CN1863868A - Polyacetal resin composition - Google Patents

Abstract

A polyacetal resin composition is composed of a polyacetal resin and a heterocyclic compound having a unit containing at least a hydroxyaryl group and an imino group and/or an amino group. The heterocyclic compound may be contained in an amount of 0.001-20 parts by weight per 100 parts by weight of the polyacetal resin. The polyacetal resin composition may further contain at least one element selected among antioxidants, heat resistance stabilizers, processing stabilizers, weathering (light resistance) stabilizers, impact strength modifiers, sliding property modifiers, coloring agents and fillers. With such a resin composition, stability of the polyacetal resin is improved, while suppressing generation of formaldehyde.

Description

Polyacetal resin composite

Technical field

The present invention relates to the polyacetal composition series, wherein significantly suppressed the discharging (or generation) of formaldehyde, extrusion performance (low volatility) and forming property excellence, frosting phenomenon can be inhibited; And relate to shaping (or molding) goods that are shaped by described resin combination.

Background technology

The mechanical property of polyacetal resin, fatigue performance, wear-resisting wiping and polishing machine, chemical resistance and forming property excellence.Therefore, polyacetal resin is widely used in every field, as trolley part, electric or electronic components, other precision optical machinery parts, building or line member, home appliances or cosmetic product parts or medical facilities parts.Yet,, need higher-quality polyacetal resin along with Application Expansion or variation.

The characteristic (or performance) that polyacetal resin is required comprises following characteristic: physical strength is not compromised in procedure of processing such as extrusion step or forming step, do not produce settling (or mold deposit) to metal die, mechanical property can not affect adversely under long-term heating condition (thermal ageing), can not find that in molded article not exclusively (or bad) is shaped as crazing or pore.As intensity or one of physicals deterioration and incomplete important factor that is shaped, the degradation of the polymkeric substance of having demonstrated.Especially, because of its chemical structure, in the polyacetal resin oxidizing atmosphere at high temperature or itself be unsettled in acidity or the alkaline environment.Therefore, the basic demand that must satisfy of polyacetal resin is to guarantee high thermal stability and in the course of processing and by formaldehyde emissions minimum in the formed article (or generation).Formaldehyde has chemically reactive, is oxidized to formic acid easily, and the resistance toheat of resin is caused disadvantageous effect.In addition, when with this resin during as electric or electronic unit, formaldehyde causes the corrosion of metal joint or because organic deposition causes the parts variable color, and comes in contact bad.And Working environment and the finished product that formaldehyde itself will pollute the parts assembling use living environment on every side.

Have chemically active terminal stabilization, known following method in order to make: for homopolymer, by acetylize or alternate manner with the polymer ends esterification method; For multipolymer, method is to make three  alkane and have in abutting connection with the monomer copolymerization of carbon bond (for example cyclic ethers or cyclic formals), decomposes then and remove unsettled end site to make unsettled end site become the end site of stable (or non-activity).Yet in heat-processed, fracture (or division) decomposition also can partly take place at the main chain of polymkeric substance.Only there is above-mentioned processing to be not enough to prevent that polymkeric substance from this type of decomposition taking place, in the practice, thinks that adding stablizer (for example antioxidant and other stablizer) is important for carrying out this restraining effect.

Yet,, also be difficult to suppress fully the decomposition (or degraded) of polyacetal resin even under the situation of having mixed these stablizers.In practice, when extrusion step for preparing composition or the melt-processed in the forming step, the heat that polyacetal resin has experienced forcing machine or the machine barrel of the machinery that is shaped is interior or the effect of oxygen, thus, from the main chain that decomposes or not the end of sufficient stabilization produce formaldehyde, as a result, extrude Working environment variation with forming process.And, under the situation that implemented for long periods is shaped, on metal die, deposited fine powder material or tarry matters (mold deposit), reduced working efficiency thus.In addition, mold deposit is one of final factor of damaging shaping product surface situation.And the decomposition of polymkeric substance has caused resin physical strength variation and variable color.From this viewpoint,, continue to have carried out a large amount of effort for determine more effective stabilizing formulation (or prescription) at polyacetal.

As the antioxidant that adds in polyacetal, it is known having sterically hindered phenol system's (phenols) compound (hindered phenol) and having sterically hindered amine compound (hindered amine).As other stablizer, melamine, alkali metal hydroxide, alkaline earth metal hydroxides and organic or inorganic hydrochlorate are known.And antioxidant and other combination of stabilizers are used usually.Yet,, also be difficult to suppress discharging from the polyacetal resin molded article (or generation) and go out formaldehyde even used such additive.And, forming property impaired (mold deposit for example occurring) or additive exudation.

Japanese Patent Application No.88136/1973 (JP-48-88136A; Patent documentation 1) discloses and in polyacetal, added stabiliser system, this system (for example comprises hydroxyphenyl alkyl ester compound and nitrogenous compound such as polymeric amide, hydantoin compound, 5, the 5-T10) or uracil compound (for example uridine), stablized the resin combination that obtains.In this way, in polyacetal resin, adding under hydantoin compound, uracil compound or other the situation, improving thermostability and suppressed the generation of formaldehyde to a certain extent.Yet, because hydantoin compound or uracil compound are high-volatile and low with the avidity of polyacetal resin, mold deposit has appearred significantly (promptly, forming property acutely descends), and hydantoin compound or other material ooze out from the molded article that is shaped by said composition.And, because low such as the compound volatility of polymeric amide, but poor with the polyacetal consistency, be difficult to suppress mold deposit.

[patent documentation 1] JP-48-88136A (claim and page 3 lower-left row)

Summary of the invention

Therefore, the purpose of this invention is to provide a kind of polyacetal resin composite, it can improve the melt stability of polyacetal resin in the thermostability of polyacetal resin and extrusion step or the forming step; And provide goods by its moulding (or be shaped).

Another object of the present invention provides a kind of polyacetal resin composite, and its mat adds a small amount of additive and promptly helps significantly to suppress the discharging of formaldehyde and improve Working environment and environment for use; And provide goods by its moulding (or be shaped).

Another object of the present invention provides a kind of polyacetal resin composite, it is suitable for suppressing the discharging of formaldehyde, even under the sedimentary rigor condition of degradation production on the inhibition mould, suppress the frosting of degradation production on the molded article or ooze out thermal degradation when with goods, it helps to promote the quality of molded article and improves forming property; And provide goods by its moulding (or be shaped).

A further object of the present invention provides a kind of polyacetal resin composite, wherein, the amount of the formaldehyde that gives off in polyacetal resin and the molded article thereof is suppressed to significantly low level, and has improved physicals, as weather-proof (light) stability, shock resistance or sliding capability; And goods are provided by its moulding (or be shaped).

The present inventor has carried out further investigation to realize above-mentioned purpose with stablizer to a series of heterogeneous ring compounds with regard to polyacetal resin, and the final unitary heterogeneous ring compound of finding to have active group (as imino-or amino) and containing hydroxyaryl at least suppressed the discharging of formaldehyde from the polyacetal resin molded article significantly, improved the phenomenon of oozing out of this type of molded article significantly.Finished the present invention based on above-mentioned discovery.

That is, polyacetal resin composite of the present invention comprises polyacetal resin and heterogeneous ring compound.Described heterogeneous ring compound has unit and at least a imino-and the amino active group of being selected from that contains hydroxyaryl at least.

Described heterogeneous ring compound can have following group (i) and (ii): (i) at least a hydroxyaryl, hydroxyaryl alkyl, hydroxyaryl-aryl, the amino group of single or two (hydroxyaryl) amino and single or two (hydroxyaryl alkyl) of being selected from; (ii) imino-, its nitrogen-atoms constitutes the heteroatomic imino-of heterogeneous ring compound, or amino.Described heterogeneous ring compound can be selected from following at least a: aminotriazine compound, cyclic ureide compound, imidazolinium compounds and imidazolium compounds; And can have at least a following group that is selected from: hydroxyl C _6-14Aryl, hydroxyl C _6-14Aryl C _1-6Alkyl, hydroxyl C _6-14Aryl-C _6-10Aryl, single or two (hydroxyl C _6-14Aryl) amino and two (hydroxyl C _6-14Aryl C _1-6Alkyl) amino.And described heterogeneous ring compound can comprise and has at least a heterocycle (or heterocyclic ring) that is selected from following group: imino-, its nitrogen-atoms constitute the heteroatomic imino-of heterogeneous ring compound, and amino; And comprise the unit that contains with the hydroxyaryl of this heterocycle bonding.The ratio of heterogeneous ring compound is about 0.001-20 weight part, with respect to the polyacetal resin meter of 100 weight parts.

This resin combination also comprises and is selected from following at least a material: antioxidant, thermo-stabilizer, processing stabilizers, weather-proof (light) stablizer, shock resistance improving agent, slip improving agent, tinting material and filler.By the way, resin combination of the present invention can significantly improve thermostability and need not to contain phosphonium flame retardant.

The present invention also comprises the molded article that is formed by described polyacetal resin composite.This molded article can be trolley part, electric or electronic components (electric and/or electronic components), building or line member (building and/or line member), home appliances or cosmetic product parts (home appliances and/or cosmetic product parts) or medical facilities parts.

Effect of the present invention

According to the present invention, have active group (imino-and/or amino) and contain the unitary heterogeneous ring compound of hydroxyaryl at least owing in polyacetal resin, added, improved the melt stability of polyacetal resin in the thermostability of polyacetal resin and extrusion or the moulding process.And, only add a spot of heterogeneous ring compound and promptly guaranteed the remarkable inhibition of the formaldehyde that produces from resin combination and molded article and significantly improved surrounding environment (for example Working environment and environment for use).And, polyacetal resin composite of the present invention can press down the discharging of formaldehyde to arriving extremely low level (even under harsh condition), suppress degradation production in the frosting or ooze out and the thermal ageing or the deterioration of goods from the molded article of the deposition on the mould (mold deposit), these products, thereby, help to improve the quality and the forming property of molded article.And, the adding of other additive (for example weather-proof (light) stablizer, shock-resistant improving agent, slip improving agent, tinting material and filler) has been guaranteed the formaldehyde amount that polyacetal resin and molded article give off is suppressed to extremely low level, and the polyacetal resin composite and the molded article that provide physicals such as weather-proof (light) stability, shock resistance and sliding capability to be improved.

Detailed Description Of The Invention

Resin combination of the present invention comprises polyacetal resin and heterogeneous ring compound, and the latter has active group (imino-and/or amino) and contains the unit of hydroxyaryl at least.

(polyacetal resin)

Polyacetal resin is to contain aerobic methylene radical (OCH ₂-) as the unitary macromolecular cpd of main composition and comprise polyacetal homopolymer or the polyoxymethylene class (for example, U.S.A.DuPont makes, and commodity are called " Delrin "; Asahi Kasei Corp. makes, and commodity are called " Tenac4010 "; Deng) and comprise the Copolyacetal (for example, Polyplastics Co., Ltd. make, and commodity are called " Duracon ") of oxygen MU (methylene unit) and comonomer unit.For these multipolymers, comonomer unit comprises the oxygen alkylidene unit of about 2-6 carbon atom (preferably about 2-4 carbon atom), for example, and oxygen ethylidene (OCH ₂CH ₂-), oxygen propylidene and oxygen tetramethylene unit.The ratio of these comonomer units can be less, for example, can be selected from about 0.01-20 mole %, preferred about 0.03-15 mole % (for example, 0.05-10 mole %), more preferably from about 0.1-10 mole % counts with respect to whole polyacetal resins (constituting whole monomeric units of polyacetal resin).

Copolyacetal can be the multipolymer that for example contains two kinds of components, the terpolymer that contains three kinds of components etc.Described Copolyacetal can also be random copolymers, segmented copolymer (for example, the multipolymer of describing among the Japanese patent gazette No.24307/1990 (JP-2-24307B), make trade(brand)name " Tenac LA ", " Tenac LM " by Asahi Kasei Corp.) or graft copolymer.And, polyacetal resin can be linearity or branching and can have crosslinking structure.The end group of polyacetal resin (end group) can be by coming esterification, carrying out the ammonia esterification or etherificate is carried out stabilization with isocyanate compound with carboxylic acid such as acetate or propionic acid or its acid anhydrides in addition.The polymerization degree, the degree of branching or degree of crosslinking to polyacetal do not have special restriction, as long as it can melt-shaping.Molecular weight to polyacetal resin does not have special restriction, and for example, weight-average molecular weight is about 5,000-500, and 000, preferred about 10,000-400,000.

