JPH09124890A - Modified resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified resin composition excellent in mechanical characteristics, etc., by compounding a polyacetal with other thermoplastic resins to form a polymer alloy. SOLUTION: This resin composition comprises (I) a modified polyacetal resin composition comprising (1a) a modified polyacetal and (1b) a non-modified polyacetal in a ratio of 100/0 to 1/99(wt.%) and (II) a modified polymer composition comprising (2a) a modified polymer excluding the modified polyacetal and (2b) a non-modified polymer excluding the polyacetal in a ratio of 100/0 to 1/99(wt.%). Functional groups such as epoxy groups, carboxyl groups or acid anhydride groups are introduced to the modified polyacetal (1a) and the modified polymer (2a). The non-modified polymer (2b) includes an olefinic polymer and a styrenic polymer. The compounding ratio of the modified polyacetal resin composition (I) to the modified polymer composition (II) is selected from the range of approximately 1/99 to 99/1 (weight ratio).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified resin composition useful for obtaining a polymer alloy and the like and a method for producing the same.

[0002]

2. Description of the Related Art Polyacetal has excellent mechanical strength,
Since it has slidability, heat resistance, chemical resistance, moldability, and electrical characteristics, it is used in a wide range of fields as an engineering plastic. However, polyacetal is not always satisfactory in terms of acid resistance, adhesiveness, paintability, printability, dyeability, weather resistance and the like. Therefore, by alloying polyacetal and other thermoplastic resin, while compensating for the drawbacks of polyacetal, imparts excellent properties of polyacetal to the alloying partner resin, a composition that effectively expresses the advantages of both resins. Be expected. But,
Polyacetal has extremely low affinity or compatibility with other materials. Therefore, even if blended with other thermoplastic resin, not only the characteristics of both resins are not effectively expressed,
Weld strength and weld elongation are significantly reduced. In particular, remarkably low weld strength and weld elongation are major obstacles to industrially producing alloys of polyacetal and other thermoplastic resins.

In order to improve the affinity of polyacetal, it is effective to introduce a suitable modifying group into the polyacetal to modify it. Conventionally, a method of modifying the polyacetal by introducing various modifying groups has been proposed. (For example, Japanese Patent Publication No. 43-23467, Japanese Patent Publication No. 47-19425.
Japanese Patent Application Laid-Open No. 3-21618, Japanese Patent Application Laid-Open No. 3-21
619 publication). However, all of these methods, formaldehyde and trioxane, during the polymerization process,
Method of directly introducing a modifying group by copolymerization using comonomers having various modifying groups as substituents (for example, cyclic ether or cyclic acetal having aminoaldehyde, nitro group, nitrile group, carboxyl group or amide group) Is. Therefore, in either method, the polymerization reactivity decreases, and it is difficult to obtain a high molecular weight copolymer in a high yield.

Further, in order to improve the reinforcing effect of the reinforcing agent, a reactive compound having various modifying groups is added to a polyacetal resin which has been polymerized in advance, and melt-kneading is performed in the presence of a filler and a radical initiator. A method for obtaining a reinforcing agent-containing resin composition has also been proposed (for example,
Japanese Patent Publication No. 58-18383, Japanese Patent Publication No. 60-6969
Issue publication). However, in these methods, the efficiency of introducing the modifying group is extremely low, and the polyacetal is decomposed and deteriorated during the treatment. Furthermore, since the compositions obtained by these methods contain a specific reinforcing agent in advance, they cannot be applied to a wide range of polymer alloys composed of two or more kinds of resins that are incompatible with each other, and thus they cannot be used for each application. It is necessary to prepare the resin composition. Particularly, it is difficult to uniformly melt-mix two or more kinds of thermoplastic resins which are incompatible with each other, and therefore it is difficult to uniformly modify and polymer-alloy them by the above method.

Further, when the razircal initiator and the polyacetal are melt-kneaded, the polyacetal resin is oxidatively decomposed by the radical polymerization initiator to lower the molecular weight (JP-A-60-219252 and JP-A-49-74790). , British Patent No. 1172741). Therefore, when a radical polymerization initiator such as an organic peroxide is used, it is difficult to modify the polyacetal while maintaining high molecular weight, mechanical properties and electrical properties. In addition, the mechanical properties of the resin composition cannot be sufficiently improved even if the polyacetal is made into a composite by alloying with a decrease in the molecular weight. Probably because of this, Japanese Patent Laid-Open No. 21421/1993
Japanese Patent Laid-Open No. 2 (1994) proposes modifying a polyoxymethylene resin by adding a modified polyolefin modified with a polymerizable monomer having a glycidyl group and an amide bond without directly modifying the polyacetal. .

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a modified resin composition capable of alloying polyacetal and a wide range of thermoplastic resins and effectively exhibiting the properties of the polyacetal and the thermoplastic resin. It is in. Another object of the present invention is to provide a modified resin composition capable of forming a composite of polyacetal and another thermoplastic resin and having high weld strength and elongation. Still another object of the present invention is to provide a method for producing a modified resin composition, which can efficiently obtain a composition having the above-mentioned high properties by a simple operation.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have combined a modified polyacetal obtained by modifying a polyacetal with a polymerizable compound, and a modified polymer other than the modified polyacetal,
The inventors have found that the properties of both polymers are effectively exhibited, and that a thermoplastic resin incompatible with polyacetal can be efficiently alloyed by combining the modified polyacetal and the modified polymer, and the present invention has been completed.

That is, the modified resin composition of the present invention comprises a modified polyacetal resin composition (I) containing a modified polyacetal (1a) and a modified polymer composition containing a modified polymer (2a) other than the modified polyacetal (1a). (II) and is composed of. The modified polyacetal (1a) is
For example, epoxy group, carboxyl group, acid anhydride group, ester group, hydroxyl group, ether group, amide group, amino group, nitrile group, isocyanate group, imide group, cycloalkyl group, aryl group, and nitrogen atom as a hetero atom. The residue of the polymerizable compound having at least one functional group selected from the group consisting of heterocyclic groups having
It may be a modified polyacetal introduced to the polyacetal component. The introduced amount of the residue of the polymerizable compound in the modified polyacetal (1a) is about 0.1 to 30% by weight. The modified polyacetal resin composition (I) may include an unmodified polyacetal (1b) in addition to the modified polyacetal (1a), and the modified polymer composition (II) further includes the polyacetal (1b). Other unmodified polymer (2b) may be included. In the method of the present invention, a modified resin composition is produced by mixing the modified polyacetal resin composition (I) and the modified polymer composition (II).

In the present specification, "modification" means a component other than the component constituting the basic skeleton of the polymer,
This means introducing a functional group. "Polyacetal"
Unless otherwise specified, means a polyacetal homopolymer or a polyacetal copolymer. Also,
The term “residue of a polymerizable compound” means not only a monomer unit of the polymerizable compound but also a polymer thereof (for example, a dimer, trimer, tetramer or polymer component generated by polymerization). The “non-self-condensable functional group” means a functional group capable of condensing without intervening reaction components, such as a methylol group. Further, unless otherwise specified, acrylic monomers and methacrylic monomers are collectively referred to as “(meth) acrylic monomers”.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The contents of the modified polyacetal resin composition (I) and the modified polymer composition (II) are as follows.

[Modified Polyacetal Resin Composition (I)]
The modified polyacetal resin composition (I) contains at least the modified polyacetal (1a), and the modified polyacetal (1a) can be obtained by modifying the polyacetal (1b). The modified polyacetal resin composition (I) may be composed of the modified polyacetal (1a) alone, or may be composed of the modified polyacetal (1a) and the unmodified polyacetal (1b) in combination.

Polyacetal (1b) The unmodified polyacetal (1b) is an oxymethylene group (-
It is a polymer compound containing CH ₂ O-) as a main constituent unit. Polyacetals include polyoxymethylene homopolymers and polyacetal copolymers.
This copolymer has 2 carbon atoms in addition to the oxymethylene group.
To about 6 and preferably about 2 to 4 carbon oxyalkylene units (for example, oxyethylene group (—CH ₂ CH ₂
O-), an oxypropylene group, an oxytetramethylene group, etc.) as a constitutional unit. The proportion of the oxyalkylene group having about 2 to 6 carbon atoms can be appropriately selected according to the use of the polyacetal, and is, for example, 0.1 to 30 mol%, preferably 1 to 2 with respect to the entire polyacetal.
It is about 0 mol%.

The polyacetal copolymer may be composed of a plurality of components such as a copolymer composed of two components and a terpolymer composed of three components, and may be a block copolymer. Further, the polyacetal may have not only a linear structure but also a branched structure and a crosslinked structure. Furthermore, the terminal of the polyacetal may be stabilized by, for example, esterification with a carboxylic acid such as acetic acid, propionic acid or butyric acid.
The degree of polymerization, the degree of branching and the degree of crosslinking of the polyacetal are not particularly limited as long as they can be melt-molded.

