JPH107880A - Polyacetal resin composition and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a resin composition having excellent mechanical properties and the like by alloying a polyacetal resin and another thermoplastic resin. SOLUTION: The resin composition contains a polyacetal resin (A), a thermoplastic resin (B) having a plurality of reactive groups for an epoxy group in a molecule, and an epoxy resin (C). However, at least one of the resins (B) and (C) has three or more reactive groups or epoxy groups. The resin (B) includes polyester, polyamide, polyurethane, or an elastomer thereof, and the resin (C) includes a novolak-type epoxy resin. Further, a catalyst such as a quaternary phosphonium salt or a quaternary amine salt may be added to the resin composition. The ratio of each component is as follows: 100 parts by weight of resin (A) and 1 part of resin (B).
To 100 parts by weight, 0.01 to 10 parts by weight of the resin (C), and 0.001 to 1 part by weight of the catalyst.

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 containing a thermoplastic resin, which is useful as a molding material having improved surface conditions, impact strength, weld properties, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Polyacetal has excellent mechanical properties,
It is widely used as an engineering plastic having electrical properties, chemical resistance, and heat resistance. But,
As the field of application expands, further improvements are required in the properties of materials including polyacetals.
For example, molded articles used as automobile parts are required to have high impact resistance over a wide temperature range. Conventionally, many attempts have been made to improve the impact characteristics of polyacetal. For example, JP-B-45-18023 discloses the addition of a so-called ionomer and JP-B-45-262.
No. 31 discloses addition of an ethylene-acrylic acid copolymer,
Japanese Patent Publication No. 50-33095 proposes the addition of an aliphatic polyether. Further, Japanese Patent Application Laid-Open No. Sho 59-1452
No. 43 and JP-A-61-19652 propose the addition of thermoplastic polyurethane to polyacetal.

[0003] These compositions show some improvement in physical properties such as impact resistance, but are not always sufficient.
In addition, the above-mentioned additive resin has an adverse effect not only on the moldability but also on the surface state of the molded article, and in a molded article molded using the polyacetal resin composition, a peeling phenomenon occurs on the surface,
Often the appearance is significantly impaired. These causes are:
This is due to poor affinity and compatibility between polyacetal and the added resin, and poor dispersibility of the added resin in the polyacetal. For this reason, it is speculated that the added resin does not disperse finely and not only can not significantly improve the impact resistance, but also has a small adhesive force at the interface between the polyacetal and the added resin, causing peeling on the surface of the molded product. You. JP-A-3-2124
No. 43 proposes adding a polyester polymer to polyacetal in order to improve coatability. However, even with this composition, the compatibility of the polyester with the polyacetal is inferior, resulting in a decrease in weld properties, which is a serious obstacle to practical use.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to effectively alloy a polyacetal resin and a specific thermoplastic resin, have high weld properties,
An object of the present invention is to provide a polyacetal resin composition having improved impact resistance and a method for producing the same. Another object of the present invention is to provide a polyacetal resin composition having high moldability and being useful for obtaining a molded article without surface peeling, and a method for producing the same. It is still another object of the present invention to provide a molded article of a polyacetal resin composition which can suppress surface peeling and has high weld properties and impact resistance, and a molding method thereof.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object. As a result, even when a small amount of a polyfunctional epoxy resin is added, a polyacetal resin and a specific thermoplastic resin are added. It has been found that a molded article having a high weld property without surface peeling can be obtained effectively, and the present invention has been completed. That is, the polyacetal resin composition of the present invention includes (A) a polyacetal resin, (B) a thermoplastic resin having a plurality of reactive groups for an epoxy group in a molecule, and (C) an epoxy resin. In this polyacetal resin composition, at least one of the thermoplastic resin (B) and the epoxy resin (C) has three or more reactive groups or epoxy groups. This polyacetal resin composition may further contain (D) an epoxy reaction accelerator. In the thermoplastic resin (B),
For example, a thermoplastic polyester resin, a polyamide resin, a thermoplastic polyurethane resin, and the like are included. In this resin composition, the melting temperature of the thermoplastic resin (B) is about 100 to 210 ° C.

In the method of the present invention, (A) a polyacetal resin, (B) a thermoplastic resin having a plurality of reactive groups,
(C) The said polyacetal resin composition is manufactured by mixing with an epoxy resin. If necessary, (D) an epoxy reaction accelerator may be added to the polyacetal resin composition. The method of the present invention includes a method of melting and kneading the polyacetal resin composition and molding, and a molded article formed from the resin composition. In addition,
In the present specification, "acid component", "dicarboxylic acid component",
“Carboxylic acid” and “dicarboxylic acid” include carboxylic acid equivalents, for example, acid anhydrides, derivatives capable of forming an ester bond (eg, lower alkyl esters such as dimethyl ester, etc.) unless otherwise specified. Used to include the meaning.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the components of the resin composition of the present invention will be described in detail. [(A) polyacetal resin] Polyacetal resins are polymer compounds containing oxymethylene group (-CH ₂ O-) as the main structural unit, the polyacetal resin,
Includes polyoxymethylene homopolymers and polyacetal copolymers. This copolymer has about 2 to 6 carbon atoms, preferably 2 carbon atoms, in addition to the oxymethylene group.
To 4 about oxyalkylene units (e.g., an oxyethylene group (-CH ₂ CH ₂ O-), oxypropylene group, oxytetramethylene group, etc.) containing a constituent unit. The ratio of the oxyalkylene group having about 2 to 6 carbon atoms is
It can be appropriately selected according to the use of the polyacetal and the like, and is, for example, about 0.1 to 30 mol%, preferably about 1 to 20 mol% based on the entire polyacetal.

The polyacetal copolymer may be composed of a plurality of components such as a copolymer composed of two components, a terpolymer composed of three components, or may be a block copolymer. Further, the polyacetal resin may have a branched structure as well as a linear structure, and may have a crosslinked structure. Furthermore, the terminal of the polyacetal resin may be stabilized, for example, by esterification with a carboxylic acid such as acetic acid, propionic acid, butyric acid, or the like. The degree of polymerization, degree of branching, and degree of crosslinking of the polyacetal resin are not particularly limited as long as they can be melt-molded. Preferred polyacetal resins include polyoxymethylene homopolymers and polyacetal copolymers (eg, copolymers composed of at least oxymethylene units and oxyethylene units). From the viewpoint of thermal stability, a polyacetal copolymer is preferred.

