JPH11343383A - Weather-resistant polyacetal resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyacetal resin compsn. which not only has an improved weather resistance but also gives a colored article improved in uneven coloration and mold deposition tendency by compounding a polyacetal resin with specific fatty acid ester compds. and a weather-resistant additive. SOLUTION: This compsn. contains (A) a polyacetal resin, (B) a fatty acid diester compd. of formula I: R1 -COO(R3 O)n -COR2 , (C) a fatty acid monoester compd. of formula II: R4 -COO-(R5 O)m H, and (D) a weather-resistant additive. In formula I, R1 and R2 are each independently a 10-36C alkyl or alkenyl; R3 O is a 2-6C alkylene glycol unit; and (n) is 1. In formula II, R4 means the same as R1 and R2 ; R5 O means the same as R3 O; and (m) is 1. Pref., the sum of amts. of ingredients Band C is 0.005-3 pts.wt. based on 100 pts.wt. ingredient A; and the wt. ratio of ingredient B/ingredient C is (99.9/0.1)-(0.1/99.9).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weather-resistant polyacetal resin composition having improved color unevenness and mold deposit resistance when a pigment is added to and kneaded with a polyacetal resin.

[0002]

2. Description of the Related Art Polyacetal resins are well-balanced in mechanical strength, chemical resistance and slidability, and are easy to process. Are widely used mainly in automobile parts and other mechanical parts.

When a polyacetal resin is used in these fields, many of these electric devices and mechanical components of the electric devices are colored with a pigment or the like to obtain a desired molded product. In recent years, as the field of application of polyacetal resins has expanded, the colors used have also become diversified, and further improvements in colorability and mold deposit resistance have been desired. In particular, in the case of automobile parts and other mechanical parts, color unevenness during coloring becomes a serious problem and is one of the important characteristics.

[0004] Further, in order to improve the weather resistance of the polyacetal resin, many weathering agents are added. However, since the affinity between the polyacetal resin and the weathering agent is poor, the mold depositability is significantly deteriorated. Therefore, improvement in mold deposit resistance of a polyacetal resin in which a weathering agent is added to the polyacetal resin is urgently desired.

However, it has not yet been reported that the color unevenness and the mold deposit resistance of a polyacetal resin molded product obtained by adding a weathering agent and a pigment to a polyacetal resin have been improved at the same time. A polyacetal resin composition obtained by adding a fatty acid ester compound and a weathering agent to a polyacetal resin is disclosed in Japanese Patent Publication No. 5-70664.
No., JP-A-6-184402, Japanese Patent Publication No. 4-1709
In each of the above publications, it has already been disclosed.

In Japanese Patent Publication No. 5-70664, it is reported that a weathering agent and one or more fatty acid ester compounds comprising a fatty acid having 12 or more carbon atoms and an alcohol are added to a polyacetal resin to improve weather resistance. Have been.
The fatty acid ester compound referred to here is a fatty acid ester compound composed of a fatty acid and an alcohol, specifically, polyethylene glycol distearate and polyethylene glycol monostearate, wherein the number of polyethylene glycol units is 2 or more. The fatty acid ester compounds (B) and (C) of the present invention have one unit of polyethylene glycol, which is different from the fatty acid ester compound described in Japanese Patent Publication No. 5-70664. According to the examples in the publication, polyethylene glycol distearate and polyethylene glycol monostearate are used alone, and these polyethylene glycol distearate and polyethylene glycol monostearate are used in combination. Examples are not described. Looking further at the effects, the invention of this publication is excellent in maintaining physical properties after a weathering test,
This is different from the effect of the present invention.

In Japanese Patent Application Laid-Open No. 6-184402,
It has been reported that a weathering agent and one or more fatty acid esters composed of a fatty acid comprising a polyalkylene glycol having an average degree of polymerization of 2 or more and a fatty acid are added to the polyacetal resin to improve the weather resistance of the polyacetal resin. The fatty acid ester compound described in this publication is disclosed in
Similarly to the invention described in Japanese Patent No. 70664, a fatty acid ester compound composed of a fatty acid and an alcohol, specifically, a polyethylene glycol distearate and a polyethylene glycol monostearate in the fatty acid ester compound. The number of units is 2 or more, polyethylene glycol distearate and polyethylene glycol monostearate are each used alone,
There is no description that polyethylene glycol distearate and polyethylene glycol monostearate are used in combination. Of course, there is no description of an example that is also used in the embodiment. In addition, the effect is also described in Tokuhei 5-7066.
Similar to the invention described in Japanese Patent Publication No. 4 (1994), it has excellent physical property retention after the weather resistance test, and is different from the effect of the present invention.

[0008] Japanese Patent Publication No. 14709/1992 reports that a hindered amine compound, a fatty acid ester compound and one or more polyalkylene glycols are added to a polyacetal resin to improve the discoloration resistance of the tape. The fatty acid ester referred to here is a glycerin-based fatty acid ester compound, which is different from the fatty acid ester compounds (B) and (C) of the present invention.

As described above, all of the above methods are effective in improving weather resistance, but cannot simultaneously improve the color unevenness and mold deposit resistance of a colored polyacetal resin molded product.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyacetal resin composition which is improved in color unevenness and mold deposit resistance of a colored product of a polyacetal resin and which has excellent weather resistance.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, surprisingly, by adding a specific fatty acid ester compound and a weathering agent to the polyacetal resin, the polyacetal resin is colored. The present inventors have found that the color unevenness of the product and the mold deposit resistance can be improved at the same time, and arrived at the present invention.

That is, the present invention relates to (1) (A) a polyacetal resin, (B) a fatty acid diester compound represented by the following general formula (I), and (C) a fatty acid monoester compound represented by the following general formula (II). A polyacetal resin composition comprising an ester compound and (D) a weathering agent, a general formula (I): R ₁ —COO (R ₃ O) _n —COR ₂ (R ₁ and R ₂ are each an alkyl having 10 to 36 carbon atoms. The alkyl or alkenyl group substituted by a group or alkenyl group or one hydroxyl group, wherein R ₁ and R ₂
It may be different even in the same, R ₃ O represents an alkylene glycol unit having 2 to 6 carbon atoms. Also,
n represents 1. General formula (II) R ₄ —COO (R ₅ O) _m —H (R ₄ is an alkyl or alkenyl group having 10 to 36 carbon atoms or an alkyl or alkenyl group substituted with one hydroxyl group. , R ₅ O represents an alkylene glycol unit having 2 to 6 carbon atoms, and m represents 1.) (2) The total addition amount of (B) the fatty acid diester compound and (C) the fatty acid monoester compound is polyacetal. The polyacetal resin composition according to (1), which is 0.005 to 3 parts by weight based on 100 parts by weight of the resin, (3)
The weight ratio ((B) / (C)) of (B) the fatty acid diester compound to (C) the fatty acid monoester compound is 99.9 /
(1) The polyacetal resin composition according to (1), wherein the weathering agent (D) is a benzotriazole-based ultraviolet absorber, an oxalic anilide-based ultraviolet absorber, and a hindered amine-based light stabilizer. The polyacetal resin composition according to (1), which is one or more selected from agents, and is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyacetal resin, (5) the polyacetal resin is The polyacetal resin composition according to (1), wherein the amount of formaldehyde gas generated when heated at 230 ° C. for 50 minutes in a nitrogen atmosphere is 500 ppm by weight or less, (6)
A polyacetal resin composition obtained by adding (E) a fatty acid and (F) a fatty acid metal salt to the polyacetal resin composition according to (1).

