JP3086266B2 - Stabilized polyoxymethylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyoxymethylene resin having excellent heat stability and a composition thereof.

[0002]

2. Description of the Related Art Polyoxymethylene resins are well-balanced in various physical properties and are easy to process, so that they can be used as typical engineering plastics, such as electric / electronic parts, automobile parts, etc. It is widely used as a mechanical component. However, with the expansion and diversification of applications, the demand for the quality thereof has been increasing. Required characteristics include a decrease in mechanical strength due to the extrusion or molding process, and adhesion to molds (mold deposit).
Generation, under long-term heating conditions (heat aging)
Reduction of mechanical properties, suppression of coloring of molded articles and the like to a low level can be mentioned. One of the important factors of these phenomena is decomposition of the polymer upon heating.

[0003] Due to its chemical structure, polyoxymethylene inherently has the property of being easily decomposed under acidic or alkaline conditions in a heated oxidizing atmosphere.
To stabilize the chemically active terminal, the terminal of the polymer is esterified by acetylation or the like (homopolymer), or trioxane and a cyclic ether are used during polymerization.
There is a method in which a monomer having an adjacent carbon bond such as cyclic formal is copolymerized, and then the unstable terminal portion is decomposed and removed to make an inactive stable terminal (copolymer). However, upon heating, a cleavage decomposition reaction also occurs in the main chain portion of the polymer, and its prevention cannot be dealt with only by the above treatment, and the addition of antioxidants and other stabilizers is practically essential. I have.

[0004] However, the polyoxymethylene composition containing these stabilizers does not completely suppress the decomposition of the polymer. In practice, during the molding, the action of heat or oxygen in the cylinder of the molding machine is not achieved. Receiving, by main chain decomposition,
Alternatively, formaldehyde is generated from the terminal that is not sufficiently stabilized, and when the working environment is deteriorated during extrusion molding or when molding is performed for a long time, fine powder or tar is attached to the mold surface (mold deposit). ),
It is one of the biggest factors that lowers the working efficiency and deteriorates the surface condition of the molded product. The decomposition of the polymer causes a decrease in mechanical strength and coloring of the resin. Further, when the molded article is heated for a long time (heat aging), the decomposition of the main chain also causes a decrease in mechanical strength and coloring. Under these circumstances, efforts are being made to find more effective stabilizer formulations.

As an antioxidant to be added to the polyoxymethylene resin, a phenol compound having a sterically hindered group (hindered phenol) or an amine compound having a sterically hindered group (hindered amine) is used. Compounds such as polyamides, urea derivatives, amidine compounds, hydroxides of alkali or alkaline earth metals, and organic or inorganic acid salts are used in combination. Hindered phenols are particularly effective as antioxidants, but phenols are weak acids, and they also become strong acids by absorbing light, so they can be used as catalysts for polymer decomposition as the amount added increases. The oxidized form is also likely to be a coloring factor. In some cases, the resin itself causes a mold deposit during molding.
Therefore, at the time of molding, heat aging, or under light irradiation conditions, it functions as a stabilizer and at the same time, it is also a factor of polymer decomposition, and the formulation of the stabilizer that balances molding stability, heat aging stability, and weather resistance is delicate. In spite of various proposals and ideas, satisfactory results have not always been obtained.
An object of the present invention is to improve the stability of such polyoxymethylene.

[0006]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and conducted a search for a more effective stabilizer for polyoxymethylene, and as a result, have found that a phenoxy unit is contained in the structure. The present inventors have found that a specific series of compounds including these compounds have an effect as a stabilizer for polyoxymethylene, which led to the present invention. That is, the present invention relates to a polyoxymethylene resin composition characterized in that 0.01 to 5% by weight of a phenoxy compound represented by the general formula (I) is added to and blended with a polyoxymethylene resin. Another object of the present invention is to improve problems based on stability, such as deterioration of a resin due to thermal decomposition, generation of a mold deposit, and deterioration during heat aging.