Preferred polyacetals include polyoxymethylene, polyacetal copolymers (eg, copolymers composed of at least oxymethylene units and oxyethylene units). In terms of thermal stability,
Polyacetal copolymers are preferred. The molecular weight of the polyacetal is not particularly limited, and may be, for example, 5,000 to
500,000, preferably 10,000-400,0
It is about 00.

The polyacetal can be produced by polymerizing aldehydes such as formaldehyde, paraformaldehyde and acetaldehyde, and cyclic ethers such as trioxane, ethylene oxide, propylene oxide and 1,3-dioxolane.

Modified polyacetal (1a) The modified polyacetal (1a) is the above-mentioned polyacetal (1a).
the polyacetals mentioned in section b) (ie polyacetal homopolymers and polyacetal copolymers),
Alternatively, it can be obtained by using a polymerizable polyacetal and modifying it with a polymerizable compound having a functional group. Hereinafter, the "polyacetal" and the "polymerizable polyacetal" may be simply referred to as "(A) polyacetal component".

The above-mentioned polymerizable polyacetal is a polymer compound having an oxymethylene group (—CH ₂ O—) as a main constituent unit and having a polymerizable functional group in the molecule. The polymerizable functional group includes, for example, an ethylenic double bond and an acetylene bond, and an ethylenically unsaturated bond is particularly preferable.

The polymerizable polyacetal is an ethylenic unsaturated copolymerized with formaldehyde or trioxane as a main monomer and a cyclic ether or cyclic formal having an ethylenically unsaturated bond as a substituent as a comonomer in the presence of a cationically active catalyst. A polyacetal copolymer having a bond and formaldehyde or trioxane as a main monomer, and a linear formal compound having an ethylenically unsaturated bond as a chain transfer agent are polymerized or copolymerized by a cationic polymerization catalyst in the presence of a linear formal compound. A polyacetal copolymer having a saturated bond and a polyacetal having an ethylenically unsaturated bond polymerized by anionic polymerization in the presence of a chain transfer agent containing formaldehyde as a main monomer and a polymerizable functional group such as an ethylenically unsaturated bond. Acetal is included. In the above-mentioned polymerization step, a cyclic ether or cyclic formal having no ethylenically unsaturated bond may coexist as a comonomer, if necessary. Further, the polymerizable polyacetal may be a polyacetal obtained by a method of using a carboxylic acid having a polymerizable functional group or its acid anhydride as a terminal esterifying agent after the polymerization reaction.

In the above-mentioned polymerizable polyacetal,
Examples of the cyclic ether or cyclic formal having an ethylenically unsaturated bond include, for example, allyl glycidyl ether, vinylbenzyl glycidyl ether, etc., and in the above method, the linear formal compound as a chain transfer agent is divinyl formal. And so on. Further, in the above-mentioned polymerizable polyacetal, as the chain transfer agent having a polymerizable functional group, allyl alcohol, alcohol having an ethylenically unsaturated bond such as crotonyl alcohol, alcohol having an acetylene bond such as propargyl alcohol is included. . Further, in the above method, the carboxylic acid having a polymerizable functional group has, for example, an ethylenically unsaturated bond such as acrylic acid, methacrylic acid, crotonic acid, vinyl glycolic acid, maleic acid, fumaric acid, or itaconic acid. A carboxylic acid having an acetylene bond such as mono- or dicarboxylic acid and propiolic acid can be used.
Acrylic acid or methacrylic acid is often used as the carboxylic acid having a polymerizable functional group.

The content of the polymerizable functional group such as ethylenic unsaturated bond in the polymerizable polyacetal is, for example,
It is about 0.001 to 5 mol / kg, preferably about 0.01 to 2 mol / kg. It is preferable to use the above-mentioned polymerizable polyacetal because the introduction efficiency of the polymerizable compound described later becomes high.

The modified polyacetal (1a) is (A)
It is obtained by introducing a residue of a polymerizable compound having a functional group into polyacetal (that is, polyacetal or polymerizable polyacetal). The type of functional group of the polymerizable compound is not particularly limited, for example, an epoxy group,
Carboxyl group, acid anhydride group, ester group, hydroxyl group, ether group, amide group, amino group, nitrile group,
It includes an isocyanate group, an imide group, a cycloalkyl group, an aryl group, and a heterocyclic group having a nitrogen atom as a hetero atom. In addition, a substituent may be bonded to the nitrogen atom of the amide group and the amino group. The polymerizable compound may be polyfunctional having the same or different functional groups in one molecule. These functional groups are useful for enhancing the affinity with the modified polymer composition (II) and additives such as reinforcing agents and fillers. These polymerizable compounds can be used alone or in combination of two or more.

The polymerizable compound having a functional group must have at least one polymerizable group in one molecule. By adding a small amount of a compound having a plurality of polymerizable groups and modifying it, it is possible to suppress excessive crosslinking and suppress melt viscosity, and it is effective to obtain a resin composition suitable for blow molding or film molding. . When fluidity is required as in injection molding materials, the polymerizable compound contains one polymerizable group (for example, an ethylenic double bond or acetylene) in one molecule in order to suppress crosslinking and enhance molding processability. Bond), especially a compound having an ethylenically unsaturated bond. Further, even a compound having a plurality of polymerizable groups, for example, a polymerizable compound such as diallylamine that cyclizes in the molecule to form a linear polymer can be used.

Examples of the compound having an epoxy group include glycidyl ethers such as allyl glycidyl ether and chalcone glycidyl ether; glycidyl (meth)
Acrylate, vinyl benzoic acid glycidyl ester, allyl benzoic acid glycidyl ester, cinnamic acid glycidyl ester, cinnamylidene acetic acid glycidyl ester, dimer acid glycidyl ester, glycidyl or epoxy ester such as ester of epoxidized stearyl alcohol and acrylic acid or methacrylic acid; Examples thereof include epoxidized unsaturated chain or cyclic olefins such as epoxyhexene and limonene oxide. The glycidyl ether type polymerizable compound may be a compound represented by the formula (1) (for example, N- [4-
(2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide etc.) are also included. Preferred polymerizable compounds having an epoxy group include glycidyl ether type or glycidyl ester type epoxy compounds having a (meth) acryloyl group.

As the compound having a carboxyl group,
For example, acrylic acid, methacrylic acid, propiolic acid,
Aliphatic unsaturated monocarboxylic acids such as crotonic acid; aromatic unsaturated monocarboxylic acids such as cinnamic acid; aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid; monomethyl maleate, maleic acid Examples thereof include maleic acid monoesters such as monoethyl acid acid, monobutyl maleate, monohexyl maleate, monooctyl maleate and mono-2-ethylhexyl maleate, and corresponding unsaturated dicarboxylic acid monoesters such as fumaric acid monoesters. Preferred compounds having a carboxyl group include (meth) acrylic acid, maleic acid, and maleic acid monoalkyl ester.

Examples of the compound having an acid anhydride group include:
Maleic anhydride, itaconic anhydride, citraconic anhydride,
Hymic acid anhydride and the like are included. Preferred compounds having an acid anhydride group include maleic anhydride.

The compound having an ester group includes, for example,
An ester of a polymerizable compound having a carboxyl group such as the unsaturated mono- or dicarboxylic acid or a polymerizable compound having an acid anhydride group and a hydroxy compound having about 1 to 20 carbon atoms is included. As the hydroxy compound,
For example, methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, 2-methyl-2-
Propanol, 1-hexanol, 1-octanol,
Aliphatic alcohols such as 1-dodecanol and stearyl alcohol having about 1 to 20 carbon atoms (preferably about 4 to 20 carbon atoms), alicyclic alcohols such as cyclohexanol, aralkyl alcohols such as benzyl alcohol, and phenols such as phenol. Is mentioned. Examples of such polymerizable compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Acid isobutyl, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate,
It includes unsaturated dicarboxylic acid esters such as dioctyl maleate, di2-ethylhexyl maleate and the corresponding fumaric acid esters. The compound having an ester group also includes an ester of a polymerizable compound having a hydroxyl group described below and an organic carboxylic acid. The compound having an ester group further includes vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprylate, vinyl laurate, vinyl myristate, vinyl oleate,
Vinyl esters of organic carboxylic acids having about 2 to 20 carbon atoms (preferably about 6 to 20 carbon atoms) such as vinyl stearyl acid are also included. The preferred polymerizable compound having an ester group is a compound having a relatively high boiling point, for example, a (meth) acrylic acid alkyl ester having an alkyl group having about 8 to 20 carbon atoms and an organic carboxylic acid moiety having 10 to 2 carbon atoms.
About 0 vinyl ester is included.

As the compound having a hydroxyl group,
For example, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerin mono. (Meth) acrylate, vinylphenol, etc. are mentioned. Preferred polymerizable compounds having a hydroxyl group include hydroxyalkyl (meth) acrylate and the like.

Examples of the compound having an ether group include methoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl. Examples include (meth) acrylate and methoxystyrene.

The compound having a hydroxyl group and an ether group includes diethylene glycol mono (meth).
Acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (Meth) acrylate etc. are mentioned.

