CN106243609A - Polyacetal resin molded body - Google Patents
Polyacetal resin molded body Download PDFInfo
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- CN106243609A CN106243609A CN201610407363.6A CN201610407363A CN106243609A CN 106243609 A CN106243609 A CN 106243609A CN 201610407363 A CN201610407363 A CN 201610407363A CN 106243609 A CN106243609 A CN 106243609A
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- molded body
- polyacetal resin
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The present invention relates to polyacetal resin molded body.The present invention provide a kind of have stable sliding, through time tone variations is few and low odor and the excellent polyacetal resin molded body of resistance to adhesive.Polyacetal resin molded body involved in the present invention is for comprising (A) polyacetal resin, (B) lubricating oil and (C) polyolefinic polyacetal resin molded body, its major diameter is 2.5mm～4.0mm and minor axis is 1.4mm～2.8mm, and ellipticity (major diameter/minor axis ratio) is more than 1.25.It addition, the above-mentioned further molding of polyacetal resin molded body is obtained component involved in the present invention.
Description
Technical field
The present invention relates to polyacetal resin molded body.
Background technology
The mechanical strength of polyacetal resin, chemical-resistant, sliding, excellent in abrasion resistance and
Its handling ease.Accordingly, as representational engineering plastics, electrical equipment etc. driver part,
The wide scope such as automobile component or other parts uses.Polyacetal resin utilizes the expansion in field due to it
Greatly, it requires that performance becomes more and more higher.
In the past, in order to make the sliding of polyacetal resin molded body improve, employ coating lubrication
The method of fat.But, the most carrying out unlubricated esterified.Such as, for the tooth of printer
For the mechanism part such as wheel, it is desirable to the stable sliding under the state not using grease.This
Being because, mechanism part needs to drive with constant coefficient of friction continuously, on the other hand, and profit
Consistent lubricant is difficult to fully reduce the skew of coefficient of friction.Corresponding to such requirement, it is known that at bunching
Urea formaldehyde adds the lubricant such as polyethylene, lubricating oil technology (for example, with reference to patent documentation 1～
3)。
It addition, vapour interior material used in vehicles etc. require that the part requirement of appearance design remains unchanged for a long period of time color.
In order to tackle this requirement, use in polyacetal resin, such as add the additive giving weatherability
Method.
Additionally, for vapour interior material used in vehicles, the drive division of office automation (OA) device interior
For part, it is desirable to reduce the stink (particularly formaldehyde) produced from molded body.Want corresponding to such
Asking, example is as used in the method for the additive adding chemistry trapping formaldehyde in polyacetal resin.
It addition, when the preservation of polyacetal resin molded body (particularly granule), transport time, sometimes
Become the state piled up for a long time by the bag being accommodated with this molded body.It is being applied with load like this
In the environment of, it is susceptible to the phenomenon (adhesion) that molded body is adhered each other.If producing such adhesion,
Then generation bridging (Bridge) when molded body being imported hopper (in internal molded body blocking, it is impossible to from
The phenomenon that outlet is discharged), therefore, it is difficult to stably article of manufacture.Therefore, for polyacetals tree
Fat molded body requires resistance to adhesive.In order to tackle this requirement, use such as add filler and at table
Face forms fine concavo-convex method, adds wax and form the side of thin overlay film on the surface of molded body
Method.
Prior art literature
Patent documentation
Patent documentation 1: No. 5301926 description of Japanese Patent No.
Patent documentation 2: Japanese Unexamined Patent Publication 8-127704 publication
Patent documentation 3: Japanese Unexamined Patent Publication 5-65390 publication
Summary of the invention
Invent problem to be solved
But, for only adding the method for lubricant, due to polyacetal resin and lubricant
The compatibility low, therefore lubricant can not be well dispersed in resin.Therefore there is following class
Topic: although initial coefficient of friction step-down, but due to the lubricant consumption existed near surface
To the greatest extent, thus coefficient of friction steeply rises, and sliding is unstable.
It addition, for using the method for the additive giving weatherability, at high temperature sudden and violent
Discoloration-resistant aspect under the conditions of dew is the most not enough.
Additionally, for the method for the additive using trapping formaldehyde, sometimes in injection continuously
Mold deposit is produced during molding.Therefore, in terms of carrying out production long-term and stably, problem is left.
During it addition, use improves the method for adhesive by interpolation filler, wax, there is slip
The problem that property is the most impaired.
The present invention makes according to such background, its object is to provide a kind of polyacetal resin
Molded body, described polyacetal resin molded body have stable sliding, through time tone variations few,
And low odor and resistance to adhesive are excellent.
For solving the means of problem
The present inventor etc. conduct in-depth research to solve above-mentioned problem, it was found that logical
Cross to make and comprise specific composition and there is the polyacetal resin molded body of specific shape, permissible
Solve above-mentioned problem, thus complete the present invention.
That is, the present invention is as described below.
[1]
A kind of polyacetal resin molded body, it is for comprising (A) polyacetal resin, (B) lubricating oil and (C)
Polyolefinic polyacetal resin molded body, wherein, the major diameter of described molded body be 2.5mm～
4.0mm and minor axis are 1.4mm～2.8mm, and ellipticity (major diameter/minor axis ratio) is more than 1.25.
[2]
According to the polyacetal resin molded body described in [1], wherein, above-mentioned (C) polyolefin comprises and has
The polyolefin of crosslinking component.
[3]
According to the polyacetal resin molded body described in [1] or [2], wherein, above-mentioned (C) polyolefin comprises
Select free polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene
Alkene, polybutadiene hydride and acid modified polyolefin composition group at least two or more.
[4]
According to the polyacetal resin molded body according to any one of [1]～[3], wherein, above-mentioned (C)
Polyolefin comprises polypropylene.
[5]
According to the polyacetal resin molded body according to any one of [1]～[4], wherein, above-mentioned (C)
Polyolefin comprises polyethylene.
[6]
According to the polyacetal resin molded body according to any one of [1]～[5], wherein, above-mentioned (B)
Lubricating oil is paraffin oil and/or silicone oil.
[7]
According to the polyacetal resin molded body according to any one of [1]～[6], wherein, above-mentioned major diameter
It is 1.6mm～2.7mm for 2.8mm～3.9mm and above-mentioned minor axis, and above-mentioned ellipticity (major diameter/
Minor axis ratio) it is 1.3～1.8.
[8]
A kind of component, it is by entering the polyacetal resin molded body according to any one of [1]～[7]
One-step shaping and obtain.
Invention effect
According to the present invention, being provided that a kind of resin-formed body, it has stable sliding, warp
Time tone variations is few, low odor excellent and resistance to adhesive is excellent.
Detailed description of the invention
Hereinafter, to detailed for implementing the mode (hereinafter referred to as " present embodiment ") of the present invention
Illustrate, but the invention is not restricted to following record, can carry out various in the range of its main idea
Deformation is implemented.
" polyacetal resin molded body "
The polyacetal resin molded body of present embodiment is for comprising (A) polyacetal resin, (B) lubricating oil
(C) polyolefinic polyacetal resin molded body, major diameter is 2.5mm～4.0mm and minor axis is
1.4mm～2.8mm, and ellipticity (major diameter/minor axis ratio) is more than 1.25.Due to by this way
Constitute, therefore the polyacetal resin molded body of present embodiment have stable sliding, through time
Tone variations is few, low odor excellent and resistance to adhesive is excellent.
It should be noted that " polyacetal resin molded body " in present embodiment is as long as comprising
(A) polyacetal resin, (B) lubricating oil and (C) polyolefin, and there is above-mentioned shape just there is no spy
Do not limit.Such as, including using extruder etc. or obtaining " one-tenth by injection moulding etc.
Type body ".Herein, molded body also includes strands, the granule such as utilizing extruder to obtain.
" (polyacetal resin molded body) major diameter " described in present embodiment, " (polyacetals
Resin-formed body) minor axis " it is to instigate polyacetal resin molded body to form steady statue in the plane
Time, by the molded body particle height represented to the height at the highest position from plane, by from molding
Body particle upper surface is to the molded body particle width of the longest width means of lower surface.By comparing
These molded body particle widths or molded body particle height, longer for major diameter, shorter for short
Footpath.
" (polyacetal resin molded body) ellipticity " described in present embodiment is major diameter and minor axis
Ratio, i.e. (ellipticity)=(major diameter)/(minor axis).When determining major diameter, minor axis, ellipticity, example can be used
Meansigma methods such as 20 molded body particles.