[0007]

Embedded image

[0008] X¹~ X^FourIs -C_pH_2p-, -C_pH_2pOC_qH_2q-, -C_pH
_2pSC_qH_2q-, -C_pH_2pN (C_rH_{2r + 1}) C_qH_2q-, -C_pH_2pCOC_qH_2q-, -C_pH_2pCO
OC_qH_2q-, -C_pH_2pCON (C_rH_{2r + 1}) C_qH_2q-, -C_pH_2pS (= O)_TwoC_qH_2q-, -C_pH_2pP (= O) (R) C_qH_2q-, -C_pH_2pP (= O) (R) OC_qH_2q-, -C_pH
_2pOP (= O) (R) OC_qH_2q-(However, p, q, r are integers from 0 to 20, R is C₁~ C₂₀Archi
, Alkoxy, phenyl, or phenoxy
Represents a divalent atomic group selected from
May be. Among them, preferably -C_pH_2p-, C_pH_2pOC_qH
_2q-, -C_pH_2pSC_qH_2q-, -C_pH_2PCON (C_rH_{2r + 1}) C_qH_2q-, -C_pH_2pCOC
_qH_2q-, -C_pH_2pCOOC_qH_2q-Yes. Ar¹~ Ar^FourRepresents an aromatic ring such as a benzene ring or a naphthalene ring
However, a benzene ring is particularly preferred. These aromatic rings are X¹~
X^FourAnd -OY¹~ -OY^FourNo substitution except for, or -C_mH_{2m + 1},-(C_mH_2mO)_nC_pH_{2p + 1}, -C_mH_2mSC_pH_{2p + 1}, -C_mH
_2mCOC_nH_{2n + 1}, -C_mH_2mCOOC_nH_{2n + 1}, -C_mH_2mOCOC_nH_{2n + 1}, -C_mH_2mS (= O)_TwoC_n
H_{2n + 1}, -C_mH_2mN (C_pH_{2p + 1}) (C_qH_{2q + 1}), -C_mH_2mCON (C_pH_{2p + 1}) (C_qH
_{2q + 1}), -C_mH_2mN (C_pH_{2p + 1}) COC_qH_{2q + 1}, -C_mH_2mPR¹R^Two, -C_mH_2m(P
= O) R¹R^Two, -C_mH_2mOPR¹R^Two, -C_mH_2mOP (= O) R¹R^Two  (However, m and n are integers of 1 to 20, p and q are integers of 0 to 20,
R¹, R^TwoIs C₁~ C₂₀Alkyl, alkoxy or
Phenyl or phenoxy group), or phenyl group, etc.
May have a substituent introduced therein.
If this occurs, increase the reactivity of this compound or
Effective in improving compatibility with simethylene resin
is there. The number of these substituents is not limited to one, but may be plural or two.
What was introduced above may be used. However, aromatic ring Ar¹~ Ar^FourTo
Those directly bonded to -OH groups are excluded from the compounds of the formula (I).

-OY ^{1 to} OY ⁴ are substituents other than a hydroxyl group, that is, as Y ^{1 to} Y ⁴ , -C _m H _{2m + 1} ,-(C _m H _2m O) _n C _p H _{2p + 1} , -C _m H _2m SC _p H _{2p + 1} , -C _m H _2m N (C _p H
_{2p + 1} ) (C _q H _{2q + 1} ), -C _m H _2m COC _n H _{2n + 1} , -C _m H _2m COOC _n H _{2n + 1} , -C _m H _2m OCOC _n H
_{2n + 1} , -C _m H _2m CON (C _p H _{2p + 1} ) (C _q H _{2q + 1} ), -C _m H _2m N (C _p H _{2p + 1} ) COC _q
H _{2q + 1} , -C _m H _2m S (= O) ₂ C _n H _{2n + 1} , -C _m H _2m P (= O) (R) C _n H _{2n + 1} , -C _m H _2m
P (= O) (R) OC _n H _{2n + 1} , -C _m H _2m OP (= O) (R) C _n H _{2n + 1} , -C _m H _2m OP (= O) (R) OC _n H _{2n + 1} (where m and n are integers from 1 to 20, p and q are integers from 0 to 20, R
Represents an alkoxy derivative represented by C ₁ -C ₂₀ alkyl, alkoxy group or phenyl or phenoxy group, and among these, -C _m H _{2m + 1} ,-(C _m H _2m O) _n C _p H _2p An alkyl group such as ₊₁ or a hydroxyalkyl and a condensate thereof are preferable, for example, a linear alkyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like as the alkyl group, and hydroxyethyl as the hydroxyalkyl group. Group, hydroxypropyl group, hydroxybutyl group, 3-hydroxy-2-methylpropyl group,
2-hydroxy-2-methylpropyl group, hydroxypentyl group, 3-hydroxy-2,2-dimethylpropyl group, etc., and ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, etc. as condensates of hydroxyalkyl groups A polycondensate. Furthermore, -C _m H _2m COOC _n H _{2n + 1} , -C _m H _2m OCOC _n H _{2n + 1} , or -C _m H _2m N (C _p H _{2p + 1} ) (C _q H
_{2q + 1} ) alkyl ester and alkyl amine represented by Y
It is preferred as the ¹ to Y ^4. The positions of the substituents bonded to Ar ^{1 to} Ar ⁴ , that is, X ^{1 to} X ⁴ and —OY ¹ to —OY ⁴ and other substituents are not particularly limited.