For example, polyacetal resin can prepare by the polymerization of following material: aldehydes, as formaldehyde, paraformaldehyde or acetaldehyde; Perhaps cyclic ether or cyclic formals be as three  alkane, oxyethane, propylene oxide, butylene oxide ring, Styrene oxide 98min., cyclohexane oxide, cyclohexene oxide, 1,3-dioxolane, 1,3-two  alkane, glycol ether formal or 1,4-butyleneglycol formal.And, but as the copolymerization component, (for example can adopt the alkyl or aryl glycidyl ether, methyl glycidyl ether, ethyl ether, phenyl glycidyl ether and naphthyl glycidyl ether), alkylidene group or polyether polyols diglycidylether (for example ethylene glycol bisthioglycolate glycidyl ether, triglycol diglycidyl ether and butanediol diglycidyl ether), alkyl or aryl glycidic alcohol, cyclic ester (for example beta-propiolactone) or vinyl compound (for example vinylbenzene and vinyl ether).

(heterogeneous ring compound)

The invention is characterized in and added the specific heterocyclic compound and improved the processing stability of polyacetal resin thus significantly and suppressed the generation of formaldehyde significantly.Described heterogeneous ring compound comprises heterocycle, contains the unit and at least a imino-and the amino active group of being selected from of hydroxyaryl at least.

Described heterogeneous ring compound can have as constituting the heteroatomic imino-of its heterocyclic (NH-).And described heterogeneous ring compound can have active group (imino-and/or amino), as on the heterocycle or constitute substituting group on the hydroxy arene ring (usually, on its heterocycle) of its hydroxyaryl.

By the way, described imino-and amino can be imino-that is substituted or the amino that monobasic replaces or binary replaces.Usually preferred described heterogeneous ring compound has at least one and is selected from active imino-(NH-) and the active group of active amino (amino of unsubstituted amino and monobasic replacement).

Described heterogeneous ring compound can contain at least one heteroatoms that is selected from oxygen, nitrogen and sulphur atom, as constituting its heterocyclic heteroatoms.Usually preferred described heterogeneous ring compound has nitrogen-atoms at least as constituting its heterocyclic heteroatoms.

Described heterogeneous ring compound can also have substituting group such as oxo base, hydroxyl, the alkyl (C of straight or branched for example _1-10Alkyl such as methyl or ethyl), aryl (C for example _6-10Aryl such as phenyl) or the alkoxyl group (C of straight or branched for example _1-10Alkoxyl group such as methoxyl group, oxyethyl group or tert.-butoxy).Substituting group can be positioned on heterocycle or the hydroxy arene ring.Described heterogeneous ring compound can have a kind of or two or more kinds of substituent combination.Substituent quantity is not defined as a kind of especially.Substituent number can be single or multiple.By the way, in substituting group, oxo base normally heterocyclic substituting group also can form carbonyl ((C=O)-) with constituting the heterocyclic carbon atom.

Have imino-and/or amino heterogeneous ring compound and comprise aminotriazine compound (for example, having amino 1,3,5-triazines compound), cyclic ureide compound [for example, single uride (for example, alkylidene group urea such as ethylidene-urea of ring-type as melamine or guanamines; The uride of α-oxygen acid is as glycolylurea; The uride of β-aldehydic acid is as uridylic, urazole or xanthene; The uride of dicarboxylic acid is as malonylurea or cyanuric acid; (imidazolone for example is as 2 (3H)-imidazolones or 2 (5H)-imidazolones for imidazolidinone compound; And Benzimidazolinone); With the two urides (for example uric acid and glycoluril) of ring-type], imidazolinium compounds (for example 2-, 3-or 4-tetrahydroglyoxaline) and imidazolium compounds (for example imidazoles and benzoglyoxaline) etc.

Described heterogeneous ring compound has the unit that contains hydroxyaryl at least.That is, in heterogeneous ring compound, Direct Bonding is together or can be via linking group (alkylidene group for example mutually for hydroxyaryl and heterocycle; Fragrance divalent group such as arylidene or inferior aralkyl) be bonded together.The heterocyclic binding site can be to constitute the heterocyclic carbon atom or constitute heterocyclic heteroatoms (for example nitrogen-atoms).And heterocycle can be via as the substituent amino of heterocyclic (for example amino of aminotriazine) or imino-and hydroxyaryl or linking group bonding.And described heterogeneous ring compound can comprise such compound, wherein hydroxy arene ring and heterocyclic fused being in the same place (for example, hydroxy benzo imidazoles and hydroxy benzo imidazolone).By the way, described linking group can have above-mentioned substituting group.

The unit (for example group etc.) that contains hydroxyaryl for example comprises hydroxyaryl (hydroxyl C for example _6-14Aryl such as hydroxy phenyl, dihydroxy phenyl, 4-hydroxy-3-methyl phenyl, 4-hydroxyl-3-tert-butyl-phenyl, 4-hydroxyl-3,5-3,5-dimethylphenyl, 4-hydroxyl-3,5-diisopropyl phenyl, 4-hydroxyl-3,5-di-tert-butyl-phenyl, 4-hydroxyl-3,5-di-tert-pentyl-phenyl, 4-hydroxy-2-methyl-5-tert-butyl-phenyl, 4-hydroxy-3-methyl-5-tert-butyl-phenyl, the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl, 2-hydroxyl-3,5-di-tert-butyl-phenyl or hydroxyl naphthyl, with the dihydroxyl naphthyl), the hydroxyaryl alkyl is [for example, corresponding to the hydroxyl C of above-mentioned hydroxyaryl _6-14Aryl C _1-6Alkyl (is carried in passing-descend, as alkyl, can be mentioned straight or branched C _1-6Alkyl such as methyl, ethyl or sec.-propyl)], hydroxyaryl aryl (for example, hydroxyl C _6-10Aryl-C _6-10Aryl is as 4 '-xenol-4-yl), single or two-(hydroxyaryl) be amino [for example, corresponding to list or two (hydroxyl C of above-mentioned hydroxyaryl _6-14Aryl) amino] and single or two (hydroxyaryl alkyl) amino [for example, corresponding to list or two (hydroxyl C of above-mentioned hydroxyaryl alkyl _6-14Aryl C _1-6Alkyl) amino] and corresponding to the hydroxy arene ring of above-mentioned hydroxyaryl.Described heterogeneous ring compound comprises a kind of in these unit or two or more kinds of these unitary combinations.

In these unit, preferably comprise hydroxyl C _6-10Aryl, hydroxyl C _6-10Aryl C _1-4Alkyl, hydroxyl C _6-10Aryl phenyl, single or two (hydroxyl C _6-10Aryl) amino and single or two (hydroxyl C _6-10Aryl C _1-4Alkyl) amino, wherein these groups have at least a straight or branched C that is selected from _1-6Alkyl and straight or branched C _1-6The substituting group of alkoxyl group.

It is enough that described heterogeneous ring compound has at least one unit that contains above-mentioned hydroxyaryl.For example, described heterogeneous ring compound can have about 1-4, and preferably about 1-3 is individual, more preferably from about 1 or 2 described unit.

And described heterogeneous ring compound can comprise heterocycle, and it has at least a following group that is selected from: imino-, and its nitrogen-atoms constitutes the heteroatomic imino-of heterogeneous ring compound, and amino; And comprise the unit that contains with the hydroxyaryl of this heterocycle bonding.

Such heterogeneous ring compound for example can comprise, the compound of following formula (1) representative etc.

[formula 1]

In the formula, ring A representative can have active group (R ¹) and/or substituting group (R ²) heterocycle; " m " and " n " is that identical or different also the representative respectively is not less than zero integer; Group-Ar-(OH) _rThe representation hydroxy aryl; " r " representative is not less than 1 integer; Radicals X is represented divalent organic group; R ³Represent hydrogen atom or hydroxyaryl alkyl; " p " and " q " is identical or different and represents integer 0 or 1 separately; " s " representative is not less than 1 integer.

In formula (1), the substituent R of ring A ¹Represent active group (as imino-and/or amino) and above-mentioned substituting group.Active group R ¹Numeral " m " preferably be not less than 1 integer (for example integer of 1-4), the more preferably integer of 1-3.Substituent R ²Numeral " n " be not defined as a kind of value especially, can be the integer of 0-6 for example.The organic group of radicals X representative comprises alkylidene group (for example, the C of straight or branched _1-6Alkylidene group such as ethylidene (preferred C _1-4Alkylidene group)) arylidene (C for example, _6-10Arylidene such as phenylene) etc.As radicals R ³The hydroxyaryl alkyl of representative can be mentioned for example corresponding to group-X-Ar-(OH) in the formula (1) _rHydroxyaryl alkyl (wherein X represents alkyl).Numeral " s " for example can be the integer of 1-4 corresponding to the unitary number that contains hydroxyaryl.

Among heterogeneous ring compound, the specific examples with unitary aminotriazine compound of hydroxyl aryl comprises triaizine compounds, and it has above-mentioned substituting group on the hydroxy arene ring, for example the aminotriazine compound of hydroxyl aryl such as 6-hydroxy phenyl-2,4-diaminostilbene, 3, the 5-triazine, 6-(4 '-hydroxy phenyl)-2,4-diaminostilbene, 3, the 5-triazine, 6-(4 '-hydroxyl-3 '-tert-butyl-phenyl)-2,4-diaminostilbene, 3, the 5-triazine, 6-(4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl)-2,4-diaminostilbene, 3, the 5-triazine, 6-(4 '-hydroxyl-3 ', 5 '-diisopropyl phenyl)-2,4-diaminostilbene, 3, the 5-triazine, 3, the 5-triazine, 6-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-2, the 4-diaminostilbene, 3, the 5-triazine, 6-(4 '-hydroxyl-2 '-methyl-5 '-tert-butyl-phenyl)-2,4-diaminostilbene, 3,5-triazine or 6-(4 '-hydroxyl-3 '-methyl-5 '-tert-butyl-phenyl)-2, the 4-diamino-1,3,5-triazines; The aminotriazine compound of hydroxyl aryl aryl such as 6-(hydroxy phenyl is imitated base)-2,4-diamino-1,3,5-triazines or 6-[4 '-xenol-4-yl]-2, the 4-diamino-1,3,5-triazines; The aminotriazine compound of hydroxyl arylalkyl such as 6-(hydroxyl)-2,4-diaminostilbene, 3, the 5-triazine [for example, 6-(hydroxy phenyl ethyl)-2,4-diaminostilbene, 3,5-triazine], 6-[β-(4 '-hydroxy phenyl) ethyl]-2, the 4-diamino-1,3,5-triazines, 6-[β-(4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) ethyl]-2, the 4-diamino-1,3,5-triazines, 6-[β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) ethyl]-2, the 4-diamino-1,3,5-triazines, 6-[β-(4 '-hydroxyl-2 '-methyl-5 '-tert-butyl-phenyl) ethyl]-2, the 4-diaminostilbene, 3,5-triazine or 6-[β-(4 '-hydroxyl-3 '-methyl-5 '-tert-butyl-phenyl) ethyl]-2, the 4-diaminostilbene, 3, the 5-triazine; The triaizine compounds of hydroxyl aryl-alkyl amino such as 6-[single or two (hydroxy phenyl methyl) amino]-2, the 4-diaminostilbene, 3, the 5-triazine, 4, two [single or two (hydroxy phenyl methyl) the amino]-2-amino-1 of 6-, 3, the 5-triazine, 2,4,6-three [(hydroxy phenyl methyl) amino]-1,3, the 5-triazine, 6-[(4 '-hydroxy phenyl methyl) amino]-2, the 4-diamino-1,3,5-triazines, 6-[(2 '-hydroxy phenyl methyl) amino]-2, the 4-diaminostilbene, 3, the 5-triazine, 6-[(4 '-hydroxyl-3 ', 5 '-dimethyl benzene ylmethyl) amino]-2, the 4-diaminostilbene, 3, the 5-triazine, 6-[(4 '-hydroxyl-3 ', 5 '-di-tert-butyl ylmethyl) amino] 2, the 4-diaminostilbene, 3, the 5-triazine, 6-[(4 '-hydroxyl-3 '-methyl-5 '-di-tert-butyl ylmethyl) amino]-2, the 4-diaminostilbene, 3, the 5-triazine, 6-[(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl methyl) amino]-2,4-diaminostilbene, 3, the 5-triazine, 4, two [(4 '-hydroxyl-3 ', 5 '-dimethyl benzene ylmethyl) the amino]-2-amino-1,3 of 6-, the 5-triazine, 4, two [(4 '-hydroxyl-3 ', 5 '-di-tert-butyl ylmethyl) the amino]-2-amino-1,3 of 6-, the 5-triazine, 4, two [(4 '-hydroxyl-3 '-methyl-5 '-di-tert-butyl ylmethyl) the amino]-2-amino-1,3,5-triazines of 6-, 4, two [(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl methyl) the amino]-2-amino-1 of 6-, 3,5-triazine or 2,4,6-three [(4 '-hydroxyls-3 ', 5 '-dimethyl benzene ylmethyl) amino]-1,3,5-triazines etc.By the way, in the aminotriazine compound, amino can be (for example, alkoxy methylization is as the methoxymethylization) of alkoxyalkylization.Heterogeneous ring compound of the present invention also comprises such compound.