The major diameter of the polyacetal resin molded body of present embodiment is 2.5mm～4.0mm, minor axis
For 1.4mm～2.8mm, the ellipticity of molded body is more than 1.25.The preferably major diameter of molded body is
2.8mm～3.9mm, minor axis be 1.6mm～2.7mm, more preferably major diameter be 3.0mm～
3.8mm, minor axis is 2.0mm～2.6mm.It is more than 2.5mm by major diameter, by molded body
Easily melt when melting mixing or injection moulding.It addition, be below 4.0mm by major diameter, can
To reduce the attachment each other of the molded body in manufacturing process.It should be noted that by minor axis be
More than 1.4mm, rupturing of molded body when molded body can be suppressed to contact with each other.Pass through minor axis
For below 2.6mm, the release of the formaldehyde that the granule after can being substantially reduced by dried produces
Amount.The ellipticity of molded body is preferably more than 1.30.The upper limit of the ellipticity of molded body is preferably 2.00
Below.More preferably less than 1.80.The major diameter of pellet particle and 1.25 that minor axis and ellipticity are regulation
Time following, contact area when molded body contacts with each other diminishes, and easily produces when imposed load
Micropowder.It addition, reduce the effect of special-shaped object generation amount when carrying molded body in manufacturing process
Not enough.Additionally, there is the tendency becoming many in the burst size of methanal produced by the granule after dried.
During it should be noted that the ellipticity of polyacetal resin molded body is less than 2.00, can be the most true
Protect the thickness of molded body as a result, there is micropowder when suppressing molded body to contact with each other further and produce
Raw tendency, additionally, there are the special-shaped object generation amount can being substantially reduced when carrying molded body
Tendency.
As the method for the ellipticity increasing polyacetal resin molded body, it is not limited to following, can enumerate
Such as increase particle width or reduce particle height.As the method increasing particle width, do not limit
In following, the size etc. of the molten resin extrusion nozzle such as increased in extruder can be enumerated.Separately
Outward, as the method reducing particle height, it is not limited to following, can enumerate and such as reduce extruder
The extrusion capacity of time per unit or increase the quantity of cutting machine blade, rotating speed etc..
The manufacture method of the polyacetal resin molded body of present embodiment is not particularly limited, permissible
After being manufactured by method described later etc., melting mixing machine coordinates required various additives also
Melting mixing, afterwards, from extruder via multiple little nozzle resin melt extrusions, utilizes and rotates
Cutting machine, such as limit cools down limit in an atmosphere and cuts, thus manufacture polyacetal resin become
Type body.
The form of polyacetal resin molded body is not limited to following, can make such as diameter or
It is about discoid, spherical, cylindric, prism, the tabular of 1mm～about 10mm, it addition,
Its shape, size can according to the extrusion capacity of the time per unit of extruder, extrusion built-in temperature,
Shape/size/the number of nozzle, the quantity/rotating speed of cutting machine blade, resin cooling condition etc. are suitable
Work as regulation.In addition it is also possible to regulate polyacetal resin molded body by suitably regulation form
Physical property (odor strength, adhesive etc.).
The polyacetal resin molded body of present embodiment be preferably shaped to short cylindrical shape, i.e. disk
Shape, the weight of every 1 molded body is usually 5mg～100mg, preferably 7mg's～50mg
Scope.
By the major diameter of polyacetal resin molded body, minor axis, ellipticity are set as above-mentioned scope,
The weight making molded body is certain scope with surface area ratio, has given play to injection moulding and has obtained
The effect that tone variations after the heating of the molded body arrived is little.It addition, by by the length of molded body
Footpath, minor axis, ellipticity are set as above-mentioned scope, have given play to the effect raising of dried, stink
The effect that intensity also reduces.
<(A) polyacetal resin>
Herein, (A) for using in the polyacetal resin molded body of present embodiment gathers
Acetal resin explains.
As the polyacetal resin that can use in the present embodiment, it is not particularly limited, can
Enumerate such as POM-H Acetal homopolymer and polyacetal copolymer.POM-H Acetal homopolymer is not particularly limited,
For example, by monomer or the formaldehyde such as its trimer (metaformaldehyde), tetramer (four polyformaldehyde) of formaldehyde
Cyclic oligomer homopolymerization and the homopolymer that obtains.Therefore, POM-H Acetal homopolymer is substantially by oxygen
MU (methylene unit) is constituted.
It addition, polyacetal copolymer is not particularly limited, can enumerate the monomer of such as formaldehyde or its
The cyclic oligomer of the formaldehyde such as trimer (metaformaldehyde), tetramer (four polyformaldehyde) and oxirane,
The glycol such as expoxy propane, chloropropylene oxide, 1,3-dioxolane, 1,4-butanediol formal, two
The cyclic ethers such as the cyclic formals of polyglycols, cyclic formals copolymerization and the copolymer that obtains.Separately
Outward, as polyacetal copolymer, it is possible to use make the monomer of formaldehyde and/or the ring-type low of formaldehyde
Polymers and monofunctional glycidyl ether copolymerization and the polyacetal copolymer with side chain that obtains or
The polyacetal copolymer with cross-linked structure obtained with polyfunctional glycidyl ether's copolymerization.
Additionally, polyacetal resin can also be for having the functional groups such as hydroxyl at two ends or single end
Compound, in the presence of such as poly alkylene glycol, make the monomer of formaldehyde or the ring-type of formaldehyde
The POM-H Acetal homopolymer with block component that oligomer is polymerized and obtains.Similarly, polyacetals
Resin can also be for having the compound of the functional groups such as hydroxyl, such as hydrogen at two ends or single end
Change in the presence of polybutadiene diol, make the monomer of formaldehyde or its trimer (metaformaldehyde), four gather
The cyclic oligomer of the formaldehyde such as thing (metaformaldehyde) and cyclic ether, cyclic formals copolymerization and obtain
There is the polyacetal copolymer of block component.As it has been described above, as the bunching in present embodiment
Urea formaldehyde, it is possible to use any one in POM-H Acetal homopolymer and Copolyacetal.It addition,
Polyacetal resin can be used alone a kind or is applied in combination two or more.Polyacetal resin is preferred
Comprise Copolyacetal.
When using metaformaldehyde to obtain polyacetal copolymer, above-mentioned 1,3-dioxolane etc. is total to
The usage amount of poly-monomer is preferably 0.1 mole～60 generally relative to metaformaldehyde 100 moles and rubs
You, more preferably 0.1 mole～20 moles, more preferably 0.13 mole～10 moles.
In present embodiment, the fusing point of polyacetal copolymer is preferably 162 DEG C～173 DEG C, more preferably
167 DEG C～173 DEG C, more preferably 167 DEG C～171 DEG C.Fusing point is 162 DEG C～173 DEG C
Polyacetal copolymer such as can by relative to metaformaldehyde 100 moles use about 1.3 moles～
The comonomer of about 3.5 moles and obtain.It addition, fusing point can be measured by DSC.
As the polymerization catalyst of the polymerization for polyacetal copolymer, it is not particularly limited, excellent
Select such as lewis acid, Bronsted acid and the cationic active catalyst such as ester or anhydride thereof.As road
Lewis acid, is not particularly limited, and can enumerate such as boric acid, stannum, titanium, phosphorus, arsenic and antimony
Halogenide, more specifically can enumerate boron trifluoride, butter of tin, titanium tetrachloride, five fluorinations
Phosphorus, phosphorus pentachloride, antimony pentafluoride and its complex or salt.It addition, as Bronsted acid,
Its ester or anhydride, be not particularly limited, and can enumerate such as perchloric acid, trifluoromethanesulfonic acid, height
The chloric acid tert-butyl ester, acetylperchlorate, trimethyl oxygenHexafluorophosphate etc..In them, excellent
Select boron trifluoride, boron trifluoride hydrate and contain oxygen atom or the organic compound of sulphur atom
With the co-ordination complex of boron trifluoride, more specifically, can enumerate boron trifluoride diethyl ether, three
Boron fluoride di-n-butyl ether is as preference.
As the manufacture method of polyacetal copolymer, it is not particularly limited, can use the most known
Method, such as No. 3027352 description, U.S. Patent No. of U.S. Patent No. can be enumerated
No. 3803094 description, Deutsche Bundespatents invent No. 1161421 description, Deutsche Bundespatent invention
No. 1495228 description, Deutsche Bundespatent invent No. 1720358 description, Deutsche Bundespatent
Invent No. 3018898 description, Japanese Laid-Open Patent Publication 58-98322 publication and Japanese Unexamined Patent Publication
Method described in 7-70267 publication.By can in the polyacetal copolymer that above-mentioned polymerization obtains
Heat-labile terminal part [-(OCH can be there is2)n-OH group], therefore it is preferable to carry out unstable end
The decomposition removing of end processes.
