyl at molecular chain two, can use wherein more than a kind or 2 kinds.
In the formula, R is a methyl, and wherein a part also can be alkyl, phenyl, halogenated alkyl, halogenation phenyl etc.In addition, R
aIt is alkyl or phenyl.
The modified silicon oil that has 2 hydroxyls at least (hereinafter to be referred as modified silicon oil) that uses among the present invention can use commercially available product, its viscosity has no particular limits, but it is below the 50000cSt (25 ℃), particularly below the 10000cSt that plasticity is improved the apparent author's viscosity of effect.Its reason will describe in detail hereinafter, it is believed that the improvement of plasticity and the reaction of hydroxyl and boronic acid compounds have much relations.When molecular weight was excessive, with the reaction of the boronic acid compounds minimizing of counting, thereby the effect of improving of plasticity was not very big.
With respect to 100 parts of (weight) polyacetal resins (A), the amount of allocating into of modified silicon oil (B) is 0,01-20 part (weight), preferably 0.5-5 part (weight).When the amount of allocating into is less than 0.01 part (weight), can not give full play to the effect that reduces frictional coefficient, otherwise, when surpassing 20 parts (weight), plasticity such as will cause extruding and extremely worsen.
In addition, making modified silicon oil (B) and following boronic acid compounds (C) reaction in advance, its resultant is allocated in the polyacetal resin, also is a kind of method of improving plasticity.
(C) composition that uses among the present invention is that boronic acid compounds can be enumerated ortho-boric acid, metaboric acid, tetraboric acid and boron trioxide etc., can use commercially available product.
The amount of allocating into of boronic acid compounds is 0.001-3 part (weight), preferably 0.003-1 part (weight), preferably 0.003-0.5 part (weight).When the amount of allocating into is lower than 0.001 part (weight), can not obtain desirable effect, when surpassing 3 parts (weight), thermostability goes wrong.
The lubricating oil that uses as (E) composition in the present invention, be meant that under the shaping processing temperature (normally 190-220 ℃) at polyacetal be the lubricating oil of liquid, friction/wearing character of improving polyacetal, specifically, be with in the ester of the phenyl ether that is selected from silicon system oil, polyalkylene glycol, alpha-olefin low polymers, paraffin oil, alkyl replacement, senior aliphat alcohol more than a kind or 2 kinds as the lubricating oil of base.In the composition of implementing, (E) use the kind different with (B).
Explain various oil below.
Silicon system oil is preferential to be selected to use with the polydimethylsiloxane shown in (3) formula, the polymethylphenylsiloxane oil as representative.
In the formula, R is a methyl, and wherein a part also can be alkyl, phenyl, halogenated alkyl, halogenation phenyl etc.
The silicone oil that uses among the present invention, its viscosity has no particular limits, consider that sliding and persistence thereof, dispersiveness, melting mixing and the shaping of oil in resin add the operability in man-hour etc., its viscosity is advisable at 100-300000cSt (25 ℃), preferably 500-300000cSt, preferably 500-100000cSt.In addition, in the present invention, the silicone oil that structure or viscosity are different more than 2 kinds can be mixed and use, also can in silicone oil, add thickening material and solvent etc., use after the adjustment viscosity.
The polyalkylene glycol that uses among the present invention has the structure of polyoxyethylene glycol, the homopolymerization of polypropylene glycol unit or random, block, graft copolymerization, is the lubricating oil that the epoxy alkane based on oxyethane, propylene oxide obtains through ring-opening polymerization.
Polyalkylene glycol also can use the derivative of terminal hydroxy group etherificate or esterification not.Representational ester, ether derivant can be enumerated, and have C on the not terminal hydroxy group of polyalkylene glycol
8Above aliphatic carboxylic acid or fatty alcohol be respectively in conjunction with the compound of the structure of ester, ether, and the ether of polyvalent alcohol such as glycerine, Polyglycerine, sorbitan and polyalkylene glycol etc.In the present invention, preferentially select polypropylene glycol, the polyoxyethylene glycol polypropylene glycol multipolymer of molecular-weight average 400-5000 for use, and these aklylene glycols be the C of representative with lauric acid, stearic acid
12The ester of above lipid acid, perhaps be the C of representative with stearyl alcohol etc.
12The ether of above fatty alcohol.
