CN104650526B - Polyacetal Rein Composition - Google Patents
Polyacetal Rein Composition Download PDFInfo
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- CN104650526B CN104650526B CN201410690927.2A CN201410690927A CN104650526B CN 104650526 B CN104650526 B CN 104650526B CN 201410690927 A CN201410690927 A CN 201410690927A CN 104650526 B CN104650526 B CN 104650526B
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Abstract
The present invention relates to a polyacetal rein composition containing 100 parts by mass of polyacetal rein (A) and 0.001-5 parts by mass of hindered amine compound (B) represented by the general formula (1).
Description
Technical field
The present invention relates to polyacetal resin composite.
Background technology
Polyacetal resin composite is crystalline resin, and rigidity, intensity, toughness, sliding and creep properties are excellent, therefore
It is widely used for mechanism part materials such as automobile component, Electrical and Electronic part and industrial part etc. all the time.
But, polyacetal resin is low to the toleration of the luminous energy such as sunlight or heat energy, when be exposed in air for a long time, has
Crack on formed products surface, the problem for causing intensity to decline.Therefore, it is however generally that, in the environment of sunlight etc. is exposed to
During use, the weathering stabilizers such as addition hindered amine compound.
In addition, in recent years, for polyacetal resin formed products, the requirement of miniaturization, thin-walled property and precise treatment is carried
Height, the manufacturing process and molding condition for easily applying thermal history than ever increase.
Shaping, the shaping of high cycle for for example carrying out using pin gate mould etc. can be enumerated, in addition, using high-viscosity
Polyacetal resin implements aforementioned manufacturing process, to realize miniaturization, thin-walled property and the precise treatment of formed products.
In above-mentioned manufacturing process, by improve shear rate or improve to shorten the plasticising time screw rod rotation or
Forming temperature, polyacetal resin is by the thermal history higher than common manufacturing process.
In addition, in other general manufacturing process, it is when cob webbing such as current mark, bonding wire, injection etc. is produced, most
In the case of by improve resin temperature tackled, this also become applying high thermal history the reason for.
In addition, when using hot flow path as mould, producing some retention of resin, thus resin temperature rises, it is possible to
Cause the decomposition of resin.
In the manufacturing process of the various thermal histories of above-mentioned applying and condition setting, as described above, in order to improve weatherability
During addition weathering stabilizers, in the relation with heat stability, the problem with the balance of properties for being difficult to obtain good.That is, weight
When coordinating weathering stabilizers in a large number depending on weathering stability, the problem with heat stability deterioration.
In addition, particularly in the field of the inner-decoration component of automobile, reducing the VOC containing formaldehyde
(VOC) requirement of burst size is increased, and present situation is the requirement weathering stability resin combination excellent with the balance of heat stability.
In the past, it is proposed that the method for improving the weathering stability of polyacetal resin.
For example, it is proposed that add hindered amine light stabilizer and oxanilide class ultra-violet absorption in polyacetal resin
The method (for example, with reference to patent documentation 1) of agent；Add hindered amine light stabilizer and benzophenone in polyacetal resin
The method (for example, with reference to patent documentation 2) of UV absorbent；In polyacetal resin add hindered amine light stabilizer and
The method (for example, with reference to patent documentation 3) of Benzotriazole Ultraviolet Stabilizer；Add hindered amines light in polyacetal resin
The method (for example, with reference to patent documentation 4) of stabilizer, various UV absorbent and fatty acid ester；In polyacetal resin
The method of addition hindered amine light stabilizer, Benzotriazole Ultraviolet Stabilizer and antioxidant is (for example, with reference to patent text
Offer 5)；Add the method (example of hindered amine light stabilizer, UV absorbent and hydrazide compound in polyacetal resin
Such as, referring to patent documentation 6)；In polyacetal resin, the method for adding liquid hindered amine light stabilizer is (for example, with reference to patent
Document is 7).
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Application 57-98545 publication
Patent documentation 2：Japanese Unexamined Patent Application 59-133245 publication
Patent documentation 3：Japanese Unexamined Patent Application 60-195155 publication
Patent documentation 4：Japanese Unexamined Patent Application 61-47744 publication
Patent documentation 5：Japanese Unexamined Patent Publication 6-157871 publication
Patent documentation 6：Japanese Unexamined Patent Publication 2006-232937 publications
Patent documentation 7：Japanese Unexamined Patent Publication 7-238208 publication
The content of the invention
Invent problem to be solved
But, the polyacetal resin composite obtained in the method described in patent documentation 1～7, although be improved resistance to
The effect of stability is waited, but is affected by the weathering stabilizers for adding, in the shaping side carried out using pin gate mould
In manufacturing process of method, high cycle manufacturing process and small-sized, thin-walled and precise part etc., shaping resin temperature appearance is exposed to
When the condition for easily rising or the condition using hot flow path, polyacetal resin is subject to high thermal history, therefore has and easily cause
The decomposition of polymer, produces the problem of mold fouling sometimes.In addition, from the formaldehyde amount reduced from resulting formed products release
Viewpoint considers, with the problem for not obtaining characteristic good in practicality.
Therefore, in the present invention, in view of above-mentioned problem of the prior art, its object is to provide by polyacetal resin
The specific hindered amine compound of middle combination, suppresses mold fouling during injection moulding, and can be greatly decreased from formed products or
The polyacetal resin composite of the formaldehyde amount of pellet release.
Means for solving the problem
The present inventor has carried out research extensively and profoundly to solve the above problems, and as a result finds, containing (A) polyacetals
The polyacetal resin composite of 0.001～5 mass parts of 100 mass parts of resin and (B) specific hindered amine compound can solve the problem that
Foregoing problems, so as to complete the present invention.
That is, the present invention is as described below.
[1] a kind of polyacetal resin composite, which contains
(A) 100 mass parts of polyacetal resin and
(B) 0.001～5 mass parts of hindered amine compound that following formulas (1) represent,
In formula (1), R1 represents the thiazolinyl of the alkyl of carbon number 1～30 or carbon number 2～30.
