CN104231536B - Polyacetal resin composite - Google Patents
Polyacetal resin composite Download PDFInfo
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- CN104231536B CN104231536B CN201410244420.4A CN201410244420A CN104231536B CN 104231536 B CN104231536 B CN 104231536B CN 201410244420 A CN201410244420 A CN 201410244420A CN 104231536 B CN104231536 B CN 104231536B
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Abstract
It is an object of the invention to provide a kind of polyacetal resin composite, the attachment (mold deposit) when it can prevent injection moulding on mould, good heat stability, and with high creep properties.The polyacetal resin composite of the present invention contains the mass parts of (A) polyacetal resin 100, the mass parts of (B) chlorite race mineral 0.001~5 and the mass parts of (C) lubricant 0.001~5.
Description
Technical field
The present invention relates to polyacetal resin composite.
Background technology
Polyacetal resin is crystalline resin, is rigidity, intensity, toughness, sliding and the excellent resin material of creep properties.
Polyacetal resin is widely used in mechanical part material such as automobile component, electrical/electronic components and industrial part etc..However,
For polyacetal resin, it is promoted to deteriorate because of use environment sometimes.In addition, present situation is due to the expansion using field
Greatly, the requirement performance more and more higher of polyacetal resin.
Characteristic is required as such, sometimes it can also require that with the original high-performance of polyacetal resin, for example above-mentioned
Excellent mechanical property balance while, heat endurance under harsh use environment is improved on the other hand and creep is special
Property.In recent years, with the feelings that electric, electronic equipment densification, temperature range of the polyacetal resin more than 100 DEG C are used
Condition increase, the balance with heat endurance and High-Temperature Creep Performance becomes more and more important.
In addition, polyacetal resin be present：Lack heat endurance and produced in forming because of thermal decomposition
Raw formaldehyde gas, so that operating environment is deteriorated；In addition, produced formaldehyde, coming from the stabilization contained in polyacetal resin
The volatile ingredient of the additives such as agent precipitate into die surface, forms so-called mold deposit, as a result serious infringement formed products surface；Or
The dimensional accuracy of formed products is caused to decline；Deng.In addition, also following problem：In the case where producing mold deposit, mold deposit is produced every time
Must all dismounting cleaning be carried out to mould, this needs substantial amounts of time and labor, causes productivity ratio to decline.Therefore, it is strong to expect
The method for the problem of solving such.
In order to solve the above problems, various schemes are proposed so far.For example, it is proposed that following method：In order to subtract
Few formaldehyde produced by thermal decomposition, adds the method for polyamide in polyacetal resin (for example, see patent document 1)；In bunching
The method of oligoamide etc. is added in urea formaldehyde (for example, see patent document 2)；Or add and be obstructed in polyacetal resin
The method of metal salt/polyamide of phenol/carboxylic acid (for example, see patent document 3).
In addition, from the viewpoint of High-Temperature Creep Performance, mechanical properties are improved, disclosing the polyacetals tree added with talcum
Oil/fat composition (for example, see patent document 4).
Prior art literature
Patent document
Patent document 1：Japanese Patent Publication 34-5440 publications
Patent document 2：Japanese Patent Publication 54-32658 publications
Patent document 3：Japanese Unexamined Patent Publication 3-14859 publications
Patent document 4：Japanese Unexamined Patent Publication 2008-156628 publications
The content of the invention
Invent problem to be solved
However, for the method described in patent document 1~3, the stabilization of resulting polyacetal resin composite
Change simultaneously it is insufficient, therefore forming when heat endurance, prevent mold deposit generation in terms of it is not satisfactory.
In addition, for adding the method for talcum as patent document 4, resulting polyacetal resin composite exists
Improve mechanical property, improve creep resistance characteristic in terms of effect it is high, but not to resistance to tone variations as caused by aging and resistance to
Mold deposit (below also referred to as " MD ") characteristic is studied.
Therefore, the present invention be in view of above-mentioned problem of the prior art and make, it is an object of the invention to provide one
Kind of polyacetal resin composite, the attachment (mold deposit) when it can prevent injection moulding on mould, becomes as caused by heat ageing
Color is few, and with heat endurance (mechanical properties after heat ageing), high creep properties.
The means used to solve the problem
The present inventor has made intensive studies to solve the above problems, and as a result finds, contains (A) polyacetal resin
100 mass parts, the mass parts of (B) chlorite race mineral 0.001~5 as specific inorganic filler and (C) lubricant 0.001~
The polyacetal resin composite of 5 mass parts can solve the problem that above mentioned problem, so as to complete the present invention.
That is, the present invention is as described below.
(1) a kind of polyacetal resin composite, it contains the mass parts of (A) polyacetal resin 100, (B) chlorite race mineral
0.001~5 mass parts and the mass parts of (C) lubricant 0.001~5.
(2) polyacetal resin composite as described above described in (1), wherein, the content of chlorite race mineral (B) is
0.001~1 mass parts.
(3) polyacetal resin composite as described above described in (1), wherein, chlorite race mineral (B) is selected from by green
At least one of group of mudstone, cookeite and manganese mackensite composition.
(4) polyacetal resin composite as described above described in (1), wherein, the average grain diameter of chlorite race mineral (B)
For 0.01~100 μm.
(5) polyacetal resin composite as described above described in (1), wherein, the amount of chlorite race mineral (B) with it is described
(C) the ratio between amount of lubricant (B/C) is 0.1~1.0.
Invention effect
According to the present invention it is possible to provide a kind of polyacetal resin composite, when it can reliably prevent injection moulding
Attachment (MD) on mould, changes colour few as caused by heat ageing, and with heat endurance (mechanical properties after heat ageing), height
Creep properties.