Hereinafter, the present invention will be described in detail. The polyacetal resin (A) referred to in the present invention refers to a substantially oxymethylene unit produced from a cyclic oligomer such as a formaldehyde monomer or its trimer (trioxane) or tetramer (tetraoxane). Polyoxymethylene homopolymer obtained by performing terminal stabilization on the resulting oxymethylene homopolymer, and the above raw material and a hindered phenolic antioxidant in an amount of 10 to 50.
0 ppm added ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolan,
1,4-butanediol, formal of glycol,
An oxyalkylene unit having 2 to 8 carbon atoms, which is produced from a cyclic formal or the like such as a formal of diglycol, is added in an amount of 0.1 to 0.2.
A polyoxymethylene copolymer obtained by performing a terminal stabilization treatment of an oxymethylene-oxyalkylene copolymer containing 1 to 20% by weight can be mentioned.

The polyacetal resin in the present invention may be a polyoxymethylene copolymer having a branched molecular chain or a polyoxymethylene (PO
M) A polyoxymethylene block copolymer comprising 50% by weight or more of a block and less than 50% by weight of a polymer block different from POM may be used. Ethylene oxide, propylene oxide, epichlorohydrin, 1,
Hindered phenolic antioxidants that can be added to comonomers such as 3-dioxolane and 1,4-butanediol are n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-). (Hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′)
-T-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t
-Butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis- [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
-Propionate], triethylene glycol-bis-
[3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy {-1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionylhexamethylenediamine, N, N'-tetramethylene-bis-3- (3'-methyl-5'-t-butyl-4'-hydroxyphenol ) Propionyldiamine, N, N′-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionyl] hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N -Salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. . Preferably,
Triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ', 5'
-Di-t-butyl-4'-hydroxyphenyl) propionate] methane.

The method for producing the polyacetal resin used in the present invention is not particularly limited, and it can be produced by a conventionally known method. For example, taking the case of copolymerization as an example, trioxane and a cyclic ether that is a comonomer are converted into water, methanol, and an impurity compound having active hydrogen such as formic acid contained in those raw material monomers by a method such as distillation and adsorption. Remove and copolymerize. The polymer can be obtained by treating the obtained polymer with a twin-screw extruder or the like to stabilize the terminal.

[0016] The polymerization method is carried out by bulk polymerization, a batch type,
It is possible by any of the continuous methods. As a batch type polymerization apparatus, a reaction vessel equipped with a stirrer can be generally used. As the continuous type, a self-cleaning type mixer such as a co-kneader, a twin-screw type continuous extrusion kneader or a twin-screw paddle type continuous mixer can be used. The polymerization is carried out at a temperature of 60 ° C to 200 ° C under normal pressure.

As the polymerization catalyst, boron trifluoride, boron trifluoride hydrate and a coordination complex compound of boron trifluoride and an organic compound containing an oxygen atom or a sulfur atom are generally used. Used as a solution in organic solvents. Since the obtained polymer contains an active polymerization catalyst, it is desirable to deactivate the polymerization catalyst. The method of deactivating the polymerization catalyst is as follows.
The reaction is performed in an aqueous solution containing a basic substance or in an organic solvent. As another deactivation method, a method in which a basic substance is added to the polyacetal resin before terminal stabilization, and deactivation is performed in a molten state using an extruder can also be used. Examples of the basic substance used for deactivation include an alkali metal or alkaline earth metal hydroxide, an inorganic weak acid salt, and an organic acid salt. Specifically, lithium, sodium, potassium, magnesium, calcium, strontium, barium hydroxide, carbonate, phosphate, silicate, formate, acetate, stearate, palmitate, propionate, Oxalate and the like. In addition, hindered amine, ammonia, and amine compounds such as triethylamine and tributylamine can also be used as the deactivator.

The method of stabilizing the terminal of the polymer after the deactivation of the polymerization catalyst includes, for example, (1) a step of injecting at least one kind of hydroxyl group-containing compound into a polymer in a molten state, followed by kneading, and (2) The volatile component is removed from the molten polyacetal resin by a twin screw extruder or the like capable of continuously performing an operation for terminal stabilization comprising at least two steps of a step of releasing the vapor of the basic substance and free formaldehyde. By removing
Terminal stabilize. It is desirable to add a basic substance such as triethylamine as a pH adjuster when the above-mentioned at least one hydroxyl-containing compound or a mixture thereof is injected and then kneaded.

The amount of formaldehyde gas generated from the polyacetal resin can be determined by the following method. The terminal-stabilized polyacetal resin is placed in an aluminum container, heated and melted at 230 ° C. for 50 minutes under a nitrogen atmosphere, and the formaldehyde gas generated at that time is absorbed in an aqueous sodium sulfite solution and titrated with 0.01 N sulfuric acid. Then, the formaldehyde gas generation amount can be obtained from the titration amount of sulfuric acid. The preferred amount of formaldehyde gas generated at this time is 50% with respect to the polyacetal resin.
0 ppm by weight or less.

