CN1412239A

CN1412239A - Polyacetal resin composition and production process

Info

Publication number: CN1412239A
Application number: CN 02144207
Authority: CN
Inventors: 原科初彦
Original assignee: Polyplastics Co Ltd
Current assignee: Polyplastics Co Ltd
Priority date: 2001-10-05
Filing date: 2002-10-08
Publication date: 2003-04-23
Anticipated expiration: 2022-10-08
Also published as: MY139543A; TWI235167B; JP3706567B2; JP2003113289A; CN1293142C; AU2002301311B2

Abstract

A polyacetal resin composition comprises, relative to 100 parts by weight of a polyacetal resin, 0.001 to 5 parts by weight of a hindered phenol-series compound, 0.001 to 20 parts by weight of a spiro-compound having a triazine ring, 0.01 to 10 parts by weight of a processing stabilizer, and 0.001 to 10 parts by weight of a heat stabilizer. The spiro-compound may be a compound represented by the following formula (I): wherein R1 and R2 are the same or different, each representing an alkylene group, an arylene group, or an aralkylene group. The polyacetal resin composition may further comprise a coloring agent. The polyacetal resin composition of the present invention realizes improvement in processing stability, and inhibition of formaldehyde emission without deteriorating an external appearance of a shaped article formed with the composition.

Description

Polyacetal resin composite and and production technique

Technical field

The present invention relates to a kind ofly have excellent working ability and stability and be subjected to press down the polyacetal resin composite that discharges (or generation) formaldehyde effectively its production method, and the moulding or the moulded parts that form by this resin combination.

Background technology

Polyacetal resin itself is because its chemical structure and unstable at high temperature or in acidity or alkaline environment under oxidizing atmosphere.Therefore, the basic demand that must satisfy polyacetal resin is in processing and forms in the process of moulded products and guarantee that high thermal stability and minimum formaldehyde discharge (or generation).If have low thermal stability, polyacetal resin treatment step as extrude or moulding process in its polymkeric substance of decomposes, the result forms on mould or generates settling (mold deposit), so mouldability, mechanical property and other degradation.Decomposing the formaldehyde that produces by polyacetal resin is chemically active and is oxidized to formic acid easily, this thermotolerance to resin has a negative impact, and cause corrosion or its variable color of metallic contact during as electric or electronic unit because of organic sediments at this resin, cause contact fault.In addition, formaldehyde itself pollutes the Working environment of parts assembling and the ecology of the finished product application places.

Therefore, in order to stablize polyacetal resin, antioxidant or other stablizer have been used.As the oxygenant that adds polyacetal resin, known have sterically hindered (benzene) phenol series (phenols) compound (sterically hindered phenol), has sterically hindered amine compound (bulky amine), and other.As other stablizer, used polymeric amide, alkali metal hydroxide, alkaline earth metal hydroxides, and other.In addition, antioxidant generally is used in combination with other stablizer.Even but using this additive, polyacetal resin is difficult to produce high stability.

Japanese Patent publication No.14709/1992 (JP-4-14709B) discloses a kind of polyacetal resin composite, wherein polyacetal resin and bulky amine series antioxidant, static inhibitor and guanamines derivative are as 3, and [2-(3 for 9-two, 5-diamino-2,4, the 6-triazinyl) ethyl]-2,4,8,10-four oxaspiros [5.5] undecane (CTU guanamines) blend is to improve thermostability and to improve the variable color tendency that is caused by tape.In the document,, use bulky amine series antioxidant to substitute conventional sterically hindered phenol series (phenols) antioxidant in order to reduce the variable color of polyacetal resin.Said composition is improved the changeable colour tendency, but the thermostability of said composition is improved deficiency.

Japanese patent application is examined the polyacetal resin composite that open No.190248/1987 (JP-62-190248A) discloses a kind of stabilization, wherein polyacetal resin with as guanamines derivative (as the benzoguanamine) blend of stablizer to reduce formaldehyde odor and to improve its mouldability.Amount is big, and the stability improvement deficiency of resin combination but the formaldehyde of this resin combination discharges (or generation).

In addition, the use of benzoguanamine in these resin combinations produces settling (mold deposit) on mould in molding step, and the gained moulded products does not have enough bleeds (bleeding out).

Summary of the invention

Therefore, an object of the present invention is to provide polyacetal resin composite with excellent stability, especially a kind ofly in molding (processing) step, prevent degradation or aged polyacetal resin composite, and production technique, and the moulded products of making or forming by this polyacetal resin composite.

Another object of the present invention provides a kind of polyacetal resin composite that helps obviously to suppress formaldehyde release under low add-on and can improve surrounding environment, and production method, and by its moulded products that is molded as.

Even providing a kind of inhibition formaldehyde that also is fit under severe condition, a further object of the present invention discharges to suppress deposition and the frosting of these products from moulded products or the thermal metamorphism of bleed and these goods of degradation production on mould, thereby help to improve the polyacetal resin composite of the mouldability of this moulded products, and production method.

The present inventor furtherd investigate a series of nitrogenous compounds as the stablizer of polyacetal resin to realize above-mentioned purpose, and final the discovery, sterically hindered phenol series (phenols) compound, being used in combination of specific spirocyclic compound and processing stabilizers and/or thermo-stabilizer produces the formaldehyde release that significantly also can greatly improve this polyacetal resin as function of stabilizer to polyacetal resin.The present invention finishes on the basis of above discovery.

That is, polyacetal resin composite of the present invention comprises (containing) polyacetal resin, and sterically hindered phenol series (phenols) compound has the spirocyclic compound of triazine ring and is selected from processing stabilizers and at least a material of thermo-stabilizer.Spirocyclic compound can have two guanamines rings as its end group.For example, spirocyclic compound can be the compound that is expressed as following structural formula (1):

R wherein ¹And R ²Identical or different, represent alkylidene group respectively, arylene group, or inferior aromatic alkyl group.

Polyacetal resin composite can comprise, relative 100 weight part polyacetal resins, about 0.001-5 weight part sterically hindered phenol series compound, about 0.001-20 weight part spirocyclic compound, about 0.01-10 weight part processing stabilizers and about 0.001-10 weight part thermo-stabilizer.Polyacetal resin composite also can comprise tinting material (colorant), and other.

In technology of the present invention, polyacetal resin composite is by mixing polyacetal resin, and the sterically hindered phenol series compound has the spirocyclic compound of triazine ring and is selected from processing stabilizers and at least a material of thermo-stabilizer and making.In addition, the present invention includes a kind of moulding or moulded parts that comprises this polyacetal resin composite.

Resin combination of the present invention comprises (containing) polyacetal resin, and the sterically hindered phenol series compound has the spirocyclic compound of triazine ring and is selected from processing stabilizers and at least a material of thermo-stabilizer (especially processing stabilizers and thermo-stabilizer).

(polyacetal resin)

Polyacetal resin is a kind of oxygen methylene group (CH that comprises ₂O-) as the unitary macromolecular cpd of main composition and comprise that polyacetal homopolymer is (as, trade(brand)name " Delrin ", by DuPont, Americanized; Trade(brand)name " Tenac 4010 " is by Asahi Kasei Corp.; Deng manufacturing) and comprise at least a other comonomer unit and the unitary Copolyacetal of oxygen methylene (as trade(brand)name " Duracon ", by Polyplastics Co., Ltd. makes).About these multipolymers, comonomer unit comprises the oxygen base alkylidene unit of about 2-6 carbon atom (preferably about 2-4 carbon atom), for example, and oxygen ethylidene (oxyethylene group) (CH ₂CH ₂O-), oxygen propylidene and oxygen tetramethylene unit.The monomeric ratio of these comonomers can be less and can be selected from about 0.01-20 mole %, preferably about 0.03-10 mole % (as 0.05-9 mole %) and the scope of 0.1-8 mole % more preferably from about, whole relatively polyacetal resin.

Copolyacetal can for example be the multipolymer that comprises two kinds of components, comprises the ter-polymers of three kinds of components, or the like.Copolyacetal also can be a random copolymers, segmented copolymer (as, Japanese Patent publication No.24307/1990 (JP2-24307B) is made trade(brand)name " Tenac LA ", " Tenac LM " by AsahiKasei Corp.), or graft copolymer.In addition, polyacetal resin can be linearity (or straight) or branching and can have crosslinking structure.In addition, the end group of polyacetal resin can by with carboxylic acid such as acetate and propionic acid, or the esterification of its acid anhydrides and stabilization.Be not particularly limited the polymerization degree, the degree of branching or degree of crosslinking, as long as it is the fusable links molding.Be not particularly limited the molecular weight of this polyacetal resin, and for example, weight average molecular weight is about 5000-500000, preferably about 10000-400000.

Polyacetal resin can be by polymerization aldehyde such as formaldehyde, PARA FORMALDEHYDE PRILLS(91,95), and acetaldehyde; Or cyclic ether or cyclic formal such as trioxane, ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min., cyclohexene oxide, 1,3-dioxolane, glycol ether methylal and 1,4-butanediol methylal and making.In addition, but component as copolymerization, can use the alkyl or aryl glycidyl ether (as, the methyl glycidyl ether, ethyl glycidyl ether, phenylglycidyl ether, naphthyl glycidyl ether), alkylidene group or polyoxy aklylene glycol diglycidyl ether (as, the ethylene glycol bisthioglycolate glycidyl ether, triglycol diglycidyl ether, butanediol diglycidyl ether), alkyl or aryl glycidyl alcohol, cyclic ester (as, beta-propiolactone), or vinyl compound (as, vinylbenzene, vinyl ether).

