JP2003048252A - Polyacetal resin composition/thermoplastic elastomer composite molding and method for molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite molding having an improved fusion bondability of an interface between a molding site made of a polyacetal resin having improved fusion bondability and a molding site made of a thermoplastic elastomer. SOLUTION: The composite molding is obtained by fusion bonding the molding site made of a polyacetal composition and a molding site made of the thermoplastic elastomer. The polyacetal composition is obtained by blending 1 to 100 pts.wt. of a polyalkylene terephthalate (having 2-4C alkylene group) copolymer having a melt flow temperature of 210 deg.C or lower and 0.1 to 15 pts.wt. of at least one compound selected from the group consisting of a core shell polymer (a) having a shell of a polymer made of a core of a rubber-like polymer and vinyl copolymer, an isocyanate compound (b), an isothiacyanate compound (c) and a modified material (d) of the compound (b) or (c) with 100 pts.wt. of the polyacetal resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molded article in which a molded article part made of a thermoplastic elastomer is fused to a molded article part made of a polyacetal resin composition, and a molding method thereof. The composite molded article is excellent in the fusion property between the molded body part made of the polyacetal resin composition and the molded body part made of the thermoplastic elastomer.

[0002]

2. Description of the Related Art Polyacetal (POM) resin, which is a type of engineering plastic, has excellent properties such as mechanical properties, thermal properties, electrical properties, slidability, and moldability. Widely used as materials and mechanical parts for electric / electronic devices, automobile parts, office equipment parts, daily sundries parts, etc. On the other hand, thermoplastic elastomers are excellent in flexibility, water resistance, cold resistance, etc. and are used in many applications. Known thermoplastic elastomers of this type include styrene-based, polyolefin-based, polyester-based, polyurethane-based and the like. The injection molding method is capable of molding even molded products with complicated shapes and is suitable for mass production.The injection molding method is applied to the above-mentioned polyacetal resin and thermoplastic elastomer, and various mechanical parts can be efficiently used. It is manufactured, or an elastomer molded body is molded with particularly high productivity. In recent years, demands for high performance and high functionality of synthetic resin (plastic) parts and members have become strict, and among them, attention has also been paid to the combination of engineering plastics and thermoplastic elastomers. Then, for compounding, it is most effective to heat-bond the two to each other (also simply referred to as fusion-bonding) by an injection molding method which is a molding means common to both.

However, in general, the thermal fusion bond between a thermoplastic engineering plastic and a thermoplastic elastomer is not always good. In particular, polyacetal resin has high crystallinity, poor surface activity, and low affinity with other resins, so that a composite molded product with a thermoplastic elastomer cannot obtain sufficient adhesive strength and fusion strength at the joint surface. There is a problem. Therefore, when trying to manufacture a composite molded body such as a high-value-added composite part or composite member by compositing a polyacetal resin and a thermoplastic elastomer, for example, by providing an uneven engaging portion at the joint between the two, mechanically Non-productive joining such as joining method, roughening the joining surface of polyacetal resin molded product side by flame treatment or hot air treatment or applying functional group, or applying adhesive to both joints Under the present circumstances, it is unavoidable to adopt a method or a method whose surface is easily deteriorated. For example, the method of mechanically joining by providing the above-mentioned concave and convex engaging portions,
There is a problem that the mold structure becomes complicated, or the number of steps increases depending on the structure. Further, it may not be possible to form a strong bond structure in view of the shape of the final composite molded body. In addition, the joining method using an adhesive may require a step such as application of the adhesive, and the adhesive strength may deteriorate due to deterioration of the adhesive.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems and to melt the interface between a molded body part made of a polyacetal resin having improved fusion bondability and a molded body part made of a thermoplastic elastomer. The object is to provide a composite molded article having improved adherence.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a polyacetal resin composition containing a specific polyalkylene terephthalate copolymer and a specific compound. As a result, it has been found that the molded body part made of the polyacetal resin composition and the molded body part made of the thermoplastic elastomer can be firmly fused to each other, and the present invention has been completed.