The fatty acid diester compound (B) and the fatty acid monoester compound (C) referred to in the present invention are represented by the following general formulas (I) and (II), respectively, and have 10 to 10 carbon atoms.
It is obtained from 35 saturated or unsaturated fatty acids or the fatty acids substituted with one hydroxyl group and alkylene glycols having 2 to 6 carbon atoms. Formula (I) R ₁ —COO (R ₃ O) _n —COR ₂ (R ₁ and R ₂ are an alkyl group or alkenyl group having 10 to 36 carbon atoms or the alkyl group or alkenyl substituted with one hydroxyl group. R ₁ and R ₂ may be the same or different, and R ₃ O represents an alkylene glycol unit having 2 to 6 carbon atoms, and n represents 1.) General formula (II) R ₄ —COO (R ₅ O) _m —H (R ₄ is an alkyl group or alkenyl group having 10 to 36 carbon atoms or an alkyl group or alkenyl group substituted with one hydroxyl group, and R ₅ O is These represent an alkylene glycol unit of the formulas 2 to 6, and m represents 1.) The fatty acid diester compound (B) and the fatty acid monoester compound (C) are obtained by adding a fatty acid diester compound to a polyacetal resin. It is preferable to add 0.005 to 3.0 parts by weight, preferably 0.01 to 1.0 part by weight, based on 100 parts by weight of the polyacetal resin in the total amount of B) and the fatty acid monoester compound (C). Is more preferable. The weight ratio of the fatty acid diester compound (B) and the fatty acid monoester compound (C) to be added ((B) /
(C)) is preferably from 99.9 / 0.1 to 0.1 / 99.9, and more preferably from 99.9 / 0.1 to 50/5.
0, more preferably 99.9 / 0.1-
More preferably, it is 90/10.

When the total amount and the weight ratio of the fatty acid diester compound (B) and the fatty acid monoester compound (C) are out of this range, the color unevenness and the mold deposit resistance of the colored polyacetal resin molded product are simultaneously reduced. It tends to be difficult to improve. The fatty acid diester compound (B) and the fatty acid monoester compound (C) referred to in the present invention include capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, and nonadecane. Acid, arachinic acid, behenic acid, ligglyceric acid,
Cerotic acid, heptacosanoic acid, montanic acid, melicic acid, lacceric acid, undecylenic acid, oleic acid, elaidic acid, setreic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearol Acid, 12-hydroxydodecanoic acid, 3-hydroxydecanoic acid, 16-hydroxyhexadecanoic acid, 10-hydroxyhexadecanoic acid, 12-
Hydroxyoctadecanoic acid, 10-hydroxy-8-octadecanoic acid, dl-erythro-9.10-dihydroxyoctadecanoic acid, etc. are used, and alkylene glycol is ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, 2-methyltetrahydrofuran, Fatty acid diester compound (B) and fatty acid monoester compound (C) using oxepane or the like. This alkylene glycol is a fatty acid ester compound in which the number of moles of addition is 1.

Among these, fatty acid diester compounds (B) and fatty acid monoester compounds (C) in which the fatty acid is myristic acid, palmitic acid and stearic acid and the alkylene glycol is ethylene glycol, and the addition of ethylene glycol is preferred. The number of moles is 1.
Specific examples of the fatty acid diester compound (B) include ethylene glycol dimyristate, ethylene glycol dipalmitate, ethylene glycol distearate, ethylene glycol (myristate-palmitate), and ethylene glycol (myristate-stearin). Acid) ester and ethylene glycol (palmitic acid-stearic acid) ester.

Specific examples of the fatty acid monoester compound (C) include ethylene glycol monomyristate, ethylene glycol monopalmitate and ethylene glycol monostearate. In the method for producing the fatty acid diester compound (B) and the fatty acid monoester compound (C), the raw material fatty acid and alkylene glycol are produced by an esterification reaction using an acid catalyst method or a non-catalytic method. The reaction temperature and the raw material concentration (eg, molar ratio, etc.) at this time are arbitrarily selected depending on the purpose, and can be obtained by purifying and separating the obtained fatty acid ester compound as required.

The obtained fatty acid diester compound (B) and fatty acid monoester compound (C) can be identified by the following method. For example, a fatty acid diester compound and a fatty acid monoester compound are added to a potassium hydroxide-methanol solution and heated to perform hydrolysis. Then, neutralize with hydrochloric acid and add hexane to extract fatty acids. This is methyl esterified, and the alkyl composition of the fatty acid is analyzed by gas chromatography.

Next, the ester analysis of the fatty acid ester compound can be performed by gas chromatography after TMS conversion. The weathering agent referred to in the present invention,
One or more selected from benzotriazole-based, oxalic anilide-based ultraviolet absorbers and hindered amine-based light stabilizers.

Examples of the benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-di-t-butyl-phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t
-Amylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-isoamyl-phenyl)
Benzotriazole, 2- [2′-hydroxy-3 ′,
5′-bis- (α, α-dimethylbenzyl) phenyl]
-H-benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole and the like. Examples of the oxalic acid alinide UV absorber include 2-ethoxy-2'-ethyloxalic acid bisanilide and 2-ethoxy-5-t-butyl-2'-.
Ethyl oxalic acid bisanilide, 2-ethoxy-3'-dodecyl oxalic acid bisanilide and the like can be mentioned. These ultraviolet absorbers may be used alone or in combination of two or more.

Examples of hindered amine light stabilizers include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-
Tetramethylpiperidine, 4-acryloyloxy-
2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4- Methoxy-2,2,6,6-
Tetramethylpiperidine, 4-stearyloxy-2,
2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2, 2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4-
(Cyclohexylcarbamoyloxy) -2,2,6
6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2 2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2
2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetramethyl-4) -Piperidyl) -adipate, bis (2,
2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2 2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltolylen-2,4-dicarbamate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tri Carboxylate,
Tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate,
1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4-
[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2 , 2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β ′,-tetramethyl-3,
9- [2,4,8,10-tetraoxaspiro (5,
5) Undecane] condensate with diethanol. The hindered amine light stabilizers may be used alone or in combination of two or more.

Among them, preferred weathering agents are 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole and 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di-t-amylphenyl) benzotriazole, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis- (N-methyl-2,2,6,6
-Tetramethyl-4-piperidinyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl)
Sebacate, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9-
This is a condensate with [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

The amount of the weathering agent to be added is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the polyacetal resin. More preferably, it is 0.1 to 3 parts by weight.
When the amount of the weathering agent is out of this range, it tends to be difficult to simultaneously improve the color unevenness and the mold deposit resistance of the colored polyacetal resin molded product.

The polyacetal resin composition of the present invention comprises:
Further, by further adding a fatty acid (E) and a fatty acid metal salt (F), a further effect is exhibited. The fatty acid (E) to be added to the polyacetal resin is a saturated or unsaturated fatty acid having 10 to 36 carbon atoms and a fatty acid substituted with one hydroxyl group, such as capric acid, undecylic acid,
Lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid,
Nonadecanoic acid, arachinic acid, behenic acid, ligglyceric acid, cerotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, oleic acid, elaidic acid, setreic acid, erucic acid, brassic acid, sorbic acid, linoleic acid Acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, 12-hydroxydodecanoic acid, 3-hydroxydecanoic acid, 16-hydroxyhexadecanoic acid, 10-hydroxyhexadecanoic acid, 12
-Hydroxyoctadecanoic acid, 10-hydroxy-8-octadecanoic acid, dl-erythro-9.10-dihydroxyoctadecanoic acid and the like. Among them, myristic acid, palmitic acid and stearic acid are preferred.