[2] polyacetal resin composite described in preceding paragraph [1], wherein,
In aforementioned formula (1), alkyl of the R1 for carbon number 8～26,
Mixture of aforementioned (B) composition for the R1 in aforementioned formula (1) different two or more hindered amine compounds.
Invention effect
According to the present invention it is possible to be inhibited injection moulding when mold fouling (mold deposit, hereinafter sometimes referred to simply as
" MD ") and the polyacetal resin composite of the formaldehyde amount for discharging can be greatly decreased from formed products or pellet.
Specific embodiment
Hereinafter, for the mode (hereinafter referred to as " present embodiment ") for implementing the present invention is illustrated.In addition, this
It is bright to be not limited to following embodiment, various modifications can be carried out to implement in the range of its main idea.
[polyacetal resin composite]
The polyacetal resin composite of present embodiment contains
(A) 100 mass parts of polyacetal resin and
(B) 0.001～5 mass parts of hindered amine compound that following formulas (1) represent,
In formula (1), R1 represents the thiazolinyl of the alkyl of carbon number 1～30 or carbon number 2～30.
((A) polyacetal resin)
(A) polyacetal resin (sometimes referred to as (A) composition, (A) in this specification) used in as present embodiment, can
To enumerate polyacetal homopolymer and Copolyacetal.
As (A) polyacetal resin, following material is not limited to, can be enumerated for example：By formaldehyde monomers or its trimer
The cyclic oligomer of the formaldehyde such as (metaformaldehyde), tetramer (four polyformaldehyde) is carried out obtained from homopolymerization, substantially only comprising oxygen
The polyacetal homopolymer of MU (methylene unit)；By the first such as formaldehyde monomers or its trimer (metaformaldehyde), tetramer (four polyformaldehyde)
Cyclic oligomer and oxirane, expoxy propane, epichlorohydrin, 1,3- dioxolane, 1,4- butanediol formals of aldehyde etc.
The cyclic ethers such as the cyclic formals of glycol or dimer diol or Copolyacetal obtained from cyclic formals copolymerization；Make single official
The cyclic oligomer of energy glycidyl ether and the formaldehyde such as formaldehyde monomers or its trimer (metaformaldehyde), tetramer (four polyformaldehyde)
Copolyacetal with side chain obtained from copolymerization；Polyfunctional glycidyl ether is made with formaldehyde monomers or its trimer (three
Polyformaldehyde), there are the polyacetals of cross-linked structure altogether obtained from the cyclic oligomer copolymerization of formaldehyde such as tetramer (four polyformaldehyde)
Polymers etc..
In addition, as polyacetal resin (A), being not limited to following material, can enumerate for example：Two ends or single
End has the compound of the functional groups such as hydroxyl, the ring-type of formaldehyde monomers or formaldehyde is specifically made in the presence of ployalkylene glycol
There is obtained from oligomer polymerization the polyacetal homopolymer of block component；There is hydroxyl in two ends or single end similarly
The compound of Ji Deng functional groups, formaldehyde monomers or its trimer (trimerization first are for example made in the presence of hydrogenated polybutadiene diol
Aldehyde), there is block obtained from the cyclic oligomer of the formaldehyde such as tetramer (four polyformaldehyde) and cyclic ether, cyclic formals copolymerization
The Copolyacetal of composition.
As described above, in the present embodiment, it is possible to use any one in polyacetal homopolymer and Copolyacetal
Kind.
In the illustration of the Copolyacetal of above-mentioned (A) polyacetal resin, with formaldehyde monomers or its trimer, tetramer
Deng the ratio of the various comonomers such as the 1 of the cyclic oligomer copolymerization of formaldehyde, 3- dioxolane, relative to aforementioned formaldehyde list
1 mole of the cyclic oligomer of the formaldehyde such as body or its trimer, tetramer preferably 0.1～60 mole of %, more preferably 0.1～20
Mole %, more preferably 0.13～10 mole %.The ratio of comonomer can then provide machinery if above range
The more excellent polyacetal resin composite of intensity.
When manufacturing Copolyacetal by copolymerization, it is possible to use polymerization catalyst.
As the polymerization catalyst, following catalyst is not limited to, preferably such as lewis acid, Bronsted acid and its ester or acid
The cationic active catalysts such as acid anhydride.
As lewis acid, following material is not limited to, can be enumerated for example：The halogenide of boron, stannum, titanium, phosphorus, arsenic and antimony.
Boron trifluoride, butter of tin, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride and its complex can specifically be enumerated
Or salt.
In addition, as Bronsted acid and its ester or anhydride, being not limited to following material, can enumerate for example：Perchloric acid, fluoroform
Sulfonic acid, the perchloric acid tert-butyl ester, acetylperchlorate, trimethyl oxygenHexafluorophosphate etc..
As polymerization catalyst, boron trifluoride, boron trifluoride hydrate is particularly preferred and containing oxygen atom or sulfur original
The organic compound of son and the co-ordination complex of boron trifluoride, specifically, from from the viewpoint of improving polymerization yield, preferred trifluoro
Change boron diethyl ether complexes, boron trifluoride di-n-butyl ether complex.
In addition, when above-mentioned Copolyacetal is obtained, in addition to cationic active catalyst, suitably can also make
With polymerization cahin extension agent such as dimethoxym ethane (chain-transferring agent).In addition, used as polymerization cahin extension agent (chain-transferring agent), preferred moisture is
Below 100ppm, methanol content are the dimethoxym ethane of below 1 mass %, and more preferably moisture is that below 50ppm, methanol content are
Dimethoxym ethane below 0.7 mass %.
As the polymerization of foregoing polyacetal copolymer, following method is not limited to, such as polymerisation in bulk can be enumerated
Method.As polymerization methodses, can be using any one of batch (-type), continuous way.
As polyplant, following device is not limited to, can be enumerated for example：Co-kneader, double-screw type are continuously extruded
Self-cleaning type extruder and mixing rolls such as kneading machine, twin screw paddle continuous mixer etc..
