JPH08127701A - Polyacetal resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyacetal resin compsn. excellent in melt flowability and thermal stability by compounding a specific polyacetal resin with a specified amt. of a substance selected from the group of substances including an antioxidant. CONSTITUTION: 100 pts.wt. polyacetal resin which contains 50-5,000ppm polyacetal oligomer having a content of comonomer (e.g. 1,3-dioxolane) units of 2-10mol% and which contains a residual catalyst (e.g. BF3 ) in an amt. of 3-11ppm in terms of fluorine is compounded with 0.1-10 pts.wt. at least one substance selected from among an antioxidant. a polymer or compd. having a formaldehyde-reactive nitrogen atom, a formic acid acceptor, a weather (light) stabilizer, and a mold release agent or a lubricant (e.g. a hindered phenol antioxidant), 0-60 pts.wt. at least one substance selected from among a reinforcement, a conductive material, a thermoplastic resin, and a thermoplastic elastomer (e.g. an inorg. filler), and 0-5 pts.wt. pigment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a well-balanced polyacetal composition having excellent fluidity and thermal stability.

[0002]

2. Description of the Related Art Polyacetal resin is a resin excellent in mechanical properties, fatigue resistance and sliding properties, and is therefore widely used in various fields such as automobiles, electric equipment and building materials. However, as the applications of polyacetal resins have expanded, the demand for quality has become more sophisticated. The required characteristics include improvement of molding processability. At the time of injection molding, the polyacetal resin has a relatively high crystallization rate and a high degree of crystallinity, so that molding strain is more likely to occur as compared with the amorphous resin. Particularly, it is not always sufficient for the purpose of molding a molded product having a complicated shape or a molded product having a thin wall thickness, or for the purpose of shortening the molding cycle, and improvement of fluidity is required.

As a method for improving the moldability of the polyacetal resin, other components are added to the polyacetal resin.
Attempts have been made to improve the melt flowability of polyacetal by blending. As other components, polyalkylene glycols are disclosed in JP-B-37-8816, esters of aliphatic alcohols in JP-B-52-3754, bisphenol derivatives in JP-A-60-90248, and JP-A-4. No. 239566 proposes a composition to which a liquid ethylene-α-olefin random copolymer is added.

However, although these compositions show an improvement in the fluidity of the polyacetal resin, they not only impair the mechanical properties of the molded article, but also deteriorate the thermal stability, which is not practical. Further, as a method for improving the thermal stability, in JP-B-63-24609, the thermal stability is improved by treating in a liquid medium insoluble to the polyacetal polymer, but the fluidity is not sufficient. Absent.

[0005]

In view of the above problems, the present invention provides a well-balanced polyacetal which has an improved melt fluidity without deteriorating the mechanical properties inherent to the polyacetal resin and is excellent in thermal stability. It is intended to provide a resin composition.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve this problem, and as a result, the polyacetal contains a catalyst residue containing an oligomer and a fluorine in a predetermined ratio. The inventors have found that a polyacetal resin composition that can achieve the object is obtained, and completed the present invention.

That is, the present invention is as follows: 50 to 5000 ppm of polyacetal oligomer having a comonomer insertion amount of 2 to 10 mol% and 3 to 5% of fluorine.
(A) antioxidant, polymer or compound containing formaldehyde-reactive nitrogen, formic acid scavenger, weathering (light) stabilizer, mold release (lubrication) per 100 weight of polyacetal resin containing 11 ppm of catalyst residue. ) At least one of the agents
0.1 to 10 parts by weight of the seed and at least one of (B) a reinforcing material, a conductive material, a thermoplastic resin, and a thermoplastic elastomer 0
Provided is a polyacetal resin composition containing 60 parts by weight to 60 parts by weight of a pigment and 0 to 5 parts by weight of a pigment (C) and having excellent fluidity and thermal stability. It is also characterized in that the antioxidant is one or more of hindered phenolic antioxidants. It is also characterized in that the polymer or compound containing formaldehyde-reactive nitrogen is one or more of a polyamide resin, acrylamide and its derivative, a polymer of them with other vinyl monomers, and an amide compound. Also,

The formic acid scavenger is an amino-substituted triazine,
Polycondensation product of amino-substituted triazine and formaldehyde, hydroxide of alkali metal or alcal earth metal,
It is also characterized in that it is at least one kind of inorganic acid salt, carboxylate or alkoxide. Another feature is that the weathering (light) stabilizer is one or more of a benzotriazole-based substance, an oxalic acid anilide-based substance and a hindered amine-based substance. It is also characterized in that the releasing (lubricating) agent is one or more of alcohol fatty acids and their fatty acid esters, polyoxyalkylene glycols, olefin compounds having an average degree of polymerization of 10 to 500, and silicones. Also,

The reinforcing agent is an inorganic filler, glass fiber,
It is also characterized in that it is at least one kind of glass beads and carbon fiber. It is also characterized in that the conductive agent is at least one kind of conductive carbon black, metal powder or fiber. It is also characterized in that the thermoplastic resin is at least one kind of olefin resin, acrylic resin, styrene resin, polycarbonate resin, and uncured epoxy resin. (10) The thermoplastic elastomer is at least one of a polyurethane elastomer, a polyester elastomer, a polystyrene elastomer, and a polyamide elastomer.
It is also characteristic in that it is a seed.