Embodiment
Hereinafter, the mode (being denoted as below " present embodiment ") for implementing the present invention is described in detail.In addition, this
Invention is not limited to following embodiment, can carry out implementing after various modifications in the range of its purport.
(polyacetal resin composite)
The polyacetal resin composite of present embodiment is to contain the mass parts of (A) polyacetal resin 100, (B) chlorite race
The polyacetal resin composite of the mass parts of mineral 0.001~5 and the mass parts of (C) lubricant 0.001~5.
＜ (A) polyacetal resins ＞
It is not particularly limited, can specifically enumerates as (A) polyacetal resin used in the present embodiment：Will
The cyclic oligomer of the formaldehyde such as formaldehyde monomers or its tripolymer (metaformaldehyde), the tetramer (four polyformaldehyde) carries out homopolymerization and obtained
The substantially polyacetal homopolymer that is only made up of oxymethylene units；Make formaldehyde monomers or its tripolymer (metaformaldehyde), four
The cyclic oligomers of the formaldehyde such as aggressiveness (four polyformaldehyde) and oxirane, expoxy propane, epoxychloropropane, 1,3- dioxolanes,
Bunching obtained from the cyclic ethers such as the glycol such as 1,4- butanediol formals, the cyclic formals of diethylene glycol (DEG) or cyclic formals copolymerization
Aldehyde copolymer；Make the Copolyacetal with side chain obtained from monofunctional glycidyl ether copolymerization；Make multifunctional shrink sweet
There is the Copolyacetal of cross-linked structure obtained from oily ether copolymerization；Deng.
In addition, being not particularly limited as polyacetal resin (A), it can also specifically enumerate：At two ends or single end
End has the compound of functional group such as hydroxyl, for example in the presence of PAG that the ring-type of formaldehyde monomers or formaldehyde is low
Polymers has the polyacetal homopolymer of block component obtained from being polymerize；It is same that there is hydroxyl etc. in two ends or single end
The compound of functional group, for example make in the presence of hydrogenated polybutadiene diol formaldehyde monomers or its tripolymer (metaformaldehyde),
The cyclic oligomers of the formaldehyde such as the tetramer (four polyformaldehyde) with have obtained from cyclic ether or cyclic formals copolymerization block into
The Copolyacetal divided.As described above, in the present embodiment, polyacetal homopolymer and Copolyacetal can make
With.Wherein, preferably Copolyacetal.
In addition, in the illustration of above-mentioned (A) polyacetal resin, the ratio of the comonomer such as DOX is relative to three
Polyformaldehyde 1mol is preferably 0.1~60mol%, more preferably 0.1~20mol%, more preferably 0.13~10mol%.
If the ratio of comonomer is above range, it can provide mechanical strength more excellent polyacetal resin composite.
In addition, being not particularly limited as polymerization catalyst of the foregoing illustrative Copolyacetal in polymerization, specifically
For, the cationic active catalyst such as preferred Lewis acids, Bronsted acid and its ester or acid anhydrides.Do not limited especially as lewis acid
It is fixed, the halide of such as boric acid, tin, titanium, phosphorus, arsenic and antimony can be enumerated, boron trifluoride, four chlorinations can be specifically enumerated
Tin, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride and its complex compound or salt.In addition, as Bronsted acid and its ester or
Acid anhydrides is not particularly limited, can specifically enumerate perchloric acid, trifluoromethanesulfonic acid, the perchloric acid tert-butyl ester, acetylperchlorate,
Trimethyl oxygenHexafluorophosphate etc..Wherein, preferred boron trifluoride；Boron trifluoride hydrate；And it is former containing oxygen atom or sulphur
The organic compound of son and the co-ordination complex of boron trifluoride, can specifically enumerate boron trifluoride diethyl ether, boron trifluoride
Di-n-butyl ether is used as preference.
It is not particularly limited, specifically, for example, can leads to as the polymerization of foregoing illustrative Copolyacetal
Cross polymerisation in bulk progress, batch-type, continous way.It is not particularly limited as used polyplant, example can be enumerated
Such as：The extrusion mixing of the self-cleaning types such as the continuous extruder and mixing roll of co-kneader, double-screw type, twin-screw blade type continuous mixer
Machine.The monomer of molten condition is supplied to the polyacetals copolymerization for obtaining solid block with the progress of polymerization to above-mentioned polymerization machine
Thing.
Terminal part (- (the OCH of thermally labile is occasionally there are in Copolyacetal obtained by polymerizeing more than2)n-OH
Base), therefore it is preferable to carry out the decomposition removing processing of the unstable terminal part.
＜ (B) chlorite race mineral ＞
The polyacetal resin composite of present embodiment contains (B) chlorite race mineral.Chlorite race mineral (B) is silicic acid
One kind of salt mineral, it is the mineral with layer structure.More specifically, chlorite race mineral (B) refer to containing selected from bag
In oxide containing Mg, Fe, Mn or Ni, the oxide comprising Al, Fe, Cr or Ti, each group of the oxide comprising Si or Al
Provide the mineral of oxide.As the crystal structure of chlorite race mineral (B), there are monoclinic system and orthorhombic system.Enumerate green mud
One example of the chemical formula of stone race mineral (B), it is by (Mg, Fe, Al)6(Si,Al)4O10(OH)8Represent, wherein it is preferred that Mg3
(SiO5)2(OH)2·3Mg(OH)2。
Manufacture method during to crushing chlorite race mineral (B) from former stone is not particularly limited, specifically, can be with
Using for example：Axial flow type mill method, ring-like mill method, roller mill method, ball-milling method, jet mill method and container rotary compression shearing-type mill
Method.In addition, the chlorite race mineral (B) after crushing preferably carry out classification processing by various graders and make particle diameter distribution uniform
Chlorite race mineral (B).It is not particularly limited as grader, can specifically enumerates such as impact type inertia force point
Level machine (variable shock machine etc.), attached wall effect utilization type intertia force classifier (bend pipe spraying machine etc.) and centrifugal force field classification
Machine (multi-cyclone, Microplex graders, scattered separator, Acucut graders, turbine classifier,
Turboplex graders, particle separator and super separator etc.).