As specific polymerization, can enumerate：The monomer of molten condition is supplied to into aforementioned polymeric device, is being carried out
The method that the Copolyacetal of solid block is obtained while polymerization.
In the Copolyacetal obtained after polymerization process, heat-labile terminal part [- (OCH is occasionally there are2)n-OH
Base], therefore it is preferable to carry out the decomposition removing process of the unstable terminal part.
The manufacture method of the polyacetal homopolymer of above-mentioned (A) polyacetal resin is illustrated below.
For example, the formaldehyde monomers as monomer or its trimer (metaformaldehyde) or tetramer (four polyformaldehyde), chain are turned
Move agent (molecular weight regulator) and polymerization catalyst is fed in the polymer reactor full of varsol, using slurry polymerization
Method obtains thick polyacetal homopolymer.The polymer terminal group thermally labile of resulting thick polyacetal homopolymer, therefore preferred pair should
The blocked polymer end group such as unstable end-group esterifying agent, etherifying agent, carries out stabilizing treatment.Thus, obtain polyacetals homopolymerization
Thing.
In addition, the formaldehyde monomers or its trimer (metaformaldehyde) or tetramer (four polyformaldehyde), chain as starting monomer
Transfer agent, hydrocarbon-based polymeric solvent, containing can chain tra nsfer the composition composition of unstable end-group (produce) such as water, methanol and first
Acid, thus preferably adjust first these can chain tra nsfer composition content, by thick polyacetal homopolymer be polymerized.
Now can chain tra nsfer composition content, relative to the formaldehyde monomers as starting monomer or its trimer (three
Polyformaldehyde) or tetramer (four polyformaldehyde), the preferably scope of 1～1000ppm, more preferably 1～500ppm, further preferably
For 1～300ppm.
The molecular weight of polyacetal homopolymer can carry out chain tra nsfer by using carboxylic acid anhydrides or carboxylic acid equimolecular quantity regulator
And be adjusted.
As the molecular weight regulator, propionic andydride, acetic anhydride, more preferably acetic anhydride is particularly preferred.
As the polymerization catalyst in the polymerization of polyacetal homopolymer, following catalyst is not limited to, preferably such as anion
Type polymerization catalyst, more preferablySalt polymerization catalyst.
It is aforementionedIn salt polymerization catalyst, preferred tetraethyl iodateTributyl ethyl phosphonium iodideIn seasonSalt
The quaternary ammonium compounds such as compound, 4 bromide, dimethyl distearyl ammonium acetate.
As long as aforesaid hydrocarbon-based polymeric solvent is then not particularly limited with the nonreactive solvent of formaldehyde, example can be enumerated
Such as：Pentane, isopentane, hexane, hexamethylene, heptane, octane, nonane, decane, benzene etc..
These varsols can be used alone one kind, it is also possible to be used in mixed way two or more.As hydrocarbon-based polymeric solvent,
Particularly preferred hexane.
In addition, as long as the polyplant of the thick polyacetal homopolymer of manufacture can supply formaldehyde as monomer, chain simultaneously
The device of transfer agent (molecular weight regulator), polymerization catalyst and varsol, then be not particularly limited, from the viewpoint of productivity ratio
Consider, preferred continuous way polyplant.
Polyacetal homopolymer used in present embodiment, as described above, in the heat-labile situation of end group of polymer
Under, preferably carry out stabilizing treatment.Specifically, it is not particularly limited, for example, it is preferable to use esterifying agent to seal the end group of polymer
Close, thus carry out stabilisation.
Esterifying agent can use anhydride.As anhydride, can enumerate for example：Benzoyl oxide, succinic anhydrides, maleic anhydride,
Glutaric anhydride, phthalic anhydride, propionic andydride, acetic anhydride, preferred acetic anhydride.
These esterifying agents can be used alone one kind, it is also possible to two or more to be used in mixed way.
((B) hindered amine compound)
The polyacetal resin composite of present embodiment contains (B) hindered amine compound (this theory that following formulas (1) are represented
In bright book, (B) composition, (B) are denoted as sometimes).
In aforementioned formula (1), R1 represents the thiazolinyl of the alkyl of carbon number 1～30 or carbon number 2～30.
In aforementioned formula (1), the alkyl of the carbon number 1～30 represented as R1 is not limited to following alkyl, Ke Yilie
Citing is such as：Methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, sec-amyl, tertiary pentyl, oneself
Base, heptyl, octyl group, iso-octyl, 2- ethylhexyls, t-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, 13
Alkyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl etc..
From from the viewpoint of the heat stability for improving polyacetal resin composite, the R1 in aforementioned formula (1) is preferably carbon
The alkyl of atomic number 8～26, more preferably carbon number are 12～21 alkyl.In addition, aforementioned (B) composition is preferably comprising front
State the mixture of the different two or more hindered amine compounds of R1 in formula (1).Aforementioned (B) composition is such mixture
When, polyacetal resin composite has mold fouling when further suppressing injection moulding, and is greatly decreased from formed products
Or the tendency of the formaldehyde amount of pellet release.
In aforementioned formula (1), the thiazolinyl of the carbon number 2～30 represented as R1 is not limited to following thiazolinyl, Ke Yilie
Citing is such as：Vinyl, acrylic, cyclobutenyl, hexenyl, octenyl etc..The position of double bond is not particularly limited, can for α positions,
Any one of ω positions, the position more closer to the inner portion than these positions.
The concrete example of the compound represented as aforementioned formula (1), is not particularly limited, and can enumerate for example：2,2,6,
The fatty acid ester compound of 6- tetramethyl -4- piperidyls, from from the viewpoint of improving heat stability, preferred following formula (2)～(8)
The compound of expression.
The manufacture method of (B) hindered amine compound represented with regard to aforementioned formula (1), is not particularly limited, it is possible to use
Known synthetic method.
Can enumerate for example：It is esterified with the direct esterification of alcohol, the reaction of carboxylic acid halides and alcohol, ester exchange reaction by acid,
And the method that the compound purification for obtaining will be reacted by these.As purification process, it is possible to use for example distillation, recrystallization,
Reprecipitation, filtration or adsorbent.