(sterically hindered phenol series compound)

The sterically hindered phenol series compound comprises conventional phenol series antioxidant, for example, monocycle shape sterically hindered phenolic compound (as, 2,6-two-t (uncle)-butyl-p-cresols), wherein encircle by hydrocarbyl group or the group that comprises sulphur atom interconnect or many rings sterically hindered phenolic compound of keyed jointing [as, C _1-10Alkylidene group-two to four (t-butylphenols) as 2,2 '-methylene radical two (4-methyl-6-t-butylphenol), 4,4 '-methylene radical two (2,6-two-t-butylphenol) and 1,1,3-three (2-methyl-4-hydroxyl-5-t-butyl phenyl) butane; C _2-10Alkylene group or alkadienylene two to four (t-butylphenol) are as 4, and 4 '-Ding pitches base two (3-methyl-6-t-butylphenol); C _6-20Arylidene or inferior aralkyl-two to four (t-butylphenols) as 1,3,5-trimethylammonium-2,4,6-three (3,5-two-t-butyl-4-hydroxybenzyl) benzene; Wherein t-butylphenol group interconnects by the group with sulphur atom or two (t-butylphenols) of keyed jointing, for example, 4,4 '-sulfo-two (3-methyl-6-t-butylphenol)], have ester group or amide group sterically hindered phenolic compound [as, have C _2-10The t-butylphenol of alkylidene group ketonic oxygen base group, for example 3-(4 '-hydroxyl-3 ', 5 '-two-t-butyl phenyl) propionic acid Octadecane base ester and 2-(4 '-hydroxyl-3 ', 5 '-two-t-butyl phenyl) propionic acid Octadecane base ester; Wherein the polyol ester of t-butylphenol group by lipid acid interconnects or two to four (t-butylphenols) of keyed jointing, for example 1, [3-(3 for 6-hexane diol-two, 5-two-t-butyl-4-hydroxy phenyl) propionic ester], triglycol-two [3-(3-t-butyl-5-methyl-4-hydroxy phenyl) propionic ester] and tetramethylolmethane four [3-(3,5-two-t-butyl-4-hydroxy phenyl) propionic ester]; Have heterocyclic group and C _2-10Two to four (t-butylphenols) of alkylidene group ketonic oxygen base group, for example 3,9-two [2-{3-(3-t-butyl-4-hydroxy-5-methyl base phenyl) propionyl oxygen base)-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane; Has C _3-10The t-alkylphenol of alkenyl carbonyl oxygen base group (as, the t-butylphenol, the t-amyl phenol), for example 2-t-butyl-6-(3 '-t-butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate and 2-[1-(2-hydroxyl-3,5-two-t-amyl group phenyl) ethyl]-4,6-two-t-amyl group phenyl acrylate; Sterically hindered phenolic compound with phosphonate groups, 4-hydroxybenzyl phosphonic acids two Octadecane bases-3 for example, 5-two-t-butyl ester; Sterically hindered phenolic compound with amide group, N for example, N '-hexa-methylene two (3,5-two-t-butyl-4-hydroxyl-dihydro cinnamon acid amides)], and other.Wherein, () oxybenzene compound especially, a plurality of t-butyl group, especially, the compound with a plurality of t-butylphenols position is preferred to have the t-butyl group.Especially, wherein the polyol ester of t-butylphenol group by lipid acid interconnects or two to four (one to four t-butylphenols) of keyed jointing, and especially, wherein t-butylphenol group passes through C _2-10Lipid acid (especially, C _2-6Lipid acid) two-interconnect or two to four (single or two t-butylphenols) of keyed jointing are preferred to four-pure ester group.

The sterically hindered phenol series compound can separately or be used in combination.

(spirocyclic compound) with triazine ring

Spirocyclic compound with triazine ring only is required to be the compound that has triazine ring on its side chain.Be not particularly limited the number of triazine ring.The preferred number of triazine ring is about 1-4, preferably about 1-2 (especially 2).Especially, preferred compound is that wherein two triazine rings interconnect by spirocyclic compound (that is, having the compound of two triazine rings as the spirocyclic compound end group) or keyed jointing the sort of.

Triazine ring comprises 1,2,3-triazine, 1,2,4-triazine and 1,3,5-triazines.Wherein, 1,3,5-triazines is preferred.In addition, triazine ring can have substituting group such as alkyl (as, C _1-4Alkyl), aryl, amino or the amino group that replaces.As triazine ring, the amino group with amino group or replacement is as substituent 1,3,5-triazines ring, and especially the guanamines ring is preferred.

Although volution part can be the volution that only is made of carbon atom, comprising heteroatoms (especially, Sauerstoffatom) is preferred as the volution of the composed atom of ring.This spirocyclic compound comprises having the spirocyclic compound of two guanamines rings as its end group, is expressed as following structural formula (1):

In said structure formula (1), be expressed as radicals R ¹And R ²Alkylidene group comprise straight or branched C _1-10Alkylidene group, for example methylene radical, ethylidene, propylidene, isopropylidene, butylidene and isobutylene group.Arylene group comprises C _6-10Arylene group such as phenylene and naphthylidene group.Inferior aromatic alkyl group comprises and connects or be keyed to group on the alkylidene group with arylene group, and is expressed as structural formula-R ³-Ar-, wherein R ³Expression alkylidene group and Ar represent arylene group.Preferred radicals R ¹And R ²Be that alkylidene group is (as C _1-6Alkylidene group), C especially _1-3Alkylidene group (as the ethylidene group), and other.In addition, radicals R ¹And R ²The substituting group that can have other, for example C _1-4Alkyl group such as methyl group, phenyl group, amino group, the amino group that N-replaces.

The example of these spirocyclic compounds is 3,9-two [(3,5-diamino-2,4,6-triazinyl) C _1-6Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane (that is, and 3,9-two [(3,5-diamino-2,4,6-triazinyl) C _1-6Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane) as 3,9-two [2-(3,5-diamino-2,4,6-triazinyl) ethyl]-2,4,8,10-four oxaspiros [5.5] undecane (CTU guanamines), 3,9-two [1-(3,5-diamino-2,4,6-triazinyl) methyl]-2,4,8,10-four oxaspiros [5.5] undecane (CMTU guanamines), 3,9-two [2-(3,5-diamino-2,4,6-triazinyl)-2-methylethyl]-2,4,8,10-four oxaspiros [5.5] undecane, 3,9-two [1-(3,5-diamino-2,4,6-triazinyl)-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane, 3, and 9-two [3-(3,5-diamino-2,4, the 6-triazinyl)-1,1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3, and 9-two [3-(3,5-diamino-2,4, the 6-triazinyl)-2, the 2-dimethyl propyl]-2,4,5,10-four oxaspiros [5.5] undecane.In spirocyclic compound, 3,9-two [(3,5-diamino-2,4,6-triazinyl) straight or branched C _1-5Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane, for example, and the CTU guanamines, the CMTU guanamines, 3,9-two [3-(3,5-diamino-2,4,6-triazinyl)-1,1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane is preferred.Especially, the CTU guanamines is preferred.

Spirocyclic compound can be the compound (hydrated compound) that comprises crystal water or (crystallization) hydrate, or anhydrous compound.Consider the dispersiveness of spirocyclic compound in polyacetal resin, the preferred especially spirocyclic compound that comprises crystal water that uses.Spirocyclic compound has the crystal water of (comprising) 0.1-3 molecule usually, the spirocyclic compound of relative 1 molecule.

These spirocyclic compounds can by a kind of dintrile that will have four oxa-volutions and Dyhard RU 100 in the presence of the basic catalyst in the serial organic solvent of alcohol the technology of reaction (Japanese patent application is examined open No.32664/1993 (JP-5-32664A)) under high pressure, by a kind of they are made or make in the method (Japanese Patent publication No.8676/1969 (JP-44-8676B)) of reacting in ether series organic solvent in the presence of the basic catalyst with by other technology.

In this reaction of dintrile with four oxa-volutions and Dyhard RU 100, also can generate and have nitrile group as an one end group and guanamines ring spirocyclic compound as another end group.Have nitrile group and comprise 3-(cyano group alkyl)-9-[(3,5-diamino-2,4,6-triazinyl as the spirocyclic compound of another end group as an one end group and guanamines ring) alkyl]-2,4,8,10-four oxaspiros [5.5] undecane [for example, 3-(cyano group C _1-6Alkyl)-and 9-[(3,5-diamino-2,4,6-triazinyl) C _1-6Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane such as 3-(2-cyano ethyl)-9-[2-(3,5-diamino-2,4, the 6-triazinyl) ethyl]-2,4,8,10-four oxaspiros [5.5] undecane (the single guanamines of CTU), and 3-(1-cyano methyl)-9-[1-(3,5-diamino-2,4, the 6-triazinyl) methyl]-2,4,8,10-four oxaspiros [5.5] undecane (the single guanamines of CMTU), (2-cyano group-2-methylethyl)-(2-(3 for 9-for 3-, 5-diamino-2,4, the 6-triazinyl)-the 2-methylethyl]-2,4,8,10-four oxaspiros [5.5] undecane, 3-(1-cyano group-1,1-dimethyl methyl)-9-[3-(3,5-diamino-2,4, the 6-triazinyl)-1,1-dimethyl methyl]-2,4,8,10-four oxaspiros [5.5] undecane, 3-(3-cyano group-2,2-dimethyl propyl)-9-[3-(3,5-diamino-2.4, the 6-triazinyl)-2,2-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3-(3-cyano group-1,1-dimethyl propyl)-9-[3-(3,5-diamino-2,4, the 6-triazinyl)-1,1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane].In these spirocyclic compounds, 3-(cyano group straight or branched C _1-5Alkyl)-and 9-[(3,5-diamino-2,4,6-triazinyl) straight or branched C _1-5Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane, for example, the single guanamines of CTU, the single guanamines of CMTU and 3-(3-cyano group-1,1-dimethyl propyl)-9-[3-(3,5-diamino-2,4, the 6-triazinyl)-1, the 1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane is preferred and the single guanamines of CTU is especially preferred.

