JP2001164084A - Polyacetal resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyacetal resin composition having further improved weather (light) resistance and excellent even in friction and abrasion characteristics. SOLUTION: This polyacetal resin composition is obtained by compounding (A) 100 pts.wt. of a polyacetal resin with (B) 0.01-5 pts.wt. of a weathering (light) stabilizer and (C) 0.01-10 pts.wt. of an alkylene glycol-based polymer having primary or secondary amino groups and 400-500,000 number-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyacetal resin composition having extremely excellent weather (light) resistance, and further having excellent surface characteristics and sliding characteristics.

[0002]

BACKGROUND OF THE INVENTION Polyacetal resins have well-balanced mechanical properties,
It is widely used in the fields of automobiles, electric and electronic products, etc. because of its excellent friction and wear resistance, chemical resistance, heat resistance, electric properties, and the like. However, the required properties in such a field are gradually becoming more advanced. For example, a material that further improves the weather (light) resistance and the sliding properties while maintaining the mechanical properties of the polyacetal resin is desired. ing. As such sliding characteristics, it is particularly desired to improve friction and wear characteristics with a resin material containing an inorganic filler.

[0003] First, examples of demand for improved weather (light) resistance include interior / exterior parts of automobiles and the like and parts of electric equipment and the like. If a general type of polyacetal resin is used for these applications, the molded product surface will be discolored or surface smooth due to the atmosphere used, such as sunlight, moisture (rain, dew condensation, etc.), or other atmospheric contact, for a long period of time. Loses luster,
Further, cracks may be generated on the surface of the component, resulting in defects such as impairing the appearance. In order to prevent these drawbacks, it has been conventionally proposed to add a weather (light) stabilizer to the polyacetal resin to improve the weather (light) stability. However, the improvement of weather (light) stability by blending a weather (light) stabilizer naturally has a limit. For the purpose of further improving weather (light) resistance, a large amount of weather (light) stabilizer is added. However, not only the weather (light) resistance is not improved, but also the appearance is poor due to the oozing out of the stabilizer, and the weather (light) resistance is sometimes lowered.

[0004] Next, as an example in which the improvement of the sliding characteristics is required, a chassis such as a CD-ROM is required to have a reduced cost.
ABS, PC / ABS,
In many cases, an inorganic filler compounding material in which a resin such as PBT / ABS is mixed with an inorganic filler such as glass fiber, glass flake, talc, and mica is used. Conventionally, gear parts and lever parts often slide against a metal boss caulked on a sheet metal chassis, and the friction and wear characteristics of the metal material counterpart were important. As a result, the importance of slidability with resin bosses and resin guides has increased. In sliding with such a material for a resin chassis, a conventional metal material is difficult to slide due to the poor friction and wear characteristics of the mating material such as ABS resin and the influence of the surface roughness of the compounded inorganic filler. Better friction and wear characteristics than were required for sliding
Wear properties were required and improvements were sought.

[0005] In general, for the purpose of improving the sliding characteristics, addition of a fluororesin or a polyolefin-based resin to a polyacetal resin, or addition of a lubricating oil such as a fatty acid, a fatty acid ester, a silicone oil or various mineral oils has been performed. The addition of fluororesin or polyolefin resin improves the sliding properties to some extent, but such different resins have poor compatibility with polyacetal resins, so the sliding properties under high surface pressure are insufficient, and inorganic fillers The abrasion resistance is poor in sliding with compounded materials. In addition, there is also a problem in moldability that peeling is easily generated on the surface of the molded product and precipitates are easily generated in a molding die. In addition, the addition of lubricating oil has various difficulties such as difficulty during extrusion or molding, or bleeding during use, and when used in combination with the above-mentioned different resin, the compatibility between the different resin and the polyacetal is reduced. However, there is a problem in that the material impairs the wear resistance significantly, and a material having improved these properties has been desired for such a problem.

In order to improve these two characteristics (slidability, weather (light) stability) without sacrificing each of them, it is very difficult to achieve both by the methods conventionally proposed. , It could not meet the demands for rationalization.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, by blending a weather (light) stabilizer and a specific alkylene glycol-based polymer with a polyacetal resin, Sliding characteristics and weather resistance (light)
The present invention has been found to provide a resin composition having excellent stability, and in particular, weather resistance (light) stability, which can be obtained by an outdoor underglass exposure test or the like, in which a resin composition with very little change in appearance due to bleeding out of the stabilizer and surface deterioration can be obtained. It is a thing.