Examples of the compound having an amide group include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and N-.
(Meth) acrylamide and its derivatives such as isopropylacrylamide, N, N-dimethylaminopropylacrylamide, and siacetoneacrylamide; and vinylsulfonamides such as vinylsulfonamide, vinylsulfonanilide, vinylsulfonmethylanilide, and vinylsulfoneacetanilide. . Preferred polymerizable compounds having an amide group include (meth) acrylamide,
N-substituted (meth) acrylamides are included.

Examples of the compound having an amino group include allyl compounds such as allylamine and diallylamine; vinyl compounds such as 4-vinylaniline and N-vinyldiphenylamine; N, N-dimethylaminoethyl (meth) acrylate, N, N. (Meth) acrylates such as diethylaminoethyl (meth) acrylate.

Examples of the compound having an imide group include maleimides such as maleimide, N-methylmaleimide, N-phenylmaleimide and bismaleimide, and their derivatives;
N-vinyl polycarboxylic acid imides such as N-vinyl succinimide, N-vinyl glutarimide, N-vinyl phthalimide and the like are included. Preferred polymerizable compounds having an imide group include maleimide and its derivatives.

Examples of the compound having a nitrile group include acrylonitrile, methacrylonitrile, 2-cyanoethyl (meth) acrylate and the like. A preferred polymerizable compound having a nitrile group includes (meth) acrylonitrile. Examples of the compound having an isocyanate group include vinyl isocyanate, methacryloyl isocyanate and m- (2-isocyano-2-propyl) -α.
-Methylstyrene and the like. Examples of the compound having a cycloalkyl group or an aryl group include vinylcyclohexane, 2-vinyl-1-nonene, styrene, α-methylstyrene, p-chloromethylstyrene,
Examples thereof include p-methylstyrene, vinyltoluene, vinylnaphthalene, vinylanthracene and the like.

The compound having a heterocyclic group is a compound having a nitrogen atom as a hetero atom, for example, 2-vinylquinoline, 3-vinylpiperidine, 2-vinylpyrazine, 2-vinylpyridine, 4-vinylpyridine, N-. Vinylpyrrole, N-vinylindole, N-vinylcarbazole, N-vinylimidazole, N-vinyl-2-
Pyrrolidone, N-vinyl-ε-caprolactam, acryloylmorpholine and the like can be mentioned. Further, the polymerizable compound having a heterocyclic group includes a compound having an oxazolone group (for example, 2-vinyl-5-oxazolone).
And cyclic imino ethers such as compounds having an oxazoline group (for example, 2-vinyl-2-oxazoline). The preferred polymerizable compound having a heterocyclic group, a heterocyclic compound in which a vinyl group is bonded to a nitrogen atom as a hetero atom, an oxygen atom together with a nitrogen atom as a hetero atom such as a cyclic iminoester group or a cyclic iminoether group. Vinyl compounds having a heterocyclic group are included.

Preferred functional groups of the polymerizable compound include, for example, an epoxy group, a carboxyl group, an acid anhydride group, an ester group, a hydroxyl group, an amide group in which a functional group may be bonded to a nitrogen atom, an amino group, A nitrile group, an isocyanate group, an imide group, and the above-mentioned heterocyclic group (such as a cyclic iminoester group and a cyclic iminoether group) are included. Preferred amide groups include N-substituted amide groups having a non-self-condensable functional group attached to the nitrogen atom.

In particular, an ethylenically polymerizable compound having an epoxy group such as glycidyl (meth) acrylate,
An ethylenic polymerizable compound having a carboxyl group such as (meth) acrylic acid, an ethylenic polymerizable compound having an acid anhydride group such as maleic anhydride, or an ethylenic polymerizable compound having an amide bond and an epoxy group is preferable. The ethylenic polymerizable compound having an epoxy group or an amide bond and an epoxy group includes a compound represented by the following formula (1).

[0037]

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ^{2 to} R ⁵ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group. n is 0 or 1) The halogen atom includes fluorine, chlorine, bromine and iodine atoms, and the alkyl group includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and s.
It includes alkyl groups having about 1 to 10 carbon atoms such as ec-butyl, t-butyl, pentyl, hexyl and octyl groups. Preferred alkyl groups include lower alkyl groups having about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms. Alkoxy groups include, for example, methoxy, ethoxy, propoxy,
A lower alkoxy group having about 1 to 6 carbon atoms such as butoxy, t-butoxy, pentyloxy, hexyloxy group is included. The alkoxycarbonyl group includes, for example, a lower alkoxycarbonyl group having about 1 to 6 carbon atoms in the alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl and hexyloxycarbonyl groups. Is often the case. Acyl groups include formyl, acetyl, propionyl, butyryl,
A lower acyl group having about 1 to 6 carbon atoms such as valeryl and pivaloyl group is included. Examples of the acyloxy group include acetyloxy, propionyloxy, butyryloxy, valeryloxy and pivaloyloxy groups. R ^{2 to} R ⁵ are often the same or different and each represents a hydrogen atom, a halogen atom, or a lower alkyl group. Especially R ²
In many cases, R ⁵ is the same or different and is a hydrogen atom or a lower alkyl group.

The compound in which n is 0 includes the glycidyl (meth) acrylate. Specific examples of the compound in which n is 1 include, for example, N- [4- (2,3-epoxypropoxy) phenylmethyl] acrylamide and N- [4-
(2,3-Epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- [4- (2,3-epoxypropoxy) -3,5-diethylbenzyl] acrylamide, N- [4- (2,3) -Epoxy propoxy)-
N-, such as 3,5-dibutylbenzyl] acrylamide
[4- (2,3-epoxypropoxy) -3,5-dialkylbenzyl] acrylamide, N- [4- (2,3
-Epoxypropoxy) -2,6-dimethylbenzyl]
Acrylamide, N- [4- (2,3-epoxypropoxy) -2,5-dimethylbenzyl] acrylamide,
N- [4- (2,3-epoxypropoxy) -2,3
Examples include 5,6-tetramethylbenzyl] acrylamide.

The polymerizable compound is often liquid or solid (non-gaseous) at room temperature and atmospheric pressure. Of these polymerizable compounds, a compound having a boiling point of 70 ° C. or higher at normal pressure, preferably 100 ° C. or higher, more preferably 120 ° C. or higher is often used, and the preferable boiling point of the polymerizable compound is maleic anhydride or (meth ) Acrylic acid, glycidyl (meth) acrylate, a compound represented by the formula (1) (for example, N- [4- (2,3-epoxypropoxy))
In most cases, the temperature is 140 ° C. or higher under normal pressure, such as −3,5-dimethylbenzyl] acrylamide).

In order to improve the modification efficiency and the utilization efficiency of the modified polyacetal and the molded article, the modified polyacetal (1a) is a polyacetal modified by the polymerizable compound in the absence of a filler or a reinforcing agent. preferable. When the modified polyacetal modified in the absence of a filler or a reinforcing agent is used, a resin composition can be prepared simply by mixing it with a plurality of thermoplastic resins according to the application, and the flexibility of alloying and compounding can be obtained. growing.

The amount of the functional group introduced can be selected within a range capable of improving the affinity with the thermoplastic resin and the additive.
(A) The polyacetal component is converted to a polymerizable compound in an amount of 0.1 to 30% by weight (for example, about 0.1 to 20% by weight), preferably 0.2 to 25% by weight (for example, 0.2 to 20% by weight).
15% by weight), more preferably 0.3 to 20% by weight (for example, about 0.3 to 10% by weight), and 0.2 to
It is often about 10% by weight.

The modified polyacetal (1a) is (A)
It can be produced by heating the polyacetal component and the polymerizable compound (B) having a functional group, and introducing the residue of the polymerizable compound into the polyacetal. (A) the polyacetal component and (B) the polymerizable compound having a functional group,
The heating may be carried out in the absence of the radical generator (C) (polymerization initiator), but the residue of the polymerizable compound can be efficiently introduced by heating in the presence of the radical generator (C).

The type of the radical generator (C) is not particularly limited as long as it is a compound that functions as a polymerization initiator that generates a free radical and initiates the polymerization of the polymerizable compound. As the radical generator, peroxides such as organic peroxides, azo compounds and other radical polymerization initiators can be used.

Examples of the peroxide include t-butyl hydroperoxide, p-menthane hydroperoxide,
Cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5
-Alkyl hydroperoxides such as dihydroperoxide; di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxycumene, 2,5-dimethyl-2,5-di (t- Butyl peroxy) hexane, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexyne-3, α, α '
-Dialkyl peroxide such as bis (t-butylperoxy-m-isopropyl) benzene; diacyl peroxide such as benzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide; methyl ethyl ketone peroxide, 1,1-bis ( t-butylperoxy)
Alkylidene peroxide such as -3,3,5-trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclododecane; n-butyl-4,4-bis (t
Examples include peroxyesters such as -butylperoxy) valerate and t-butylperoxybenzoate.