Next, the fatty acid metal salt (F) referred to in the present invention
Is a fatty acid metal salt obtained from a saturated or unsaturated fatty acid having 10 to 35 carbon atoms, a fatty acid substituted with one hydroxyl group, and a hydroxide, oxide or chloride of an alkali metal or an alkaline earth metal. The amount of unreacted metal hydroxide, chloride and oxide in the fatty acid metal salt is preferably not more than 500 ppm by weight based on the fatty acid metal salt.

Specific examples of fatty acids as raw materials for fatty acid metal salts include capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid,
Heptadecyl acid, stearic acid, nonadecanoic acid, arachinic acid, behenic acid, ligglyceric acid, cerotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, oleic acid, elaidic acid, cetreic acid, erucic acid, brassin Acids, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, 12-hydroxydodecanoic acid, 3-hydroxydecanoic acid, 16-hydroxyhexadecanoic acid, 10
-Hydroxyhexadecanoic acid, 12-hydroxyoctadecanoic acid, 10-hydroxy-8-octadecanoic acid, dl
-Erythro-9.10-dihydroxyoctadecanoic acid, etc., and as the metal compound, sodium, lithium, potassium and calcium, magnesium, barium, zinc, aluminum, alkali metal of strontium, hydroxide of alkaline earth metal or It is chloride.

Among these, the fatty acids are preferably myristic acid, palmitic acid and stearic acid, and the metal compounds are calcium hydroxides, oxides and chlorides. Specific examples of fatty acid metal salts include calcium dimyristate, calcium dipalmitate, calcium distearate, calcium (myristate-palmitate),
(Myristic acid-stearic acid) calcium and (palmitic acid-stearic acid) calcium. Among them, calcium dipalmitate and calcium distearate are preferred.

In the present invention, two or more fatty acid metal salts may be added at the same time, and there is no limitation. For example, calcium stearate and calcium palmitate may be added simultaneously, or a metal salt composed of fatty acids having different carbon numbers, for example, calcium (palmitate-stearate) may be mixed. The method for producing the fatty acid metal salt is not particularly limited, and a fatty acid metal salt having substantially 500 ppm by weight or less of an unreacted metal compound is preferable.

For example, a crude fatty acid metal salt obtained by a neutralization reaction between a fatty acid and a metal hydroxide, a metathesis reaction between a fatty acid and a metal chloride, or a neutralization reaction between a fatty acid and a metal oxide is further washed with water. The desired fatty acid metal salt used in the present invention can be obtained by performing the treatment and the drying treatment. The unreacted metal compound in the obtained fatty acid metal salt is obtained by sonicating the fatty acid metal salt, quantifying the metal component extracted in the filtrate by atomic absorption, and determining the obtained quantitative value as the raw material metal hydroxide. , Metal oxides or metal chlorides.

For coloring the polyacetal resin composition of the present invention, either an inorganic pigment or an organic pigment can be used. Specific examples include, as an inorganic pigment, rutile-type or anatase-type titanium oxide, carbon black, iron oxide, ultramarine, titanium yellow and the like, and as an organic pigment, quinacridone-based, monoazo-based, oxazine-based, Polyazo, phthalocyanine, anthraquinone, isoindoline, perylene and the like. Other pigments include fluorescent pigments and metallic pigments, and these pigments can also be used in the present invention.

In the present invention, in addition to the fatty acid diester compound (B), the fatty acid monoester compound (C), the weathering agent (D), the fatty acid (E) and the fatty acid metal salt (F),
If necessary, known additives commonly used can be used in a range that does not interfere with the purpose of the present application. For example,
Examples include an antioxidant, a polymer or compound containing a formaldehyde-reactive nitrogen atom, and a release agent. The amount of each of these additives varies depending on the type of the additive, but the amount of each additive is 0.001 to 5.0 parts by weight based on 100 parts by weight of the polyacetal resin.

As the antioxidant, one or more hindered phenolic antioxidants can be used. Specifically, for example, n-octadecyl-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, n-octadecyl-3-
(3'-methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-
Bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) -propionate], triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di) -T-butyl-4'-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-
[Hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′, 5) '-Di-t-butyl-4'-hydroxyphenyl) propionylhexamethylenediamine,
N, N'-tetramethylene-bis-3- (3'-methyl-5'-t-butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5
-Di-t-butyl-4-hydroxyphenol) propionyl] hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-
1,2,4-triazole, N, N′-bis [2- {3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy {ethyl] oxyamide; Preferably, triethylene glycol-bis- [3
-(3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-
3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane.

Examples of the polymer containing a formaldehyde-reactive nitrogen atom include polyamide resins such as nylon 4-6, nylon 6, nylon 6-6, nylon 6-10, nylon 6-12, nylon 12, and the like; Polymer,
For example, nylon 6 / 6-6 / 6-10, nylon 6 /
6-12 and the like. Further, as a copolymer of acrylamide and its derivatives, acrylamide and its derivatives and other vinyl monomers, poly-β obtained by polymerizing acrylamide and its derivatives and other vinyl monomers in the presence of a metal alcoholate is used. -Alanine copolymers. One of these polymers containing a formaldehyde-reactive nitrogen atom may be used alone, or two or more thereof may be used in combination. Examples of the compound having an amino substituent also include a formaldehyde-reactive nitrogen atom include 2,4-diamino-sym-
Triazine, 2,4,6-triamino-sym-triazine, N-butylmelamine, N-phenylmelamine,
N, N-diphenylmelamine, N, N-diallylmelamine, N, N ′, N ″ -triphenylmelamine, melem,
Melon, melam, benzoguanamine (2,4-diamino-6-phenyl-sym-triazine), acetoguanamine (2,4-diamino-6-methyl-sym-triazine), 2,4-diamino-6-butyl-sym -Triazine, 2,4-diamino-6-benzyloxy-sy
m-triazine, 2,4-diamino-6-butoxy-s
ym-triazine, 2,4-diamino-6-cyclohexyl-sym-triazine, 2,4-diamino-6-chloro-sym-triazine, 2,4-diamino-6-mercapto-sym-triazine, 2,4- Dioxy-6
-Amino-sym-triazine, 2-oxy-4,6-
Diamino-sym-triazine, N, N, N ', N'-
And tetracyanoethylbenzobuanamin, succinoguanamine, ethylenedimelamine, triguanamine, melamine cyanurate, ethylenedimelamine cyanurate, triguanamine cyanurate, ammeline, acetoguanamine and the like. These triazine derivatives may be used alone or in a combination of two or more. There is no restriction whatsoever.