That is, the present invention relates to (A) a polyacetal resin
(B) 0.01 to 5 parts by weight of a weather (light) stabilizer, and (C) 0.01 to 0.01 parts by weight of an alkylene glycol polymer having a primary or secondary amino group and a number average molecular weight of 400 to 500,000.
An object of the present invention is to provide a polyacetal resin composition containing up to 10 parts by weight.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
The polyacetal resin (A) used in the present invention, and a polymer compound having an oxymethylene group (-CH ₂ O-) as the main constituent unit, a polyoxymethylene homopolymer or an oxymethylene group as the main repeating units, In addition, any of other structural units, for example, a copolymer, a terpolymer, or a block polymer containing a small amount of a unit derived from a comonomer such as ethylene oxide, 1,3-dioxolan, and 1,4-butanediol may be used, or The molecule may have not only a linear shape but also a branched or cross-linked structure, or a known modified polyoxymethylene into which another organic group has been introduced. The degree of polymerization is not particularly limited as long as it has melt moldability. A preferred polyacetal resin is a melt index (ASTM D
-1238-89E (hereinafter abbreviated as MI) is 1 to 50 g / 10 min, and more preferably 7 to 30 g / 10 min.

In the present invention, a weather (light) stabilizer is blended as the component (B). Surprisingly, by using (C) a specific alkylene glycol-based polymer described later together with (B) a weather (light) -resistant stabilizer, the (D) modified olefin-based polymer, (E) an inorganic filler It was confirmed that the combined use of the agent produced a synergistic effect on weather (light) stability, and drastically improved weather (light) stability under the test conditions with sunlight.

Among the (B) weather (light) stabilizers of the present invention, benzotriazole-based substances, benzophenone-based substances, aromatic benzoate-based substances, cyanoacrylate-based substances, oxalic anilide-based substances and hindered amines are preferably used. One or more selected from the group consisting of system substances. The following are examples of these substances.

That is, as the benzotriazole-based substance, 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl- Phenyl) benzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di-isoamyl-phenyl) benzotriazole, 2-
[2-hydroxy-3,5-bis- (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2′-
Benzophenone-based substances such as (hydroxy-4'-octoxyphenyl) benzotriazole include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4. -Dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy- Examples of aromatic benzoate-based substances such as 4-oxybenzylbenzophenone are pt-butylphenyl salicylate and p-octylphenyl salicylate. Examples of cyanoacrylate-based substances are 2-ethylhexyl-2-cyano-3,3-diphenyl. Acrylate, Examples of oxalic anilide-based substances such as ethyl-2-cyano-3,3-diphenylacrylate include N- (2-ethyl-phenyl) -N ′-(2-ethoxy-5-t-butylphenyl) oxalic diamide, -(2-ethyl-phenyl) -N'-
(2-ethoxy-phenyl) oxalic acid diamide and the like.

[0013] The hindered amine-based substance is a piperidine derivative having a sterically hindered group.
-Acetoxy-2,2,6,6-tetramethylpiperidine, 4
-Stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, -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, bis (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, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-)
Piperidyloxy) ethane, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate, bis (1-methyl-2,2,6,6-tetramethyl-4) -Piperidyl) adipate, tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate and the like. Also, a high-molecular-weight piperidine derivative polycondensate such as dimethyl succinate-1- (2
-Hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate is also effective.

These weather (light) stabilizers have at least one
It is preferable to mix one or two or more kinds, and it is particularly preferable to use a combination of the above weather-resistant (light) stabilizer and a hindered amine-based substance.

The weather (light) stabilizer (B) used here is
0.01 to 5 parts by weight per 100 parts by weight of component (A) is appropriate, and particularly preferably 0.02 to 3 parts by weight. If these components are too small, no effect can be expected. If they are added unnecessarily, not only are there economic disadvantages, but also mechanical properties, resin coloring (discoloration), mold contamination, etc. The result is a problem.