That is, the first aspect of the present invention is that the melt flow temperature is 2 with respect to 100 parts by weight of the polyacetal resin (A1).
1 to 100 parts by weight of a polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms) copolymer (A2) at 10 ° C. or less, and a core-shell polymer having a polymer shell composed of a rubber-like polymer core and a vinyl copolymer
0.1 to 15 parts by weight of at least one compound (A3) selected from (a), an isocyanate compound (b), an isothiocyanate compound (c) and a modified product (d) of the (b) or (c). Provided is a composite molded body obtained by fusion bonding a molded body part made of the blended polyacetal resin composition (A) and a molded body part made of a thermoplastic elastomer (B). A second aspect of the present invention is that the polyacetal resin (A1) comprises formaldehyde or a cyclic oligomer of formaldehyde represented by the general formula (CH ₂ O) n [where n is an integer of 3 or more] (formula derivative (formaldehyde derivative a)) homopolymerization, or formaldehyde derivative (a
There is provided a composite molded article according to the first aspect of the present invention, which is a (co) polymer obtained by copolymerizing 1) with a comonomer (a2) composed of a cyclic ether and / or a cyclic formal. A third aspect of the present invention is that the constituent acid component of the polyalkylene terephthalate copolymer (A2) contains terephthalic acid as a main component and the rest is at least one of isophthalic acid, naphthalenedicarboxylic acid and adipic acid. A composite molded article according to 1 or 2 is provided. The fourth aspect of the present invention is
In the present invention, the constituent diol component of the polyalkylene terephthalate copolymer (A2) is one or more of 1,4-butanediol, ethylene glycol, 1,3-propylene glycol, diethylene glycol, and 1,4-cyclohexanedimethylol. A composite molded article according to any one of the first to third aspects is provided. The fifth aspect of the present invention is that the polyalkylene terephthalate-based copolymer (A2) is 90 to 60.
In the first, second, and fourth embodiments of the present invention, which is a copolyester obtained by copolymerizing an acid component consisting of mol% of terephthalic acid and 10 to 40 mol% of isophthalic acid (the total of both is 100 mol%) with butanediol. A composite molded article according to any one of the items is provided. A sixth aspect of the present invention is that the polyalkylene terephthalate copolymer (A2) comprises an acid component composed of 100 to 60 mol% of terephthalic acid and 0 to 40 mol% of isophthalic acid (the total of both is 100 mol%). , Ethylene glycol 100-60 mol% and 1,4-cyclohexanedimethylol and / or diethylene glycol 0-4
There is provided a composite molded article according to the first or second aspect of the present invention, which is a copolyester copolymerized with a diol component using 0 mol% (the total of the three is 100 mol%). 7th of this invention
Is any one of 1 to 6 of the present invention, wherein the shell part of the core-shell polymer (a) is an alkyl (meth) acrylate.
The composite molded article according to the item 1 is provided. An eighth aspect of the present invention provides the composite molded article according to any one of the first to sixth aspects of the present invention, wherein the shell portion of the core-shell polymer (a) is hydroxyethyl acrylate or glycidyl methacrylate. The ninth aspect of the present invention is that the isocyanate compound (b) or the isothiocyanate compound (c) or a modified product (d) thereof is a diisocyanate compound, a diisothiocyanate compound or a dimer or trimer thereof. The composite molded article according to any one of 1 to 7 above is provided. A tenth aspect of the present invention provides the composite molded article according to any one of the first to ninth aspects of the present invention, in which the thermoplastic elastomer (B) is a thermoplastic elastomer having a polar group. . The eleventh aspect of the present invention provides the composite molded article according to the tenth aspect of the present invention, wherein the thermoplastic elastomer having a polar group is a polyester thermoplastic elastomer (B1). First of the present invention
2 provides the composite molded article according to any one of 1 to 9 of the present invention, wherein the thermoplastic elastomer (B) contains 20% by weight or more of the polyester thermoplastic elastomer (B1). To do. In the thirteenth aspect of the present invention, the thermoplastic elastomer (B) is 100 parts by weight of the polyester-based thermoplastic elastomer (Bl) and 0 in total of the styrene-based thermoplastic elastomer (B2) and / or the olefin-based thermoplastic elastomer (B3). To 400 parts by weight are provided. The composite molded article according to any one of the first to ninth aspects of the present invention is provided. The fourteenth aspect of the present invention includes the polyacetal resin composition (A) shown in any one of the first to ninth aspects of the present invention and the heat shown in any one of the first and tenth to thirteenth aspects of the present invention. There is provided a method for molding a composite molded article, which comprises subjecting a plastic elastomer (B) to two-color injection molding. The fifteenth aspect of the present invention relates to the first aspect of the present invention after installing a primary molded article made of the polyacetal resin composition (A) according to any one of the first to ninth aspects of the present invention in a mold.
And the thermoplastic elastomer (B) shown in any one of 10 to 13 is subjected to secondary injection molding, or the thermoplastic elastomer (B) shown in any one of 1 to 10 to 13 of the present invention ( It is characterized in that after the primary molded article consisting of B) is placed in a mold, the polyacetal resin composition (A) shown in any one of the first to ninth aspects of the present invention is subjected to secondary injection molding. A fourteenth aspect of the present invention provides a method for molding a composite molded body. The sixteenth aspect of the present invention is that the surface temperature of the primary molded article made of the polyacetal resin composition (A) is 8
The method for molding a composite molded article according to the fifteenth aspect of the present invention, which comprises placing the thermoplastic elastomer (B) in a secondary injection molding after placing it in a mold in a state of being preheated to 0 ° C. or higher. I will provide a. The seventeenth aspect of the present invention is the sixteenth aspect of the present invention, wherein the secondary injection molding temperature of the thermoplastic elastomer (B) is equal to or higher than the melting point of the polyacetal resin used for the primary molded article.
Provided is a method for molding the described composite molded body.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. I. Polyacetal resin composition (A) Polyacetal resin composition (A) used in the present invention
Is a core-shell polymer (a) having a polymer shell consisting of a polyacetal resin (A1), a polyalkylene terephthalate copolymer (A2) and a rubbery polymer core and a vinyl copolymer, an isocyanate compound (b),
At least one compound (A3) selected from the isothiocyanate compound (c) and the modified product (d) of the (b) or (c).
Consists of.

Polyacetal resin (A1) The polyacetal resin (A1) is an ordinary polyacetal homopolymer or polyacetal copolymer. That is, the polyacetal resin (A1) is a polymer compound having an oxymethylene group (—CH ₂ O—) as a main constituent unit, and is a polyoxymethylene homopolymer or a copolymer containing other constituent units in addition to the oxymethylene group ( Copolymers include random, block, mixed structures of these),
It may be any of terpolymers, and the molecule may have not only a linear structure but also a branched or crosslinked structure. When there is no need to distinguish between polyoxymethylene homopolymer, copolymer and terpolymer, it is simply referred to as polyacetal.

Polyacetal Homopolymer Generally, polyacetal homopolymer is produced by polymerizing formaldehyde derivative (a). Specific examples of the formaldehyde derivative (a) include anhydrous formaldehyde, trioxane which is a cyclic triplet of formaldehyde represented by the general formula (CH ₂ O) n [where n is an integer of 3 or more], and the like. .

Polyacetal Copolymer The polyacetal copolymer has a repeating group (--CH ₂ O--).
And the following general formula (i):

[Chemical 1] (In the formula, R ¹ and R ² are each selected from the group consisting of hydrogen, lower alkyl and halogen-substituted lower alkyl groups, and two R ¹ or R ² may be different from each other; R ³ is Selected from the group consisting of alkylene, oxyalkylene, lower alkyl and haloalkyl substituted methylene, and lower alkyl and haloalkyl substituted oxyalkylene groups, m is an integer of 0 to 3, and each lower alkyl group has 1 to 2 carbon atoms. When there are a plurality of repeating groups (i) in the polymer chain, the repeating group (i) represented by the repeating groups (i) may be the same or different. Or, it has a structure existing in a block. The polyacetal copolymer is generally obtained by copolymerizing the formaldehyde derivative (a) and the comonomer (c). Examples of the comonomer (c) include cyclic ether and cyclic formal, and specifically, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, styrene oxide, oxetane,
Cyclic ethers such as 3,3-bis (chloromethyl) oxetane, tetrahydrofuran, trioxepane, and 1,3-dioxolane; and propylene glycol formal.
Diethylene glycol formal, triethylene glycol formal, 1,4-butanediol formal,
Examples include cyclic formal such as 1,5-pentanediol formal and 1,6-hexanediol formal. You may mix and use these. Of these, ethylene oxide, 1,3-dioxolane, diethylene glycol formal and 1,4-butanediol formal are preferable. The amount of the comonomer (c) used is, considering the rigidity and chemical resistance of the obtained polyacetal copolymer,
1 to 100 parts by weight of formaldehyde derivative (a)
It is 0 to 20 parts by weight, preferably 0.01 to 15 parts by weight, and particularly preferably 0.1 to 10 parts by weight in total of one kind or two or more kinds.