Examples of the release agent include polyalkylene glycol and aliphatic compounds having an amide group.
More than species can be mentioned. As the polyalkylene glycol, a polyalkylene glycol represented by the following general formula (III) can be used.

[0041]

Embedded image

[0042] Formula (III) (wherein, R ₆ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group, selected from substituted aryl group, optionally substituted by one or each of R ₆ are the same X = 2-6, Y
= 1000 to 20000. This polyalkylene glycol can be obtained by ring-opening polymerization of an alkylene oxide. Specific examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, oxetane, 3,3-bis (chloromethyl) oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, and oxepane. These polyalkylene glycols may be used alone or in combination of two or more.

Examples of the aliphatic compound having an amide group include:
An aliphatic compound represented by the following general formula (IV).

[0044]

Embedded image

Formula (IV) (wherein, R ₇ represents a fatty acid having 9 to 35 carbon atoms, and R ₈ represents an alkylene group having 1 to 6 carbon atoms.) As a specific example, ethylene bispalmitic acid amide , Ethylenebisstearic acid amide, ethylenebislauric acid amide, ethylenebisoleic acid amide, and ethylenebiserucic acid amide.
These aliphatic compounds having an amide group may be used alone or in combination of two or more.

The polyacetal resin of the present invention may contain various organic pigments, inorganic pigments, various reinforcing materials such as glass fibers, and a nucleating agent according to the purpose. The addition form of these additives may be a powder or a molten state. The method for producing the polyacetal resin composition of the present invention is not particularly limited. In general, an extruder is used to melt and knead the polyacetal resin, (B) a fatty acid diester compound, (C) a fatty acid monoester compound, and (D) a weathering agent, and, if desired, an optional additive. Thereby, the polyacetal resin composition of the present invention can be produced. The extruder at this time may be single-screw or twin-screw. Further, an additive may be added during the polymerization of the polyacetal resin.

The temperature of the extruder is usually from 170.degree.
The temperature may be appropriately selected in the range of ° C, and is not particularly limited. The method for molding the resin composition of the present invention is not particularly limited, and the resin composition can be molded by any of known molding methods such as extrusion molding, injection molding, compression molding, vacuum molding, blow molding, and foam molding.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to examples and comparative examples. In the following description, ppm,% and parts are by weight pp unless otherwise specified.
m,% by weight and parts by weight. The method for producing the polyacetal resin, the method for quantifying the amount of formaldehyde gas generated, and the color unevenness, mold deposit resistance, and weather resistance of the colored product of the polyacetal resin were evaluated according to the methods described below. (1) Formaldehyde gas generation amount 3 g of a polyacetal resin was put in an aluminum container, and was heated and melted at 230 ° C. for 50 minutes under a nitrogen stream (6 liters / hour).
ol / liter sodium sulfite aqueous solution,
Titrate with 0.01 N sulfuric acid to determine the amount of formaldehyde gas generated, and determine the weight per weight of the polyacetal resin, p
pm. (2) Production method of polyacetal resin [Production of polyacetal resin (a-1)] Having two jacketed stirring blades through which a heat medium can pass.
The kneader for liter was adjusted to 80 ° C., and 3 kg of trioxane containing 15 ppm of water and 100 ppm of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-).
4-Hydroxyphenyl) propionate] 1,3-dioxolane to which methane is added is added to 1 mol of trioxane.
Then, 4.0 mol%, and 0.7 × 10 ⁻³ mol of methylal as a molecular weight regulator were added and mixed. As a polymerization catalyst, this mixture was mixed with boron trifluoride dibutyl ether in an amount of 0.15 × 10 ⁻⁴ mol per 1 mol of trioxane.
l was added to carry out polymerization.

After a lapse of 30 minutes from the start of the reaction, a heating medium at 30 ° C. was passed through the jacket, and 2 liters of an aqueous solution containing 1% triethylamine was added. The catalyst was deactivated for 1 hour, and the reaction was stopped. . Then, after taking out the contents of the kneader and filtering, the filter cake was dried at 100 ° C.,
2.7 kg of polyacetal resin was obtained. The obtained polyacetal resin was supplied to a twin-screw extruder (L / D ratio: 32) having one 30 mm vent port. The extruder temperature was 200 ° C., the amount of water and triethylamine used as a basic substance to be injected into the reaction zone of the extruder were 0.2% by weight and 0.1% by weight with respect to the resin, respectively, Terminal stabilization and degassing of the polyacetal resin were performed under the conditions of 200 Torr, and a terminal-stabilized polyacetal resin (a-1) was obtained in the form of pellets.
The amount of formaldehyde gas generated from the obtained polyacetal resin (a-1) was 1100 ppm, and the melt index value was 10 g / 10 minutes. [Production of Polyacetal Resin (a-2)] The extruder venting degree at the end stabilization of the polyacetal resin was adjusted to 3
The polyacetal resin (a-
By substantially the same operation as in the production of 1), a terminal-stabilized polyacetal resin (a-2) was obtained. The polyacetal resin (a-2) obtained had a formaldehyde gas generation amount of 260 ppm and a melt index value of 10 g / 1.
It was 0 minutes. The obtained polyacetal resin (a-
The formaldehyde gas generation amounts and melt index values of 1) and (a-2) are shown in Table 1 below.

[0050]

[Table 1]

(3) Color Unevenness of Colored Polyacetal Resin The color unevenness of the colored polyacetal resin was evaluated according to the following method. <Preparation method of colored polyacetal resin> Pigment (acetylene black: 0.01 parts by weight) was extruded into a polyacetal resin composition in a uniaxial 30 mm extruder (cylinder temperature: 2).
(00 ° C.), and the resulting colored product of the polyacetal resin was dried at 80 ° C. for 3 hours. Thereafter, molding was performed under the molding conditions shown below. <Molding conditions> Molding machine: 5 oz injection molding machine Cylinder temperature: 200 ° C Mold temperature: 30 ° C Molding cycle: Injection / cooling = 20/10 seconds Injection pressure: 40 kg / cm ² G <Shape of molded article> 1 point Pin gate flat plate Size: vertical / horizontal / thickness = 70/60/1 mm Pin gate size: 1 mm φ <Color unevenness determination criteria> The color difference (ΔE) between the four corners and the center of the flat plate is measured using a color difference meter (Minolta color) Color difference meter CR-20
0), and the color unevenness was determined based on the difference between the maximum value and the minimum value. The criteria are shown in Table 2.