In the polyacetal resin composite of present embodiment, relative to above-mentioned 100 mass parts of (A) polyacetal resin, contain
There are 0.001～5 mass parts, preferably comprise (B) aforementioned formula of 0.001～3 mass parts, further preferably 0.001～1 mass parts
(1) hindered amine compound for representing.
The content of aforementioned (A) composition and (B) composition can then obtain more excellent poly- of heat stability if above range
Acetal resin composition.
(other additives)
In the polyacetal resin composite of present embodiment, in order to further give other characteristics, can add containing other
Plus agent.
As other additives, following additive is not limited to, can be enumerated for example：Antioxidant, heat stability and first
The stabilizers such as sour trapping agent, releasing agent, lubricant, the hindered amine compound in addition to the compound that aforementioned formula (1) is represented, purple
Ultraviolet absorbers, inorganic filler, organic filler, conductive agent, thermoplastic resin, thermoplastic elastomer (TPE), pigment etc..
<Antioxidant>
As antioxidant, preferred hindered phenol anti-oxidants.
As hindered phenol anti-oxidants, following antioxidant is not limited to, can be enumerated for example：3- (3 ', 5 '-two uncles
Butyl -4 '-hydroxy phenyl) propanoic acid n-octadecane base ester, 3- (3 '-methyl -5 '-the tert-butyl group -4 '-hydroxy phenyl) propanoic acid positive 18
Arrcostab, 3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propanoic acid n-tetradecane base ester, two [3- (3,5- bis- of 1,6-HD
Tert-butyl-hydroxy phenyl) propionic ester], 1,4- butanediols two [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], three
Ethylene glycol bisthioglycolate [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester], four [methylene -3- (3 ', 5 '-two of tetramethylolmethane
The tert-butyl group -4 '-hydroxy phenyl) propionic ester] methane etc..
From from the viewpoint of improving heat stability, two [3- (the 3- tert-butyl group -5- methyl -4- hydroxy benzeness of preferred triethylene glycol
Base) propionic ester] and tetramethylolmethane four [methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic ester] methane.
These antioxidants can be used alone one kind, it is also possible to be used in combination.
As long as the scope of adding proportion without prejudice to the object of the invention of antioxidant is then not particularly limited, it is general and
Speech, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.01～5 mass parts, more preferably 0.01～1 mass
The scope of part, the more preferably scope of 0.05～0.5 mass parts.
<Heat stabilizer>
As heat stabilizer, following material is not limited to, can be enumerated for example：Nylon 4-6, nylon 6, nylon 6-6, nylon
The polyamides such as 6-10, nylon 6-12, nylon 12, and their polymer, such as nylon 6/6-6/6-10, nylon 6/6-
12 etc..
In addition, as heat stabilizer, can enumerate acrylamide and its derivant, acrylamide and its derivant and other
The copolymer of vinyl monomer.Following material is not limited to, can be enumerated for example：Acrylamide and its derivant and other ethylene
Base monomer poly- Beta-alanine copolymer obtained from being polymerized in the presence of metal alkoxide.
In addition, as heat stabilizer, amide compound, the triaizine compounds of amino replacement, amino can be enumerated and replaced
The addition product of triaizine compounds and formaldehyde, the condensation substance of the triaizine compounds that amino replaces and formaldehyde, urea, urea derivative, hydrazine spread out
Biology, imidazolium compoundss, imide compound.
As foregoing amides compound, following material is not limited to, can be enumerated for example：The polynary carboxylic such as isophtalamide
Sour amide, anthracene amide.
As the triaizine compounds that aforesaid amino replaces, following material is not limited to, can be enumerated for example：2,4- diaminos
Base s-triazine, 2,4,6- tri-amino-p-triazines, N- melamine-butyls, N phenyl melamine, N, N- diphenyl tripolycyanamide,
N, N- diallyl melamine, benzoguanamine (2,4- diaminourea -6- phenyl s-triazine), methyl guanamines (2,4- diaminourea -6- first
Base s-triazine), 2,4- diaminourea -6- butyl s-triazine etc..
The compound in triazine class replaced as aforementioned amino and the addition product of formaldehyde, are not limited to following material, Ke Yilie
Citing is such as：N- melamine methylols, N, N '-dihydroxymethyl tripolycyanamide, N, N ', N "-trimethylol melamines.
The compound in triazine class replaced as aforementioned amino and the condensation substance of formaldehyde, are not limited to following material, Ke Yilie
Citing is such as：Condensate of melamine and formaldehyde.
As aforementioned urea derivative, following material is not limited to, can be enumerated for example：N- substituted ureas, urea condensation compound, sub- second
Base urea, hydantoin compound, urea-based compound.
As aforesaid N- substituted ureas, following material is not limited to, can be enumerated for example：The first that the substituent groups such as alkyl replace
Base urea, two urea of alkylidene, aryl substituted urea.
As aforementioned urea condensation compound, following material is not limited to, can be enumerated for example：Condensation substance of urea and formaldehyde etc..
As aforementioned hydantoin compound, following material is not limited to, can be enumerated for example：Hydantoin, 5,5- bis-
Methyl hydantoin, 5,5- diphenyl hydantoins etc..
As aforementioned urea-based compound, following material is not limited to, can be enumerated for example：Allantoin.
As aforementioned hydrazine derivate, following material is not limited to, can be enumerated for example：Hydrazide compound.
As aforementioned hydrazide compound, following material is not limited to, can be enumerated for example：Two hydrazides of dicarboxylic acids, specifically
Acid dihydrazide, succinum acid dihydrazide, glutaric, adipic dihydrazide, two hydrazides of 1,5-pentanedicarboxylic acid., pungent can be enumerated in ground
Dihydrazi, two hydrazides of Azelaic Acid, sebacic dihydrazide, two hydrazides of dodecanedioic acid, isophthalic dihydrazide, adjacent benzene two
First acid dihydrazide, two hydrazides of 2,6- naphthalenedicarboxylic acids etc..
