JPH0995594A - Thermoplastic resin composition and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the mechanical properties, electrical properties, thermal properties, etc., of a thermoplastic resin by enhancing the affinity of the thermoplastic resin for a filler to effectively composite them. SOLUTION: This resin compsn. comprises (1) a thermoplastic resin such as polyacetal, (2) a modified polyacetal having residues of a polymerizable compd. introduced thereinto in an amt. of 0.1 to 30wt.% based on the polyacetal component, provided that the polymerizable compd. has a functional group such as an epoxy group, a carboxyl group or an acid anhydrive group, and (3) a filler. The proportion of the components is such that thermoplastic resin (1)/modified polyacetal (2)=ca. 99/1 to 50/50 (wt. ratio), and total amt. of components (1) and (2)/filler (3)=ca. 50/50 to 99.9/0.1 (wt. ratio).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition containing a modified polyacetal having improved affinity with a polymer and a filler, 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. Further, in order to improve mechanical properties and electrical properties, thermoplastic resins such as polyacetal are added with various fillers such as glass fiber and calcium carbonate. However, since the polyacetal has a low affinity for the filler, the properties of the resin and the filler are not effectively expressed, and it is difficult to effectively form a complex with the polyacetal or the filler. Further, it is difficult to impart high strength, rigidity, abrasion resistance, non-deformability and the like to the molded product by adding a small amount of the filler. In order to improve the affinity of the polyacetal for the filler, 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. 43-23
No. 467, Japanese Patent Publication No. 47-19425, Japanese Patent Laid-Open No. 3-21618, Japanese Patent Laid-Open No. 3-21619, etc.). However, all of these methods use comonomers having various modifying groups as a substituent (for example, aminoaldehyde, nitro group, nitrile group, carboxyl group or cyclic ether having amide group) with formaldehyde or trioxane in the polymerization process. Alternatively, a modifying group is directly introduced by copolymerization using a cyclic acetal). Therefore, in either method, the polymerization reactivity decreases, and it is difficult to obtain a high molecular weight copolymer in a high yield.

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 Bulletin). However, in these methods, the efficiency of introducing the modifying group is extremely low, and the polyacetal is decomposed and deteriorated during the treatment. For example, when a razyl cal initiator and a polyacetal are melt-kneaded, the polyacetal resin is oxidatively decomposed by the radical polymerization initiator to lower the molecular weight (JP-A-60-219252, JP-A-49-7479).
No. 0, 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. Further, as the polyacetal has a lower molecular weight, it is not possible to sufficiently improve the mechanical properties of the resin composition even if it is compounded with a filler. From such a point, the above method cannot be said to be an effective modification method of polyacetal. Furthermore, since the composition obtained by these methods contains a specific reinforcing agent in advance, it is necessary to prepare the resin composition for each application. In order to solve such a problem, JP-A-5-214
No. 212 discloses that a polyoxymethylene resin is modified by adding a modified polyolefin modified with a polymerizable monomer having a glycidyl group and an amide bond without directly modifying the polyacetal. .

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a thermoplastic resin composition capable of enhancing the affinity between the thermoplastic resin and the filler and effectively expressing the characteristics of the thermoplastic resin and the filler. To do. Another object of the present invention is to
It is an object of the present invention to provide a thermoplastic resin composition capable of exhibiting high mechanical properties, electrical properties, thermal properties and the like by effectively combining a polyacetal and a filler. Still another object of the present invention is to provide a production method capable of efficiently obtaining a resin composition having the above-mentioned high properties by a simple operation.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that modified polyacetal obtained by modifying polyacetal with a polymerizable compound can be used not only for thermoplastic resins such as polyacetal but also for various filling. The present invention has been completed by finding that it has a high affinity for the agent and can effectively combine the thermoplastic resin and the filler.

That is, the thermoplastic resin composition of the present invention comprises the thermoplastic resin (1), 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 and a nitrile. Group, an isocyanate group, an imide group, an aryl group, and a residue of a polymerizable compound having at least one functional group selected from the group consisting of a heterocyclic group having a nitrogen atom as a hetero atom,
It contains a modified polyacetal (2) introduced into the polyacetal component and a filler (3). The thermoplastic resin (1) includes various resins such as polyacetal. The introduced amount of the residue of the polymerizable compound in the modified polyacetal is about 0.1 to 30% by weight. In the method of the present invention, a thermoplastic resin composition is produced by mixing the thermoplastic resin (1), the modified polyacetal (2) and the filler (3).