In the production of the polyacetal, a polyfunctional compound capable of forming a conventional branched / crosslinked compound such as a diglycidyl ether compound or the like is polymerized by using a molecular weight adjusting component such as methylal in combination. In addition, it is also possible to polymerize. Examples of the molecular weight adjusting component include conventionally known low molecular weight acetal compounds and the like, and specifically include an alkoxy group such as methylal, methoxymethylal, dimethoxymethylal, trimethoxymethylal, and oxymethylenedi-n-butyl ether. And compounds having the same.

The above-mentioned polyacetal is produced in the presence of a catalyst. As the catalyst, a cationic polymerization catalyst is generally used, and specific examples thereof include lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony trichloride, phosphorus pentafluoride, and pentapentane. Antimony fluoride, boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetic unhydrate, boron trifluoride triethylamine complex compound, etc. Boron trifluoride coordination compound, perchloric acid, acetyl perchlorate, t-butyl perchlorate, hydroxyacetic acid, trichloroacetic acid, trifluoroacetic acid, p
-Inorganic and organic acids such as toluenesulfonic acid, triethyloxonium tetrafluoroborate, triphenylmethyl hexafluoroantimonate, allyldiazonium hexafluorophosphate, complex salt compounds such as allyldiazonium tetrafluoroborate, diethyl zinc, triethylaluminum, diethyl Alkyl metal salt such as aluminum chloride, heteropoly acid, isopoly acid, etc. 1
Or two or more species. Among them, boron trifluoride,
Boron trifluoride coordination compounds such as boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetic unhydrate, and boron trifluoride triethylamine complex compound are preferable. . These cationic polymerization catalysts can be used as they are or after being diluted with an organic solvent or the like in advance, and the preparation method is not particularly limited.

The method for producing the polyacetal is not particularly limited, but generally, liquefied trioxane and the comonomer (c) are bulk polymerized using a catalyst to obtain a solid powder lump polyacetal. . The polymerization device is not particularly limited, a known device is used,
Any method such as a batch method or a continuous method is possible. The polymerization temperature is preferably maintained at 65 to 135 ° C.

Deactivation of the catalyst in the polyacetal after polymerization is carried out by adding a basic compound or an aqueous solution thereof to the reaction product discharged from the polymerization machine after the polymerization reaction or the reaction product in the polymerization machine. . Examples of the basic compound for neutralizing and deactivating the polymerization catalyst include ammonia, amines such as triethylamine, tributylamine, triethanolamine, tributanolamine, and hydroxide salts of alkali metals and alkaline earth metals. Other known catalyst deactivators are used. Further, it is preferable to rapidly add these aqueous solutions to the product to deactivate it after the polymerization reaction. After the polymerization method and the deactivation method, washing, separation and recovery of unreacted monomers, drying and the like are further performed by a conventionally known method, if necessary. The obtained polyacetal is
Further, if necessary, stabilization treatment is carried out by a known method such as decomposition and removal of unstable terminal portions by hydrolysis or sealing of unstable terminals by a stable substance.

The polyacetal has a melt index of 0.1 to 1,000 g / lOmin, preferably 0.2 to 500 g / lOmin.

Various stabilizers such as an antioxidant, a heat resistance stabilizer (decomposition inhibitor), a weather resistance (light) stabilizer and the like are usually added to the polyacetal. Examples of the various stabilizers include hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, carboxylates, and the like. These may be used alone or in combination of two or more. Good.

Polyalkylene terephthalate type copolymer (A2) The polyalkylene terephthalate type copolymer (A2) means 100 to 50 mol% of terephthalic acid and an aliphatic or alicyclic dicarboxylic acid having 6 or more carbon atoms or aromatic. A polyester obtained by copolycondensing a component composed of 0 to 50 mol% of dicarboxylic acid (excluding terephthalic acid) and an alkylene diol component having 2 to 8 carbon atoms,
The melting flow temperature is 210 ° C or lower. If we show examples of acid components other than terephthalic acid used here,
First, examples of the aliphatic dicarboxylic acid having 6 or more carbon atoms include adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, dimer acid and the like. Further, as the alicyclic dicarboxylic acid having 6 or more carbon atoms, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid and the like can be mentioned.
Examples of aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid and diphenylsulfonedicarboxylic acid. Further, aliphatic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid; p-β-hydroxyethoxybenzoic acid, p-
It is also possible to use other bifunctional carboxylic acids such as oxyacids such as oxybenzoic acid, oxycaproic acid and the like.
Also, these dicarboxylic acid compounds can be used for polymerization in the form of an ester-formable derivative, for example, a lower alcohol ester such as dimethyl ester. Two or more kinds of these acid components may be used in combination. Of these acid components, adipic acid, sebacic acid, isophthalic acid, naphthalenedicarboxylic acid and decanedicarboxylic acid are preferred. More preferred are isophthalic acid, naphthalenedicarboxylic acid and adipic acid. On the other hand, the alkylene diol having 2 to 8 carbon atoms used here is 1,4-
Butanediol, ethylene glycol, trimethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 1,1-cyclohexanedimethylol, diethylene glycol, 1,4-
Cyclohexane dimethylol, 2,2-bis (4-β-
Hydroxyethoxyphenyl) propane, bis (4-β
-Hydroxyethoxyphenyl) sulfone and the like. Two or more of these alkylene diols may be used in combination. Preferred are 1,4-butanediol, ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethylol. More preferably, it is at least one of 1,4-butanediol, ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethylol. The polyalkylene terephthalate polymer (A2) used in the present invention is a copolyester obtained by copolymerizing an acid component and a diol component as described above, and has a melt flow temperature measured by the method described in Examples. 21
It is 0 ° C or lower, preferably 190 ° C or lower. When the melt flow temperature is higher than 210 ° C., the polyalkylene terephthalate is poorly dispersed, resulting in stripes or spots on the surface of the molded article made of the polyacetal resin composition (A), which significantly impairs the commercial value of the composite molded article. At the same time, the mechanical strength and impact resistance deteriorate. Any polyalkylene terephthalate can be used as the component (A2) of the present invention as long as the melt flow temperature is 210 ° C or lower. Examples of preferred copolymers include an acid component in which a part of terephthalic acid is substituted with one or more of isophthalic acid, naphthalenedicarboxylic acid and adipic acid, and 1,4-butanediol, ethylene glycol, diethylene glycol and 1,4-cyclohexane. It is a copolyester composed of one or more diol components of dimethylol. Particularly preferably, 90-60 mol% of terephthalic acid and 10
Copolyester obtained by copolymerizing an acid component consisting of ˜40 mol% of isophthalic acid with butanediol, 100 to 60
An acid component consisting of mol% terephthalic acid and 0-40 mol% isophthalic acid, and a diol component in which ethylene glycol 100-60 mol% and 1,4-cyclohexanedimethylol and / or diethylene glycol 0-40 mol% are used in combination. Is a copolyester obtained by copolymerizing The intrinsic viscosity (IV) of the copolyester resin is not particularly limited, but in order to obtain a good dispersion state, the intrinsic viscosity of the copolyester is adjusted so that the melt viscosity of the copolyester at the melt kneading temperature is as close as possible to the melt viscosity of the polyacetal. It is desirable to choose. From these, 0.3 or more and 1.2 or less are preferable, and 0.4 is especially preferable.
It has an intrinsic viscosity of 0.8 or more and 0.8 or less. The intrinsic viscosity defined here is measured at 40 ° C. by a commonly used method using a phenol / tetrachloroethane mixed solvent as a solvent.