Next, the alkylene glycol-based polymer having a primary or secondary amino group as the component (C) is a homopolymer or copolymer of ethylene glycol, propylene glycol, or tetramethylene glycol, and the terminal or A polymer having a primary or secondary amino group in the molecular chain. Further, it may be a polymer which is slightly modified such as forming an ester with a fatty acid or an ether with an aliphatic alcohol. Examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers of these structural units having at least one aminopropyl group and aminooctyl group.

The number average molecular weight of the alkylene oxide polymer having a primary or secondary amino group as the component (C) is as follows:
It is 400 to 500,000, preferably 400 to 100,000. If the molecular weight is less than 400, the mechanical properties of the polyacetal resin,
If the sliding property is impaired, and if it exceeds 500,000, the melt viscosity becomes high, and it becomes difficult to disperse the polyacetal resin.

The compounding amount of the alkylene glycol polymer having a primary or secondary amino group as the component (C) is 0.01 to 10 parts by weight, preferably 100 to 100 parts by weight of the component (A).
0.1 to 5 parts by weight. If the amount of the component (C) is too small, the modifying effect cannot be sufficiently obtained, and if the amount is too large, the mechanical properties deteriorate, which is not preferable. Such an alkylene glycol-based polymer (C) not only contributes to the improvement of the slidability, but also produces a synergistic effect when used in combination with a weather (light) stabilizer, and it is not at all possible that the weather resistance is also improved. It is unexpected and surprising.

The polyacetal resin composition of the present invention comprising the above (A) to (C) further comprises, as a component (D), an olefin polymer (d-1), an unsaturated carboxylic acid and an acid anhydride thereof. And a modified olefin polymer modified with at least one compound (d-2) selected from the group consisting of:

The olefin polymer (d-1) used to form the modified olefin polymer (D) includes ethylene, propylene, 1-butene, 1-hexene, 1-heptene, Octene, 1-nonene, 1-decene, homopolymer of α-olefin such as 1-dodecene,
And copolymers composed of two or more of these, and α-olefins thereof and α, such as acrylic acid and methacrylic acid.
β-unsaturated acid or methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate,
Α, β such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and hydroxyethyl methacrylate
An unsaturated carboxylic acid ester, a non-conjugated diene such as 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 2,5-norbonadiene; a conjugated diene component such as butadiene, isoprene and piperylene; α-
Aromatic vinyl compounds such as methyl styrene, vinyl ethers such as vinyl methyl ether and random, block or graft copolymers comprising at least one of comonomer components such as derivatives of these vinyl compounds, and the like. The degree of polymerization, the presence or absence and degree of side chains and branches, the copolymer composition ratio, and the like are not limited.

More specific examples of the olefin polymer (d-1) include high pressure polyethylene, medium / low pressure polyethylene, vapor phase ethylene-α-olefin copolymer, L
LDPE, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-
There are butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-propylene-diene terpolymer and the like. Preferably, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer is there.

The (D) modified olefin copolymer used in the present invention is the above-mentioned olefin polymer (d-1)
With at least one compound selected from the group consisting of unsaturated carboxylic acids, acid anhydrides and derivatives thereof (d-
Modified in 2).

Here, (d-2) used for the denaturation refers to non-aqueous acids such as acrylic acid, methacrylic acid, maleic acid, citraconic acid, itaconic acid, tetrahydrophthalic acid, nadic acid, methylnadic acid and allylsuccinic acid. Saturated carboxylic acids and unsaturated carboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, allyl succinic anhydride, and derivatives thereof. is there.

As the modification method, one or more compounds selected from the group consisting of an olefin (co) polymer (d-1) and an unsaturated carboxylic acid, an acid anhydride thereof, and derivatives thereof (d-1) are used. -2) is heated and reacted with a suitable radical initiator such as an organic peroxide in a solution state or a molten state, but the method is not particularly limited thereto. The compounding ratio in the reaction of both components is 0.1 parts by weight of the compound (d-2) per 100 parts by weight of the olefin polymer (d-1).
-20 parts by weight, preferably 0.1-10 parts by weight, is suitable.
Effective compound (d-) in modified olefin polymer (D)
If the amount of 2) is too small, the affinity between the (A) polyacetal resin and the (C) component and the (D) modified olefin polymer is not sufficiently improved, so that the effects of the present invention cannot be obtained. On the other hand, if the amount is too large, physical properties such as sliding characteristics to be improved may be reduced.