The average grain diameter of chlorite race mineral (B) is preferably 0.01~100 μm, more preferably 0.05~80 μm, further
Preferably 0.1~50 μm.From the viewpoint of the sufficient heat resistance of polyacetal resin composite and rigidity is assigned, chlorite race ore deposit
The average grain diameter of thing (B) is preferably more than 0.01 μm；From the viewpoint of the sufficient dispersiveness of chlorite race's mineral (B) is assigned,
The average grain diameter of chlorite race mineral (B) is preferably less than 100 μm.Here, average grain diameter refers to by determination of laser diffraction method
(Shimadzu Seisakusho Ltd.'s system：SALD-3100 the median particle diameter D50% of size distribution obtained from) being measured.
For the polyacetal resin composite of present embodiment, contain (B) in (A) polyacetal resin by being formed
The composition of chlorite race mineral, can effectively improve heat endurance, keep mechanical properties.
In the polyacetal resin composite of present embodiment, contain relative to the above-mentioned mass parts of (A) polyacetal resin 100
(B) mass parts of chlorite race mineral 0.001~5, preferably comprise 0.001~1 mass parts, further preferably 0.001~0.5 mass
Part.If the content of (B) chlorite race mineral is such scope, it can provide heat endurance more excellent polyacetals tree
Oil/fat composition.
Wherein, (B) chlorite race mineral are preferably selected from the group that is made up of chlorite, cookeite and manganese mackensite
At least one.They can be used alone, can also and with two or more.It is excellent particularly from the viewpoint of being readily available
Select chlorite.In addition, as chlorite, preferably chemical formula is with 5MgOAl2O3·3SiO2·4H2The chlorite that O is represented.
＜ (C) lubricants ＞
The polyacetal resin composite of present embodiment contains (C) lubricant.
It is not particularly limited, can be enumerated for example as lubricant (C)：Alcohol, aliphatic acid and their fatty acid ester；It is average
The degree of polymerization is 10~500 olefin(e) compound；And polysiloxanes.
These lubricants (C) both can be used alone it is a kind of, can also be applied in combination it is two or more.Wherein preferred fatty acid
Fatty acid ester with them, the di-fatty acid for being more preferably derived from the higher fatty acids with 10~20 carbon numbers
Ester.The higher fatty acids for the di-fatty acid esters for being derived from the higher fatty acids with 10~20 carbon numbers as constituting
It is preferred that the higher fatty acids with linear chain structure, is not particularly limited, can enumerate for example：Laurate, myristic acid, palm
The unrighted acid such as the saturated fatty acids such as acid, stearic acid, arachidic acid and oleic acid is as representative examples.It is used as preferred ethylene glycol two
Fatty acid ester, is diglycol stearate.
In the polyacetal resin composite of present embodiment, the content of (C) lubricant is relative to (A) polyacetal resin 100
Mass parts are 0.001~5 mass parts, are preferably 0.001~3 mass parts, are more preferably 0.005~2 mass parts.
It is more than 0.001 mass parts, to carry by making the content of (C) lubricant relative to the mass parts of (A) polyacetal resin 100
The high formability of polyacetal resin composite；In addition, by making the content of (C) lubricant be that below 5 mass parts, can obtain
The excellent polyacetal resin composite of mechanical properties.
In the polyacetal resin composite of present embodiment, the ratio between the amount of (B) chlorite race mineral and the amount of (C) lubricant
(B/C) be preferably 0.1~10 scope.More preferably 0.1~1.0 scope.(B) amount of chlorite race mineral lubricates with (C)
When the ratio between amount of agent (B/C) is above range, tone and mechanical property after aging tend to be more excellent.
＜ other materials ＞
In addition to above-mentioned (A) polyacetal resin, (B) chlorite race's mineral and (C) lubricant, present embodiment it is poly-
Acetal resin composition can also contain other inorganic fillers and organic filler etc..These fillers can be by surface
The filler of processing.
It is not particularly limited, can be used for example as inorganic filler：Threadiness, granular, tabular and hollow form
Filler.
It is not particularly limited, can be enumerated for example as fibrous filler：Glass fibre, carbon fiber, silica fibre, dioxy
SiClx-alumina fibre, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre, potassium titanate fibre and stainless
The inorganic fibres such as the metallic fibers such as steel, aluminium, titanium, copper, brass.In addition, also including the short potassium titanate crystal whisker of fibre length, oxidation
The whisker class such as zinc whisker.
It is not particularly limited, can be enumerated for example as granular filler：Carbon black, silica, quartz powder, glass
The silicate such as pearl, glass dust, calcium silicates, magnesium silicate, alumina silicate, kaolin, clay, diatomite, wollastonite；Iron oxide, oxidation
The metal oxides such as titanium, aluminum oxide；The metal sulfates such as calcium sulfate, barium sulfate；The carbonate such as magnesium carbonate, dolomite；And its
Its carborundum, silicon nitride, boron nitride, various metal dusts etc..
It is not particularly limited, can be enumerated for example as tabular filler：Mica, sheet glass, various metal foils.