Have in the unitary aminotriazine compound of hydroxyl aryl at these, preferably comprise the aminotriazine such as the 6-(4 '-hydroxy phenyl)-2 of hydroxyl aryl, the 4-diamino-1,3,5-triazines; The aminotriazine of hydroxyl aryl aryl such as 6-(4 '-xenol-4-yl)-2, the 4-diamino-1,3,5-triazines; The aminotriazine of hydroxyl arylalkyl such as 2-[β-(4 '-hydroxy phenyl) ethyl]-2,4-diamino-1,3,5-triazines etc.

By the way, these triaizine compounds can prepare by ordinary method, for example, corresponding to the unitary nitrile of hydroxyl aryl (for example, hydroxyaryl nitrile, hydroxyl aralkyl nitrile and hydroxyaryl-aryl nitrile) and the reaction of Dyhard RU 100 in the presence of basic catalyst, perhaps (for example, ester is as alkyl ester or aryl ester corresponding to the unitary carboxylic acid derivative that contains nitrile or hydroxyaryl; Acyl halide such as acyl chlorides) and the reaction of biguanides.But the details reference example of these reactions such as Japanese Patent Application No.271280/1991 (JP-3-271280A), 228578/1995 (JP-7-228578A), 95598/1997 (JP-9-95598A) and 80508/1999 (JP-11-80508A), U.S. Patent No. 2423071,2423353 and 2425287 specification sheets and the communique of English Patent No.569100.

In heterogeneous ring compound, as cyclic ureide compound with hydroxyl aryl unit, the cyclic ureide compound that can mention can have above-mentioned substituting group (for example, alkyl and alkoxyl group) and can have above-mentioned substituting group (for example alkyl and aryl) on its uride ring on its hydroxy arene ring.For example, such compound comprises the hydroxyaryl glycolylurea, and is single-or 5 as 5-, 5-two (hydroxy phenyl) glycolylurea,

5-(p-hydroxybenzene) glycolylurea,

5-(hydroxy phenyl) glycolylurea,

5-(o-hydroxy-phenyl) glycolylurea,

5-(4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) glycolylurea,

5-(4 '-hydroxyl-3 ', 5 '-diisopropyl phenyl) glycolylurea,

5-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) glycolylurea,

5-(hydroxy phenyl)-the 5-alkyl hydantoin (for example,

5-(p-hydroxybenzene)-5-methyl glycolylurea), or 5-(hydroxy phenyl)-5-aryl glycolylurea (such as 5-(p-hydroxybenzene)-5-phenyl glycolylurea and

5-(hydroxy phenyl)-5-phenyl glycolylurea); Hydroxyaryl alkyl hydantoin such as 5-list-or 5,5-two (hydroxyl) glycolylurea; The compound of describing among the Japanese Patent Application No.135937/1994 (JP-6-135937A) etc.By the way, these hydantoin compounds can be D-type, L-type, DL-type or its mixture.These cyclic ureide compounds can prepare by ordinary method, for example Japanese Patent Application No.364150/1992 (JP-4-364150A), 135937/1994 (JP-6-135937A), 193876/2002 (JP-2002-193876A), 193943/2002 (JP-2002-193943A) and 363168/2002 (JP-2002-363168A).

Unitary imidazolinium compounds with hydroxyl aryl comprises 2-hydroxyaryl tetrahydroglyoxaline, its on the hydroxy arene ring, can have above-mentioned substituting group (for example alkyl) [for example, 2-(hydroxy phenyl) tetrahydroglyoxaline as 2-(adjacent-,-or right-hydroxy phenyl) tetrahydroglyoxaline] and each corresponding to as described in the hydroxyaryl alkyl imidazoline and the hydroxyaryl Aryimidazole quinoline of hydroxyaryl tetrahydroglyoxaline.

Example with unitary imidazolium compounds of hydroxyl aryl comprises 2-(hydroxyaryl)-imidazoles, it [for example can have above-mentioned substituting group (for example alkyl and aryl) on hydroxy arene ring and/or imidazole ring, 2-(neighbour, between or right-hydroxy phenyl) imidazoles, 2-(neighbour, between or right-hydroxy phenyl)-4, the 5-diphenyl-imidazole, and the compound of describing in the specification sheets of U.S. Patent No. 3205083 and 3637584], with the hydroxyaryl alkyl imidazole, hydroxyaryl Aryimidazole and hydroxyaryl benzoglyoxaline, all separately corresponding to described hydroxyaryl imidazoles [for example, 2-(neighbour, between or right-hydroxy phenyl) benzoglyoxaline; The compound of describing with the specification sheets of U.S. Patent No. 5412059,5637670,2985661 or 2995540].

By the way, in the heterogeneous ring compound of the unit with hydroxyl aryl and imino-and/or amino, part or all of hydroxyaryl can form metal-salt (for example an alkali metal salt and alkaline earth salt).Such derivative (metal-salt) is also included within the specific heterogeneous ring compound of the present invention.

Can use these unit, imino-and/or amino heterogeneous ring compound alone or in combination with hydroxyl aryl.

In polyacetal resin, add the stabilization that a spot of this heterocyclic compounds has realized being much better than conventional stablizer, the processability of the polyacetal resin composite of Huo Deing (demolding performace, mold deposit) excellence like this.And because described heterogeneous ring compound sublimability is low, the loss via venting port has significantly been reduced heterogeneous ring compound in moulding such as extrusion moulding process owing to volatilize.And the avidity height of described heterogeneous ring compound and polyacetal resin has significantly improved the phenomenon of oozing out (or frosting) heterogeneous ring compound from the molded article that is formed by polyacetal resin composite.

The ratio of described heterogeneous ring compound can be selected from for example about 0.001-20 weight part, preferably about 0.002-10 weight part (for example about 0.002-5 weight part), and 0.003-3 weight part more preferably from about is with respect to the polyacetal resin meter of 100 weight parts.Especially, even when aforementioned proportion is about 0.005-2 weight part/100 weight part polyacetal resins, also suppressed the generation of formaldehyde significantly.Under the too low situation of the ratio of heterogeneous ring compound, be difficult to reduce effectively the quantity discharged of formaldehyde.Under the too high situation of aforementioned proportion, there is the possibility that makes processability or mechanical property variation.

Described heterogeneous ring compound can be given polyacetal resin remarkable stability and processing stability, even when using described heterogeneous ring compound separately.And described heterogeneous ring compound can be selected from following combinations of substances and uses with at least a: antioxidant, processing stabilizers, thermo-stabilizer, weather-proof (light) stablizer, shock resistance improving agent, slip improving agent, tinting material and filler.

(antioxidant)

Antioxidant can comprise hindered phenol series compound and hindered amine series compound etc.

The hindered phenol series compound comprises conventional phenol series antioxidant or stablizer, and for example, the monocycle hindered phenol compound (for example, 2,6-di-t-butyl-p-Cresol), encircle hindered phenol compound more, wherein encircle via alkyl or the group that contains sulphur atom and interconnect or bonding [for example, C _1-10-alkylidene group-two is to four (tert.-butyl phenols), as 2, and 2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4 '-methylene-bis (2,6 di t butyl phenol) or 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; C _2-10Alkylene group or alkadienylene-two to four (tert.-butyl phenols) as 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol); C _6-20Arylidene or inferior aralkyl-two to four (tert.-butyl phenols) as 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; With two (tert.-butyl phenols), wherein the tert.-butyl phenol group interconnects or bonding via the group with sulphur atom, and for example 4,4 '-thiobis (3 methy 6 tert butyl phenol)], the hindered phenol compound with ester group or amide group [for example, has C _2-10The tert.-butyl phenol of alkylidene group ketonic oxygen group, for example Octadecane base-3-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester or Octadecane base-2-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester; Two to four (tert.-butyl phenols), wherein the tert.-butyl phenol group interconnects or bonding via the polyol ester of lipid acid, for example 1, [3-(3 for 6-hexylene glycol-two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], triglycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester] or tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; Have heterocyclic radical and C _2-10Alkylidene group ketonic oxygen group two to four (tert.-butyl phenols), for example 3,9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane; Has C _3-10The tertiary alkyl phenol of alkenyl carbonyl oxygen groups (for example tert.-butyl phenol and tert.-amyl phenol), for example the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate or 2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate; Hindered phenol compound with phosphonate group, two Octadecane bases-3 for example, 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester; Hindered phenol compound with amide units; N for example; N '-hexa-methylene two (3; 5-di-t-butyl-4-hydroxyl-dihydro cinnamon acid amides); N; [3-(3 for N '-ethylenebis; the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; N, N '-tetramethylene two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; N; N '-hexa-methylene is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; N, N '-ethylenebis [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid amide]; N, N '-hexa-methylene two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid amide]; N; N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; N, N '-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionyl] hydrazine; 1; 3; 5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester or 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester] etc.Wherein, preferably have the phenolic compound of the tertiary butyl (particularly a plurality of tertiary butyl), particularly have the compound in a plurality of tert.-butyl phenols site.Can use these hindered phenol series compounds alone or in combination.

The hindered amine series compound can comprise the piperidine derivative with steric group, for example contains piperidine derivative [for example, aliphatics acyloxy piperidines (for example, the C of ester group _2-20Aliphatics acyloxy-tetramethyl piperidine) as 4-acetoxyl group-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6,6-tetramethyl piperidine or 4-acryloxy-2,2,6,6-tetramethyl piperidine; Aromatics acyloxy piperidines (for example, C _7-11Aromatics acyloxy-tetramethyl piperidine) as 4-benzoyloxy-2,2,6, the 6-tetramethyl piperidine; Aliphatics two-or tricarboxylic acid-two-or three piperidyl ester (for example, C _2-20Aliphatic dicarboxylic acid-dipiperidino ester) as two (2,2,6,6-tetramethyl--4-piperidyl) barkite,

Two (2,2,6,6-tetramethyl--4-piperidyl) malonic ester,

Two (2,2,6,6-tetramethyl--4-piperidyl) adipic acid ester,

Two (1,2,2,6,6-pentamethyl--4-piperidyl) adipic acid ester,

Two (2,2,6,6-tetramethyl--4-piperidyl) sebate,

Two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate; Aromatics two to tetracarboxylic acid-two to four piperidyl esters (for example, aromatics two or tricarboxylic acid-two-or three piperidyl esters) as two (2,2,6,6-tetramethyl--4-piperidyl) terephthalate or three (2,2,6,6-tetramethyl--4-piperidyl) benzene-1,3, the 5-tricarboxylic ester] and contain piperidine derivative [for example, the C of ether _1-10Alkoxyl group piperidines (for example, C _1-6Alkoxyl group-tetramethyl piperidine) as 4-methoxyl group-2,2,6, the 6-tetramethyl piperidine; C _5-8Cycloalkyloxy piperidines such as 4-cyclohexyl oxygen-2,2,6, the 6-tetramethyl piperidine; Aryloxy piperidines such as 4-phenoxy group-2,2,6, the 6-tetramethyl piperidine; C _6-10Aryl-C _1-4Alkoxyl group piperidines such as 4-benzyl oxygen-2,2,6, the 6-tetramethyl piperidine; Or two piperidines (for example, the C of alkylidene dioxygen _1-10Alkylidene dioxygen-two piperidines), two (2,2,6,6-tetramethyl--4-piperidyl oxygen) ethane of 2-as 1], piperidine derivative [for example, formamyl Oxypertine such as 4-(phenyl amino formyl radical oxygen)-2,2,6, the 6-tetramethyl piperidine of amide-containing; With alkylidene dioxygen-two piperidines of carbamoyloxy replacement, for example, two (2,2,6,6-tetramethyl--4-piperidyl) hexa-methylene-1,6-diurethanes].And the hindered amine series compound can also comprise for example polycondensate of high molecular piperidine derivative (for example, dimethyl succinate ester and 1-(2-hydroxyethyl)-4-hydroxyl-2,2,6, the polycondensate of 6-tetramethyl piperidine and poly-(6-[1,1,3, the 3-tetramethyl butyl) imino--1,3,5-triazine-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl) amino] [4-(2 for hexa-methylene, 2,6, the 6-tetramethyl-piperidyl) imino-]).Can be used alone or in combination these hindered amine series compounds.