The present invention will be described in detail below. The polyacetal resin of the present invention is a formaldehyde monomer, or its trimer (trioxane) or quadruplex (tetraoxane), etc., and ethylene glycol, propylene oxide, shrimp chlorohydrin, 1,3-dioxolane, glycol formal. An oxymethylene copolymer containing 0.1 to 20% by weight of an oxyalkylene unit having 2 to 8 carbon atoms, which is produced from a cyclic ether such as Particularly, a polyacetal resin obtained from a combination of trioxane and 1,3-dioxolane is preferable.

The polyacetal oligomer contained in the polyacetal resin has oxymethylene as a main constituent unit and is 2 to 10 mol% (based on the number of moles of oxymethylene unit).
Is an acetal polymer having a comonomer insertion amount of (oxyethylene unit mol number). Comonomers are cyclic ethers having oxyalkylene units with two or more adjacent carbon atoms, such as ethylene oxide, 1,3
-Dioxolane, diethylene glycol formal,
1,4-butanediol formal and the like can be mentioned. The most preferred comonomer is a low catalytic amount, highly active 1,3-dioxolane. The Mn of the oligomer is 500 to 3
It is a low molecular weight substance of 000 (Mn; number average molecular weight) and is relatively stable chemically and thermally.

The amount of oligomer contained in the polyacetal resin composition is 50 to 5000 ppm, preferably 100 to 5000 ppm.
1000 ppm, particularly preferably 300-600 ppm
Is suitable. When the content of the oligomer is less than 50 ppm, the fluidity is lowered, and when it exceeds 5000 ppm, the thermal stability is impaired. Fluorine 3-11pp
The catalyst residue contained in m is 3 to 11 ppm, preferably 3 to 8 ppm of trifluoride used as a polymerization initiator. If it is less than 3 ppm, the effect of improving the fluidity cannot be obtained, and if it exceeds 11 ppm, the polyacetal resin itself is decomposed at the time of processing and the thermal stability is deteriorated, which is not preferable.

The polyacetal resin of the present invention may be prepared by any method as long as both the amount of the oligomer and the fluorine content derived from the polymerization catalyst are within the predetermined ranges, and the oligomer may be added in the predetermined range for adjustment. The detailed method will be described in Examples. At least one of the antioxidant, the polymer or compound containing formaldehyde-reactive nitrogen, the formic acid scavenger, the weather (light) stabilizer, and the release (lubricant) used in the present invention is 0.
It is used in the range of 1 to 10 parts by weight. If it is less than 0.1 part by weight, the purpose of addition of each additive cannot be achieved, and if it exceeds 10 parts by weight, the thermal stability is significantly deteriorated, which is not preferable. Each additive will be described with reference to specific examples.

The antioxidant is preferably a hindered phenol type antioxidant, 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-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'-g
-Butyl-4-hydroxyphenol) prepionylhexamethylenediamine, N, N'-tetramethylenebis-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-dibutyl-4-hydroxyphenyl) propionyloxy) ethyl) oxyamide, and the like. These antioxidants may be used alone or in combination of two or more, without any limitation. Particularly preferred are 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. .

Examples of the polymer or compound containing formaldehyde-reactive nitrogen include (a) polyamide resin. Examples of polyamide resins include nylon 4-6, nylon 6, nylon 6-6, nylon 6-10, nylon 6-12, nylon 12 and the like, and copolymers thereof, such as nylon 6 / 6-6 / 6-. 10, nylon 6/6
-12 etc. are mentioned. Further, (b) acrylamide and its derivatives or acrylamide and its derivatives and other vinyl monomers are polymerized in the presence of a metal alcoholate to obtain a primary amide content of 1.4 to 10 mmol-polymer of 1 g of a polymer. Also included are β-alanine copolymers. These polymers can be produced by the methods described in JP-A-63-118328 and JP-A-3-234729.

(C) Polymers obtained by polymerizing acrylamide and its derivatives or acrylamide and its derivatives and other vinyl monomers in the presence of a radical polymerization catalyst are also included. These pollenaux are disclosed in JP-A-3-2826.
It can be produced by the method described in JP-A-0. (D) Amide compounds may be mentioned. Examples of amide compounds include aliphatic monocarboxylic acids, dicarboxylic acids or aromatic monocarboxylic acids, dicarboxylic acids and aliphatic monoamines,
It is produced from diamine, or aromatic monoamine and diamine. Stearyl stearic acid amide, stearyl oleic acid amide, ethylenediamine-distearic acid amide, hexamethylenediamine-distearic acid amide, ethylenediamine-dioleic acid amide, ethylenediamine-dierucic acid amide, xylylenediamine-dierucic acid amide, di (xylylenediamine- Stearic acid amide) sebacic acid amide and the like. In particular, nylon 6-6, a particle size of 10 μm or less, preferably 6 μm or less, and the poly-β-alanine copolymer described in (ii), ethylenediamine-distearic acid amide, or ethylenediamine-dioleic acid amide are preferable.