Specifically, in the decomposition removing of unstable terminal part processes, by following formula (1) table
In the presence of at least one quaternary ammonium compound shown, more than the fusing point of polyacetal copolymer and 260
At a temperature of below DEG C, implement heat treated when making polyacetal copolymer melted.
[R1R2R3R4N+]nX-n…(1)
Herein, in formula (1), R1、R2、R3And R4Represent carbon number 1～30 independently of one another
Substituted or unsubstituted alkyl；The aryl of carbon number 6～20；Carbon number 1～30
At least one hydrogen atom in substituted or unsubstituted alkyl is taken by the aryl of carbon number 6～20
Aralkyl after Dai；Or at least one hydrogen atom in the aryl of carbon number 6～20 is by carbon
Alkaryl after the substituted or unsubstituted alkyl replacement of atomic number 1～30, replaces or unsubstituted
Alkyl be straight-chain, branched or ring-type.Substituent group in above-mentioned replacement alkyl is that halogen is former
Son, hydroxyl, aldehyde radical, carboxyl, amino or amide groups.It addition, above-mentioned unsubstituted alkyl,
Hydrogen atom in aryl, aralkyl, alkaryl can be substituted with halogen atoms.N represents 1～3
Integer.X represent hydroxyl or the carboxylic acid of carbon number 1～20, hydracid in addition to hydrogen halides,
The sour residue of organic thionic acid of oxyacid, inorganic thionic acid or carbon number 1～20.
As long as the compound that quaternary ammonium compound is represented by above-mentioned formula (1) is just not particularly limited,
But from the viewpoint of the effect above more effectively and reliably having given play to present embodiment, formula (1)
In R1、R2、R3And R4The alkyl or the carbon that are preferably carbon number 1～5 independently of one another are former
The hydroxyalkyl of subnumber 2～4, even more preferably R1、R2、R3And R4In at least one be
Ethoxy.As such quaternary ammonium compound, it is not particularly limited, specifically can enumerate such as:
Tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetra-n-butyl ammonium, cetyltrimethyl ammonium,
Ammonium, 1,6-hexa-methylene double (trimethyl ammonium), the double (trimethyl of decamethylene
Ammonium), trimethyl-3-chlorine-2-hydroxyl propyl ammonium, trimethyl (2-hydroxyethyl) ammonium, triethyl group (2-hydroxyl
Base ethyl) ammonium, tripropyl (2-hydroxyethyl) ammonium, three normal-butyls (2-hydroxyethyl) ammonium, trimethyl
Hexadecyldimethyl benzyl ammonium, triethylbenzyl ammonium, tripropyl hexadecyldimethyl benzyl ammonium, three normal-butyl hexadecyldimethyl benzyl ammoniums, trimethylbenzene
Base ammonium, triethyl group phenyl ammonium, trimethyl-2-hydroxyethyl ammonium, monomethyl trihydroxyethyl ammonium, one
The hydrogen-oxygen of ethyl trihydroxyethyl ammonium, octadecyl three (2-hydroxyethyl) ammonium, four (ethoxy) ammonium etc.
The hydrohalogenic acid salts such as compound, the hydrochloric acid of above-mentioned quaternary ammonium, hydrobromic acid, Fluohydric acid.；The sulphuric acid of above-mentioned quaternary ammonium,
Nitric acid, phosphoric acid, carbonic acid, boric acid, chloric acid, iodic acid, silicic acid, perchloric acid, chlorous acid, secondary
The oxysalts such as chloric acid, chlorosulfonic acid, sulfamic acid, pyrosulfuric acid, tripolyphosphate；Above-mentioned quaternary ammonium
Thion hydrochlorate, the formic acid of above-mentioned quaternary ammonium, acetic acid, propanoic acid, butanoic acid, the isobutyl such as thiosulfuric acid
The carboxylates etc. such as acid, valeric acid, caproic acid, octanoic acid, capric acid, benzoic acid, oxalic acid.In them,
Preferably hydroxide (OH-), sulphuric acid (HSO4-、SO4 2-), carbonic acid (HCO3-、CO3 2-), boric acid
(B(OH)4 -) and the salt of carboxylic acid.In carboxylic acid, particularly preferred formic acid, acetic acid, propanoic acid.Season
Ammonium compounds can be used alone a kind, or can also be applied in combination two or more.It addition,
In addition to above-mentioned quaternary ammonium compound, it is also possible to be applied in combination as known unstable terminal part
The amines etc. such as the ammonia of decomposition accelerating agent, triethylamine.
The usage amount of quaternary ammonium compound is scaled relative to polyacetal copolymer and quaternary ammonium compound
The nitrogen quantity coming from quaternary ammonium compound that add up to quality, that represented by following formula (2), is preferably
0.05～50 mass ppm, more preferably 1～30 mass ppm.
Usage amount=P × the 14/Q of quaternary ammonium compound ... (2)
Herein, in formula (2), P represents the quaternary ammonium compound concentration (matter relative to polyacetal copolymer
Amount ppm), 14 is the atomic weight of nitrogen, and Q represents the molecular weight of quaternary ammonium compound.
It is more than 0.05 mass ppm by the usage amount of quaternary ammonium compound, there is unstable end
The tendency that the decomposition removal rate in portion improves further.It addition, by below for 50 mass ppm,
There is more excellent the inclining of tone decomposing the polyacetal copolymer after removing of unstable terminal part
To.
The unstable terminal part of the polyacetal resin in present embodiment by more than fusing point and
At a temperature of less than 260 DEG C, carry out heat treatment when making Copolyacetal melted, tool
There is the tendency that can fully decompose removing.Spy is not had as the device processed for this decomposition removing
Do not limit, the most such as extruder, kneader etc..The formaldehyde produced by decomposition is generally existed
Decompression is lower to be removed.As the method that quaternary ammonium compound and polyacetal copolymer are mixed the most especially
Limit, can enumerate and such as add as an aqueous solution in the operation making polymerization catalyst inactivate
Method, the method etc. jetted in the Copolyacetal powder generated by polymerization.No matter make
Use any method, as long as in the operation that Copolyacetal is carried out heat treated at this altogether
Polymers exists quaternary ammonium compound.For example, it is also possible at melting mixing and extrusion polyformaldehyde
The extruder of copolymer injects quaternary ammonium compound.Or use this extruder etc. to be total at polyformaldehyde
When polymers coordinates filler, pigment, first quaternary ammonium compound can be impregnated into polyformaldehyde copolymerization
In the resin particle of thing, filler later, pigment cooperation time carry out unstable end and remove
Process.
Unstable terminal part decompose removing process can also make with by being polymerized the poly-first obtained
Carry out after the polymerization catalyst inactivation that aldehyde copolymer coexists, it is also possible to do not make polymerization catalyst inactivate
And carry out.Inactivation as polymerization catalyst processes, and the alkalescence that can be set forth in amine etc. is water-soluble
In liquid by polymerization catalyst and inactivation method.When not carrying out the inactivation of polymerization catalyst,
At a temperature of below the fusing point of polyacetal copolymer, heat this copolymer under inert gas atmosphere,
After reducing polymerization catalyst by volatilization, the decomposition carrying out unstable terminal part removes operation also
It it is effective method.
The polyacetal copolymer obtained by the decomposing removing process of above-mentioned unstable terminal part
There's almost no unstable terminal part, there is the tendency that heat stability is more excellent.
It addition, (A) polyacetal resin can be used alone a kind, alternatively, it is also possible to and with 2 kinds
Below such as molecular weight is different polyacetal resin, the Copolyacetal that amount of comonomers is different
Deng.
<(B) lubricating oil>
Then, (B) lubricating oil that can use in the present embodiment is described in detail.
(in this specification, (B) composition is designated as (B) sometimes.)
Do not have relative to the lower limit of the content of (B) lubricating oil of (A) polyacetal resin 100 mass parts
Have and limit especially, preferably 0.1 mass parts, more preferably 0.2 mass parts, more preferably
0.3 mass parts.It addition, the higher limit of above-mentioned content is it is not also specifically limited, preferably 5.0 matter
Amount part, more preferably 4.5 mass parts, more preferably 4.2 mass parts.(B) content is upper
When stating scope, there is the tendency that the wearability of polyacetal resin molded body improves.Particularly (B)
When content is more than 0.1 mass parts, has and may insure that what sufficient sliding, wearability improved
Tendency.During it addition, the content of (B) is below 5.0 mass parts, has and can suppress the soft of resin
Change and may insure that the intensity of the polyacetal resin molded body that can tolerate the purposes such as gear
Tendency.