Can use these antioxidants alone or in combination.The ratio of antioxidant is about 0.001-5 weight part, preferably about 0.005-3 weight part, and 0.01-2 weight part more preferably from about is with respect to the polyacetal resin meter of 100 weight parts.

(processing stabilizers)

Processing stabilizers comprises at least a following composition that is selected from: (a) longer chain fatty acid or derivatives thereof, (b) polyalkylene oxide glycol, (c) silicone series compound etc.

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

Long-chain or higher fatty acid can be saturated fatty acid or unsaturated fatty acids.And a part of hydrogen atom in the higher fatty acid can be substituted base and replace as hydroxyl.Such higher fatty acid for example, has saturated unary fatty acid [for example, the saturated C that is no less than 10 carbon atoms for example for to have list or the difatty acid that is no less than 10 carbon atoms _10-34Lipid acid (preferred saturated C _10-30Lipid acid) as capric acid, lauric acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, stearic acid, eicosanoic acid, docosoic acid or montanic acid], have unsaturated unary fatty acid [for example unsaturated C that is no less than 10 carbon atoms _10-34Lipid acid (preferred unsaturated C _10-30Lipid acid) as oleic acid, linolic acid, linolenic acid, arachidonic acid or erucic acid], have binary lipid acid (binary lipid acid) [for example, the saturated C that is no less than 10 carbon atoms _10-30Binary lipid acid (preferred saturated C _10-26Binary lipid acid) as sebacic acid, dodecanedioic acid, tetradecane diacid or プ ミ ア acid and unsaturated C _10-30Binary lipid acid (preferred unsaturated C _10-26Binary lipid acid) as octene dicarboxylic acid or laurylene diacid] etc.Described lipid acid can also comprise (for example, the hydroxyl-saturated C that has one or more hydroxyl in the molecule _10-26Lipid acid such as 12-oxystearic acid).Can use these lipid acid alone or in combination.In these lipid acid, preferred saturated or unsaturated C _10-26Unary fatty acid and saturated or unsaturated C _10-20Binary lipid acid.

The derivative of described higher fatty acid can comprise for example fatty acid ester, fatty acid amide etc.With regard to fatty acid ester, its structure there is not specific limited, the ester of straight or branched lipid acid all can adopt.What can mention as high-grade aliphatic ester is for example above-mentioned higher fatty acid and the ester (for example, having the ester of one or more ester bond, as monoesters, diester, three esters or four esters) of alcohol.The alcohol that constitutes high-grade aliphatic ester specifically is not limited on a certain specific kind.Such alcohol can be monohydroxy-alcohol.As such alcohol, adopt polyvalent alcohol in many cases usually.

Described polyvalent alcohol comprises have about 2-8 carbon atom polyvalent alcohol or its polymkeric substance of (preferably about 2-6 carbon atom), for example, and as dibasic alcohol [for example, the C of aklylene glycol _2-8Aklylene glycol (preferred C _2-6Aklylene glycol) as ethylene glycol, glycol ether or propylene glycol]; Trivalent alcohol is glycerol, TriMethylolPropane(TMP) or derivatives thereof for example; Tetravalent alcohol, for example tetramethylolmethane, anhydro sorbitol or derivatives thereof; And polyvalent alcohol all or multipolymer [for example the polyalkylene oxide glycol all or multipolymer such as polyoxyethylene glycol or polypropylene glycol, Polyglycerine, Dipentaerythritol and polypentaerythritol].The mean polymerisation degree of polyalkylene oxide glycol is not less than 2 (for example about 2-500), and preferably about 2-400 (for example about 2-360) more preferably is not less than 16 (for example about 20-200).By the way, adopting under the situation of polyalkylene oxide glycol as polyvalent alcohol, as long-chain (or senior) lipid acid that constitutes described ester, the preferred employing has the lipid acid that is no less than 12 carbon atoms, for example saturated or undersaturated C _12-26Unary fatty acid and saturated or undersaturated C _12-20Binary lipid acid.Can use described alcohol alone or in combination.

The example of this long-chain or high-grade aliphatic ester comprises glycol monomethyl or dipalmitate, glycol monomethyl or SUNSOFT Q-182S, glycol monomethyl or two behenates, glycol monomethyl or two montanates, the glycerine list is to tripalmitate, the glycerine list is to tristearate, glycerine Dan Zhisan behenate, glycerine Dan Zhisan montanate, tetramethylolmethane Dan Zhisi cetylate, the tetramethylolmethane list is to tetrastearate, tetramethylolmethane Dan Zhisi behenate, tetramethylolmethane Dan Zhisi montanate, the Polyglycerine tristearate, the TriMethylolPropane(TMP) monopalmitate, tetramethylolmethane list undecylate, Arlacel-60, the list or the dilaurate of polyalkylene glycol (as polyoxyethylene glycol or polypropylene glycol), the list of polyalkylene glycol or dipalmitate, the list of polyalkylene glycol or SUNSOFT Q-182S, the list of polyalkylene glycol or two behenates, the list of polyalkylene glycol or two montanates, the list of the list of polyalkylene glycol or dioleate and polyalkylene glycol or dilinoleic acid ester.

In these derivatives,, can adopt for example acid amides (for example monoamide or bisamide) of higher fatty acid (senior monobasic or binary lipid acid) and amine (as monoamine, diamine or polyamines) as fatty acid amide.In described acid amides, preferred especially bisamide.

As monoamide, can mention for example primary amide of saturated fatty acid (as decyl amide, laurylamide, myristamide, palmitic amide, stearylamide, peanut acid amides, mountain Yu acid amides or brown coal acid amides); The primary amide of unsaturated fatty acids (as oleylamide); Secondary amide (as stearyl-stearylamide or stearyl-oleylamide) with saturated and/or unsaturated fatty acids and monoamine.

Described bisamide can comprise for example lipid acid and C _1-6Alkylenediamine (C particularly _1-2Alkylenediamine) bisamide.The specific examples of bisamide comprises quadrol-two palmitic amide, quadrol-distearyl acid acid amides (ethylenebisstearylam,de), hexamethylene-diamine-distearyl acid acid amides, quadrol-two mountain Yu acid acid amides, quadrol-two montanic acid acid amides, quadrol-two amine hydroxybenzene and quadrol-two erucicamide.And, can also adopt such bisamide, wherein different types of acyl group independently with the amine position bonding of Alkylenediamine, as quadrol-(stearylamide) oleylamide.In described acid amides, the lipid acid that preferably constitutes acid amides is saturated fatty acid.

Can use these long-chains (or senior) fatty amide or derivatives thereof alone or in combination.

(b) polyalkylene oxide glycol

The polyalkylene oxide glycol can comprise aklylene glycol [C for example _2-6Aklylene glycol such as ethylene glycol, propylene glycol or butyleneglycol (preferred C _2-4Aklylene glycol)] all or multipolymer and derivative thereof.

The specific examples of polyalkylene oxide glycol comprises poly-C _2-6The alkylene oxide glycol is as polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol (preferably poly-C _2-4The alkylene oxide glycol), multipolymer such as polyoxyethylene-polyoxypropylene multipolymer (for example random or segmented copolymer), polyoxyethylene-polyoxypropylene glyceryl ether or polyoxyethylene-polyoxypropylene single-butyl ether etc.Wherein, preferably comprise polymkeric substance, for example polyoxyethylene glycol, polyoxyethylene-polyoxypropylene multipolymer and derivative thereof with oxygen ethylene unit.

The number-average molecular weight of described polyalkylene oxide glycol is about 3*10 ²-1*10 ⁶(for example, about 5*10 ²-5*10 ⁵), preferably about 1*10 ³-1*10 ⁵(for example, about 1*10 ³-5*10 ⁴).Can use the polyalkylene oxide glycol alone or in combination.

(c) silicone series compound

Described silicone series compound comprises (gathering) organo-siloxane etc.The example of (gathering) organo-siloxane (for example comprises single organo-siloxane such as dialkylsiloxane, dimethyl siloxane), alkylaryl siloxanes (for example phenyl methyl siloxanes) or diaromatic siloxane (for example, diphenyl siloxane), its homopolymer (for example, polydimethylsiloxane and PSI) or its multipolymer.By the way, described organopolysiloxane can be an oligopolymer.

And; (gathering) organo-siloxane that described (gathering) organo-siloxane can comprise modification (for example; modified silicone); has substituting group (as epoxy group(ing), hydroxyl, alkoxyl group, carboxyl, amino or amino (for example, dialkyl amido), ether, vinyl or (methyl) acryl of being substituted) at its molecular backbone chain or end.Can use these silicone series compounds alone or in combination.

The ratio of processing stabilizers can be selected from for example about 0.001-10 weight part, preferably about 0.01-5 weight part, and 0.03-3 weight part more preferably from about is with respect to 100 weight part polyacetal resin meters.Especially, this ratio can be about 0.03-2 weight part.

(thermo-stabilizer)

Thermo-stabilizer can comprise the basic cpd that (a) is nitrogenous, (b) metal-salt of organic carboxyl acid, (c) alkali or alkaline earth metal compound, (d) hydrotalcite, (e) zeolite, (f) phosphine compound etc.

(a) nitrogenous basic cpd

As nitrogenous basic cpd (or basic nitrogen compound), can adopt be selected from following at least a: aminotriazine compound, guanidine compound, carbamide compound, amino-acid compound, amino alcohol compound, imide compound, amide compound and hydrazine compound.By the way, these nitrogenous basic cpds are different with specific heterocyclic compound of the present invention, can not have hydroxyaryl basically usually.

The aminotriazine compound [for example can comprise the melamine or derivatives thereof, the condenses of melamine, melamine (melam, melem, melon)], the guanamines or derivatives thereof, and aminotriazine resins [for example, the condensation copolymerization resin of melamine (for example, melamine-formaldehyde resin, phenol-melamine resin, melamine-phenol-formaldehyde resin, benzoguanamine-melamine resin and aromatic polyamine-melamine resin) and the condensation copolymerization resin (for example, benzoguanamine-formaldehyde resin and benzoguanamine-phenol-formaldehyde resin) of guanamines].