The molecular weight of the polyacetal resin is not particularly limited, and is, for example, about 5,000 to 500,000, preferably about 10,000 to 400,000. The polyacetal resin can be produced by a conventional method, for example, by polymerizing aldehydes such as formaldehyde, paraformaldehyde and acetaldehyde, and cyclic ethers such as trioxane, ethylene oxide, propylene oxide and 1,3-dioxolan. [(B) Thermoplastic resin] The thermoplastic resin (B) includes a resin having a plurality of reactive groups for an epoxy group in a molecule. Examples of such a reactive group include functional groups having an active hydrogen atom such as a carboxyl group, an acid anhydride group, an amino group, an amide group, an imide group, a hydroxyl group, and a mercapto group. Preferred reactive groups include carboxyl groups, acid anhydride groups, amino groups, hydroxyl groups and the like. Examples of the thermoplastic resin having a plurality of such reactive groups include a thermoplastic polyester resin, a polyamide resin, a thermoplastic polyurethane resin, an olefin resin, an acrylic resin, and a styrene resin. Preferred thermoplastic resins include thermoplastic polyester resins, polyamide resins, thermoplastic polyurethane resins, and the like.

[(B) Polyester Resin] The thermoplastic polyester resin is a polymer having an ester bond in the main chain, and has a carboxyl group or a hydroxyl group at the terminal of the polymer chain, or a carboxyl group from the main chain. In many cases, a functional group containing a group or a hydroxyl group is suspended. Examples of the polyester-based resin include polyalkylene terephthalate (for example, poly C _2-4 alkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate), and polyalkylene naphthalate (for example, poly C such as polyethylene naphthalate and polybutylene naphthalate). _2-4 alkylene naphthalate), an alkylene terephthalate and / or an alkylene naphthalate as a main repeating unit, and an acid component or a part of an alkylene glycol in which part of terephthalic acid and / or naphthalene dicarboxylic acid is substituted with another dicarboxylic acid. Copolyester containing a copolymer component such as a diol component substituted with another diol (hereinafter, these are collectively simply referred to as polyester copolymer), aromatic polyester (for example, bisphenol A) Which, aromatic diol, terephthalic acid, such as polyarylate produced by esterification of aromatic dicarboxylic acids such as isophthalic acid) and the like. The polyester-based resin also includes a polyester elastomer and a liquid crystalline polyester.
These polyester resins can be used alone or in combination of two or more.

[0011] The polyester resin may have not only a linear structure but also a branched chain structure, or may be crosslinked, as long as the melt moldability and the like are not impaired. Among these polyester resins, polyalkylene terephthalate, polyalkylene naphthalate, polyester copolymers containing alkylene terephthalate and / or alkylene naphthalate as a main repeating unit, and polyester elastomers are preferable. The molecular weight of the polyester-based resin is not particularly limited.
1,000,000, preferably 30,000-70
0000, more preferably 50,000 to 500,
It can be selected from the range of about 000. The intrinsic viscosity of the polyester resin is not particularly limited, but in order to obtain a good dispersion state, at a melt kneading temperature, a melt viscosity close to or overlapping with the melt viscosity of the polyacetal resin,
It is desirable to select the intrinsic viscosity of the polyester resin. The intrinsic viscosity of the polyester resin is, for example, 0.3
-1.2, preferably about 0.4-0.8. The intrinsic viscosity is a value measured at 40 ° C. using a phenol / tetrachloroethane mixed solvent as a solvent.

Polyester copolymer (B-1) The polyester copolymer (B-1) contains 99 to 50 mol% (preferably 95 to 55 mol%) of terephthalic acid and / or naphthalenedicarboxylic acid and terephthalic acid. And / or 1 to 50 mol% (preferably 5 to 45 mol%) of dicarboxylic acid components other than naphthalenedicarboxylic acid (for example, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid)
(Mol%) and a diol component. Examples of the dicarboxylic acid component other than terephthalic acid and / or naphthalenedicarboxylic acid include, for example, aliphatic dicarboxylic acids (for example,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Dicarboxylic acids having about 6 to 40 carbon atoms, preferably dicarboxylic acids having about 6 to 14 carbon atoms, such as sebacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and dimer acid, and alicyclic dicarboxylic acids (for example, 1,4- Dicarboxylic acids having about 8 to 12 carbon atoms, such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids (for example, isophthalic acid, phthalic acid, diphenyldicarboxylic acid, Dicarboxylic acids having about 8 to 14 carbon atoms, such as phenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, and diphenyl sulfone dicarboxylic acid). As the dicarboxylic acid component, tetrahydrophthalic acid, tetrahydroterephthalic acid, tetrahydroisophthalic acid, alicyclic dicarboxylic acids such as hymic acid,
Halogen-containing dicarboxylic acids such as tetrabromophthalic acid, tetrabromoterephthalic acid, tetrachlorophthalic acid, and hetanoic acid can be used, and p-
Hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid, p-hydroxybenzoic acid, hydroxyphenylacetic acid, glycolic acid, and hydroxycaproic acid, and lactones such as propiolactone, butyrolactone, caprolactone, and valerolactone may also be used. Dicarboxylic acid components other than terephthalic acid and / or naphthalenedicarboxylic acid may be used alone or in combination of two or more.

Further, if necessary, a polycarboxylic acid such as trimellitic acid or pyromellitic acid may be used in combination as long as the thermoplasticity can be maintained. Preferred dicarboxylic acid components other than terephthalic acid and / or naphthalenedicarboxylic acid include those having 6 carbon atoms such as adipic acid and sebacic acid.
About 14 (preferably about 6 to 12 carbon atoms) such as aliphatic dicarboxylic acid, isophthalic acid, phthalic acid, etc.
About to 12 aromatic dicarboxylic acids or derivatives thereof (such as acid anhydrides or lower alkyl esters) are included. More preferred dicarboxylic acid components include adipic acid, isophthalic acid and the like. As the diol component, alkylene diols having about 2 to 12 carbon atoms (for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol,
1,3-butanediol, hexamethylene glycol,
Aliphatic glycols having about 2 to 10 carbon atoms such as octanediol, decamethylene glycol and neopentyl glycol), polyoxyalkylene glycols [glycols having an alkylene group of about 2 to 4 carbon atoms and having a plurality of oxyalkylene units] For example, di (oxyethylene) glycol, di (oxypropylene) glycol, di (oxytetramethylene) glycol, tri (oxyethylene) glycol, tri (oxypropylene)
Glycol, tri (oxytetramethylene) glycol, etc.), diols composed of polyester oligomers having hydroxyl groups at both ends, alicyclic diols (for example, 1,1-cyclohexane dimethylol, 1,4-
Cyclohexane dimethylol, hydrogenated bisphenol A
), Aromatic diols [for example, 2,2-bis- (4
-Β-hydroxyethoxyphenyl) propane, 2,2
-Bis- (4-β-hydroxypropoxyphenyl) propane, 2,2-bis- (4-β-hydroxyethoxyphenyl) sulfone, xylene glycol and the like].