[0052]

[Table 2]

(4) Method for Evaluating Mold Deposit Resistance of Polyacetal Resin Composition In accordance with the method shown below, evaluation of mold deposit resistance of the polyacetal resin composition was performed. Pigment polyacetal resin composition <Preparation method of the polyacetal resin composition> (acetylene black: 0.01 parts by weight) of the single-axis of 30mm extruder (cylinder temperature: 2
(00 ° C.), and the resulting colored product of the polyacetal resin composition was dried at 80 ° C. for 3 hours. Thereafter, molding was performed under the molding conditions shown below, and the mold deposit resistance was evaluated. <Molding conditions> Molding machine: 1 ounce injection molding machine Cylinder temperature: 200 ° C Molding cycle: Injection / cooling = 5/10 seconds Mold temperature: 30 ° C Shot count: 1000 <Molded product> One-point pin gate pentagonal shaped product (No degassing part) Molded product size: Resin flow direction 35 mm Direction perpendicular to resin flow direction 15 mm Thickness 2 mm <Mold deposit resistance criteria> Mold deposit resistance was determined according to the criteria shown in Table 3 below. .

[0054]

[Table 3]

(5) Weather Resistance Evaluation Method The weather resistance of the polyacetal resin composition was evaluated according to the method described below. <Preparation method of polyacetal resin composition> A pigment (acetylene black: 0.2 parts by weight) was extruded into a polyacetal resin composition in a uniaxial 30 mm extruder (cylinder temperature: 20).
(0 ° C.), and the resulting colored product of the polyacetal resin composition was dried at 80 ° C. for 3 hours. Thereafter, molding was performed under the following molding conditions, and weather resistance was evaluated. <Molding conditions> Molding machine: 5 oz injection molding machine Cylinder temperature: 200 ° C Molding cycle: Injection / cooling = 15/20 seconds Mold temperature: 70 ° C <Molded product> Single-point pin gate flat molded product Molded product size: Resin Flow direction 67 mm Direction perpendicular to the resin flow direction 13 mm Thickness 3 mm <Weather resistance test condition> Tester: Suga tester (manufactured) Xenon weather meter weather tester EL-2WL type Black panel temperature: 89 ° C Humidity: 50% R H Exposure time: 1000 hours <Color difference (ΔE) measurement method> Test machine: Color-difference meter CR-200 manufactured by Minolta <Criteria for weather resistance> Weather resistance was determined according to the criteria shown in Table 4 below.

[0056]

[Table 4]

The additives used in the following Examples and Comparative Examples are as follows. (6) Additives See additive preparation method (Preparation Example 2) In preparing the additives, the following fatty acid diester compound (B) and fatty acid monoester compound (C),
Weathering agent (D), fatty acid (E), fatty acid metal salt (F)
Was used. -Fatty acid diester compound (B) b-1: Ethylene glycol dipalmitate (the number of moles of ethylene glycol added: 1) b-2: Ethylene glycol distearate (the number of moles of ethylene glycol added: 1) b-3: Ethylene glycol (myristic acid-palmitic acid) ester (addition mole number of ethylene glycol:
1) b-4: ethylene glycol (palmitic acid-stearic acid) ester (addition mole number of ethylene glycol:
1) b-5: ethylene glycol distearic acid ester (number of moles of ethylene glycol added: 7) fatty acid monoester compound (C) c-1: ethylene glycol monopalmitate (number of moles of ethylene glycol added: 1) c -2: ethylene glycol monostearate (number of moles of ethylene glycol added: 1) c-3: ethylene glycol monostearate (number of moles of ethylene glycol added: 7)-Weathering agent (D) d-1: 2 -[2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole d-2: 2- (2′-hydroxy-3 ′, 5′-di-t
-Butylphenyl) benzotriazole d-3: 2- (2'-hydroxy-3 ', 5'-di-t
-Amylphenyl) benzotriazole d-4: bis (1,2,2,6,6-pentamethyl-4)
-Piperidinyl) sebacate d-5: bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate d-6: bis (2,2,6,6-tetramethyl-4-) Piperidinyl) sebacate d-7: 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3 , 9-
Condensate with [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol ・ fatty acid (E) e-1: palmitic acid e-2: stearic acid ・ fatty acid metal salt (F) f- 1: Calcium dipalmitate (unreacted calcium hydroxide: 190 ppm) f-2: Calcium distearate (unreacted calcium hydroxide: 780 ppm) f-3: Calcium distearate (unreacted calcium hydroxide: 220 ppm) (7) Other additives • Hindered phenolic antioxidant g-1: triethylene glycol-bis- [3- (3-
t-butyl-5-methyl-4-hydroxyphenyl) propionate] Compounds and polymers containing a formaldehyde-reactive nitrogen atom h-1: nylon 6,6 Release agent i-1: polyethylene glycol (molecular weight 6000) i -2: ethylenebisstearylamide

[0058]

[Preparation Example] [Preparation of additive (X-1)] 99.9% by weight of ethylene glycol distearate (b-2)
And ethylene glycol monostearate (c-
2) 0.1% by weight is put into a Henschel mixer, and 860r
The mixture was homogenously mixed for 1 minute at a speed of pm. The additive (X-1) obtained here was used in Examples and Comparative Examples. [Preparation of Additives (X-2) to (X-6)]
The same operation as in 1) was performed, and the additives (X-
2) to (X-6) were prepared. The resulting additive (X
-2) to (X-6) were used in Examples and Comparative Examples.

[0059]

[Table 5]

[Preparation of Additive (X-7)] 99.9% by weight of ethylene glycol distearate (b-2) and ethylene glycol monostearate (c)
-2) 0.1% by weight of stearic acid (d-2) per 100 parts by weight of the total amount of ethylene glycol distearate (b-2) and ethylene glycol monostearate (c-2) The parts by weight were put into a Henschel mixer and uniformly mixed at a speed of 860 rpm for 1 minute. The obtained additive (X-7) was used in Examples and Comparative Examples. [Preparation of Additives (X-8) to (X-11)]
-7), and the additives (X
-8) to (X-11) were prepared. The obtained additives (X-2) to (X-6) were used in Examples and Comparative Examples.