Examples of the formic acid scavenger include (a) amino-substituted triazine. For example, guanamine (2,4-diamino-sym-triazine), melamine (2,4,6-triamino-sym-triazine), N-butylmelamine, N-phenylmelamine, N, N-diphenylmelamine, N, N. -Diallyl melamine, N, N ', N "-triphenylmelamine, N-methylolmelamine, N,
N′-dimethylolmelamine, N, N ′, N ″ -trimethylolmelamine, benzoguanamine (2,4-diamino-6-phenyl-sym-triazine),

2,4-diamino-6-methyl-sym-
Triazine, 2,4-diamino-6-butyl-sym-
Triazine, 2,4-diamino-6-benzyloxy-
sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sym-triazine, 2,4-diamino-6
-Chloro-sym-triazine, 2,4-diamino-6
-Mercapto-sym-triazine, 2,4-dioxy-6-amino-sym-triazine (amelite), 2
-Oxy-4,6-diamino-sym-triazine (amerine), N, N ', N'-tetracyanoethylbenzoguanamine and the like.

(B) A cocondensation product of amino-substituted triazine and formaldehyde can be mentioned. For example, melamine-
Formaldehyde polycondensate and the like. (C) Examples thereof include hydroxides, inorganic acid salts, carboxylates or alkoxides of alkali metals or alkaline earth metals. For example, hydroxides such as sodium, potassium, magnesium, calcium or barium, carbonates, phosphates, silicates and borates of the above metals. As the carboxylic acid of the metal carboxylate, 10-
Saturated or unsaturated aliphatic carboxylic acids having 36 carbon atoms, these carboxylic acids being optionally substituted by hydroxyl groups.

As the saturated aliphatic carboxylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid,
Examples include cerotic acid, montanic acid, melissic acid, and ceroplastic acid. Examples of the unsaturated aliphatic carboxylic acid include undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid and stearolic acid. In addition, examples of the alkophid include methoxide and ethokid of the above metals.

Among these formic acid scavengers, melamine, melamine-formaldehyde polycondensate, especially hot-water-soluble melamine-formaldehyde polycondensate, calcium laurate, calcium stearate, calcium behenate, especially those having a calcium ion content of 1 to 50 ppm. Is preferred. As the weather resistance (light) stabilizer, benzotriazole type substances, oxalic acid anlide type substances and hindered amine type substances are preferable. As the bebenzotriazole-based substance,
For example, 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole, 2- [2'-hydroxy-
3,5-di-t-butyl-phenyl) benzotriazole, 2- [2'-hydroxy-3,5-di-isoamyl-phenyl) benzotriazole, 2- [2'-hydroxy-3,5-bis- (Α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole and the like can be mentioned. On the other hand, examples of the oxalic acid anilide-based substance include 2-ethoxy-2′-ethyl oxalic acid bisanilide, 2-ethoxy-5-t-butyl-2′-ethyl oxalic acid bisanilide, and 2-ethoxy-2′-ethyl oxalic acid bisanilide. Ethoxy-3'-dodecyl oxalic acid bisanilide and the like can be mentioned.

These substances may be used alone or in combination of two or more. As a hindered amine-based substance, 4-acetoxy-2,2,2
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-2,26,6-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-piperidine) -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-piperidyl) tolylene- 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-tricarboxylate, tris (2,2,6,6-
Tetramethyl-4-piperidyl) -benzene-1,3
4-tricarboxylate etc. are mentioned.

The above hindered amine materials may be used alone or in combination of two or more kinds. Further, a combination with the above-mentioned benzotriazole-based substance and oxalic acid anilide-based substance is most preferable. As the releasing agent (lubricant), alcohol, fatty acid and fatty acid ester thereof, polyoxyalkylene glycol, and the average degree of polymerization of 1
Olefin compounds of 0-500, silicones are preferred.

Alcohols include monohydric alcohols and polyhydric alcohols. Examples of monohydric alcohols include octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol. , Bentadecyl alcohol, cetyl alcohol, hebutadecyl alcohol, stearyl alcohol, oleyl alcohol, nonadecyl alcohol, eicosyl alcohol, pehenyl alcohol, ceryl alcohol. Examples thereof include melysyl alcohol, 2-hexyldecanol, 2-isoheptyl isundecanol, 2-octyldodecanol, 2-decyltetradecanol, 2-ratylstearin alcohol, and uniline alcohol.

The polyhydric alcohol is a polyhydric alcohol containing 2 to 6 carbon atoms, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol dipropylene glycol, butanediol, pentanediol, hexanediol. , Glycerin, diglycerin, triglycerin, threitol, erythritol, pentaerythritol,
One or more selected from arabitol, ribitol, xylitol, sorbite, sorbitan, sorbitol, and mannitol.

As the fatty acid, capric acid, lauric acid, myristic acid, palmitic acid stearic acid, 12-
Hydroxystearic acid, araginic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, mericic acid,
Examples include ceroplastic acid. Unsaturated aliphatic carboxylic acid comprises undecylenic acid, oleic acid, elaidic acid, cetrainic acid, erucic acid, brassic acid, sorbic acid linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid and such components. Examples thereof include naturally occurring fatty acids and mixtures thereof. These fatty acids may be substituted with a hydroxy group.