Specific examples of preferred modified olefin copolymers include polyethylene, polypropylene, ethylene-propylene copolymer modified with maleic anhydride,
Examples thereof include an ethylene-ethyl acrylate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl methacrylate copolymer, and an ethylene-methyl methacrylate copolymer.

In the present invention, a modified olefin polymer mainly composed of an α-olefin modified with maleic anhydride, an α-olefin modified with maleic anhydride, and an α, β-unsaturated carboxylic acid ester Such as maleic anhydride-modified polyethylene and / or maleic anhydride-modified polypropylene and maleic anhydride-modified ethylene methyl methacrylate copolymer and / or
Alternatively, by using a maleic anhydride-modified ethylene-ethyl acrylate copolymer in combination, more favorable friction and wear characteristics can be exhibited, and it can be more preferably used.

Preferred modified olefin copolymers have an MI of 0.01 to 100 g / 10 min, more preferably have an MI of 0.1 to 50 g / 10 min, and particularly preferably have an MI of 0.1 to 50 g / 10 min. 0.2 to 30 g / 10 min.

When compounding the component (D), the mixing ratio of the polyacetal resin (A) and the modified olefin polymer (D) is based on 100 parts by weight of the polyacetal resin (A).
(D) 0.5 to 100 parts by weight, preferably 0.5 to 50 parts by weight, particularly preferably 0.5 to 20 parts by weight, of the modified olefin polymer. If the amount of the component (D) is too small, the sliding characteristics and the like are insufficiently improved. If the amount is too large, the mechanical properties are deteriorated and the appearance of the molded product is deteriorated.

The polyacetal resin composition of the present invention comprises:
Further, it is preferable to blend an inorganic filler as the component (E), which is effective in improving the sliding property against metal.

(E) As the inorganic filler, at least one selected from calcium carbonate, potassium titanate, barium carbonate, talc, wollastonite, mica, zinc oxide and the like is preferably used, more preferably calcium carbonate. , Potassium titanate, barium carbonate and zinc oxide. Such (E) inorganic filler, particle shape, fiber shape, regardless of the shape such as aspect ratio, if the inorganic fillers listed in this group,
Either one can be used.

The amount of the inorganic filler as the component (E) is as follows:
It is 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (A). If the amount of the component (E) is too small, the effect of improving the sliding property against metal cannot be sufficiently obtained, and if the amount is too large, the sliding property against resin is deteriorated, which is not preferable.

As described above, the composition of the present invention comprises (A) a polyacetal resin, (B) a weather (light) stabilizer and (C) an alkylene glycol having a primary or secondary amino group. Even with this alone, weather resistance (light) resistance, sliding characteristics,
Having good properties such as moldability, and by further using (D) a modified olefin polymer or (D) an inorganic filler,
Although it has a particularly remarkable effect, the above (A) ~
A further effect can be obtained by using (F) a lubricant in addition to the (E) component.

In the present invention, the lubricant (F) is selected from the group consisting of silicone, α-olefin oligomer, paraffin, substituted diphenyl ether, derivatives of fatty acids having 10 or more carbon atoms, and derivatives of aliphatic alcohols having 10 or more carbon atoms. At least one selected from them is preferably used.
Any of such specific lubricants can be suitably used,
Among such lubricants, certain viscosities, average molecular weights, and / or
Alternatively, a lubricant having a substituent is more preferably used.
Hereinafter, such a lubricating oil will be described in detail.

As the silicone, polydimethylsiloxane and polymethylphenylsiloxane represented by the structure (1) are preferably used as representatives.

[0035]

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(Where R is a methyl group, part of which is an alkyl group, a phenyl group, a halogenated alkyl group,
It may be a halogenated phenyl group, polyalkylene glycol, or the like. ) A part of methyl groups of dimethyl siloxane, halogenated phenyl group represented by chlorophenyl group, C ₈ or more alkyl groups, alkylene glycols represented by polyethylene glycol, derivatives of C ₈ or more aliphatic carboxylic acids A higher aliphatic ester group,
A modified polyorganosiloxane substituted with various substituents such as a halogenated alkyl group represented by a trifluoromethyl group can also be used. In the present invention, such a silicone oil has a kinematic viscosity (25 ° C.) of 100,000 to 100,000.
Those in the range of cSt are preferably used.