It is not particularly limited, can be enumerated for example as hollow form filler：Glass hollow microballoon, hollow silica are micro-
Ball, white sand (シ ラ ス) hollow microsphere, metal hollow microballoon etc..
It is not particularly limited, can be enumerated for example as organic filler：Aromatic polyamide resin, fluorine resin, third
The high-melting-point organic fiber shape filler such as olefin(e) acid resinoid.
These fillers can use a kind of or and with two or more.
These fillers can use it is any in surface treated filler, not surface treated filler,
From the aspect of flatness, mechanical property from profiled surface, it is sometimes preferred to use the filler for implementing surface treatment.It is used as table
Face inorganic agent is not particularly limited, and can use known surface conditioning agent.It is not particularly limited as surface conditioning agent,
It can use for example：The various coupling processing agent such as silanes, titanate ester, aluminium system, zirconium system；Resin acid, organic carboxyl acid, organic carboxylic
The surfactants such as hydrochlorate.It is not particularly limited, can be specifically enumerated for example as surface conditioning agent：N- (2- amino second
Base)-APTES, 3- glycidoxypropyltrime,hoxysilanes, isopropyl three (stearyl) titanium
Acid esters, diisopropoxy QAE quaternary aminoethyl acetic acid esters, zirconium-n-butylate etc..
In addition, for the other characteristics of the polyacetal resin composite for assigning present embodiment, other additions can also be added
Agent, stabilizer, weathering stabilizers, conductive agent, thermoplastic resin, heat such as antioxidant, heat stabilizer and formic acid agent for capturing
Thermoplastic elastic or pigment.These additives can both use one kind, can also be applied in combination two or more.For example relative to
(A) mass parts of polyacetal resin 100, can at least one of each additive containing 0.01~10 mass parts.
It is used as antioxidant, preferably hindered phenol anti-oxidants.It is not particularly limited as hindered phenol anti-oxidants, can
To enumerate for example：N-octadecane base -3- (3', 5'- di-t-butyl -4'- hydroxyphenyls)-propionic ester, n-octadecane base -3- (3'- first
Base -5'- the tert-butyl group -4'- hydroxyphenyls)-propionic ester, n-tetradecane base -3- (3', 5'- di-t-butyl -4'- hydroxyphenyls)-propionic acid
Ester, 1,6-HD-bis--[3- (3,5- di-t-butyl -4- hydroxyphenyls)-propionic ester], 1,4- butanediols-bis--[3- (3,5- bis-
The tert-butyl group -4- hydroxyphenyls)-propionic ester], triethylene glycol-bis--[3- (the 3- tert-butyl group -5- methyl -4- hydroxyphenyls)-propionic ester], season
Penta tetrol four [methylene -3- (3', 5'- di-t-butyl -4'- hydroxyphenyls) propionic ester] methane etc..Preferably triethylene glycol-bis--
[3- (the 3- tert-butyl group -5- methyl -4- hydroxyphenyls)-propionic ester] and pentaerythrite four [methylene -3- (3', 5'- di-t-butyl -
4'- hydroxyphenyls) propionic ester] methane.These antioxidants can both use one kind, can also be applied in combination two or more.
It is not particularly limited, can be enumerated for example as heat stabilizer：Nylon 4-6, nylon 6, nylon 6-6, nylon 6-10,
The polyamides such as nylon 6-12, nylon 12 and their polymer (such as nylon 6/6-6/6-10, nylon 6/6-12).
In addition, being not particularly limited as other heat stabilizers, it can enumerate for example：Acrylamide and its derivative, acrylamide and
The copolymer of its derivative and other vinyl monomers, can specifically be enumerated acrylamide and its derivative and its for example
Its vinyl monomer poly- Beta-alanine copolymer obtained from being polymerize in the presence of metal alcoholate.It is used as other heat
Stabilizer is not particularly limited, and can enumerate for example：Amide compound, amino substitution triaizine compounds, amino substitution triazine
Addition product, the amino of compound and formaldehyde replace condensation product, urea, urea derivative, hydrazine derivate, the imidazoles of triaizine compounds and formaldehyde
Compound, imide compound.
It is not particularly limited, can be enumerated for example as the concrete example of amide compound：M-phthalic acid diamides etc. is more
First carboxylic acid amide, anthranilamide.The concrete example for replacing triaizine compounds as amino is not particularly limited, and can enumerate
For example：2,4- diaminourea-s-triazine, 2,4,6- triamidos-s-triazine, N- melamine-butyls, N phenyl melamine, N, N-
Diphenyl melamine, N, N- diallyl melamines, benzoguanamine (2,4- diaminourea -6- phenyl-s-triazine), methylguanidine
Amine (2,4- diaminourea -6- methyl-s-triazine), 2,4- diaminourea -6- butyl-s-triazine etc..Replace triazine chemical combination as amino
The concrete example of the addition product of thing and formaldehyde is not particularly limited, and can enumerate for example：N- melamine methylols, N, N '-dihydroxy
Methyl melamine, N, N ', N "-trimethylol melamine.Replace the condensation product of triaizine compounds and formaldehyde as amino
Concrete example is not particularly limited, and can enumerate for example：Carbamide condensation product.As the example of urea derivative without spy
Do not limit, can enumerate for example：N- substituted ureas, urea condensation compound, ethylidene-urea, hydantoin compound, urea-based compound.As
The concrete example of N- substituted ureas is not particularly limited, and can enumerate for example：MU, the alkylidene two of the substituents such as alkyl substitution
Urea, aryl substituted urea.It is not particularly limited, can be enumerated for example as the concrete example of urea condensation compound：The condensation product of urea and formaldehyde
Deng.It is not particularly limited, can be enumerated for example as the concrete example of hydantoin compound：Hydantoins, 5,5- dimethyl second
Interior uride, 5,5- diphenyl hydantoins etc..It is not particularly limited, can be enumerated for example as the concrete example of urea-based compound：
Allantoin etc..Hydrazide compound can be enumerated as hydrazine derivate.It is not particularly limited as the concrete example of hydrazide compound, can
To enumerate for example：Dicarboxyl acid dihydrazide, more specifically can enumerate acid dihydrazide, amber acid dihydrazide, glutaric acid two
Hydrazides, adipic dihydrazide, the hydrazides of pimelic acid two, the hydrazides of suberic acid two, the hydrazides of azelaic acid two, sebacic dihydrazide, dodecane
Dihydrazi, isophthalic dihydrazide, O-phthalic acid dihydrazide, the hydrazides of 2,6 naphthalene dicarboxylic acid two etc..It is used as acid imide
The concrete example of compound is not particularly limited, and can enumerate for example：Succinimide, glutarimide, phthalimide.