As the diol component, for example, tetrabromobisphenol A, tetrabromobisphenol A
Halogenated diols such as alkylene oxide (e.g., ethylene oxide and propylene oxide) adducts can also be used. Furthermore, as long as thermoplasticity can be maintained,
A polyol such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination. These diol components may be used alone or in combination of two or more. Preferred diol components include linear alkylene glycols having about 2 to 6 carbon atoms (such as ethylene glycol and 1,4-butanediol), and polyoxyalkylene glycols having oxyalkylene units having about 2 to 4 repeats [such as diethylene glycol. Glycol containing a poly (oxy-linear C _2-4 alkylene) unit], and 1,4-cyclohexane dimethylol. More preferred diol component is at least one diol selected from linear C _2-4 alkylene glycol (especially 1,4-butanediol or ethylene glycol),
Or part of the linear C _2-4 alkylene glycol is diethylene glycol and 1,4-cyclohexane diol substituted with at least one member selected from dimethylol, two or more linear C _2-4 When an alkylene glycol is used, the diol may be constituted by combining 1,4-butanediol and ethylene glycol.

Preferred polyester copolymer (B-1)
Has an acid component in which a part of terephthalic acid and / or naphthalenedicarboxylic acid is substituted with at least one other dicarboxylic acid selected from isophthalic acid and adipic acid, and a linear C _2-4 alkylene glycol. The selected diol (particularly, 1,4-butanediol or ethylene glycol) or a part of this diol is ethylene glycol (when 1,4-butanediol is used), diethylene glycol, 1,4-cyclohexane dimethylol And a diol component substituted with at least one diol component selected from the group consisting of:
Particularly preferred copolymers are an acid component composed of 90 to 60 mol% of terephthalic acid and / or naphthalenedicarboxylic acid and 10 to 40 mol% of isophthalic acid, ethylene glycol, 1,4-butanediol, A copolyester copolymerized with at least one diol component selected from 2,4-cyclohexane dimethylol.

Polyester Elastomer (B-2) The polyester elastomer (B-2) is useful for greatly improving the impact resistance and the like of a molded article. The polyester elastomer (B-2) includes a polyester block copolymer, for example, a hard segment composed of a polyester unit containing a low molecular weight diol, and a (poly) ester unit containing a polyether diol or an aliphatic polyester diol. And a soft copolymer. The ratio between the hard segment and the soft segment can be selected from a range of about 5/95 to 95/5 (% by weight), and is 25/75 to 75/25.
(% By weight) in many cases. Examples of the dicarboxylic acid component forming the polyester hard segment include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and bis- (4
-Carboxyphenyl) methane and the like, aromatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid, and alicyclic dicarboxylic acids such as adipic acid and sebacic acid. From the viewpoint of mechanical properties and heat resistance, at least 50 mol% or more (for example, 60 to 1) of the dicarboxylic acid component.
(00 mol%) is preferably an aromatic dicarboxylic acid. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid are particularly preferable.

The diol component forming the hard segment includes aliphatic diols having about 2 to 12 carbon atoms (eg, ethylene glycol, propylene glycol,
4-butanediol, 1,4-butenediol, neopentyl glycol, 1,5-pentanediol, 1,6
An aliphatic diol having about 2 to 6 carbon atoms such as -hexanediol), an alicyclic diol (e.g., 1,4-cyclohexanediol, 1,4-cyclohexanedimethylol, etc.), an aromatic diol [e.g., bis- ( Bisphenols such as p-hydroxy) diphenyl, bis- (p-hydroxydiphenyl) methane, bis- (p-hydroxydiphenyl) propane, and mixtures thereof can be used. Preferred diol components have 2 to 2 carbon atoms.
8 aliphatic diols, particularly those having about 2 to 4 carbon atoms.

The hard segment is made of poly C such as polyethylene terephthalate and polybutylene terephthalate.
Often composed of _2-4 alkylene-terephthalate units or corresponding poly _C2-4 alkylene-isophthalate units, polybutylene terephthalate units, and the like. As the dicarboxylic acid component constituting the soft segment of the polyester elastomer (B-2), the acid component constituting the hard segment is used, and as the diol component, polyether diol [particularly poly (oxyalkylene) glycol] or aliphatic Polyester diols are preferred. Examples of the poly (oxyalkylene) glycol include poly (oxyethylene) glycol, poly (oxytrimethylene) glycol, and poly (oxypropylene).
Glycol, poly (oxytetramethylene) glycol, polyethylene oxide-polypropylene oxide block copolymer glycol, polyethylene oxide-
Examples thereof include glycols of a poly (oxytetramethylene) block copolymer. These polyether diols can be used alone or in combination of two or more. Preferred polyether diols include poly (oxy-linear C _2-4 alkylene) glycols, especially poly (oxytetramethylene) glycol.
The number average molecular weight of the polyether diol is, for example, about 2
It can be selected from the range of about 00 to 6000.

Aliphatic polyester diols include diols having hydroxyl groups at both terminals formed by polycondensation of the aliphatic dicarboxylic acid and the aliphatic diol, for example, C _4-15 aliphatic dicarboxylic acid and C _2-6 Polyester diols formed by polycondensation with aliphatic diols are included. Preferred polyester diols include polyester diols formed by polycondensation of C _4-12 aliphatic dicarboxylic acids and C _2-4 aliphatic diols, particularly using polyethylene adipate or polybutylene adipate having hydroxyl groups at both ends. Often. The number average molecular weight of the polyester diol is, for example, about 200 to 60.
It can be selected from a range of about 00. The soft segment is
It is often composed of an ester of a poly (oxy-linear C _2-4 alkylene) glycol such as polyoxytetramethylene glycol and an aromatic dicarboxylic acid selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid.