In the present specification, the term "polyacetal" means an unmodified polyacetal homopolymer or polyacetal copolymer, unless otherwise specified. Further, the “residue of the polymerizable compound” means not only the monomer unit of the polymerizable compound but also a polymer thereof (for example, a dimer, trimer, tetramer or polymer component produced by polymerization). In addition, "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”. Furthermore, the term "filler" is used to include a reinforcing filler (reinforcing agent) and the like.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Thermoplastic resin (1), modified polyacetal (2) and filler (3) constituting the resin composition of the present invention
Is as follows.

(1) Thermoplastic resin "Thermoplastic resin" means a thermoplastic resin other than the modified polyacetal. The type of the thermoplastic resin is not particularly limited, for example, olefin polymer, diene polymer, acrylic polymer, styrene polymer, vinyl polymer such as polyvinyl chloride, polyester, polyamide, polycarbonate, polyurethane, polyether, Examples include polyacetal, polyphenylene ether, polysulfone, polyether sulfone, polyetherimide, polyamideimide, fluorine-containing resin, and other thermoplastic resins.

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 copolymer, block copolymer, (Graft copolymer), a random copolymer, a block copolymer, a graft copolymer and the like, which contains the above α-olefin as a main component and at least one comonomer component. Examples of the comonomer component include non-conjugated dienes (1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 2,
5-norbornadiene etc.), conjugated dienes (eg butadiene, isoprene, piperylene etc.), α, β-unsaturated carboxylic acids or derivatives thereof (eg acrylic acid, methacrylic acid, their anhydrides, alkyl (meth) acrylate) Ester etc.), acrylonitrile, aromatic vinyl compound (eg styrene, α-methylstyrene etc.), vinyl ester (eg vinyl acetate etc.), vinyl ether (eg vinyl methyl ether etc.),
Derivatives of these vinyl compounds 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 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- Ethylene-vinyl ester copolymers such as olefin copolymers (for example, ethylene-propylene copolymer, ethylene-1-butene copolymer, etc.), ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, etc. , Ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer (for example, ethylene-ethyl acrylate copolymer, etc.), ionomer and the like. Preferred olefin-based polymers include ethylene-α-olefin copolymers such as polyethylene, polypropylene, ethylene-propylene copolymers and ethylene-1-butene copolymers.

The diene polymer includes homopolymers or copolymers mainly composed of conjugated dienes such as butadiene, isoprene and chloroprene. Examples of the diene-based polymer include polybutadiene, polyisoprene, polychloroprene, and acrylonitrile-butadiene copolymer.

Examples of the styrene 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), and a copolymer of the aromatic vinyl compound and an acrylic monomer and / or maleic anhydride or a derivative thereof. Examples of acrylic monomers include acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid,
(Meth) such as methyl acrylate and methyl methacrylate
Examples of the acrylic acid ester include maleic anhydride or a derivative thereof such as maleic anhydride and N-
Examples include methylmaleimide and N-phenylmaleimide. In addition, the aromatic vinyl compound and an acrylic monomer are combined with a diene monomer (such as butadiene), an olefin (such as ethylene or propylene) or an elastomer (butadiene rubber, acrylic rubber, chlorinated polyethylene, ethylene-propylene-diene rubber, ethylene-acetic acid). A copolymer obtained by polymerizing with a rubber component such as a vinyl copolymer) or a hydrogenated product thereof can also be used. These copolymers are not particularly limited in the form of copolymerization such as random, block, and graft, the degree of polymerization, the presence or absence of side chains or branches and their degree, and the copolymer composition ratio. Examples of the styrene-based polymer include polystyrene, styrene- (meth) acrylic acid copolymer, acrylonitrile-styrene copolymer,
Impact-resistant polystyrene, styrene-maleic anhydride copolymer, styrene-methyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylonitrile-butadiene copolymer Hydrogenated products, styrene-acrylonitrile-ethylene copolymers, styrene block copolymers (for example, styrene-butadiene-styrene (SBS) copolymers, styrene-isoprene-styrene (SIS) copolymers, styrene-ethylene-butylene- Styrene (SEBS) copolymer and the like) are included. Preferred styrenic polymers include polystyrene, acrylonitrile-styrene copolymers, styrene-maleic anhydride copolymers, high impact polystyrene, styrene-acrylonitrile-butadiene copolymers, styrenic block copolymers and the like.