In addition, spirocyclic compound of the present invention comprises having the spirocyclic compound (as guanamines ring) of triazine ring as an one end group, and has triazine ring as the spirocyclic compound of an one end group with have the mixture of two triazine rings (as the guanamines ring) as the spirocyclic compound of two end group.

Wherein, comprise at least that to have two guanamines rings be preferred as the spirocyclic compound of the spirocyclic compound of its end group.For example, spirocyclic compound can be to comprise (containing) 3,9-two [(3,5-diamino-2,4, the 6-triazinyl) alkyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3-(cyano group alkyl)-9-[(3,5-diamino-2,4, the 6-triazinyl) alkyl]-2,4,8,10-four oxaspiros [5.5] are undecanoic the sort of, especially comprise 3, and 9-two [(3,5-diamino-2,4, the 6-triazinyl) C _1-6Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3-(cyano group C _1-6Alkyl)-and 9-[(3,5-diamino-2,4,6-triazinyl) C _1-6Alkyl)-2,4,8,10-four oxaspiros [5.5] are undecanoic the sort of.

(processing stabilizers)

Processing stabilizers comprises at least a following material that is selected from: (a) length-chain or higher fatty acid or derivatives thereof, and (b) polyoxyalkylene glycol, (c) silicone compounds, and other.

(a) length-chain or higher fatty acid or derivatives thereof

Higher fatty acid can be saturated fatty acid or unsaturated fatty acids.In addition, a part of hydrogen atom in the higher fatty acid can be substituted the base replace as oh group.These higher fatty acid are for example for having the list that is not less than 10 carbon atoms-or two-carboxylic lipid acid, for example, have saturated mono-carboxylic lipid acid of being not less than 10 carbon atoms [as, saturated C _10-34Lipid acid (preferred saturated C _10-30Lipid acid), lauric acid, tetradecanoic acid, pentadecyl acid, palmitinic acid, stearic acid, eicosanoic acid, behenic acid and montanic acid as capric acid], have unsaturated list-carboxylic lipid acid of being not less than 10 carbon atoms [as, unsaturated C _10-34Lipid acid (preferred unsaturated C _10-30Lipid acid), linolic acid, linolenic acid, arachidonic acid and erucic acid as oleic acid], have two-carboxylic lipid acid (two alkaline fat acid) of being not less than 10 carbon atoms [as, saturated dicarboxyl C _10-30Lipid acid (preferred saturated two-carboxylic C _10-20Lipid acid) as sebacic acid, dodecanedioic acid, 14 carbon diacid and thapsic acid (thapsic acid); And unsaturated two-carboxylic C _10-30Lipid acid (preferred unsaturated two-carboxylic C _10-20Lipid acid) as nonene diacid and decene dicarboxylic acid].Lipid acid can separately or be used in combination.Lipid acid is also included within molecule and has the sort of (as, the saturated C of hydroxyl of one or more oh groups _10-26Lipid acid such as 12-oxystearic acid).

The derivative of higher fatty acid comprises fatty acid ester, fatty acid amide, and other.As for high-grade aliphatic ester, be not particularly limited its structure, and can use the ester of straight or branched chain fatty acids.As high-grade aliphatic ester, for example can mention, the ester of above-mentioned higher fatty acid and alcohol (as, have the ester of one or more ester bonds, as monoesters, diester, three esters and four esters).Be not particularly limited the alcohol that constitutes high-grade aliphatic ester, and preferred alcohol is polyvalent alcohol.Polyvalent alcohol comprises have about 2-8 carbon atom polyvalent alcohol or its polymkeric substance of (preferably about 2-6 carbon atom), and for example glycol such as aklylene glycol are [as, C _2-8Aklylene glycol (preferred C _2-6Aklylene glycol) as ethylene glycol, glycol ether and propylene glycol]; Triol such as glycerine, TriMethylolPropane(TMP), or derivatives thereof; Tetrol such as tetramethylolmethane, anhydro sorbitol, or derivatives thereof; And polyvalent alcohol all or multipolymer [as, poly suboxygen alkyl (second) glycol such as polyoxyethylene glycol and polypropylene glycol, Polyglycerine, Dipentaerythritol and polypentaerythritol all or multipolymer].The mean polymerisation degree of polyalkylene glycol is to be not less than 2 (as, about 2-500), preferably about 2-400 (as, about 2-300), and preferred mean polymerisation degree is not less than 16 (as, about 20-200).These polyalkylene glycols preferably with have 12 or use during the esterification of the lipid acid of more carbon atoms.Preferred polyhydric alcohols is that mean polymerisation degree is not less than 2 polyalkylene glycol.Polyvalent alcohol can separately or be used in combination.

The example of these esters of higher fatty acid is single-or the glycol ester of two-palmitinic acid, single-or two-stearic glycol ester, single-or the glycol ester of two-behenic acid, single-or the glycol ester of two-montanic acid, single-to the glyceryl ester of three-palmitinic acid, single-to three stearic glyceryl ester, single-to the glyceryl ester of three-behenic acid, single-to the glyceryl ester of three-montanic acid, single-to the pentaerythritol ester of four-palmitinic acid, single-to four-stearic pentaerythritol ester, single-to the pentaerythritol ester of four-behenic acid, single-to the pentaerythritol ester of four-montanic acid, three stearic polyglycerol esters, the trihydroxymethylpropanyl ester of single palmitinic acid, the pentaerythritol ester of single undecyl acid, the Isosorbide Dinitrate of Stearinsaeure, and the mono-laurate of polyalkylene glycol (as polyoxyethylene glycol and polypropylene glycol), monopalmitate, monostearate, single elm acid esters, single montanate, dilaurate, dipalmitate, SUNSOFT Q-182S, two elm acid esters, two montanates, dioleate and dilinoleic acid ester.

The fatty acid amide that uses comprises higher fatty acid (single-or two-carboxylic higher fatty acid) and amine such as monoamine, the sour acid amides of diamines and polyamine (as, monoamide and diamide).As monoamide, for example can mention the primary acid acid amides of saturated fatty acid (as capric acid acidamide, lauric amide, tetradecanoic acid acid amides, palmitic amide, stearic amide, eicosanoic acid acid amides, behenic acid acid amides and montanic acid acid amides); The primary acid acid amides (as amine hydroxybenzene) of unsaturated fatty acids; Para-acid acid amides (as stearylstearic amide and stearyl amine hydroxybenzene) with saturated and/or unsaturated fatty acids and monoamine.Preferred fatty acid amide is a diamide.Diamide comprises lipid acid and C _1-6Alkylenediamine (especially, C _1-2Alkylenediamine) diamide, ethylene diamine-two palmitic amide for example particularly, ethylene diamine-distearyl acid acid amides (ethylene stearyl acid amides), hexamethylene-diamine distearyl acid acid amides, ethylene diamine-two behenic acid acid amides, ethylene diamine-two montanic acid acid amides, ethylene diamine-two amine hydroxybenzene and ethylene diamine-two erucicamides.In addition, also can use the different material of carboxyl groups wherein to be keyed to diamide on the amine position of Alkylenediamine, for example ethylene diamine-(stearic amide) amine hydroxybenzene respectively.In sour acid amides, be included in the lipid acid saturated fatty acid preferably in the sour acid amides.

The higher fatty acid or derivatives thereof can separately or be used in combination.

(b) poly suboxygen alkyl (second) glycol (Polyoxyalkylene glycol)

The example of poly suboxygen alkyl (second) glycol is that aklylene glycol is [as, C _1-6Aklylene glycol (preferred C _2-4Aklylene glycol), propylene glycol and tetramethylene glycol as ethylene glycol] homopolymer, the derivative of its multipolymer and homopolymer or multipolymer.Particularly, the poly suboxygen alkyl glycol comprises poly-C _2-6Oxyalkylene glycol (preferably poly-C _2-4The oxyalkylene glycol) as polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol; And multipolymer such as poloxalkol (as, random or segmented copolymer), polyoxyethylene polyoxypropylene glycidyl ether copolymer and polyoxyethylene polyoxypropylene monobutyl ether multipolymer.Preferred poly suboxygen alkyl glycol comprises the polymkeric substance with oxygen ethylene unit, for example, and polyoxyethylene glycol, poloxalkol and its derivative.In addition, the number-average molecular weight of poly suboxygen alkyl glycol is about 3 * 10 ²-1 * 10 ⁶(as, about 5 * 10 ²-5 * 10 ⁵) and preferred about 1 * 10 ³-1 * 10 ⁵(as, about 1 * 10 ³-5 * 10 ⁴).

The poly suboxygen alkyl glycol can separately or be used in combination.

(c) silicone compounds

The example of siloxane series compound is an organopolysiloxane.Organopolysiloxane can be dialkylsiloxane (as a dimethyl siloxane), the alkylaryl siloxanes (as, methylphenyl siloxane), the homopolymer of diaromatic siloxane (as, diphenyl siloxane) or analogue, for example, polydimethylsiloxane, polyphenyl methyl siloxane and its multipolymer.Organopolysiloxane can be an oligopolymer.In addition; as organopolysiloxane; also can mention molecule (as; the siloxanes of modification) has substituting group such as epoxy in a end or the main chain, hydroxyl, alkoxyl group; carboxyl; amino or replace amino group (as dialkyl amino group), or ether, the organopolysiloxane of the modification of vinyl or (methyl) acryl group.The siloxane series compound can separately or be used in combination.