These compounds of the formula (I) are added in an amount of 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the polyoxymethylene resin. When the amount of these compounds is too small, the stabilizing effect is poor. On the other hand, when the amount is excessive, the decomposition and discoloration of the polymer may be accelerated, which is not preferable.

A polyoxymethylene compound containing these additives is a high molecular compound having an oxymethylene group as a main structural unit and containing a small amount of a polyoxymethylene homopolymer or other structural units in addition to the oxymethylene group. Any of the following copolymers, terpolymers and block copolymers may be used, and the molecules may have not only a linear but also a branched or crosslinked structure. The degree of polymerization is not particularly limited, and any degree may be employed as long as molding is possible.

Although the above compounds have a remarkable stabilizing effect when used alone, they further contain other nitrogen-containing compounds such as amines and amides, hydroxides of inorganic or alkaline earth metals, inorganic acid salts and carboxylic acids. It is also possible to use one or more metal-containing compounds such as salts or alkoxides and sterically hindered phenol compounds in combination.

Here, the nitrogen-containing compound is nylon 12,
Polyamides such as Nylon 6.12, Nylon 6.66.610, homo- or copolymerized polyamides, substituted polyamides having a methylol group, etc., nylon salts, polyesters such as polyesteramides synthesized from a combination with caprolactam, polyaminotriazole, dicarboxylic acid Acid dihydrazide, heat condensate synthesized by heating from urea, uracils, cyanoguanidines, dicyandiamide, guanamine (2,4-diamino-sym-triazine), melamine, N-butylmelamine, N-phenylmelamine;
N, N-diphenylmelamine, N, N-diallylmelamine, N, N ′, N ″ -triphenylmelamine, N, N
N ', N "-trimethylolmelamine, benzoguanamine, 2,4-diamino-6-methyl-sym-triazine, 2,4-diamino-6-butyl-sym-triazine, 2,4-diamino-6-benzyloxy -Sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sy
m-triazine, 2,4-diamino-6-chloro-sym
-Triazine, 2,4-diamino-6-mercapto-sy
m-triazine, 2,4-dioxy-6-amino-sym
-Triazine (Ameride), 2-oxy-4,6-diamino-sym -Triazine (Ameline), N, N,
N ', N'-tetracyanoethylbenzoguanamine and the like. Further, hindered amines described below are also included.

Examples of the metal compound include hydroxides such as sodium, potassium, magnesium, calcium and barium, carbonates, phosphates, silicates, borates, and the like.
Carboxylates such as oxalates, malonates, succinates, adipates, etc., and higher (C ₁₀
-C ₃₂₎ such as salts of substituted higher fatty acids having a substituent such as fatty acid salts and hydroxyl group can be mentioned. Further, basic compounds containing at least one tertiary nitrogen atom and a metal of a carboxylic acid in the same molecule, for example, sodium N-methyliminodiacetate, trisodium nitrilotriacetate, tetrasodium ethylenediaminetetraacetate, dicalcium ethylenediaminetetraacetate, Examples include pentasodium diethylenetriaminepentaacetate, pentapotassium diethylenepentaacetate, pentasodium triethylenetetramine hexaacetate, and sodium ethyleneoxybis (ethylamine) -N, N, N ', N'-4 acetate.

When the compound of the formula (I) in the present invention is used in combination with a known antioxidant, such as a hindered phenol or a hindered amine, the compound further has a remarkable synergy in improving heat stability, especially heat aging characteristics. The effect is recognized.

Examples of the hindered phenol-based antioxidant used in combination for this purpose include 2,2'-methylenebis (4-methyl-6-tert-butylphenol) and
1,6-hexanediol-bis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3
-Tert-butyl-5-methyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) and the like.

The hindered amine compound is a piperidine derivative having a sterically hindered group. Examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine and 4-stearoyloxy-2,2. , 6,6-
Tetramethylpiperidine, 4-acryloyloxy-
2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy- 2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6
6-tetramethylpiperidine, 4-benzyloxy-
2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate , Screws (2, 2, 6,
6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-)
Piperidyl) sebacate and the like. Also, a high-molecular-weight piperidine derivative polycondensate, for example, dimethyl succinate-1
-(2-hydroxyethyl) -4-hydroxy-2,
2,6,6-tetramethylpiperidine polycondensate is also effective.