In the aminotriazine compound, the derivative of guanamines can comprise aliphatics guanamines compound [for example, single guanamines (for example, C _1-24The guanamines that alkyl replaces is as penta guanamines, own guanamines, heptan guanamines, hot guanamines or 18 guanamines) and alkylidene group biguanides amine (C for example _1-24Alkylidene group biguanides amine; as W-37 amine; penta 2 guanamines; oneself two guanamines; pimeloyl amine; hot two guanamines; the ninth of the ten Heavenly Stems two guanamines; or Synthalin A amine)]; alicyclic guanamines series compound [for example; single guanamines (hexanaphthene carbon (carbo) guanamines for example; norborneol olefinic carbon guanamines; hexamethylene olefinic carbon guanamines; norbornane carbon guanamines and by introducing compound that functional group obtains to it (for example; a kind of derivative; its naphthenic hydrocarbon residue has 1-3 as substituent functional group; as alkyl; hydroxyl; amino; acetylamino; nitryl; carboxyl; alkoxy carbonyl; formamyl; alkoxyl group; phenyl; cumyl or hydroxy phenyl))]; aromatics guanamines series compound [for example; single guanamines (benzoguanamine and for example by introducing compound that functional group obtains to it (for example; a kind of benzoguanamine derivative; its phenyl residues has the functional group as substituent 1-5; as alkyl; aryl; amino; acetylamino; nitryl; carboxyl; alkoxy carbonyl; formamyl; alkoxyl group; phenyl or cumyl: for example; adjacent; between; or to the toluene guanamines; adjacent; between or the p-Xylol guanamines; adjacent; between or to the phenyl benzoguanamine; and neighbour; between or to the nitryl benzoguanamine); α-or β-naphtho-guanamines and the derivative by obtaining to its introducing functional group; polyguanidine amine (for example adjacent phenyldiguanide amine; between phenyldiguanide amine; to phenyldiguanide amine; naphthalene two guanamines; with biphenyl two guanamines); with aralkyl or inferior aralkyl guanamines (for example; benzene second guanamines; β-phenylpropyl alcohol guanamines and neighbour; between or p-Xylol biguanides amine))]; [for example contain heteroatomic guanamines series compound; the guanamines that contains acetal radical (for example; 2; 4-diamino-6-(3; 3-dimethoxy propyl group-s-triazine); the guanamines that contains two  alkane rings { for example; [2-(4 '; the ethyl of 6 '-diamino-s-triazine-2 '-yl)]-1; 3-two  alkane; [2-(4 '; the ethyl of 6 '-diamino-s-triazine-2 '-yl)]-4-ethyl-4-hydroxymethyl-1; 3-two  alkane }; the guanamines that contains four oxo volutions (for example; CTU-guanamines and CMTU-guanamines); the guanamines that contains the isocyanuric acid ring (for example; 1; 3; [2-(4 ' for 5-three; the ethyl of 6 '-diamino-s-triazine-2 '-yl)] isocyanuric acid ester and 1; 3; [3-(4 ' for 5-three; the propyl group of 6 '-diamino-s-triazine-2 '-yl)] isocyanuric acid ester), the guanamines compound of description among guanamines of imidazole ring-containing (for example guanamines compound of describing among the Japanese Patent Application No.41120/1972 (JP-47-41120A)) and the Japanese Patent Application No.154181/2000 (JP-2000-154181A))).And described aminotriazine compound can also comprise the compound [for example single to hexamethoxy methyl cyanuramide, single to tetramethoxy methyl benzoguanamine and single to eight methoxymethyies-CTU-guanamines] that for example has alkoxy methyl on the amino of melamine, melamine derivative or guanamines series compound.

Described guanidine compound can comprise for example non-annularity guanidine (for example guanidoacetic acid, guanolin, guanidine and dicyanodiamide), ring-type guanidine (for example, glycocyamidine compound such as glycocyamidine or creatinine; With oxalyl guanidine with similar structures or ring-type guanidine, as oxalyl guanidine or 2,4-diimino parabanic acid); The urazole compound (for example, imino-urazole and guanazine) that imino-replaces; Isocyanide urea imide (for example, isoammelide and isoammeline); Malonylguanidine, the tartronyl guanidine; Mesoxalyl guanidine etc.

Described carbamide compound can comprise hydrazo-dicarbonamide, biuret, the joint compound that contracts (urea formaldehyde) of urea and formaldehyde, ring-type urea series compound [for example, hydantoin compound (for example, glycolylurea, 5-methyl glycolylurea, 5-ethyl glycolylurea, 5-sec.-propyl glycolylurea, 5, the 5-T10,5, the 5-five methene glycolylurea, 5-methyl-5-phenyl glycolylurea, 5, the 5-diphenyl hydantoin, 5-benzyl glycolylurea and 5-(neighbour, between or p-aminophenyl) glycolylurea), wallantoin, the metal-salt of wallantoin (for example, aluminium salt: wallantoin dihydroxyl aluminium salt), the crotonylidene allophanamide, acetylene urea, Dan Zhisi alkoxy methyl glycoluril (for example single) to tetramethoxymethylglycoluril, uric acid and urazole].

Described amino acid whose example comprises that a-amino acid [for example, mono amino monocarboxylic acid (glycine for example, L-Ala, Xie Ansuan, norvaline, leucine, nor-leucine, Isoleucine, phenylalanine, tyrosine, diiodotyrosine, N-methyltyrosine, Threonine, Serine, proline(Pro), oxyproline, tryptophane, methionine(Met), Gelucystine, halfcystine, citrulline, butyrine, piperolinic acid, teanine, with neighbour or m-Tyrosine), the mono amino dicarboxylic acid (for example, aspartic acid, L-glutamic acid, l-asparagine, glutamine, six hydrogen, two pyridine carboxylic acids and six hydrogen quinolinic acids) and diamino monocarboxylate's (Methionin for example, oxylysine, arginine and Histidine)], beta-amino acids (Beta-alanine for example, beta-aminobutyric acid and six hydrogen cinchomeronic acids), gamma-amino acid (for example, γ-An Jidingsuan), δ-amino acid (for example, the positive valeric acid of δ-amino) etc., by the way, these amino acid can be D-, L-or DL-formula.Described amino acid can also comprise amino acid derivative, and wherein carboxyl is through metal salinization (for example an alkali metal salt, alkaline earth salt), amidation, hydrazidesization or esterification (for example, methyl-esterified, ethyl esterification).

Described amino alcohol compound comprises amino C _1-10Aliphatics list or polyvalent alcohol, as monoethanolamine, diethanolamine, 2-amino-1-butanols, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, ammediol, 2-amino-2-ethyl-1, ammediol or three (methylol) aminomethane.

The example of imide compound comprises aromatic polycarboxylic acid imide such as phthalic imidine, inclined to one side benzene trimellitic imide or equal diimides etc.

Described amide compound for example comprises aliphatic carboxylic acid amide (Malonamide for example, adipamide, sebacoyl amine and dodecane diamide), cyclic carboxylic acids acid amides (for example ε-Ji Neixianan) and aromatic carboxylic acid's acid amides (benzamide for example, adjacent, between or Para Amino Benzamide, m-phthalic acid diamide and terephthalamide), polymeric amide series resin [for example, 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, nylon 6-66-610 and nylon 9 T], polyesteramide, polyamidoimide, urethane, poly-(methyl) acrylamide all or multipolymer, its can be crosslinked [for example, the polymkeric substance of describing among the US patent No.5011890], poly-(vinyl lactam) all or multipolymer [for example, poly-(N-vinyl pyrrolidone) all or multipolymer (for example, describe among Japanese Patent Application No.52338/1980 (JP-55-52338A) and the US patent No.3204014 all or multipolymer)], poly-(N-vinyl carboxylic acid acid amides), the multipolymer of N-vinyl carboxylic acid acid amides and another kind of vinyl monomer (for example, Japanese Patent Application No.247745/2001 (JP-2001-247745A), 131386/2001 (JP-2001-131386A), 311302/1996 (JP-8-311302A) and 86614/1984 (JP-59-86614A) and US patent No.5455042, describe in 5407996 and 5338815 all or multipolymer), or the like.

Described hydrazine compound can comprise for example fatty acyl hydrazide (for example, bay hydrazides, stearic hydrazide, adipic dihydrazide, sebacic dihydrazide and dodecanedioic acid two hydrazides) and aromatic carboxylic acid's hydrazides (for example phenylformic acid hydrazides, naphthoic acid hydrazides, O-phthalic acid dihydrazide, isophthalic dihydrazide, terephthaldehyde's acid dihydrazide, naphthalic acid two hydrazides, para hydroxybenzene formyl hydrazine and salicylyl hydrazine).

(b) metal salt of organic carboxylic acid

Described metal salt of organic carboxylic acid can comprise for example salt (for example, basic metal such as Li, Na or K, alkaline-earth metal such as Mg or the Ca of organic carboxyl acid and metal; With transition metal such as Zn).

Described organic carboxyl acid can be low-molecular weight compound or high-molecular weight compounds.As organic carboxyl acid, beyond saturated or unsaturated senior aliphatic carboxylic acid, can adopt to have the saturated or unsaturated lower aliphatic carboxylic acid that is less than 10 carbon atoms and the polymkeric substance of unsaturated aliphatic carboxylic acid with the form example of higher fatty acid.And these aliphatic carboxylic acids can have hydroxyl.Saturated lower aliphatic carboxylic acid can comprise saturated C _1-9Monocarboxylic acid (for example, acetate, propionic acid, butyric acid, isopropylformic acid, valeric acid, isovaleric acid, PIVALIC ACID CRUDE (25), caproic acid and sad), saturated C _2-9Dicarboxylic acid (for example, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, cork acid and nonane diacid) and alcohol acid (for example, oxyacetic acid, lactic acid, R-Glyceric acid, hydroxybutyric acid and citric acid) thereof.

Unsaturated lower aliphatic carboxylic acid can comprise for example unsaturated C _3-9Monocarboxylic acid [for example (methyl) vinylformic acid, Ba Dousuan and iso-crotonic acid], unsaturated C _4-9Dicarboxylic acid (for example, toxilic acid and fumaric acid) and alcohol acid (for example propynoic acid) thereof.

And, [for example can be used as polymkeric substance that the unsaturated aliphatic carboxylic acid enumerates and can be the polymerizable unsaturated carboxylic acid, α, β-ethylene type (alkene chain type) unsaturated carboxylic acid, for example, monoesters (for example, single C of polycarboxylic acid of the acid anhydrides of polymerisable unsaturated monocarboxylic acid (as (methyl) vinylformic acid), the unsaturated polycarboxylic acid of polymerizable (as methylene-succinic acid, toxilic acid or fumaric acid), polycarboxylic acid or polycarboxylic acid _1-10Alkyl ester is as ethyl maleate) with alkene (α-C for example _2-10Alkene is as ethene or propylene) multipolymer.

Can use the salt of these metals of organic carboxyl acid alone or in combination.

Preferred metal salt of organic carboxylic acid (for example can comprise organic carboxyl acid and alkali-metal salt, Lithium Citrate de, Tripotassium Citrate, Trisodium Citrate, lithium stearate and 12-hydroxy lithium stearate), the salt of organic carboxyl acid and alkaline-earth metal (for example magnesium acetate, calcium acetate, magnesium citrate, citrate of lime, calcium stearate, Magnesium Stearate, 12-oxystearic acid magnesium and 12-oxystearic acid calcium), ionomer resin (in the multipolymer of unsaturated polycarboxylic acid of polymerizable and alkene contained at least a portion carboxyl by metal ion neutral resin) etc.The ACLYN that described ionomer resin for example is purchased (Allied Signal Inc. production), Himilan (Du Pont-MitsuiPolychemicals Co., Ltd. produces), Surlyn (Du Pont production) etc.

In metal-salt, consider stabilization effect, preferred bases earth metal salt such as citrate of lime, Magnesium Stearate, calcium stearate, 12-oxystearic acid magnesium or 12-oxystearic acid calcium (particularly citrate of lime).

(c) basic metal or alkaline earth metal compound

Described basic metal or alkaline earth metal compound can comprise mineral compound, and for example metal oxide (as CaO or MgO), metal hydroxides are (as LiOH, Ca (OH) ₂Or Mg (OH) ₂) and the salt of mineral acid and metal [for example inorganic acid salt is (as the salt of carbonic acid and metal (as Li ₂CO ₃, Na ₂CO ₃, K ₂CO ₃, CaCO ₃Or MgCO ₃), borate and phosphoric acid salt)].Especially, preferable alloy oxide compound and metal hydroxides.And, in described compound, the preferred bases earth metal compound.

Can use these basic metal or alkaline earth metal compound alone or in combination.

(d) hydrotalcite

As hydrotalcite, the hydrotalcite of enumerating among Japanese Patent Application No.1241/1985 (JP-60-1241A) and the Japanese Patent Application No.59475/1997 (JP-9-59475A) is an available such as the hydrotalcite compound that following formula characterized.

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

In the formula, M ²⁺Represent Mg ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺Or any other divalent-metal ion; M ³⁺Represent Al ³⁺, Fe ³⁺, Cr ³⁺Or any other trivalent metal ion; A ^N-Represent CO ₃ ^2-, OH ^-, HPO ₄ ^2-, SO ₄ ^2-Or its n valency negatively charged ion of any base (particularly monovalence or dianion); X is 0＜x＜0.5; M is 0≤m＜1.