(thermo-stabilizer)

Thermo-stabilizer comprises (a) basic nitrogen compound, (b) phosphine compound, (c) metal-salt of organic carboxyl acid, (d) alkalescence or alkaline earth metal compound, (e) hydrotalcite and (f) zeolite.

(a) basic nitrogen compound

Above-mentioned basic nitrogen compound can be low molecular compound or macromolecular compound (resinamines).Nitrogenous low-molecular weight compound for example comprises, aliphatic amine (as, monoethanolamine, diethanolamine), aromatic amine (as, the aromatics second month in a season or tertiary amine such as o-, m-, p-(adjacent-, between-, right-) Tolylamine, o-, m-, the p-phenylenediamine, o-, m-, p-benzaminic acid and ethyl o-, m-, the p-Aminobenzoate), amide compound (as, poly carboxylic acid acid amides such as Malonamide and isophthaloyl amine, o-, m-, p-aminobenzamide), the hydrazine or derivatives thereof is [as hydrazine, hydrazone and hydrazides such as poly carboxylic acid hydrazides (as, adipic dihydrazide, sebacic dihydrazide, dodecanedioic acid two hydrazides, isophthalic dihydrazide], the polyamino triazine [as guanamines, or derivatives thereof, as guanamines, acetoguanamine, benzoguanamine, amber guanamines, the fat guanamines, 1,3,6-three (3,5-diamino-2,4, the 6-triazinyl) hexane and phthalein guanamines, the melamine or derivatives thereof (as, melamine; The condenses of melamine,, melem, mellon as melam)], the uridylic or derivatives thereof (as, uridylic, uridine) and cytosine(Cyt) and its derivative (as, cytosine(Cyt), cytidine).The guanidine or derivatives thereof (as, non-annularity guanidine such as guanidine and dicyanodiamide; Ring-type guanidine such as creatinine), the urea or derivatives thereof [as, biuret, biurea, ethylidene-urea, acetylene urea, isobutyl are pitched basic two ureas, crotonylidene two ureas, the condenses of urea and formaldehyde, glycolylurea, the hydantoin derivatives of replacement (as, single or two C _1-4The compound of alkyl-replacement such as 1-methyl glycolylurea, 5-propyl group glycolylurea and 5,5-T10; The compound of aryl-replacement such as 5-phenyl glycolylurea and 5, the 5-diphenyl hydantoin; And the compound of alkylaryl-replacement such as 5-methyl-5-phenyl glycolylurea), wallantoin, the wallantoin derivative of replacement (as, single, two or three C _1-4The compound of alkyl-replacement, the compound that replaces with aryl), the metal-salt of wallantoin (as, with the salt of the metallic element of periodic table of elements 3B family, as wallantoin dihydroxyl aluminium, wallantoin monohydroxy aluminium and Nippon Kayaku)), the reaction product of wallantoin and aldehyde cpd (as, the adducts of wallantoin and formaldehyde), the compound of wallantoin and imidazolium compounds (as, d1-pyrrolidone carboxylic acid wallantoin sodium), organic acid salt, and other].

Resinamines for example comprise, aminoresin (condensation resins such as the guanamine resin that can obtain by reaction with formaldehyde, melamine resin and guanidine resin, with cocondensation resin such as phenol-melamine resin, benzoguanamine-melamine resin and aromatics polyamine-melamine resin), aromatic amine-formaldehyde resin (aniline resin etc.), polyamide resin (as, the polymeric amide of homopolymerization or copolymerization such as nylon 3 (poly-Beta-alanine), nylon 46, nylon 6, nylon 66, Ni Long11, nylon 12, nylon MXD 6, nylon 6-10, nylon 6-11, nylon 6-12 and nylon 6-66-610, the polymeric amide that comprises the replacement of methylol or alkoxy methyl group, Deng), polyesteramide, polyamidoimide, urethane, poly-(methyl) acrylamide, the multipolymer of (methyl) acrylamide and other vinyl monomer, poly-(vinyl lactam), the multipolymer of vinyl lactam and other vinyl monomer [as, be described in Japanese patent application and do not examine open No.52338/1980 (JP-55-52338A), homopolymerization or the multipolymer of US patent No.3204014], poly-(N-vinyl carboxylic acid acid amides), the multipolymer of N-vinyl carboxylic acid acid amides and other vinyl monomer [as, be described in Japanese patent application and do not examine open No.247745/2001 (JP-2001-247745A), Japanese patent application is not examined open No.131386/2001 (JP-2001-131386A), Japanese patent application is not examined open No.311302/1996 (JP-8-311302A), Japanese patent application is not examined open No.86614/1984 (JP-59-86614A), US patent No.5455042, homopolymerization or the multipolymer of US patent No.5407996 or US patent No.5338815, trade(brand)name " Noniolex " or " Cleatech " are made by Showa Denko K.K.].

Basic nitrogen compound can independently or be used in combination.

Preferred nitrogenous compound comprise guanamines (as, the fat guanamines), melamine or derivatives thereof [especially melamine or melamine condensates (as melam and melem)], guanidine derivative (as Dyhard RU 100 and creatinine), urea derivatives [as, biurea, the condenses of urea and formaldehyde, the metal-salt of wallantoin and wallantoin (as wallantoin dihydroxyl aluminium)], resinamines [as, aminoresin (aminoresin such as melamine resin and melamine-formaldehyde resin; Crosslinked aminoresin such as crosslinked melamine resin), polyamide resin, poly-(methyl) acrylamide, poly-(N-vinyl carboxylic acid acid amides) and poly-(vinyl lactam)].

(b) phosphine compound

As phosphine compound, can mention that phosphine compound such as alkylphosphines are (as, three C _1-10Alkylphosphines such as triethyl phosphine, tripropyl phosphine and tributylphosphine), the cycloalkyl phosphine (as, three C _5-12Cycloalkyl phosphine such as tricyclohexyl phosphine), aryl phosphine (as, three C _6-12Aryl phosphine such as triphenylphosphine, p-tolyl diphenylphosphine, two-p-tolyl Phenylphosphine, three-m-aminophenyl phosphine, three-2, the 4-dimethylphenylphosphine, three-2,4,6-trimethylphenyl phosphine, three-o-tolylphosphine, three-m-tolylphosphine and three-p-tolylphosphine), alkyl aryl phosphine (as, three C _6-12Aryl C _1-4Alkylphosphines is as three-o-anisyl phosphine and three-p-anisyl phosphine), the aromatic yl alkenyl phosphine (as, two C _6-12Aryl C _2-10Alkenyl phosphine such as diphenylacetylene phosphine and allyl group diphenylphosphine), the aryl alkyl aryl phosphine (as, two C _6-12Aryl C _6-12Alkyl aryl phosphine such as p-anisyl diphenylphosphine, and C _6-12Aryl two C _6-12Aryl C _1-4Alkylphosphines is as two-p-anisyl Phenylphosphine), the alkylaryl alkyl aryl phosphine (as, C _1-10Alkyl C _6-12Aryl C _6-12Aryl C _1-4And diphosphine [for example, two (two C alkylphosphines such as aminomethyl phenyl-p-anisyl phosphine), _6-12The aryl phosphino-) C _1-10Alkane is as 1,4-two (diphenylphosphino) butane].Phosphine compound can separately or be used in combination.

(c) metal-salt of organic carboxyl acid

The metal-salt of organic carboxyl acid comprise organic carboxyl acid and metal (as, basic metal such as Na and K; Alkaline-earth metal such as Mg and Ca; With transition metal such as Zn) salt.

Above-mentioned organic carboxyl acid can be low-molecular-weight compound or high-molecular weight compound.As organic carboxyl acid,, can use to have the saturated or unsaturated lower alphatic carboxylic acid that is lower than 10 carbon atoms and the polymkeric substance of unsaturated aliphatic carboxylic acid except the saturated or unsaturated higher aliphatic carboxylic acid that in the higher fatty acid item, exemplifies.In addition, aliphatic carboxylic acid can have oh group.Saturated lower alphatic carboxylic acid comprises saturated C _1-9Monocarboxylic acid (as, acetate, propionic acid, butyric acid, isopropylformic acid, valeric acid, isovaleric acid, PIVALIC ACID CRUDE (25), caproic acid, sad), saturated C _2-9Dicarboxylic acid (as, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, cork acid, nonane diacid) and its oxygen acid (as, oxyacetic acid, lactic acid, R-Glyceric acid, hydroxybutyric acid, citric acid).

Unsaturated lower alphatic carboxylic acid comprises unsaturated C _3-9Monocarboxylic acid [as, (methyl) vinylformic acid, Ba Dousuan, iso-crotonic acid], unsaturated C _4-9Dicarboxylic acid (as, toxilic acid, fumaric acid) and its oxygen acid (as, propynoic acid).

In addition, the example of the polymkeric substance of unsaturated aliphatic carboxylic acid is polymerizable unsaturated carboxylic acid [α, β-ethene-type (olefinic) unsaturated carboxylic acid, polymerizable unsaturated monocarboxylic (as (methyl) vinylformic acid) for example, and the unsaturated poly carboxylic acid of polymerizable (as methylene-succinic acid, toxilic acid, fumaric acid), polycarboxylic acid anhydrides, polycarboxylic monoesters (as, polycarboxylic single C _1-10Alkyl ester such as toxilic acid list ethyl ester), and other] and alkene (as, α-C _2-10Alkene such as ethene and propylene) multipolymer.

The metal-salt of organic carboxyl acid can separately or be used in combination.