The composition of the present invention contains
Or to impart properties according to the purpose to the molded product, general additives to thermoplastic resins, for example, coloring agents such as dyes and pigments, lubricants, nucleating agents, release agents, antistatic agents and other surfactants, Alternatively, one or more kinds of organic polymer materials, inorganic or organic fibrous, powdery, and plate-like fillers can be added.

The method of preparing the composition of the present invention is not particularly limited, and for example, it is effective to simply blend well.
After mixing the respective components, the mixture may be melt-kneaded and extruded by an extruder or the like to form pellets, which may be formed. A method of once preparing pellets having different compositions, mixing the pellets in a predetermined amount, subjecting the mixture to molding, and obtaining a molded article having a desired composition after molding, or a method of directly charging one or more of each component to a molding machine, Either can be used. Further, it is an effective method to make a part of the resin component into a fine powder and to mix and add the other components in order to make the compounding of the additive uniform. Further, the resin composition according to the present invention can be molded by any of extrusion molding, injection molding, compression molding, vacuum molding, blow molding, foam molding and the like.

[0020]

As shown in the above description and Examples, the compound of formula (I) according to the present invention does not itself contain an element as an acid and hardly becomes a coloring substance. The resin composition has a great effect on suppressing polymer decomposition during molding, preventing the generation of decomposition gas, suppressing the decrease in the degree of polymerization and the accompanying decrease in mechanical strength, and suppressing the occurrence of mold deposits and preventing coloring. In addition, the present invention provides a polyoxymethylene resin or a composition thereof, which is effective for preventing mechanical strength reduction and coloring during heat aging, improving weather resistance, and the like, and having balanced thermal stability. Things.

[0021]

EXAMPLES In order to specifically demonstrate the effects of the present invention,
The present invention will be described with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 3 and Comparative Examples 1 to 2 As Examples 1 to 3, 100 parts of a polyoxymethylene copolymer resin containing no stabilizer were taken and pulverized. A compound of

[0023]

Embedded image

0.3 parts by weight of each was added and mixed well under a nitrogen atmosphere. In order to evaluate the degree of polymer main chain decomposition based on the change over time in the melt viscosity accompanying a decrease in molecular weight, 10 g of this mixture was charged into a Takara Kogyo MX101 type melt indexer and melted and retained at 210 ° C for a predetermined time. , Inner diameter 2.09
The weight (MI value) of the resin flowing out per 10 minutes was measured through a mm orifice while applying a load of 2.16 kg.
The measurement was performed after the resin was charged for 7 minutes, 30 minutes, and 60 minutes, and the increase in MI value after 60 minutes, ΔMI = MI (60
Min) -MI (7 minutes). For comparison, a polyoxymethylene copolymer resin without any additives,
And pentaerythritol-tetrakis [3- (3,3) as a known representative hindered phenolic antioxidant
5-Di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, Ciba-Geigy) 0.3
Polyoxymethylene copolymer resin
The same measurement was performed for those added to 100 parts by weight (Comparative Examples 1 and 2, respectively). Table 1 shows the results.

[0025]

[Table 1]

By adding a phenoxy compound, the initial MI
Some values increased, but this was thought to be due to the lubricating effect of the additive, and due to a different mechanism from the decomposition of the polymer. The increase of the MI value of the composition of the present invention after 30 minutes is small, and the decomposition of the polymer chain is extremely efficiently suppressed. Further, even after 60 minutes, the increase (ΔMI) is extremely small.

Examples 4 to 6, Comparative Examples 3 to 4 Polyoxymethylene copolymer resin and additives (A) to (C) were blended according to the same formulation as in Examples 1 to 3,
The mixture was melt-kneaded and extruded at 00 ° C. using an extruder to form pellets. Put 8g of these pellets in the melt indexer,
After being melted and retained at 200 ° C for 5 minutes, the mixture is discharged under a load, the formaldehyde generated is collected, measured by the acetylacetone method, and expressed as the weight (ppm) of formaldehyde generated relative to the resin per unit weight. did. For comparison, no additive was added (Comparative Example 3), and
Irganox 1010 was similarly blended (Comparative Example 4).