Can use these hydrotalcites alone or in combination.

By the way, described hydrotalcite can be from Kyowa Chemical Industry Co., and Ltd. buys with the trade(brand)name of " DHT-4A ", " DHT-4A-2 " or " Alcamizer ".

(e) zeolite

Described zeolite is not specific be limited to specific a kind of, the zeolite of non-H-type zeolite all can adopt, for example the zeolite of enumerating among the Japanese Patent Application No.62142/1995 (JP-7-62142A) [zeolite of the microcrystal silicon aluminate that its least unit lattice is basic metal and/or alkaline-earth metal (A-, X-, Y-, L-and ZSM-type zeolite, mordenite type zeolite; Chabazite, mordenite, faujusite and other natural zeolite)].

Can use these zeolites alone or in combination.

By the way, A type zeolite is with " ZEOLAM-series (A-3, A-4, A-5) ", " ZEOSTAR-series (KA-100P, NA-100P, CA-100P) " etc., X-type zeolite is with " ZEOLAM-series (F-9) ", " ZEOSTAR-series (NX-100P) " etc., from Tosoh Corp. or Nippon ChemicalIndustrial Co., Ltd. buys y-type zeolite with " HSZ series (320NAA) " etc.

(f) phosphine compound

The example of described phosphine compound can comprise phosphine compound, as alkylphosphines (three C for example _1-10Alkylphosphines is as triethyl phosphine, tripropyl phosphine or tributylphosphine), cycloalkyl phosphine (for example, three C _5-12The cycloalkyl phosphine is as tricyclohexyl phosphine), aryl phosphine (for example, three C _6-12Aryl phosphine, it can have substituting group (as amino or C _1-4Alkyl), as triphenylphosphine, p-methylphenyl diphenylphosphine, di-p-tolyl Phenylphosphine, three-m-aminophenyl phosphine, three (2, the 4-3,5-dimethylphenyl) phosphine, three (2,4, the 6-trimethylphenyl) alkyl aryl phosphine (for example, three (C phosphine or three (adjacent, or p-methylphenyl) phosphine), _6-12Aryl C _1-4Alkyl) phosphine is as three (adjacent, or to the anisyl phosphine), aromatic yl alkenyl phosphine (for example, single or two C _6-12Aryl-two-or single C _2-10Alkenyl phosphine such as diphenylacetylene phosphine or allyl group diphenylphosphine), aryl alkyl aryl phosphine (for example, single or two C _6-12Aryl-two-or single (C _6-12Aryl C _1-4Alkyl) phosphine is as to anisyl diphenylphosphine or two (to anisyl) Phenylphosphine; And C _6-12Aryl-(C _6-12Aryl C _1-4Alkyl) phosphine, it can have substituting group (as C _1-10Alkyl), as aminomethyl phenyl-to the anisyl phosphine) or diphosphine compound [for example, two (two C _6-12The aryl phosphino-) C _1-10Alkane is as 1, two (diphenylphosphino) butane of 4-] etc.Can use these phosphine compounds alone or in combination.

Can use these thermo-stabilizers alone or in combination.Especially, be used in combination nitrogenous basic cpd and at least a be selected from following composition in, can also be that resin combination is given thermostability: the metal-salt of organic carboxyl acid, alkali or alkaline earth metal compound, hydrotalcite, zeolite and phosphine compound with the thermo-stabilizer of less amount.By the way, do not containing substantially under the situation of phosphonium flame retardant, resin combination of the present invention also can improve thermostability.

Contain at resin combination under the situation of thermo-stabilizer, the ratio of thermo-stabilizer is selected from for example about 0.001-10 weight part, and preferably about 0.001-5 weight part (particularly about 0.01-2 weight part) is with respect to the polyacetal resin meter of 100 weight parts.

(weather-proof (light) stablizer)

Described weather-proof (light) stablizer comprises (a) benzotriazole series compound, (b) benzophenone series compound, (c) aromatic benzoate series compound, (d) alpha-cyanoacrylate ester series compound, (e) careless aniline series compound, (f) hydroxyaryl-1,3,5-triazine series compound, (g) hindered amine series compound etc.

(a) benzotriazole series compound

The example of benzotriazole series compound comprises having by hydroxyl and C _1-6The benzotriazole cpd of the aryl that alkyl replaces, as 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two (tertiary butyl) phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two (tert-pentyl) phenyl) benzotriazole or 2-(2 '-hydroxyl-3 ', 5 '-diisoamyl phenyl) benzotriazole; Have by the benzotriazole cpd of the aryl of hydroxyl and aralkyl (or aryl) replacement, as 2-[2 '-hydroxyl-3 ', 5 '-two (α, α-Er Jiajibianji) phenyl] benzotriazole; Have by hydroxyl and alkoxyl group (C for example _1-12Alkoxyl group) benzotriazole cpd of the aryl of Qu Daiing is as 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole) etc.

In these benzotriazole series compounds, have by hydroxyl and C particularly preferred comprising _3-6The C that alkyl replaces _6-10The benzotriazole cpd of aryl (particularly phenyl) and having by hydroxyl and C _6-10Aryl-C _1-6Alkyl (phenyl-C particularly _1-4Alkyl) benzotriazole cpd of the aryl of Qu Daiing.

(b) benzophenone series compound.

As benzophenone series compound example be benzophenone compound with a plurality of hydroxyls (for example, two-to tetrahydroxybenzophenone such as 2,4 dihydroxy benzophenone; The benzophenone compound of the aryl or aralkyl that has hydroxyl and replaced by hydroxyl is as 2-hydroxy-4-hydroxymethyl base benzyl benzophenone); Has hydroxyl and alkoxyl group (C for example _1-16Alkoxyl group) benzophenone compound (for example 2-hydroxyl-4-methoxyl group benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-dodecyloxy benzophenone, 2,2 '-dihydroxyl-4-methoxyl group benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy benzophenone and 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone) etc.

In these benzophenone series compounds, the benzophenone series compound preferably includes the C that has hydroxyl and replaced by hydroxyl _6-10Aryl (or C _6-10Aryl-C _1-4Alkyl) benzophenone compound, the phenyl-C that particularly has hydroxyl and replaced by hydroxyl _1-4Alkyl.

(c) aromatic benzoate series compound

Described aromatic benzoate series compound comprises that the alkylaryl salicylate is as to tert-butyl-phenyl salicylate or p-octylphenyl salicylate (particularly alkyl phenyl salicylate).

(d) alpha-cyanoacrylate ester series compound

As alpha-cyanoacrylate ester series compound example be the diaryl acrylic acid ester such as the 2-ethylhexyl-2-cyano group-3 of cyano-containing, 3-diphenylacrylate ester or ethyl-2-cyano group-3,3-diphenylacrylate ester (the particularly diphenylacrylate ester of cyano-containing).

(e) careless aniline series compound

Described careless aniline series compound comprises for example oxalyl amine compound, it has aryl (as phenyl) on nitrogen-atoms, wherein aryl can have substituting group, for example N-(2-ethylphenyl)-N '-(2-oxyethyl group-5-tert-butyl-phenyl) oxalyl amine, and N-(2-ethylphenyl)-N '-(2-oxyethyl group-phenyl) oxalyl amine.

(f) hydroxyaryl-1,3,5-triazines series compound

Hydroxyaryl-1,3,5-triazines series compound as weather-proof (light) stablizer is different with above-mentioned heterogeneous ring compound, can adopt the compound that does not contain active imino-and active amino substantially.

The example of this type of hydroxyaryl-1,3,5-triazines series compound comprises 2,4-two C _6-10Aryl-6-(list or dihydroxyl C _6-10Aryl)-and 1,3,5-triazines [for example, 2,4-two C _6-10Aryl-6-(list or dihydroxyl C _6-10Aryl)-and 1,3,5-triazines, on its aryl, can have substituting group (as C _1-10Alkyl, C _1-18Alkoxyl group, C _1-10Alkoxy C _1-10Alkoxyl group, C _6-10Aryloxy or C _6-10Aryl C _1-6Alkoxyl group), for example the hydroxyaryl triazine is as 2,4-phenylbenzene-6-(2-hydroxy phenyl)-1,3,5-triazines or 2,4-phenylbenzene-6-(2, the 4-dihydroxy phenyl)-1,3,5-triazines; Hydroxy alkoxy base aryl-triazine is as 2,4-phenylbenzene-6-(2-hydroxyl-4-p-methoxy-phenyl)-1,3, the 5-triazine, 2,4-phenylbenzene-6-(2-hydroxyl-4-ethoxyl phenenyl)-1,3, the 5-triazine, 2,4-phenylbenzene-6-(2-hydroxyl-4-propoxy-phenyl)-1,3,5-triazines, 2,4-phenylbenzene-6-(2-hydroxyl-4-butoxy phenyl)-1,3, the 5-triazine, 2,4-phenylbenzene-6-(2-hydroxyl-4-hexyloxy phenyl)-1,3, the 5-triazine, 2,4-phenylbenzene-6-(2-hydroxyl-4-octyloxyphenyl)-1,3, the 5-triazine, 2,4-phenylbenzene-6-(2-hydroxyl-4-dodecyloxy phenyl)-1,3,5-triazines or 2,4-two (p-methylphenyl or 2 ', 4 '-3,5-dimethylphenyl)-6-(2-hydroxyl-C _1-16Alkoxyl phenyl)-1,3,5-triazines, corresponding to these 2, each of 4-phenylbenzene-6-(2-hydroxyl-alkoxyl phenyl)-1,3,5-triazines; Hydroxy aralkyl oxygen base aryl-triazine is as 2,4-phenylbenzene-6-(2-hydroxyl-4-benzyloxy phenyl)-1,3,5-triazines or 2,4-two (p-methylphenyl or 2 ', 4 '-3,5-dimethylphenyl)-6-(2-hydroxyl-4-benzyloxy phenyl)-1,3,5-triazines; Hydroxy alkoxy base alkoxy aryl triazine is as 2,4-phenylbenzene-6-(2-hydroxyl-4-(2-butoxy oxyethyl group) phenyl)-1,3,5-triazines or 2,4-di-p-tolyl-6-(2-hydroxyl-4-(2-hexyloxy oxyethyl group) phenyl)-1,3,5-triazines etc.In these compounds, preferred hydroxy phenyl-1,3,5-triazines series compound.

(g) hindered amine series compound

As the hindered amine series compound, can adopt the hindered amine series compound of example in above-mentioned antioxidant paragraph.

Can use these weather-proof (light) stablizers alone or in combination.Can be used in combination weather-proof (light) stablizer of identical or different kind.

By the way, preferably hindered amine series compound and other weather-proof (light) combination of stabilizers is used.Especially, preferably benzotriazole series compound and hindered amine series compound are used in combination.The hindered amine series compound can for example be about 0/100-80/20 with respect to the ratio (weight ratio) [hindered amine series compound (g)/other weather-proof (light) stablizer] of other weather-proof (light) stablizer (particularly benzotriazole series compound), preferred about 10/90-70/30, more preferably from about 20/80-60/40.

The ratio of weather-proof (light) stablizer is for example for about 0-5 weight part (for example about 0.01-5 weight part), preferably about 0.1-4 weight part, and 0.1-2 weight part more preferably from about is with respect to the polyacetal resin meter of 100 weight parts.

(tinting material)

As tinting material, can adopt various dyestuffs or pigment.As dyestuff, the preferred solvent dyestuff comprises for example azo series dyestuff, anthraquinone series dyestuff, phthalocyanine series dyes or naphthoquinones series dyes.Described pigment can be mineral dye or pigment dyestuff.

What can be used as the mineral dye example is titanium series (titaniferous) pigment, zinc series (containing zinc) pigment, carbon black (for example black ト of furnace black, thermally oxidized black, acetylene black and ケ Star チ ユ Application), 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.

Pigment dyestuff comprises azo series pigment, anthraquinone series pigment, phthalocyanine serial pigment, quinacridone series pigment, perylene serial pigment, perinone serial pigment, isoindoline serial pigment, two  piperazine serial pigments or ス レ Application serial pigment.