The polyester elastomer (B-2) can be produced by a conventional method and can be obtained as a commercial product. Preferred polyester elastomers have polyethylene terephthalate, polybutylene terephthalate, polybutene terephthalate or polyethylene naphthalate units as hard segments and a molecular weight of 20.
It is a polyester elastomer having an ester of about 0 to 6000 polyoxyethylene glycol or polyoxytetramethylene glycol and terephthalic acid and / or isophthalic acid as a soft segment. [(B) Polyamide-based resin] A polyamide-based resin is a polymer having an amide bond in the main chain, and has an amino group or a carboxyl group at the terminal of the polymer chain, or has an amino or carboxyl group from the main chain. In many cases, the functional group is suspended. The polyamide resin is usually obtained by ring-opening polymerization of a lactam, polycondensation of an aminocarboxylic acid, or polycondensation of a diamine and a dicarboxylic acid. The polyamide-based resin includes an aliphatic polyamide, an aromatic polyamide and the like. The polyamide resin also includes a liquid crystalline polyamide, a liquid crystalline copolyesteramide, and a polyamide elastomer. These polyamide resins can be used alone or in combination of two or more.

The polyamide resin may have not only a linear structure but also a branched structure, or may be crosslinked, as long as the melt moldability is not impaired. Among these polyamide resins, an aliphatic polyamide or polyamide elastomer obtained by ring-opening polymerization of a lactam, polycondensation of an aminocarboxylic acid, or polycondensation of a diamine and a dicarboxylic acid is preferable. The molecular weight of the polyamide resin is not particularly limited, and is, for example, 10,000 to 1,000,000.
0, preferably 30,000 to 700,000, more preferably 50,000 to 500,000. Polyamides include, for example, polyamides obtained by ring-opening polymerization of lactams (eg, polyamide 6, polyamide 12, etc.), polyamides obtained by polycondensation of aminocarboxylic acids (eg, polyamide 11, etc.), and diamines and dicarboxylic acids. Polyamides obtained by polycondensation with an acid (for example, polyamide 46, polyamide 66, polyamide 610, polyamide 612, etc.) and copolymerized polyamides containing monomer units of these polyamides are included.

Preferred aliphatic polyamides include, for example,
Examples thereof include polyamide 6, polyamide 66, polyamide 11, and polyamide 12. Particularly preferred aliphatic polyamides include polyamide 6 and polyamide 12. Polyamide Elastomers (B-3, B-4) Polyamide elastomers (B-3, B-4) are useful for greatly improving the impact resistance of molded articles. The polyamide elastomer includes, for example, a block copolymer containing a hard segment composed of the polyamide unit and a soft segment composed of a polyoxyalkylene unit. This copolymer can be produced, for example, by polycondensation of a polyamide oligomer having a carboxyl group or an amino group at a terminal (hard segment) and a polyether diamine or polyether dicarboxylic acid (soft segment). The hard segments are, for example, polyamide 6, polyamide 11, polyamide 12,
Polyamide 46, polyamide 66, polyamide 610,
Often composed of at least one segment selected from polyamide 612. As the polyoxyalkylene segment, a segment corresponding to the polyoxyalkylene glycol exemplified in the section of the polyester elastomer can be used.

The ratio between the hard segment and the soft segment can be selected from a range of about 5/95 to 95/5 (% by weight), and is often 25/72 to 75/25 (% by weight). [(B) Polyurethane-based resin] A thermoplastic polyurethane-based resin is a polymer having a urethane bond in the main chain, and usually has a reactive functional group such as a hydroxyl group at the terminal of the polymer chain, or has a main chain. In many cases, a functional group containing a hydroxyl group or the like is suspended. Polyurethane resins include, for example, polyisocyanate components (for example, polyisocyanate components such as aliphatic, alicyclic, and aromatic polyisocyanates) and polyol components (for example, aliphatic, alicyclic, and aromatic polyols). And a thermoplastic polyurethane produced by a reaction with a molecular weight polyol component or a polyether diol, a polyester diol, a polycarbonate diol, or the like. In preparing the polyurethane, a chain extender (for example, a diol or a diamine) may be used. Further, the polyurethane-based resin also includes a polyurethane elastomer. These polyurethane resins can be used alone or in combination of two or more.

The polyurethane resin may have not only a straight chain but also a branched structure as long as the thermoplasticity can be maintained, and may be crosslinked. Among these polyurethane resins, polyurethanes and polyurethane elastomers formed by a reaction between a diisocyanate component and a diol component are preferred. The molecular weight of the polyurethane is not particularly limited.
1,000,000, preferably 30,000-700,0
00, more preferably 50,000 to 500,000.
You can choose from a range of degrees. Examples of the polyurethane (B-5) diisocyanate component include aliphatic diisocyanates (eg, 1,6-hexamethylene diisocyanate), alicyclic diisocyanates (eg, isophorone diisocyanate), and aromatic diisocyanates (eg, 2,4 -Toluene diisocyanate, 2,6
-Toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, etc.).

The diol component includes, for example, C _2-10 alkylene diol, polyoxyalkylene glycol [for example, poly (oxyethylene) glycol, poly (oxypropylene) glycol, poly (oxytetramethylene) glycol, or a combination thereof. Polymer glycols (for example, polyethylene oxide-polypropylene oxide block copolymers, etc.), and polyester diols (for example, C such as polyethylene adipate or polybutylene adipate having a hydroxyl group at a terminal).
_And polyester diols formed by polycondensation of _4-12 aliphatic dicarboxylic acids and C _2-6 aliphatic diols. Polyurethane Elastomer A polyurethane elastomer is useful for greatly improving the impact resistance and the like of a molded article. The polyurethane elastomer includes, for example, a polyurethane elastomer produced by reacting the diisocyanate component with a diol component such as a polyoxyalkylene glycol or a polyester diol containing a polyoxyalkylene glycol unit.