Alpha-olefin low polymers is to have C
8～C
20The independent polymerization of alpha-olefin or with ethene and C
8～C
20The aliphatic hydrocarbon of structure of alpha-olefin copolymer.In the present invention, preferentially select the ethylene ' alpha '-olefin co-oligomer of number-average molecular weight 400-4000 for use.
Paraffin oil is meant the mineral oil with the refining so-called paraffin series that obtains of petroleum fractions.Preferentially select the paraffin oil of molecular-weight average 300-800 in the present invention for use.
The phenyl ether that alkyl replaces shown in following (4) formula, is to import C more than a kind at least with the substituent form that is selected from alkyl, ester group, ether in the phenyl of phenyl ether
12The compound of above representative examples of saturated aliphatic chain.Its molecular weight has no particular limits, all alkyl diphenyl ethers can use, described substituting group can import on arbitrary position of phenyl, consider from the synthetic angle, preferably arbitrary position has substituent alkyl substituted diphenylamine ether, preferably 4,4 ' 2 substituents in 2,4,6,2 ', 4 ', 6 '.
In the formula, R is alkyl, ether or the ester group in part or all importing of 2～6 and 2 '～6 '.
The substituting group of the phenyl ether that alkyl replaces can be enumerated the branched-chain alkyl shown in straight chained alkyl such as dodecyl, tetradecyl, hexadecyl, octadecyl or (5) formula.
In the formula, n, m are integer and n+m 〉=11 more than 0.
Ester group can be enumerated dodecyloxy carbonyl, tetradecyloxyaniline carbonyl, n-Hexadecane oxygen base carbonyl, octadecane oxygen base carbonyl, bay acyloxy, Semen Myristicae acyl-oxygen base, palm acyloxy, stearoyl-oxy etc.Ether can be enumerated lauroyl, tetradecanoyl, hexadecanoyl, octadecanoyl etc.In addition, the aliphatics hydrocarbon chain of these ester groups, ether has branched structure, for example can be the derivative of isooctadecanol or Unimac 5680.
The ester of described senior aliphat alcohol is the ester of senior aliphat alcohol and monobasic saturated fatty acid or diprotic acid, from practical standpoint, and preferably above saturated fatty acid alcohol of 16 carbon atoms and saturated fatty acid and/or polybasic esters more than 16 carbon atoms.
C
16Above fatty alcohol can be enumerated hexadecanol, stearyl alcohol, isooctadecanol, behenyl alcohol, erucyl alcohol, n-Hexacosanol, policosanol etc.C
16Above lipid acid can be enumerated straight chain such as palmitinic acid, stearic acid, Unimac 5680, eicosanoic acid, mountain Yu's acid, montanic acid and/or side chain unsaturated fatty acids etc.The ester of unary fatty acid and monobasic fatty alcohol all can use.
In addition, as with above-mentioned C
16Above fatty alcohol can be enumerated phthalic acid, hexanodioic acid, sebacic acid, trimellitic acid etc. in conjunction with the diprotic acid that constitutes ester.Consider that from the angle of the thermostability that keeps polyacetal the ester that is formed by diprotic acid and fatty alcohol is ester entirely preferably.
In the aliphatic ester that forms by such carboxylic acid and alcohol; consider from price, easily acquisition (synthetic, refining) and friction and wear characteristic, preferably stearic acid stearyl, mountain Yu acid docosyl ester, distearyl acyl group adipic acid ester, distearyl acyl group phthalyl ester.In the present invention, can use in these aliphatic esters more than a kind or 2 kinds.
Allocate (E) lubricant of 0.05-20 part (weight) into respect to (A) polyacetal resin of 100 parts (weight), demonstrate the effect of improving friction and wear characteristic.When the amount of allocating into is lower than 0.05 part (weight), can not give full play to the effect that reduces frictional coefficient, otherwise, when surpassing 20 parts (weight), cause plasticity and rubbing characteristics extremely to worsen, thus all inadvisable.Preferably the amount of allocating into is 0.5-5 part (weight).
To improve mechanism still not fully aware of for the plasticity of polyacetal resin composite among the present invention, infer according to the inventor, be since during melting mixing in polyacetal resin modified silicon oil (B) and boronic acid compounds (C) reaction, form gelatinous material, thereby improved the wedging of forming mill screw rod, in addition, it is fine concavo-convex that this spawn forms appropriateness in polyacetal surface, reduce the sliding contact area and played the effect that keeps unreacted modified silicon oil, thereby formation is difficult for peeling off the lubricant film of removing on the molding surface, perhaps because the oozing out of unreacted silicone oil that remain in the spawn is subjected to suitable inhibition, thereby the good sliding properties that had of silicone oil itself improves effect and is able to long-term maintenance.