Acrylic polymers include homopolymers or copolymers containing acrylic acid, methacrylic acid or their ester units as main components, for example, polymethylmethacrylate,
Methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate-alkyl acrylate copolymer, acrylic-styrene copolymer, acrylic rubber and the like are included. Of these acrylic resins, polymethylmethacrylate, acrylic rubber, etc. are often used.

Examples of the vinyl polymer include polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl ether, polyvinyl ketone, polyvinyl pyrrolidone, and vinyl chloride-vinyl acetate copolymer, in addition to the polyvinyl chloride.

The polyester means a polymer having an ester bond in the main chain, and is obtained by polycondensation of dicarboxylic acid or its derivative with a dihydric alcohol, polycondensation of hydroxycarboxylic acid, or ring-opening polymerization of cyclic ester. To be The polyester includes, for example, polyalkylene terephthalate (eg, polyethylene terephthalate, polybutylene terephthalate, etc.), a copolyester containing alkylene terephthalate as a main repeating unit and further containing a copolymerization component such as isophthalic acid, bisphenol A, cyclohexanedimethanol, Aromatic polyesters (for example, polyarylate produced by esterification of aromatic diol such as bisphenol A and aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid) are included. The liquid crystal polyester and the elastomer are also included in the polyester. Of these polyesters, polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, aromatic polyesters, liquid crystalline polyesters and polyester elastomers are preferable.

Polyamide is a polymer having an amide bond in the main chain, and is usually obtained by polycondensation of dicarboxylic acid and diamine or ring-opening polymerization of a cyclic lactam. Polyamides include aliphatic polyamides (eg, polyamide 6, polyamide 12, polyamide 11, polyamide 4).
6, polyamide 66, polyamide 610, polyamide 6
12 and copolymerized polyamides containing the constituent monomer units of these polyamides) and aromatic polyamides.
Polyamides also include liquid crystal polyamides, liquid crystal copolyesteramides and elastomers. Among these polyamides, aliphatic polyamides such as polyamide 6, polyamide 66, polyamide 11 and polyamide 12, aromatic polyamides, liquid crystalline copolyesteramides and polyamide elastomers are preferable.

Polycarbonate means a polymer having a carbonate bond in the main chain, and is usually obtained by polycondensation of a dihydroxy compound and phosgene or transesterification reaction of a dihydroxy compound and a carbonic acid ester. The polycarbonate may be any of aliphatic, alicyclic and aromatic polycarbonates. Preferred polycarbonates include aromatic polycarbonates, especially
Bisphenol type polycarbonates such as bisphenol A type polycarbonates are included.

Polyurethane is a polymer having a urethane bond in its main chain. For example, polyisocyanate components such as aliphatic, alicyclic and aromatic polyisocyanates (hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane). (Diisocyanate, naphthalene diisocyanate, etc.)
And a thermoplastic polyurethane formed by the reaction of a low molecular weight to high molecular weight polyol component (ethylene glycol, propylene glycol, 1,4-butanediol, polyester diol, polyether diol, polycarbonate diol, etc.). The polyurethane may be an elastomer.

Polyether is a polymer having an ether bond in the main chain and is obtained by ring-opening polymerization of cyclic ether and self-condensation of glycol. Polyether includes, for example, polyethylene oxide, polypropylene oxide, polytetramethylene oxide, and the like.

Polyacetal (polyacetal component) is a polymer compound containing an oxymethylene group (--CH ₂ O--) as a main constituent unit. Polyacetals include polyoxymethylene homopolymers and polyacetal copolymers. In addition to the oxymethylene group, this copolymer has about 2 to 6 carbon atoms, preferably 2 to 6 carbon atoms.
It contains about 4 oxyalkylene units (eg, oxyethylene group (—CH ₂ CH ₂ O—), oxypropylene group, oxytetramethylene group) as constituent units. 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 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.