Of the above fatty acid ester compounds, preferably fatty acids derived from a fatty acid selected from palmitic acid, stearic acid, behenic acid and montanic acid and a polyhydric alcohol selected from glycerin, pentaerythritol, sorbitan and sorbitol. It is an ester. These fatty acid ester compounds may or may not have a hydroxyl group. There is no restriction.

For example, it may be a monoester, a diester or a triester. Further, the hydroxyl group may be blocked with boric acid or the like. Examples of preferred fatty acid ester compounds include glycerin monopalmitate, glycerin dipalmitate, glycerin tripalmitate,
Glycerin monostearate, glycerin distearate, glycerin tristearate, glycerin monobehenate, glycerin dibehenate, glycerin tribehenate, glycerin monomontanate, glycerin dimontanate, glycerin trimontanate,

Pentaerythritol monopalmitate,
Pentaerythritol dipalmitate, pentaerythritol tripalmitate, pentaerythritol tetrapalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol monobehenate, pentaerythritol Dibehenate, pentaerythritol tribehenate, pentaerythritol tetrabehenate, pentaerythritol monomontanate,
Pentaerythritol dimontanate, pentaerythritol trimontanate, pentaerythritol tetramontanate,

Sorbitan monopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monobehenate, sorbitan dibehenate, sorbitan tribehenate, sorbitan Monomontanate, sorbitan dimontanate, sorbitan trimontanate, sorbitol monopalmitate, sorbitol dipalmitate, sorbitol tripalmitate, sorbitol monostearate, sorbitol distearate, sorbitol tristearate, sorbitol monobehenate, sorbitol. Dibehenate, sorbitol tribehenate sorbitol monomontanate, sorbitol dimontanate,
Sorbitol trimontanate.

As an aliphatic ester compound having a hydroxyl group blocked with boric acid or the like, there is a boric acid ester of fatty acid ester such as glycerin (JP-A-49-60762). These fatty acid ester compounds may be used alone or as a mixture of two or more kinds.

As the polyoxyalkylene glycol,
For example, the first group includes polycondensates containing alkylene glycol as a monomer. For example, polyethylene glycol, polypropylene glycol, polyethylene glycol polypropylene glycol block polymer, etc. may be mentioned. The preferable range of the number of moles of these polymerizations is 5 to 1000, and the more preferable range is 10 to 500.

The second group is an ether compound of the first group and an aliphatic alcohol. For example, polyethylene glycol oleyl ether (ethylene oxide polymerization mole number 5 to 50), polyethylene glycol cetyl ether (ethylene oxide polymerization mole number 5 to 2)
0), polyethylene glycol stearyl ether (ethylene oxide polymerization mol number 5-30), polyethylene glycol lauryl ether (ethylene oxide polymerization mol number 5-30), polyethylene glycol tridecyl ether (ethylene oxide polymerization mol number 5-30),
Examples thereof include polyethylene glycol nonyl phenyl ether (ethylene oxide polymerization mole number 2 to 100), polyethylene glycol octyl phenyl ether (ethylene oxide polymerization mole number 4 to 50) and the like.

The third group is ester compounds of the first group and higher fatty acids. For example, polyethylene glycol monolaurate (ethylene oxide polymerization mol number 2-30), polyethylene glycol monostearate (ethylene oxide polymerization mol number 2-50), polyethylene glycol monooleate (ethylene oxide polymerization mol number 2-10), etc. Is mentioned. Of these polyalkylene glycols, the first group is more preferable.

The olefin compound having an average degree of polymerization of 10 to 500 is represented by the general formula (1):

Embedded image (R _3, R ₃ 'is hydrogen, an alkyl group, an aryl group, selected from ether groups, each be the same or different is also good .k = 10 to 500.) At least one represented by An olefin compound composed of olefin units. In the above formula, the alkyl group is, for example,
There are ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, lauryl group, cetyl group, stearyl group and the like. Examples of aryl groups include phenyl group, p
-Nonylphenyl group, benzyl group, p-octylphenyl group, p-nonylphenyl group, benzyl group, p-putylbenzyl group, tolyl group, xylyl group and the like. Further, examples of the ether group include an ethyl suther group, a propyl ether group, a butyl ether group and the like.

Preferred olefin units include those of formula (2).

Embedded image

The olefin compound used in the present invention is
A compound composed of one olefin unit, or 2
It may be any compound composed of at least one different olefin unit. That is, for example, it is composed of polyethylene units and polypropylene units. An olefin compound having a block structure or a graft structure is also included in the olefin compound of the present invention.

The structure of the olefin compound is preferably a linear structure as compared with the graft structure. Examples of the monomer constituting the olefin compound include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-1-butene, and 3-.
Methyl-1-detene, 2,3-dimethyl-2-butene,
There are diolefin-based monomers represented by 1-butene, 1-hexane, 1-octene, 1-nonene, 1-decene and the like.