The amount of the polyalkylene terephthalate copolymer (A2) used here is 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the polyacetal resin (A1). . If the amount of the component (A2) is too small, the heat-sealing property between the molded body part made of the polyacetal resin composition and the molded body part made of the thermoplastic elastomer (B) will not be sufficiently exerted, and excessively added unnecessarily. Also has an unfavorable effect on the mechanical properties and thermal stability of the molded part.

Compound (A3) In the present invention, the core-shell polymer (a), the isocyanate compound (b), the isothiocyanate compound (c) and the
By adding at least one compound (A3) selected from the modified product (d) of (b) or (c) to the polyacetal resin (A1) and the polyalkylene terephthalate copolymer (A2) component, A component which exhibits the compatibilizing effect of the components (A1) and (A2), improves the surface uniformity and surface peeling of the molded body part made of the polyacetal resin composition, and obtains a molded body part having a good surface property by ordinary molding. Is.
Acrylic core-shell polymer (a) used in the present invention
Shows a sufficient compatibilizing effect with a commonly used all-acrylic core-shell polymer. In order to further improve the thermal stability of the polyacetal resin, an acrylic core-shell polymer emulsion-polymerized by using a nonionic surfactant or an oligomer-type surfactant and using an azo-based and / or peroxide-based polymerization initiator is preferable. Is desirable. By using the core-shell polymer obtained by using the surfactant and the polymerization initiator, the decomposition of the polyacetal resin is suppressed as much as possible, and as a result, the compatibilizing effect of the components (A1) and (A2) is further exerted. At the same time, the obtained molded body part and the molded body part made of a thermoplastic elastomer have a heat fusion property, and at the same time, the excellent mechanical properties of the polyacetal are retained. In addition, the use of an acrylic core-shell polymer having a hydroxyl group in the shell part increases the compatibility of the oxygen-containing polar group in the shell part with the polyacetal resin (A1) and the polyalkylene terephthalate copolymer (A2) component, and the obtained molding Exhibits excellent thermal fusion bonding between the body part and the molded body part made of the thermoplastic elastomer (B). The core-shell polymer used herein may be produced by any commonly used method. The core-shell polymer in the present invention has a rubber-like polymer core and a polymer shell composed of a vinyl-based copolymer. For example, in the seed emulsion polymerization method, the polymer of the previous stage is the polymer of the latter stage. It is obtained by a continuous multi-stage emulsion polymerization method such as coating sequentially. However, the core-shell polymer usable in the present invention is not limited to this method.

The preferred isocyanate compound (b) or isothiocyanate compound (c) or modified product (d) thereof used in the present invention has the general formula O = C = N-R-N.
= C = O or S = C = NR-N = C = S (R; a divalent group), and modified products thereof. For example, 4,4′-methylenebis (phenyl isocyanate), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate,
1,6-Hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, or their corresponding diisothiocyanates and their dimers, trimers, and even isocyanate groups (-NCO) protected in some form Although all of the compounds mentioned above are effective, when considering various properties such as discoloration during melt processing or safety in handling, 4,
4'-methylenebis (phenylisocyanate), isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate,
2,4-Tolylene diisocyanate, 2,6-Tolylene diisocyanate and modified products (or derivatives) such as dimers and trimers thereof are particularly desirable. In view of the increase in viscosity, the effect is that the component reacts with the polyacetal resin (A1) and / or the polyalkylene terephthalate copolymer (A2) during the melt processing, and in some cases takes a part of a three-dimensional structure. ) And (A2), or the adhesiveness of the interface is improved. The compounding amount of the compound (A3) used here is 0.1 to 100 parts by weight of the polyacetal resin (A1).
15 parts by weight, preferably 2 to 10 parts by weight. If the amount of the compound (A3) component is too small, the surface uniformity of the molded product is insufficient, and if it is added in excess, the fluidity is lowered and the injection molding may be hindered. .

Further, in the present invention, the polyacetal resin composition (A) is improved in its physical properties depending on the application.
Various known additives may be added. Examples of additives include various stabilizers, colorants, lubricants, release agents, nucleating agents, surfactants, different polymers, organic polymer modifiers, and fibrous and powdery particles of inorganic, organic, metal, etc. , Plate-like fillers may be used, and one or more of these may be mixed and used.

The polyacetal resin composition (A) can be prepared by the equipment and method generally known as a method for preparing a synthetic resin composition. That is, mix the necessary ingredients,
The composition may be kneaded using a uniaxial or biaxial extruder and extruded into pellets for molding and then molded, or the composition may be prepared simultaneously with molding by a molding machine.
Further, in order to improve the dispersion and mixing of the respective components, a method of pulverizing a part or all of the resin components and mixing them to form melt-extruded pellets, or a part constituting the composition (for example, (A
The component (1) and the component (A2) and / or a part of the component (A3) are melt-kneaded in advance (masterbatch), and this is further kneaded with the remaining components to form a composition or molded product of the predetermined components. The method and the like are preferable because they further enhance the effects of the present invention. Further, the above-mentioned stabilizers, additives and the like may be added at any arbitrary stage, and it is of course possible to add and mix them immediately before obtaining the final molded product.