The α-olefin oligomer is mainly composed of C ₆ to
Alone α- olefins to C ₂₀ or ethylene and C _3,
It is an aliphatic hydrocarbon having a structure obtained by copolymerizing an α-olefin having a carbon number of ~ ₂₀ . In the present invention, the number average molecular weight is
400-4000 α-olefin oligomers and / or ethylene / α-olefin cooligomers are preferably used.

Paraffin is a so-called paraffinic mineral oil obtained mainly by refining a petroleum fraction. In the present invention, those having an average molecular weight of 300 to 800 are preferably used.

The substituted diphenyl ether, as shown by the following (2), the phenyl ether, C ₁₂ or higher saturated aliphatic chain, an alkyl group, an ester group, in the form of substituents selected from ether group, at least 1 Shows compounds that have been introduced in more than one species. There is no specific molecular weight.
Any alkyl-substituted diphenyl ether is preferably used.

[0040]

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(R is an alkyl group, an ether group, or an ester group introduced at a part or all of the 2-6 position and the 2′-6 ′ position) As the substituent of the alkyl-substituted diphenyl ether, a dodecyl group, Linear alkyl groups such as tetradecyl, hexadecyl, and octadecyl groups;
And a branched alkyl group represented by (3).

[0042]

Embedded image

Examples of the ester group include a dodecyloxycarbonyl group, a tetradecyloxycarbonyl group, a hexadecyloxycarbonyl group, an octadecyloxycarbonyl group, a lauroyloxy group, a myristoyloxy group, a palmitoloxy group, and a stearoyloxy group. And the like. Examples of the ether group include a lauroyl group, a myristoyl group, a palmitoyl group, and a stearoyl group. Furthermore, derivatives such as isosuaryl alcohol and isostearic acid, in which the ester or ether group aliphatic hydrocarbon chain has a branched structure, may be used.

The effect of such a substituted diphenyl ether is as follows:
The position of the substituent is not limited at all, and any substituted diphenyl ether is preferably used. However, from the viewpoint of synthesis, any or all of the 2,4,6,2 ', 4', 6 'positions are preferably used. Is a substituted diphenyl ether having a substituent, particularly preferably a disubstituted compound at the 4,4′-position.

The derivatives of fatty acids having 10 or more carbon atoms in the present invention include esters of fatty acids having 10 or more carbon atoms with mono- or polyvalent aliphatic and / or aromatic alcohols having 10 or more carbon atoms, or Amides of 10 or more fatty acids with primary, secondary or tertiary amines are included.

The derivatives of aliphatic alcohols having 10 or more carbon atoms include esters of aliphatic alcohols having 10 or more carbon atoms and mono- or polyvalent aliphatic and / or aromatic carboxylic acids having 10 or more carbon atoms. Is mentioned.

The details of such esters and amides will be described below.

The fatty acids having 10 or more carbon atoms constituting such esters include lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linoleic acid, arachidic acid, behenic acid, Examples include saturated fatty acids such as lignoceric acid, cetironic acid, montanic acid, and melicic acid, unsaturated fatty acids, straight-chain fatty acids, and branched fatty acids, and 2-bromostearic acid, 18-bromostearic acid, and 18-hydroxystearic acid. All such fatty acid derivatives are preferably used.

Examples of alcohols constituting such fatty acids and esters include n-octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, n-decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and 14-methylhexadecane. -1-ol, stearyl alcohol, oleyl alcohol, 16-methylhexadecanol, 18-methylnonadecanol, 18-methyleicosanol, docosanol, 20-methylhenicosanol, 20-
Monohydric saturated and unsaturated aliphatic alcohols such as methyldocosanol, tetracosanol, tetracosanol, hexacosanol, and octacosanol, straight-chain and branched alcohols, etc., are preferably used.