These heat stabilizers can both use one kind, can also be applied in combination two or more.
It is not particularly limited, can be enumerated for example as formic acid agent for capturing：Amino substitution triaizine compounds, amino substitution three
The condensation product of piperazine class compound and formaldehyde, such as carbamide condensation product.It is used as other formic acid agent for capturing, Ke Yilie
Lift hydroxide, inorganic acid salt, carboxylate or the alkoxide of alkali metal or alkaline-earth metal.Formic acid agent for capturing can use one kind,
It can be applied in combination two or more.
As weathering stabilizers, it is preferably selected from by benzotriazole compound, oxanilide class compound and hindered amine
At least one of group of class light stabilizer composition.
It is not particularly limited, can be enumerated for example as benzotriazole compound：2- (2 '-hydroxyl -5 '-aminomethyl phenyl)
BTA, 2- (2 '-hydroxyl -3,5- di-tert-butyl-phenyls) BTA, the 2- [double (bis (alpha, alpha-dimethylbenzyl)s of 2 '-hydroxyl -3,5-
Base) phenyl] BTA, 2- (2 '-hydroxyl -3,5- di-tert-pentyl-phenyls] BTA, 2- (2 '-hydroxyl -3,5- diisoamyl
Phenyl) BTA, 2- [2 '-hydroxyl -3,5- double-(alpha, alpha-dimethylbenzyl) phenyl] -2H- BTAs, 2- (2 '-hydroxyl -
4 '-octyloxyphenyl) BTA etc..These compounds both can be each used alone, can also be used in combination of two or more.
It is not particularly limited, can be enumerated for example as oxanilide class compound：- 2 '-Ethyl oxalyl of 2- ethyoxyls two
Aniline, -2 '-ethyloxanilide of the 2- ethyoxyl -5- tert-butyl groups, 2- ethyoxyl -3 '-dodecyl butoxanilides etc..This
A little compounds both can be each used alone, can also be used in combination of two or more.
As the example of hindered amine light stabilizer, 4- acetoxyl groups -2,2,6,6- tetramethyl piperidines can be enumerated；4- is hard
Acyl epoxide -2,2,6,6- tetramethyl piperidines；4- acryloxy -2,2,6,6- tetramethyl piperidines；4- (phenylacetyl epoxide)-
2,2,6,6- tetramethyl piperidines；4 benzoyloxy 2,2,6,6 tetramethyl piperidine；4- methoxyl group -2,2,6,6- tetramethyl piperazines
Pyridine；4- tristearin epoxide -2,2,6,6- tetramethyl piperidines；4- cyclohexyloxy -2,2,6,6- tetramethyl piperidines；4- benzyloxy -2,2,
6,6- tetramethyl piperidines；4- phenoxy group -2,2,6,6- tetramethyl piperidines；4- (ethylcarbamoyl epoxide) -2,2,6,6- tetramethyls
Phenylpiperidines；4- (cyclohexyl carboxyamide epoxide) -2,2,6,6- tetramethyl piperidines；4- (phenylcarbamoyl epoxide) -2,2,6,
6- tetramethyl piperidines；Double (2,2,6,6- tetramethyl -4- piperidyls)-carbonic esters；Double (2,2,6,6- tetramethyl -4- piperidyls) -
Oxalate；Double (2,2,6,6- tetramethyl -4- piperidyls)-malonates；Double (1,2,2,6,6- pentamethyl -4- piperidyls) last of the ten Heavenly stems two
Acid esters；Double-(N- methyl -2,2,6,6- tetramethyl -4- piperidyls) sebacate；Double (2,2,6,6- tetramethyl -4- piperidyls) -
Sebacate；Double (2,2,6,6- tetramethyl -4- piperidyls)-adipate esters；Double (2,2,6,6- tetramethyl -4- piperidyls)-it is right
Phthalic acid ester；Double (2,2,6,6- tetramethyl -4- piperidines the epoxide)-ethane of 1,2-；α, α '-bis- (2,2,6,6- tetramethyl -4- piperazines
Pyridine epoxide)-paraxylene；Double (2,2,6,6- tetramethyl -4- piperidyls) Toluene-2,4-diisocyanates, 4- diurethanes；Double (2,2,6,6-
Tetramethyl -4- piperidyls)-hexa-methylene -1,6- diurethanes；Three (2,2,6,6- tetramethyl -4- piperidyls)-benzene -1,
3,5- tricarboxylic esters；Three (2,2,6,6- tetramethyl -4- piperidyls)-benzene -1,3,4- tricarboxylic esters；1- [2- { 3- (the uncles of 3,5- bis-
Butyl -4- hydroxyphenyls) propionyloxy } butyl] -4- [3- (3,5- di-t-butyl -4- hydroxyphenyls) propionyloxy] 2,2,6,6- tetra-
Methyl piperidine；1,2,3,4- BTCAs and 1,2,2,6,6- pentamethyl -4- piperidine alcohols and β, β, β ', β '-tetramethyl -3,9-
The condensation product of [oxaspiros of 2,4,8,10- tetra- (5,5) hendecane] diethanol；Deng.Above-mentioned hindered amine light stabilizer both can be each
From being used alone, can also be used in combination of two or more.