The preferred metal-salt of organic carboxyl acid be organic carboxyl acid and alkaline-earth metal salt (as, lime acetate, citrate of lime, calcium stearate, Magnesium Stearate and 12-oxystearic acid calcium), from polyimide precursor resin (wherein be included in the multipolymer of unsaturated poly carboxylic acid of polymerizable and alkene at least a portion carboxylic group by the ion of above-mentioned metal institute neutral resin), and other.For example can be used as ACLYN (making) from polyimide precursor resin, Himilan (by DuPont-Mitsui Polychemicals Co., Ltd. makes), Surlyn (making) and other and buy by Du Pont by Allied Signal Inc..

(d) alkalescence or alkaline earth metal compound

Alkalescence or alkaline earth metal compound comprise mineral compound for example metal oxide (as CaO, MgO), metal hydroxides is (as Ca (OH) ₂, Mg (OH) ₂), and the salt of mineral acid and metal is [as, the salt of mineral acid (as the salt of carbonic acid and metal (as Na ₂CO ₃, K ₂CO ₃, CaCO ₃And MgCO ₃), borate, phosphoric acid salt)].Especially, metal oxide and metal hydroxides are preferred.In these compounds, alkaline earth metal compound is preferred.

Alkalescence or alkaline earth metal compound can separately or be used in combination.

(e) hydrotalcite

As hydrotalcite, can use the hydrotalcite of examining narration among open No.1241/1985 (JP-60-1241A) and the careful open No.59475/1997 (JP-9-59475A) of Japanese patent application at Japanese patent application, as be expressed as the hydrotalcite compound of following structural formula.

[N ²⁺ _1-xM ³⁺ _x(OH) ₂] ^x+[A ^n- _x/n·mH ₂O] ^x-

In structural formula, M ²⁺Expression Mg ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺Or any other divalent-metal ion; M ³⁺Expression Al ³⁺, Fe ³⁺, Cr ³⁺, or any other trivalent metal ion; A ^N-Expression CO ₃ ^2-, OH ^-, HPO ₄ ^2-, SO ₄ ^2-, or any other n-valency negatively charged ion (especially, unit price or dianion); X is 0＜x＜0.5; With m be 0≤m＜1.Hydrotalcite can separately or be used in combination.

Incidentally, hydrotalcite can trade(brand)name " DHT-4A ", ' DHT-4A-2 ", or " Alcamizer " derives from Kyowa Chemical Indus try Co., Ltd..

(f) zeolite

Although be not particularly limited zeolite, but can use those zeolites of non-H-type, [its minimum structure cell is the zeolite (A-with crystal aluminosilicate of alkalescence and/or alkaline-earth metal as examining the zeolite of narrating among the open No.62142/1995 (JP-7-62142A) at Japanese patent application, X-, Y-, L-and ZSM-type zeolite, mordenite type zeolite; Chabazite, mordenite, faujusite and other the zeolite that generates naturally)].

Zeolite can separately or be used in combination.

Incidentally, A-type zeolite can trade(brand)name " Zeolam A-3 ", " Zeolam A-4 ", or " Zeolam A-5 ", and X-type zeolite derives from Tosoh Corp with trade(brand)name " Zeolam F-9 " and Y-type zeolite with trade(brand)name " HSZ-320NAA ".

Thermo-stabilizer can separately or be used in combination.By with at least a phosphine compound that is selected from, the metal-salt of organic carboxyl acid, alkalescence or alkaline earth metal compound, the material of hydrotalcite and zeolite is used in combination with basic nitrogen compound, also can give polyacetal resin with thermostability, even the add-on of thermo-stabilizer is little.

(ratio of every kind of component or ratio)

In resin combination of the present invention, the ratio or the ratio of sterically hindered phenol series compound be, relative 100 weight part polyacetal resins, about 0.001-5 weight part, preferably about 0.005-3 weight part and 0.01-1 weight part more preferably from about.

The ratio or the ratio of spirocyclic compound be, relative 100 weight part polyacetal resins, about 0.001-20 weight part, preferably about 0.01-10 weight part and 0.03-5 weight part more preferably from about.

The ratio or the ratio of above-mentioned processing stabilizers be, relative 100 weight part polyacetal resins, and about 0.01-10 weight part, preferably about 0.03-5 weight part (as, about 0.05-3 weight part) and especially about 0.05-2 weight part.

The ratio of thermo-stabilizer or ratio can be at about 0.001-10 weight parts, select relative 100 weight part polyacetal resins in the scope of preferably about 0.001-5 weight part (especially about 0.01-2 weight part).

Particularly, if use the basic nitrogen inclusion compound as thermo-stabilizer, the ratio of this basic nitrogen compound or ratio can be selected relative 100 weight part polyacetal resins in the scope of about 0.001-1 weight part and preferably about 0.005-0.5 weight part (especially about 0.01-0.15 weight part).

(tinting material)

In addition, polyacetal resin composite of the present invention also can have (comprising) tinting material.Tinting material comprises various dyestuffs or pigment.As dyestuff, solvent dye is preferred, and comprises the azo series dyestuff, anthraquinone series dyestuff, phthalocyanine series dyes and naphthoquinones series dyes.Pigment can use mineral dye or pigment dyestuff.

The example of mineral dye is titanium series (titaniferous) pigment, zinc series (containing zinc) pigment, carbon black (as, furnace black, thermally oxidized black, acetylene black, Ketjen is black), iron series (iron content) pigment, molybdenum series (containing molybdenum) pigment, cadmium series (containing cadmium) pigment, plumbous series (leaded) pigment, cobalt series (containing cobalt) pigment and aluminium series (containing aluminium) pigment.

The example of pigment dyestuff is an azo series pigment, anthraquinone series pigment, phthalocyanine serial pigment, quinacridone series pigment, perylene series (perylene-series) pigment, Naphtocyclinon (perinone) serial pigment, isoindoline serial pigment ， dioxazine serial pigment or threne serial pigment.

Above-mentioned tinting material can use separately or with multiple colorant combination.Have the tinting material [as carbon black, titanium white (titanium oxide) and phthalocyanine serial pigment, especially carbon black] of high shaded effect by use, can improve the weather resisteant (photostabilization) of polyacetal resin composite.

The content of tinting material is, for example, and relative 100 weight part polyacetal resins, about 0-5 weight part (as, about 0.01-5 weight part), preferably about 0.1-4 weight part and 0.1-2 weight part more preferably from about.

Can be optionally in polyacetal resin composite of the present invention separately or in conjunction with adding conventional additives.As additive, can mention antioxidant (as, amine series, phosphorous acid series, sulphur series, quinhydrones series and quinoline series antioxidant), weather resisteant (photostabilization) stablizer, releasing agent (releasing agent), nucleator, static inhibitor, (friction/wearing and tearing) improving agent slides, impact modifier (impact modifying agent), fire retardant, tensio-active agent, antiseptic-germicide, anti-mycotic agent, perfume compound, food flavouring, various polymkeric substance [as, acrylic resin (C _1-10The homopolymerization or the multipolymer of alkyl (methyl) acrylate such as polymethylmethacrylate), vinylformic acid core-shell polymer, polycarbonate series resin, polyolefin resin, urethane series resin, polyester series resin, fluorine resin, with the siloxane series resin], filler, and other.

In addition, if desired, resin combination can with independent or bonded conventional fillers (as fibering, tabular or particulate filler) blend to improve the performance of moulded products.The fibering filler comprise inorganic fibre (as, glass fibre, carbon fiber, boron fibre, potassium titanate fiber (whisker)), organic fibre (as, nylon), and other.As plate-like fillers, can mention sheet glass, mica, graphite, various tinsels, and other.Particulate filler comprise metal oxide (as, zinc oxide, alumina), vitriol is (as calcium sulfate, sal epsom), carbonate (as lime carbonate), glass (as, the levigated fiber, granulated glass sphere, glass sphere), silicate (talcum, kaolin, silica, diatomite, clay, wollastonite), sulfide (as, molybdenumdisulphide, tungsten disulfide), carbide (as, the graphite fluorochemical, silicon carbide), boron nitride, and other.

(production technique of polyacetal resin composite)

Polyacetal resin composite of the present invention can be particulate mixtures or molten mixture, and it can pass through polyacetal resin and sterically hindered phenol series compound, above-mentioned spirocyclic compound, with processing stabilizers and/or thermo-stabilizer, if desired, other additive mixes in a usual manner and makes.For example, adopt (1) a kind of technology, comprise, add every kind of component by main feeder, mediate and the gained mixture is extruded into pellet with single shaft or biaxial extruder, with this pellet of molding, (2) a kind of technology comprises, adds a kind of component that does not have spirocyclic compound by main feeder, at least comprise the component of spirocyclic compound (as other component by the side feeder adding, can mention polyacetal resin, stablizer, other additive, and analogue), mediate and the gained mixture is extruded into pellet and this pellet of molding with single shaft or biaxial extruder, (3) once make the different pellet (masterbatch) of composition, to determine that ratio mixes (dilution) pellet, with being obtained, gained pellet molding has the moulded products of determining composition, or (4) a kind of technology, comprise, by for example spraying inhibitor is administered on the polyacetal resin of granulation and gained pellet molding obtained having and determine the moulded products formed.In addition, be used for the preparation of compositions of moulded products, advantageously will as powdery (granular) polyacetal of base material (as, by grinding the powder (granular) that a part or all polyacetal resins obtain) with other component (as, sterically hindered phenolic compound, processing stabilizers, thermo-stabilizer, spirocyclic compound) mixes and melt-kneaded subsequently, improve the dispersiveness of additive like this.