The thermoplastic resin includes a resin whose melting point clearly appears (for example, a crystalline polymer) and a resin whose melting point does not clearly appear (for example, an amorphous polymer). Therefore, in the present specification, the “melting temperature” means the “melting point” or “melt flow temperature” of the thermoplastic resin. In addition,
"Melting point" refers to the value obtained by using a differential scanning calorimeter (DSC).
It means the melting peak temperature when measured according to the measuring method specified in ISK7121. The “melt flow temperature” refers to the flow start when a pellet is filled in a flow tester (manufactured by Shimadzu Corporation) equipped with a nozzle (inner diameter 1 mm), and the temperature is increased by applying a load of 500 kg. Means temperature. The thermoplastic resin (B) is used to improve the kneadability, moldability and characteristics of a molded product of the resin composition.
A suitable melting temperature, for example, 100 to 210 ° C. (for example,
130-210 ° C), preferably 150-200 ° C, more preferably 190 ° C or less (for example, 150-190 ° C).
It is desirable to have a melting temperature of about (° C.).

The amount of the thermoplastic resin (B) to be used can be selected according to the characteristics of the desired molded article, and is, for example, 1 to 10 parts by weight based on 100 parts by weight of the polyacetal resin (A).
0 parts by weight (for example, 1 to 80 parts by weight), preferably 5 to
70 parts by weight, more preferably about 10 to 50 parts by weight, and often about 5 to 60 parts by weight. If the amount of the component (B) is less than 1 part by weight, the impact resistance is not so much improved. If it exceeds 100 parts by weight, the high-temperature rigidity and the load deflection temperature, which are the characteristics of the polyacetal resin, are likely to decrease. [(C) Epoxy resin] (A) Polyacetal resin
And (B) when adding the epoxy resin to the thermoplastic resin having a plurality of reactive groups, at least one of the thermoplastic resin (B) and the epoxy resin (C) has three or more reactive groups. Alternatively, if a resin having an epoxy group is used, the polyacetal resin (A) and the thermoplastic resin (B) can be effectively alloyed, probably because the thermoplastic resin (B) and the epoxy resin (C) are crosslinked. A polyacetal resin composition having weld properties and having significantly improved impact resistance can be obtained.

Examples of epoxy resins include glycidyl ether type (bisphenol type, novolak type, polyoxyalkylene glycol diglycidyl ether, etc.), glycidyl ester type, glycidylamine type, cycloaliphatic type, linear aliphatic type, Epoxy resins such as heterocyclic resins are included. As the epoxy resin, a resin having two or more epoxy groups in a molecule can be used. Examples of the bifunctional epoxy resin having two epoxy groups in a molecule include bisphenol type epoxy resin, ethylene glycol diglycidyl ether,
Glycidyl ether type such as polyoxyalkylene glycol diglycidyl ether such as propylene glycol diglycidyl ether; glycidyl ester type such as diglycidyl phthalate and diglycidyl tetrahydrophthalate; glycidyl amine type such as diglycidyl aniline; 1-epoxyethyl-3; Examples of the epoxy resin include cycloaliphatic resins such as 4-epoxycyclohexane, alicyclic diepoxy acetal, and alicyclic diepoxy adipate. Examples of the polyfunctional epoxy resin having three or more epoxy groups in the molecule include glycidyl ether type such as phenol novolak type and cresol novolak type epoxy resin, triglycidyl-p-aminophenol, and tetraglycidyl diaminodiphenylmethane. And epoxy resins such as glycidylamine type such as tetraglycidyl meta-xylylenediamine, heterocyclic type epoxy resins such as triglycidyl isocyanate or hydantoin type epoxy resin, and tetrakis (glycidyloxyphenyl) ethane. These epoxy resins can be used alone or in combination of two or more.

Among these epoxy resins, a bifunctional epoxy resin is a bisphenol type epoxy resin,
A novolak-type epoxy resin is preferable as the trifunctional or higher functional polyfunctional epoxy resin. Examples of the bisphenol-type epoxy resin include bisphenol F-type epoxy resin, bisphenol AD-type epoxy resin, and the like, in addition to bisphenol A-type epoxy resin. The bisphenol-type epoxy resin is not limited in molecular weight and molecular weight distribution as long as the melt moldability is not impaired, and may further have a substituent such as a halogen atom (for example, fluorine, chlorine, bromine and the like). Examples of the resin having such a substituent include a tetrabromobisphenol A type epoxy resin.

Preferred bisphenol type epoxy resins include bisphenol A type, F type and AD type epoxy resins. These bisphenol type epoxy resins are
They can be used alone or in combination of two or more. The novolak type epoxy resin includes, for example, a phenol novolak type and a cresol novolak type epoxy resin.
The novolak type epoxy resin is not limited in molecular weight and molecular weight distribution as long as the melt moldability is not impaired, and may have a branched chain structure or a crosslinked structure including resol type.
These novolak epoxy resins can be used alone or in combination of two or more. The thermoplastic resin (B) and the epoxy resin (C) are combined so as to form a crosslinked system according to the number of reactive groups of the thermoplastic resin (B) and the number of epoxy groups of the epoxy resin (C). Can be The combination of the thermoplastic resin (B) and the epoxy resin (C) includes a bifunctional thermoplastic resin (B) having two reactive groups and a polyfunctional epoxy resin (B) having three or more epoxy groups. C), a combination of a polyfunctional thermoplastic resin (B) having three or more reactive groups and a bifunctional epoxy resin (C) having two epoxy groups, having three or more reactive groups. Examples include a combination of a polyfunctional thermoplastic resin (B) and a polyfunctional epoxy resin (C) having three or more epoxy groups. In order to effectively exhibit the properties of the polyacetal resin and the thermoplastic resin by alloying, at least two reactive groups are required.
It is advantageous to combine a polyfunctional thermoplastic resin (B) (e.g., a thermoplastic resin having a reactive group at both ends) with a polyfunctional epoxy resin (C) having three or more epoxy groups. is there.

The epoxy resin (C) is used in a small amount,
The polyacetal resin (A) and the thermoplastic resin (B) can be effectively alloyed, and a polyacetal resin composition having high weld properties and impact resistance can be obtained. Therefore, the amount of the epoxy resin to be used can be selected from a wide range as long as the properties of the molded article are not impaired. For example, 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight, per 100 parts by weight of the polyacetal resin (A). ~ 5 parts by weight, more preferably 0.0
It is about 5 to 2.5 parts by weight, and often about 0.05 to 1 part by weight. [(D) Epoxy reaction accelerator] When a (D) catalyst (epoxy reaction accelerator) is added to a system in which a polyacetal resin (A), a thermoplastic resin (B), and an epoxy resin (C) coexist, an epoxy resin By activating the resin (C), the affinity and compatibility of the resins (A) and (B) can be improved, the surface peeling during the molding process can be further suppressed, and a molding material excellent in impact strength, weld characteristics, and the like can be obtained. Obtainable.