Wherein preferred weathering stabilizers are 2- [double (bis (alpha, alpha-dimethylbenzyl) base) phenyl of 2 '-hydroxyl -3,5-] BTA；
2- (2 '-hydroxyl -3,5- di-tert-butyl-phenyls) BTA；2- (2 '-hydroxyl -3,5- di-tert-pentyl-phenyls] BTA；It is double
(1,2,2,6,6- pentamethyl -4- piperidyls) sebacate；Double-(N- methyl -2,2,6,6- tetramethyl -4- piperidyls) decanedioic acid
Ester；Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate；1,2,3,4- BTCAs and 1,2,2,6,6- pentamethyls-
4- piperidine alcohols and β, β, β ', the condensation product of β '-tetramethyl -3,9- [oxaspiros of 2,4,8,10- tetra- (5,5) hendecane] diethanol.
It is not particularly limited, can be enumerated for example as conductive agent：Conductive carbon black, metal dust or fiber.Conductive agent
Both one kind can be used, can also be applied in combination two or more.
It is not particularly limited, can be enumerated for example as thermoplastic resin：Vistanex, acrylic resin, benzene second
Olefine resin, polycarbonate resin, uncured epoxy resin.In addition, also including their modifier.Thermoplastic resin both can be with
Using one kind, it can also be applied in combination two or more.
It is not particularly limited, can be enumerated for example as thermoplastic elastomer (TPE)：Polyurethane elastomer, polyesters elasticity
Body, polystyrene type elastomer, polyamide-based elastomer.Thermoplastic elastomer (TPE) is that can use one kind, can also be applied in combination
It is two or more.
It is not particularly limited, can be enumerated for example as pigment：Inorganic pigment and organic pigment, metal class pigment,
Fluorescent pigment etc..Inorganic pigment refers to the pigment for being generally used for coloring resin, can enumerate for example：Zinc sulphide, titanium dioxide,
Barium sulfate, titan yellow, cobalt blue, firing pigment, carbonate, phosphate, acetate, carbon black, acetylene black, lampblack etc..It is used as organic
Pigment is not particularly limited, and can enumerate for example：Azo condensation class, quinones, phthalocyanines, monoazo class, bisazo class, polyazo
Class, Anthraquinones, heterocyclic, purple cyclic ketones class, quinacridine ketone, thioindigo class, perylene class, twoThe pigment such as piperazine class, phthalocyanines.Pigment
Adding proportion significantly changes with tone, therefore, it is difficult to clear and definite, is generally according to relative to the mass parts of (A) polyacetal resin 100
The scope of 0.05~5 mass parts is used.Pigment can use one kind, can also be applied in combination two or more.
The manufacture method ＞ of ＜ polyacetal resin composites
The polyacetal resin composite of present embodiment can by the way that mentioned component is mixed, using extruder, heating roller,
The kneading machines such as kneader, banbury mixers are kneaded and obtained.Particularly from the viewpoint of productivity ratio, preferably by crowded
Go out machine to be kneaded.Preferred processing temperature of the melting temperature according to matrix resin, 140~260 are used as with reference to most
DEG C scope, preferably 180~230 DEG C scope.For a large amount of and stably manufacture present embodiment polyacetal resin combination
Thing, preferably uses single screw rod or double screw extruder.
＜ purposes ＞
The polyacetal resin composite obtained by present embodiment has a balance in mechanical property, heat endurance, resistance to
Mold deposit, creep resistance are excellent, and weatherability is excellent.It therefore, it can the formed products for various uses.
For example it can be used for：With the mechanical part for representative such as gear, cam, sliding part, bar, axle, bearing and guide；
The resin component of injection moulding (outsert molding) on matrix；The resin component of insert part forming (insert molding)；
Frame (シ ャ ー シ)；Pallet；Side plate；Using printer and duplicator as the business automation equipment part of representative；With number
Video camera, camera and digital camera are the camera or image documentation equipment part of representative；Tape player, music, image or
Information equipment, communication equipment part；Electrical equipment is with part, electronic equipment part.In addition, as automotive part, can
So that to be suitable for fuel tank, fuel oil pump assembly, valve class, oil tank flange etc. be the fuel circumferential component of representative, door circumferential component, peace
Full band circumferential component, stacked switch part, Switch.The Ministry of Industry using residential equipment machine as representative can also be suitable as
Part.
Embodiment
The present invention is further illustrated below by embodiment and comparative example, but the present invention is not defined in any way
This.In addition, the term and assay method in embodiment and comparative example are as described below.
《Assay method》
Mechanical properties ＞ after ＜ heat ageings
The IS-100GN injection machines manufactured using Toshiba Machinery Co., Ltd., are obtained in embodiment and comparative example
Polyacetal resin composite makes ISO test films.The gill formula heat of made test film input タ バ イ companies manufacture is old
Change testing machine (geer oven), the burin-in process of 1 month is carried out at 140 DEG C.Test film after heat ageing is old from gill formula heat
Change testing machine to take out, placed 24 hours in 23 DEG C, the thermostatic chamber of 50% humidity of holding.Under the following conditions to the examination after placement
Test piece and carry out tension test, determine tensile strength.It regard the average value of 3 measured values (n=3) as the test film after heat ageing
Tensile strength.The tensile strength is bigger, then is evaluated as heat endurance higher.