In composition of the present invention,, can also allocate solid lubricants such as graphite, molybdenumdisulphide, metallic soap, polyvinyl resin, teflon resin etc. into and give polymkeric substance of good lubrication etc. in order further to improve sliding properties.
If composition of the present invention further adds various known stablizers, can enhanced stability.In addition, in order to improve its rerum natura according to application target, can also allocate various known additives into, the polymkeric substance of for example various tinting materials, lubricant, releasing agent, nucleating agent, static inhibitor, other tensio-active agent, other kind, organic amendment etc. can also add fibrous, tabular, granulous inorganic fillers such as glass fibre certainly.
Secondly, composition of the present invention can also adopt known in the past resin combination preparation method easily to create.For example, various compositions are mixed, then with single screw rod or twin screw extruder is mixing extrudes, make pellet, different pellets (masterbatch) is formed in preparation subsequently, this pellet is measured mixing (dilution) in accordance with regulations be used for being shaped, and obtains having the molding of the composition that requires after the shaping.
In addition, when preparing such composition, also the polyacetal resin as matrix partly or entirely can be pulverized, with its with extrude after other composition mixes, can improve the dispersiveness of additive like this.
The invention provides a kind of polyacetal resin composite, the frictional coefficient of said composition reduces, and have excellent abrasive resistance and sliding, and shaping processability is improved greatly.
Embodiment
Below by embodiment the present invention is described, but the present invention is not subjected to the restriction of these embodiment.Embodiment 1-9 must contain (A), (B) and composition (C), and embodiment 11-29 must contain (A), (B), (C) and composition (E).
Comparative example 1-11 and comparative example 21-38 compare with embodiment respectively.
Embodiment 1-9, comparative example 1-11
Press the use level shown in the table 1, mixed and modified silicone oil and boronic acid compounds in polyacetal resin (Port リ プ ラ ス チ Star Network ス (strain) make, ジ ュ ラ コ Application M450) are 200 ℃ forcing machine melting mixing then with barrel zone temperature, make granular composition.Then, be processed into test piece by this granular composition, measure rerum natura described below, the results are shown in the table 1 with injection molding machine.
In order to compare, as shown in table 2, the composition of making as silicone oil representative, that do not have hydroxyl with polydimethylsiloxane, the composition of only allocating the composition of modified silicon oil into and only allocating boronic acid compounds into are used in same preparation, and estimate, and the results are shown in the table 2.
The method of measuring and estimating is as follows.
[frictional coefficient]
Use Suzuki formula friction wear testing machine, pressurization 0.75kg/cm
2, linear velocity 180mm/sec, contact area 2.0cm
2, the material that cooperates with it uses polyacetal resin material (Port リ プ ラ ス チ Star Network ス (strain) makes, trade(brand)name M90-44), measures the kinetic friction coefficient behind just begun to slide back (initial stage) and the slip certain hour.
[plasticity]
Measure the plasticizing metering time of Suzuki formula test piece when being shaped.The metering time is long more, and plasticity is poor more.
Molding condition is as follows.