Further, the thermoplastic resins other than polyacetal include engineering plastics such as polyphenylene ether (polyphenylene oxide) such as polyphenylene ether and modified polyphenylene ether, polysulfone, polyether sulfone, polyether imide and polyamide imide. .

Examples of the fluorine-containing resin include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether,
Homogeneous or copolymers containing fluorine-containing monomer units such as vinylidene fluoride and vinyl fluoride, for example, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoro Examples thereof include ethylene-perfluoroalkyl vinyl ether copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride.

Other thermoplastic resins include, for example,
Examples thereof include cellulosic polymers such as cellulose acetate and polymer particles having a multiphase structure such as a core-shell structure.

[0027] Of these thermoplastic resins, in order to effectively exhibit excellent properties by compounding with a filler,
For example, polyethylene, polypropylene, ethylene-α
-Olefin polymers such as olefin copolymers and olefin elastomers; acrylic polymers such as polymethylmethacrylate and acrylic rubber; polystyrene,
Impact-resistant polystyrene, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-based polymers such as styrene-based polymers; polyvinyl chloride; polyalkylene terephthalate, alkylene terephthalate Polyesters mainly containing, polyesters such as liquid crystalline polyesters and polyester elastomers; aliphatic polyamides (eg, polyamide 6, polyamide 66, polyamide 11, polyamide 12), aromatic polyamides, liquid crystalline copolyesteramides, polyamides Polyamides such as elastomers; polycarbonates such as bisphenol A type polycarbonates; polyurethanes; polyacetals; polyphenylene ethers; polices Hong; polyether sulfone; polyetherimides; polyamideimide; and fluorine-containing resins such as polytetrafluoroethylene is preferable. Particularly preferred thermoplastic resins include olefin elastomers; acrylic elastomers such as acrylic rubber; impact-resistant polystyrene, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-butadiene copolymer, Styrene-based polymers such as styrene-based block copolymers; polyalkylene terephthalates, copolyesters mainly composed of alkylene terephthalates, polyarylate, polyesters such as liquid crystalline polyesters and polyester elastomers; aliphatic polyamides, aromatic polyamides, liquid crystalline copolyesteramides, Polyamides such as polyamide elastomers; polycarbonates such as bisphenol A type polycarbonates; polyurethanes, polyurethane elastomers; polyaceta Le; polyphenylene ether; polysulfones; polyethersulfones; polyetherimides; etc. polyamideimide. In particular, when a polyacetal, a modified polyacetal and a filler are combined, the properties of the filler are effectively exhibited, and a molded article having high mechanical properties, electrical properties, thermal properties and the like can be obtained. The thermoplastic resin (1) may be modified, but even if it is an unmodified thermoplastic resin, the modified polyacetal is used in combination to form a composite of the thermoplastic resin and the filler, and both properties are effective. Can be expressed in.

(2) Modified polyacetal The modified polyacetal is a polyacetal component (that is, a polyacetal homopolymer and a polyacetal copolymer) described in the section (1) Thermoplastic resin, or a polymerizable polyacetal, and a polymerizable compound having a functional group. It can be obtained by denaturing with. Less than,
The "polyacetal" and "polymerizable polyacetal" may be simply referred to as "(A) polyacetal".

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 polyacetal component. 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, a polyacetal having an ethylenically unsaturated bond polymerized by anionic polymerization in the presence of a chain transfer agent containing a 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 an ethylenically 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 can be obtained by introducing a residue of a polymerizable compound having a functional group into (A) polyacetal (that is, polyacetal or polymerizable polyacetal). The functional group of the polymerizable compound includes epoxy group, carboxyl group, acid anhydride group, ester group, hydroxyl group, ether group, amide group, amino group, nitrile group, isocyanate group, imide group, aryl group, and hetero atom. And a heterocyclic group having a nitrogen atom are included. 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 in increasing the affinity with additives such as the thermoplastic resin (1) and the filler (3). 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 compounds having a hydroxyl group and an ether group include 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, 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, p-methylstyrene, vinyltoluene, vinylnaphthalene, vinylanthracene and the like can be mentioned.

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).

[0050]

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.

