JP2002138185A - Jointed structure of thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a jointed structure having excellent weld strength between a polyacetal resin and other thermoplastic resin represented by polyethylene. SOLUTION: This jointed structure of thermoplastic resin comprising two or more resin components is characterized in that at least one of the adjacent two components constitutes a structure consisting of (A) component and (B) component, where (A) component is a resin composition comprising 5 to 80 wt.% of polyacetal resin (A-1 component) and 20 to 95 wt.% of one or more resin composition (A-2 component) selected from the group consisting of a polyolefin resin, an olefinic elastomer and a hydrogenated butadiene elastomer and (B) component is a thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a joined structure in which a polyacetal resin molded product and a thermoplastic resin molded product are integrated, and a vehicle component, an electric / electronic device component, and an OA-related component comprising the structure. And various industrial miscellaneous parts.

[0002]

2. Description of the Related Art Polyacetal resins have excellent mechanical strength, creep properties, lubrication properties, and electrical properties.
For example, they are widely used for automobile parts, electric / electronic device parts, OA-related parts, various industrial miscellaneous parts, and the like. In particular,
Taking advantage of the excellent fuel resistance characteristics of polyacetal resin, for example, automobile materials such as bracket materials, fuel tank flanges, valves, etc. for in-tank type fuel pump devices as disclosed in JP-A-8-279373. It is often used for fuel parts.

[0003] In recent years, from the viewpoint of environmental protection, there has been studied a direction in which the total amount of hydrocarbons emitted from a vehicle is regulated (commonly known as an evaporation regulation). When mounting the polyacetal resin valve to be mounted on a multi-layer, multi-layer blow-molded resin fuel tank whose outermost layer is made of polyethylene resin, for example, a method of screwing in using a rubber O-ring at the seal portion However, this has a problem of fuel evaporation from the O-ring portion. One way to solve this problem is to weld a polyacetal resin valve to the outermost layer of polyethylene, which is a resin fuel tank.
The fusion of the interface with the dissimilar material was insufficient, and the interface was easily peeled off by an external force, and did not satisfy the function as an integral structure in use. For the purpose of supplementing the fusibility between the polyacetal resin and the dissimilar material, there have been some ideas such as providing a shape structure having a mechanical anchor effect such as providing an undercut or a through hole, but the shape has been complicated, The process is complicated and economically disadvantageous, and is not desirable in terms of production efficiency.

In particular, with regard to polyacetal resin, there has been a strong demand for the development of a joint structure integrated with a different material. Numerous proposals have been made for a method of joining and integrating a polyacetal resin and another thermoplastic resin.
A multilayer blow-molded product sandwiching an adhesive resin layer made of a modified olefin polymer for the purpose of increasing the bonding strength between the two layers is shown, but in this case, a polyacetal resin layer and a modified olefin polymer layer The bonding strength between them is insufficient and is not practical. Also, JP-A-2000-8
No. 981 discloses a method of integrating a polyethylene resin component and a polyacetal resin component by using a cyclic welding portion made of a modified polyolefin resin to which a polar functional group is added. The welding strength between the part and the polyacetal resin part is extremely small and cannot be put to practical use.

In Japanese Patent Application Laid-Open No. 11-320605, an injection molded article of a polyacetal resin is mounted on a mold, and a surface skin layer of the molded article is treated with a flame or the like.
Injection molding of another thermoplastic resin, a composite molded product by so-called resin insert injection molding is shown, but in this case, the bonding strength between the polyacetal resin and the other thermoplastic resin is still insufficient, In addition, the process for heat-treating the surface of the polyacetal resin molded product using a flame, hot air, or the like is complicated and not economically feasible.

Japanese Patent Application Laid-Open No. 11-320606 discloses a composite molded product obtained by mounting a polyacetal resin injection molded product in a mold and injection molding a polyalkylene terephthalate resin by so-called resin insert injection molding. In this case, the width of the injection molding conditions of the polyalkylene terephthalate resin on the secondary side is narrow, for example, unless carefully selecting a plasticizing cylinder temperature, a filling time, and the like,
There is a possibility that a composite molded product with insufficient bonding strength may be obtained, and there is a problem that the setting of the conditions is complicated and a large amount of labor is required for quality control during mass production at a molding factory or the like.

[0007]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a joint structure in which a polyacetal resin and a dissimilar material are integrated, and a resin product such as an automobile part comprising the joint structure. It is intended to do so.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have been selected from polyacetal resins and polyolefin resins, olefin elastomers, or hydrogenated butadiene elastomers. A bonded structure of a resin composition in which one or more resins are mixed and a thermoplastic resin has been found, and the present invention has been achieved. That is, in the present invention, in a thermoplastic resin bonded structure composed of two or more resin components, the component (A) is used in an amount of 5 to 80% by weight of a polyacetal resin, a polyolefin resin, an olefin-based elastomer, or hydrogen. A resin composition comprising 20 to 95% by weight of at least one resin selected from added butadiene-based elastomers, the component (B) being a thermoplastic resin, and the two other components being component (A) -component (B) It is a structure in which the components are joined together. Preferably, the component (C) is a polyacetal resin,
The present invention relates to a thermoplastic resin joint structure having at least one structure joined in the order of component- (A) component- (B) component, and a resin product such as an automobile part comprising the resin joint structure. .

Hereinafter, the present invention will be described in detail. The polyacetal resin used as the component (A-1) in the present invention is obtained by polymerizing cyclic oligomers such as formaldehyde or its trimeric trioxane or tetramer tetraoxane, and terminating the polymer with ether and / or ether.
Or a polyacetal homopolymer blocked by an ester group, and a cyclic oligomer such as formaldehyde, its trimer trioxane or its tetramer tetraoxane, ethylene oxide, propylene oxide, 1,3-dioxolane, Polyacetal copolymer obtained by copolymerizing and / or block copolymerizing cyclic ethers such as glycol formal and diglycol formal, and / or a polymer having a hydroxyl group, carboxyl group, amino group, ester group or alkoxy group. 80 mol of oxymethylene units derived from a cyclic oligomer such as formaldehyde, its trimer trioxane or its tetramer tetraoxane.
% Or more.

Of these, a polyacetal copolymer is preferred, and the molecular terminal of the polyacetal copolymer contains a hydroxyalkyl group. The concentration of the hydroxyalkyl group terminal is 5.times.10 ^A polyacetal copolymer having a content of ^-5 mol or more is preferred. More specifically, there are various methods for adjusting the concentration of hydroxyalkyl group terminals in the polyacetal copolymer.
Water, alcohols such as methanol and ethanol, acids such as formic acid and the like may be chain-transferred, and polymers containing hydroxyl groups may be chain-transferred. If necessary, formal such as methylal may be added at the same time.

A particularly preferred polyacetal copolymer is a polyacetal block copolymer obtained by chain-transferring a polymer containing a hydroxyl group and having a molecular weight of 500 to 10,000. For example, one end or both ends are hydroxyl groups. Polyacetal block copolymers obtained by chain transfer of certain polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like can be given. More preferably, the number average molecular weight represented by the following (formula 1) is 10,000 to 500,0.
00 is a polyacetal block copolymer.