(B) lower limit of the molecular weight of lubricating oil is preferably 100, and more preferably 400, the most excellent
Elect 500 as.It addition, the upper limit is preferably 5000000, more preferably 2000000, the most excellent
Elect 1000000 as.(B) lower limit of the fusing point of lubricating oil is preferably-50 DEG C, and more preferably-30
DEG C, more preferably-20 DEG C.(B) higher limit of the fusing point of lubricating oil is preferably 20 DEG C, more excellent
Elect 30 DEG C as, more preferably 50 DEG C.By molecular weight is set as more than 100, have
The sliding of lubricating oil becomes good tendency.It addition, by molecular weight is set as 1,000,000 with
Under, the dispersion with lubricating oil becomes good, the tendency of wearability raising.It addition, by melting
Point be set as more than-50 DEG C, may remain in molded body surface exist lubricating oil mobility,
Suppression abrasion, thus has the tendency that the wearability of molded body improves.It addition, by by fusing point
It is set as less than 50 DEG C, has easily and polyacetal resin is mixing, the dispersibility of lubricating oil improves
Tendency.According to above-mentioned viewpoint, molecular weight and the fusing point of (B) lubricating oil are preferably set to above-mentioned model
In enclosing.Above-mentioned fusing point is the temperature of lower than the pour point of lubricating oil 2.5 DEG C.Above-mentioned pour point can foundation
JIS K2269 measures.
(B) lubricating oil used in present embodiment is not limited to following material, as long as making
The material that the friction of polyacetal resin molded body, wearing character improve, can enumerate and such as send out
Native hydrocarbon or paraffin oil (the Idemitsu Kosen Co., Ltd. Diana Process such as motivation oil, steam cylinder oil
Oil PS32 etc.), naphthenic oil (Idemitsu Kosen Co., Ltd. Diana Process Oil NS90S etc.),
Synthesis hydrocarbon, the work such as aromatic oil (Idemitsu Kosen Co., Ltd. Diana Process Oil AC12 etc.)
For silicone oil (KCC of SHIN-ETSU HANTOTAI G30 series etc.) with polydimethylsiloxane as representative
Silicone oil, silicone rubber, modified silicon rubber, as long as from the most commercially available lubricating oil suitably select,
Suitably coordinate directly or according to needs and use.In them, paraffin oil and silicone oil are from slip
From the viewpoint of property also excellent and industrial can be readily available, thus preferably.These lubrications
Oil may be used alone, can also be used in combination.
From the viewpoint of the wearing character improved when sliding and sliding stability excellence, preferably
Scope as above institute by the content of (B) lubricating oil in the polyacetal resin molded body of present embodiment
State situation about being adjusted.
<(C) polyolefin>
Then, (C) polyolefin that can use in the present embodiment is explained.
Do not have relative to the lower limit of (C) polyolefinic content of (A) polyacetal resin 100 mass parts
Have and limit especially, preferably 0.5 mass parts, more preferably 0.7 mass parts, more preferably
1.0 mass parts.It addition, the higher limit of (C) polyolefinic content is it is not also specifically limited, be preferably
5.0 mass parts, more preferably 4.5 mass parts, more preferably 4.0 mass parts.From fully
From the viewpoint of guaranteeing the wearability of molded body, preferably polyolefinic to (C) content is set in above-mentioned
In the range of.When particularly (C) polyolefinic content is more than 0.5 mass parts, there is molded body
The tendency that sliding improves.During it addition, (C) polyolefinic content is below 5.0 mass parts, tool
There is the tendency being possible to prevent the stripping of resinous principle, wearability to improve.For present embodiment
For polyacetal resin molded body, excellent from the wearing character improved when sliding and sliding stability
From the viewpoint of different, preferably by the feelings of the scope regulation proceeded as above of polyolefinic to (C) content
Condition.
As (C) polyolefin, it is not limited to following, is preferably selected from by the alkene shown in following formula (3)
The homopolymer of hydrocarbon compound, with the alkenes compounds shown in following formula (3) as principal monomer
Polymer and their modifier composition group in more than one polyolefin.
In above-mentioned formula (3), R11For hydrogen atom or methyl, R12For hydrogen atom, carbon number 1～
Alkyl, carboxyl, the alkylation carboxyl comprising 2～5 carbon atoms of 10, there are 2～5 carbon
The acyloxy of atom or vinyl.As other monomer, can be from can be with above-mentioned formula (3)
The monomer of shown alkenes compounds polymerization suitably selects.
As (C) polyolefin that can use in the present embodiment, it is not limited to following material,
Such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, second can be enumerated
Alkene-alpha olefin copolymer, polypropylene-butene copolymer, polybutene, the hydride of polybutadiene,
Vinyl-acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer
Thing, vinyl-vinyl acetate copolymer etc. have block and the hydrophilic polymer of polyolefin (c1)
(c2) block is via selecting free ester bond, amido link, ehter bond, amino-formate bond and imide bond
The block polymer of the structure that is alternately and repeatedly bonded of at least one key in the group of composition, with
And their modifier, their thermoplastic elastomer (TPE).
As the concrete example of polyolefin (c1), it is not limited to following material, polyethylene can be enumerated, gather
Propylene, polybutadiene etc..It addition, as the concrete example of hydrophilic polymer (c2), be not limited to
Under material, polyvinyl acetate, polymethyl methacrylate, polylactic acid etc. can be enumerated.
As (C) polyolefin, it is possible to use modified polyolefin (modifier).Change as this
Property thing, is not limited to following, can enumerate that the polymer such as made and form olefin resin is different one
Plant the graft copolymer of above other vinyl compound grafting, use alpha, beta-unsaturated carboxylic acid
(acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, Na Dike acid
Deng) or the material of its anhydride (as required and with peroxide) modification, make olefines chemical combination
The material of thing and anhydride copolymers.
Thermoplastic elastomer (TPE) can also be used as (C) polyolefin.Hereinafter, sometimes by such poly-
Alkene is referred to as " having crosslinking component " polyolefin.The polyolefin with crosslinking component is not limited to
Hereinafter, can be by the most in the presence of radical initiators by radical crosslinking elastomer
Do not show the resin melting of radical crosslinking mixing while, by radical crosslinking bullet
Gonosome crosslinking manufactures.More specifically, this thermoplastic elastomer (TPE) can be by by following (1)～(5)
The method manufacture represented.It addition, the hardness as the thermoplastic elastomer (TPE) of the index of flexibility (depends on
According to ASTMD2240 type A) also depend on its purpose, but preferably 30～90.Hard by this
Degree is more than 30, has the molded body that obtained by the polyacetal resin molded body of present embodiment
Mechanical performance, particularly resistance to impact, percentage elongation become good tendency, are 90 by this hardness
Hereinafter, the hardness of the polyacetal resin molded body with present embodiment becomes good tendency.
(1) organic peroxide is being utilized described in Japanese Laid-Open Patent Publication 59-006236 publication
Make olefin rubber and olefine kind resin partial cross-linked, and coordinate the embedding of A-(B-A) N-shaped wherein
Section copolymer and the method that obtains thermoplastic elastomer (TPE).
(2) organic peroxide is being utilized described in Japanese Unexamined Patent Publication 03-292342 publication
Hydrogenated styrene analog is added after oil-filled olefin copolymer rubber, olefin resin and softening agent being cross-linked
Thermoplastic elastomer (TPE) and the method that obtains thermoplastic elastomer (TPE).
(3) at the thermoplastic by containing crosslinking rubber described in Japanese Unexamined Patent Publication 07-11067 publication
Property elastomer, SBC, softening agent and polyolefin resin are obtained by mixing
The method of thermoplastic elastomer (TPE).
(4) specific ethylene-α will comprised described in Japanese Unexamined Patent Publication 10-287775 publication
Olefin copolymer, to comprise at least 1 polymer based on vinyl aromatic compounds embedding
Section A and at least 1 polymer blocks B based on conjugated diene compound and hydrogenation form
The mixture of block copolymer, acronal and rubber oil utilize radical initiator
Cross-link with crosslinking coagent, thus obtain the thermoplasticity as soft composition for thermoplastic elastomer
The method of elastomer.
(5) making comprising later described in No. 2000/61681 separate edition of International Publication
With the ethylene-alpha-olefin copolymer of metallocene catalyst manufacture and olefine kind resin and the degree of cross linking it is
The ethylene-alpha-olefin copolymer of more than 50% adds thermoplastic elastomer (TPE) and obtains as rubber group
The method of the thermoplastic elastomer (TPE) of compound.