Polymerizable compounds are 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 product, the modified polyacetal is a polyacetal modified with the above-mentioned polymerizable compound in the absence of a filler. When the modified polyacetal modified in the absence of a filler is used, the resin composition can be prepared only by mixing with a plurality of thermoplastic resins depending on the application, and the degree of freedom in alloying and compounding increases.

The amount of the functional group introduced can be selected within a range capable of improving the affinity with the thermoplastic resin (1) and the filler (3). For example, the amount of the polymerizable compound converted to the polyacetal (A) is 0.1 to 30% by weight (eg 0.1 to 2
0% by weight), preferably 0.2 to 25% by weight (for example, 0.2 to 15% by weight), and more preferably 0.3.
It is about 20% by weight (for example, about 0.3 to 10% by weight), and is often about 0.2 to 10% by weight.

The modified polyacetal can be produced by heating (A) polyacetal and (B) a polymerizable compound having a functional group, and introducing the residue of the polymerizable compound into the polyacetal. The (A) polyacetal and the (B) functional group-containing polymerizable compound may be heated in the absence of the (C) radical generator (polymerization initiator), but in the presence of the (C) radical generator. By heating at, the residue of the polymerizable compound can be introduced efficiently.

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 free radicals 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
-Butyl peroxy) valerate, peroxide esters such as t-butyl peroxy benzoate, and the like.

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, for example, 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,
It is often a peroxide ester or azo compound.

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. For example, (A) polyacetal 1
It is 0.1 to 30 parts by weight, preferably 0.3 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and most often 1 to 20 parts by weight, relative to 00 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.

The ratio of the radical generator (C) to the polyacetal (A) can be selected from the range in which the excessive reduction of the molecular weight of the polyacetal can be suppressed and the modification efficiency is not impaired. For example, 100 parts by weight of the polyacetal (A) is used. With respect to 3.5 parts by weight or less (for example, about 0.01 to 3.5 parts by weight), preferably 0.01 to 3 parts by weight, more preferably about 0.01 to 1.5 parts by weight, 0.05 ~
It is often about 0.5 part by weight. The ratio of the radical generator (C) to the total amount of the (A) polyacetal 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, the processing temperature, the processing time, etc. It can be selected according to, and 2. to 100 parts by weight in total of (A) polyacetal and (B) polymerizable compound.
5 parts by weight or less (for example, about 0.01 to 2.5 parts by weight), preferably 0.01 to 2 parts by weight, more preferably about 0.01 to 1 part by weight, and 0.05 to 0.5 parts by weight. It is often about weight part. 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. In addition, (B) polymerizable compound 100
The ratio of the (C) radical generator with respect to parts by weight is 0.1.
-25 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably about 1 to 10 parts by weight.

As a method for easily modifying the polyacetal, a method of mixing the polyacetal (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 or a roll mill 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. In the melt-mixing or melt-kneading treatment, (A) polyacetal, (B) polymerizable compound, and, if necessary, (C) radical generator are individually and sequentially supplied to the mixer or kneader, or two components ( A) (B)
Alternatively, the mixture of the three components (A), (B) and (C) may be simultaneously provided by using the above 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 (A) polyacetal and (C) radical generator are melt-mixed or melt-kneaded, the polyacetal is remarkably reduced in molecular weight due to the radical generator. On the contrary,
When (A) polyacetal and (C) radical generator are melt-mixed or melt-kneaded in the presence of (B) polymerizable compound, the polyacetal can be modified by the polymerizable compound and, depending on the amount of the radical generator, It is possible to prevent the molecular weight from becoming excessively low. Therefore, in the molten mixture of (A) polyacetal and (C) radical generator, (B)
When a polymerizable compound having a functional group is added and mixed in a molten state of the polyacetal, a modified polyacetal having a relatively low molecular weight modified by the polymerizable compound can be obtained. Such modified polyacetal is a compatibilizer or
It can be used as an adhesion improver for resins, metals, adhesives, paints, etc.

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, (A) polyacetal and (B) a polymerizable compound having a functional group are used. (C) The radical generator is added by mixing or kneading the three components with the radical generator in the molten state of the polyacetal, or in the coexistence of the (A) polyacetal and the (B) polymerizable compound,
A method of mixing or kneading in a molten state of polyacetal,
(C) A radical generator is added to a mixture of (A) polyacetal and (B) a polymerizable compound having a functional group, particularly a homogeneous mixture (preferably a compound or a melt mixture), and the polyacetal is mixed or kneaded in a molten state. The method of doing is useful. In such a method, the functional group of the polymerizable compound can be efficiently introduced while maintaining the high molecular weight and the excellent properties of the 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.