[0012]

Embedded image

(Wherein, other than A (hereinafter referred to as B block)
Is m = 2-98 mol%, n = 2-98 mol%, n + m
= 100 mol%, and the units in parentheses of m are present at random or in blocks with respect to the units in parentheses of n, and hydrogenated at both ends by hydroxyalkylation having a number average molecular weight of 500 to 10,000. It is a liquid polybutadiene residue. However, the B block has an iodine value of 20 g-I
_It may have an unsaturated bond of 2/100 g or less. k is an integer selected from 2 to 6, and two k's may be the same or different. R is selected from hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and may be the same or different. A is a polyoxymethylene copolymer residue represented by the following (Formula 2).

[0014]

Embedded image

(R ₁ is selected from hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and may be the same or different, and j is an integer selected from 2 to 6. X = 95 to 99.9 mol%, y =
5 to 0.1 mol%, x + y = 100 mol%, the units in parentheses of y are present at random with respect to the units in parentheses of x. ), (Formula 1), the average number average molecular weight of the two A blocks is 5,000 to 250,000. )

As the polymerization catalyst for the polyacetal copolymer, a cationic active catalyst such as a Lewis acid, a protonic acid and its ester or anhydride is preferable. As Lewis acids,
Examples include halides of boron, tin, titanium, phosphorus, arsenic, and antimony. Specifically, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, and antimony pentafluoride And its complex compounds or salts. Examples of the protonic acid, its ester or anhydride include perchloric acid, trifluoromethanesulfonic acid, perchloric acid-tertiary butyl ester, acetyl perchlorate, trimethyloxonium hexafluorophosphate, and the like. Among them, boron trifluoride, boron trifluoride hydrate, and a coordination complex compound of an organic compound containing an oxygen atom or a sulfur atom and boron trifluoride are preferable, and specifically, boron trifluoride diethyl ether And boron trifluoride di-n-butyl ether as a preferred example. The amount of these polymerization catalysts used is
When trioxane is used for the origin of oxymethylene,
The amount is preferably from 1 × 10 ⁻⁶ mol to 1 × 10 ⁻³ mol, more preferably from 5 × 10 ⁻⁶ mol to 1 × 10 ⁻⁴ mol, per 1 mol of the total amount of the trioxane and the cyclic ether and / or cyclic formal.

The polymerization method is not particularly limited as long as it is a conventionally known polymerization method for a polyacetal copolymer.
For example, bulk polymerization can be mentioned, and this bulk polymerization may be either a batch type or a continuous type. This bulk polymerization generally uses a monomer in a molten state, and generally obtains a solid bulk polymer as the polymerization proceeds. Deactivation of the polymerization catalyst in the polymerized polyacetal copolymer is achieved by converting the polyacetal copolymer obtained by the above polymerization reaction to ammonia, triethylamine, tri-n-
An amine such as butylamine, or an alkali metal or alkaline earth metal hydroxide, an inorganic acid salt, an aqueous solution or an organic solvent solution containing at least one catalyst neutralizing deactivator such as an organic acid salt, and slurry. In this state, the stirring is generally performed for several minutes to several hours. After the catalyst is neutralized and deactivated, the slurry is filtered and washed to remove unreacted monomers and catalyst deactivator, and then dried. Further, a method of inactivating a polymerization catalyst by contacting a vapor of ammonia, triethylamine or the like with the polyacetal copolymer, or a method of hindered amines, at least one of triphenylphosphine, calcium hydroxide, and the like and the polyacetal copolymer. A method of deactivating the catalyst by contacting with a mixer can also be used.

Next, the terminal stabilization treatment of the polyacetal copolymer after the deactivation of the polymerization catalyst will be described. As a method for decomposing and removing the unstable terminal, for example, using a single-screw extruder with a vent or a twin-screw extruder with a vent, ammonia, triethylamine, aliphatic amines such as tributylamine, calcium hydroxide Melting the polyacetal copolymer in the presence of a basic substance capable of decomposing unstable terminal portions such as hydroxides, inorganic weak acid salts, and organic weak acid salts of a representative alkali metal or alkaline earth metal, Unstable ends can be removed. Among them, preferred is a method of treating a thermally unstable terminal using at least one quaternary ammonium compound represented by the following (formula 3), and the polyacetal copolymer stabilized by the above method. Almost no unstable ends remain in the coalescence.

[0019]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently an unsubstituted or substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, Number 1
An aralkyl group having at least one unsubstituted alkyl group or substituted alkyl group substituted with at least one aryl group having 6 to 20 carbon atoms, or an unsubstituted alkyl group or substituted alkyl group having 1 to 30 carbon atoms. Wherein the unsubstituted or substituted alkyl group is linear, branched or cyclic. In the unsubstituted alkyl group, aryl group, aralkyl group, and alkylaryl group, a hydrogen atom may be substituted with halogen. n represents an integer of 1 to 3. X is a hydroxyl group or 1 to 20 carbon atoms
Represents an acid residue of a carboxylic acid, a hydrogen acid, an oxo acid inorganic thioacid or an organic thioacid having 1 to 20 carbon atoms. )

With respect to the quaternary ammonium salt compound, specifically, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetra-n-butylammonium, cetyltrimethylammonium, tetradecyltrimethylammonium,
6-hexamethylenebis (trimethylammonium),
Decamethylene-bis- (trimethylammonium), trimethyl-3-chloro-2-hydroxypropylammonium, trimethyl (2-hydroxyethyl) ammonium, triethyl (2-hydroxyethyl) ammonium, tripropyl (2-hydroxyethyl) ammonium, -N-butyl (2-hydroxyethyl) ammonium, trimethylbenzylammonium, triethylbenzylammonium, tripropylbenzylammonium, tri-n-butylbenzylammonium, trimethylphenylammonium, triethylphenylammonium, trimethyl-2-oxyethylammonium,
Hydroxides such as monomethyltrihydroxyethylammonium, monoethyltrihydroxyethylammonium, octadecyltri (2-hydroxyethyl) ammonium, tetrakis (hydroxyethyl) ammonium, etc .; nitric acid,
Phosphoric acid, carbonic acid, boric acid, chloric acid, iodic acid, silicic acid, perchloric acid, chlorous acid, hypochlorous acid, chlorosulfuric acid, amidosulfuric acid,
Oxic acids such as disulfuric acid, tripolyphosphoric acid, etc. Carboxylate and the like. Among them, hydroxide (OH ⁻ ), sulfuric acid (HSO ₄ ⁻ ,
Preferred are salts of SO ₄ ²⁻ ), carbonic acid (HCO ₃ ⁻ , CO ₃ ²⁻ ), boric acid (B (OH) ₄ ⁻ ), and carboxylic acid. Particularly preferred are the salts of formic acid, acetic acid and propionic acid.

These quaternary ammonium compounds may be used alone or in combination of two or more. The addition amount of the quaternary ammonium compound is calculated based on the amount of nitrogen derived from the quaternary ammonium compound represented by the following (Formula 4) with respect to the polyacetal copolymer.
It is 0.05 to 50 ppm by weight. P × 14 / Q (Formula 4) (where, P represents the concentration (wt ppm) of the quaternary ammonium compound with respect to the polyacetal copolymer, 14 is the atomic weight of nitrogen, and Q is the quaternary ammonium compound. Represents molecular weight.)