Examples of the azo compound include 1-[(1
-Cyano-1-methylethyl) azo] formamide,
Azoamide compounds such as 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}; 1,1-azobis (cyclohexane-1-carbonitrile), 2- Phenylazo-4-
Methoxy-2,4-dimethylvaleronitrile, 2,2 '
-Azobis [2- (hydroxymethyl) propionitrile], azobisisobutyronitrile and other azonitrile compounds; and 2,2'-azobis (2,4,4-trimethylpentane) and other alkylazo compounds. .

As other radical generators, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate can be used. These radical generators may be used alone or in combination of the same kind or different kinds.

In order to efficiently introduce the functional group of the polymerizable compound (B) into the polyacetal (A), a preferable radical generator has a temperature corresponding to a half-life of 1 minute of 130 ° C. or higher, preferably 150 ° C. or higher, More preferably 160
Includes compounds at or above ° C. Such radical generators include alkyl hydroperoxides, dialkyl peroxides,
Peracid ester (particularly alkyl hydroperoxide, dialkyl peroxide) and the above-mentioned azo compound are often used.

The proportion of the polymerizable compound (B) having a functional group can be selected according to the desired degree of modification and the intended use of the modified polyacetal, and is, for example, 0.1 with respect to 100 parts by weight of the polyacetal component (A). -30 parts by weight, preferably 0.3-25 parts by weight, more preferably 0.5-20
It is about part by weight, and often about 1 to 20 parts by weight. When the proportion of the polymerizable compound (B) is small, the degree of modification of the polyacetal is small, and when it is excessive, the mechanical properties of the polyacetal may deteriorate depending on the type of the polymerizable compound.

(A) Polyacetal component to (C)
The proportion of the radical generator can be selected from a range that can suppress excessive reduction of the molecular weight of the polyacetal and does not impair the modification efficiency. For example, 3.5 parts by weight or less (100 parts by weight of the (A) polyacetal component For example, 0.01-3.
5 parts by weight), preferably 0.01 to 3 parts by weight, and more preferably 0.01 to 1.5 parts by weight.
In many cases, it is about 05 to 0.5 parts by weight. Also,
The ratio of the radical generator (C) to the total amount of the (A) polyacetal component and the polymerizable compound (B) is determined by the half-life of the radical generator at the processing temperature, the amount of the polymerizable compound,
It can be selected according to the processing temperature, the processing time, etc., and is 2.5 parts by weight or less (for example, 0.01 to about 100 parts by weight of the (A) polyacetal component and the (B) polymerizable compound).
2.5 parts by weight), preferably 0.01 to 2 parts by weight,
More preferably, it is about 0.01 to 1 part by weight, and 0.1.
In many cases, it is about 05 to 0.5 parts by weight. When the amount of the radical generator (C) used is too small, the degree of modification by the polymerizable compound (B) tends to decrease, and even when it is too large, the degree of modification does not improve so much. Further, if the amount of the radical generator used is too large, the polyacetal may be excessively decomposed depending on the type of the radical generator. The ratio of the radical generator (C) to 100 parts by weight of the polymerizable compound (B) is 0.1 to 25 parts by weight, preferably 0.5 to 15 parts.
It is often about 1 to 10 parts by weight, more preferably about 1 to 10 parts by weight.

A simple method for modifying the polyacetal is to mix the polyacetal component (A) and the polymerizable compound having a functional group (B) in the molten state of the polyacetal in the presence of the radical generator (C). In particular, a method of melt kneading is included.

For the melt mixing and melt kneading treatment, a conventional mixer or kneader, such as an extruder, a Brabender, a kneader, a Banbury mixer, a roll mill, etc. can be used. Preferred melt mixing or kneading machines include closed type equipment such as extruders, kneaders and the like. The kneading temperature can be selected in the range of the melting point of polyacetal to the decomposition temperature, and is preferably 5 to 70 ° C. (preferably 1 ° C.) higher than the melting point of polyacetal.
(0 to 50 ° C.) high temperature. The treatment time can be selected according to the mixing or kneading temperature, and is, for example, 20 seconds to 2 hours, preferably about 30 seconds to 1 hour, and 30 seconds to 3
It is often about 0 minutes. The melt mixing or melt kneading treatment is carried out by (A) polyacetal component, (B) polymerizable compound,
And, if necessary, the radical generator (C) may be separately supplied to the mixer or the kneader one by one, or the two components (A) may be prepared in advance.
You may carry out simultaneously by providing (B) or the mixture of three components (A) (B) (C) to the said mixer or kneader. The melt mixing or melt kneading treatment may be carried out in the presence of an antioxidant.

In the absence of the polymerizable compound (B),
When the (A) polyacetal component and the (C) radical generator are melt-mixed or melt-kneaded, the radical generator causes
Polyacetal has a significantly low molecular weight. On the other hand, when the polyacetal component (A) and the radical generator (C) are melt-mixed or melt-kneaded in the presence of the polymerizable compound (B), the polymerizable compound can be modified and the amount of the radical generator can be increased. Although it depends on the polyacetal, it is possible to prevent the polyacetal from having an excessively low molecular weight. Therefore, when a polymerizable compound having a functional group (B) is added to a melted mixture of the (A) polyacetal component and the (C) radical generator and mixed in the molten state of the polyacetal, the composition is modified by the polymerizable compound. A modified polyacetal having a relatively low molecular weight can be obtained. Such a modified polyacetal can be used as a compatibilizing agent, an adhesiveness improving agent with resins, metals, adhesives, paints and the like.

In order to effectively utilize the radical generator for modification while suppressing the decomposition of polyacetal and to enhance the modification efficiency of the polymerizable compound, the polymerizable compound having (A) polyacetal component and (B) functional group is used. And (C) radical generator are mixed or kneaded in a molten state of polyacetal, or (C) radical generator is added in the presence of (A) polyacetal component and (B) polymerizable compound. A method of mixing or kneading the polyacetal in a molten state, a mixture of (A) a polyacetal component and (B) a polymerizable compound having a functional group, particularly a homogeneous mixture (preferably a compound or a molten mixture) with a radical (C). A method of adding a generator and mixing or kneading the polyacetal in a molten state is useful. In this way,
A functional group of a polymerizable compound can be efficiently introduced while maintaining a high molecular weight and excellent properties of polyacetal. In particular, the above method has an advantage over the first method in that the modification efficiency can be increased while suppressing the lowering of the molecular weight of the (A) polyacetal component.

Such a method includes, for example, supplying the three components and the compound to an apparatus such as the extruder,
This can be carried out by melting and mixing the polyacetal and the polymerizable compound in the device, then adding or injecting the radical generator into the device, and mixing or kneading. Further, a mixture of the compound and the radical generator may be supplied to the device and mixed or kneaded. The compound is often used in the form of powder or pellets.

Further, in order to increase the degree of modification by the polymerizable compound and the utilization efficiency of the radical generator, the above-mentioned melt mixing or melt kneading is preferably carried out in the absence of a filler such as a reinforcing filler. That is, when melt mixing or melt kneading is performed in the presence of a filler, it is often difficult to control the modification efficiency and the melt viscosity of the polymerizable compound with respect to the polyacetal. On the other hand, when modified in the absence of the filler and the reinforcing agent, the radical generator and the polymerizable compound can be effectively used for the modification of the polyacetal, and are modified by the relatively large amount of the filler and the reinforcing agent. Since it is not quality, a wide range of compositions can be obtained by combining the modified polyacetal with various thermoplastic resins.

If necessary, a resin composition containing an additive, for example, a stabilizer such as an antioxidant may be subjected to the above-mentioned melt mixing or melt kneading operation. At that time, in order to enhance the modification efficiency of the polyacetal by the polymerizable compound and the utilization efficiency of the radical generator, the addition amount of the additive is preferably small, for example, with respect to 100 parts by weight of the total amount of the polyacetal and the polymerizable compound. 10 parts by weight or less, preferably 0.001 to 5 parts by weight, and more preferably 0.01 to 3 parts by weight.

Of the above additives, the addition of an antioxidant is useful for increasing the stability of the modified polyacetal. The antioxidant, for example, hindered phenols,
Includes hindered amines and other compounds. Hindered phenols include, for example, 2,6-di-t-butyl-p-cresol and 2,2'-methylenebis (4-
Methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,
4'-butylidene bis (3-methyl-6-t-butylphenol), 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy) Phenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) benzene, n-octadecyl-
3- (4 ', 5'-di-t-butylphenol) propionate, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenol) propionate, distearyl-3,5-di-t- Butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl-4-methylphenyl acrylate, N, N'-hexamethylenebis (3,5 -Di-t-butyl-4-hydroxy-hydrocinnamamide), 3,9-bis {2- [3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4
8,10-tetraoxaspiro [5,5] undecane,
4,4'-thiobis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane, etc. are included.