Forming mill: day smart PS20E2ASE
Barrel zone temperature: 190 ℃
Screw speed: 100r.p.m
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |||
| Form weight part | (A) polyacetal resin | ???100 | ??100 | ??100 | ???100 | ????100 | ????100 | ???100 | ???100 | ???100 | |
| (B) modified silicon oil | ???B-1 ???2.0 | ??B-2 ??1.0 | ??B-2 ??1.0 | ???B-2 ???2.0 | ????B-2 ????2.0 | ????B-2 ????2.0 | ???B-2 ???2.0 | ???B-2 ???4.0 | ???B-2 ???2.0 | ||
| (B) ' silicone oil | |||||||||||
| (C) boronic acid compounds | ???C-1 ???0.03 | ??C-1 ?0.005 | ??C-1 ??0.03 | ???C-1 ??0.005 | ???C-1 ???0.03 | ???C-1 ???0.05 | ???C-1 ???0.10 | ???C-1 ???0.03 | ???C-2 ???0.03 | ||
| Frictional coefficient (μ) | Initial stage | ???0.20 | ??0.20 | ??0.21 | ???0.17 | ???0.20 | ???0.18 | ???0.21 | ???0.16 | ???0.20 | |
| After 1 hour | ???0.20 | ??0.21 | ??0.22 | ???0.19 | ???0.21 | ???0.20 | ???0.22 | ???0.18 | ???0.22 | ||
| After 5 hours | ???0.23 | ??0.23 | ??0.24 | ???0.20 | ???0.24 | ???0.23 | ???0.24 | ???0.18 | ???0.24 | ||
| After 24 hours | ???0.25 | ??0.25 | ??0.26 | ???0.22 | ???0.25 | ???0.26 | ???0.26 | ???0.22 | ???0.25 | ||
| Plasticity (second metering time) | ????18 | ???17 | ???14 | ????20 | ????12 | ???12 | ???14 | ???22 | ???13 | ||
*B-1: two do not hold the silicone oil (55cSt) with alcoholic hydroxyl
(eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system, BY16-848)
B-2: two do not hold the silicone oil (2500cSt) with silanol base
(eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system, BY16-873)
B '-1: the silicone oil of polydimethylsiloxane type
C-1: ortho-boric acid
C-2: tetraboric acid
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 | Comparative example 10 | Comparative example 11 | |||
| Form weight part | (A) polyacetal resin | ???100 | ??100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | |
| (B) modified silicon oil | ???B-1 ???2.0 | ??B-2 ??1.0 | ???B-2 ???2.0 | ||||||||||
| (B) ' silicone oil | ???B’-1 ????1.0 | ???B’-1 ????2.0 | ???B’-1 ????1.0 | ???B’-1 ????2.0 | ???B’-1 ????2.0 | ||||||||
| (C) boronic acid compounds | ????C-1 ???0.005 | ???C-1 ???0.005 | ????C-1 ????0.03 | ???C-1 ???0.03 | ???C-1 ???0.005 | ||||||||
| Frictional coefficient (μ) | Initial stage | ???0.18 | ??0.20 | ???0.17 | ???0.18 | ???0.19 | ????0.19 | ???0.17 | ????0.20 | ???0.24 | ???0.24 | ????0.24 | |
| After 1 hour | ???0.20 | ??0.20 | ???0.18 | ???0.19 | ???0.20 | ????0.20 | ???0.19 | ????0.22 | ???0.28 | ???0.27 | ????0.28 | ||
| After 5 hours | ???0.02 | ??0.24 | ???0.22 | ???0.21 | ???0.23 | ????0.23 | ???0.21 | ????0.23 | ???0.28 | ???0.27 | ????0.28 | ||
| After 24 hours | ???0.24 | ??0.25 | ???0.25 | ???0.25 | ???0.24 | ????0.25 | ???0.24 | ????0.25 | ???0.30 | ???0.29 | ????0.31 | ||
| Plasticity (second metering time) | ???28 | ??26 | ????30 | ????27 | ????30 | ????26 | ????29 | ????29 | ????18 | ????18 | ????18 | ||
*B-1: two do not hold the silicone oil (55cSt) with alcoholic hydroxyl
(eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system, BY16-848)
B-2: two do not hold the silicone oil (2500cSt) with silanol group
(eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system, BY16-848)
E-1: polydimethylsiloxane (500 cSt)
(eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system, SH-510) (identical) with B '-1
C-1: ortho-boric acid
C-2: tetraboric acid
Embodiment 11-29, comparative example 21-38
Press the use level shown in table 3 and the table 4, in polyacetal resin (Port リ プ ラ ス チ Star Network ス (strain) manufacturing, ジ ユ ラ コ Application M450), mix various modified silicon oils (as (B) composition), various boronic acid compounds (as (C) composition) and various lubricating oil (as (E) composition) as (A) composition, use the twin screw extruder melting mixing then, make granular composition, use injection molding machine to be processed into test piece by this granular composition, measure rerum natura described below, the results are shown in table 3 and the table 4.
In order to compare, shown in table 5 and table 6, make the composition of a kind of having added among (B), (C), (E) or 2 kinds equally and estimate, the results are shown in table 3 and the table 4.
Mensuration and evaluation method are similarly to Example 1.