The polyacetal resin of the component (A-1)
Preferably, it is a polyacetal copolymer, in which the molecular terminal contains a hydroxyalkyl group, and the average terminal concentration of the hydroxyalkyl group is at least 5 × 10 ⁻⁵ mol per mol of oxymethylene unit. , More preferably at least 10 × 10 ⁻⁵ mol, even more preferably at least 30 × 10 ⁻⁵ mol. The hydroxyalkyl group terminal concentration referred to in the present invention is obtained by reacting the polyacetal copolymer with acetic anhydride at a temperature not higher than its melting point,
It refers to a value obtained by acetylating a terminal hydroxyalkyl group, quantifying the number of acetylated terminals by an infrared absorption spectrum, and converting the number to the number of moles per mole of oxymethylene.

Regarding the constitution of the polyacetal resin of the component (A-1), the above-mentioned polyacetal copolymer may be used alone or as a mixture of two or more kinds. Further, for example, a mixture with one or more polyacetal polymers having a hydroxyalkyl group terminal concentration of less than 5 × 10 ⁻⁵ mol per mol of oxymethylene unit may be used. Examples of the polyacetal polymer that can be used include formaldehyde or a polyacetal homopolymer obtained by polymerizing a cyclic oligomer such as trioxane (trimer) or tetraoxane (tetramer) and terminating the polymer with ether and / or ester groups. And formaldehyde, or trioxane or its trimer, trioxane or tetramer, and copolymerized with cyclic ethers such as ethylene oxide, propylene oxide, 1,3-dioxolan, and 1,4-butanediol formal. Polyacetal copolymer, a polymer having a crosslinked or branched molecular chain, or a polyacetal block copolymer containing a segment composed of oxymethylene units and a heterogeneous component segment, wherein the terminal of the polymer is ether and / or Those blocked with ester bonds. Preferred polyacetal polymers include polyacetal homopolymer, ethylene oxide and 1,3-
A polyacetal copolymer obtained by copolymerizing dioxolane is exemplified. More preferably, it is a polyacetal copolymer obtained by copolymerizing ethylene oxide or 1,3-dioxolane. The melting point of the polyacetal copolymer used as the polyacetal polymer in the present invention is not particularly limited, and is selected according to the polyacetal resin as the component (A-1) described later. Preferably,
140-173 ° C. The melting point in the present invention is defined as a differential scanning calorimeter (DSC7 manufactured by PerkinElmer).
It is a value measured using. The polyacetal copolymer sample was cut out from a sample formed into a film by a press machine heated to 200 ° C., and 5 mg was cut out and used for measurement.
The measurement conditions were as follows: the temperature was raised from 30 ° C. to 200 ° C. at 320 ° C./min, held for 2 minutes, lowered to 130 ° C. at 10 ° C./10 min, and further raised from 130 ° C. at 2.5 ° C./min. I do. When the temperature rises last, an endothermic peak accompanying crystallization is observed, and the peak top temperature at this time is defined as the melting point.

The melt index (hereinafter, referred to as MFR) of the polyacetal polymer is not particularly limited, and is selected according to the polyacetal resin as the component (A-1) described later. Preferably, 0.1 to 200 g
/ 10 minutes. The MFR in the present invention is ASTM-
It is a value measured at 190 ° C. under a load of 2160 g according to D1238. Next, the terminal group of the copolymer chain contained in the polyacetal copolymer preferably used in the component (A-1) in the present invention will be described in detail.

In the present invention, the component (A-1)
One or more types of polyacetal copolymer
End groups of polyacetal copolymer chains
Is a methoxyl group (-OCH_Three)) And other alkoxyl groups,
Hydroxyethyl group (-CH _TwoCH_TwoOH)
A xyalkyl group and a formate group. Carbon number
But at least one terminal alkosyl group is
Formed by the added molecular weight regulator formal
It is. For example, in general, methylal [(CH_ThreeO)_Two
CH_Two] Is used as a molecular weight modifier, but in this case,
A methoxyl group is formed as an end group. Terminal alkoxy
The carbon number of the sil group is not particularly limited, but it may be a molecular weight regulator.
From the viewpoint of synthesis and purification of a certain formal, C 1-10
Is generally, and may have 1 to 3 carbon atoms.
preferable.

A terminal hydroxyalkyl group such as a hydroxyethyl group or a hydroxybutyl group is used when a water, alcohol (for example, methanol) or acid (for example, formic acid) or the like is used as a molecular weight regulator in a polymerization step, or a hydroxyl group is added to a terminal. When a compound or the like having a chain transfer is used, first, a hydroxymethyl group (—CH ₂ OH) is generated.
When the polyacetal copolymer having a hydroxymethyl group at its terminal is subjected to post-treatment, for example, heat treatment in the presence of an aqueous solution of an alkaline substance such as an aqueous solution of triethylamine, the unstable portion containing the hydroxymethyl group is decomposed.
When this decomposition proceeds inward in the main chain containing the oxymethylene unit and the oxyalkylene unit and reaches the oxyalkylene unit, the oxyalkylene unit in that portion becomes stable, such as a hydroxyethyl group or a hydroxybutyl group. To a terminal structure. The number of carbon atoms of the hydroxyalkyl group is not particularly limited, but is preferably at least two. In particular, those having 2 to 10 carbon atoms are preferable from the viewpoint of synthesis and purification of cyclic ether and cyclic formal.

In the present invention, the above-mentioned decomposition of the unstable portion containing a hydroxymethyl group having 1 carbon atom is completely achieved, and all the hydroxymethyl groups are substituted with hydroxyalkyl groups having 2 or more carbon atoms. This is the most preferred form. However, even if some amount of hydroxymethyl group remains, it can be preferably used in the present invention. The remaining amount of the hydroxymethyl group can be quantified using the amount of formaldehyde gas generated from the polyacetal copolymer used as the component (A-1) as an index.
That is, the unreacted portion of the decomposition reaction is accelerated by heat, and the amount of formaldehyde generated by the decomposition is measured,
In this method, the value is used as an index instead of the remaining amount of the hydroxymethyl group. Specifically, the polyacetal copolymer is placed in an aluminum container, heated and melted at 230 ° C. for 50 minutes under a nitrogen atmosphere, and the formaldehyde gas generated at that time is absorbed in an aqueous solution of sodium sulfite, and the sulfuric acid is adjusted to a moderately specified concentration of sulfuric acid. In this method, the amount of formaldehyde gas generated is determined from the titer. In the present invention, the amount of formaldehyde gas generated is preferably 2500 ppm or less, more preferably 1500 ppm or less, based on the polyacetal copolymer. At this time, it is important that a necessary amount of an antioxidant or a heat stabilizer described below is blended with the polyacetal copolymer used as a sample. The amount of the antioxidant alone depends on the type of the antioxidant, but is generally about 10% by weight of the polyacetal copolymer.
0.3 parts by weight or more is preferable to 0 parts by weight.

The melting point of the polyacetal resin of the component (A-1) of the present invention is not particularly limited, and may be selected, for example, from the conditions used for automobile parts. Preferably, it is 140 ° C to 173 ° C. Also, (A-1)
The MFR of the polyacetal resin as a component is not particularly limited, and may be selected according to the conditions to be used, similarly to the melting point, and is generally preferably 0.1 to 200 g / 10 min, more preferably 0.1 to 200 g / 10 min. ~ 120 g / 10 min. The polyolefin resin used as the component (A-2) in the present invention is a homo- or copolymer of an olefin-based unsaturated compound represented by the following (formula 5) or a modified product thereof, and a mixture of two or more thereof. It is.