Polyacetal resin composite of the present invention is realized: the formaldehyde that produces because of the oxidation of polyacetal resin or thermolysis discharges and obviously is restricted or suppresses, and the Working environment in molding and processing (especially melt molding and processing) step improves or improves.In addition, degradation production or the additive deposition (mold deposit) on mould, frosting or the bleed of these products from moulded products can obviously be restricted or suppress, and the variety of issue when molding and treatment step is improved.Therefore, resin combination of the present invention can be by ordinary method such as injection moulding, extrusion molding, and compression moulding, blowing, vacuum moulding, foam moulded, rotational molding and gas injection moulding and be used to make various moulded products.

(moulded products)

The molded polyacetal resin product of the present invention that is formed by above-mentioned polyacetal resin composite comprises (containing) sterically hindered phenolic compound simultaneously, specific spirocyclic compound, with processing stabilizers and/or thermo-stabilizer, and in extrusion molding and/or moulding technology, have excellent stability, discharge (or generation) very small amount of formaldehyde simultaneously.In other words, the relatively large formaldehyde of moulded products release by the conventional molded polyacetal resin that comprises antioxidant and other stablizer causes corrosion and variable color, and pollutes the live and work environment.For example, the release of the formaldehyde of commercially available common molded polyacetal resin product is the about 2-5 μ g/lcm under drying conditions (in freeze-day with constant temperature atmosphere) ²Surface-area and the about 3-6 μ g/lcm under wet condition (in constant temperature humidification atmosphere) ²Surface-area.

On the other hand, the formaldehyde of molded polyacetal resin product of the present invention is released under the drying conditions (in freeze-day with constant temperature atmosphere) and is no more than 1.5 μ g/lcm ²The moulded products surface-area, preferably about 0-1.3 μ g, 0-1 μ g more preferably from about, about usually 0.01-1 μ g.In addition, under wet condition, formaldehyde discharges and is no more than 2.5 μ g (about 0-2 μ g)/lcm ²The moulded products surface-area, preferably about 0-1.7 μ g, 0-1.5 μ g more preferably from about, about usually 0.01-1.5 μ g.

Under drying conditions or wet condition, have above-mentioned formaldehyde according to moulding molded polyacetal resin product of the present invention and discharge, but it generally shows above emission levels under these two kinds of conditions.

Formaldehyde release under drying conditions can be measured as follows.

At the moulded products that cuts polyacetal resin as required and after measuring its surface-area, these goods of suitable part (as are equivalent to the about 10-50cm of surface-area ²Amount) be placed in the container (20ml capacity), 80 ℃ of lower seals of temperature and placement (or maintenance) 24 hours.Then, with 5ml water and according to JIS K0102,29 (under the formaldehyde titles) are analyzed the formaldehyde in the aqueous solution with sealing container dress, and the formaldehyde of Units of Account surface-area moulded products discharges (μ g/cm ²).

Formaldehyde release under wet condition can be determined as follows.

At the moulded products that cuts polyacetal resin as required and after measuring its surface-area, these goods of suitable part (as are equivalent to the about 10-100cm of surface-area ²Amount) hang by the lid of the container that comprises 50 ml distilled waters (1L capacity).After sealed vessel, this container is placed (or maintenance) 3 hours down at 60 ℃ in constant temperature oven.Then, container was at room temperature placed 1 hour and according to JIS K0102,29 (under the formaldehyde titles) are analyzed the formaldehyde in the aqueous solution in this container, the formaldehyde of Units of Account surface-area moulded products discharges (μ g/cm ²).

The above-mentioned quantitative restriction that PARA FORMALDEHYDE PRILLS(91,95) of the present invention discharges is not only to getting self-contained polyacetal resin, the sterically hindered phenol series compound, specific spirocyclic compound, with processing stabilizers and/or thermo-stabilizer and be with or without conventional additives (conventional stablizer, releasing agent, Deng) the moulded products of polyacetal resin composite, and it is effective to the moulded products of the suitable resin combination of self-contained mineral filler of molding and/or other polymkeric substance, the major portion that only requires these goods (for example, the total surface area of 50-100%) constitutes (for example, polychrome goods or coated article) by polyacetal resin.

Can be applicable to according to moulded products of the present invention that wherein formaldehyde is horrible (for example, as the handle and the lever of trolley part) any use field, and can be advantageously used for the parts and the element in various fields, comprise trolley part, Electrical and Electronic element (driving element and drive element) parts, Constracture unit and pipelining parts, family expenses and makeup parts, and medical facilities (being used for diagnosis or therepic use) parts.

Particularly, trolley part includes, but is not limited to passenger vehicle internal part such as interior handle, the propellant bottle opener, the seat bracelet, auxiliary knee, various switches, handle, lever, clip, Deng, electrical system parts such as instrument and junctor, Electrical and Electronic parts or equipment in the vehicle relevant with the passenger vehicle navigational aid with audio-frequency apparatus, with the parts of metallic contact, common window regulator base plate, door lock drive element, mirror element, wiper motor system parts, and fuel system component.

Electric or electronic component parts (mechanical part) for example comprise, by molded polyacetal resin product constitute and be furnished with the parts of many metallic contact or element [as audio-frequency apparatus such as tape recorder, video equipment such as video tape recorder (VTR), 8mm or other video camera, Deng, office automation (OA) equipment such as duplicating machine, facsimile recorder, word processor, computer, etc., by the toy of the drive force of electric notor or spring, phone is as the keyboard or the analogue of computer annex].Specifically, can mention the chassis, gear, lever, cam, pulley, and bearing.In addition, the present invention can be applicable to the optics made by the molding polyacetal resin to small part and magnetic recording media parts (as metallic film tape cassete, disk cartridge, the optical disc box, etc.) and more specifically, be used for the metallic magnetic tape drum of music, the digital audiotape box, the 8mm video cassette cartridge, floppy disk cartridge, mini-disk cartridge, Deng as particular optical and magneticmedium parts, can mention magnetic tape unit (tape body, spool, center, liner, roller bearing, detainer, lid, Deng) and disk cartridge parts (disk box body (shell), shutter, clamping plate, etc.).

In addition, can be advantageously used in Constracture unit and conduit component such as set lights parts according to the moulded products of polyacetal resin of the present invention, the interior architectural applications element is (as device, anchor clamps, stuff), pipeline, tap, cock, toilet associated components, Deng, relate to the various products of daily life, makeup, and medical facilities, for example fastening parts (as slide fastener, the snapper fastening parts, hoop and ring fastening parts, the railing fastening parts), stationery, lipstick or lipstick case, cleaning equipment, water clearer, nozzle, spraying equipment or container, aerosol container, universal container, the syringe anchor clamps, or the like.

Because polyacetal resin composite of the present invention comprises (containing) sterically hindered phenol series compound, specific spirocyclic compound, with processing stabilizers and/or thermo-stabilizer, this polyacetal resin composite is obtained huge thermostability and is improved in the extrusion molding of polyacetal resin and/or moulding technology.In addition, add the formaldehyde that a spot of said components can suppress polyacetal resin and goods thereof and discharge, cause low-down burst size, and can improve with flying colors surrounding environment (as, Working environment and environment for use).In addition, discharge even polyacetal resin composite of the present invention also suppresses formaldehyde under severe condition, thereby suppress: the deposition (mold deposit) of degradation production in mould; Frosting and the bleed of these products from moulded products; With the thermal ageing of these goods or rotten, thereby can improve the quality and the mouldability of this moulded products.

Specific embodiments

Embodiment

Following examples are used for more detailed description the present invention and should not be construed as limiting the scope of the invention.

Incidentally, for embodiment and Comparative Examples, thermostability, mouldability (amount of settling on mould), the amount that the formaldehyde of molding (or moulding) goods under dry and moist (wetting) condition discharges, and bleed (degree of bleed) is assessed by the following method.

[thermostability]

The ratio (%/min.) that thermostability descends because of heat weight according to the pellet per minute, wherein pellet was heated in air under 230 ℃ 45 minutes.

[mouldability (amount of settling on mould)]

The pellet that is formed by polyacetal resin composite passes through to use injection moulding machine (1,000 injection volume) continuous or order moulding or molding, obtains goods (size: the 20mm * 1mm), assess the deposition degree on the mould then and be divided into 5 grades of certain shape.Incidentally, number of degrees is more little, and sediment yield is low or more little more, and promptly the mold deposit amount is low or more little more.

[amount that the formaldehyde of moulded parts in dry environment discharges]

Will be by 10 testing plate (2mm * 2mm * 50mm; The about 40cm of total surface area ²) every kind of resin sample forming be placed on container (capacity 20ml) sealing and in constant temperature oven 80 ℃ of heating 24 hours down.To room temperature, use syringe to inject container 5ml distilled water in air cooling.The formaldehyde content of this aqueous solution is according to JIS K0102, and 29 (under the formaldehyde titles) are measured and the formaldehyde gas of Units of Account surface-area discharges (μ g/cm ²).

[amount that the formaldehyde of moulded parts in wet environment discharges]

With board test sheet (100mm * 40mm * 2mm; The about 85.6cm of total surface area ²) hang by the stopper or the lid of the polyethylene bottle that comprises 50ml distilled water (capacity 1L).Sealing was placed in 60 ℃ of constant temperature ovens 3 hours, at room temperature placed subsequently 1 hour.The formaldehyde content of the aqueous solution in this bottle is according to JIS K0102, and the formaldehyde gas that the per surface area of these goods was analyzed and calculated to 29 (under the formaldehyde titles) discharges (μ g/cm ²).

[bleed (bleeding out)]

Template die is moulded goods (70mm * 40mm * 3mm) at 120 ℃ of whole day and nights of following thermal treatment.Then, observe the surface of moulded parts and according to following criterion evaluation bleed degree.