Using these pellets, the pellets were allowed to stay at a temperature of 200 ° C. for 1 hour in an injection molding machine, and then were placed in a 40 mm × 70 mm
A 2 mm × 2 mm plate-like molded product was molded, and the coloring associated with the melt retention was measured with a Nippon Denshoku Industries Co., Ltd. Z-1001DP colorimeter, and the yellowness (JIS K7103) was measured. In addition, these pellets are
Injection molding at a cylinder temperature of 00 ℃, 40mm x 70mm x 2
A JIS K7113 No. 1 type (thickness: 3 mm) tensile test piece was prepared. After leaving this molded product at 140 ° C. for 8 days (heat aging), the retention of tensile elongation was measured using a tensile test piece, and the coloring (displayed as yellowness) was measured using a plate-like molded product. Table 2 also shows these results.

[0029]

[Table 2]

The compositions (Examples) of the present invention have a significant reduction in the amount of formaldehyde generated, little coloring during melt retention, an improvement in elongation retention after heat aging, and an effect in preventing coloring. Was.

Examples 7 to 9 and Comparative Examples 5 to 6 Each of the compound (A) was added in an amount of 0.1, 100 parts by weight to 100 parts by weight of a polyoxymethylene copolymer resin containing no additive.
1 and 2 parts by weight were added, and the same evaluation as in Examples 1 to 6 was performed. For comparison, 0.005 parts by weight of compound (A) and 10 parts by weight
In the same manner, the addition of 100 parts by weight of the polyoxymethylene copolymer resin was evaluated. Table 3 shows the results.

[0032]

[Table 3]

Although those having an addition amount within the range of the present invention gave favorable results, the addition of 0.005 parts by weight had little effect on polymer decomposition, gas generation and elongation retention, while
Addition of 10 parts by weight resulted in large coloring.

Examples 10 to 12, Comparative Example 7 Compounds (A) to (A) shown in Examples 1 to 3 were added to 100 parts by weight of a polyoxymethylene copolymer resin containing no additive.
(C) was added in an amount of 0.3 part by weight and 0.2 part by weight of melamine to each, and evaluated in the same manner as in Examples 1 to 6. As a comparative example, the same evaluation was performed when only 0.2 part by weight of melamine was similarly added. The results are shown in Table 4.

[0035]

[Table 4]

Also in this case, the composition of the present invention showed an improvement effect in terms of suppression of formaldehyde gas generation, retention of elongation after heat aging, and the like.

Examples 13 to 18, Comparative Examples 8 to 9 0.2 parts by weight of each of the compounds shown in Examples 1 to 3 and Irganox 1010 which is a phenolic antioxidant or bis (2,2) which is a hindered amine antioxidant 2,6,6-
Tetramethyl-4-piperidyl) sebacate (Sanol LS)
-770, Sankyo Co., Ltd.) 0.2 parts by weight each, plus melamine
0.2 parts by weight was added to 100 parts by weight of the polyoxymethylene copolymer resin, and the same evaluation as in Examples 1 to 6 was performed. As comparative examples, 0.4 parts by weight of Irganox 1010 and 0.2 parts by weight of melamine (Comparative Example 8), or Sanol LS-770 0.4
2 parts by weight and melamine 0.2 part by weight (Comparative Example 9) were added and evaluated in the same manner as in the Examples. The results are summarized in Table 5.

[0038]

[Table 5]

Also in this case, the composition of the present invention has MI change,
Effective in suppressing formaldehyde gas generation,
The elongation retention was also good. In addition, although the coloring tendency was slightly observed when used in combination with hindered phenol, the coloring level was lower than that of the hindered phenol single addition system (Comparative Example 8).

Continuation of the front page (56) References JP-A-62-225511 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 59/00-59/04

Claims (5)