As aforementioned imidazolium compoundss, following compound is not limited to, can be enumerated for example：Methylimidazole., dimethyl miaow
Azoles, phenylimidazole.
As aforesaid imide compound, following compound is not limited to, can be enumerated for example：Butanimide, penta
Imidodicarbonic diamide, phthalimide.
Above-mentioned heat stabilizer can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of adding proportion without prejudice to the object of the invention of heat stabilizer is then not particularly limited, it is general and
Speech, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.001～5 mass parts, more preferably 0.001～1 matter
The scope of amount part, the more preferably scope of 0.01～0.5 mass parts.
<Formic acid trapping agent>
As formic acid trapping agent, following compound is not limited to, can be enumerated for example：The triaizine compounds of amino replacement,
The triaizine compounds that amino replaces and the condensation substance of formaldehyde, can specifically enumerate condensate of melamine and formaldehyde etc..
As other formic acid trapping agents, following material is not limited to, can be enumerated for example：The hydrogen of alkali metal or alkaline-earth metal
Oxide, inorganic acid salt, carboxylate or alkoxide.
Formic acid trapping agent can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of adding proportion without prejudice to the object of the invention of formic acid trapping agent is then not particularly limited, it is general and
Speech, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.001～5 mass parts, more preferably 0.001～1 matter
The scope of amount part, the more preferably scope of 0.01～0.5 mass parts.
<Releasing agent, lubricant>
As releasing agent and lubricant, following material is not limited to, can be enumerated for example：Alcohol, fatty acid and fatty acid ester,
Average degree of polymerization is 10～500 olefin(e) compound, polysiloxanes.
Wherein, preferred fatty acid and fatty acid ester, second two more preferably derived from the higher fatty acids of carbon number 10～20
Alcohol di fatty acid ester.
As the senior fat for constituting di-fatty acid esters derived from the higher fatty acids of aforementioned carbon number 10～20
Fat acid, the preferably higher fatty acids with linear chain structure, are not limited to following material, can enumerate for example：Lauric acid, Semen Myristicae
The unsaturated fatty acid such as the satisfied fatty acid such as acid, Palmic acid, stearic acid, arachidic acid and Oleic acid.
As di-fatty acid esters, preferred glycol distearate.
Releasing agent and lubricant can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of adding proportion without prejudice to the object of the invention of releasing agent and lubricant is then not particularly limited, and one
As for, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.001～20 mass parts, more preferably 0.001
The scope of～10 mass parts, the more preferably scope of 0.005～5 mass parts.
<Hindered amine compound in addition to the compound that formula (1) is represented>
As the hindered amine compound in addition to the compound that formula (1) is represented, following compound, Ke Yilie are not limited to
Citing is such as：Carbonic acid two (2,2,6,6- tetramethyl -4- piperidine esters), oxalic acid two (2,2,6,6- tetramethyl -4- piperidine esters), malonic acid
Two (2,2,6,6- tetramethyl -4- piperidine esters), decanedioic acid two (1,2,2,6,6- pentamethyl -4- piperidine esters), two (N- first of decanedioic acid
Base -2,2,6,6- tetramethyl -4- piperidine esters), decanedioic acid two (2,2,6,6- tetramethyl -4- piperidine esters), adipic acid two (2,2,6,
6- tetramethyl -4- piperidine esters), p-phthalic acid two (2,2,6,6- tetramethyl -4- piperidine esters), double (the 2,2,6,6- tetramethyls of 1,2-
Base -4- piperidyl epoxides) ethane, α, α '-bis- (2,2,6,6- tetramethyl -4- piperidyl epoxides) xylol, Toluene-2,4-diisocyanate, 4- bis-
Carbamic acid two (2,2,6,6- tetramethyl -4- piperidine esters), hexa-methylene -1,6- diamino acids two (2,2,6,6- tetramethyls -
4- piperidine esters), benzene -1,3,5- tricarboxylic acids three (2,2,6,6- tetramethyl -4- piperidine esters), benzene -1,3,4- tricarboxylic acids three (2,2,6,
6- tetramethyl -4- piperidine esters), 1- [2- { 3- (3,5- di-tert-butyl-hydroxy phenyls) propionyloxy } butyl] -4- [3- (3,5-
Di-tert-butyl-hydroxy phenyl) propionyloxy] -2,2,6,6- tetramethyl piperidines, 1,2,3,4- ethylene-dimalonic acids and 1,2,2,6,
6- pentamethyl -4- piperidine alcohols and β, β, β ', β '-tetramethyl -3,9- [2,4,8,10- tetra- oxaspiros (5.5) hendecanes] diethanol
Condensation substance etc..
Above-mentioned hindered amine compound each can only be used alone one kind, it is also possible to be used in combination.
Except formula (1) as long as the adding proportion without prejudice to mesh of the present invention of hindered amine compound in addition to the compound for representing
Scope be then not particularly limited, it is however generally that, relative to 100 mass parts of (A) polyacetal resin, preferably 0.01～10 matter
The scope of amount part, the more preferably scope of 0.01～5 mass parts, the more preferably scope of 0.05～5 mass parts.
<UV absorbent>
As UV absorbent, following material is not limited to, can be enumerated for example：2- (2 '-hydroxyl -5 '-methylbenzene
Base) benzotriazole, 2- (2 '-hydroxyl -3,5- di-tert-butyl-phenyls) benzotriazole, the 2- [double (alpha, alpha-dimethyls of 2 '-hydroxyl -3,5-
Benzyl) phenyl] benzotriazole, 2- (2 '-hydroxyl -3,5- di-tert-pentyl-phenyls) benzotriazole, 2- (2 '-hydroxyl -3,5- diisoamyls
Base phenyl) benzotriazole, 2- [2 '-hydroxyl -3,5- double (bis (alpha, alpha-dimethylbenzyl) base) phenyl] -2H- benzotriazole, 2- (2 '-hydroxyls
Base -4 '-octyloxyphenyl) benzotriazole etc..