" A ": do not observe bleed

" B ": observe slight bleed

" C ": observe tangible bleed

Embodiment 1-41 and Comparative Examples 1-5

With 100 weight part polyacetal resins and sterically hindered phenol series compound, spirocyclic compound, processing stabilizers and thermo-stabilizer are with the mixed shown in the table 1-4 and use biaxial extruder (30mm diameter) that every kind of mixture melt extrusion molding is obtained granulating composition.By using pellet, the thermostability of assessment molten resin composition.In addition, the test film of regulation uses injection moulding machine to be made by pellet, and the mold deposit during the assessment molding.In addition, the burst size of methanal and the bleed thereof of the testing plate of every kind of regulation of assessment.The results are shown in table 1-4.

For relatively, according to the following sample of above-mentioned assessment: by the CTU guanamines being added the sample that the foundational system that comprises polyacetal resin and sterically hindered phenol series compound is made; By benzoguanamine (the guanamines compound that does not have volution) is added the sample that this foundational system is made; By melamine (thermo-stabilizer) is added the sample that this foundational system is made; By with benzoguanamine, processing stabilizers and thermo-stabilizer add this foundational system and the sample made; With by with melamine (thermo-stabilizer), processing stabilizers and other thermo-stabilizer add this foundational system and the sample made.The results are shown in table 5.

The polyacetal resin that is used for embodiment and Comparative Examples, the sterically hindered phenol series compound, spirocyclic compound, processing stabilizers, thermo-stabilizer and tinting material are as follows.

1. polyacetal resin " a "

(a-1): comprise the multipolymer (a kind of by fusion hydrolysis method stabilized resins, melt index=9g/10 minute) of polyacetal resin as main ingredient

(a-2): comprise polyacetal resin as main ingredient (a kind of by solution water solution stabilized resins, melt index=9g/10 minute)

Incidentally, melt index is to use the value of measuring under the condition of 2169 gram resins (g/10 minute) down for 190 ℃ according to ASTM-D1238 and in temperature.

2. sterically hindered phenol series compound " b "

(b-1): triglycol two [3-(3-t-butyl-5-methyl-4-hydroxy phenyl) propionic ester]

(b-2): tetramethylolmethane four [3-(3,5-two-t-butyl-4-hydroxy phenyl) propionic ester]

3. spirocyclic compound " c "

(c-1): comprise the crystal water CTU guanamines of [comprising 8% weight crystal water]

(c-2): anhydrous CTU guanamines [by obtaining in 3 hours] at thermal treatment under nitrogen atmosphere (c-1) CTU guanamines under 200 ℃

(c-3): comprise the single guanamines mixture of the CTU guanamines of crystal water/CTU (mixture that comprises the single guanamines of 5% weight crystal water and 3% weight CTU]

(c-4): the CMTU guanamines

(c-5): 3,9-two [3-(3,5-diamino-2,4,6-triazinyl)-1,1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane

(c-6): benzoguanamine [by Tokyo Kasei Kogyo Co., Ltd. makes]

4. processing stabilizers " d "

(d-1): ethylene stearyl acid amides

(d-2): polyoxyethylene glycol (number-average molecular weight: 35,000)

(d-3): the anhydro sorbitol list-or SUNSOFT Q-182S

(d-4): Zerol

(d-5): Unister E 275

(d-6): pentaerythritol tetrastearate

(d-7): glycerine list elm acid esters

(d-8): polyoxyethylene-polyoxypropylene (50/50 (mol ratio)) segmented copolymer (number-average molecular weight: 6,000)

(d-9): montanate

(d-10): polyoxyethylene glycol (number-average molecular weight: 6,000)

5. thermo-stabilizer (metal-salt of organic carboxyl acid, alkaline earth salt) " e "

(e-1): calcium 12-hydroxy stearic acid ester

(e-2): from aggressiveness [by Du Pont-Mitsui Polychemicals Co., Ltd. makes, and Himilan 1702]

(e-3): magnesium oxide

(e-4): citrate of lime

(e-5): lime acetate

(e-6): Magnesium Stearate

(e-7): magnesium hydroxide

(e-8): hydrotalcite [by Kyowa Chemical Indus try Co., Lt d. makes, DHT-4A]

(e-9): zeolite A-4[is made by Tosoh Corp., Zeolam A-4]

6. thermo-stabilizer (basic nitrogen compound, phosphine compound) " f "

(f-i): melamine

(f-2): melamine-formaldehyde resin, derive from following steps,

Use the 1.2mol formaldehyde of relative 1mol melamine.With formaldehyde and melamine at the aqueous solution, under pH8 70 ℃ down reaction obtain melamine-formaldehyde resin (water-soluble initial or premature condensation thing), and white opacity does not appear in reaction system.Then, reaction system under agitation is adjusted to pH6.5 and maintenance or continues stirring with the precipitation melamine-formaldehyde resin, obtaining the thick melamine-formaldehyde resin of powdery by drying from throw out then is the gained throw out.This powder with hot water (60 ℃) washing 30 minutes is also filtered, and then resistates is obtained the melamine-formaldehyde resin of white powder with washing with acetone and drying.

(f-3): melem [by Nissan Chemical Industries, Ltd. makes]

(f-4): nylon 6-66-610

(f-5): wallantoin [by Kawaken Fine Chemicals Co., Ltd. makes]

(f-6): wallantoin dihydroxyl aluminium [by Kawaken Fine Chemicals Co., Ltd., ALDA makes]

(f-7): nylon-66 (average particle size particle size: 3 μ m)

(f-8): biurea

(f-9): poly-(N-vinyl acetamide)

(f-10): poly-(vinyl pyrrolidone)

(f-11): triphenylphosphine

(f-12): adipic dihydrazide

7. tinting material " g "

(g-1): carbon black (acetylene black)

(g-2): phthalocyanine series blue dyes

(g-3): titanium oxide

(g-4): ultramarine

Table 1

Embodiment

1 2 3 4 5 6 7 8 9 10 11 12 13"a" a-1 a-1 a-2 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 ( ) 100 100 100 100 100 100 100 100 100 100 100 100 100 b-1 b-2 b-1 b-1 b-1 b-1 b-1 b-2 b-1 b-1 b-1 b-1 b-1"b" 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 ( ) "c" c-1 c-1 c-1 c-1 c-1 c-1 c-1 c-2 c-1 c-1 c-1 c-1 c-1 ( ) 0.3 0.3 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3"d" d-1 d-1 d-1 d-2 d-1 d-2 d-4 d-4 d-5 d-1 d-1 d-1 d-4 ( ) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2"e" e-1 e-1 e-1 e-1 e-1 e-2 e-3 e-3 e-4 e-5 e-1 e-1 e-6 0.1 0.1 0.1 0.1 0.1 0.03 0.03 0.03 0.1 0.01 0.1 0.1 0.1 ( ) "f"----f-1 f-1 f-2 f-3 f-4 f-4 f-5 f-6 f-7

0.1 0.03 0.03 0.1 0.1 0.1 0.03 0.03 0.1 colouring agent " g "-------------(weight portion) heat endurance (%/min) 0.016 0.0160 0.013 0.014 0.013 0.013 0.014 0.015 0.012 0.012 0.017 0.015 0.015 mold deposit 1111311111111 burst size of methanal 0.9 0.9 0.4 0.6 0.4 0.6 0.7 0.7 0.6 0.6 0.3 0.3 0.7 dryings (μ g/cm²) burst size of methanal 1.1 1.2 0.5 0.9 0.6 0.7 0.9 0.9 0.5 0.5 0.4 0.4 0.6 humidities (μ g/cm ²) bleed A A A A B A A A A A A A A

Table 2

Embodiment

14 15 16 11 18 19 20 21 22 23 24 25"a" a-1 a-2 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 ( ) 100 100 100 100 100 100 100 100 100 100 100 100 "b" b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 ( ) 0.3 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.3 0.3"c" c-1 c-1 c-1 c-1 c-1 c-2 c-3 c-3 c-4 c-5 c-3 c-3 ( ) 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5"d" d-6 d-7 d-8 d-1 d-1 d-1 d-4 d-4 d-4 d-4 d-1 d-2 d-2 d-4 ( ) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 1.0 1.0 0.2"e" e-7 e-8 e-9 e-1 e-6 e-1 e-1 e-6 e-1 e-1 e-6 e-1 ( ) 0.03 0.05 0.05 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1"f" f-1 f-1 f-1---------

0.05 0.03 0.03 colouring agent " g "------------(weight part) heat endurance (%/min) 0.016 0.012 0.012 0.014 0.014 0.015 0.014 0.014 0.013 0.014 0.013 0.013 mold deposit 211111111111 burst size of methanal drying (μ g/cm²) 0.7 0.4 0.5 0.5 0.5 0.6 0.5 0.4 0.4 0.5 0.3 0.3 burst size of methanal humidity (μ g/cm ²) 0.8 0.5 0.5 0.9 0.8 1.1 0.8 0.7 0.7 0.8 0.7 0.7 bleed B A A A A A A A A A A A

Table 3

Embodiment

26 27 28 29 30 31 32 33 34 35"a" a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 ( ) 100 100 100 100 100 100 100 100 100 100"b" b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 b-1 ( ) 0.3 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.5 0.3"c" c-3 c-3 c-3 c-3 c-3 c-3 c-3 c-3 c-3 c-3 ( ) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5"d" d-4 d-4 d-4 d-4 d-1 d-9 d-8 d-10 d-2 d-4 ( ) 0.2 0.2 0.2 0.2 0.2 0.2 0.5 0.5 0.5 0.2"e" e-1 e-1 e-1 e-1 e-2 e-5 e-1 e-1 e-1 e-1 e-1 ( ) 0.1 0.1 0.1 0.1 0.03 0.01 0.1 0.1 0.1 0.1 0.1"f" f-1 f-5 f-6 f-8 f-4 f-7 f-9 f-9 f-10 f-11