Examples of the hindered amines include 4-acetoxy-2,2,6,6-tetramethylpiperidine,
4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6
6-tetramethylpiperidine, 4-methoxy-2,2
6,6-Tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2 6,6-Tetramethylpiperidine, 4-benzyloxy-2,2,6,6
-Tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,2 6,6-Tetramethyl-4-piperidyl) malonate, bis (2,2,2
6,6-tetramethyl-4-piperidyl) adipate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1,2,2)
2,6,6-Pentamethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, 1,2-bis (2,2,6,6)
-Tetramethyl-4-piperidyloxy) ethane, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate, tris (2,2
2,6,6-Tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, phenyl-α-
Naphthylamine, phenyl-β-naphthylamine, N,
Examples thereof include N'-diphenyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine.

Other antioxidants include, for example, sulfur type antioxidants such as dimyristyl thiodipropionate, dilauryl thiodipropionate and distearyl thiodipropionate; triisodecyl phosphite and triphenyl phosphite. Phosphorus antioxidants such as fighting; 2,5
-Hydroquinone antioxidants such as di-t-butylhydroquinone and 2,5-diamylhydroquinone; quinoline antioxidants such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; Including mercaptobenzimidazole and the like. These antioxidants can be used alone or in combination of two or more. Preferred antioxidants include hindered phenols (phenolic antioxidants) and hindered amines (amine antioxidants).

When the polyacetal is modified in the presence of an antioxidant, the antioxidant may be added in the polyacetal component (A) or in the modification process. The amount of antioxidant used is
With respect to 100 parts by weight of the (A) polyacetal component, 0.
001 to 2 parts by weight, preferably 0.01 to 1 part by weight. The polyacetal (1a) and / or the modified polyacetal (1b) may be pelletized, if necessary, and used in combination with the modified polymer composition (II) described below.

In the modified polyacetal resin composition (I), the ratio of the modified polyacetal (1a) to the unmodified polyacetal (1b) is determined by the types of the modified polymer (2a) and the unmodified polymer (2b), the modified polyacetal (1a). Can be selected according to the molecular weight, desired characteristics, intended use, and the like.
(Wt%), preferably 95/5 to 5/95 (wt%), more preferably about 90/10 to 10/90 (wt%), and about 20/80 to 80/20 (wt%). Often there is.

[Modified Polymer Composition (II)] The modified polymer composition (II) contains at least a modified polymer (2a) other than the modified polyacetal (1a), and the modified polymer (2a) is It can be obtained by modifying an unmodified polymer (2b) other than the polyacetal (1b). The modified polymer composition (II) may be composed of the modified polymer (2a) alone, or the modified polymer (2a).
It may be constituted by combining a) and the unmodified polymer (2b). Furthermore, when the modified polymer (2a) and the unmodified polymer (2b) are combined, a plurality of modified polymers (2a) and one or more unmodified polymers (2b) can be used in combination. Modified polymer (2a)
The unmodified polymer (2b) corresponding to is not only a polymer (2b) having a main chain of the same or similar chemical structure as the modified polymer (2a) as a main component, but also the structure of the main chain of the modified polymer (2a). Even when they are different, it means an unmodified polymer (2b) having a high affinity for the modified polymer (2a).

Unmodified Polymer (2b) and Modified Polymer
(2a) The type of the unmodified polymer (2b) is not particularly limited, and examples thereof include olefin polymers, diene polymers, acrylic polymers, styrene polymers, vinyl polymers such as polyvinyl chloride, polyethers and polyphenylene ethers. , Polysulfones, polyethersulfones, polyetherimides, polyamideimides, and other thermoplastic resins.

On the other hand, the modified polymer (2a) has various functional groups with respect to the unmodified polymer (2b), for example, functional groups introduced into the modified polyacetal (1a).
Thermoplastic resin in which an epoxy group, a carboxyl group, an acid anhydride group, an ester group, a hydroxyl group, an ether group, an amide group, an amino group, an imide group, an isocyanate group, and a heterocyclic group having a nitrogen atom as a hetero atom are introduced. Is included. For introducing the functional group into the unmodified polymer (2b), a polymerizable compound having the same functional group as described above or a compound having a functional group depending on the reaction method can be used. Preferred functional groups in the modified polymer (2b) include the same functional groups as those in the modified polyacetal (1a), particularly an epoxy group, a carboxyl group, an acid anhydride group and an amino group. The unmodified polymer (2b) and the modified polymer (2a) corresponding to the unmodified polymer will be described below in association with each other.

Examples of the olefin polymer include homopolymers or copolymers of α-olefins such as ethylene, propylene, butene, hexene, octene, nonene, decene and dodecene (for example, random copolymers, block copolymers, (Graft copolymer), a random copolymer, a block copolymer, a graft copolymer, etc., which contains the above α-olefin as a main component and at least one comonomer component. Examples of the comonomer component include, for example, non-conjugated dienes (1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 2,5-norbonadiene, etc.), conjugated dienes (eg, butadiene, isoprene, piperylene). Etc.) etc. are included. The degree of polymerization of the olefin-based polymer, the presence or absence of side chains or branches, the degree of branching, the copolymer composition ratio, etc. are not particularly limited.

More specifically, examples of the olefin-based polymer include polyethylene such as high-density polyethylene, medium-density polyethylene, low-density polyethylene and linear low-density polyethylene, polypropylene, polybutene, polybutylene, methylpentene resin, ethylene. -Α-olefin copolymer (for example, ethylene-propylene copolymer, ethylene-1-butene copolymer, etc.), ethylene-
A propylene-diene copolymer and the like are included. Preferred olefin-based polymers include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-1-
Included are ethylene-α-olefin copolymers such as butene copolymers.

The modified olefin polymer includes the above α-
Olefin, and optionally the diene component, and a comonomer component having a functional group, for example, α, β-unsaturated carboxylic acid or a derivative thereof (for example, acrylic acid, methacrylic acid, their anhydrides, (meth) acrylic) Acid alkyl ester, etc.), a polymerizable compound having an acid anhydride group (eg, maleic anhydride), a polymerizable compound having a glycidyl group (eg, glycidyl (meth) acrylate), a vinyl ester (eg, vinyl acetate, etc.) ), Vinyl ether (for example, vinyl methyl ether, etc.),
Copolymers with derivatives of these vinyl compounds are included.

More specifically, the modified olefin polymer is, for example, an ethylene-vinyl ester copolymer such as an ethylene-vinyl acetate copolymer, a carboxyl-modified polyolefin (for example, ethylene- (meth) acrylic acid copolymer). Polymer, ionomer, etc.), acid anhydride modified polyolefin (eg, maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, etc.), glycidyl modified polyolefin (eg, ethylene-glycidyl (meth) acrylate copolymer, etc.), ethylene-acrylic Examples thereof include acid ester copolymers (eg, ethylene-ethyl acrylate copolymer).

The diene-based polymer includes homopolymers or copolymers mainly containing conjugated dienes such as butadiene, isoprene and chloroprene, for example, polybutadiene, polyisoprene, polychloroprene and acrylonitrile-butadiene copolymer.

As the modified diene-based polymer, for example,
Examples thereof include acid anhydride-modified polybutadiene (such as maleic anhydride-modified polybutadiene) and carboxyl-modified polybutadiene (such as (meth) acrylic acid-modified polybutadiene).

Examples of the styrene-based polymer include homopolymers or copolymers (random copolymers, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chloromethylstyrene).
Block copolymer or graft copolymer), the aromatic vinyl compound and (meth) acrylonitrile, diene monomer (butadiene etc.), olefin (ethylene,
Examples thereof include copolymers obtained by polymerizing with propylene) and elastomers (rubber components such as butadiene rubber, acrylic rubber, chlorinated polyethylene, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer) and hydrogenated products thereof. In these copolymers, random,
The form of copolymerization such as block and graft, the degree of polymerization, the presence or absence of side chains or branches and their degree, and the copolymer composition ratio are not particularly limited.

Specific examples of the styrene-based polymer include polystyrene, acrylonitrile-styrene copolymer, high-impact polystyrene, styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-
Hydrogenated product of acrylonitrile-butadiene copolymer,
Styrene-acrylonitrile-ethylene copolymer, styrene block copolymer (for example, styrene-butadiene-styrene (SBS) copolymer, styrene-isoprene-styrene (SIS) copolymer, styrene-ethylene-butylene-styrene (SEBS) Copolymers, etc.) and the like. Preferred styrenic polymers include
Examples thereof include acrylonitrile-styrene copolymer, high-impact polystyrene, styrene-acrylonitrile-butadiene copolymer, and styrene block copolymer.