The aromatic alcohol constituting the ester includes phenol, catechol, naphthol and the like. Further, as the aliphatic polyhydric alcohol, ethylene glycol, propylene glycol,
1,4-butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,2-octanediol, hexadecane-1,2-diol, octadecane-1,2-diol, icosane-1,2-diol, glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol, 1, 2-cyclononanediol, 1,2
Polyhydric alcohols such as cyclodecanediol and dipentaerythritol, tripentaerythritol, diethylene glycol, diglycerol, triglycerol, polyglycerol, polyethylene glycol, polypropylene glycol and the like, condensates of such polyhydric alcohols, and succinic acid, Examples include polybasic acids such as adipic acid and partial esters of such polyhydric alcohols, all of which are preferably used.

The primary, secondary or tertiary amine includes ammonia, ethylenediamine, tetramethylenediamine, monoethaninolamine and the like.

Examples of the aliphatic alcohol having 10 or more carbon atoms include lauryl alcohol, myristyl alcohol, cetyl alcohol, 14-methylhexadecane-1-ol,
Stearyl alcohol, oleyl alcohol, 16-methylhexadecanol, 18-methylnonadecanol, 18-
Saturated and unsaturated aliphatic alcohols, straight-chain and branched alcohols such as methylicosanol, docosanol, 20-methylhenicosanol, 20-methyldocosanol, tetracosanol, tetracosanol, hexacosanol, octacosanol, etc. And the like, all of which are preferably used.

The fatty acids constituting such alcohols and esters include the above-mentioned fatty acids, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linoleic acid, arachidic acid, behenic acid, Saturated fatty acids such as lignoceric acid, cetironic acid, montanic acid, and melicic acid, unsaturated fatty acids, straight-chain fatty acids, and branched fatty acids.
Derivatives of such fatty acids such as bromostearic acid, 18-bromostearic acid and 12-hydroxystearic acid are all preferably used.

Examples of the aromatic carboxylic acid include benzoic acid and phthalic acid. Aliphatic polybasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecamethylenedicarboxylic acid, 1,14-tetradecaic acid Aliphatic polybasic acids such as methylene dicarboxylic acid, 1,16-hexadecamethylene dicarboxylic acid, 1,18-octadecamethylene dicarboxylic acid, trimellitic acid, maleic acid, and fumaric acid, and derivatives of such carboxylic acids. Are preferably used.

The above-mentioned ester composed of a carboxylic acid and an alcohol and the amide composed of a carboxylic acid and an amine are all preferably used, but the following esters and amides are more preferably used in view of availability. That is, lauryl laurate, lauryl stearate, cetyl palmitate, isotridecyl stearate, oleyl oleate, stearyl stearate, isostearyl stearate, isostearyl isostearate, behenyl behenate, ethylene glycol distearate,
Glycerin monostearate, glycerin monobehenate, glycerin di, tristearate, trimethylolpropane triisostearate, pentaerythritol tetraisostearate, pentaerythritol tetrastearate, polyethylene glycol dilaurate,
Esters such as polyethylene glycol distearate, diisotridecyl adipate, and diisotridecyl phthalate; amides such as palmitic amide, stearic amide, ethylene bisstearic amide, and tetramethylene bisstearic amide; and the like. One or more of these are preferably used.

In the present invention, when such a lubricant (F) is blended, the amount of the lubricant (F) is adjusted according to the amount of the polyacetal resin (A).
It is 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight based on parts by weight. If the amount is less than 0.1 part by weight, the inherent effect of the lubricant is hardly exhibited, and if the amount is more than 20 parts by weight, the properties of the base polyacetal are impaired.

The composition of the present invention contains a coloring component (G).
Can be blended. Such a coloring component is used when a specific appearance is required. However, when a coloring component is added to the resin composition of the present invention, the weather resistance is generally improved, which is preferable. The amount of the coloring component is preferably 0.1 to 4 parts by weight based on 100 parts by weight of the polyacetal resin (A). When the compounding amount is small, not only the coloring function, which is the original purpose, becomes insufficient, but also the contribution to improving the weather resistance is small. Conversely, when the amount is too large, not only the mechanical properties are impaired, but also the weather resistance may be adversely affected.