[0030]

Embedded image (Wherein, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a carboxyl group, an alkylcarboxy group containing 2 to 5 carbon atoms,
An acyloxy group having 2 to 5 carbon atoms or a vinyl group is meant. )

Specifically, polyethylene (high-density polyethylene, medium-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene), polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer Polymer, polypropylene-butene copolymer, polybutene, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and saponified product thereof And the like. Examples of the modified body include a graft copolymer obtained by grafting one or more other vinyl compounds, and a modified body having a compound having an acid anhydride group or a glycidyl group.

Among them, homopolymers and copolymers of polyethylene (high-density polyethylene, medium-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene), ethylene-propylene copolymer And block copolymers and ionomers containing ethylene as a main component, such as ethylene-butene copolymers. The molecular weight of these polyolefin-based resins is not particularly limited, but is preferably 10,10 in weight average molecular weight.
It is in the range of 000 to 1,000,000, more preferably 10,000 to 500,000, and still more preferably 10,000 to 300,000. Also, a copolymer of ethylene and glycidyl methacrylate and, if necessary, a monomer such as vinyl acetate or methyl acrylate, or a block copolymer of such a monomer can be preferably used.

As the olefin elastomer used as the component (A-2), a modified α-olefin polymer can be preferably used. The modified α-olefin polymer was obtained by graft copolymerizing an unsaturated carboxylic acid or an acid anhydride component unit thereof in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the α-olefin polymer as a base material. And the unsaturated carboxylic acid or the acid anhydride component unit of the graft monomer component constituting the polymer includes acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid. Acid, endocis-bicyclo [2,2,
1] Unsaturated carboxylic acids such as hept-5-ene-2,3 dicarboxylic acid (nadic acid) and methyl-endosis-bicyclo [2,2,1] hept-5-ene-2,3 dicarboxylic acid (methylnadic acid) Acids, anhydrides of the unsaturated carboxylic acids, specifically maleic anhydride, citraconic anhydride,
Examples include itaconic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and the like. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferred, and maleic acid or maleic anhydride is particularly preferred. The α-olefin component units constituting the modified α-olefin polymer include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, heptene-1, and octene-.
1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, or eicosene-1
1, aliphatic substituted vinyl monomers such as isobutylene and the like, and one or more of the above. Further, aromatic vinyl monomers such as styrene and substituted styrene, vinyl acetates, acrylates, methacrylates, glycidyl acrylates, glycidyl methacrylates, hydroxyethyl methacrylates, and other ester-based vinyl monomers, acrylamide , Allylamine, vinyl-p-aminobenzene,
A nitrogen-containing vinyl monomer such as acrylonitrile and a diene such as butadiene, cyclopentadiene, 1,4-hexadiene and isoprene may be contained as constituents.

Further, the α-olefin polymer is preferably produced using a single-site catalyst.
The single-site catalyst is described in Japanese Patent Publication No. 4-12283, JP-A-60-35006, JP-A-60-35.
007, JP-A-60-35008, JP-A-63-280703, JP-A-5-155930, JP-A-3-1630088, U.S. Pat.
No. 72236, a metallocene catalyst containing 1 to 3 molecules of cyclopentadienyl or substituted cyclopentadienyl, and a catalyst having uniform active site properties such as a catalyst by geometric control. . The preferred content of cyclopentadienyl or substituted cyclopentadienyl is 1-2 molecules. Further, more preferably used metal components are titanium, zirconium, silicon and hafnium.

Specific preferred metallocene catalysts include cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) zirconium dichloride, and bis (cyclopentadienyl) zirconium monomethyl monochloride. Chloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dialkyl, bis (cyclopentane Dienyl) zirconium diphenyl, dimethylsilyl dicyclopentadienyl zirconium dimethyl, methyl phosphine dicyclopentadienyl zyl Zirconium compounds of sulfonium such as dimethyl, bis (indenyl) titanium diphenyl, bis (cyclopentadienyl) titanium dialkyl, bis (cyclopentadienyl) titanium diphenyl, bis (methylcyclopentadienyl) titanium dialkyl, bis (1,
Titanium compounds such as 2-dimethylcyclopentadienyl) titanium diphenyl and bis (1,2-dimethylcyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl and the like And a vanadium compound such as bis (cyclopentadienyl) vanadium chloride.

Specific preferred catalysts by geometric control include (tertiary butyl amide)-(tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl zirconium dichloride and (tertiary tertiary butyl). Butyramide)-(tetramethyl-η5-cyclopentadienyl)
-1,2-ethanediyltitanium dichloride, (methylamide)-(tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide)-(tetramethyl-η5-cyclopentadienyl) -methylenetitanium dichloride,
(Tertiary butylamide) dimethyl- (tetramethyl-η
5-cyclopentadienyl) silane titanium dichloride, (tert-butylamido) dimethyl (tetramethyl-
η5-cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl- (tetramethyl-η5-cyclopentadienyl) silanetitanium dichloride, (phenylphosphido) dimethyl- (tetramethyl-η5-cyclopentadienyl) ) Silane zirconium dibenzyl and the like.

It is also preferable to use a co-catalyst as the single-site catalyst at the same time. For specific co-catalysts,
Those described in the above publications can be used. Preferred co-catalysts include methylaluminoxane,
Organoaluminum oxy compounds having an alkyloxyaluminum unit as a repeating unit such as ethylaluminoxane; organoaluminum compounds such as alkylaluminum and trialkylaluminum; [Bu ₃ NH]
One or more selected from [B (C ₆ H ₄ R) ₄ ], C ₂ B ₉ H ₁₃ , water, Lewis acid, ammonium salt and the like.

Among the α-olefin polymers produced using the single-site catalyst, particularly preferred are copolymers of ethylene and one or more α-olefins having 3 to 20 carbon atoms. In addition, as the α-olefin-based copolymer, a copolymer of propylene and one or more α-olefins having 3 to 20 carbon atoms can be preferably used.
Further, a hydrogenated polybutadiene elastomer can be preferably used as the component (A-2).
Further, it is more preferable to use two or more kinds of preferable substances as the component (A-2).

The mixing ratio of the component (A) in the present invention is as follows:
The polyacetal resin of the component (A-1) is 5 to 80% by weight based on the total weight of the component (A), the polyolefin resin of the component (A-2), an olefin-based elastomer, or
The content of one or more resins selected from hydrogenated butadiene elastomers is 20 to 95% by weight. (A-
If the amount of the component (2) is less than 20% by weight, the bonding strength between the component (B) and the thermoplastic resin is undesirably reduced. or,
When the amount of the component (A-2) exceeds 95% by weight, the component (A-1)
It is not preferable because physical properties such as fuel permeation resistance inherent in the polyacetal copolymer as a component are significantly impaired. The preferred compounding ratio is such that the component (A-1) is 10 to 80% by weight,
The component (A-2) is 20 to 90% by weight, and a more preferable compounding ratio is that the component (A-1) is 15 to 80% by weight,
The component (A-1) is 15 to 60% by weight, and the component (A-1) is more preferably 20 to 85% by weight.
2) The component is 40 to 85% by weight. Furthermore, (A-
1) The component is 20 to 60% by weight, and the component (A-2) is 40 to 40% by weight.
A blending ratio of 80% by weight is more preferred. In fact, for example,
When used as an automobile part, it is preferable to select the mixing ratio based on conditions such as the environment in which the part is used.