0.03 0.03 0.03 0.03 0.1 0.1 0.1 0.1 0.1 0.05 colouring agent " g "----------(weight part) heat endurance (%/min) 0.013 0.016 0.015 0.015 0.013 0.014 0.013 0.013 0.014 0.015 mold deposit 1111112221 burst size of methanal drying (μ g/cm²) 0.3 0.2 0.2 0.3 0.5 0.6 0.6 0.6 0.7 0.3 burst size of methanal humidity (μ g/cm ²) 0.7 0.4 0.4 0.6 0.4 0.5 0.4 0.4 0.5 0.6 bleed A A A A A A A A A A

Table 4

Embodiment

36 37 38 39 40 41 polyacetal resins " a " a-1 a-1 a-1 a-1 a-1 a-1 (weight portion), 100 100 100 100 100 100 sterically hindered phenol series compound " b " b-1 b-1 b-1 b-1 b-1 b-1 (weight portion) 0.3 0.3 0.3 0.3 0.3 0.3 spiro-compounds " c " c-3 c-3 c-3 c-3 c-4 c-3 (weight portion) 0.5 0.5 0.5 0.5 0.5 0.3 processing stabilizers " d " d-4 d-4 d-4 d-4 d-4 d-1 (weight portion) 0.2 0.2 0.2 0.2 0.2 0.2 heat stabilizers " e " e-1 e-1 e-1 e-1 e-1 e-1 (weight portion) 0.1 0.1 0.1 0.1 0.1 0.1 " f " f-12

-----0.1 colouring agent " g " g-1 g-2 9-3 g-4 g-1 g-1 (weight part) 0.5 0.5 0.5 0.5 0.5 0.5 heat endurances (%/min.) 0.015 0.015 0.013 0.015 0.015 0.013 mold deposit burst size of methanal 111111 dryings (μ g/cm²) 0.5 0.5 0.4 0.5 0.5 0.3 burst size of methanal humidity (μ g/cm ²) 0.8 0.8 0.8 0.8 0.6 0.7 bleed A A A A A A

Table 5

Comparative Examples

12345 polyacetal resins " a " a-1 a-1 a-1 a-1 a-1, (weight portion) 100 100 100 100 100 sterically hindered phenol series compound " b " b-1 b-1 b-1 b-1 b-1, (weight portion) 0.3 0.3 0.3 0.3 0.3 spiro-compounds " c " c-1 c-6 c-6, (weight portion) 0.3 0.3 0.3 processing stabilizers " d "---d-1 d-1, (weight portion) 0.2 0.2 heat stabilizers " e "---e-1 e-1, (weight portion) 0.1 0.1 " f "--f-1-f-1

0.3 0.2 tinting material " g "-----(weight part) thermostability (%/min.) 0.027 0.029 0.025 0.017 0.019 mold deposit 15554 burst size of methanal drying (μ g/cm ²) 1.7 1.7 1.6 1.1 1.3 burst size of methanal humidity (μ g/cm ²) 2.8 2.9 2.6 1.7 2.0 bleed A C C C C

Obviously find out, compare to have the thermostability of excellence according to the resin combination of embodiment with the resin combination of Comparative Examples by table.In addition, have a spot of mold deposit according to the resin combination of embodiment when the molding and on mouldability, be improved.In addition, this resin combination can obviously reduce or reduce the amount that formaldehyde discharges, and can greatly summarize surrounding environment.In addition, the moulded parts that is formed by this resin combination does not have the additive bleed, and is applicable to external component.

Claims

1. a polyacetal resin composite comprises polyacetal resin, and the sterically hindered phenol series compound has the spirocyclic compound and at least a material that is selected from processing stabilizers and thermo-stabilizer of triazine ring.

2. according to the polyacetal resin composite of claim 1, wherein the triazine ring of spirocyclic compound has at least one amino group.

3. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound has two guanamines rings as its end group.

4. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound is a kind of compound that is expressed as following structural formula (1):

5. according to the polyacetal resin composite of claim 4, the R in the structural formula (1) wherein ¹And R ²Expression is straight-or branching C _1-10Alkylidene group.

6. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound comprises 3,9-two [(3,5-diamino-2,4,6-triazinyl) C _1-10Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane.

7. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound comprises 3,9-two [(3,5-diamino-2,4,6-triazinyl) C _1-6Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane.

8. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound comprises at least a following material that is selected from: 3, and [2-(3 for 9-two, 5-diamino-2,4, the 6-triazinyl) ethyl]-2,4,8,10-four oxaspiros [5.5] undecane, 3, and 9-two [1-(3,5-diamino-2,4, the 6-triazinyl) methyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3, [3-(3 for 9-two, 5-diamino-2,4, the 6-triazinyl)-1, the 1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane.

9. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound comprises anhydrous spirocyclic compound or aqueous spirocyclic compound.

10. according to the polyacetal resin composite of claim 1, wherein moisture spirocyclic compound comprises a kind of spirocyclic compound that comprises crystal water.

11. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound comprises a kind of 3 of crystal water that comprises, 9-two [(3,5-diamino-2,4,6-triazinyl) straight or branched C _1-5Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane.

12. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound comprises 3,9-two [(3,5-diamino-2,4, the 6-triazinyl) alkyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3-(cyano group alkyl)-9-[(3,5-diamino-2,4, the 6-triazinyl) alkyl]-2,4,8,10-four oxaspiros [5.5] undecane.

13. according to the polyacetal resin composite of claim 1, wherein spirocyclic compound comprises 3,9-two [(3,5-diamino-2,4,6-triazinyl) C _1-6Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3-(cyano group C _1-6Alkyl)-and 9-[(3,5-diamino-2,4,6-triazinyl) C _1-6Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane.

14. according to the polyacetal resin composite of claim 1, wherein the sterically hindered phenol series compound comprises C _1-10Alkylidene group-two is to four (t-butylphenols); C _2-10Alkylene group or alkadienylene two to four (t-butylphenol); C _6-20Arylidene or inferior aralkyl-two are to four (t-butylphenols); Wherein t-butylphenol group interconnects by the group with sulphur atom or two (t-butylphenols) of keyed jointing; Has C _2-10The t-butylphenol of alkylidene group ketonic oxygen base group; Wherein the polyol ester of t-butylphenol group by lipid acid interconnects or two to four (t-butylphenols) of keyed jointing; Have heterocyclic group and C _2-10Two to four (t-butylphenols) of alkylidene group ketonic oxygen base group; Has C _3-10The t-alkylphenol of alkenyl carbonyl oxygen base group; Sterically hindered phenolic compound with phosphonate groups; With sterically hindered phenolic compound with amide group.

15. according to the polyacetal resin composite of claim 1, wherein processing stabilizers comprises at least a higher fatty acid or derivatives thereof that is selected from, the material of polyether polyols and silicone compounds.

16. according to the polyacetal resin composite of claim 15, wherein the higher fatty acid or derivatives thereof comprises having the list that is not less than 10 carbon atoms-or two-carboxylic lipid acid, its ester and its sour acid amides.

17. according to the polyacetal resin composite of claim 15, wherein silicone compounds comprises dialkylsiloxane, the homopolymer of alkylaryl siloxanes and diaromatic siloxane, its oligopolymer and its multipolymer.

18. according to the polyacetal resin composite of claim 1, wherein thermo-stabilizer comprises at least a basic nitrogen compound that is selected from, phosphine compound, the metal-salt of organic carboxyl acid, alkalescence or alkaline earth metal compound, the material of hydrotalcite and zeolite.

19. according to the polyacetal resin composite of claim 18, wherein basic nitrogen compound comprises aliphatic amine, aromatic amine, amide compound, the hydrazine or derivatives thereof, polyamino triazine, uridylic or derivatives thereof, cytosine(Cyt) and its derivative, the guanidine or derivatives thereof, urea or derivatives thereof, and resinamines.

20. according to the polyacetal resin composite of claim 18, its neutral and alkali or alkaline earth metal compound comprise metal oxide, metal hydroxides, and the salt of mineral acid and metal.

21. according to the polyacetal resin composite of claim 1, wherein thermo-stabilizer comprises at least a melamine or derivatives thereof that is selected from, guanidine derivative, the material of urea derivatives and resinamines.

22. according to the polyacetal resin composite of claim 1, it comprises, relative 100 weight part polyacetal resins, 0.001-5 weight part sterically hindered phenol series compound, 0.001-20 weight part spirocyclic compound, 0.01-10 weight part 20 processing stabilizers and 0.001-10 weight part thermo-stabilizer.

23. according to the polyacetal resin composite of claim 1, it also comprises tinting material.

24. according to the polyacetal resin composite of claim 23, wherein tinting material comprises carbon black.

25. a method that is used to produce polyacetal resin composite, it comprises, with polyacetal resin, and the sterically hindered phenol series compound, spirocyclic compound and at least a material that is selected from processing stabilizers and thermo-stabilizer with triazine ring mix.

26. polyacetal resin moulded products that forms by the described polyacetal resin composite of claim 1.

27. according to the polyacetal resin moulded products of claim 26, wherein (1) keeps the formaldehyde release of 24 hours moulded products to be no more than 1.5 μ g/cm down 80 ℃ of temperature in enclosed space ²Product surface long-pending, and/or (2) in enclosed space under saturated humidity 60 ℃ of temperature keep the formaldehyde of 3 hours moulded products to discharge down being no more than 2.5 μ g/cm ²Product surface long-pending.

28. according to the polyacetal resin moulded products of claim 26, it is at least a trolley part that is selected from, electric or electronic unit, building or conduit component, household implements or makeup parts and medical facilities parts.