These UV absorbent can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of adding proportion without prejudice to the object of the invention of UV absorbent is then not particularly limited, typically
For, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.01～10 mass parts, more preferably 0.01～5
The scope of mass parts, the more preferably scope of 0.05～5 mass parts.
<Inorganic filler>
As inorganic filler, following material is not limited to, can be enumerated for example：Threadiness, granular, tabular and in
The filler of empty shape.
As fibrous filler, following material is not limited to, can be enumerated for example：Glass fibre, carbon fiber, silicon are fine
Dimension, silica alumina fiber, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre, potassium titanate fibre, with
And the inorganic fibre such as the metallic fiber such as rustless steel, aluminum, titanium, copper, pyrite.In addition, also including that the short potassium titanate of fibre length is brilliant
The whisker class such as palpus, ZnOw.
As granular filler, following material is not limited to, can be enumerated for example：White carbon black, silicon dioxide, silica flour
End, glass microballoon, glass dust, calcium silicates, hydrous magnesium silicate (Talcum), aluminium silicate, Kaolin, clay, kieselguhr, wollastonite etc.
Silicate；The metal-oxides such as ferrum oxide, titanium oxide, aluminium oxide；The metal sulfates such as calcium sulfate, barium sulfate；Magnesium carbonate, white clouds
The carbonate such as stone；And carborundum, silicon nitride, boron nitride, various metal dusts etc..
As tabular filler, following material is not limited to, can be enumerated for example：Muscovitum, flake glass, various metals
Paper tinsel.
As hollow form filler, following material is not limited to, can be enumerated for example：Glass hollow microsphere, silicon dioxide
Hollow microsphere, white sand hollow microsphere, metal hollow microsphere etc..
These inorganic fillers can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of the adding proportion without prejudice to purpose of the present invention of inorganic filler is then not particularly limited, typically
For, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.001～60 mass parts, more preferably 0.001～
The scope of 50 mass parts, the more preferably scope of 0.005～50 mass parts.
In addition, above-mentioned inorganic filler can be using the filler of surface treated, the filler that is not surface-treated
Any one, from the viewpoint of the flatness, mechanical property from formed body surface, it is sometimes preferred to implement the filling of surface treatment
Agent.
As surface conditioning agent, following material is not limited to, it is possible to use existing known surface conditioning agent.
As surface conditioning agent, following material is not limited to, it is possible to use for example：Silanes, titanate ester, aluminum class, zirconium
The various coupling processing agent such as class, resinic acid, organic carboxyl acid, salt of organic carboxyl acid etc., surfactant.
As surface conditioning agent, can enumerate for example：N- (2- amino-ethyls)-APTES, 3-
Glycidoxypropyltrime,hoxysilane, three stearyl titanate esters of isopropyl, diisopropoxy ethyl acetic acid ammonium, the positive fourth of zirconic acid
Ester etc..
<Organic filler>
As organic filler, following material is not limited to, can be enumerated for example：Aromatic polyamide resin, fluorine-containing tree
Fat, acrylic resin etc. have dystectic organic fiber shape filler.
These organic fillers can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of the adding proportion without prejudice to purpose of the present invention of organic filler is then not particularly limited, typically
For, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.001～50 mass parts, more preferably 0.001～
The scope of 40 mass parts, the more preferably scope of 0.005～40 mass parts.
<Conductive agent>
As conductive agent, following material is not limited to, can be enumerated for example：Conductive carbon black, metal dust or metal are fine
Dimension.
Conductive agent can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of the adding proportion without prejudice to purpose of the present invention of conductive agent is then not particularly limited, it is general and
Speech, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.01～50 mass parts, more preferably 0.01～30 matter
The scope of amount part, the more preferably scope of 0.1～30 mass parts.
<Thermoplastic resin>
As thermoplastic resin, following material is not limited to, can be enumerated for example：Vistanex, acrylic resin,
Styrene resin, polycarbonate resin, uncured epoxy resin.In addition, also including their modifier.
Thermoplastic resin can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of the adding proportion without prejudice to purpose of the present invention of thermoplastic resin is then not particularly limited, typically
For, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.001～60 mass parts, more preferably 0.01～
The scope of 50 mass parts, the more preferably scope of 0.1～50 mass parts.
<Thermoplastic elastomer (TPE)>
As thermoplastic elastomer (TPE), following material is not limited to, can be enumerated for example：Polyurethane elastomer, polyesters
Elastomer, polystyrene type elastomer, polyamide-based elastomer.
Thermoplastic elastomer (TPE) can only be used alone one kind, it is also possible to be used in combination.
As long as the scope of the adding proportion without prejudice to purpose of the present invention of thermoplastic elastomer (TPE) is then not particularly limited, and one
As for, relative to 100 mass parts of (A) polyacetal resin, the preferably scope of 0.001～60 mass parts, more preferably 0.01
The scope of～50 mass parts, the more preferably scope of 0.1～50 mass parts.
<Pigment>
As pigment, following material is not limited to, can be enumerated for example：It is inorganic pigment and organic pigment, metallic pigments, glimmering
Delustering pigment etc..
As inorganic pigment, it is possible to use be generally used for any one in the pigment of coloring resin, it is not limited to following
Material, can enumerate for example：Zinc sulfide, titanium oxide, barium sulfate, titan yellow, cobalt blue, calcined pigment, carbonate, phosphate, acetic acid
Salt or white carbon black, acetylene black, lampblack etc..
As organic pigment, following material is not limited to, can be enumerated for example：Condensation azo, quinones, phthalocyanines, list
Azo, bisazo class, polyazo class, Anthraquinones, heterocyclic, purple cyclic ketones class, quinacridine ketone, thioindigo class, perylene class, twoPiperazine
The organic pigments such as class, phthalocyanines.
The adding proportion of pigment is adjusted according to desired tone, it is however generally that, relative to (A) polyacetal resin
100 mass parts, the preferably scope of 0.0005～5 mass parts.