Next, additives that can be added to the component (A) of the present invention are used in conventional polyacetal resins, polyolefin resins, olefin elastomers, and hydrogenated butadiene elastomers. Additives, such as heat stabilizers, antioxidants,
One or more of a weather (light) stabilizer, a releasing agent, a lubricant, a crystal nucleating agent, and an antistatic agent may be used in combination and added in a desired amount as needed. In addition, inorganic fillers such as glass fiber, talc, wollastonite and hydrotalcite, carbon black, pigments and the like can be added in desired amounts as needed. Examples of additives and the like conventionally used in polyacetal resins are as follows. Examples of the heat stabilizer include (i) hydroxides, inorganic acid salts, carboxylate salts or alkoxides of alkali metals or alkaline earth metals, (b) compounds containing formaldehyde-reactive nitrogen, and polymers.

(A) Examples of the alkali metal or alkaline earth metal hydroxide, inorganic acid salt, carboxylate or alkoxide include hydroxides such as sodium, potassium, magnesium, calcium and barium;
Examples of the metal include a carbonate, a phosphate, a silicate, a borate, and a carboxylate. The carboxylic acid of the carboxylate is a saturated or unsaturated aliphatic carboxylic acid having 10 to 36 carbon atoms, and these carboxylic acids may be substituted with a hydrosyl group. Examples of the saturated aliphatic carboxylic acid include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, melicic acid, and celloplastic acid. Examples of the unsaturated aliphatic carboxylic acids include undecylenic acid, oleic acid, elaidic acid, setleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, and stearic acid. Examples of the alkoxide include methoxide and ethoxide of the above metals. Among them, calcium difatty acid comprising at least one fatty acid having 10 to 36 carbon atoms is preferably used, and particularly, palmitic acid, heptadecyl acid and stearic acid are preferable. The addition amount of these calcium fatty acid is 100% of the total of the component (A).
It is preferably used in the range of 0.01 to 2 parts by weight based on part by weight.

(B) Formaldehyde The compounds containing reactive nitrogen include (1) dicyandiamide, (2) amino-substituted triazine, and (3) co-condensates of amino-substituted triazine and formaldehyde. (2) As the amino-substituted triazine, for example, guanamine (2,
4-diamino-sym-triazine), melamine (2,
4,6-triamino-sym-triazine), N-butylmelamine, N-phenylmelamine, N, N-diphenylmelamine, N, N-diallylmelamine, N, N ',
N "-triphenylmelamine, N-methylolmelamine, N, N'-dimethylolmelamine, N, N ', N"
-Trimethylolmelamine, benzoguanamine (2,4
-Diamino-6-phenyl-sym-triazine),
2,4-diamino-6-methyl-sym-triazine,
2,4-diamino-6-butyl-sym-triazine,
2,4-diamino-6-benzyloxy-sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-s
ym-triazine, 2,4-diamino-6-chloro-s
ym-triazine, 2,4-diamino-6-mercapto-sym-triazine, 2,4-dioxy-6-amino-sym-triazine, 2-oxy-4,6-diamino-sym-triazine, N, N ' , N "-tetracyanoethylbenzoguanamine. (3) Examples of the co-condensate of an amino-substituted triazine with formaldehyde include a melamine-formaldehyde polycondensate.
Of these, dicyandiamide, melamine and melamine-formaldehyde polycondensates are preferred.

Further, (b) the polymer having a formaldehyde-reactive nitrogen group includes (1) a polyamide resin,
(2) a polymer obtained by polymerizing acrylamide and its derivative, or acrylamide and its derivative and another vinyl monomer in the presence of a metal alcoholate, (3) acrylamide and its derivative, or acrylamide and its derivative and other Polymers obtained by polymerizing vinyl monomers in the presence of a radical polymerization catalyst, (4) polymers having a nitrogen group such as amines, amides, urea and urethane, and the like.

As the polyamide resin (1), nylon 4-6, nylon 6, nylon 6-6, nylon 6-6
10, nylon 6-12, nylon 12, etc. and copolymer resins thereof, for example, nylon 6 / 6-6, nylon 6
/ 6-6 / 6-10, nylon 6 / 6-12 and the like. (2) As a polymer obtained by polymerizing acrylamide and a derivative thereof, or acrylamide and a derivative thereof and another vinyl monomer in the presence of a metal alcoholate, a poly-β-alanine copolymer may be mentioned. These polymers are described in JP-B-6-12259 and JP-B-5-8.
No. 7096, JP-B 5-47568 and JP-A-3-2.
It can be produced by the method described in each publication of No. 34729. (3) A polymer obtained by polymerizing acrylamide and a derivative thereof, or acrylamide and a derivative thereof and another vinyl monomer in the presence of a radical polymerization catalyst is to be produced by a method described in JP-A-3-28260. Can be.

As the antioxidant, a hindered phenol-based antioxidant is preferable, for example, n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -propionate, -Octadecyl-3
-(3'-methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis- (3- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate), 1,4-butanediol-bis- (3- (3,5-di-tert-butyl-4-).
Hydroxyphenyl) -propionate), triethylene glycol-bis- (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate),
Tetrakis- (methylene-3- (3 ′, 5′-di-t-
Butyl-4'-hydroxyphenyl) propionate methane, 3,9-bis- (2- (3- (3-t-butyl-
4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) 2,4,8,10-
Tetraoxaspiro (5,5) undecane, N, N'-
Bis-3- (3 ', 5'-di-t-butyl-4-hydroxyphenol) propionylhexamethylenediamine, N, N'-tetramethylenebis-3- (3'-methyl-5'-t-butyl -4-hydroxyphenol) propionyldiamine, N, N'-bis- (3- (3,5
-Di-t-butyl-4-hydroxyphenol) propionyl) hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-
1,2,4-triazole, N, N′-bis (2- (3
-(3,5-di-butyl-4-hydroxyphenyl) propionyloxy) ethyl) oxyamide. Among these hindered phenolic antioxidants, triethylene glycol-bis- (3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) -propionate), tetrakis- (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate methane, and triethylene glycol- Bis- (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate) is particularly preferred.

As the weather (light) stabilizer, (a) a benzotriazole-based substance, (b) an oxalic anilide-based substance and (c) a hindered amine-based substance are preferable. (A) As the benzotriazole-based substance, for example, 2- (2 ′
-Hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3,5-di-t-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3,5-di- Isoamyl-phenyl) benzotriazole, 2- (2′-hydroxy-3,5-bis- (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, 2- (2′-hydroxy-4′-octoxy) Phenyl) benzotriazole and the like,
Preferably 2- (2'-hydroxy-3,5-bis-
(Α, α-dimethylbenzyl) phenyl) -2H-benzotriazole and 2- (2′-hydroxy-3,5-di-t-butyl-phenyl) benzotriazole.

(B) As the oxalic acid anilide-based substance,
For example, 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-t-butyl-
2'-ethyloxalic acid bisanilide, 2-
Ethoxy-3'-dodecyloxalic acid bisanilide and the like.