II. Thermoplastic Elastomer (B) Thermoplastic Elastomer (B) Used in the Present Invention
For example, polyester-based elastomer (B
1), highly polar elastomers such as polyurethane elastomers and polyamide elastomers; polystyrene elastomers (B2); polyolefin elastomers (B3); vinyl chloride elastomers. You may use 2 or more types together. As the thermoplastic elastomer (B), a polar group such as -C (= O) O-, -NHC (= O) O- group, -NH in the constituent polymer molecule is used.
An elastomer having a C (= O)-group is suitable, and a polyester elastomer (Bl) is particularly preferable. The polyester-based elastomer (B1) may be a single type or a combination of a plurality of types with other elastomer components. Among the other elastomer components, polystyrene-based elastomer (B2) and polyolefin-based elastomer (B3) are preferable. is there.

Polyester Elastomer (Bl) Examples of the polyester elastomer (Bl) include the following polyester elastomers and the like. Polyester elastomer: A polyester / polyether type block copolymer in which the hard segment is an aromatic polyester block (b1) and the soft segment is an aliphatic polyether block (b2). Polyester elastomer: A polyester / polyester block copolymer in which the hard segment is an aromatic polyester block (b1) and the soft segment is an aliphatic (chain or alicyclic) polyester block (b3). Among them, polyester elastomers are particularly preferable because they are excellent in flexibility and moldability. The aromatic polyester block (b1) is composed of a polycondensate containing an aromatic dicarboxylic acid component and a diol component as main components. Aromatic dicarboxylic acid components include phthalic acid, terephthalic acid, isophthalic acid, 1,4- or 2,6
-Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid and 4,4'-diphenyletherdicarboxylic acid, or alkyl esters thereof, and these are used in combination. You may. As the diol component, aliphatic diols such as ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and hexamethylene glycol; alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; Examples thereof include aromatic diols such as 4,4′-dihydroxybiphenyl and 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, which may be used in combination. The aliphatic polyether block (b2) is polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol; a block or random copolymer of ethylene oxide and propylene oxide,
It is composed of a polyalkylene ether glycol such as a block or random copolymer of ethylene oxide and tetrahydrofuran. The aliphatic polyester block (b3) is composed of an aliphatic dicarboxylic acid, an aliphatic diol, and / or an aliphatic hydroxycarboxylic acid or a cyclic ester thereof. As the aliphatic dicarboxylic acid, chain aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, azelaic acid and sebacic acid;
Examples thereof include alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, and dicyclohexyl-4,4′-dicarboxylic acid, which may be used in combination. Aliphatic diols include chain aliphatic diols such as ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and hexamethylene glycol; alicyclic compounds such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol. Examples thereof include diols, which may be used in combination. Examples of the aliphatic hydroxycarboxylic acid include ε-oxycaproic acid, and examples of the cyclic ester thereof include ε-caprolactone. These may be used in combination. The polyester-based elastomer (B1) is manufactured by a known method, for example, “HYTREL”
(Product name of Toray Dubon Co., Ltd.); "Perprene S",
"Perprene P" (trade name of Toyobo Co., Ltd.); "Grelax E" (trade name of Dainippon Ink & Chemicals Co., Ltd.); "Nuberan" (trade name of Teijin Co., Ltd.) Can be used.

Polystyrene Elastomer (B2) The polystyrene elastomer (B2) is a known styrene elastomer, that is, the hard segment is a polymer block of a styrene compound and the soft segment is a polymer block of a conjugated diene compound. Styrene-conjugated diene block copolymers or hydrogenated products thereof are mentioned. Among them, hydrogenated products are preferable from the viewpoint of compatibility with the polyester elastomer. Examples of the styrene compound include styrene, α-methylstyrene,
Examples thereof include p-methylstyrene and dimethylstyrene, with styrene being preferred. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. Among them, butadiene, isoprene, or a combination of both is preferable. Examples of the styrene-conjugated diene block copolymer include a styrene-butadiene-styrene block copolymer and a styrene-isoprene-styrene block copolymer. Further, specific examples of hydrogenated products of styrene-conjugated diene block copolymers include hydrogenated products of the styrene-butadiene-styrene block copolymers and hydrogenated products of styrene-isoprene-styrene block copolymers. Can be mentioned.
Furthermore, modification by copolymerization with a comonomer having a polar group copolymerizable with them, such as (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid glycidyl ester, vinyl acetate, maleic anhydride, etc. Copolymers are also preferably used. The polystyrene-based elastomer (B2) is produced by a known method,
For example, from "Clayton G" (trade name of Shell Japan Co., Ltd.), "Tuftec" (trade name of Asahi Kasei Co., Ltd.), "Septon", "High Blur" (both are trade names of Kuraray Co., Ltd.), etc. Can be appropriately selected and used. The styrene elastomer (B2) in the present invention is commercially available as a compound in which the styrene elastomer is mixed with a propylene resin, a hydrocarbon rubber softening agent, an inorganic filler and the like. For example, "Clayton G compound" (trade name of Shell Japan), "Tuftec compound"
(Asahi Kasei product name), "Lavalon" (Mitsubishi Chemical product name), "Sumitomo TPE (SB series)" (Sumitomo Chemical product name) and the like.

Polyolefin Elastomer (B3) The polyolefin elastomer (B3) is produced by a known method, for example, a mixture in which the hard segment is a propylene resin and the soft segment is an ethylene rubber, Alternatively, a partially crosslinked product thereof can be used. As the propylene-based resin, for example,
Homopolymer of propylene, propylene and ethylene, butene-1, pentene-1, hexene-1, heptene-
1, other octons such as 1, octene-1 with 2 to 10 carbon atoms
Examples thereof include copolymers with olefins. Examples of the ethylene rubber include ethylene and propylene,
Butene-1, pentene-1, hexene-1, heptene-
1, copolymers of octene-1, etc. with α-olefins having about 3 to 10 carbon atoms; and, in addition to these, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2. -A copolymer obtained by copolymerizing non-conjugated dienes such as norbornene and dicyclopentadiene, for example, EPDM. Furthermore, modified copolymers obtained by copolymerizing these with the comonomer having a polar group capable of copolymerization as exemplified above are also preferably used. The polyolefin-based elastomer (B3) is manufactured by a known method, and is used as a compound containing a softening agent for hydrocarbon-based rubber, an inorganic filler, etc., for example,
From "Millastomer" (trade name of Mitsui Chemicals, Inc.), "Thermo Run" (trade name of Mitsubishi Chemical Co., Ltd.), "Sumitomo TPE" (trade name of Sumitomo Chemical Co., Ltd.), etc.,
It can be appropriately selected and used.