Pigment can only be used alone one kind, it is also possible to be used in combination.
[manufacture method of polyacetal resin composite]
The polyacetal resin composite of present embodiment can be by above-mentioned composition be mixed and using general extrusion
Machine is manufactured.
As extruder, single screw rod or multiscrew mixing extruder etc. can be enumerated, in particular it is preferred that having decompressor
Double screw extruder.
Preferred molten temperature of the melting temperature according to base resin, it is as the scope that benchmark is 140～260 DEG C, excellent
Select 180～230 DEG C of scope, more preferably 190～210 DEG C of scope.
As the method for manufacture polyacetal resin composite, the method that following (1)～(4) can be enumerated.
(1) (A) polyacetal resin is fed by extruder hopper, recycles quantitative feeder etc. to add (B) from side charging aperture
Hindered amine compound, other additives as needed the method for carrying out melting mixing.
(2) part of (A) polyacetal resin is fed by extruder hopper, quantitative feeder etc. is recycled from side charging aperture
Addition (B) hindered amine compound, other additives as needed and remaining polyacetal resin (A) simultaneously carry out melting mixing
Method.
(3) (A) polyacetal resin is fed by extruder hopper, recycles quantitative feeder etc. to use poly- from the addition of side charging aperture
Acetal resin etc. defines (B) hindered amine compound of masterbatch, other additives as needed and carries out the side of melting mixing
Method.
(4) will be (A) polyacetal resin mixed using Henschel with (B) hindered amine compound, other additives as needed
The batch mixed such as conjunction machine, rotary drum, V-type blender, the method for then carrying out melting mixing using extruder.
In addition, from from the viewpoint of the heat stability of the resulting polyacetal resin composite of improvement, preferably in polyacetals
Add (B) hindered amine compound, the system of above-mentioned (1)～(3) of other additives as needed in the state of resin (A) melting
Make method.
Alternatively, it is also possible to pre-production comprising (A) polyacetal resin and (B) hindered amine compound and as needed its
The high concentration masterbatch of its additive, and be diluted with (A) polyacetal resin in injection moulding, thus manufacture polyacetal resin
Compositionss.
[purposes]
The polyacetal resin composite of present embodiment has good mechanical balance, is greatly decreased from formed products or granule
The formaldehyde amount of release, good heat stability, therefore can be used for the formed products of various uses.
The polyacetal resin composite of present embodiment can be used for for example：With gear, cam, slide block, lever, axle, axle
Hold and guide rail etc. be the mechanism part of representative, the resin component that shapes on inserts, the resin component of insert part forming, chassis, pallet,
Side plate, the business automation equipment part with printer and photocopier as representative, with DV, photographing unit and digital phase
Machine is the photographing unit of representative or video equipment part, magnetic tape sound reproducer, music, image or information equipment, communication apparatus portion
Part, electrical equipment part, electronic equipment part.
In addition, the polyacetal resin composite of present embodiment is used as the fuel tank of automotive part, petrolift
Module, valve class, fuel tank flange etc. are the fuel associated components of representative, car door associated components, seat belt associated components, cubicle switch
Part, Switch.
In addition, the polyacetal resin composite of present embodiment can be used for the Ministry of Industry that premises equipment devices are representative
Part.
Embodiment
Hereinafter, the present invention will be described to enumerate specific embodiment and comparative example, but, the invention is not restricted to following
Embodiment.
The physical property measurement method applied in embodiment and comparative example and raw material are as described below.
[physical property measurement method]
<From formed products release formaldehyde amount it is quantitative>
The IS-100GN injection machines manufactured using Toshiba Machinery Co., Ltd., in barrel temperature：Condition 1=200 DEG C,
Condition 2=220 DEG C, injection pressure 70MPa, 15 seconds injection time, 20 seconds cool times, under conditions of 80 DEG C of mold temperature, by
The polyacetal resin composite obtained in embodiment described later and comparative example is configured to test film (longitudinal 100mm of given size
× horizontal 40mm × thickness 3mm).
The formaldehyde amount for discharging is determined from resulting test film according to following VDA275 methods, and is obtained from formed products release
Formaldehyde amount.
VDA275 methods：By distilled water 50mL and the test film of given size (longitudinal 100mm × horizontal 40mm × thickness 3mm)
It is in being put into polyethylene can and closed, formaldehyde is extracted in distilled water while heating 3 hours for 60 DEG C, be subsequently cooled to room
Temperature.After cooling, in the distilled water 5ml for absorbing formaldehyde, add 0.4 mass % aqueous solution of 5m1 acetylacetone,2,4-pentanediones and 5ml acetic acid
20 mass % aqueous solution of ammonium, carries out 15 minutes heating at 40 DEG C, carries out the reaction of formaldehyde and acetylacetone,2,4-pentanedione, so as to be mixed
Thing.The mixed liquor is cooled to into room temperature again, then the first in the quantitative distilled water of absworption peak using UV spectrophotometers by 412nm
Aldehyde amount.Obtained from the formaldehyde amount (mg/kg) of formed products release by following formula.
Polyacetal resin formed products (kg) used in formaldehyde amount (mg) in distilled water/measure=from formed products release
Formaldehyde amount (mg/kg)
<MD characteristics>
The Ti-30G injection machines manufactured using Toyo Jukikai Metal Corp., in 200 DEG C of barrel temperature, injection speed
Spend 100mm/S, injection pressure 100kgf, under conditions of 15 seconds cycle time, obtain in repeating embodiment and comparative example
Polyacetal resin composite injection moulding.10000 injection mouldings are carried out, observation is attached to attached on 30 DEG C of low temperature moulds
Thing, and MD characteristics are evaluated based on following standard.
(evaluation criterion of MD characteristics)
1：Attachment is observed in the range of more than the 80% of mould
2：In mould 30% less than attachment is observed in the range of 80%
3：In mould 10% less than attachment is observed in the range of 30%
4：Attachment is observed in the range of mould is less than 10%
5：Without attachment
[raw material]
Following compositions used in embodiment, comparative example.