(57) [Claims] (1) A compound represented by the general formula (I):
A stabilized polyoxymethylene resin composition containing about 5% by weight. Embedded image X ^{1 to} X ⁴ are -C _p H _2p- , -C _p H _2p OC _q H _2q- , -C _p H _2p SC _q H _2q- , -C _p H _2p N (C _r H _{2r + 1} ) C _{q H 2q -, -C p H} 2p COC q H 2q -, -C p H 2p CO
OC _q H _2q- , -C _p H _2p CON (C _r H _{2r + 1} ) C _q H _2q- , -C _p H _2p S (= O) ₂ C _q H _2q- , -C
_p H _2p P (= O) (R) C _q H _2q- , -C _p H _2p P (= O) (R) OC _q H _2q- , -C _p H _2p OP (= O) (R) OC _q represents a divalent atomic group selected from H _2q- (where p, q, and r are integers of 0 to 20, and R represents a C _{1 to} C ₂₀ alkyl, alkoxy group or phenyl or phenoxy group) , May be the same or different. Ar ^{1 to} Ar ⁴ represent a benzene or naphthalene ring (excluding those having a direct hydroxyl group as a substituent). Y ^{1 to} Y ⁴ are -C _m H _{2m + 1} ,-(C _m H _2m O) _n C _p H _{2p + 1} , -C _m H _2m SC _p H
_{2p + 1} , -C _m H _2m N (C _p H _{2p + 1} ) (C _q H _{2q + 1} ), -C _m H _2m COC _n H _{2n + 1} , -C _m H
_2m COOC _n H _{2n + 1} , -C _m H _2m OCOC _n H _{2n + 1} , -C _m H _2m CON (C _p H _{2p + 1} ) (C _q H _{2q + 1} ), -C _m H _2m N ( C _p H _{2p + 1} ) COC _q H _{2q + 1} , -C _m H _2m S (= O) ₂ C _n H _{2n + 1} , -C _m H _2m P (= O) (R) C _n H _{2n + 1} , -C _m H _2m P (= O) (R) OC _n H _{2n + 1} , -C _m H _2m OP (= O) (R) C _n H _{2n + 1} , -C _m H _2m OP (= O) (R) OC _n H _{2n + 1} (where m and n are integers from 1 to 20, p and q are integers from 0 to 20, R
Is a monovalent atomic group selected from C _{1 to} C ₂₀ alkyl, alkoxy groups or phenyl and phenoxy groups),
They may be the same or different. 2. A compound represented by the general formula (I), X ¹ ~X ⁴ is _{-C p H 2p -, C p} H 2p OC q H 2q -, -C p H 2p SC q H 2q -, -C _p H _2P CON (C _r H _{2r + 1} ) C _q H _2q- , -C _p H _2p COC _q H _2q- , -C _p H _2p C
OOC _q H _2q - (where, p, q, r is an integer of 0 to 20) stabilized polyoxymethylene resin composition according to claim 1, wherein an atomic group selected from. 3. The compound represented by the general formula (I), wherein Y ^{1 to} Y ⁴ are -C _m H _{2m + 1} ,-(C _m H _2m O) _n C _p H _{2p + 1} , -C _m H _2m COOC _n H _{2n + 1} , -C _m
H _2m OCOC _p H _{2p + 1} , -C _m H _2m N (C _p H _{2p + 1} ) (C _q H _{2q + 1} ) (where m and n are integers from 1 to 20, p and q are 0 to 0) The stabilized polyoxymethylene resin composition according to claim 1 or 2, which is an atomic group selected from the group consisting of: 4. In the general formula (I), Ar¹~ Ar^FourBut,
 -X¹~ -X^FourAnd -OY¹~ -OY^FourOther than unsubstituted, or
-C_mH_{2m + 1},-(C_mH_2mO)_nC_pH_{2p + 1}, -C_mH_2mSC_pH_{2p + 1}, -C_mH_2mCOC_nH_{2n + 1}, -C_mH_2mCOOC_nH
_{2n + 1}, -C_mH_2mOCOC_nH_{2n + 1}, -C_mH_2mS (= O)_TwoC_nH_{2n + 1}, -C_mH_2mN (C_pH_{2p + 1}) (C_qH_{2q + 1}), -C_mH_2mCON (C_pH_{2p + 1}) (C_qH
_{2q + 1}), -C_mH_2mN (C_pH_{2p + 1}) COC_qH_{2q + 1}, -C_mH_2mPR¹R^Two, -C_mH_2m(P
= O) R¹R^Two, -C_mH_2mOPR¹R^Two, -C_mH_2mOP (= O) R¹R^Two  (However, m and n are integers of 1 to 20, p and q are integers of 0 to 20,
R¹, R^TwoIs C₁~ C₂₀Alkyl, alkoxy or
Phenyl, phenoxy group), and phenyl group
A benzene ring having the selected atomic group as a substituent
The stabilized polyoxy according to any one of claims 1 to 3,
Simethylene resin composition. 5. A phenolic compound, a nitrogen-containing compound, an alkali or alkaline earth metal, containing 0.01 to 5% by weight of the compound represented by the general formula (I) according to any one of claims 1 to 4. A stabilized polyoxymethylene resin composition comprising one or more of a hydroxide, an inorganic acid salt and a carboxylate.