Further, the thermoplastic elastomer (B) in the present invention may be blended with various known stabilizers and additives depending on the intended use. Examples of the stabilizer include an antioxidant, a heat resistance stabilizer (decomposition inhibitor), a weather resistance (light) stabilizer, and the like. The additives include, for example, various plasticizers, colorants, lubricants, release agents and the like, inorganic, organic,
Examples include fibrous, powdery, and plate-shaped fillers such as metal. Examples of the plasticizer include hydrocarbon rubber softeners. Hydrocarbon softeners for rubber are aromatic rings,
A mixture of naphthene ring and paraffin chain,
Paraffin chain carbon number occupies 50% or more of the total carbon paraffin oil, naphthene ring carbon number 30 to 50% of the total carbon naphthene oil, aromatic carbon number 30 of the total carbon. % Or more are classified as aromatic oils. Of these, paraffinic oil is preferably used from the viewpoint of weather resistance. Examples of the inorganic filler include talc, mica, glass fiber, whiskers, carbon fiber, calcium carbonate, titanium oxide, carbon black, glass balloons and the like. Among these, it is preferable to use calcium carbonate in terms of balance with flexibility.

III. Composite molded article The composite molded article of the present invention has a molded article part made of the polyacetal resin composition (A) and a molded article part made of the thermoplastic elastomer (B), and is a composite formed by fusion of both molded article parts. It is a molded body. As the molding method of the composite molded body, any molding method may be used as long as it is a molding method such as injection molding, extrusion molding, compression molding, etc., in which the conditions for thermal fusion are set, From the viewpoint of, the injection molding method is preferable. Specifically, a two-color molding method in which the primary molding portion is made of primary resin and the secondary molding portion is made of secondary resin alternately by injection molding; a primary molding body previously molded of the primary resin is made into a mold. Insert molding method in which the secondary side resin is injection-molded around the primary molded body to be integrated with the primary molded body; or a primary molded body previously molded with the primary side resin is inserted into the mold. However, there is an outsert molding method in which a secondary resin is injection-molded on a part or a plurality of parts of the primary molded product to integrate it with the primary molded product. Depending on the shape, structure and intended use of the molded product, even if the polyacetal resin composition (A) is used as the primary resin and the thermoplastic elastomer (B) is used as the secondary resin, the reverse combination is obtained. Good. However, in general, it is better to mold a primary molding with a hard polyacetal resin composition (A) and then to secondary molding with a soft thermoplastic elastomer (B). Alternatively, it is preferable for preventing deformation after secondary molding.

In order to firmly heat-bond both molded parts to each other, in the secondary molding, depending on the resin temperature of the thermoplastic elastomer (B), the bonding surface of the primary molded product made of the polyacetal resin composition (A) is changed. It is necessary that the surface layer (interface) part be melted. Therefore, the resin temperature of the thermoplastic elastomer (B) in the secondary molding is not lower than the melting point of the polyacetal resin used in the primary molded product. As a method of raising or keeping the temperature of the resin, there are a method of raising the temperature of the injected resin itself within an allowable range, a method of using a hot runner mold, and a method of keeping the heated or heated resin after injection. . Examples of the latter include a method in which a heat insulating material is used in the mold portion that affects the heat retention of the interface portion, a heating medium is passed through the mold portion, and a heating means by a heater is provided. By increasing the mold temperature to a certain degree, the heat loss during flow of the thermoplastic elastomer decreases, so the improvement of heat fusion is expected due to the synergistic effect of preheating, which will be described later, of the polyacetal resin (A), which is the primary molding. To be done. However, when the mold temperature is increased, the mold release property of the thermoplastic elastomer (particularly the sprue and runner) is deteriorated. In this case, by using a hot runner, the problem of releasability can be solved, and a molded product having a constant heat fusion property can be stably obtained. Further, it is basically possible to raise the mold temperature further, and it is expected that the heat fusion property will be further improved. In addition, in order to increase the molding cycle, it is possible to use a temperature control system for rapid heating and rapid cooling of the mold together. That is, a hot runner was used by increasing the mold temperature during injection molding of the thermoplastic elastomer and rapidly cooling the mold upon completion of the injection molding to promote solidification of the thermoplastic elastomer, particularly sprue and runner. The same effect as the case can be obtained. Also,
In order to improve the heat-sealing property, it is preferable to increase the amount of heat of the primary molded body made of the polyacetal resin composition (A) during the secondary molding as much as possible. Especially in the insert molding method and the outsert molding method, it is desirable to preheat the primary molded body sufficiently before or after inserting the mold within a range in which discoloration or dimensional change does not matter.
At the time of injection of the thermoplastic elastomer (B), the surface temperature of the primary molding made of the polyacetal resin composition (A) is 8
The temperature is 0 ° C or higher, preferably 110 ° C to 150 ° C. Examples of the preheating method before inserting the mold include hot air heating, ultrasonic heating, and heating with heating wire.As the preheating method after inserting the mold, known means for heating the inside or outside surface of the mold can be used. Specifically, heating by passing a heated medium through the inside or outside of the mold, heating by electric heating, heating of the outside of the mold by high frequency waves, ultrasonic waves, heat rays, and the like can be mentioned. Examples of the medium include water, an inorganic liquid such as a calcium chloride aqueous solution; an organic liquid such as an alkylated aromatic hydrocarbon, polyethylene glycol, silicone oil, animal oil, and vegetable oil; water vapor, a gas such as air, and the like.
These are appropriately selected depending on the type of resin, the size of the molded product, and the like.

[0030]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In addition, the polyacetal resin (A
1), polyalkylene terephthalate copolymer (A
2), the compound (A3) and the thermoplastic elastomer (B) are shown below.