The olefin compound used in the present invention includes two of these olefin monomers and diolefin monomers.
It may be a compound obtained by copolymerizing at least one species. When the olefin compound is a compound obtained by polymerizing a diolefin-based monomer, from the viewpoint of improving the thermal stability of the present oxymethylene polymer composition, a carbon-carbon unsaturated bond is formed by using a conventional hydrogenation method. Was reduced as much as possible.
It is preferable to use an olefin compound. The average degree of polymerization k of the olefin unit constituting the olefin compound is 10 to
Must be between 500. When the average degree of polymerization k is less than 10, long-term lubrication characteristics are deteriorated and the moldability of the mold is also adversely affected. If k is greater than 500, the initial lubrication characteristics will be significantly reduced.

The average degree of polymerization k of the olefin unit is 15 to 3
It is preferable that it is between 00, and further 20 to 100
It is more preferable that it is between Further, as a preferable olefin compound, an olefin compound modified with an ether group can be used. What is an ether group?
Is composed of a polyalkylene oxide unit. From the viewpoint of improving slidability, the polyalkylene oxide unit forming the ether group is more preferably the same as the polyalkylene oxide unit forming one end of the oxymethylene polymer.

[0047]

Embedded image (R ₄ and R ₄ 'are selected from hydrogen, an alkyl group and an aryl group and may be the same or different. Also, R ₄ and R ₄ ' bonded to different carbon atoms may be the same. May be different. X = 6 and y = 1 to 1,000.)

At least one of the reinforcing material, conductive material, thermoplastic resin and thermoplastic elastomer used in the present invention is 0.
Used in the range of up to 60 parts by weight. When it exceeds 60 parts by weight, the physical properties inherent to the polyacetal resin are deteriorated and the thermal stability is deteriorated, which is not preferable. Each material will be described with reference to specific examples. Inorganic fillers, glass fibers, glass beads, and carbon fibers are preferable as the reinforcing material.

As the inorganic filler, talc, naika,
Examples thereof include wollastonite, asbestos, clay, bentonite, diatomaceous earth, ceramic fiber and rock wool, and talc and wollastonite are particularly preferable. The inorganic filler, glass fiber, glass beads, and carbon fiber may be treated with a polyurethane emulsion containing a silana coupling agent. The silane coupling agent is preferably an aminoalkylsilane, for example, δ
-Aminobrobimetreethoxysilane, δ- (N-aminoethyl) aminobutyltriethoxysilane, δ- (N
-Methylethyl (N-aminoethyl) amineiminobutyltriethoxysilane, bisγ-N-brovyldiethylaminobrovyldimethoxysilane,

Bis β- (N-aminoethyl) diethoxysilane, β-N-ethylaminoaminoethyltotrimethyloxysilane, γ-brovyl (N-aminoethyl) aminotriltoxysilane and β-N-ethylamineethyltriβ -Methoxyethoxysilane.

Hexamethylene diisocyanate, lysine diisocyanate, water addition 2, as the isocyanate compound constituting the urethane in the polyurethane emulsion
Non-yellowing diisocyanates such as 4-toluylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, dicyclohexyldimethinemethane p, p'-diisocyanate, diethyl fumarate diisocyanate, water-added xylylenediisocyanate and 2 , 4-toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene isocyanate, p-phenylmethane isocyanate, naphthalene-1,5-diisocyanate, triphenylmethane triisocyanate, polythymylene polyphenyl isocyanate Examples include aromatic polyisocyanates.

As the polyhydroxy compound, carboxylic acids such as adipic acid, sebacic acid, maleic acid and dimer acid, and ethylene glycol, brobilene glycol,
Polyethylene and ethylene oxide of hydroxy compounds such as butylene glycol and trimethylolbroban,
Polyols obtained by ring-opening alkylene oxides such as propylene oxide and teslahydrofuran, or glycerin, neoventil, trimethylolbroban, solbit and other polyhydric alcohols in which the above alkylene oxides have been disabled, and ethylene glycol and brobilene glycol. , Butylene glycol, hexamethylene glycol, trimethylolbroban, trimethylolethane, glycerin, 1,2,6-hexanetriol,
A single volume such as Ventaeri slit may be mentioned.

As the conductive material, conductive carbon black,
Metal powders or fibers are preferred. The conductive carbon black preferably has a small particle size or a large surface area and has a chain structure developed, but dibutyl phthalate (hereinafter referred to as D
The oil absorption amount (abbreviated as BP) must be for maintaining 200 ml / 100 g. For example, Toka Black # 4500 (oil absorption is 230 ml / 100 g, manufactured by Tokai Carbon Co., Ltd.), # 450, # 3750 (oil absorption is 2
45 ml / 100 g, manufactured by Mitsubishi Kasei Co., Ltd., Ketjen Black (oil absorption: 480 ml / 100 g, Lion-
Akzo Co., Ltd., Brintex XE2 (oil absorption 370
ml / 100 g, manufactured by Degussa) and the like. Iron, nickel, as the metal used in the metal powder or fiber,
Examples include copper, silver and stainless steel.

Polyolefin resin as the thermoplastic resin,
Acrylic resin, styrene resin, polycarbonate resin,
An uncured epoxy resin is preferred. Examples of the polyolefin resin include polyolefin, copolymers of olefin and vinyl compounds, and modified products thereof. The polyolefin is, for example, high density polyethylene, low density polyethylene, polypropylene, polybutene-1, poly-4-.
Methyl pentene-1 etc. are mentioned. Copolymers of olefins and vinyl compounds include, for example, copolymers of olefins such as ethylene, propylene and butene with vinyl compounds such as vinyl acetate, vinyl formate, methyl acrylate, butyl methacrylate, acrylonitrile, butyl vinyl ether, isobutyl vinyl suter. Etc.