Examples of the modified styrenic polymer include a copolymer of the above aromatic vinyl compound and an acrylic monomer and / or maleic anhydride or a derivative thereof. Examples of acrylic monomers include (meth) acrylic acid esters such as acrylic acid, methacrylic acid, methyl acrylate, and methyl methacrylate, and examples of maleic anhydride or a derivative thereof include maleic anhydride. Examples thereof include N-methylmaleimide and N-phenylmaleimide. The copolymer may be random, block,
The form of copolymerization such as grafting, the degree of polymerization, the presence or absence of side chains or branches and their degree, and the copolymer composition ratio are not particularly limited. Modified styrenic polymers include, for example, styrene-
(Meth) acrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-methyl acrylate copolymer, styrene-acrylonitrile-maleic anhydride copolymer,
Styrene-acrylonitrile-butadiene- (meth) acrylic acid copolymer, styrene-acrylonitrile- (meth) acrylic acid copolymer, styrene-methyl methacrylate copolymer and the like are included. Preferred modified styrenic polymers include styrene-maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride copolymer, styrene-acrylonitrile-butadiene- (meth) acrylic acid copolymer, styrene-acrylonitrile- (meth). Acrylic acid copolymers, styrene-methyl methacrylate copolymers and the like are included.

Acrylic polymers include homo- or copolymers containing (meth) acrylic acid alkyl ester as a main component, for example, polymethyl methacrylate, methyl methacrylate-alkyl acrylate copolymer, acrylic-styrene copolymer. Includes polymers, acrylic rubber and the like. Of these acrylic polymers, polymethylmethacrylate, acrylic rubber, etc. are often used. The modified acrylic polymer is a polymer having a unit of acrylic acid or methacrylic acid introduced into a homopolymer or a copolymer containing (meth) acrylic acid alkyl ester as a main component, for example, methyl methacrylate- (meth) acrylic acid. Copolymer, methyl methacrylate-alkyl acrylate- (meth) acrylic acid copolymer, alkyl acrylate-styrene- (meth) acrylic acid copolymer, methyl methacrylate-glycidyl (meth) acrylate copolymer , Methyl-2-hydroxyethyl methacrylate (meth) acrylate copolymer and the like are included.

Examples of the vinyl polymer include polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl ether, polyvinyl ketone, polyvinylpyrrolidone, and vinyl chloride-vinyl acetate copolymer, in addition to the above polyvinyl chloride. Modified vinyl-based polymers include the above-mentioned vinyl-based polymers (meta)
Copolymers into which acrylic acid, maleic anhydride, etc. have been introduced, such as vinyl acetate- (meth) acrylic acid copolymers and vinyl ether-maleic anhydride copolymers, are included.

The polyether is a polymer having an ether bond in the main chain, and is obtained by ring-opening polymerization of cyclic ether, self-condensation of glycol, oxidative polymerization of diol compound and the like. Polyether includes, for example, polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyphenylene ether, and the like. As the modified polyether, for example, a polymerizable compound having a functional group such as maleic anhydride, (meth) acrylic acid, or glycidyl (meth) acrylate is added to these polyethers, and a radical initiator may be added if necessary. A polymer produced by adding and heat treating is exemplified. Further, the unmodified polymer includes engineering plastics such as polysulfone, polyethersulfone, polyetherimide, polyamideimide and the like. Other modified polymers include, for example, cellulose esters such as cellulose acetate, cellulose ethers such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose and hydroxymethyl cellulose.

Among these thermoplastic resins, preferred unmodified polymer (2b) is, for example, polyethylene,
Polypropylene, ethylene-α-olefin copolymer,
Olefin polymers such as olefin elastomers; acrylic resins such as polymethylmethacrylate, acrylic polymers such as acrylic rubber; polystyrene, high impact polystyrene, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, styrene Styrenic polymers such as block copolymers; polyvinyl chloride; polyphenylene ether; polysulfone; polyether sulfone; polyether imide; polyamide imide.

The preferred modified polymer (2a) is a polymer modified with an epoxy group, a carboxyl group, an acid anhydride group, an amino group or the like, for example, an acid-modified polyolefin (eg (meth) acrylic acid-modified polyethylene, (Meth) acrylic acid modified polypropylene, maleic anhydride modified polyethylene, maleic anhydride modified polypropylene and the like), glycidyl modified polyolefin (for example, ethylene-glycidyl (meth) acrylate copolymer and the like) modified polyolefin, acid modified polystyrene (for example , Styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, etc.), acid-modified acrylonitrile-styrene copolymer (for example, acrylonitrile-styrene- (meth) acrylic acid copolymer), Acid-modified ABS resin ( For example, acrylonitrile-butadiene-styrene- (meth) acrylic acid copolymer), glycidyl-modified polystyrene (for example, styrene-glycidyl (meth) acrylate copolymer, etc.), acid-modified acrylic polymer (for example, methyl methacrylate-). Examples thereof include (meth) acrylic acid copolymers) and glycidyl-modified acrylic polymers (eg, methyl methacrylate-glycidyl (meth) acrylate copolymers).

In the modified polymer resin composition (II),
The ratio of the modified polymer (2a) to the unmodified polymer (2b) can be selected according to the type of the modified polymer and the application, for example, the former (2a) / the latter (2b) = 100/0 to 1/99.
(Wt%), preferably 95/5 to 5/95 (wt%), more preferably about 90/10 to 10/90 (wt%), and about 20/80 to 80/20 (wt%). Often there is.

By combining the modified polyacetal (1a) and the modified polymer (2a), even a wide range of unmodified polymers (2b) that are incompatible with the polyacetal (1b) can be effectively used as the polyacetal (1b). Can be alloyed. Therefore, in the present invention, even when an unmodified or immiscible unmodified polymer (2b) with respect to polyacetal is used, the properties of the polyacetal (1b) and the unmodified polymer (2b) are effectively exhibited, and high mechanical properties are achieved. It is possible to obtain a composite resin composition having high physical properties, particularly high weld strength and weld elongation, and a composite resin composition having high impact resistance.

The modified polyacetal resin composition (I)
The ratio of the modified polymer composition (II) to the modified polymer composition (II) can be selected from a wide range according to the type of each component and desired properties, and for example, modified polyacetal resin composition (I) / modified polymer composition (II) = 1 / 99 to 99/1 (weight ratio), preferably 5/95 to 95/5 (weight ratio), and more preferably about 10/90 to 90/10 (weight ratio).

The thermoplastic resin composition of the present invention is mixed by various methods, for example, modified polyacetal (1a), unmodified polyacetal (1b), modified polymer (2a) and unmodified polymer (2b) in the form of powder. However, the resin composition is often produced by mixing in a molten state or a solution state. When mixing in the molten state,
A conventional mixer or kneader, such as an extruder, a Brabender, a kneader, a Banbury mixer, or a roll mixer can be used. Preferred melt mixing or kneading machines include closed type equipment such as extruders, kneaders and the like.

The mixing temperature is the modified polyacetal (1a),
In the temperature range from the lower limit (eg, melting point) of the melting temperature of each of the unmodified polyacetal (1b), the modified polymer (2a) and the unmodified polymer (2b) to the decomposition temperature, overlapping temperature ranges, for example, 100-240 ° C, preferably 130-230 ° C, more preferably 160-240 ° C
It can be appropriately selected from the range of about 220 ° C.

When the modified polyacetal (1a) is produced by melt mixing as described above, the unmodified polyacetal (1b), modified polymer (2a) or unmodified is added to the melt mixing system of the polyacetal and the polymerizable compound. Polymer (2b)
It is also possible to obtain the composition of the present invention by coexisting with.

In the case of mixing in a solution state, the modified polyacetal (1a), the unmodified polyacetal (1b), the modified polymer (2a) and the unmodified polymer (2b) are dissolved or dispersed in a common solvent and mixed. For example, the composition can be obtained by, for example, a method of removing the solvent by means such as heating or decompression, a method of injecting the solution or dispersion into a poor solvent for both resins to cause precipitation. The method of mixing in a solution state is the above-mentioned components (1a) (1b) (2a) and (2b)
This is effective when the meltable temperatures do not overlap with each other or when the meltable temperatures are significantly different.

Further, the modified polyacetal and the modified polymer exhibit high affinity, compatibility and wettability with respect to the reinforcing agent and the filler depending on the kind and the amount of the functional group of the polymerizable compound. Therefore, in the present invention, a resin composition further containing a reinforcing agent, a filler and the like is also preferable. Examples of the reinforcing agent include organic fibers (for example, polypropylene fibers,
Vinylon fiber, polyacrylonitrile fiber, polyamide fiber, aramid fiber, polyester fiber, etc.), inorganic fiber (glass fiber, alumina fiber, carbon fiber, metal fiber, etc.) and whiskers (eg alumina, beryllium oxide, boron carbide, silicon carbide) , Whiskers such as silicon nitride) and the like. These reinforcing agents may be used alone or in combination of two or more.

As the filler, for example, alumina, silica, kaolin, clay, glass, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, potassium titanate, and dinitrate. Examples thereof include molybdenum sulfide, carbon, graphite and metal powder. These fillers may be used alone or in combination of two or more.

The amounts of the reinforcing agent and the filler used can be selected in accordance with the types of the reinforcing agent and the filler, so long as the characteristics such as moldability are not impaired. For example, a thermoplastic resin and a modified polyacetal are used. Reinforcing agent and / or filler is 1 to 500 parts by weight, preferably 5 to 250 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the resin composition.
It can be selected from a range of about parts by weight.