(1) Polyacetal resin (a) Polyplastics Co., Ltd. DURACON (registered trademark) M90-34 (melt index 9 g / 10 m
in, 190 ° C.) (2) Polyalkylene terephthalate copolymer b-1: Modified polybutylene terephthalate obtained by copolymerizing 30 mol% of isophthalic acid with respect to all acid components, melt flow temperature = 160 ° C., IV = 0.5 b-2: 12.5 mol% of isophthalic acid based on all acid components
Copolymerized modified polybutylene terephthalate, melt flow temperature = 205 ° C., IV = 0.7 b-3: 1,4-cyclohexane dimethylol 10 mol% to all diol components, isophthalic acid 20 to all acid components Modified polyethylene terephthalate copolymerized by mol%, melt flow temperature = 150 ° C., IV = 0.7 b-4: Modified polyethylene terephthalate copolymerized with 30 mol% of isophthalic acid based on all acid components, melt flow temperature = 155 ° C., IV = 0.6 As for the melt flow temperature, pellets were filled in a flow tester (manufactured by Shimadzu Corporation) equipped with a nozzle having a diameter of 1 mm, and a load of 500 kg was applied to raise the temperature to start the flow. The measured temperature was measured. (3) Core-shell polymer c-1: Acrylic core-shell polymer, core / shell ratio 70:30, core composition is 2% ethyl acrylate, 87% butyl acrylate, 10 methyl methacrylate
%, Cross-linking monomer 1%, shell composition 10% ethyl acrylate, methyl methacrylate 89%, cross-linking monomer 1%. c-2: Acrylic core-shell polymer, core / shell ratio 70:30, core part composition is ethyl acrylate 2.0
%, Butyl acrylate 87.0%, methyl methacrylate 10.0%, cross-linking monomers 1.0%, shell part composition is ethyl acrylate 10.0%, methyl methacrylate 44.0%, styrene 30.0%, hydroxyethyl. Methacrylate 15.0%, crosslinking monomer 1.0
%. (4) Isocyanate compound d-1: Isophorone diisocyanate d-2: 4,4'-methylenebis (phenylisocyanate) (5) Thermoplastic elastomer (B) B-1: Urethane elastomer (manufactured by Nippon Polyurethane Industry Co., Ltd., Miractolan P485RSUD) B-2: Styrene-based elastomer (manufactured by Kuraray Co., Ltd.,
Septon 2043) B-3: Polyester elastomer (Mitsubishi Chemical Corporation)
Manufactured by Primalloy A1500N) B-4: olefin elastomer (Mitsui Chemicals, Inc., Mirastomer 9070N)

Preparation of pelletized polyacetal resin composition (1) to (4) were blended in the composition shown in Table 1, mixed in a Henschel mixer, and melted using a twin screw extruder with a cylinder temperature of 210 ° C. The mixture was kneaded to prepare pellets of the polyacetal resin composition. Table 1 shows the composition (unit: parts by weight) of the polyacetal resin compositions A-1 to A-14.

[0033]

[Table 1]

Evaluation of Adhesion by Fusing Surface Adhesion Method The pelletized polyacetal resin composition obtained above was injection-molded to have a length of 130 mm, a width of 13 mm and a thickness of 3.2.
mm primary molding product, which is inserted into a secondary molding die having a cavity size of 130 mm in length, 13 mm in width, and 6.4 mm in thickness, and then secondary injection with a thermoplastic elastomer (B). Molding was performed to obtain a double molded product. Regarding the insertion of the primary molded product into the mold, the primary molded product was heated in an oven so that the surface temperature was 90 ° C to 120 ° C and then inserted into the mold. The peel strength between the molded body part made of the polyacetal resin composition and the molded body part made of the thermoplastic elastomer of this molded product was evaluated by a 90-degree peel test.

Evaluation of Surface Condition of Primary Molded Product The surface condition of the primary molded product made of the polyacetal resin composition depends on the degree of stripes, spots, and peeling conditions on the surface of the molded product caused by poor dispersion of the polyalkylene terephthalate copolymer. It was visually evaluated in five levels. As for the evaluation criteria for both patterns, 5 is a state where the surface is uniform and there is no pattern, and 1 is a state where a striped pattern or spot pattern spreads over the entire surface of the molded product.
Regarding the peeled state, 5 is a state where there is no peeling on the surface, and 1 is a state where there is peeling on almost the entire surface of the molded product.

Details of molding conditions Primary molding (polyacetal resin composition (A)) Cylinder temperature: 200 ° C. Mold temperature: 80 ° C. Injection speed: 0.6 m / min Holding pressure: 50 MPa Injection / holding time: 20 seconds Cooling Time: 20 seconds Secondary molding (thermoplastic elastomer (B)) Cylinder temperature: 250 ° C Mold temperature: 60 ° C Injection speed: 10 m / min Holding pressure: 20 MPa Injection / holding time: 15 seconds Cooling time: 40 seconds ( Test of Composite Molded Body) Test Method The peel strength of the test piece prepared above was evaluated by the 90-degree peel test according to the following. The results are shown in Table 3. Peeling test conditions Apparatus: RTM-100 manufactured by Orientec Co., Ltd. Test speed: 100 mm / min Atmospheric temperature: 23 ° C. After the secondary molding, the test was carried out at a temperature of 23 ° C. and a humidity of 50
% It was carried out after being left for 48 hours in the environment.

[0037]

[Table 2]

[0038]

[Table 3]

As can be seen from Table 3, the strength of fusion between the molded body part made of the polyacetal resin composition (A) and the molded body part made of the thermoplastic elastomer (B) of the composite molded body was determined by the peel test. As a result, the peel strength is improved when the polyalkylene terephthalate copolymer and the acrylic core shell polymer or the isocyanate compound are blended, and particularly 30 parts by weight of the alkylene terephthalate copolymer is blended with 100 parts by weight of the polyacetal resin. Further, it was found that the improvement was further improved when a polyester elastomer was used as the thermoplastic elastomer. This is a polyacetal resin composition (A)
It is presumed that the polyalkylene terephthalate-based copolymer therein effectively acted, and the compatibility between the polyacetal resin composition side interface and the thermoplastic elastomer side interface was improved.