As the epoxy reaction accelerator, a conventional reaction accelerator such as an amine-based curing agent, an organic acid-based curing agent, a basic active hydrogen compound (eg, dicyanamide, organic acid dihydrazide, etc.) can be used. However, if a phosphonium salt (especially a quaternary phosphonium salt) or an amine salt (especially a quaternary amine salt) is used, an epoxy resin can be activated, and a polyacetal resin having excellent mechanical properties such as impact resistance and weld strength is remarkably excellent. A composition can be obtained. These epoxy reaction accelerators can be used alone or in combination of two or more. The phosphonium salt or the amine salt is, for example, a mono-substituted salt represented by the formula [RXH ₃ ] ⁺ Y ⁻ (such as a monoalkylphosphonium salt), a formula [R ₂
XH _2] ⁺ Y ^- (dialkyl phosphonium salt) di substituted salts represented by the formula [R ₃ XH] ⁺ Y ^- a tri-substituted salts represented (such as trialkyl phosphonium salt) Although it is good, it is preferably a quaternary salt represented by the formula [R ₄ X] ⁺ Y ⁻ . In the above formula, R represents the same or different alkyl group, aryl group, cycloalkyl group, aralkyl group, X represents a phosphorus atom or a nitrogen atom,
Y represents a halogen atom or an acid group.

In the phosphonium salt or the amine salt, R
Examples of the alkyl group represented by are linear or branched C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and octyl groups. Preferred alkyl groups include linear or branched C _1-6 alkyl groups. The aryl group includes a phenyl, a C _6-12 aryl group such as a naphthyl group, and the cycloalkyl group includes a C _4-10 cycloalkyl group such as a cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl group. Examples of the aralkyl group include C _7-14 aralkyl groups such as benzyl, phenethyl and benzhydryl groups.

In the phosphonium salt or the amine salt substituted by a plurality of substituents R, the type of the substituent R may be different depending on the number of the substituents. In the phosphonium salt or the amine salt, the halogen atom represented by X includes
The acid groups include chlorine, bromine and iodine atoms, and the acid groups include organic acids such as formic acid and acetic acid and anionic residues of oxycarboxylic acids. X is often a chlorine anion, a bromine anion or an iodine anion. Quaternary phosphonium salts Preferred quaternary phosphonium salts include compounds in which R is a C _1-6 alkyl group, phenyl group, or benzyl group, and the number and combination of these substituents R are not particularly limited. Quaternary phosphonium salts include, for example, tetra-C
_1-6 alkylphosphonium halide (eg, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, etc.), tetra-C _6-10 arylphosphonium halide (eg, tetraphenylphosphonium bromide, etc.), C _1-6 alkyl- Tri-C _6-10 arylphosphonium halides (eg, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, etc.), di-C _1-6 alkyl-di-C _6-10 arylphosphonium halides ( For example, dimethyl diphenyl phosphonium bromide, diethyl diphenyl phosphonium bromide, etc. dibutyl diphenyl bromide), tri -C _1-6 alkyl - Mo -C _6-10 aryl phosphonium halide (e.g., trimethylphenyl phosphonium bromide, triethyl phenyl phosphonium bromide, tri-butylphenyl bromide), tri -C _1-6 alkyl - mono -C _{7 - 14} aralkyl phosphonium halide (e.g., trimethyl benzyl Phosphonium bromide, triethylbenzylphosphonium bromide, tripropylbenzylphosphonium bromide, tributylbenzylphosphonium bromide, etc., C _7-14 aralkyl-tri-C _6-10 aryl phosphonium halide (for example, benzyltriphenylphosphonium chloride, phenethyltriphenylphosphonium chloride) Etc.) are included. These quaternary phosphonium salts can be used alone or in combination of two or more.

Examples of the quaternary phosphonium salt include tetra-C, such as tetrabutylphosphonium bromide.
C _1-6 alkyl-tri-C _6-10 aryl phosphonium such as _1-6 alkyl phosphonium halide, tetra-C _6-10 aryl phosphonium halide such as tetraphenyl phosphonium bromide, methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide In many cases, a C _7-14 aralkyl-tri-C _6-10 aryl phosphonium halide such as a halide and benzyltriphenylphosphonium chloride is used. Quaternary amine salts Preferred quaternary amine salts include compounds in which R is a C _1-6 alkyl group, phenyl group, or benzyl group, and the number and combination of substituents R are not particularly limited.
Examples of the quaternary amine salt include tetra-C _1-6 alkylammonium halides (eg, tetramethylammonium chloride, tetraethylammonium chloride,
Tetrabutylammonium bromide), tetra-
C _6-10 arylammonium halide (eg, tetraphenylammonium chloride), C _1-6 alkyl-tri-C _6-10 arylammonium halide (eg, methyltriphenylammonium chloride, ethyltriphenylammonium chloride, butyltriphenyl) Ammonium chloride), di-C _1-6 alkyl-di-C _6-10 aryl ammonium halide (eg, dimethyldiphenylammonium chloride, diethyldiphenylammonium chloride, etc.), tri-
C _1-6 alkyl-mono-C _6-10 arylammonium halides (eg, trimethylphenylammonium chloride, triethylphenylammonium chloride, etc.), tri-C _1-6 alkyl-mono-C _7-14 aralkylammonium halides (eg, Trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tripropylbenzylammonium chloride, etc., C _7-14 aralkyl-tri-C _6-10 aryl ammonium halide (eg, benzyltriphenylammonium chloride, phenethyltriphenylammonium chloride, etc.), etc. Is included. Amine salts include N-alkylpyridinium halides (eg, N-alkylpyridinium halides).
-Methylpyridium chloride).
These quaternary amine salts can be used alone or in combination of two or more.