It is preferable that the resin composition of the present invention contains various stabilizers selected as necessary. Examples of the stabilizer include any one or more of a hindered phenol compound, a nitrogen-containing compound, an alkali or alkaline earth metal hydroxide, an inorganic salt, and a carboxylate. Furthermore, as long as the objects and effects of the present invention are not impaired, a general additive to the thermoplastic resin, for example, a lubricant, a release agent, an antistatic agent, a surfactant, or an organic polymer material, if necessary. And the like can be added alone or in combination of two or more.

Next, the composition of the present invention is easily prepared by a known method generally used as a conventional method for preparing a resin composition. For example, after mixing each component, kneading and extruding with a single-screw or twin-screw extruder to prepare pellets, once preparing pellets (master batch) having different compositions, and mixing (diluting) the pellets in a predetermined amount (dilution) Any method can be used.

In the preparation of such a composition, pulverizing part or all of each component, mixing this with other components, and extruding, etc. is necessary for improving the dispersibility of the additive. This is the preferred method.

When the lubricant (F), especially a liquid, is used, the lubricant is mixed with each component in advance and impregnated.
A method of kneading the mixture and extruding it is also a preferable method from the viewpoint of facilitating the preparation of the composition and improving the processability and the slidability.

A member obtained by processing the composition of the present invention by a method such as molding and / or extrusion has an unprecedented excellent weather resistance and also has excellent friction and wear characteristics. It is excellent not only in motion but also in sliding against resin, and is suitably used not only for various sliding parts in the fields of AV and OA, but also for interior and exterior parts of automobiles.

[0063]

(Friction wear test)

<Slidability against GF-ABS> Sliding with GF-ABS (Sebian, manufactured by Daicel Chemical Industries, Ltd.) was performed using a Suzuki friction and wear tester, and the dynamic friction coefficient and the specific wear amount were measured.

Sliding condition tester Suzuki type friction and wear tester (manufactured by Orientec Co., Ltd.) Surface pressure 0.06 MPa Linear velocity 15 cm / sec Sliding for 24 hours <Slidability against steel> Using Suzuki type friction and wear tester , Steel (S
55C), and the dynamic friction coefficient and the specific wear amount were measured.

Sliding condition tester Suzuki type friction and wear tester (manufactured by Orientec Co., Ltd.) Surface pressure 0.98 MPa Linear velocity 15 cm / sec Sliding for 24 hours [Weather (light) resistance test (A, B)] Crack generation time and changes in surface state were evaluated by two types of weather (light) resistance tests.

Test A: A test was carried out using a xenon weather meter (XEL-2WN type, manufactured by Suga Test Instruments Co., Ltd.) in the following light-dark cycle.

Light Irradiation 3.8Hrs / 89 ° C, 50% RH Dark 1.0Hrs / 38 ° C, 50% RH Test B Method: Long-term sunlight exposure was performed by an underglass exposure test (completely closed system) in Okinawa.

(A) Cracking time The test piece was exposed under predetermined conditions, and the presence or absence of cracking on the surface of the test piece was observed with a 10-fold loupe. The time when cracks were first observed was defined as the cracking time. . The higher the value, the better.

(B) Surface condition-1, 2 (confirmation of oozing state) The test piece was exposed for a certain period of time under predetermined conditions, and the change in hue, gloss, and cracks of the test piece before and after exposure were observed. Then, the degree of the change is displayed in five stages. The smaller the number, the smaller the change, ie, the less discoloration, gloss change and crack generation. In addition, the surface state-1 and the surface state-2 evaluated the exposure test piece in the state shown below, respectively. -Surface condition-1. The test piece after the exposure treatment was directly observed and evaluated. In order to remove the cause of discoloration due to oozing, the surface of the test piece after the exposure treatment was washed with a water cloth and then observed. That is, when the score was high in surface condition-1 and low in surface condition-2 It is considered that the cause of discoloration due to oozing is large, and when both points of surface state-1 and surface state-2 are high, deterioration due to weather (light) resistance is considered to be the main cause.