Polyacetal resin composition A in Table 2
No. 14 lacked the compound (A3) according to the present invention, and due to poor dispersion of polyalkylene terephthalate, a striped pattern or spotted pattern was formed on the surface of the molded product. These poor surface conditions significantly impair the commercial value of the molded product and reduce the mechanical strength and impact resistance. Therefore, secondary molding using the resin composition A-14 was not carried out, and the peel strength of the elastomer has not been evaluated.

As is clear from the above description and examples, by combining the polyacetal resin composition according to the present invention and the thermoplastic elastomer, both composite molded articles having excellent heat fusion properties, which have never existed in the past, can be obtained. Can be manufactured. Further, the composite molded article is also excellent in adhesiveness and fusion bondability with other polyacetal resin molded articles and thermoplastic elastomer molded articles.

[0042]

EFFECTS OF THE INVENTION The present invention effectively provides a composite molded article having the advantages of both a polyacetal resin and a thermoplastic elastomer, so that it can be used in electric / electronic devices, automobile parts, office equipment parts, daily sundries parts, etc. It can be suitably used for new applications such as sealing applications and damping applications.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 59/00 C08L 59/00 // (C08L 59/00 67:02 67:02 51:04 51:04) B29K 21 : 00 B29K 21:00 59:00 59:00 F Term (reference) 4F206 AA23 AA45 AD05 AR064 JA07 JB12 JB28 JL02 4F211 AA23 AA24E AA45 AH17 AH33 TA08 TC02 TD11 TN82 TN87 4J002 BN123 CB001 CF052 CF062 CF002 CF072 CF072 ER072

Claims (17)

[Claims] 1. 1 to 100 parts by weight of a polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms) copolymer (A2) having a melt flow temperature of 210 ° C. or less with respect to 100 parts by weight of a polyacetal resin (A1), Core-shell polymer (a) having a rubber-like polymer core and a polymer shell composed of a vinyl-based copolymer, an isocyanate compound
(b), isothiocyanate compound (c) and the (b) or (c)
Of at least one compound (A)
3) A composite molded body obtained by fusion bonding a molded body portion made of the polyacetal resin composition (A) containing 0.1 to 15 parts by weight and a molded body portion made of the thermoplastic elastomer (B). 2. The polyacetal resin (A1) comprises formaldehyde or a general formula (CH ₂ O) n [where n is 3
A homopolymerization of a cyclic oligomer of formaldehyde represented by the above integers (both are collectively referred to as formaldehyde derivative (a1)), or a comonomer composed of formaldehyde derivative (a1) and cyclic ether and / or cyclic formal ( The composite molded article according to claim 1, which is a (co) polymer obtained by copolymerizing a2). 3. The polyalkylene terephthalate copolymer (A2), wherein the constituent acid component is terephthalic acid as a main component, and the balance is at least one of isophthalic acid, naphthalenedicarboxylic acid and adipic acid. Composite molded body of. 4. The constituent diol component of the polyalkylene terephthalate copolymer (A2) is one or more of 1,4-butanediol, ethylene glycol, 1,3-propylene glycol, diethylene glycol, and 1,4-cyclohexanedimethylol. The composite molded body according to any one of claims 1 to 3. 5. A polyalkylene terephthalate-based copolymer (A2) comprises 90 to 60 mol% of terephthalic acid and 10
Consists of ~ 40 mol% isophthalic acid (both total 1
(00 mol%) an acid component and butanediol are copolymerized copolyesters.
The composite molded article according to item. 6. The polyalkylene terephthalate copolymer (A2) comprises 100 to 60 mol% of terephthalic acid and 0.
Consists of ~ 40 mol% isophthalic acid (both total 1
(00 mol%) acid component and ethylene glycol 100 to 6
3. A copolyester obtained by copolymerizing 0 mol% with a diol component using 0,40 mol% of 1,4-cyclohexanedimethylol and / or diethylene glycol (the total of the three is 100 mol%). Composite molded body of. 7. The composite molded article according to claim 1, wherein the shell portion of the core-shell polymer (a) is an alkyl (meth) acrylate. 8. The molded composite article according to claim 1, wherein the shell portion of the core-shell polymer (a) is hydroxyethyl acrylate or glycidyl methacrylate. 9. An isocyanate compound (b) or an isothiocyanate compound (c) or a modified product (d) thereof.
Is a diisocyanate compound, a diisothiocyanate compound or a dimer or trimer thereof.
The composite molded article according to any one of items 1 to 7. 10. The composite molded article according to any one of claims 1 to 9, wherein the thermoplastic elastomer (B) is a thermoplastic elastomer having a polar group. 11. The composite molded article according to claim 10, wherein the thermoplastic elastomer having a polar group is a thermoplastic polyester elastomer (B1). 12. The thermoplastic elastomer (B) comprises 20% by weight of the polyester thermoplastic elastomer (B1).
Any of the above-mentioned items 1 to 11 characterized by including the above.
The composite molded article according to item. 13. The thermoplastic elastomer (B) comprises 100 parts by weight of the polyester thermoplastic elastomer (Bl) and 0 in total of the styrene thermoplastic elastomer (B2) and / or the olefin thermoplastic elastomer (B3).
1 to 400 parts by weight.
13. The composite molded article according to any one of 12. 14. A polyacetal resin composition (A) according to any one of claims 1 to 9 and claims 1 and 1.
A method for molding a composite molded article, which comprises subjecting the thermoplastic elastomer (B) shown in any one of 0 to 13 to two-color injection molding. 15. A primary molded article made of the polyacetal resin composition (A) according to any one of claims 1 to 9 is placed in a mold, and then any one of claims 1 and 10 to 13. Secondary injection molding of the thermoplastic elastomer (B) shown in claim 1 or a primary molded article made of the thermoplastic elastomer (B) shown in any one of claims 1 to 10 to gold. The polyacetal resin composition (A) according to any one of claims 1 to 9 after being placed in a mold.
15. The method for molding a composite molded article according to claim 14, characterized by performing secondary injection molding. 16. A primary molded article composed of the polyacetal resin composition (A) is placed in a mold in a state of being preheated so that the surface temperature thereof is 80 ° C. or higher, and then the thermoplastic elastomer (B) is secondary. Injection molding is carried out, The molding method of the composite molded object of Claim 15 characterized by the above-mentioned. 17. The method for molding a composite molded article according to claim 16, wherein the secondary injection molding temperature of the thermoplastic elastomer (B) is not less than the melting point of the polyacetal resin used for the primary molded article.