The modified polyolefin resin is a polyolefin obtained by reacting a polyolefin with a reaction material such as a peroxide to cause a polymer reaction to add a polar group such as a carboxyl group. For example, unsaturated organic acids such as maleic acid, itaconic acid, acrylic acid and methacrylic acid, anhydrides of unsaturated organic acids such as maleic anhydride, itaconic anhydride and citraconic anhydride; monomethyl maleate,
Esters of unsaturated organic acids such as methyl acrylate; amides of unsaturated organic acids such as fumaric acid monoamide and acrylic acid amide; imides of unsaturated organic acids such as itaconic acid imide; polystyrene, styrene-copolymer, poly Methyl methacrylate, particularly low density polyethylene, and low density polyethylene grafted with polystyrene or a styrene-acrylonitrile copolymer are preferred.

As the acrylic resin, either a homopolymer or a copolymer of methacrylic acid ester can be used. A homopolymer of an alkyl ester of methacrylic acid having 1 to 6 carbon atoms, particularly methyl polymethacrylate is preferable. On the other hand, as a copolymer of methallyl ester,
One obtained by copolymerizing two or more kinds selected from methallylic acid having 1 to 6 carbon atoms, particularly a copolymer of methyl methacrylate and methacrylic acid having 2 to 6 carbon atoms, and A copolymer of methyl methacrylate and an alkyl ester of acrylic acid having 1 to 6 carbon atoms can also be used.

Further, a homopolymer of an alkyl ester of methacrylic acid having 1 to 6 carbon atoms or the above-mentioned random or block copolymer is added to an alkyl ester of methacrylic acid having 1 to 6 carbon atoms or an acrylic ester,
Graft-polymerization of an alkyl ester of acrylic acid having 1 to 6 carbon atoms, particularly poly (methyl methacrylate), a random or block copolymer of methyl methacrylate and methyl methacrylate and an alkyl ester of acrylic acid having 2 to 6 carbon atoms. Random or block copolymer main chain of polymer or methyl methacrylate and alkyl ester of acrylic acid having 1 to 6 carbon atoms, the alkyl ester of methacrylic acid having 2 to 6 carbon atoms or acrylic having 1 carbon atom
Graft copolymers obtained by graft-polymerizing alkyl esters of ~ 6 can also be preferably used.

Also included are multiphase polymers having a rubbery core and a methacrylic acid ester polymer shell. Examples of the monomer that constitutes the rubbery core include conjugated dienes such as butydiene, isoprene, and chlorobrene, and alkyl acrylates having 2 to 8 carbon atoms, such as ethyl acrylate, brovyl acrylate, butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate. It is possible to use two or more of these in combination.

Examples of the styrene resin include styrene polymers, α-methylstyrene polymers, styrene and / or α.
Examples thereof include a copolymer of methylstyrene and acrylonitrile, and a terpolymer of styrene and / or α-methylstyrene, acrylonitrile, and butadiene.

The polycarbonate resin is derived from an aromatic dihydric phenol, an alicyclic hydrocarbon or an aliphatic hydrocarbon having two hydroxyl groups in the molecule, or a mixture thereof. Examples of the aromatic divalent phenol include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) broban, 2,2-bis (3 -Broro-4-
Examples thereof include hydroxyphenyl) propane, 4,4′-dihydrosidiphenyl ether, and 4,4′-dihydroxydiphenyl sulfide.

Or, as the alicyclic hydrocarbon having two hydrogen groups in the molecule, for example, 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-bis (4-hydroxy-3, 5-dibromocyclohexyl) broban, 2,2-bis (4-hydroxycyclohexyl) butane, 4,4′-dihydrosidicyclohexyl ether, 4,4′-dihydroxydicyclohexylfide and the like can be mentioned. Examples of the aliphatic hydrocarbon having two hydrogen groups in the molecule include 1,3-propanediol,
Examples include 1,4-butanediol and 1,6-hexanediol. The polycarbonate resin can be obtained by reacting these compounds with phosgene or diphenyl carbonate.

As the uncured epoxy resin, a mono- or polyfunctional glycidyl derivative is suitable. Examples thereof include 2-ethylhexyl glycidyl ether, 2-methyl octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether,
Behenyl glycidyl ether, ethylene glycidyl ether, polyethylene glycidyl ether, (ethylene oxide unit: 2-30), brobilene glycol diglycidyl ether, polyethylene glycidyl ether, (bropyrene oxide unit: 2-30),

Neobenthyl glycol diglycidyl ether, 1,6-hexanediol digeridin silyl ether, glycerin digericidyl ether, glycerin triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated gosphenol A diglycidyl ether, sorbitan mono Ester diglycidyl ether, benthaerythritol triglycidyl ether, pentaerythritol triglycidyl ether, diglycerin tetraglycidyl ether, condensate of cresol novolac and ebichlorohydrin (epoxy equivalent; 100 to 4
00, softening point; 20 ° C to 150 ° C) and the like.