Examples of the quaternary amine salts include, for example, tetra-C _1-6 alkylammonium halides such as tetrabutylammonium chloride and tri-C _1-6 alkyl-mono-monomers such as triethylbenzylammonium chloride.
In many cases, C _7-10 aralkyl ammonium halide is used. Quaternary phosphonium salt and quaternary amine salt (D)
With a very small addition amount, the epoxy resin (C) can be activated to improve the affinity and compatibility between the polyacetal resin (A) and the thermoplastic resin (B), and the weld properties and impact resistance of the polyacetal resin composition can be improved. Performance can be improved. Therefore, the addition amount of the quaternary phosphonium salt and the quaternary amine salt (D) is
You can choose from a wide range as long as the characteristics of the molded product are not impaired,
For example, based on 100 parts by weight of the polyacetal resin (A), 0.001 to 1 part by weight, preferably 0.005 to 1 part by weight.
0.5 parts by weight, more preferably about 0.01 to 0.3 parts by weight, about 0.01 to 0.2 parts by weight (for example,
0.01 to 0.1 parts by weight) in many cases.

The composition of the present invention may contain various additives, for example, stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, weather (light) stabilizers, lubricants, release agents, etc. Molding agents, flame retardants, antistatic agents, lubricants, organic polymer improvers, coloring agents, fillers, etc. may be included.The fillers are composed of inorganic compounds, organic compounds, metals, ceramics, etc. Fibrous, powdery or plate-like fillers. These additives can be used alone or in combination of two or more. When the polyacetal resin composition of the present invention is melt-kneaded and molded, the thermoplastic resin (B) constituting the domain in the matrix is cross-linked, and is not stretched into a fine needle shape against a high shear force at the time of molding. Perhaps because the particulate form can be maintained, the molded article has high weld characteristics and impact resistance, and can effectively prevent surface peeling and occurrence of flow marks of the molded article. In particular, even when an elastomer (for example, polyester elastomer, polyamide elastomer, polyurethane elastomer, or the like) is used as the thermoplastic resin (B), the thermoplastic resin (B) constituting the domain has a high dispersibility in the matrix polyacetal resin (A). In addition, since the particles can be maintained in the form of particles even when subjected to high shearing force during molding, weld characteristics can be greatly improved, and surface peeling and flow marks of molded articles can be more effectively prevented. Therefore, the polyacetal resin composition is useful as a molding material.

The acetal resin composition of the present invention can be molded by a conventional method such as melt-kneading, extrusion molding, injection molding and the like. A preferred molding method includes an injection molding method. In the injection molding, the number of gates is not particularly limited, and molding may be performed by performing injection from a plurality of gates (for example, two gates). In particular, with the resin composition of the present invention, a molded product having high weld characteristics can be obtained by injection molding using a plurality of gates. In the molded article obtained in this manner, the aspect ratio of the dispersed phase (thermoplastic resin phase) in the surface layer portion of the molded article is 1 to 3, preferably about 1 to 2, so that surface layer peeling and generation of flow marks may occur. It is possible to obtain a molded article with high precision. Although the resin composition or molded article of the present invention exhibits excellent physical properties without any treatment, it is stable while improving the properties of the composition or molded article when heat-treated after adjusting the composition or molding the molded article. In some cases. The heat treatment temperature can be selected according to the components of the resin composition and the ratio thereof.
A temperature not lower than 0 ° C. and not exceeding the heat deformation temperature of the resin composition, for example, about 80 to 130 ° C., preferably 80 to 130 ° C.
It is about 20 ° C.

[0039]

According to the resin composition of the present invention, a polyacetal resin, a thermoplastic resin having a plurality of reactive groups, and an epoxy resin are combined, so that the polyacetal resin and the thermoplastic resin can be effectively alloyed. Thus, the characteristics of the polyacetal resin and the thermoplastic resin can be effectively exhibited, and the weld characteristics and impact resistance can be greatly improved. Furthermore, the resin composition has high moldability and can greatly reduce surface peeling of a molded product. In the method of the present invention, a polyacetal resin composition having the above-mentioned excellent properties can be obtained by a simple operation of mixing the above components. According to the molding method of the present invention, it is possible to obtain a molded article having no surface peeling, high weld characteristics and excellent impact resistance only by melting and kneading the components.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to these examples. The peel test and the mechanical properties of the molded product were evaluated as follows. [Surface Peeling Test] Cellophane tape ^R was attached to the surface of the test piece, and after rapidly peeling off, the state of peeling on the surface of the molded product was visually observed and evaluated according to the following four grades. ◎: No peeling at all ○: Very slight peeling Δ: Slight peeling ×: Peel off more than half of the area where the tape is adhered [Weld property] Weld test with gates at both ends and thickness of 2 mm Using the pieces, the weld tensile strength and the weld tensile elongation were measured according to ASTM D-638.

[Izod impact strength] ATSM D-2
The Izod impact strength of the notched test piece was measured according to 56. In Examples and Comparative Examples,
The following polyester resin, polyamide resin, polyurethane resin, epoxy resin and phosphonium salt were used. [(B) Thermoplastic resin] B-1: Modified polybutylene terephthalate obtained using an acid component containing 30 mol% of isophthalic acid (melt flow temperature 160 ° C, intrinsic viscosity IV = 0.5) B-2: Polyester elastomer (Lightflex 635, manufactured by Hoechst Celanese) (melt flow temperature 1
B-3: Polyamide 12 elastomer (manufactured by Daicel Huls, E62S1) (melting point 170 ° C.) B-4: Polyamide 12 elastomer (manufactured by Daicel Huls, E40S3) (melting point 150 ° C.) B-5: Heat Plastic polyurethane (Milactran E375MSJP-1 manufactured by Nippon Milactran Co., Ltd.) (melt flow temperature: 110 ° C.) [(C) epoxy resin] C-1: polyfunctional epoxy resin (Epicoat 180S65 manufactured by Yuka Shell Epoxy Co.) C-2 : Bisphenol A type epoxy resin (Epicoat 1004K, manufactured by Yuka Shell Epoxy) C-3: phenoxy resin (YP-50, manufactured by Toto Kasei Co., Ltd.) [(D) epoxy reaction accelerator] D: quaternary phosphonium salt (tetra Butylphosphonium bromide) Examples 1-8 and Comparative Examples 1-7 Polyacetator (Polyplastics Co., Ltd., Jerakon M90) and, the modified polybutylene terephthalate (B-1) or polyester elastomer (B-2)
And polyfunctional epoxy resin (C-1), bisphenol A
Epoxy resin (C-2) or phenoxy resin (C-
After dry-blending 3) and tetrabutylphosphonium bromide (D) at the ratios shown in Tables 1 and 2, the mixture was melt-kneaded at 190 ° C with a twin-screw extruder and pelletized.
The pellets were molded by an injection molding machine to prepare a weld test piece and an impact test piece having gates at both ends. AS
The weld strength and weld elongation of the obtained test piece were measured according to TM D638, and the ASTM
Izod impact strength was measured according to D256. In addition, a peel test was also performed. Tables 1 and 2 show the results.