Cupping machine：The AG-IS of Shimadzu Scisakusho Ltd's manufacture
Draw speed：5mm/ minutes
<Tonal properties>
The IS-100GN injection machines manufactured using Toshiba Machinery Co., Ltd., are obtained in embodiment and comparative example
Polyacetal resin composite makes ISO test films.
By the gill formula thermal aging test machine of made test film input タ バ イ companies manufacture.In addition, before feeding intake,
The hand-held color evaluating (CR-200) manufactured using MINOLTA, overlapping two panels test film determines heat using D65 light source
The yellowing (b values) of test film before aging.
Then, the burin-in process of 1 month has been carried out at 140 DEG C to test film.By the test film after heat ageing from gill
Take out, placed 24 hours in 23 DEG C, the thermostatic chamber of 50% humidity of holding in formula thermal aging test machine.For the experiment after placement
Piece it is above-mentioned it is same under conditions of determine the yellowing (b values) of the test film after heat ageing.
＜ High-Temperature Creep Performances ＞
The IS-100GN injection machines manufactured using Toshiba Machinery Co., Ltd., in 200 DEG C of barrel temperature, injection pressure
Under conditions of 60MPa, 25 seconds injection time, 15 seconds cool times, 90 DEG C of mold temperature, obtained in embodiment and comparative example
Polyacetal resin composite manufactured size is 110mm × 6.5mm × 3mm strip test film.Institute's strain is made using Japan's precision
The creep testing machine of formula commercial firm manufacture, the following High-Temperature Creep Performance for determining made test film.First, the test film is hanged
Hang over and be set as in 80 DEG C of creep testing machine, apply load using bearing strength test as 20MPa tensile stress, determine in atmosphere
Until the time that test film is destroyed.The High-Temperature Creep Performance of test film is evaluated with the average value of 2 measured values (n=2).
Until the time that test film is destroyed is longer, High-Temperature Creep Performance is evaluated as more excellent.
＜ MD characteristics ＞
The Ti-30G injection machines manufactured using Toyo Jukikai Metal Corp., in 200 DEG C of barrel temperature, injection speed
100mm/S, injection pressure 100kgf, cycle timer are spent under conditions of 15 seconds, are repeated in embodiment and comparative example and are obtained
The injection moulding of the polyacetal resin composite arrived.10000 injection mouldings are carried out, observation is adhered on 30 DEG C of low temperature mould
Attachment, according to following standard evaluate MD characteristics.
(evaluation criterion of MD characteristics)
1：Attachment is observed in more than 80% scope of mould
2：30% in mould less than 80% scope observes attachment
3：10% in mould less than 30% scope observes attachment
4：Attachment is observed in the scope less than 10% of mould
5：Without attachment
《Material composition》
Following compositions are used in embodiment, comparative example.
＜ (A) polyacetal resins ＞
By with can be by the twin-screw self-cleaning type polymerization machine (L/D=8 (L of the chuck of heating agent：Polymerisation machine
By the distance (m) of raw material supply mouth to outlet, D：The internal diameter (m) of polymerisation machine.Similarly hereinafter.)) it is adjusted to 80 DEG C.By trimerization
Formaldehyde using 4kg/ hours, as the 1,3- dioxolanes of comonomer using 128.3g/ hours (relative to metaformaldehyde 1mol as
3.9mol%), (it is 0.20 × 10 relative to metaformaldehyde 1mol as the dimethoxym ethane of chain-transferring agent-3Mol) it is added continuously to
In above-mentioned polymerization machine.Further, using as the boron trifluoride di-n-butyl ether compound of polymerization catalyst (relative to metaformaldehyde 1mol
For 1.5 × 10-5Mol) it is added continuously to be polymerize in above-mentioned polymerization machine.The Copolyacetal that will be discharged by polymerization machine
Put into the aqueous solution of triethylamine 0.1%, carry out the inactivation of polymerization catalyst.The polyacetals after inactivation is filtered with centrifugal separator to be total to
Polymers, is then dried.Dried Copolyacetal is supplied to the double-screw type extruder with exhaust outlet, relatively
The mass parts of Copolyacetal 100 melted in extruder, add the water of 0.5 mass parts, are 200 in extruder design temperature
DEG C, in extruder the residence time be that the decomposition of the unstable end section that Copolyacetal is carried out under conditions of 7 minutes is removed.
The Copolyacetal that unstable end section is decomposed devolatilization under conditions of exhaust outlet vacuum is 20Torr, by squeezing
Machine outlet mould portion is extruded with strands shape, and is granulated.Copolyacetal after granulation is used as (A) polyacetal resin.
＜ (B) chlorite race mineral ＞
B-1：Chemical formula is with 5MgOAl2O3·3SiO2·4H2The volume average particle size that O is represented is 13.2 μm of chlorite
(talcum Industrial Co., Ltd of Fuji manufactures：Trade name " WL-13L ")
B-2：Chemical formula is with 5MgOAl2O3·3SiO2·4H2The volume average particle size that O is represented is 5.6 μm of chlorite
(talcum Industrial Co., Ltd of Fuji manufactures：Trade name " WL-13J ")
Here, volume average particle size is that (Shimadzu Seisakusho Ltd. manufactures by determination of laser diffraction method：SALD-3100) determine
The median particle diameter D50% of the size distribution arrived.