(6) thermoplastic elastomer (TPE) is being obtained described in No. 2610663 description of Japanese Patent No.
Method, it is characterised in that make to comprise crystalline olefin polymer portion and amorphism olefinic polymerization
The polymer particle in thing portion and cross-linking agent are less than the fusing point of crystalline olefin polymer or amorphism
Contact at a temperature of any one higher temperature in the glass transition temperature of olefin polymer
And the thermoplastic elastomer (TPE) after cross-linking in obtaining particle.
Be there is by use the polyolefin of crosslinking component, there is coefficient of friction when obtaining slip more
The tendency of the resin combination that low, sliding stability is more excellent, result has the polyacetals obtained
The tendency that the physical property of resin-formed body also improves.
In them, can suitably use any one, but (1), (4), (5), (6) method due to
Can the degree of cross linking be controlled higher, the most more preferably.
These above-mentioned (C) polyolefin are either independent or mixture can use.
In them, as (C) polyolefin, preferably polyethylene is (high-pressure process low-density polyethylene, linear
Low Density Polyethylene, ultra-low density polyethylene), polypropylene, ethylene-propylene copolymer, ethylene-
Butylene copolymer, ethylene-octene copolymer, polybutadiene, polybutadiene hydride, acid modification
Polyolefin, thermoplastic elastomer (TPE).It addition, (C) polyolefin more preferably comprise choosing free polyethylene,
Polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polybutadiene hydrogen
Compound and acid modified polyolefin composition group at least two or more.In the present embodiment,
In above-mentioned, particularly preferably comprise polyethylene (high-pressure process low-density polyethylene, linear low density polyethylene
Alkene, ultra-low density polyethylene), polypropylene, ethylene-propylene copolymer, thermoplastic elastomer (TPE).Logical
Crossing use said polyolefins, coefficient of friction when can obtain slip is low, sliding stability is excellent
Resin combination.It addition, the polyacetal resin in time comprising the polyolefin with crosslinking component
From the viewpoint of dispersibility in molded body, (C) polyolefin preferably comprises polyethylene.It addition, from
From the viewpoint of the sliding stability of resin combination, (C) polyolefin preferably comprises polypropylene.
(C) polyolefin used in present embodiment is 190 DEG C, molten under 2.16kg load-up condition
Body flow rate (being also denoted as " MFR " below) is preferably 0.01～100g/10 minute.By inciting somebody to action
(C) polyolefinic MFR sets within the range, has and can suppress rubbing under small load-up condition
Wiping, the deterioration of wearing character, the tendency that noise occurs can also be suppressed.(C) polyolefinic MFR
Lower limit be more preferably 0.02g/10 minute, more preferably 0.05g/10 minute, the most excellent
Elect 0.07g/10 minute as.It addition, the upper limit of (C) polyolefinic MFR is more preferably 90g/10
Minute, more preferably 80g/10 minute, particularly preferably 70g/10 minute.It addition, (C)
Polyolefinic fusing point is not particularly limited, preferably 30 DEG C～the scope of 230 DEG C, further preferably
It is 50 DEG C～the scope of 200 DEG C, particularly preferably 90 DEG C～170 DEG C.It addition, C composition is molten
Point can measure according to JIS K7121.
<other composition>
The polyacetal resin molded body of present embodiment is at the model of the purpose not damaging present embodiment
In enclosing, can be containing the various stabilizers used in polyacetal resin molded body in the past.As
Stabilizer, is not limited to following material, can enumerate example inorganic filler described as follows, antioxidation
The agent for capturing of agent, formaldehyde or formic acid.They can only be used alone a kind, it is also possible to combination makes
Use two or more.
As above-mentioned antioxidant, from the viewpoint of the heat stability improving polyacetal resin molded body
Consider, preferably hindered phenol anti-oxidants.
As hindered phenol anti-oxidants, be not limited to following material, can enumerate such as 3-(3 ', 5 '-
Di-t-butyl-4 '-hydroxyphenyl) propanoic acid n-octadecane base ester, 3-(3 '-methyl-the 5 '-tert-butyl group-4 '-oxybenzene
Base) propanoic acid n-octadecane base ester, 3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propanoic acid n-tetradecane base
Ester, 1,6-HD-bis-(3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic esters), 1,4-butanediol-bis-
(3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester), triethylene glycol-bis-(3-(the 3-tert-butyl group-5-methyl
-4-hydroxyphenyl) propionic ester) etc..
It addition, as hindered phenol anti-oxidants, be not limited to following material, can enumerate such as
Four (methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester) methane, double (2-(3-(uncle 3-of 3,9-
Butyl-4-hydroxy-5-methyl base phenyl) propionyloxy)-1,1-dimethyl ethyl)-2,4,8,10-four oxaspiro
(5.5) hendecane, N, N '-bis--3-(3 ', 5 '-di-t-butyl-4-hydroxyl phenol) propiono hexa-methylene two
Amine, N, the double-3-of N '-tetramethylene (3 '-methyl-5 '-tertiary butyl-4-hydroxy phenol) propiono diamidogen,
N, N '-bis-(3-(3,5-di-t-butyl-4-hydroxyl phenol) propiono) hydrazine, N-salicyl-N '-Asia water
Yankee hydrazine, 3-(N-salicyl) amino-1,2,4-triazole, N, N '-bis-(2-(3-(3,5-dibutyl-4-
Hydroxyphenyl) propionyloxy) ethyl) epoxide amide etc..
In above-mentioned hindered phenol anti-oxidants, from the heat stability improving polyacetal resin molded body
From the viewpoint of, preferably triethylene glycol-bis-(3-(the 3-tert-butyl group-5-methyl-4-hydroxyphenyl) propionic esters),
Four (methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester) methane.
As formaldehyde, the agent for capturing of formic acid, it is not limited to following material, can enumerate and such as contain
Formaldehyde reactivity nitrogen compound and the hydroxide of polymer, alkali metal or alkaline-earth metal thereof,
Inorganic acid salt and carboxylate.
As above-mentioned containing formaldehyde reactivity nitrogen compound with its polymer, it is not limited to following
Material, can enumerate the condensation polymer of such as dicyandiamide, tripolycyanamide, tripolycyanamide and formaldehyde；Buddhist nun
Dragon 4-6, nylon 6, nylon 6-6, nylon 6-10, nylon 6-12, nylon 12, nylon 6/6-6,
The polyamides such as nylon 6/6-6/6-10, nylon 6/6-12；Poly-Beta-alanine, polyacrylamide.
Wherein, can enumerate tripolycyanamide and the condensation polymer of formaldehyde, polyamide, poly-Beta-alanine and
Polyacrylamide, from the viewpoint of the heat stability improving polyacetal resin molded body, more excellent
Select polyamide and poly-Beta-alanine.
As above-mentioned alkali metal or the hydroxide of alkaline-earth metal, inorganic acid salt and carboxylate, no
Be limited to following material, can enumerate such as sodium, potassium, magnesium, calcium or barium etc. hydroxide,
The carbonate of above-mentioned metal, phosphate, silicate, borate, carboxylate.From improving bunching
From the viewpoint of the heat stability of urea formaldehyde molded body, specifically preferred calcium salt.As this calcium salt,
It is not limited to following material, such as calcium hydroxide, calcium carbonate, calcium phosphate, silicic acid can be enumerated
Calcium, Calcium pyroborate and fatty acid calcium salt (calcium stearate, calcium myristate etc.).The fat of fatty acid calcium salt
Fat acid composition can be optionally substituted by a hydroxyl group.In them, steady from the heat improving polyacetal resin molded body
From the viewpoint of qualitative, more preferably fatty acid calcium salt (calcium stearate, calcium myristate etc.).
From the viewpoint of the heat stability improving polyacetal resin molded body, above-mentioned various stable
Preferably being combined as especially with triethylene glycol-bis-(3-(the 3-tert-butyl group-5-methyl-4-hydroxyphenyl) of agent
Propionic ester) or four (methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester) methane is representative
Hindered phenol anti-oxidants, especially containing as representative with polyamide and poly-Beta-alanine
There are polymer and the especially alkaline-earth metal with fatty acid calcium salt as representative of formaldehyde reactive nitrogen
The combination of soap.
Above-mentioned inorganic filler is not limited to following material, for selecting free fibrous particle and/or plate
At least one compound in the group of shape particle, inorganic pigment composition.Threadiness described herein
Particle and platy particles refer to fibrous particle, tabular present in the polyacetal resin molded body
The average aspect ratio of particle is the particle of more than 5.