Such a method includes, for example, supplying the three components or 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 improve 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 carried out in the absence of a 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 a filler, the radical generator and the polymerizable compound can be effectively used for modifying the polyacetal, and since they are not modified by the filler used in a relatively large amount, By combining the modified polyacetal with fillers and various thermoplastic resins,
A wide range of compositions can be obtained.

If necessary, an additive, for example, a resin composition containing 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 triphenylphosphite. 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; Includes mercapto-henzoimidazole 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 (A) or in the modification process. The amount of antioxidant used is
(A) 0.00 based on 100 parts by weight of polyacetal
It is 1 to 2 parts by weight, preferably 0.01 to 1 part by weight. The modified polyacetal thus obtained may be pelletized if necessary.

The modified polyacetal (2) has a high affinity and compatibility with the thermoplastic resin (1) depending on the type and amount of the functional groups of the polymerizable compound, and High affinity and wettability for the filler (3). Therefore, the properties of the thermoplastic resin (1) and the filler (3) such as polyacetal are effectively exhibited, and mechanical properties such as strength, rigidity, and impact resistance, electrical properties such as conductivity, and heat deformation temperature are included. It is possible to greatly improve the thermal properties of the resin, the moldability such as warpage of molded products, the surface properties such as slipperiness, lubricity, printability, and adhesiveness.

(3) Filler The filler includes organic or inorganic fillers, and the kind thereof is not particularly limited. As the filler, powdery, fibrous, plate-like or hollow fillers are often used. Examples of the particulate filler include alumina, silica, kaolin, clay, talc, diatomaceous earth, wollastonite, calcium silicate, aluminum silicate, glass (glass beads), zinc oxide, magnesium oxide, zirconium oxide, and oxide. Titanium, aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, potassium titanate, molybdenum disulfide, carbon, inorganic powder such as metal powder (aluminum powder, copper powder, etc.), fluororesin, polypropylene, polyamide, acrylic An organic powdery material such as a resin is exemplified. The average particle diameter of the powdery filler is, for example,
0.01 to 100 μm, preferably 0.01 to 50 μm
m, and more preferably about 0.01 to 10 μm.

Examples of the fibrous filler include organic fibers (for example, polypropylene fibers, vinylon fibers, polyacrylonitrile fibers, polyamide fibers, aramid fibers, polyester fibers, etc.), inorganic fibers (glass fibers, silica fibers, alumina fibers, Zirconia fibers, carbon fibers, metal fibers, etc.) and whiskers (for example, whiskers of alumina, beryllium oxide, boron carbide, silicon carbide, silicon nitride, etc.) and the like. The fiber diameter of the fibrous filler is, for example, 0.1 to 200 μm, preferably 0.1 to 200 μm.
The thickness is 150 μm, more preferably about 0.1 to 100 μm. The fibrous filler is often used as a short fiber having a fiber length of 0.1 to 20 mm, preferably 0.1 to 10 mm. The aspect ratio of the fibrous filler is, for example,
It is 5 to 1,000, preferably about 10 to 500.
Examples of the plate-like filler include mica, glass flakes, graphite, various metal foils, and the like, and examples of the hollow filler include shirasu balloon, glass balloon, armosphere (fly ash ball), and the like.
These fillers include surface treatment agents such as organosilanes,
It may be surface-treated with organic borane, organic titanate or the like, and the surface-treated filler is preferable in many cases because it can more effectively impart the characteristics of the filler.

These fillers may be used either individually or in combination of two or more, depending on the application. For example, in order to increase rigidity and strength, fibrous fillers such as glass fiber and carbon fiber can be used, and in order to increase rigidity and suppress warpage, granular fillers can be used to improve wear resistance. Carbon fibers, lubricating inorganic substances such as molybdenum disulfide, and lubricating organic substances such as fluororesins can be used to increase the conductivity, and conductive fibers such as carbon fibers and metal fibers and carbon can be used to increase the conductivity. Conductive powder such as black can be used.