Further, the resin composition may contain a stabilizer such as an antioxidant and an ultraviolet absorber, an antistatic agent, if necessary.
It may contain additives such as a lubricant, a flame retardant, and a coloring agent. The antioxidant may be added to the modified polyacetal.

The thermoplastic resin composition of the present invention is useful in obtaining various molded products by molding. Molded products are
It can be obtained by a conventional method such as injection molding or extrusion molding.

[0091]

INDUSTRIAL APPLICABILITY The modified resin composition of the present invention can effectively alloy polyacetal and a wide range of modified polymers with the modified polyacetal, and can effectively exhibit the characteristics of the polyacetal and the modified or unmodified polymer. Also,
With the modified polyacetal and the modified polymer, even an unmodified polymer that is incompatible with the polyacetal can be combined with the polyacetal, and a resin composition having high weld strength and elongation can be obtained. In the method of the present invention, the resin composition having the above-mentioned high properties can be efficiently obtained by a simple operation of mixing the above-mentioned components. Furthermore, by using a modified polyacetal modified in the absence of a reinforcing agent or a filler, it is possible to efficiently cope with the preparation of various resin compositions containing polyacetal,
The degree of freedom for use can be expanded.

[0092]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. [Preparation of Modified Polyacetal] Preparation Example 1 (Preparation of Modified Polyacetal 1) (A) Polyacetal [manufactured by Polyplastics Co., Ltd.,
Trade name DURACON M25, polyacetal copolymer,
Melt flow rate 2.5 g / 10 minutes (190 ° C., 2.
16 kg)] 95 parts by weight and (B) polymerizable compound [N
-[4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide (Kanefuchi Chemical Industry Co., Ltd.)
Made, trade name AXE]] 5 parts by weight (polyacetal 10
After dry-blending (5.3 parts by weight with respect to 0 parts by weight), the mixture was melt-kneaded with a twin-screw extruder at a temperature of 190 ° C. for about 2 minutes to obtain pellets. The resulting pellets and (C) radical generator [α, α'-bis (t-butylperoxy-m
-Isopropyl) benzene (produced by NOF CORPORATION, trade name Perbutyl P)] 0.1 part by weight (polyacetal 100
(0.11 parts by weight with respect to parts by weight) was dry blended, and then melt-kneaded again at a temperature of 190 ° C. for about 2 minutes by a twin-screw extruder to obtain modified polyacetal pellets.

The amount of modification with the polymerizable compound was 1.9% by weight. The amount of modification was measured as follows.
In order to remove the (B) polymerizable compound that did not bind to the polyacetal, the modified polyacetal was purified by the reprecipitation method, and the (B) polymerizable compound introduced into the polyacetal was quantified by proton NMR. The modification amount was expressed as a weight% as a ratio to the polyacetal component. In addition, reprecipitation was performed using modified polyacetal 15
A solution of 0 mg and 4 ml of hexafluoroisopropanol was added dropwise to the reprecipitation solvent (acetone), and the precipitated polymer was recovered by filtration. This operation was repeated three or more times to purify the modified polyacetal.

Preparation Example 2 (Preparation of modified polyacetal 2) (A) 90 parts by weight of polyacetal and (B) polymerizable compound [N- [4- (2,3-epoxypropoxy)-
A modified polyacetal was obtained in the same manner as in Preparation Example 1 except that 10 parts by weight of 3,5-dimethylbenzyl] acrylamide (11 parts by weight based on 100 parts by weight of polyacetal) was used. The amount of modification with the polymerizable compound was 3.3% by weight.

Preparation Example 3 (Preparation of Modified Polyacetal 3) Preparation Example 1 is the same as Preparation Example 1 except that 5.3 parts by weight of the polymerizable compound [glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.) is used with respect to 100 parts by weight of polyacetal. Example 1
A modified polyacetal was obtained in the same manner as in. The amount of modification with the polymerizable compound was 1.5% by weight. In purification by reprecipitation, chloroform was used as a solvent for reprecipitation.

Preparation Example 4 (Preparation of modified polyacetal 4) In Preparation Example 1, the polymerizable compound [2-vinyl-2-oxazoline (the method described in JP-A-63-10773) was used with respect to 100 parts by weight of the polyacetal. Was synthesized in accordance with the procedure)], and a modified polyacetal was obtained in the same manner as in Preparation Example 1 except that 5.3 parts by weight was used. The amount of modification with the polymerizable compound was 1.3% by weight. In purification by reprecipitation, chloroform was used as a solvent for reprecipitation.

Preparation Example 5 (Preparation of Modified Polyacetal 5) In Preparation Example 1 except that 5.3 parts by weight of the polymerizable compound [maleic anhydride (Tokyo Kasei Kogyo Co., Ltd.)] is used with respect to 100 parts by weight of polyacetal. A modified polyacetal was obtained in the same manner as in Preparation Example 1. The amount of modification with the polymerizable compound was 2.0% by weight, and chloroform was used as a solvent for reprecipitation during purification by reprecipitation.

Preparation Example 6 (Preparation of modified polyacetal 6) 3.3 wt% of 1,3-dioxolane, 0.8 wt% of allyl glycidyl ether and 100 ppm of methylal were added to trioxane containing boron trifluoride and trioxane. To 60ppm to cationically polymerize,
A polymerizable polyacetal was prepared. A modified polyacetal was obtained in the same manner as in Preparation Example 1 except that the polymerizable polyacetal was used instead of the polyacetal in Preparation Example 1. The amount of modification with the polymerizable compound was 3.1% by weight.

Preparation Example 7 (Preparation of modified polyacetal 7) 3.3% by weight of 1,3-dioxolane and 400 pp
To trioxane containing m-divinyl formal, 60 ppm of boron trifluoride was added with respect to trioxane, and cationic polymerization was performed to prepare a polymerizable polyacetal.
A modified polyacetal was obtained in the same manner as in Preparation Example 1 except that the polymerizable polyacetal was used instead of the polyacetal in Preparation Example 1. The amount of modification with the polymerizable compound was 2.5% by weight.

Preparation Example 8 (Preparation of modified polyacetal 8) 150 ppm of allyl alcohol as a chain transfer agent, 5.5 of dibutyltin dimethoxide as an anionic polymerization catalyst
Formaldehyde gas having a purity of 99.9% was supplied to 500 parts by weight of cyclohexane containing x10 ^-4 mol / L at a rate of 100 parts by weight / hr. In addition to the supply of formaldehyde, cyclohexane containing the chain transfer agent and the anionic polymerization catalyst at the same concentration as above is also added.
It was fed at a rate of 0 parts by weight / hr. And temperature 55 ℃
Polymerize for 3 hours, separate the polymer from cyclohexane,
A polymerizable polyacetal was prepared by washing, drying and acetylating. A modified polyacetal was obtained in the same manner as in Preparation Example 1 except that the polymerizable polyacetal was used instead of the polyacetal in Preparation Example 1. The amount of modification with the polymerizable compound was 2.4% by weight.

Examples 1 to 11 and Comparative Examples 1 to 3 (1a) modified polyacetals 1 to 4 obtained in the above preparation examples and (1b) polyacetal (manufactured by Polyplastics Co., Ltd., Duracon M90) And (2a) acid anhydride-modified olefin elastomer (Mitsui Petrochemical Industry Co., Ltd.,
N-Tufmer MP0620) and (2b) olefin elastomer (Mitsui Petrochemical Co., Ltd., Tufmer P068)
0) was dry-blended in the proportions shown in Tables 1 and 2, and then melt-kneaded at 190 ° C. in a twin-screw extruder to form pellets. This pellet was molded by an injection molding machine to prepare a weld test piece (thickness 2 mm) having gates at both ends. When the weld strength and weld elongation of the obtained test piece were measured according to ASTM D638, the results shown in Table 1 and Table 2 were obtained.

[0102]

[Table 1]

[0103]

[Table 2] From Table 1 and Table 2, as compared with the resin composition of Comparative Example, using the resin composition of Example containing the modified polyacetal,
Weld strength and elongation can be greatly improved.

Examples 12 to 34 and Comparative Examples 4 to 8 (1a) Modified polyacetals 1 to 8 obtained in the above Preparation Example and (1b) Polyacetal (manufactured by Polyplastics Co., Ltd., DURACON M90) And (2a) acid anhydride-modified low-density polyethylene resin (Mitsui Petrochemical Industry Co., Ltd.,
N-Tufmer TX-436) or (2a) ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., Bondfast 2C) and low density polyethylene resin (Nippon Petrochemical Co., Ltd., Lexron W3300) are listed. When the weld strength and weld elongation of the test pieces prepared in the same manner as in the above-mentioned Examples were measured except that the proportions shown in 3 to 6 were used, the results shown in Tables 3 to 6 were obtained.

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

[0108]

[Table 6] From Tables 3 to 6, the resin compositions of Examples containing the modified polyacetal have higher weld strength and elongation than the resin compositions of Comparative Examples.