The other mineral ＞ of ＜
B-3：Talcum (Japanese talcum Co., Ltd. manufacture：Trade name " MS (surface is untreated) ") average grain diameter be 12.6 μm
B-4：Mica (Network ラ レ Co. Ltd. systems：Trade name " ス ゾ ラ イ ト マ イ カ 200-HK ")
B-5：Silica (Wako Pure Chemical Industries, Ltd.'s system：Reagent name " シ リ カ gel60 ")
Here, average grain diameter is that (Shimadzu Seisakusho Ltd. manufactures by determination of laser diffraction method：SALD-3100) determine what is obtained
The median particle diameter D50% of size distribution.
＜ (C) lubricants ＞
C-1：Diglycol stearate
(embodiment 1~5)
Using Henschel mixer using (A) polyacetal resin (164.5 DEG C of fusing point) 100 mass parts of above-mentioned manufacture, as
The triethylene glycol of antioxidant-bis- [3- (the 3- tert-butyl group -5- methyl -4- hydroxyphenyls)-propionic ester] 0.3 mass parts and it is used as formic acid
The sour mass parts of calcium 0.15 of the distearyl of agent for capturing carry out being obtained by uniformly mixingg mixture.By the mixture from being set as 200
DEG C L/D=30 the double screw extruder with 30mm exhaust outlets main feed mouthful charging.(B) of amount shown in table 1 is green
Mudstone race mineral and (C) lubricant are by being arranged on the side throat-fed in the downstream of main feed mouthful, using screw speed as 100rpm
Melting mixing is carried out, so as to obtain polyacetal resin composite.By the method for above-mentioned record to resulting polyacetals tree
The tonal properties after mechanical properties, heat ageing, High-Temperature Creep Performance and MD characteristics after the heat ageing of oil/fat composition are commented
Valency.It the results are shown in table 1.
(comparative example 1)
In addition to (B) chlorite race's mineral and (C) lubricant is not used, polyacetals has been obtained similarly to Example 1
Resin combination.By the method for above-mentioned record to the mechanical properties after the heat ageing of resulting polyacetal resin composite,
Tonal properties, High-Temperature Creep Performance and MD characteristics after heat ageing are evaluated.It the results are shown in table 1.
(comparative example 2)
In addition to (B) chlorite race mineral are not used, polyacetal resin composite has been obtained similarly to Example 1.
By the method for above-mentioned record to the mechanical properties after the heat ageing of resulting polyacetal resin composite, the color after heat ageing
Characteristic, High-Temperature Creep Performance and MD characteristics is adjusted to be evaluated.It the results are shown in table 1.
(comparative example 3~6)
(B) chlorite race mineral B-1 is replaced using other mineral B-3~B-5, is obtained similarly to Example 1 in addition
Polyacetal resin composite is arrived.By the method for above-mentioned record to the heat ageing of resulting polyacetal resin composite after
Tonal properties, High-Temperature Creep Performance and MD characteristics after mechanical properties, heat ageing are evaluated.It the results are shown in table 1.
As shown in table 1, the tone after the heat ageing of the polyacetal resin composite obtained in embodiment 1~5 is confirmed special
Mechanical properties, MD characteristics and High-Temperature Creep Performance after property, heat ageing are excellent.
On the other hand, the tone after the heat ageing of the polyacetal resin composite obtained in comparative example 1~6 is confirmed special
Mechanical properties, MD and High-Temperature Creep Performance after property, heat ageing decline to a great extent.
Industrial applicability
The polyacetal resin composite of the present invention has the balance in the mechanical property that polyacetal resin is possessed, thermally-stabilised
Property, resistance to mold deposit are excellent, and endurance quality, weatherability are excellent, thus can be suitable for automobile, electrical/electronic, Qi Tagong
In the wide fields such as industry.
Claims (4)
1. a kind of polyacetal resin composite, it contains the mass parts of (A) polyacetal resin 100, (B) chlorite race mineral 0.001
~5 mass parts and the mass parts of (C) lubricant 0.001~5.
2. polyacetal resin composite as claimed in claim 1, wherein, the content of chlorite race mineral (B) is 0.001
~1 mass parts.
3. polyacetal resin composite as claimed in claim 1, wherein, chlorite race mineral (B) are selected from by green mud
At least one of group of stone, cookeite and manganese mackensite composition.
4. polyacetal resin composite as claimed in claim 1, wherein, the average grain diameter of chlorite race mineral (B) is
0.01 μm~100 μm.
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| JP2013-119015 | 2013-06-05 | ||
| JP2013119015A JP6068269B2 (en) | 2013-06-05 | 2013-06-05 | Polyacetal resin composition |
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| JPS545884A (en) * | 1977-06-13 | 1979-01-17 | Grace W R & Co | Clay material inserted with middle layer useful as catalyst and adsorbent |
| JP2000351887A (en) * | 1999-06-10 | 2000-12-19 | Showa Denko Kk | Low-warpage high-stiffness polyacetal composite |
| US6936651B2 (en) * | 2002-12-17 | 2005-08-30 | E. I. Du Pont De Nemours And Company | Compatibility improvement in crystalline thermoplastics with mineral fillers |
| JP5317312B2 (en) * | 2003-10-24 | 2013-10-16 | 旭化成ケミカルズ株式会社 | Polyacetal resin composition and molded article thereof |
| US8137592B2 (en) * | 2010-05-04 | 2012-03-20 | Sabic Innovative Plastics Ip B.V. | Method of incorporating an additive into a polymer composition and dispersion used therein |
| JP5764520B2 (en) * | 2012-04-04 | 2015-08-19 | 旭化成ケミカルズ株式会社 | Polyacetal resin composition |
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