Table 3
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | |||
| Form weight part | (A) polyacetal resin | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | |
| (E) lubricating oil | ???E-1 ???1.0 | ???E-1 ???1.0 | ???E-2 ???1.0 | ???E-3 ???1.0 | ???E-4 ???1.0 | ???E-5 ???1.0 | ???E-6 ???1.0 | ???E-7 ???1.0 | ???E-8 ???1.0 | ||
| (B) modified silicon oil | ???B-1 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ||
| (C) boronic acid compounds | ???C-1 ???0.03 | ???C-1 ???0.0 | ???C-1 ???0.03 | ???C-1 ???0.10 | ???C-1 ???0.03 | ???C-1 ???0.03 | ???C-1 ???0.03 | ???C-1 ???0.03 | ???C-1 ???0.03 | ||
| Estimate | Frictional coefficient (μ) | Initial stage | ???0.14 | ???0.13 | ???0.12 | ???0.14 | ???0.18 | ???0.14 | ???0.15 | ???0.17 | ???0.17 |
| After 24 hours | ???0.17 | ???0.19 | ???0.18 | ???0.18 | ???0.20 | ???0.17 | ???0.17 | ???0.21 | ???0.20 | ||
| Plasticity (second metering time) | ????21 | ????16 | ????17 | ????18 | ????18 | ????20 | ????18 | ????15 | ????16 | ||
Table 4
| Embodiment 20 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | |||
| Form weight part | (A) polyacetal resin | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| (E) lubricating oil | E-9 1.0 | E-9 1.0 | E-9 1.0 | E-9 1.0 | E-9 1.0 | E-9 1.0 | E-9 1.0 | E-9 1.0 | E-9 1.0 | E-10 1.0 | ||
| (B) modified silicon oil | B-1 2.0 | B-2 1.0 | B-2 2.0 | B-2 2.0 | B-2 2.0 | B-2 2.0 | B-2 2.0 | B-2 1.0 | B-2 2.0 | B-2 2.0 | ||
| (C) boronic acid compounds | C-1 0.03 | C-1 0.005 | C-1 0.005 | C-1 0.03 | C-2 0.03 | C-2 0.005 | C-1 0.10 | C-1 0.03 | C-1 0.10 | C-1 0.03 | ||
| Estimate | Frictional coefficient (μ) | Initial stage | 0.15 | 0.18 | 0.16 | 0.13 | 0.14 | 0.15 | 0.14 | 0.18 | 0.14 | 0.16 |
| After 24 hours | 0.20 | 0.21 | 0.19 | 0.16 | 0.17 | 0.18 | 0.18 | 0.20 | 0.18 | 0.19 | ||
| Plasticity (second metering time) | 22 | 24 | 22 | 17 | 17 | 19 | 14 | 18 | 15 | 18 | ||
Table 5
| Comparative example 21 | Comparative example 22 | Comparative example 23 | Comparative example 24 | Comparative example 25 | Comparative example 26 | Comparative example 27 | Comparative example 28 | Comparative example 29 | |||
| Form weight part | (A) polyacetal resin | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | |
| (E) lubricating oil | ???E-1 ???1.0 | ???E-1 ???1.0 | ???E-2 ???1.0 | ???E-3 ???1.0 | ???E-3 ???1.0 | ???E-4 ???1.0 | ???E-5 ???1.0 | ???E-5 ???1.0 | ???E-6 ???1.0 | ||
| (B) modified silicon oil | ???B-1 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ||||
| (C) boronic acid compounds | |||||||||||
| Estimate | Frictional coefficient (μ) | Initial stage | ???0.13 | ???0.13 | ???0.13 | ???0.14 | ???0.12 | ???0.17 | ???0.14 | ???0.15 | ???0.15 |
| After 24 hours | ???0.17 | ???0.18 | ???0.18 | ???0.17 | ???0.17 | ???0.20 | ???0.17 | ???0.16 | ???0.17 | ||
| Plasticity (second metering time) | ????18 | ????33 | ????32 | ????29 | ????35 | ????32 | ????32 | ????37 | ????32 | ||
Table 6
| Comparative example 30 | Comparative example 31 | Comparative example 32 | Comparative example 33 | Comparative example 34 | Comparative example 35 | Comparative example 36 | Comparative example 37 | Comparative example 38 | |||
| Form weight part | (A) polyacetal resin | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | ???100 | |
| (E) lubricating oil | ???E-7 ???1.0 | ???E-7 ???1.0 | ???E-8 ???1.0 | ???E-9 ???1.0 | ???E-9 ???1.0 | ???E-9 ???1.0 | ???E-9 ???1.0 | ???E-9 ???1.0 | ???E-10 ???1.0 | ||
| (B) modified silicon oil | ???B-2 ???2.0 | ???B-2 ???2.0 | ???B-2 ???1.0 | ???B-2 ???2.0 | ???B-2 ???2.0 | ||||||
| (C) boronic acid compounds | ???C-1 ??0.005 | ???C-1 ???0.03 | |||||||||