As fibrous particle, be not particularly limited, can enumerate such as glass fibre, carbon fiber,
Potassium titanate fibre, asbestos fibre, silicon carbide fibre, silicon nitride fiber, calcium metasilicate fibers,
Or aramid fibre etc..
It addition, as platy particles, be not particularly limited, can enumerate such as Talcum, Muscovitum,
Kaolin, glass flake, bentonite etc..In them, preferably talc, Muscovitum, glass flake.
By using them, there is the tendency that mechanical strength is more excellent and more economical.
It addition, as inorganic pigment, be not particularly limited, such as zinc sulfide, oxidation can be enumerated
Titanium, zinc oxide, ferrum oxide, barium sulfate, titanium dioxide, barium sulfate, hydrated chromium oxide, oxygen
Change chromium, cobalt aluminate, blanc fixe, zinc yellow 1 type, zinc yellow 2 type, ferric potassium ferrocyanide, height
Ridge soil, titan yellow, cobalt blue, ultramarine, cadmium, NiTi, Griffith's zinc white., strontium, umber, loess, indigo plant
Copper mine, malachite, azur malachite, Orpimentum (Auripigmentum), Realgar, Cinnabaris, turquoise, manganese spar,
Reddish brown Huang, terre verte, sienna, raw umber, Vandyke brown (Cassel earth), Chalk, stone
Cream, burnt sienna, cologne earth, celestite, chessy copper, malachite, coral powder, white mica,
Cobalt blue, cerulean blue, cobalt violet, cobalt green, zinc white, titanium white, light red, chrome oxide green, Ma Ersi
Black (Mars Black), chrome green, reddish brown Huang, alumina white, cadmium yellow, cadmium red, bright red, Talcum, white
White carbon black, clay, mineral violet, Flos Rosae Rugosae cobalt violet, silvery white, bronze, bronze powder, aluminium powder, Pu Lu
Scholar's indigo plant, cobalt yellow, mica titanium, white carbon black, acetylene black, dim, furnace black, plant are black, bone black,
Calcium carbonate, barba hispanica etc..
In them, from giving from the viewpoint of higher wearability, preferably zinc sulfide, zinc oxide,
Ferrum oxide, titanium dioxide, titan yellow, cobalt blue, carbonate, substantially low from Mohs' hardness, enter one
From the viewpoint of step gives high abrasiveness, more preferably zinc oxide, titan yellow.
The addition of above-mentioned each stabilizer is not particularly limited, relative to polyacetal resin (A) 100
Mass parts, preferably: antioxidant such as hindered phenol anti-oxidants is 0.1～2 mass parts, first
The agent for capturing of aldehyde or formic acid such as contain the polymer of formaldehyde reactive nitrogen be 0.1～3 mass parts,
The soap of alkaline-earth metal be 0.1～1 mass parts, inorganic filler be 0.002～0.5 mass
The scope of part.
" manufacture method of polyacetal resin molded body "
The polyacetal resin molded body of present embodiment such as can gather by comprising above-mentioned (A)
Acetal resin, (B) lubricating oil and (C) polyolefinic resin-formed body melting mixing, and it is shaped to spy
Fixed shapes etc. manufacture.
As the device of the polyacetal resin molded body manufacturing present embodiment, it is not particularly limited,
The mixing roll generally used can be applied.As this mixing roll, it is not limited to following device, can
To use such as single screw rod or multiscrew mixing extruder, roller, Banbury mixer etc..Wherein,
Decompressor and the double screw extruder of side apparatus for feeding are preferably equipped with it.
As the shape of the polyacetal resin molded body of present embodiment, preferably graininess, as
It is processed as granular means, is not particularly limited, such as, use double screw extruder conduct
During mixer, preferably after the thermoplastic resin after melting mixing is made strands shape, with cutting
Strands patterning method that machine cuts off, with cutting machine the thermoplastic resin of molten condition is cut off fervent
Cut method, the underwater cutting process cut off by the thermoplastic resin of molten condition in water with cutting machine.
Wherein, more preferably thermal cutting method.
" component "
The component of present embodiment comprises above-mentioned polyacetal resin molded body.That is, present embodiment
Component can be by the above-mentioned further molding of polyacetal resin molded body be obtained.
About the method by further for polyacetal resin molded body molding, it is not particularly limited, can
With the known forming method of application.Can pass through such as extrusion molding, injection moulding, vacuum becomes
Type, blow molding, injection compression molding, decorated molded, dissimilar materials molding, gas auxiliary
Injection moulding, foam injection molding, low pressure molding, (ultrahigh speed is injected in ultra-thin-wall injection moulding
Type), any one in the forming method such as composite molding (molding on insert moulding, inserts) in mould
Plant molding.
As the purposes of the component of the present embodiment obtained by above-mentioned polyacetal resin molded body,
The sliding being intended to aspire for stability being suitable for, the cosmetic variation after molding are excellent, the use of low odor
On the way.
As the purposes of the component of present embodiment, it is not limited to following, can enumerate the most general
The purposes of polyacetal resin.As the concrete example of such purposes, it is not limited to following, can enumerate
Such as with cam, slide block, lever, arm, clutch, felt clutch, idler gear, pulley,
Roller, cylinder (U ロ), key core (key stem), keycap (key top), baffle plate, spool, rotary shaft
(shaft), the mechanism part that joint, axle, bearing and guide rail etc. are representative；The tree of molding on inserts
Fat parts, the resin component of insert moulding, chassis, pallet, side plate, with printer and duplicating
Machine is the business automation equipment parts of representative；With VTR (magnetic tape video recorder), video camera, number
Code video camera, photographing unit and photographing unit that digital camera is representative or video equipment parts；
Tape player, DAT, LD (laser disk), MD (minidisk), CD (compact disk) (bag
Include CD-ROM (read only memory), CD-R (recordable type), CD-RW (erasable rewritable type)),
DVD (digital video disk) (include DVD-ROM, DVD-R, DVD+R, DVD-RW,
DVD+RW, DVD-R DL, DVD+R DL, DVD-RAM (random access memory),
DVD-Audio), Blu-ray Disc (registered trade mark), HD-DVD, other CD drive；With
MFD (multiple functional displays), MO (magneto-optic disk), navigation system and mobile personal computer are representative
Music, image or information equipment, with mobile phone and facsimile machine the communication equipment parts as representative；
Electrical equipment parts；Electronic equipment parts etc..It addition, the molded body of present embodiment is also
Can be suitable for as automotive part is convex with fuel tank, fuel pump module, valve class, fuel tank
The fuel associated components that edge etc. are representative；With door lock, door handle, window regulator, speaker
The car door associated components that grid etc. are representative；Peace with seat belt slip ring, button etc. as representative
Full band associated components；The parts such as cubicle switch parts, Switch, clip class；And automatic lead
The nib of pen, the mechanism part pen core of propelling pencil released and loads；Washstand, draining
Mouth and drain cock opening and closing mechanism part；The opening/closing portion blocking mechanism of automatic vending machine, commodity are discharged
Mechanism part；The sling of clothing, actuator, button；The nozzle of watering, water spray hose
Jointing；Balustrade portion and the building product of the supporter as earth material；With once
Property photographing unit, toy, securing member, chain, conveyer belt, bracelet, sporting goods, automatic selling
Cargo aircraft, furniture, musical instrument, residential equipment machine are the industrial part of representative.
Owing to the polyacetal resin molded body of present embodiment as mentioned above can be high as applying
The component of load uses, can also use as the component applying small load, the most any
Molded body can give play to stable sliding properties, it can be said that be excellent polyacetals tree
Fat molded body.
Embodiment
Hereinafter, specifically describe present embodiment by embodiment, but present embodiment is not limited to
These embodiments.
First, the details of the composition used in embodiment described below and comparative example and evaluation methodology.
[using the details of composition]
((A) polyacetals)
As polyacetals, use the following grade that can obtain from Asahi Chemical Corp
Polyacetals.
Tenac (registered trade mark) 4520 (hereinafter also referred to as " A1 "), MFR (190 DEG C, 2.16kg
Load)=3g/10 minute (copolymer)
Tenac (registered trade mark) 7520 (hereinafter also referred to as " A2 "), MFR (190 DEG C, 2.16kg
Load)=9g/10 minute (copolymer)
Tenac (registered trade mark) 4010 (hereinafter also referred to as " A3 "), MFR (190 DEG C, 2.16kg
Load)=10g/10 minute (copolymer)
((B) lubricating oil)
As lubricating oil, use the profit of the following grade that can obtain from Idemitsu Kosen Co., Ltd.