The ratio of the thermoplastic resin (1) to the modified polyacetal (2) can be selected from a wide range according to the desired characteristics of the resin composition. For example, the thermoplastic resin (1) /
Modified polyacetal (2) = 99/1 to 50/50 (weight ratio), preferably 95/5 to 60/40 (weight ratio),
More preferably, it is about 90/10 to 70/30 (weight ratio).

The ratio of the total amount of the thermoplastic resin (1) and the modified polyacetal (2) to the filler (3) is
It can be selected according to the type of each component, and for example, the total amount of the components (1) and (2) / the filler (3) = 50/50 to 9
9.9 / 0.1 (weight ratio), preferably 60 / 40-9
9.5 / 0.5 (weight ratio), more preferably 70/3
0 to 99/1 (weight ratio) and 70/30 to 95
It is often about / 5 (weight ratio).

The thermoplastic resin composition of the present invention can be prepared by various methods, for example, a powdery or granular thermoplastic resin (1), a powdery or granular modified polyacetal (2), and a powdery or granular filler (3) in a molten state. It can be manufactured by mixing with. When mixing in a molten state, a conventional mixer or kneader, for example, extruder, Brabender, kneader, Banbury mixer,
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 a temperature range from the lower limit (for example, melting point) of the melting temperature of the thermoplastic resin (1) and the melting temperature of the modified polyacetal (2) to the decomposition temperature. 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 (2) is produced by melt mixing as described above, the polyacetal and the polymerizable compound are melt mixed, and the polyacetal as the thermoplastic resin (1) and the modified polyacetal (2) are mixed.
It is also possible to obtain a resin composition composed of

The resin composition may optionally contain stabilizers such as antioxidants and ultraviolet absorbers, additives such as antistatic agents, lubricants, flame retardants and colorants.
The antioxidant may be added to the modified polyacetal as described above.

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

[0085]

INDUSTRIAL APPLICABILITY The resin composition of the present invention can improve the affinity between the thermoplastic resin and the filler by the modified polyacetal and can effectively exhibit the characteristics of the thermoplastic resin and the filler. In addition, thermoplastic resin and filler can be effectively compounded by modified polyacetal, and mechanical strength such as strength, rigidity and impact resistance, electrical characteristics such as conductivity, thermal characteristics such as heat deformation temperature, lubrication, etc. It is possible to greatly improve surface properties such as properties. In particular, when polyacetal is used as the thermoplastic resin, it is possible to obtain a resin composition having excellent properties. According to the method of the present invention, a resin composition having the above-mentioned high properties can be efficiently obtained by a simple operation of mixing a thermoplastic resin, a modified polyacetal and a filler. 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.

[0086]

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) 90 parts by weight of (A) 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 was used. The amount of modification by the polymerizable compound is 3.3% by weight
Met.

Preparation Example 3 (Preparation of Modified Polyacetal 3) Preparation Example 1 was the same as Preparation Example 1 except that 5.3 parts by weight of the polymerizable compound [glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.) was 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 except that 5.3 parts by weight of the polymerizable compound [maleic anhydride (Tokyo Kasei Kogyo Co., Ltd.)] was 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 reprecipitation solvent during purification by reprecipitation.

Preparation Example 5 (Preparation of modified polyacetal 5) 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 6 (Preparation of modified polyacetal 6) To trioxane containing 3.3% by weight of 1,3-dioxolane, 0.8% by weight of allyl glycidyl ether and 100 ppm of methylal, boron trifluoride and trioxane were added. 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 13 and Comparative Examples 1 to 3 The modified polyacetals 1 to 1 obtained in the above preparation examples
8 and polyacetal (manufactured by Polyplastics Co., Ltd.,
DURACON M90) and glass fiber (Chopped strand glass fiber manufactured by Asahi Fiber Glass Co., Ltd., fiber diameter 10 μm, fiber length about 3 mm) are dry-blended at the ratios shown in Table 1 and Table 2 and then biaxially extruded. At the machine 19
The mixture was melt-kneaded at 0 ° C. and pelletized. This pellet was molded by an injection molding machine to prepare a test piece. ASTM
The tensile strength of the obtained test piece was measured according to D638, and the bending strength and the flexural modulus were measured according to ASTM D790. Also, ASTM D256
The Izod impact strength was measured according to. Table 1 shows the results
And shown in Table 2.