As the thermoplastic elastomer, a polyurethane elastomer, a polyester elastomer, a polystyrene elastomer, and a polyamide elastomer are preferable. Examples of the polyurethane elastomer include the following. As a hard segment, 4,4'-
Urethane obtained by reacting diisocyanate such as diphenylmethane diisocyanate or 4,4′-dicyclohexylmethane diisocyanate with glycol such as ethylene glycol or tetramethylene glycol, polyethylene adipate as a soft segment,
There is a polyurethane elastomer in which a polyester diol such as polybutylene adipate and a polyether diol such as polypropylene glycol and polytetramethylene glycol are combined.

Among these polyurethane elastomers, a polyurethane synthesized from 4,4'-diphenylmethane diisocyanate, tetramethylene glycol and polytetramethylene glycol is particularly preferable. As the polyester-based elastomer, there are polyester elastomers such as polyethylene terephthalate, polybutylene tephthalate, modified polyethylene terephthalate, and polyethylene / butylene terephthalate as hard segments, and polyether elastomers such as polypropylene glycol and polytetramethylene glycol as soft segments. .

Among these polyester elastomers, polybutylene terephthalate-polytetramethylene glycol block copolymer and polyethylene / butylene terephthalate-peritetramethylene glycol block copolymer are particularly preferable. As the polystyrene-based elastomer, there is a polystyrene-based elastomer in which polystyrene is used as the hard segment, diene-based such as polybutadiene and polyisoprene is used as the soft segment, and hydrogenated diene-based such as hydrogenated polybutadiene and hydrogenated polyisoprene is combined.

Among these polystyrene-based elastomers, polystyrene-polybutadiene block copolymers and polystyrene-hydrogenated polybutanediene block copolymers are particularly preferable. Polyamide elastomer as hard segment nylon 6 and nylon 6-
6, polyamides such as nylon 6-10, nylon 11 and nylon 12, and polyamide elastomers in which soft segments such as polyethers such as polypropylene glycol and polytetramethylene glycol, polyesters such as polyethylene adipate and polybutylene succinate are combined. Among these polyamide elastomers, nylon 6-polypropylene glycol block copolymer and nylon 6-polytetramethylene glycol block copolymer are particularly preferable.

The pigment used in the present invention is used in the range of 0 to 5 parts by weight. If it exceeds 5 parts by weight, the thermal stability is remarkably lowered, which is not preferable. The pigment is an inorganic pigment or an organic pigment. Inorganic pigments are those commonly used for coloring resins, for example, zinc sulfide, zinc oxide, titanium oxide, barium sulfate, titanium yellow, iron oxide, ultramarine blue, cobalt blue, fuel pigment, carbonic acid. Salt, phosphate, acetate, carbon black, styrene black,
I say lamp black. Organic pigments include condensed azo pigments, isoindoline pigments, disazo pigments, monoazo pigments, anthraquinone pigments, heterocyclic pigments, pennon pigments, quinacridone pigments, thioindico pigments, berylylene pigments, dioxazine pigments and phthalocyanine pigments. Other additives such as a nucleating agent and a thermosetting resin may be added to the composition of the present invention as long as the effects of the present invention are not impaired.

[0069]

EXAMPLES Examples and comparative examples of the present invention will be shown below.
These do not limit the scope of the invention. Terms in the examples,
And the measuring method is as follows. % And ppm all indicate weight. Polyacetal oligomer content: Polymer 10g
Was placed in an autoclave, and a 15% aqueous methanol solution (p
H = 10, adjusted with ammonia water) 100 ml was added and extracted at 120 ° C. for 4 hours, then 100-80
At ℃, the polymer solids were removed by filtration, and the liquid was cooled to room temperature (1
It was left at 0 to 30 ° C. for 24 to 48 hours. The precipitated white solid is separated by a centrifuge, weighed and shown in ppm by weight.

Fluorine content derived from boron trifluoride-based polymerization catalyst: Trace amount of elemental fluorine contained in the polymerized polymer was analyzed, and is shown in ppm by weight. Insertion amount of comonomer in oligomer: JP-A-6-34
Based on JP-A No. 583 (Asahi Kasei Co., Ltd.), a proton nuclear magnetic resonance spectrum is measured to quantitatively analyze the comonomer content from the peak area of the signal. The amount of comonomer is shown by the molar ratio of ethylene oxide units to methylene oxide units.

Flowability: 1 mmt × 6 mmw with a molding machine set under the following conditions using a sample composed of the composition of Table 1.
Was molded and the fluidity was evaluated from its flow length (filled length). Cylinder temperature 200 ℃, injection pressure 980k
gf / cm ² , mold temperature 80 ° C. Thermal stability: The sample obtained has a cylinder temperature of 220 ° C.
When the test piece was molded by the 3 ounce molding machine set to, the limit residence time (minute) until the occurrence of silver streak on the surface of the test piece was measured.