(C) As the hindered amine-based substance,
For example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,
6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2 , 6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6
-Tetramethylpiperidine, 4-stearyloxy-
2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy- 2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4-
(Cyclohexylcarbamoyloxy) -2,2,6
6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2 2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2
2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetramethyl-4) -Piperidyl) -adipate, bis (2,
2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2 2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) tolylene-2,4-dicarbamate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate,
Tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate,
Tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate and the like are preferable, and bis (2,2,6,6-tetramethyl-4) is preferable. -Piperidyl) -sebacate. The hindered amine-based substances may be used alone or in combination of two or more. Also, a combination of the above-mentioned benzotriazole-based material or an oxalic anilide-based material and a hindered amine-based material is most preferable.

As the lubricant, (1) a silicone compound and a modified product thereof, (2) an alcohol or a fatty acid, and
Examples thereof include esters of alcohol and fatty acid, (3) esters of alcohol and dicarboxylic acid, (4) polyoxyalkylene glycol compounds, and (5) olefin compounds having an average degree of polymerization of 10 to 500. (1) As the silicone compound and its modified product, dimethylpolysiloxane and its methyl group are hydrogen, an alkyl group, an aryl group, an ether group, an ester group or a reactive substituent such as an amino group, an epoxy group, a carboxyl group, and a carboxy group. Examples include silicone compounds substituted with a hydroxyl group, a methacryl group, a mercapto group, a phenol group, a vinyl group, a polyether group, or a fluorine-containing alkyl group. Also, for example, polyethylene,
Polypropylene, polymethylpentene, polystyrene,
And those obtained by grafting a silicone compound to a copolymer thereof, an ethylene-vinyl acetate copolymer, or the like.

(2) In alcohols or fatty acids and esters of alcohols and fatty acids, examples of the alcohol include monohydric alcohols and polyhydric alcohols. Examples of the monohydric alcohol include octyl alcohol,
Caprylic alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, oleyl alcohol,
Examples include nonadecyl alcohol, eicosyl alcohol, behenyl alcohol, seryl alcohol, melisyl alcohol, 2-hexadecanol, 2-octyldodecanol, 2-decyltetradecanol, and 2-decylstearin alcohol. As polyhydric alcohol,
Polyhydric alcohols having 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol,
Examples include hexanediol, glycerin, diglycerin, triglycerin, pentaerythritol, arabitol, ribitol, xylitol, sorbite, sorbitan, sorbitol, mannitol and the like.

The fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, nanodecanoic acid, arachidic acid, and behenic acid. Acid, lignoceric acid, serotinic acid, heptaconic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, oleic acid, elaidic acid, setreic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, Propiolic acid,
Examples thereof include stearic acid and the like, and naturally occurring fatty acids containing such components or mixtures thereof. These fatty acids may be substituted with a hydroxy group. As esters of alcohols and fatty acids,
Examples of the above-mentioned monohydric and polyhydric alcohols and esters of alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol and the above-mentioned fatty acids are also mentioned.

(3) Esters of alcohol and dicarboxylic acid include octyl alcohol, nonyl alcohol,
Decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, oleyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol, behenyl alcohol, melisyl alcohol , Hexyl decyl alcohol, octyl dodecyl alcohol, decyl myristyl alcohol, saturated or unsaturated primary alcohols such as decyl stearyl alcohol and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Monoesters and diesters with dicarboxylic acids such as sebacic acid, undecanoic acid, brassic acid, maleic acid, fumaric acid, and glutaconic acid Le and mixtures thereof.

(4) Polyoxyalkylene glycol compounds include three types of compounds. The first group is a polycondensate containing an alkylene glycol as a monomer, for example, polyethylene glycol,
Examples thereof include polypropylene glycol and a block polymer of ethylene glycol and propylene glycol.
The second group is an ether compound of the first group and an aliphatic alcohol. For example, polyethylene glycol oleyl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol lauryl ether, polyethylene glycol tridecyl ether, polyethylene glycol nonyl phenyl ether and the like can be mentioned. Third
Is an ester compound of the first group and a higher fatty acid, such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate. These additives and the like that can be added to the component (A) include (A)
It may be derived from either the -1) component or the (A-2) component.

In the present invention, the component (A-1) and the component (A-2)
The component (A) can also be made into a composition of the component (A) by mixing and integrating the components with, for example, a conventionally known extrusion kneader or the like. For example, the components (A-1) and (A-
2) The composition is prepared by physically mixing the components and using a conventionally known molding machine such as an injection molding machine, a blow molding machine, an extrusion molding machine or a press molding machine to produce a molded article as the component (A). It is also possible to use At this time, it is also possible to use a master batch or the like in which the concentration of each component is increased. Furthermore, other thermoplastic resins may be mixed with the resin composition of the component (A) as long as the effects of the present invention are not impaired.

The thermoplastic resin used as the component (B) in the present invention is not particularly limited. Examples thereof include polypropylene, polyethylene, polyacetal, polyamide, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, and polystyrene. , ABS, AS, polycarbonate,
Examples of such resins include polymethyl methacrylate and the like, copolymers containing these as a main component, and conventionally known alloys such as polycarbonate-ABS and polycarbonate-polybutylene terephthalate. Among them, polyolefin resins represented by polypropylene and polyethylene are preferable. Also, 6-nylon, 6-6
Polyamides represented by nylon and the like can also be preferably used. Furthermore, in plastic fuel tank related parts for automobiles, polyethylene (high-density polyethylene,
Medium-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene) homopolymers, and ethylene as the main component, such as copolymers, ethylene-propylene copolymers, and ethylene-butene copolymers Particularly preferred are block copolymers and ionomers.

Next, the polyacetal resin as the component (C) refers to a polyacetal homopolymer, copolymer, block copolymer or the like, which is a conventionally known polyacetal resin. Further, as described in detail of the component (A-1) of the present invention, the molecular terminal contains a hydroxyalkyl group, and the concentration of the hydroxyalkyl group terminal is at least 5 × 10 ⁻⁵ mol per mol of oxymethylene unit. And the concentration of hydroxyalkyl groups at the molecular terminals is 5 × 10 ⁻⁵ per mole of oxymethylene unit.
Also included are polyacetal polymers that are less than mol. These polyacetal resins constituting the component (C) may be used alone or as a mixture of two or more.

MFR of polyacetal resin of component (C)
Is not particularly limited, and can be selected in a range where the joint structure of the present invention is preferably used. In general,
0.1 to 200 g / 10 min is preferable, and 0.1 to 120 g
g / 10 minutes is more preferred. When the polyacetal resin of the component (C) is a polyacetal copolymer, the melting point thereof is preferably from 140 ° C to 175 ° C. In addition, the polyacetal resin of the component (C) may contain conventionally known additives such as a heat stabilizer, an antioxidant, a weather (light) stabilizer, a release agent, a lubricant, a crystal nucleating agent, and an antistatic agent. One or two or more of them can be used in combination and added in a desired amount as needed.
In addition, inorganic fillers such as glass fiber, talc, wollastonite and hydrotalcite, carbon black, pigments and the like can be added in desired amounts as needed. Specific examples of these additives and the like are the same as those exemplified in the detailed description as the additives in the resin composition of the component (A). Further, the polyacetal resin as the component (C) of the present invention can be preferably used also as the component (B).