Lubricating oil.
Diana (registered trade mark) Process Oil PS32 (hereinafter also referred to as " B1 "), 40 DEG C move
State viscosity 31.4mm2/ s (paraffin oil)
Diana (registered trade mark) Process Oil PW380 (hereinafter also referred to as " B2 "), 40 DEG C
Dynamic viscosity 408.8mm2/ s (paraffin oil)
((C) polyolefin)
As polyolefin, use the polyolefin of the following grade that can obtain from each company.
Suntec (registered trade mark)--LDL1850A (hereinafter also referred to as " C1 ") Asahi Chemical Industry chemistry
Co., Ltd.'s system (polyethylene)
MFR=6.7g/10 minute (JISK7210 code D)
Suntec (registered trade mark)--LDM6555 (hereinafter also referred to as " C2 ") Asahi Chemical Industry's chemistry strain
Formula commercial firm system (polyethylene)
MFR=55g/10 minute (JISK7210 code D)
Suntec (registered trade mark)--HD J240 (hereinafter also referred to as " C3 ") Asahi Chemical Industry's chemistry strain
Formula commercial firm system (polyethylene)
MFR=5g/10 minute (JISK7210 code D)
Sunallomer (registered trade mark) PL500A (hereinafter also referred to as " C4 ") Sunallomer strain
Formula commercial firm system (polypropylene)
MFR=3.0g/10 minute, density 0.9g/cm3(JISK6921-2)
JSRRB830 (hereinafter also referred to as " C5 ") JSR Corp.'s system
MI=3.0g/10 minute (ASTMD1238), density 0.909g/cm3(JISK7112) (poly-fourth
Dienes thermoplastic elastomer (TPE))
Engage (registered trade mark) 8842 (hereinafter also referred to as " C6 ") Dow Chemical's system (heat
Thermoplastic elastic)
MFR=1.0g/10 minute (JISK7210 code D), density 0.857g/cm3
Chemical conversion industrial group of Umex (registered trade mark) 1001 (hereinafter also referred to as " C7 ") Sanyo system
(maleic acid anhydride group modified polypropene)
Proportion 0.95 (ASTMD792), softening point 153 DEG C (JISK2531)
Milastomer (registered trade mark) 7030NS (hereinafter also referred to as " C8 ") Mitsui Chemicals strain
Formula commercial firm system (olefin hydrocarbons thermoplasticity elastic body)
MFR=30g/10 minute (230 DEG C, 10kg, load reference ISO1133), density 880kg/m3
(ASTMD1505), there is the polyolefin of crosslinking component.
Thermorun (registered trade mark) QT60MB (hereinafter also referred to as " C9 ") Mitsubishi Chemical's strain
Formula commercial firm system (olefin hydrocarbons thermoplasticity elastic body)
MFR=2g/10 minute (230 DEG C, 49N ISO1133), density 0.90g/cm3(ISO1183)
A ※ part has crosslinking component.
JSR EXCELINK (registered trade mark) 1404B (hereinafter also referred to as " C10 ") JSR strain formula
Commercial firm's system (olefin hydrocarbons thermoplasticity elastic body)
MFR=2g/10 minute (230 DEG C, 21N ISO1133), density 0.88g/cm3(ISO1183),
There is the polyolefin of crosslinking component.
Then, the manufacture method of the polyacetal resin molded body of embodiment described below and comparative example
With the assessment item to molded body.
1) manufacturing condition
[1] extrusion molding (strands patterning method, hereinafter referred to as A method)
Use double screw extruder (Toshiba Machinery Co., Ltd.'s TEM-26SS extruder
(L/D=48, band vent).Barrel temperature is set to 200 DEG C.By (A)～(C) composition one
Secondary property mixes to obtain the composition described in table 1～5, extruder main charging oral area utilize quantitatively
Charger supplies, under conditions of extrusion capacity 15kg/ hour, screw speed 150rpm, with line
The material mixing thing of shape extrusion resin.With strands bath quickly cooling, cut off with strands cutting machine, thus
Obtain columned granular molded body.
[2] extrusion molding (thermal cutting method, hereinafter referred to as B method in air)
Use double screw extruder (Toshiba Machinery Co., Ltd.'s TEM-26SS extruder
(L/D=48, band vent).Barrel temperature is set to 200 DEG C.By (A)～(C) composition one
Secondary property mixes to obtain the composition described in table 1～5, extruder main charging oral area utilize quantitatively
Charger supplies, extrusion tree under conditions of extrusion capacity 15kg/ hour, screw speed 150rpm
The mixing thing of fat.Make cutting machine blade and contact before mould and make it rotate, in atmosphere will
The strands extruded from the spinning mouth of proper circle shape is cut off, and is water-cooled afterwards, thus obtains discoid
Granular molded body.
[3] extrusion molding (thermal cutting method, hereinafter referred to as C method in water)
Use double screw extruder (Toshiba Machinery Co., Ltd.'s TEM-26SS extruder
(L/D=48, band vent).Barrel temperature is set to 200 DEG C.By (A)～(C) composition one
Secondary property mixes to obtain the composition described in table 1～5, extruder main charging oral area utilize quantitatively
Charger supplies, extrusion tree under conditions of extrusion capacity 15kg/ hour, screw speed 150rpm
The mixing thing of fat.Make cutting machine blade and contact before mould and make it rotate, will be from water
The strands of the spinning mouth extrusion of proper circle shape is cut off, thus obtains spherical granular molded body.
[4] it is dried
For the molded body obtained by above-mentioned [1] [2] [3], aerator is used to carry out air-flow conveying, and
It is stored in storage bin.In this storage bin, make the nitrogen as circulated gases with described later dry
Dry condition amount circulates, so that molded body is dried.With drying condition a method: 80 DEG C, 30 minutes；
B method: 100 DEG C, 60 minutes；C method: implement for 100 DEG C, 90 minutes.
[5] particle size
When making the molded body obtained by above-mentioned [4] become steady statue in the plane, determine from flat
Face is to the molded body particle height represented by the height of highest portion position with from molded body particle upper surface
To the molded body particle width represented by the width that lower surface is the longest.It should be noted that use
Mitutoyo Corp's digimatic calipers measures molded body particle width and molded body particle is high
Degree, uses the meansigma methods of 20 molded body particles as each value.The molded body grain that will so obtain
Sub-width and molded body particle height compare, using long as major diameter, using shorter as
Minor axis.Ellipticity (=(major diameter)/(minor axis)) is calculated by the value of the major diameter so obtained, minor axis.
[6] micropowder amount
Weigh the molded body 1kg obtained by above-mentioned [4], cross the sieve of 18 mesh, calculate by 18
Weight after mesh sieve.Micropowder amount is calculated by following formula (4).
Micropowder amount (ppm)=by weight (g)/1000 × 10 after sieve6…(4)
[7] adhesive
The molded body that will be obtained by above-mentioned [4] loads plastic cup, is applying 4000kg/m2Load
State under 80 DEG C heat 360 minutes, naturally cool to room temperature.Particle adhesion and generate
In block, the block that selected 1 major diameter is maximum, measure its major diameter with ruler.According to following benchmark
Judge adhesive.
A length of below the 1cm of A: major diameter
The length of B: major diameter is more than 1cm and be below 5cm
The length of C: major diameter is more than 5cm and be below 10cm
The length of D: major diameter is more than 10cm
[8] burst size of methanal
The molded body 3g obtained by above-mentioned [4] is put into aluminium vessel, by (6NL/ under nitrogen flowing
Minute) when melting and heat 60 minutes for 230 DEG C, the formaldehyde gas of generation imports the sulfurous of 1mol/L
In acid sodium solution, with the HCI of 0.01 equivalent, measure the generation amount of the formaldehyde gas produced.
Represent with the ppm of every sample Unit Weight.
2) evaluation of physical property
[1] molding (multipurpose test film)
Use Toshiba Machinery Co., Ltd.'s EC-75NII forming machine.Barrel temperature is set as
205 DEG C, be 90 DEG C by mold temperature set.In 35 seconds injection time, cool time 15 seconds
Under injecting condition, the polyacetal resin molded body obtained with comparative example by embodiment is become further
Type, thus obtains the multipurpose test film according to ISO294-1.
[2] molding (flat board)
Use Toshiba Machinery Co., Ltd.'s EC-75NII forming machine.Barrel temperature is set as
205 DEG C, be 90 DEG C by mold temperature set.In 35 seconds injection time, cool time 15 seconds
Under injecting condition, the polyacetal resin molded body obtained with comparative example by embodiment is become further
Type, thus obtains flat-plate molded body (flat board of 100mm × 100mm × 3mm).