[0061]

[Table 6]

[0062]

[Example 1] The amount of formaldehyde gas generated was 260 pp
m of the polyacetal resin (a-2) and 0.005 parts by weight of the additive (X-5), and 2- [2′-hydroxy-3 ′, 5′-bis ( α,
α-dimethylbenzyl) phenyl] benzotriazole (d-1) in an amount of 0.5 part by weight and bis (2,2,6,6-
Tetramethyl-4-piperidinyl) sebacate (d-
6) Charge 0.25 parts by weight to the Henschel mixer,
The mixture was uniformly mixed at a rotation speed of 0 rpm for 2 minutes and discharged. The resulting mixture was extruded with a 30 mm vented twin screw extruder (L
/ D: 32), and the mixture was pelletized. At this time, the cylinder temperature was 200 ° C., the discharge rate was 5 kg / hr, the screw rotation speed was 100 rpm, and the vent vacuum was 30 T.
orr. After the pelletized polyacetal resin composition was dried at 80 ° C. for 5 hours, the color unevenness of the colored product and the mold deposit-resistant polyacetal resin composition were evaluated. Table 7 shows the composition and Table 11 shows the results of evaluating the physical properties.

[0063]

Examples 2 to 5 The same operation as in Example 1 was performed except that the amount of the additive (X-5) was changed. Table 7 shows the composition.
Table 11 shows the physical property evaluation results.

[0064]

Examples 6 to 9 The types of additives were (X-1) to (X-
4) except that the amount of the additive was 0.1 parts by weight.
The same operation as in Example 1 was performed. Table 7 shows the composition and Table 11 shows the results of evaluating the physical properties.

[0065]

Examples 10 to 14 The types of additives were (X-7) to (X
-11), and the same operation as in Example 1 was performed, except that the amount of the additive was changed to 0.1 part by weight. Table 8 shows the composition and Table 12 shows the results of evaluating the physical properties.

[0066]

Embodiment 15 The amount of formaldehyde gas generated is 260p
0.1 parts by weight of the additive (X-11) with respect to 100 parts by weight of the polyacetal resin (a-2) at pm, and 2- (2'-hydroxy-3 ', 5'-di- t-butylphenyl) benzotriazole (d-2)
Parts by weight and bis (1,2,2,6,6-pentamethyl-
0.25 parts by weight of 4-piperidinyl) sebacate (d-4) was charged into a Henschel mixer, uniformly mixed at a rotation speed of 860 rpm for 2 minutes, and discharged. The resulting mixture is
The mixture was melt-kneaded with a twin screw extruder (L / D: 32) with a vent of 0 mm and formed into pellets. At this time, the cylinder temperature was 200 ° C., the discharge rate was 5 kg / hr, the screw rotation speed was 100 rpm, and the degree of vent vacuum was 30 Torr. After the pelletized polyacetal resin composition was dried at 80 ° C. for 5 hours, the color unevenness of the colored product and the mold deposit-resistant polyacetal resin composition were evaluated. Table 8 shows the composition and Table 12 shows the results of evaluating the physical properties.

[0067]

Example 16 The type of weathering agent was 0.5 parts by weight of 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole (d-1),
Bis- (N-methyl-2,2,6,6-tetramethyl-
The same operation as in Example 15 was performed, except that the amount was changed to 0.25 part by weight of (4-piperidinyl) sebacate (d-5).
Table 8 shows the composition and Table 12 shows the results of evaluating the physical properties.

[0068]

Example 17 The type of polyacetal resin was changed to (a-1)
Then, the same operation as in Example 1 was performed except that the amount of the additive (X-5) was changed to 0.1 part by weight. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0069]

Embodiment 18 The amount of formaldehyde gas generated is 260p
0.1 parts by weight of the additive (X-5) with respect to 100 parts by weight of the polyacetal resin (a-2) at pm, and 2- [2′-hydroxy-3 ′, 5′-bis ( α, α
-Dimethylbenzyl) phenyl] benzotriazole (d-1) in an amount of 0.5 part by weight and bis (2,2,6,6-
Tetramethyl-4-piperidinyl) sebacate (d-
0.25 parts by weight of 6) and 0.05 parts by weight of calcium distearate (f-3) were charged into a Henschel mixer, uniformly mixed at a rotation speed of 860 rpm for 2 minutes, and discharged. The resulting mixture was melt-kneaded with a 30 mm vented twin-screw extruder (L / D: 32) and pelletized.
The cylinder temperature at this time was 200 ° C, and the discharge rate was 5 kg /
hr, the screw rotation speed was 100 rpm, and the degree of vent vacuum was 30 Torr. After the pelletized polyacetal resin composition was dried at 80 ° C. for 5 hours, the color unevenness of the colored product and the mold deposit-resistant polyacetal resin composition were evaluated. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0070]

Embodiment 19 The types of additives were changed from (X-5) to (X-1).
Except having changed to 1), the same operation as Example 18 was performed. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0071]

Embodiment 20 The amount of formaldehyde gas generated is 260p
0.1 parts by weight of the additive (X-11) based on 100 parts by weight of the polyacetal resin (a-2) of pm, and 2- [2′-hydroxy-3 ′, 5′-bis ( α,
α-dimethylbenzyl) phenyl] benzotriazole (d-1) in an amount of 0.5 part by weight and bis (2,2,6,6-
Tetramethyl-4-piperidinyl) sebacate (d-
0.25 parts by weight of 6) and 0.05 parts by weight of calcium dipalmitate (f-1) were charged into a Henschel mixer, uniformly mixed at a rotation speed of 860 rpm for 2 minutes, and discharged. The resulting mixture was melt-kneaded with a 30 mm vented twin-screw extruder (L / D: 32) and pelletized.
The cylinder temperature at this time was 200 ° C, and the discharge rate was 5 kg /
hr, the screw rotation speed was 100 rpm, and the degree of vent vacuum was 30 Torr. After the pelletized polyacetal resin composition was dried at 80 ° C. for 5 hours, the color unevenness of the colored product and the mold deposit-resistant polyacetal resin composition were evaluated. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0072]

Example 21 The same operation as in Example 20 was performed except that the fatty acid metal salt was changed to calcium distearate (f-2). Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0073]

Example 22 The same operation as in Example 20 except that the fatty acid metal salt was changed to 0.025 parts by weight of calcium dipalmitate (f-1) and 0.025 parts by weight of calcium distearate (f-3). Was done. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0074]

Embodiment 23 The amount of formaldehyde generated is 260p
0.1 parts by weight of the additive (X-11) based on 100 parts by weight of the polyacetal resin (a-2) of pm, and 2- [2′-hydroxy-3 ′, 5′-bis ( α,
α-dimethylbenzyl) phenyl] benzotriazole (d-1) in an amount of 0.5 part by weight and bis (2,2,6,6-
Tetramethyl-4-piperidinyl) sebacate (d-
6) in an amount of 0.25 parts by weight and 0.05 parts by weight of calcium distearate, ethylenebisstearylamide (i-
2) 0.05 parts by weight were charged into a Henschel mixer, and
The mixture was uniformly mixed at a rotation speed of 0 rpm for 2 minutes and discharged. The resulting mixture was extruded with a 30 mm vented twin screw extruder (L
/ D: 32), and the mixture was pelletized. At this time, the cylinder temperature was 200 ° C., the discharge rate was 5 kg / hr, the screw rotation speed was 100 rpm, and the vent vacuum was 30 T.
orr. After the pelletized polyacetal resin composition was dried at 80 ° C. for 5 hours, the color unevenness of the colored product and the mold deposit-resistant polyacetal resin composition were evaluated. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0075]