Can use tinting material separately, perhaps, can be used in combination multiple these tinting materials.Use the tinting material [as carbon black, titanium white (titanium oxide), phthalocyanine serial pigment, perylene serial pigment (particularly carbon black, perylene series black pigment)] of high light shield effect to guarantee the improvement of polyacetal resin composite weather-proof (light) performance.

The content of tinting material is for example for about 0-5 weight part (for example, about 0.01-5 weight part), preferably about 0.1-4 weight part, and 0.1-2 weight part more preferably from about is with respect to 100 weight part polyacetal resin meters.

Can in polyacetal resin composite of the present invention, randomly add conventional additives, for example antioxidant (for example, phosphorous, sulfur-bearing, quinhydrones series and quinoline series antioxidant), specific carboxylic acid (for example carboxylic acid of describing among the Japanese Patent Application No.239484/2000 (JP-2000-239484A)), shock resistance improving agent [vinylformic acid core-shell polymer for example, urethane series resin and polyester series resin], slip improving agent [olefin resin for example, silicone series plastics and fluorine resin], releasing agent (stripper), nucleator, static inhibitor, fire retardant, tensio-active agent, antiseptic-germicide, anti-mycotic agent, perfume compound, spices, various polymkeric substance [for example, acrylic resin (C _1-10Alkyl (methyl) acrylate all or multipolymer as poly-(methyl methacrylate)), polycarbonate series resin, polyolefin elastomer or resin, polyvinyl alcohol series resin and aliphatic polyester series resin (for example, the multipolymer of poly-(L-lactic acid), poly-(D-lactic acid), poly-(D/L lactic acid), polyglycolic acid and oxyacetic acid and lactic acid (for example D-, L-or D/L-lactic acid))], reach filler etc.Can add these components alone or in combination.Be used in combination under the situation that is no less than two kinds of these components, these components can be identical or different species.

And if necessary, described resin combination can be further mixes to improve the performance of molded article of the present invention mutually with a kind of conventional fillers of or combination (as fibrous, sheet or granulated filler).The example of bat wool comprises inorganic fibre (for example glass fibre, carbon fiber, boron fibre and potassium titanate fiber (whisker)), organic fibre (for example, nylon) etc.As laminal filler, what can mention is sheet glass, mica, graphite, various tinsels etc.The example of granulated filler comprises metal oxide (zinc oxide for example, aluminum oxide), vitriol (for example calcium sulfate, sal epsom), carbonate (for example lime carbonate), glass (for example milled fibre, granulated glass sphere and glass envelope), silicate (for example talcum, kaolin, silica, diatomite, clay and wollastonite), sulfide (for example, molybdenumdisulphide and tungsten disulfide), carbide is (for example, fluorographite and silicon carbide), boron nitride etc.

(preparation method of polyacetal resin composite)

Polyacetal resin composite of the present invention can be granular mixture or molten mixture, and can prepare by polyacetal resin is mixed in a usual manner with specific heterocyclic compound and (if necessary) other additive [for example stablizer (antioxidant, processing stabilizers, thermo-stabilizer, weather-proof (light) stablizer), shock resistance improving agent, slip improving agent, tinting material and/or filler].For example, adopted following method, method (1) comprises: add whole components via main opening for feed, with forcing machine (for example single shaft or biaxial extruder) mixture that obtains is mediated and extruded to granular, go out molded article from described grain forming, method (2) comprises: through main opening for feed add do not contain specific heterogeneous ring compound component (for example, polyacetal resin and above-mentioned other additive), at least contain the component of specific heterogeneous ring compound (as other component via the interpolation of side loading mouth, what can mention is polyacetal resin, above-mentioned other additive etc.), with forcing machine particle is mediated and be extruded into to the mixture that obtains, by described grain forming molded article, method (3) comprises: contain the component of some specific heterogeneous ring compound (as other component through main opening for feed interpolation, be polyacetal resin, other additive etc.) and via the side loading mouth add the component of the specific heterogeneous ring compound that contains remainder (as other component, polyacetal resin, other additive etc.), adopt forcing machine to mediate and extrude the component of interpolation with the preparation particle, from described grain forming molded article; (4) different particles (masterbatch) is formed in preparation; mix (dilution) described particle with specified proportion then; the molded article that has specific composition by the grain forming that obtains; or method (5) comprises: make specific heterocyclic compound and the coexistence of granular polyacetal resin or adhesion thereon by for example spraying or apply (for example surface-coated), had the molded article of specific composition by the grain forming that obtains.

In these methods, preferred method (1), (2) and (3).Especially, preferably come each component of melt kneading by having the single shaft or the biaxial extruder that are no less than 1 venting port.And described heterogeneous ring compound can come the side to add via the charging opening that is positioned at venting port upstream or downstream.And, extrude with preparation process in, can further reduce the amount of the formaldehyde that from shaping (or molding) goods that obtained, gives off by following preparation method, this method via the charging opening premix processing aid of venting port upstream such as water and/or alcohol (for example comprises, methyl alcohol, ethanol, Virahol and n-propyl alcohol) or inject processing aid, discharge and remove the volatile constituent that contains water and/or alcohol from venting port.The water and/or the pure amount of adding as this processing aid are not limited on the specified quantitative.The amount of water and/or alcohol can be selected from about 0-20 weight part usually, and with respect to 100 weight part polyacetal resin meters, and preferably about 0.01-10 weight part, more preferably 0.1-5 weight part is with respect to 100 weight part polyacetal resin meters.

By the way, be used for the preparation of compositions of molded article, will be (for example as Powdered (particulate state) polyacetal resin of substrate (for example by means of abrasion or whole powder (particle) of obtaining of polyacetal resin) and other component, specific heterocyclic compound, other additive (for example stablizer, shock resistance improving agent, slip improving agent, tinting material and/or filler)) mix, next therefore melt kneading is favourable to improve the dispersity of additive.

Polyacetal resin composite of the present invention has realized polyacetal resin because the remarkable restriction of the formaldehyde emissions that oxidation or thermolysis etc. cause or inhibition and to the improvement or the improvement of Working environment, particularly in the step of moulding and processing (particularly melt molding and processing).And, the deposition of degradation production or additive or decomposition (mold deposit) on the mould, these products or additive from the molded article frosting or ooze out and can obtain significant restriction or suppress, and overcome problem in various moulding and the procedure of processing.

(molded article)

The present invention also comprises the molded article that is formed by described resin combination.This molded article contains polyacetal resin and specific heterocyclic compound with array mode and has excellent extruding and/or moulding process stability, and formaldehyde emissions (or generation) amount is few.In other words, discharge quite a large amount of formaldehyde, cause corrosion and variable color and the pollution of live and work environment by the molded article of the conventional polyacetal resin moulding that contains antioxidant and other stablizer.For example, the formaldehyde that (in the dry atmosphere of homothermic) gives off from the common molded polyacetal resin product of commercialization under drying conditions is about 2-5 μ g/1cm ²Surface-area and/or under wet condition (in the moistening atmosphere of homothermic) about 3-6 μ g/1cm ²Surface-area.

On the other hand, in polyacetal resin molded article of the present invention, can reduce the amount of the formaldehyde that from molded article, gives off effectively by more a spot of specific heterogeneous ring compound.And, under the situation that is used in combination specific heterogeneous ring compound and thermo-stabilizer (formaldehyde inhibitor), also can suppress formaldehyde emission largely.Particularly, under drying conditions, formaldehyde emission is no more than 1.5 μ g/1cm ²The molded article surface-area, preferably about 0-1.0 μ g, more preferably from about 0-0.6 μ g is generally about 0.001-1.0 μ g, and then about 0-0.1 μ g also can realize.And under wet condition, formaldehyde emissions is no more than 2.5 μ g (for example about 0-2 μ g)/1cm ²The molded article surface-area, preferably about 0-1.2 μ g, 0-0.4 μ g more preferably from about, and then about 0-0.2 μ g also can realize.Amount under the wet condition is generally about 0.001-1.2 μ g.

Molded article of the present invention can demonstrate above-mentioned formaldehyde emission under drying conditions or wet condition.Especially, under dry and wet condition, described molded article demonstrates above-mentioned formaldehyde emissions level under many circumstances.Therefore, molded article of the present invention can be as adapting to the more material of harsh and unforgiving environments.

By the formaldehyde emission under the following mensuration drying conditions.

After the polyacetal resin molded article being cut as required and measure its surface-area, the suitable part of goods (for example, is equivalent to about 10-50cm ²The amount of surface-area) is placed in the container (20ml capacity), at 80 ℃ temperature lower seals and left standstill (or keep) 24 hours.Then, in the container of sealing, add 5ml water and according to JIS (Japanese Industrial Standards) K0102,29 (formaldehyde clauses and subclauses) are analyzed the formaldehyde in the aqueous solution, to calculate formaldehyde emission (the μ g/cm of molded article per surface area ²).

Can be by the formaldehyde emission under the following mensuration wet condition.

After the polyacetal resin molded article being cut as required and measure its surface-area, the suitable part of goods (for example, is equivalent to about 10-100cm ²The amount of surface-area) is suspended on the lid of the sealable container (1L capacity) that contains 50ml distilled water.After container sealing, make this container leave standstill (or keep) in the baking oven of 60 ℃ of constant temperature 3 hours.Afterwards, this container was at room temperature left standstill 1 hour, according to JISK0102,29 (formaldehyde clauses and subclauses) are analyzed the formaldehyde in the aqueous solution, to calculate formaldehyde emission (the μ g/cm of goods per surface area ²).

The quantification definition of above PARA FORMALDEHYDE PRILLS(91,95) quantity discharged of the present invention is applicable to polyacetal resin and specific heterocyclic compound, i.e. this definition is not only applicable to by (for example comprising conventional additives, conventional stablizer and releasing agent) the molded article of polyacetal resin composite moulding, also be applicable to molded article by the suitable resin combination moulding that contains mineral filler and/or other polymkeric substance, even be most of product surface (for example, the 50-100% of total surface area) constitutes (for example, polychrome goods or goods) by bunching resin aldehyde through applying.

Industrial applicability

Resin combination of the present invention can be used for coming the various molded articles of moulding by conventional moulding (or shaping) method (for example injection moulding, extrusion moulding, compression molding, blow molding, vacuum forming, foaming, rotoforming and gas injection moulding).

And, molded article of the present invention (or moulded parts) can be applicable to any formaldehyde can hurtful Application Areas (for example handling knob and bar as attachments of a bicycle) and can be advantageously used for part and element in the multiple field, comprises parts, Constracture unit and pipeline installation parts, family expenses (daily) and cosmetic preparation parts and medical facilities (diagnosis or the treatment are used) parts of trolley part, Electrical and Electronic assembly (driven unit and passive component).

More specifically, described trolley part comprise automobile inner part such as inside handle, fuel manifold opener, buckle of safety belt, auxiliary security band, various switch, handle knob, bar and folder; Electrical system parts such as instrument and web member; Electrical and Electronic parts or annex in the car relevant with stereo set or Vehicular navigation equipment, with the parts of metallic contact, window regulator board, mechanical part such as door lock actuating parts, mirror element, rain brush motor system parts and prime the fuel system parts are arranged typically.

Described electric or electronic package parts (mechanical part) comprise the parts that for example are made of the polyacetal resin molded article and are installed together with a plurality of metal joints or element (for example stereo set such as tape type sound-track engraving apparatus, image documentation equipment such as belt video recorder (VTR), 8mm or other pick up camera etc., office automation (OA) equipment such as duplicating machine, facsimile recorder, word processor, computer, the toy that is driven by electro-motor or spiral spring power, phone, as the keyboard of computer auxiliary equipment etc.).What particularly, can mention is chassis (base), gear, bar, cam, pulley and bearing.And, described electric or electronic package parts can be used for optics and the magnetic recording media parts (for example metallic film tape cassete, disk cartridge, optomagnetic tray salver etc.) made by the moulding polyacetal resin to small part, more specifically, music metal tape drum, digital sound tape drum, 8mm picture recording tape drum, floppy disk (registered trademark) box, minifloppy box etc.As specific optics and magneticmedium parts, what can mention is tape drum parts (belt box body, tape spool, core, guide wheel, roll shaft, baffle plate, lid etc.) and tray salver parts (tray salver body (outer box), valve, fixed plate etc.).