[0096]

[Table 1]

[0097]

[Table 2] From Table 1 and Table 2, the mechanical properties are improved when the resin composition of the example containing the modified polyacetal is used as compared with the resin composition of the comparative example.

Examples 14 to 16 and Comparative Examples 4 to 6 Modified polyacetal 1 obtained in the above preparation example
And the polyacetal (manufactured by Polyplastics Co., Ltd., DURACON M90) and the following fillers in the proportions shown in Table 3 were used, and the mechanical properties of the test pieces prepared in the same manner as in the above Examples were measured. However, the results shown in Table 3 were obtained. The fillers used are as follows. Toho Rayon Co., Ltd., carbon fiber Toshiba Ballotini Co., Ltd., glass beads Nippon Sheet Glass Co., Ltd., glass flakes

[0099]

[Table 3] From Table 3, the resin composition of the example containing the modified polyacetal has higher mechanical properties than the resin composition of the comparative example.

Claims (12)

[Claims] 1. A thermoplastic resin (1) and 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, a cycloalkyl group. A modified polyacetal (2) in which a residue of a polymerizable compound having at least one functional group selected from the group consisting of a group, an aryl group, and a heterocyclic group having a nitrogen atom as a hetero atom is introduced into a polyacetal component (2) And a thermoplastic resin composition containing a filler (3). 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (1) is polyacetal. 3. The modified polyacetal (2) comprises a residue of the polymerizable compound in an amount of 0.1 to 30 relative to the polyacetal component.
The thermoplastic resin composition according to claim 1, which is a modified polyacetal having introduced therein wt%. 4. The thermoplastic resin composition according to claim 1, wherein the polymerizable compound having a functional group has one ethylenically unsaturated bond in one molecule. 5. 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. 2. The thermoplastic resin composition according to claim 1, which is a compound having a boiling point of 70 ° C. or higher at normal pressure. 6. The thermoplastic resin composition according to claim 1, 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. . 7. The 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 thermoplastic resin composition according to claim 1, which is a compound represented by the formula (n is 0 or 1). 8. The thermoplastic resin composition according to claim 1, wherein the filler is at least one selected from powdery, granular, fibrous, plate-like and hollow fillers. 9. The ratio of the thermoplastic resin (1) to the modified polyacetal (2) is thermoplastic resin (1) / modified polyacetal (2) = 99/1 to 50/50 (weight ratio). The thermoplastic resin composition according to 1. 10. The ratio of the total amount of the thermoplastic resin (1) and the modified polyacetal (2) to the filler (3) is such that the total amount of the components (1) and (2) / the filler (3) = 50 / Fifty
The thermoplastic resin composition according to claim 1, which is ˜99.9 / 0.1 (weight ratio). 11. A polyacetal (1) and 1 in the molecule
A composition comprising a modified polyacetal (2) having two ethylenically unsaturated bonds and modified by a polymerizable compound having a boiling point of 120 ° C. or higher, and a filler (3), the modified polyacetal (2) Is an epoxy group, a carboxyl group, an acid anhydride group, an ester group, a hydroxyl group, an amide group having a non-self-condensable functional group, an amino group, a nitrile group, an isocyanate group, an imide group, a cyclic iminoester group and a cyclic iminoether The residue of the polymerizable compound having at least one functional group selected from the group consisting of groups is 0.3 to 20% by weight based on the polyacetal component.
The modified polyacetal introduced, the total amount of the polyacetal (1) and the modified polyacetal (2),
The thermoplastic resin composition according to claim 1, wherein the ratio with the filler (3) is the total amount of the components (1) and (2) / the filler (3) = 70/30 to 99/1 (weight ratio). . 12. A thermoplastic resin (1), an epoxy group,
Carboxyl group, acid anhydride group, ester group, hydroxyl group, ether group, amide group, amino group, nitrile group,
A residue of a polymerizable compound having at least one functional group selected from the group consisting of an isocyanate group, an imide group, a cycloalkyl group, an aryl group, and a heterocyclic group having a nitrogen atom as a hetero atom, is introduced into the polyacetal component. The manufacturing method of the thermoplastic resin composition which mixes the modified polyacetal (2) and the filler (3).