| Estimate | Frictional coefficient (μ) | Initial stage | ???0.15 | ??0.16 | ???0.16 | ???0.15 | ???0.13 | ??0.12 | ???0.16 | ???0.14 | ??0.15 |
| After 24 hours | ???0.20 | ??0.20 | ???0.20 | ???0.20 | ???0.18 | ??0.17 | ???0.20 | ???0.20 | ??0.18 | ||
| Plasticity (second metering time) | ????31 | ????35 | ????34 | ????30 | ????32 | ???37 | ????30 | ????29 | ???34 | ||
Annotate)
E-1: polydimethylsiloxane (5000cSt, eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) manufacturing, SH-200)
E-2: PSI (500cSt, eastern レ ダ ゥ コ-ニ Application グ シ リ コ-Application (strain) manufacturing, SH-510)
E-3: polypropylene glycol (580cSt, Sanyo change into industry (strain) manufacturing, PP3000)
E-4: poly-(ethylene glycol propylene glycol copolymers) (1700cSt, Sanyo change into industry (strain) manufacturing, 50HB-5100)
E-5: alpha-olefin low polymers (900cSt, Mitsui petroleum industry (strain) manufacturing, Le-カ Application ト HC40)
E-6: alpha-olefin low polymers (28000cSt, Mitsui petroleum industry (strain) manufacturing, Le-カ Application ト HC600)
E-7: paraffin oil (1000cSt, bright dipping (strain) manufacturing, プ ロ セ ス オ ィ Le)
E-8: (200cSt, (strain) loose village petroleum chemistry institute make the phenyl ether that alkyl replaces, モ レ ス コ Ha ィ Le-プ)
E-9: stearic acid stearyl
E-10: distearyl adipic acid ester
Claims (6)
1. polyacetal resin composite is characterized in that, contains (A) 100 parts of (weight) polyacetal resins, (B) 0.01-20 part (weight) and has the modified silicon oil of 2 hydroxyls and (C) 0.001-3 part (weight) boronic acid compounds at least.
2. the described composition of claim 1, wherein, (B) modified silicon oil of composition is the silicone oil that the molecular chain two ends have alcoholic hydroxyl.
3. the described composition of claim 1, wherein, (B) modified silicon oil of composition is the silicone oil that the molecular chain two ends have the silanol base.
4. the described composition of claim 1, wherein, (B) modified silicon oil of composition is the modified silicon oil with the following viscosity of 50000cSt.
5. the described composition of claim 1 wherein, also contains (E) 0.05-20 part (weight) keeps liquid state under the shaping processing temperature of polyacetal resin lubricating oil.
6. the described composition of claim 5, wherein, (E) lubricating oil of composition is silicon system oil, polyalkylene glycol, alpha-olefin low polymers, paraffin oil, the phenyl ether of alkyl replacement or the ester of senior aliphat alcohol.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40879/97 | 1997-02-25 | ||
| JP4087997 | 1997-02-25 | ||
| JP40879/1997 | 1997-02-25 | ||
| JP80317/1997 | 1997-03-31 | ||
| JP8031797 | 1997-03-31 | ||
| JP80317/97 | 1997-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1195676A true CN1195676A (en) | 1998-10-14 |
| CN1125134C CN1125134C (en) | 2003-10-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98107727 Expired - Fee Related CN1125134C (en) | 1997-02-25 | 1998-02-25 | Polyacetal resin composition |
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| Country | Link |
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| CN (1) | CN1125134C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339438C (en) * | 2003-07-08 | 2007-09-26 | 汎塑料株式会社 | Sliding parts made of polyacetal resin |
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1998
- 1998-02-25 CN CN 98107727 patent/CN1125134C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339438C (en) * | 2003-07-08 | 2007-09-26 | 汎塑料株式会社 | Sliding parts made of polyacetal resin |
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| CN1125134C (en) | 2003-10-22 |
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