In addition, polyacetal resin molded article of the present invention can be advantageously used in Constracture unit and line member, as associated components between set lights parts, interior architecture element (as joint, stationary installation, furnishings), pipeline, bolt, faucet, wash water etc., multiple product, makeup and the medical facilities relevant, for example fastening piece (as slide fastener, hasp, hoop fastener, slide rail bar fastener), stationery, lipstick or lipstic case, washer, water purifier, nozzle, spraying plant or container, aerosol container, universal container and syringe tray with daily daily life.

Embodiment

Following examples are intended to describe in more detail the present invention, and, never be interpreted as this

Defining of invention scope.

By the way, reference example and Comparative Examples, the formaldehyde amount that under dry and wet condition, from moulding (or molding) goods, gives off and ooze out performance and be based on that following method assesses.

[the formaldehyde amount that from molded article, gives off under the drying conditions]

With each by 10 samples (sample: 2mm*2mm*50mm; Total surface area: about 40cm ²) resin sample formed be placed on container (volume, 20ml) in sealing, and heating 24 hours in 80 ℃ constant temperature oven.To room temperature, adopt syringe in container, to inject 5ml distilled water in air cooling.According to JISK0102,29 (formaldehyde clauses and subclauses) are measured the formaldehyde content of this aqueous solution and formaldehyde gas quantity discharged (the μ g/cm of Units of Account surface-area ²).

[the formaldehyde amount that from molded article, gives off under the wet condition and ooze out performance]

With sheet specimen (100mm*40mm*2mm; Total surface area: 85.6cm ²) be suspended on the lid of the polyethylene bottle (volume 1L) that contains 50ml distilled water.Seal this bottle, in 60 ℃ constant temperature oven, left standstill 3 hours, then at room temperature left standstill 1 hour.According to JISK0102,29 (formaldehyde clauses and subclauses) are measured the formaldehyde content of the aqueous solution in the bottle and are calculated formaldehyde gas quantity discharged (the μ g/cm of goods per surface area ²).

And then, the surface of the sheet sample (molded article) after the visual inspection test, the degree of oozing out based on following criterion evaluation.

" A ": do not observe and ooze out.

" B ": observe slightly and ooze out.

" C ": observe CR Critical oozing out.

Embodiment 1-18

Polyacetal resin multipolymer, heterogeneous ring compound, antioxidant, processing stabilizers, thermo-stabilizer, tinting material and weather-proof (light) stablizer in ratio premix 100 weight parts of indication in table 1 and 2 with hydroxyl aryl unit.For each mixture that obtains like this, with the main charging opening supply of mixture via the biaxial extruder with a venting port (30mm diameter), melting mixing is with the preparation particulate composition.

By the particle of such acquisition,,, measure the formaldehyde amount that gives off from sample and ooze out performance for each sample with injection moulding machine manufacturing regulation sample.The results are shown in table 1 and 2.

Comparative Examples 1-4

For comparing, adopt the sample of no heterogeneous ring compound preparation and added the not sample of the heterogeneous ring compound of hydroxyl aryl, use with embodiment in the identical mode sample that has been shaped, and assessed the formaldehyde emission of each sample.The results are shown in the table 3.

By the way, it is as follows to be used for polyacetal resin multipolymer, heterogeneous ring compound, antioxidant, processing stabilizers, thermo-stabilizer, tinting material and weather-proof (light) stablizer of embodiment and Comparative Examples.

1, Copolyacetal " a "

(a-1): polyacetal resin multipolymer (melting index=9g/10 minute)

(a-2): polyacetal resin multipolymer (melting index=27g/10 minute)

By the way, melting index is under the condition of 190 ℃ and 2169g, the value of measuring according to ASTM-D1238 (g/10 minute).

2, heterogeneous ring compound " b "

(b-1): 6-(4 '-hydroxy phenyl)-2,4-diamino-1,3,5-triazines

(b-2): 6-[β-(4 '-hydroxy phenyl) ethyl]-2, the 4-diamino-1,3,5-triazines

(b-3): 5-(4 '-hydroxy phenyl) glycolylurea

(b-4): 2-(2 '-hydroxy phenyl)-4,5-diphenyl-imidazole

(b-5): 2-(2 '-hydroxy phenyl)-benzoglyoxaline

(b-6): melamine

(b-7): glycolylurea

3, antioxidant " c "

(c-1): triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester]

(c-2): tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]

4, processing stabilizers " d "

(d-1): ethylenebisstearamide

(d-2): montanate [Toyo-Petrolite Co., Ltd. makes, " LUZAWAX-EP "]

(d-3): polyoxyethylene glycol [molecular weight: 35000]

5, thermo-stabilizer (metal salt of organic carboxylic acid, alkaline earth salt, nitrogenous basic cpd) " e "

(e-1): 12-oxystearic acid calcium

(e-2): Magnesium Stearate

(e-3): magnesium oxide

(e-4): citrate of lime

(e-5): wallantoin

(e-6): hydrazo-dicarbonamide

(e-7): nylon 6 (median size=3 μ m)

(e-8): dodecanedioic acid two hydrazides

(e-9): sebacic dihydrazide

6, tinting material " f "

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

7, weather-proof (light) stablizer " g "

(g-1): 2-[2 '-hydroxyl-3 ', 5 '-two (α, α-Er Jiajibianji) phenyl] benzotriazole

(g-2): two (2,2,6,6-tetramethyl--4-piperidyl) sebate

Table 1

	Embodiment
													1	2	3	4	5	6	7	8	9	10	11	12
	Polyacetal resin multipolymer " a " (weight part)	a-1 100	a-1 100	a-1 100	a-1 100	a-1 100	a-2 100	a-2 100	a-1 100	a-1 100	a-1 100	a-1 100													a-1 100
Heterocycle imino-compound " b " (weight part)													b-1 0.8	b-2 0.8	b-3 0.3	b-1 0.8	b-3 0.3	b-1 0.8	b-3 0.3	b-1 0.2	b-1 0.2	b-1 0.8	b-3 0.1	b-3 0.1
	Antioxidant " c " (weight part)	c-1 0.3	c-1 0.3	c-1 0.3	c-1 0.3	c-1 0.3	c-2 0.3	c-2 0.3	c-1 0.3	c-1 0.3	c-1 0.3	c-1 0.3													c-1 0.3
Processing stabilizers " d " (weight part)													d-1 0.2	d-1 0.2	d-1 0.2	d-2 0.2	d-2 0.2	d-3 0.2	d-3 0.2	d-1 0.2	d-1 0.2	d-1 0.2	d-1 0.2	d-1 0.2
	Thermo-stabilizer " e " (weight part)	e-1 0.1	e-1 0.1	e-1 0.1	e-2 0.1	e-2 0.1	e-3 0.03	e-3 0.03	e-4 e-5 0.1 0.05	e-3 e-6 0.03 0.05	e-4 e-7 0.1 0.05	e-4 e-7 0.1 0.05													e-4 e-8 0.1 0.05
Tinting material " f " (weight part)													-	-	-	-	-	-	-	-	-	-	-	-
	Weather-proof (light) stablizer " g " (weight part)	-	-	-	-	-	-	-	-	-	-	-													-
Formaldehyde emission, dry (μ g/cm 2)													0.13	0.15	0.09	0.14	0.10	0.12	0.08	0.07	0.06	0.11	0.08	0.05
	Formaldehyde emission, moist (μ g/cm 2)	0.12	0.18	0.10	0.11	0.11	0.11	0.09	0.09	0.08	0.11	0.08													0.07
Ooze out performance													A	A	A	A	A	A	A	B	A	A	A	A

Table 2

	Embodiment
							13	14	15	16	17	18
	Polyacetal resin multipolymer " a " (weight part)	a-1 100	a-1 100	a-1 100	a-1 100	a-1 100							a-1 100
Heterocycle imino-compound " b " (weight part)							b-4 0.5	b-5 0.3	b-1 0.8	b-3 0.3	b-1 0.8	b-3 0.3
	Antioxidant " c " (weight part)	c-1 0.3	c-1 0.3	c-1 0.3	c-1 0.3	c-1 0.03							c-1 0.03
Processing stabilizers " d " (weight part)							d-1 0.2	d-1 0.2	d-1 0.2	d-1 0.2	d-1 0.2	d-1 0.2
	Thermo-stabilizer " e " (weight part)	e-1 0.1	e-3 e-9 0.03 0.05	e-1 0.1	e-1 0.1	e-1 0.1							e-1 0.1
Tinting material " f " (weight part)							-	-	f-1 0.5	f-1 0.5	-	-
	Weather-proof (light) stablizes chaste tree " g " (weight part)	-	-	-	-	g-1 g-2 0.4 0.2							g-1 g-2 0.4 0.2
Formaldehyde emission, dry (μ g/cm 2)							0.14	0.06	0.15	0.12	0.31	0.28
	Formaldehyde emission, moist (μ g/cm 2)	0.13	0.09	0.17	0.14	0.25							0.20
Ooze out performance							A	A	A	A	A	A

Table 3

	Comparative Examples
					1	2	3	4
	Copolyacetal " a " (weight part)	a-1 100	a-1 100	a-1 100					a-1 100
Formaldehyde inhibitor " b " (weight part)					-	-	b-6 0.8	b-7 0.3
	Anti-oxidant chaste tree " c " (weight part)	c-1 0.3	c-1 0.03	c-1 0.3					c-1 0.3
Processing stabilizers " d " (weight part)					d-1 0.2	d-1 0.2	d-1 0.2	d-1 0.2
	Thermo-stabilizer " e " (weight part)	e-1 0.1	e-1 0.1	e-1 0.1					e-1 0.1
Tinting material " f " (weight part)					-	-	-	-
	Weather-proof (light) stablizer " g " (weight part)	-	g-1 g-2 0.4 0.2	-					-
Formaldehyde emission, dry (μ g/cm 2)					2.80	2.54	0.12	0.10
	Formaldehyde emission, moist (μ g/cm 2)	1.35	2.30	0.19					0.15
Ooze out performance					A	A	c	c

Apparent from table, to compare with Comparative Examples, the formaldehyde emission among the embodiment obviously descends or has reduced, and means remarkable work and the environment for use improved.And embodiment has improved and has oozed out performance, has improved the quality of molded article thus.

Claims (8)

1, polyacetal resin composite comprises polyacetal resin and heterogeneous ring compound, and wherein this heterogeneous ring compound has unit and at least a imino-and the amino active group of being selected from that contains hydroxyaryl at least.

2, the resin combination of claim 1, wherein this heterogeneous ring compound has following group (i) and (ii):

(i) at least a be selected from hydroxyaryl, hydroxyaryl alkyl, hydroxyaryl aryl, list or two (hydroxyaryl) are amino and single or two (hydroxyaryl alkyl) are amino group and

(ii) imino-, its nitrogen-atoms constitutes the heteroatomic imino-of heterogeneous ring compound, or amino.

3, the resin combination of claim 1, wherein this heterogeneous ring compound be selected from following at least a: aminotriazine compound, cyclic ureide compound, imidazolinium compounds and imidazolium compounds; And has an at least a following group that is selected from: hydroxyl C _6-14Aryl, hydroxyl C _6-14Aryl C _1-6Alkyl, hydroxyl C _6-14Aryl-C _6-10Aryl, single or two (hydroxyl C _6-14Aryl) amino and two (hydroxyl C _6-14Aryl C _1-6Alkyl) amino.

4, the resin combination of claim 1, wherein this heterogeneous ring compound comprises and has at least a heterocycle that is selected from following group: imino-, its nitrogen-atoms constitute the heteroatomic imino-of heterogeneous ring compound, and amino, and comprise the unit that contains with the hydroxyaryl of this heterocycle bonding.

5, the resin combination of claim 1, wherein the ratio of this heterogeneous ring compound is the 0.001-20 weight part, with respect to the polyacetal resin meter of 100 weight parts.

6, the resin combination of claim 1, it further comprises at least a following composition that is selected from: antioxidant, thermo-stabilizer, processing stabilizers, weather-proof (light) stablizer, shock resistance improving agent, slip improving agent, tinting material and filler.

7, the molded article that is shaped by the polyacetal resin composite described in the claim 1.

8, the molded article of claim 7, it is trolley part, electric or electronic components, building or line member, home appliances or cosmetic product parts or medical facilities parts.