[3] sliding test
For the multipurpose test film obtained by above-mentioned [1], use reciprocal dynamic friction wear test
Machine (Precision Co., Ltd of Japan AFT-15MS type), in load 19.6N, linear velocity 30mm/
Second, reciprocal distance 20mm, reciprocal time 30000 times, temperature 23 DEG C, the bar of humidity 50%
Under part, implement sliding test.Coefficient of friction uses value when sliding 30,000 times.
1) from material sliding test
Use is shaped to the polyacetal resin molded body of front end R=2.5mm (front end is circular rod)
The molded body of system is as subject material.
2) resin sliding test
Use is shaped to the one-tenth of the Tenac4520 of front end R=2.5mm (front end is circular rod)
Type body is as subject material.
3) metal slide test
Use SUS304 test film (ball of diameter 5mm) as subject material.
4) coefficient of friction variation value
The ratio of variation of the coefficient of friction for starting from sliding to the period terminated of sliding, by following
Formula (5) calculates.
Coefficient of friction variation value=maximum friction coefficient/minimum coefficient of friction ... (5)
[4] odor strength
The flat-plate molded body obtained by above-mentioned [2] is cut into 25mm × 50mm × 3mm, puts into
The resin container of 100ml, and seal.Then, heat 60 minutes at 60 DEG C.Natural cooling
To room temperature, open lid and hear taste.Strong according to 6 following level evaluations stink now
Degree, by average for the value of 10 experimenters.
6: stink is extremely strong
5: stink is strong
4: smell an offensive odor
3: somewhat smell an offensive odor
2: almost can't smell stink
1: can't smell stink
[5] tone variations
The molded body that will be obtained by above-mentioned [2] heats 24 hours at 140 DEG C.Naturally cool to room temperature,
Measure the b value (according to JIS-8730) on the surface of this molded body.It addition, also measure the former of molded body
The b value (according to JIS-8730) of the polyacetal resin molded body of material, is set to Δ b value by their difference.
This value is the least, and tone variations is the most excellent.
[embodiment 1,2, comparative example 1～4]
Coordinate each composition according to the ratio shown in table 1, and melt according to above-mentioned manufacture method
Mixing, thus obtain resin-formed body.Use the molded body obtained, have rated various physical property.
By changing preparation method according to this result, can obtain that there is the desired shape of present embodiment
Molded body, it is known that: in the embodiment 1～2 obtaining such molded body, the reduction of micropowder amount,
Adhesive is improved and burst size of methanal reduces.Also know that: the tone after injection moulding becomes
Change, odor strength improves.
[table 1]
[embodiment 1,3～7]
Coordinate each composition according to the ratio shown in table 2, and melt according to above-mentioned manufacture method
Mixing, thus obtain resin-formed body.Use the molded body obtained, have rated various physical property.
Understand: formed by change, micropowder amount, adhesive, burst size of methanal are maintained at certain
Level, the in this case performance of matrix band, coefficient of friction change, coefficient of friction variation is worth
To improving.
[table 2]
[embodiment 1,8～11]
Coordinate each composition according to the ratio shown in table 3, and melt according to above-mentioned manufacture method
Mixing, thus obtain resin-formed body.Use the molded body obtained, have rated various physical property.
Understand: by and with (C) composition, sliding capability improves further, and coefficient of friction variation value also must
To improving.In addition we know: by and use, be possible not only to improve from material sliding test and
Resin sliding test, metal slide test can be improved.
[table 3]
[embodiment 9,13,14]
Coordinate each composition according to the ratio shown in table 4, and melt according to above-mentioned manufacture method
Mixing, thus obtain resin-formed body.Use the molded body obtained, have rated various physical property.
Understand: by and with multiple (C) composition, sliding capability improves further, coefficient of friction variation value
Also improved.
[table 4]
[embodiment 1,15～19, comparative example 5,6]
Coordinate each composition according to the ratio shown in table 5, and melt according to above-mentioned manufacture method
Mixing, thus obtain resin-formed body.Use the molded body obtained, have rated various physical property.
If comparing embodiment 15,16, then understand: by changing preparation method 2, the stink of injection molded article
Improved strength.But, if embodiment 16 and comparative example 5 are compared, then understand: by making system
Method 2 is fixing and changes preparation method 1, it is impossible to improve odor strength, tone variations.
[table 5]
Industrial applicability
The coefficient of friction that polyacetal resin molded body involved in the present invention has molded body is low, sliding
Dynamic property stable (coefficient of friction deviation amplitude during slip is little), tone variations are few, low odor, viscous
The effect that even property is excellent, therefore, it is possible to to comprise electrical equipment, automobile component and other precision
As engineering plastic in broad range of purposes in broad range centered by the mechanism part of machinery
Material uses.
Claims (8)
1. a polyacetal resin molded body, it is for comprising (A) polyacetal resin, (B) lubricating oil
(C) polyolefinic polyacetal resin molded body, wherein, the major diameter of described molded body be 2.5mm～
4.0mm and minor axis are 1.4mm～2.8mm, and ellipticity i.e. major diameter/minor axis ratio is more than 1.25.
Polyacetal resin molded body the most according to claim 1, wherein, described (C) polyene
Hydrocarbon comprises the polyolefin with crosslinking component.
Polyacetal resin molded body the most according to claim 1 and 2, wherein, described (C)
Polyolefin comprises choosing free polyethylene, polypropylene, ethylene-propylene copolymer, Ethylene/Butylene copolymerization
In the group of thing, polybutadiene, polybutadiene hydride and acid modified polyolefin composition at least 2
More than Zhong.
4. according to the polyacetal resin molded body according to any one of claims 1 to 3, wherein,
Described (C) polyolefin comprises polypropylene.
5. according to the polyacetal resin molded body according to any one of Claims 1 to 4, wherein,
Described (C) polyolefin comprises polyethylene.
6. according to the polyacetal resin molded body according to any one of Claims 1 to 5, wherein,
Described (B) lubricating oil is paraffin oil and/or silicone oil.
7. according to the polyacetal resin molded body according to any one of claim 1～6, wherein,
Described major diameter is 2.8mm～3.9mm and described minor axis is 1.6mm～2.7mm, and described flat
Rate i.e. major diameter/minor axis ratio is 1.3～1.8.
8. a component, it is by by the polyacetals tree according to any one of claim 1～7
The further molding of fat molded body and obtain.
Applications Claiming Priority (2)
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| JP2015119334A JP6474156B2 (en) | 2015-06-12 | 2015-06-12 | Polyacetal resin molding |
| JP2015-119334 | 2015-06-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109061042A (en) * | 2018-08-16 | 2018-12-21 | 国家能源投资集团有限责任公司 | A kind of method of unstable hydroxy radical content in measurement polyformaldehyde |
| TWI675061B (en) * | 2017-08-25 | 2019-10-21 | 日商旭化成股份有限公司 | POM resin molded body, sliding member, and hard disk lamp |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7057113B2 (en) * | 2017-12-08 | 2022-04-19 | 旭化成株式会社 | Resin composition and resin molded product |
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| JP6189139B2 (en) * | 2013-08-23 | 2017-08-30 | 旭化成株式会社 | Polyacetal resin molding |
| JP2015101599A (en) * | 2013-11-21 | 2015-06-04 | ポリプラスチックス株式会社 | Method for producing polyoxymethylene resin composition |
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| JPH06287405A (en) * | 1993-04-02 | 1994-10-11 | Oiles Ind Co Ltd | Polyacetal resin composition and sliding part |
| JPH0812848A (en) * | 1994-07-04 | 1996-01-16 | Polyplastics Co | Polyacetal resin composition |
| CN104812835A (en) * | 2012-11-27 | 2015-07-29 | 旭化成化学株式会社 | Polyacetal resin composition and molded body molded therefrom |
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| TWI675061B (en) * | 2017-08-25 | 2019-10-21 | 日商旭化成股份有限公司 | POM resin molded body, sliding member, and hard disk lamp |
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| CN109061042A (en) * | 2018-08-16 | 2018-12-21 | 国家能源投资集团有限责任公司 | A kind of method of unstable hydroxy radical content in measurement polyformaldehyde |
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| Publication number | Publication date |
|---|---|
| JP6474156B2 (en) | 2019-02-27 |
| CN106243609B (en) | 2018-08-24 |
| JP2017002227A (en) | 2017-01-05 |
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