((A) polyacetal resin)
Metaformaldehyde and Copolyacetal obtained from 1,3- dioxolane copolymerization.
1,3- dioxolane additions：4.2 moles of % (relative to metaformaldehyde)
Fusing point：164℃
MFR：9.0g/10 minute
((B) hindered amine compound)
(B-1)：Stearic acid 2,2,6,6- tetramethyl -4- piperidine esters.
(B-2)：Palmic acid 2,2,6,6- tetramethyl -4- piperidine esters
(B-3)：Decanedioic acid two (2,2,6,6- tetramethyl -4- piperidine esters)
(B-4)：Decanedioic acid two (1,2,2,6,6- pentamethyl -4- piperidine esters)
(B-5)：1,2,3,4- ethylene-dimalonic acids and 1,2,2,6,6- pentamethyl -4- piperidine alcohols and β, β, β ', β '-tetramethyl
The condensation substance of base -3,9- [2,4,8,10- tetra- oxaspiros (5.5) hendecanes] diethanol
[embodiment 1～7]
As described in Table 1, by above-mentioned 100 mass parts of (A) polyacetal resin and (B) hindered amine compound with matching somebody with somebody for specifying
Composition and division in a proportion carries out mix homogeneously using Henschel mixer, so as to obtain mixture.
Aforementioned mixture is entered from the master of the double screw extruder of the band 30mm air vents of the L/D=30 for being set as 200 DEG C
Material mouth feeds, and carries out melting mixing, so as to obtain polyacetal resin composite under conditions of screw speed 100rpm.
Using foregoing polyacetal resin compositionss, according to aforesaid<From formed products release formaldehyde amount it is quantitative>And<
MD characteristics>, evaluate the formaldehyde amount and MD characteristics from formed products release.Evaluation result is as described in Table 1.
[comparative example 1]
Above-mentioned (A) polyacetal resin is configured to into test film (longitudinal 100mm × horizontal 40mm × thickness of aforementioned given size
Degree 3mm), to the formed products according to aforesaid<From formed products release formaldehyde amount it is quantitative>And<MD characteristics>, evaluate from into
The formaldehyde amount and MD characteristics of shape product release.Evaluation result is as described in Table 1.
[comparative example 2～4]
As described in Table 1, (B-3～B-5) is used as (B) hindered amine compound, it is in addition, same with embodiment 1
Polyacetal resin composite has been manufactured sample.
Foregoing polyacetal resin compositionss are configured to into test film (longitudinal 100mm × horizontal 40mm of aforementioned given size
× thickness 3mm), to the formed products according to aforesaid<From formed products release formaldehyde amount it is quantitative>And<MD characteristics>, evaluate
From the formaldehyde amount and MD characteristics of formed products release.Evaluation result is as described in Table 1.
Table 1
As shown in table 1, confirm the polyacetal resin composite that obtains of embodiment 1～7 under the conditions of each forming temperature from into
The formaldehyde amount of shape product release is greatly decreased, and MD characteristic goods.
On the other hand, confirm the formaldehyde amount from formed products release of the polyacetal resin composite that comparative example 1～4 is obtained
It is many, and MD characteristics are remarkably decreased.
The Japanese patent application (Patent 2013-243258) that the application was proposed based on November 25th, 2013, this application
Content be incorporated to this specification as reference.
Industrial applicability
The polyacetal resin composite of the present invention, used as automotive part, various electrical and electronic equipment parts, other are various
Industrial components etc., with industrial applicability.
Claims (2)
1. a kind of polyacetal resin composite, which contains
(A) 100 mass parts of polyacetal resin and
(B) 0.001～5 mass parts of hindered amine compound that following formulas (1) represent,
In formula (1), R1 represents the thiazolinyl of the alkyl of carbon number 1～30 or carbon number 2～30.
2. polyacetal resin composite as claimed in claim 1, wherein,
In the formula (1), alkyl of the R1 for carbon number 8～26,
Mixture of (B) composition for the R1 in the formula (1) different two or more hindered amine compounds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-243258 | 2013-11-25 | ||
| JP2013243258A JP6270432B2 (en) | 2013-11-25 | 2013-11-25 | Polyacetal resin composition |
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| Publication Number | Publication Date |
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| CN104650526A CN104650526A (en) | 2015-05-27 |
| CN104650526B true CN104650526B (en) | 2017-04-12 |
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| EP3378898B2 (en) * | 2015-12-07 | 2023-02-08 | Kaneka Corporation | Curable composition and cured product thereof |
| JP6951939B2 (en) * | 2017-10-24 | 2021-10-20 | 旭化成株式会社 | Polyacetal resin composition |
| JP6951938B2 (en) * | 2017-10-24 | 2021-10-20 | 旭化成株式会社 | Polyacetal resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101273073A (en) * | 2005-08-26 | 2008-09-24 | 巴斯夫欧洲公司 | Method for production of polyoxymethylene homo- or co-polymers |
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| JPH07233307A (en) * | 1994-02-24 | 1995-09-05 | Mitsubishi Gas Chem Co Inc | Polyacetal resin composition |
| JP3335252B2 (en) * | 1994-06-27 | 2002-10-15 | 三菱エンジニアリングプラスチックス株式会社 | Polyacetal resin composition |
| JP3578540B2 (en) * | 1996-02-19 | 2004-10-20 | 旭化成ケミカルズ株式会社 | Polyacetal resin composition with excellent aging properties |
| JP2001164087A (en) * | 1999-12-03 | 2001-06-19 | Polyplastics Co | Branched polyacetal resin composition |
| US7816433B2 (en) * | 2003-10-24 | 2010-10-19 | Asahi Kasei Chemicals Corporation | Polyacetal resin composition and article thereof |
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| CN101273073A (en) * | 2005-08-26 | 2008-09-24 | 巴斯夫欧洲公司 | Method for production of polyoxymethylene homo- or co-polymers |
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| CN104650526A (en) | 2015-05-27 |
| JP6270432B2 (en) | 2018-01-31 |
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