[0042]

[Table 1]

[0043]

[Table 2]

Tables 1 and 2 show that the resin compositions of the examples have higher weld strength, weld elongation, and Izod impact strength than the resin compositions of the comparative examples. In the peel test, the resin composition of the comparative example was peeled, but the resin composition of the example was not peeled at all. Examples 9 to 14 and Comparative Examples 8 to 12 Polyacetal (manufactured by Polyplastics, Gelacon M90) and the polyamide 12 elastomer (B-
3) or (B-4) and a polyfunctional epoxy resin (C-1)
Alternatively, except that phenoxy resin (C-3) and tetrabutylphosphonium bromide (D) were used in the proportions shown in Tables 3 and 4, the weld strength, weld elongation, and Izod of the test piece prepared in the same manner as in the above example When the impact strength was measured and a peel test was performed, the results shown in Tables 3 and 4 were obtained.

[0045]

[Table 3]

[0046]

[Table 4]

As can be seen from Tables 3 and 4, the resin compositions of Examples have higher weld strength, weld elongation and Izod impact strength than the resin compositions of Comparative Examples. In the peel test, the resin composition of the comparative example was peeled, but the resin composition of the example was not peeled at all. Examples 15 to 17 and Comparative Examples 13 to 15 Polyacetal (manufactured by Polyplastics Co., Ltd., Geracon M90), the polyurethane (B-5), and a polyfunctional epoxy resin (C-1) or a phenoxy resin (C-3) )
And tetrabutylphosphonium bromide (D)
Except for using at the ratio shown in the above, the preparation was carried out in the same manner as in the above example. And, while measuring the weld strength, weld elongation and Izod impact strength of the obtained test piece,
When a peeling test was performed, the results shown in Table 5 were obtained.

[0048]

[Table 5]

From Table 5, it can be seen that, compared to the resin composition of the comparative example,
The resin compositions of the examples have large weld strength, weld elongation and Izod impact strength. In the peel test, the resin composition of the comparative example was peeled, but the resin composition of the example was not peeled at all.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 63/00 NJM C08L 63/00 NJM 67/02 LPC 67/02 LPC LPK LPK 75/08 NGJ 75/08 NGJ 77/00 LQT 77/00 LQT 101/02 LTA 101/02 LTA

Claims (17)

[Claims] 1. A polyacetal resin composition comprising (A) a polyacetal resin, (B) a thermoplastic resin having a plurality of reactive groups for an epoxy group in a molecule, and (C) an epoxy resin. A polyacetal resin composition wherein at least one of the thermoplastic resin (B) and the epoxy resin (C) has three or more reactive groups or epoxy groups. 2. The polyacetal resin composition according to claim 1, wherein the thermoplastic resin (B) has at least one reactive group selected from a carboxyl group, an acid anhydride group, an amino group, and a hydroxyl group. 3. The thermoplastic resin (B) is at least one selected from a thermoplastic polyester resin, a polyamide resin, and a thermoplastic polyurethane resin.
The polyacetal resin composition according to the above. 4. The thermoplastic polyester resin is at least one selected from the group consisting of polyalkylene terephthalate, polyalkylene naphthalate, polyalkylene terephthalate copolymer, polyalkylene naphthalate copolymer, and polyester elastomer. 3. The polyacetal resin composition according to 3. 5. A polyalkylene terephthalate copolymer comprising 90 to 60 mol% of terephthalic acid and 10 to 4
A dicarboxylic acid component composed of 0 mol% of isophthalic acid, ethylene glycol, 1,4-butanediol,
The polyacetal resin composition according to claim 4, which is a copolymer obtained by polycondensation with at least one diol component selected from 1,4-cyclohexane dimethylol. 6. The polyacetal resin composition according to claim 3, wherein the polyamide resin is at least one selected from polyamide 6, polyamide 66, polyamide 11, polyamide 12, and polyamide elastomer. 7. The polyacetal resin composition according to claim 3, wherein the thermoplastic polyurethane resin is a polyurethane or a polyurethane elastomer obtained by reacting a polyisocyanate with a polyoxyalkylene polyol or a polyester polyol. 8. The temperature of the thermoplastic resin (B) is 100 to 210 ° C.
The polyacetal resin composition according to claim 1, which has a melting temperature of: 9. The polyacetal resin composition according to claim 1, wherein the epoxy resin (C) is a polyfunctional epoxy resin having three or more epoxy groups in a molecule. 10. The polyacetal resin composition according to claim 1, wherein the epoxy resin (C) is a novolak type epoxy resin. 11. The method according to claim 1, wherein 1 to 100 parts by weight of the thermoplastic resin (B) and 0.01 to 10 parts by weight of the epoxy resin (C) are contained based on 100 parts by weight of the polyacetal resin (A). Polyacetal resin composition. 12. The polyacetal resin composition according to claim 1, further comprising (D) an epoxy reaction accelerator. 13. An epoxy reaction accelerator (D) having the formula [R ₄
X] ⁺ Y ⁻ (R represents the same or different and represents an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, X represents a phosphorus atom or a nitrogen atom, and Y represents a halogen atom or an acid group) The polyacetal resin composition according to claim 12, which is a quaternary phosphonium salt or a quaternary amine salt. 14. The content of (D) the epoxy reaction accelerator is based on 100 parts by weight of the polyacetal resin (A).
The polyacetal resin composition according to claim 12, which is 0.001 to 1 part by weight. 15. A method of mixing a polyacetal resin (A), a thermoplastic resin (B) having a plurality of reactive groups for an epoxy group in a molecule, and an epoxy resin (C), A method for producing a polyacetal resin composition using a resin having three or more reactive groups or epoxy groups as at least one of the resin (B) and the epoxy resin (C). 16. A molded article formed from the polyacetal resin composition according to claim 1. 17. A molding method for melting and kneading the polyacetal resin composition according to claim 1.