[0070]

[Table 1]

Polyacetal resin: polyoxymethylene copolymer (MI = 27 g / 10 min) B-1: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate B-2: 2- [2-hydroxy −3,5-bis- (α, α
-Dimethylbenzyl) phenyl] benzotriazole C-1: polyethylene glycol di (aminopropyl) ether (Mw = 4000) C-2: polyethylene glycol di (aminopropyl) ether (Mw = 10000) D-1: 2% anhydrous maleic Acid-modified polyethylene D-2: 1% maleic anhydride-modified polyethylene E-1: calcium carbonate (heavy calcium carbonate, average particle size
4.3 μm) F-1: polydimethylsiloxane (average molecular weight 18000, viscosity 1000 cSt) G-1: quinacridone red

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/05 C08K 5/05 5/07 5/07 5/09 5/09 5/10 5/10 5/18 5 / 18 5/20 5/20 5/3417 5/3417 C08L 23/00 C08L 23/00 83/04 83/04 // (C08L 59/00 (C08L 59/00 71:02 71:02 23:26) 23:26)

Claims (14)

[Claims] (A) a polyacetal resin (100 parts by weight), (B) 0.01 to 5 parts by weight of a weather (light) stabilizer, and (C) 1 part by weight.
Number average molecular weight having a secondary or secondary amino group is 400 to 5000
A polyacetal resin composition comprising 0.01 to 10 parts by weight of the alkylene glycol polymer of No. 00. 2. The (B) weather (light) stabilizer is selected from the group consisting of benzotriazole-based substances, benzophenone-based substances, aromatic benzoate-based substances, cyanoacrylate-based substances, oxalic anilide-based substances and hindered amine-based substances. The polyacetal resin composition according to claim 1, which is one or more compounds. 3. The (B) weather (light) stabilizer is selected from the group consisting of benzotriazole-based substances, benzophenone-based substances, aromatic benzoate-based substances, cyanoacrylate-based substances, and oxalic anilide-based substances. The polyacetal resin composition according to claim 1, wherein two or more compounds and one or more compounds selected from hindered amine-based substances are used in combination. 4. The olefin polymer (d-1) is further modified with at least one compound (d-2) selected from the group consisting of unsaturated carboxylic acids, acid anhydrides and derivatives thereof. The polyacetal resin composition according to any one of claims 1 to 3, wherein the modified olefin polymer (D) is blended in a ratio of 0.5 to 100 parts by weight based on 100 parts by weight of the polyacetal resin. 5. The modified olefin polymer (D) comprises 100 parts by weight of the olefin polymer (d-1) in maleic anhydride (d-2).
The polyacetal resin composition according to claim 4, wherein the polyacetal resin composition is modified with 1 to 20 parts by weight. 6. The polyacetal resin composition according to claim 4, wherein the olefin polymer (d-1) is an olefin (co) polymer mainly composed of α-olefin. 7. The polyacetal resin composition according to claim 4, wherein the olefin polymer (d-1) is an olefin copolymer of an α-olefin and an α, β-unsaturated carboxylic acid ester compound. . 8. The α, β-unsaturated carboxylic acid ester compound comprises methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. The polyacetal resin composition according to claim 7, which is at least one compound selected from the group. 9. The olefin polymer (d-1) is polyethylene, polypropylene, ethylene-propylene copolymer,
The ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer selected from the group consisting of ethylene-ethyl methacrylate copolymer. Polyacetal resin composition. 10. The polyacetal resin according to claim 1, further comprising an inorganic filler (E) in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the polyacetal resin (A). Composition. 11. The polyacetal resin composition according to claim 10, wherein the inorganic filler (E) is selected from calcium carbonate, potassium titanate, barium carbonate and zinc oxide. 12. The method according to claim 12, wherein the lubricant (F) is a polyacetal resin.
The polyacetal resin composition according to any one of claims 1 to 11, wherein the polyacetal resin composition is blended in a ratio of 0.1 to 20 parts by weight with respect to (A) 100 parts by weight. 13. The lubricant (F) is selected from the group consisting of silicone, α-olefin oligomer, paraffin, substituted diphenyl ether, derivatives of fatty acids having 10 or more carbon atoms, and derivatives of aliphatic alcohols having 10 or more carbon atoms. The polyacetal resin composition according to claim 12, which is at least one compound. 14. The polyacetal resin composition according to claim 1, further comprising 0.1 to 4 parts by weight of the coloring component (G) based on 100 parts by weight of the polyacetal resin (A). object.