(Examples 1 to 6 and Comparative Example 1) A 5-liter kneader having two stirring blades with a jacket capable of passing a heat medium was adjusted to a temperature range of 65 to 90 ° C., and 2
Kg trioxane, methylal as molecular weight regulator
1.14 ml, 75 g of 1,3-oxolane as comonomer
Was thrown in. Boron trifluoride diethyl ether was added to this in an amount of 8.0 × 10 ^{−6 to} 2.0 × 10 ⁻⁵ mol per 1 mol of the mixture to initiate polymerization. At the time of this polymerization, efforts were made to minimize the inclusion of atmospheric water and oxygen. Then, 20 minutes later, 2 liters of a 0.1% tributylamine aqueous solution was added to the kneader to stop the reaction.
Further, add 200 ml of methanol so that the volume becomes about 10%.
In addition, the contents were taken out after thorough washing at 100 ° C. for 30 to 120 minutes. The contents are washed with acetone and dried,
Samples with various amounts of oligomer and fluorine were prepared and used as the base polymer.

For each base polymer, triethylene glycol-bis- (3- (3-t-butyl-5-methyl-4-
Hydroxyphenyl) propionate 0.3 part by weight, poly-β-alanine copolymer 0.1 part by weight, calcium ion content 15 ppm calcium stearate 0.2
Part by weight and 0.5 part by weight of glycerin monostearate were mixed and granulated with a twin-screw extruder. The flow length and thermal stability of each sample were measured and are shown in Table 1.

(Example 7, Comparative Example 2) The oligomer used for oligomer measurement was added to the base polymer of Example 5 to prepare a base polymer, and the same additives as in Example 1 were blended and granulated. The same measurement as 1 was performed. The results are shown in Table 1. (Comparative Example 3) In Example 1, ethylene oxide was used as a comonomer, and boron trifluoride diethyl ether 8.0 was used.
The same additive as in Example 1 was added to the sample obtained by polymerization by adding 10 ⁻⁵ mol, and the mixture was granulated, and the same measurement as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 4 The same measurement as in Example 1 was carried out by adding the oligomer used for measuring the oligomer to the base polymer of Comparative Example 3 to prepare a base polymer. The results are shown in Table 1. (Examples 8 to 18, Comparative Examples 5 to 26) After adding the additive of Example 1 to the base polymers of Example 1, Comparative Example 1 and Comparative Example 4, various compounding agents shown in Table 2 were added to carry out the operation. Granulation was carried out in the same manner as in Example 1 and the same measurement was carried out. The results are shown in Tables 2 to 4.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

As described above, according to the present invention, the mechanical properties inherent to the polyacetal resin are lowered by containing the catalyst residue containing the oligomer and the fluorine in the polyacetal resin in a predetermined ratio. It is possible to provide a well-balanced polyacetal resin composition having improved melt fluidity and excellent thermal stability.

Claims (10)

[Claims] 1. An antioxidant and formaldehyde (A) based on 100 parts by weight of a polyacetal resin containing 50 to 5000 ppm of a polyacetal oligomer having a comonomer insertion amount of 2 to 10 mol% and a catalyst residue containing 3 to 11 ppm of fluorine. 0.1 to 10 parts by weight of a polymer or compound containing reactive nitrogen, a formic acid scavenger, a weathering (light) stabilizer, and a release (lubricant) agent, and a reinforcing material (B),
A polyacetal resin excellent in fluidity and thermal stability, characterized by containing 0 to 60 parts by weight of at least one kind of conductive material, thermoplastic resin and thermoplastic elastomer and 0 to 5 parts by weight of (C) pigment. Composition. 2. The antioxidant is one or more of hindered phenolic antioxidants, characterized in that
Polyacetal resin composition of. 3. A polymer or compound containing formaldehyde-reactive nitrogen is a polyamide resin, acrylamide or a derivative thereof or a polymer thereof with another vinyl monomer,
The polyacetal resin composition according to claim 1, which is one or more kinds of amide compounds. 4. A formic acid scavenger is an amino-substituted triazine, a polycondensation product of amino-substituted triazine and formaldehyde,
The polyacetal resin composition according to claim 1, which is one or more kinds of hydroxides, inorganic acid salts, carboxylates or alkoxides of alkali metals or alcal earth metals. 5. The polyacetal resin composition according to claim 1, wherein the weather resistance (light) stabilizer is one or more of a benzotriazole-based substance, an oxalic acid anilide-based substance and a hindered amine-based substance. 6. The release agent is one or more of alcohol fatty acids and fatty acid esters thereof, polyoxyalkylene glycols, olefin compounds having an average degree of polymerization of 10 to 500, and silicone.
The polyacetal resin composition according to claim 1. 7. The polyacetal resin composition according to claim 1, wherein the reinforcing agent is one or more of an inorganic filler, glass fiber, glass beads, and carbon fiber. 8. The polyacetal resin composition according to claim 1, wherein the conductive agent is at least one kind of conductive carbon black, metal powder or fiber. 9. The polyacetal resin composition according to claim 1, wherein the thermoplastic resin is at least one kind of olefin resin, acrylic resin, styrene resin, polycarbonate resin, and uncured epoxy resin. Stuff. 10. The polyacetal resin composition according to claim 1, wherein the thermoplastic elastomer is at least one of a polyurethane elastomer, a polyester elastomer, a polystyrene elastomer, and a polyamide elastomer.