Examples 35 to 52 and Comparative Examples 9 to 13 (1a) modified polyacetals 1 to 4 obtained in the above preparation examples and (1b) polyacetal (manufactured by Polyplastics Co., Ltd., DURACON M90) And (2a) acid anhydride-modified polypropylene resin (Sanyo Kasei Co., Ltd., Umex 1001) and (2b) polypropylene resin (Sumitomo Chemical Co., Ltd., Noblen D501) at the ratios shown in Tables 7 to 9. A test piece was prepared in the same manner as in the above-described example except that it was used, and the weld strength and weld elongation of the test piece were measured, and the results shown in Tables 7 to 9 were obtained.

[0110]

[Table 7]

[0111]

[Table 8]

[0112]

[Table 9] From Tables 7 to 9, the resin compositions of Examples containing the modified polyacetal have higher weld strength and elongation than the resin compositions of Comparative Examples.

Examples 53 to 70 and Comparative Examples 14 to 18 (1a) modified polyacetals 1 to 4 obtained in the above preparation example and (1b) polyacetal (manufactured by Polyplastics Co., Ltd., DURACON M90) And (2a) styrene-
Acrylic Chemical Co., Ltd. (Dailark 250, manufactured by Arco Chemical Co., Ltd.) and high impact polystyrene resin (2b) (Daicel Chemical Industry Co., Ltd., Daicel Styrol HITS R)
80) was used in the proportions shown in Tables 10 to 12, and test pieces were prepared in the same manner as in the above-mentioned Examples, and the weld strength and weld elongation of the test pieces were measured.
The results shown in 12 were obtained.

[0114]

[Table 10]

[0115]

[Table 11]

[0116]

[Table 12] From Table 10 to Table 12, as compared with the resin compositions of Comparative Examples, the resin compositions of Examples containing the modified polyacetal have higher weld strength and elongation.

Examples 71 to 79 and Comparative Examples 19 to 22 (1a) modified polyacetals 1 to 4 obtained in the above preparation examples and (1b) polyacetal (manufactured by Polyplastics Co., Ltd., DURACON M90) And (2a) modified acrylic resin (methyl methacrylate-methacrylic acid copolymer obtained by radical polymerization of methyl methacrylate and methacrylic acid in a weight ratio of 95/5, number average molecular weight 3 × 10 ⁴ ).
And (2b) acrylic resin (Sumitomo Chemical Co., Ltd., Sumivex LG6) in the proportions shown in Table 13 and Table 14, except that the test pieces were prepared in the same manner as in the above-mentioned Examples, and the weld strength of the test pieces was prepared. When the weld elongation was measured, the results shown in Tables 13 and 14 were obtained.

[0118]

[Table 13]

[0119]

[Table 14] From Table 13 to Table 14, the resin compositions of Examples containing the modified polyacetal have higher weld strength and elongation than the resin compositions of Comparative Example. The resin composition of Comparative Example 20 could not be molded, and the characteristics of the test piece could not be measured.

Examples 80 to 81 and Comparative Example 23 (1a) modified polyacetal 1 obtained in the above preparation example, (1b) polyacetal (manufactured by Polyplastics Co., Ltd., DURACON M90), and (2a) ) Acid-modified styrene-acrylonitrile-butadiene copolymer (acid-modified A
ABS resin (manufactured by Daicel Chemical Industries, Ltd., ABS DP
T651) and (2b) styrene-acrylonitrile-butadiene copolymer (ABS resin) (manufactured by Daicel Chemical Industries, Ltd., ABS DPT611) were used in the same manner as in the above-mentioned examples except that the ratios shown in Table 15 were used. Pieces were prepared. Weld strength of the obtained test piece, weld elongation,
When the flexural strength and flexural modulus were measured, the results shown in Table 15 were obtained.

[0121]

[Table 15] From Table 15, the resin compositions of Examples have higher weld strength, weld elongation, bending strength, and bending elastic modulus than the resin compositions of Comparative Examples.

Claims (16)

[Claims] 1. A modified resin composition comprising a modified polyacetal resin composition (I) containing a modified polyacetal (1a) and a modified polymer composition (II) containing a modified polymer (2a) other than the modified polyacetal. . 2. A modified polyacetal resin composition (I)
Is composed of 1 to 100% by weight of the modified polyacetal (1a) and 0 to 99% by weight of the polyacetal (1b), and the modified polymer composition (II) is the modified polymer (2a) 1 to 100%.
Wt% and unmodified polymer other than polyacetal (2b)
The modified resin composition according to claim 1, which is composed of 0 to 99% by weight. 3. The modified resin composition according to claim 2, wherein the unmodified polymer (2b) is an unmodified polymer corresponding to the modified polymer (2a). 4. The ratio of the modified polyacetal resin composition (I) and the modified polymer composition (II) is the former (I) / the latter (II) = 1/99 to 99/1 (weight ratio). Item 1. The modified resin composition according to item 1. 5. The modified polyacetal (1a) is an epoxy group, a carboxyl group, an acid anhydride group, an ester group, a hydroxyl group, an ether group, an amide group, an amino group, a nitrile group, an isocyanate group, an imide group or a cycloalkyl group. ,
The residue of the polymerizable compound having at least one functional group selected from the group consisting of an aryl group and a heterocyclic group having a nitrogen atom as a hetero atom is a modified polyacetal introduced into a polyacetal component.
The modified resin composition described. 6. The modified polyacetal (1a) comprises a residue of a polymerizable compound in an amount of 0.1 to 30 relative to the polyacetal component.
The modified resin composition according to claim 1, which is a modified polyacetal having a weight% introduced therein. 7. The modified polyacetal (1a) comprises a polyacetal component, wherein the residue of the polymerizable compound is 0.2 to 25.
The modified resin composition according to claim 1, which is a modified polyacetal having a weight% introduced therein. 8. The modified resin composition according to claim 5, wherein the polymerizable compound having a functional group has one ethylenically unsaturated bond in one molecule. 9. A polymerizable compound having a functional group comprises one ethylenic double bond in one molecule, an epoxy group, a carboxyl group, an acid anhydride group, an ester group, a hydroxyl group,
At least one functional group selected from the group consisting of an N-substituted amide group having a non-condensable functional group bonded to a nitrogen atom, an amino group, a nitrile group, an isocyanate group, an imide group, a cyclic iminoester group and a cyclic iminoether group. The modified resin composition according to claim 5, which is a compound having a boiling point of 70 ° C. or higher at normal pressure. 10. The modified resin composition according to claim 5, wherein the polymerizable compound having a functional group is an ethylenic polymerizable compound having an epoxy group, a carboxyl group, an acid anhydride group, or an amide bond and an epoxy group. 11. A polymerizable compound having a functional group is maleic anhydride or a compound represented by the following formula (1): (Wherein, R ¹ is a hydrogen atom or a methyl group, R ^{2 to} R ⁵ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group. The modified resin composition according to claim 5, which is a compound represented by the formula (n is 0 or 1). 12. The modified polyacetal (1a) has one ethylenically unsaturated bond in the molecule and has a boiling point of 120.
The modified resin composition according to claim 5, wherein the residue of the polymerizable compound at a temperature of not less than 0 ° C. is a modified polyacetal introduced in an amount of 0.3 to 20% by weight based on the polyacetal component. 13. The modified polymer (2a) is an olefin polymer, a diene polymer, an acrylic polymer, a styrene polymer, a vinyl polymer, a polyether,
Selected from the group consisting of polyphenylene ether, polysulfone, polyether sulfone, polyetherimide, and polyamideimide, and epoxy group, carboxyl group, acid anhydride group, ester group, hydroxyl group, ether group, amide group, amino group, The modified resin composition according to claim 1, which is a thermoplastic resin into which at least one functional group selected from the group consisting of an imide group, an isocyanate group, and a heterocyclic group having a nitrogen atom as a hetero atom is introduced. 14. The unmodified polymer (2b) is polyethylene, polypropylene, ethylene-α-olefin copolymer, olefin elastomer, polymethyl methacrylate, acrylic rubber, polystyrene, styrene copolymer, polyvinyl chloride, Polyphenylene ether, polysulfone, polyether sulfone, polyetherimide,
The modified resin composition according to claim 2, which is an unmodified thermoplastic resin selected from the group consisting of: 15. A modified polyacetal resin composition (I) containing 5 to 95% by weight of modified polyacetal (1a) and 95 to 5% by weight of polyacetal (1b), and 5 to 95% by weight of modified polymer (2a) other than modified polyacetal. % And a modified polymer composition (II) containing 95 to 5% by weight of an unmodified polymer (2b) other than polyacetal, and a ratio of the modified polyacetal resin composition (I) and the modified polymer composition (II). However, the former (I) / the latter (II) = 5
/ 95-95 / 5 (weight ratio), The modified resin composition according to claim 1. 16. A modified resin composition comprising mixing a modified polyacetal resin composition (I) containing a modified polyacetal (1a) and a modified polymer composition (II) containing a modified polymer (2a) other than the modified polyacetal. Method.