The thermoplastic resin bonded structure referred to in the present invention is a thermoplastic resin bonded structure composed of two or more types of resin components.
Component and component (B) have at least one structure, and component (A) and component (B) are welded, two or more types of dissimilar material injection molding, resin insert injection molding, two or more layers Structures that are integrated by molding methods such as co-extrusion molding of different materials, multi-layer blow molding of two or more layers, and
A thermoplastic resin bonded structure composed of two or more types of resin components has at least one structure bonded in the order of component (C) -component (A) -component (B), and Structure in which the resin components are integrated by molding methods such as welding, injection molding of two or more different materials, resin injection injection molding, coextrusion of two or more layers of different materials, and multilayer blow molding of two or more layers. Body. in this case,
The component (B) and the component (C) may be the same, or a thermoplastic elastomer such as a polyurethane-based, polyester-based, or polyamide-based elastomer may be integrated with the structure.

Further, in the case of a structure in which the components (C), (A), and (B) are joined in this order, for example, dissimilar materials such as the components (B) and (C) are used for the resin (A). When the component (A) is composed of a single structure when the components are formed into an integrated joint structure with the components being neutral, the components (A) and (B) and the component (A)-(C It is necessary to select the composition of the component (A) with due consideration of the balance of the respective bonding strengths between the components, but in certain applications, the range of selection may be reduced. In this case, (A)
By forming the component into a bonded body of two or more components (A) having different compositions, the component (A) is directly bonded to the component (B) and the component (A) is directly bonded to the component (C). The composition can be selected independently of each other, the bonding strength between the respective resin components is sufficiently increased, and a stronger thermoplastic resin bonded structure can be formed overall.
In such a joined body of the components (A), the concentration of the component (A-1) in the component (A) directly joined to the component (C) is different from that of the component (B). It is preferable that the concentration of the component (A-1) in the component (A) is larger than that of the component (A-1). Furthermore, when the joined body of the components (A) is composed of three or more types of the components (A), (A-1) in each of the components (A)
It is preferable that the component concentration decreases gradually from the component (A) directly bonded to the component (C) to the component (A) directly bonded to the component (B).

The details of the integration method will be described below.
The components (A) and (B) are composed of (a) welding, (b) injection molding of two or more different materials, (c) injection molding of resin insert, (d) co-extrusion of two or more layers of different materials, E) 2
It is integrated by multi-layer blow molding of more than one layer. (A) welding is conventionally known, (1) a hot-air welding method in which air or gas is used as a heating source to melt a welded portion of a resin component, and (2) a heated hot plate or a hot appliance is welded to a welded portion. Hot plate welding method in which the welded part is melted by direct contact with or without direct contact and heated by radiant heat, (3) heat seal welding or impulse seal welding using a heating ribbon, (4) A high-frequency welding method that melts a welded part by applying a high-frequency electric field to cause intermolecular friction, (5) An ultrasonic welding method that melts a welded part by ultrasonic vibration, (6) Friction between resins to be welded (7) A laser-absorbing substance such as carbon black is blended in the resin in advance, and a laser such as a diode, YAG, or an excimer is illuminated. And a laser welding method for melting weld, (8) Other, infrared, flame, welding method and the like used as a heating source solar like. Among them,
Hot plate welding, high frequency welding, ultrasonic welding, and laser welding are preferred. Further, it is also possible to preferably use a method in which the resin components formed in advance are overlapped with each other, and the resin is melted by using a press hot plate as a heat source using a press molding machine or the like, and further subjected to pressure compression and welding. in this case,
It is also possible to simultaneously weld three or more resin layers.

(B) For the injection molding of two or more different materials, a conventionally known method can be applied. After the component (A) is injection-molded first, the component (B) may be injection-molded,
Alternatively, injection molding may be performed in the reverse order. At this time, the previously injected components are cooled in the mold and fully solidified,
The latter component may be injection-molded, or the latter component may be injection-molded before the former component is sufficiently solidified in the mold. Further, a resin component other than the component (A) and the component (B) may be added, and three or more materials may be formed of different materials.

(C) In the resin insert injection molding, the component (A) or the component (B) is molded in advance by a conventionally known molding method, and the molded product is placed at a desired position in a mold. Later, the remaining components are injection molded,
It is preferably used in the present invention. (D) Coextrusion molding of two or more layers of different materials can also be preferably used in the present invention. If the two components are the component (A) and the component (B), together with the other components,
Three or more layers may be co-extruded. (E) Multi-layer blow molding of two or more layers can also be preferably used in the present invention. In this processing method, (A)
As long as the component and the component (B) are two components, multi-layer blow molding with three or more layers may be performed together with the other components.

Next, a structure joined in the order of component (C)-(A) -component (B) will be described. It is preferable that the two components, which have become the component (A) and the component (B), be integrated as described above. Similarly, for the two components that have become the component (C) and the component (A), (a) welding,
Processing methods such as (b) injection molding of two or more different materials, (c) injection molding of resin insert, (d) co-extrusion molding of two or more layers of different materials, and (e) multi-layer blow molding of two or more layers are preferably used. The preferred specific method is the same as described above.

The components (C), (A) and (B) are integrated in this order. First, the components (A) and (B) are integrated, and then the components (C) and (B) are integrated. It is possible to integrate the component (A) and the component (C) and the component (A), and then to integrate the component (A) and the component (B). It is. Also, each of the three components may be molded and integrated at the same time. In the forming method, it is preferable that the processing order and the like be selected from the product shape, the application to be used, environmental conditions, economy, and the like. The thermoplastic resin structure of the present invention is preferably used for automobile parts, electronic / electric machine parts, OA-related parts, various industrial goods parts and the like. In particular,
It is preferably used for automobile parts, and more preferably for various parts integrated with a resin fuel tank and a tank as shown in FIG.

Specific examples of the parts include floats arranged on various breather lines such as an evaporation line, a vent line, and a recirculation line integrated with a multi-layer, multi-layer, blow-molded fuel tank using a polyethylene resin as the outermost layer. Various valves such as valves, ball valves, bulk valves, and tubes, flanges, etc., bulk valves, float valves, etc.
Various valves, such as ball valves, and tubes, flanges, and other drain valves, and valves, such as drain valves, and tubes, flanges, etc. that release the pressure inside the fuel tank to the outside. Valves, such as pressure relief valves, tubes, flanges, etc., fuel sender modules, and their flanges, canisters, their flanges, and fuel supply pumps arranged in the line to be served And a swirl tank installed on the bottom of the tank for the purpose of preventing cavitation. Further, it can be preferably used for a fuel tank for automobiles.

[0066]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. First, measurement items and measurement conditions in the examples will be described. (1) Quantification of hydroxyalkyl group in polyacetal copolymer composition The polyacetal copolymer composition was reacted with acetic anhydride at a temperature of 148 ± 2 ° C. for 2 hours, and —O existing at the terminal was observed.
The H group was acetylated, the number of acetylated terminals was quantified using an infrared absorption spectrum, and the number of moles per mole of oxymethylene was evaluated. (2) Evaluation of Adhesive Strength The sample shown in FIG. 2 was welded by hot plate non-contact welding, using an Autograph AG-1000B manufactured by Shimadzu Corporation at a pulling speed of 5 mm / min, in the direction shown in 5 of FIG. And the welding strength was evaluated.