EXAMPLE 24 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-weather were used as weathering agents.
Piperidinol and β, β, β ', β'-tetramethyl-
Condensate with 3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol (d-
7) 0.025 parts by weight of polyethylene glycol (i
-1) 1.0 part by weight was further added to Example 23, and the same operation as in Example 23 was performed. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0076]

[Example 25] In addition to Example 24, triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4)
-Hydroxyphenyl) propionate] (g-1)
The same operation as in Example 24 was performed except that 0.02 parts by weight was added. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0077]

Embodiment 26 In addition to Embodiment 23, nylon 6,6 (h
-1) The same operation as in Example 23 was performed by adding 0.025 parts by weight. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0078]

Embodiment 27 In addition to Embodiment 24, nylon 6,6 (h
-1) The same operation as in Example 24 was performed by adding 0.025 parts by weight. Table 9 shows the composition, and Table 13 shows the physical property evaluation results.

[0079]

[Comparative Example 1] The amount of formaldehyde gas generated was 1100p
0.1 parts by weight of polyethylene glycol distearate (b-5) with respect to 100 parts by weight of the polyacetal resin (a-1) at pm, and 2- [2 '
-Hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole (d-1) in an amount of 0.5 part by weight and bis (2,2,6,6-tetramethyl-4-piperidinyl) ) 0.25 parts by weight of sebacate (d-6) was charged into a Henschel mixer, uniformly mixed at a rotation speed of 860 rpm for 2 minutes, and discharged. The resulting mixture was melt-kneaded with a 30 mm vented twin-screw extruder (L / D: 32) and pelletized. At this time, the cylinder temperature was 200 ° C., the discharge rate was 5 kg / hr, the screw rotation speed was 100 rpm, and the degree of vent vacuum was 30 Torr.
The pelletized polyacetal resin composition is heated to 80 ° C.
After drying for 5 hours, the color unevenness of the colored product and the mold deposit-resistant polyacetal resin composition were evaluated.
Table 10 shows the composition and Table 14 shows the physical property evaluation results.

[0080]

Comparative Example 2 The same operation as in Comparative Example 1 was performed, except that the polyethylene glycol distearate (b-5) was changed to 0.1 part by weight of the polyethylene glycol monostearate (c-3). Table 10 shows the composition.
Table 14 shows the physical property evaluation results.

[0081]

Comparative Example 3 The same operation as in Comparative Example 1 was carried out except that the polyethylene glycol distearate (b-5) was changed to 0.1 part by weight of palmitic acid (e-1).
Table 10 shows the composition and Table 14 shows the physical property evaluation results.

[0082]

Comparative Example 4 The same operation as in Comparative Example 1 was carried out except that the polyethylene glycol distearate (b-5) was changed to 0.1 part by weight of stearic acid (e-2).
Table 10 shows the composition and Table 14 shows the physical property evaluation results.

[0083]

Comparative Example 5 The same operation as in Comparative Example 1 was performed except that the fatty acid ester compounds (B) and (C) were not added.
Table 10 shows the composition and Table 14 shows the physical property evaluation results.

[0084]

Comparative Example 6 The same operation as in Example 1 was performed, except that the additive (X-5) was changed to the additive (X-6) and the amount of addition was 3.0 parts by weight. Table 10 shows the composition and Table 14 shows the physical property evaluation results.

[0085]

[Table 7]

[0086]

[Table 8]

[0087]

[Table 9]

[0088]

[Table 10]

[0089]

[Table 11]

[0090]

[Table 12]

[0091]

[Table 13]

[0092]

[Table 14]

[0093]

According to the present invention, the polyacetal resin composition comprises:
Various molded products that require weather resistance, such as outdoor handles for automobiles, inner handles, and front covers, because they improve the color unevenness of colored products and the mold deposit resistance, as well as the weather resistance. It can be suitably used for, for example, front fenders and the like, and is very useful in industry.

Claims (6)

[Claims] 1. A polyacetal resin (A), (B) a fatty acid diester compound represented by the following general formula (I), (C) a fatty acid monoester compound represented by the following general formula (II), and (D) weather resistance And a polyacetal resin composition. General formula (I) R ₁ —COO (R ₃ O) _n —COR ₂ (R ₁ and R ₂ are each an alkyl or alkenyl group having 10 to 36 carbon atoms or an alkyl group substituted with one hydroxyl group. Or an alkenyl group, R ₁ and R ₂
It may be different even in the same, R ₃ O represents an alkylene glycol unit having 2 to 6 carbon atoms. Also,
n represents 1. General formula (II) R ₄ —COO (R ₅ O) _m —H (R ₄ is an alkyl or alkenyl group having 10 to 36 carbon atoms or an alkyl or alkenyl group substituted with one hydroxyl group. , R ₅ O represents an alkylene glycol unit having 2 to 6 carbon atoms, and m represents 1.) 2. The total addition amount of the fatty acid diester compound (B) and the fatty acid monoester compound (C) is 0.005 to 3 with respect to 100 parts by weight of the polyacetal resin.
The polyacetal resin composition according to claim 1, which is in parts by weight. 3. A composition comprising (B) a fatty acid diester compound and (C)
Fatty acid monoester compound weight ratio ((B) / (C))
The polyacetal resin composition according to claim 1, wherein = 99.9 / 0.1 to 0.1 / 99.9. 4. The weathering agent (D) is at least one member selected from the group consisting of a benzotriazole-based ultraviolet absorber, an oxalic anilide-based ultraviolet absorber, and a hindered amine-based light stabilizer, and 100 parts by weight of a polyacetal resin. Against
The polyacetal resin composition according to claim 1, wherein the amount is 0.1 to 5 parts by weight. 5. The polyacetal resin composition according to claim 1, wherein the amount of formaldehyde gas generated when the polyacetal resin is heated at 230 ° C. for 50 minutes in a nitrogen atmosphere is 500 ppm by weight or less. 6. A polyacetal resin composition obtained by adding (E) a fatty acid and (F) a fatty acid metal salt to the polyacetal resin composition according to claim 1.