Example 1 A jacketed twin-screw paddle type continuous polymerization machine capable of passing a heat medium was adjusted to 80 ° C., and 40 mol / hour of trioxane containing 4 ppm of water + formic acid was simultaneously added to a cyclic formal. 1,3-dioxolane is supplied to a polymerization machine at a rate of 2 mol / hour, and boron trifluoride di-n dissolved in cyclohexane is used as a polymerization catalyst.
-Butyl etherate is added 5 × to 1 mol of trioxane.
10 so that the ^-5 mol, and methylal _{[(CH 3 O) 2 CH} 2] trioxane 1 mole 2 × 10- ³ continuously fed so that the mole out the polymerization with respect to a chain transfer agent did. After pouring the polymer discharged from the polymerization machine into a 1% aqueous solution of triethylamine to inactivate the polymerization catalyst, the polymer was filtered and washed, and 1 part by weight of the crude polyacetal copolymer after the filtration and washing was added. As the quaternary ammonium compound, triethyl (2-hydroxyethyl) ammonium formate is obtained by using the above (Formula 4).
It was added so as to be 20 ppm by weight in terms of the amount of nitrogen, mixed uniformly, and dried at 120 ° C. for 6 hours.

Next, triethylene glycol-bis (3- (3-t-butyl-5-methyl-methyl) was used as an antioxidant with respect to 100 parts by weight of the dry crude polyacetal copolymer.
0.3 parts by weight of 4-hydroxyphenyl) propionate) was added and fed to a vented twin screw extruder. To the molten polyacetal copolymer in the extruder was added 2 parts by weight of an aqueous triethylamine solution adjusted to water: triethylamine = 80: 1 based on 100 parts by weight of the polyacetal copolymer, and the extruder was set at a temperature of 200.
Decomposition of the unstable terminal portion was carried out at a temperature of 5 ° C. and a residence time of 5 minutes in the extruder. The polyacetal copolymer subjected to the decomposition treatment of the unstable terminal portion was degassed under the condition of a vent vacuum of 20 Torr, extruded as a strand from the extruder die, and pelletized (polyacetal copolymer (X1-
1)).

A part of the polyacetal copolymer (X1-1) thus obtained was taken out, and the terminal hydroxyalkyl group was quantified. Table 1 shows the results. Further, (A) was added to 100 parts by weight of the polyacetal copolymer (X1-1).
-2) As a component, high density polyethylene manufactured by Nippon Polychem Co., Ltd. (trade name: Novatec HDHJ330, hereinafter referred to as PO
-1) in an amount of 26.6 parts by weight (21.0% by weight as component (A-2)).
After adding 0.5 parts by weight of nylon 6-6 adjusted to μ and mixing uniformly, the mixture was supplied to the twin-screw extruder and melt-kneaded again to obtain pellets. 80 ℃
After drying for 24 hours using a SH-75 molding machine manufactured by Sumitomo Heavy Industries, which was adjusted to a cylinder temperature of 200 ° C and a mold temperature of 70 ° C, it was molded into an ASTM No. 1 dumbbell (X-1).

On the other hand, high-density polyethylene PO-1 was formed into an ASTM No. 1 dumbbell using a SH-75 molding machine manufactured by Sumitomo Heavy Industries, Ltd., which was adjusted to a cylinder temperature of 200 ° C. and a mold temperature of 70 ° C. (Y-1). . ASTM obtained as described above
Using a hot plate in which the No. 1 dumbbells (X-1) and (Y-1) were adjusted to the range shown in FIG.
Heating was performed for 30 seconds by a non-contact heating method using radiant heat, and a length of 1.5 mm was welded in the longitudinal direction to melt. Thereafter, as shown in FIG. 2, a test piece having a total length of 120 mm was cut out centering on the welded portion, and the welding strength was measured. Table 1 shows the measurement results.

Example 2 To 100 parts by weight of the polyacetal copolymer (X1-1) used in Example 1, 60 parts by weight of PO-1 (37.5% by weight as the component (A-2)) was added. Other than that, the same operation and molding as in Example 1
STM1 dumbbell was obtained (X-2). (X-2) and (Y-1) were welded in the same manner as in Example 1. Table 1 shows the results.

Example 3 Maleic anhydride-modified ethylene-butene-polymer was prepared by graft copolymerizing 0.9 part by weight of maleic anhydride with 100 parts by weight of the polyacetal copolymer (X1-1) used in Example 1. 1 copolymer (density 0.89g
/ Cm ³ , crystallinity 15%; hereinafter referred to as PO-2)
Except that 0 parts by weight (28.6% by weight as the component (A-2)) was added, the operation and molding were performed in the same manner as in Example 1;
TM1 dumbbell was obtained (X-3). (X-3) and (Y-1) were welded in the same manner as in Example 1. Table 1 shows the results.

Example 4 Polymerization and post-treatment were performed in the same manner as in Example 1, except that methanol was used as a chain transfer agent in an amount of 2 × 10 ⁻³ mol per mol of trioxane, instead of methylal. The operation was performed to obtain a pellet (polyacetal copolymer (X1-4)). A portion of the polyacetal copolymer (X1-4) thus obtained was taken out, and the terminal hydroxyalkyl group was quantified.
Table 1 shows the results. Polyacetal copolymer (X1-
4) 40 parts of PO-2 used in Example 3 was added to 100 parts by weight.
The same operation and molding process as in Example 1 were carried out except that parts by weight (28.6% by weight as the component (A-2)) and 0.04 parts by weight of calcium monopalmitate-monostearate as a heat stabilizer were added. Obtained ASTM No. 1 dumbbell (X
-4). (X-4) and (Y-1) were welded in the same manner as in Example 1. Table 1 shows the results.

(Example 5) Trioxane containing 4 ppm of water + formic acid was supplied to a polymerization machine at a rate of 40 mol / hour, and at the same time, 1,3-dioxolane as a cyclic formal was supplied to a polymerization machine at a rate of 2 mol / hour, and dissolved in cyclohexane as a polymerization catalyst. The boron trifluoride di-n-butyl etherate was used in an amount of 10 × 10 ⁻⁵ mol per 1 mol of trioxane,
As a chain transfer agent, polyethylene having hydroxyl groups at both terminals (Mn = 5000) was added in an amount of 0.5 to 1 mol of trioxane.
The polymerization was carried out by continuously feeding so as to give × 10 ^-3 mol. Except for the above, the same operation as in Example 1 was performed to obtain a pellet (polyacetal copolymer (X1-5)). The polyacetal copolymer composition (X1-
A part of 5) was taken out, and the terminal hydroxyalkyl group was quantified. Table 1 shows the results.

On the other hand, as a catalyst (tertiary butyl amide)
-(Tetramethyl-η5-cyclopentadienyl)-
Using 1,2-ethanediyltitanium dichloride, the ethylene-octene-1 copolymer produced by the method described in JP-A-3-16388 was used to prepare maleic anhydride 0.9.
30 parts by weight of a maleic anhydride graft-modified ethylene-octene-1 copolymer (hereinafter referred to as PO-3) obtained by graft copolymerizing parts by weight with a polyacetal copolymer (X1-
5) To 100 parts by weight, as a heat stabilizer, 0.04 parts by weight of monopalmitic acid-calcium monostearate were added (23.1% by weight as component (A-2)), and the mixture was uniformly mixed. The mixture was supplied to a screw extruder and melt-kneaded again to obtain pellets. This pellet was formed into an ASTM No. 1 dumbbell in the same manner as in Example 1 (X-5). (X
-5) and (Y-1) were welded in the same manner as in Example 1. Table 1 shows the results.

(Example 6) Trioxane containing 4 ppm of water + formic acid was supplied to a polymerization machine at a rate of 40 mol / hour, and at the same time, 1,3-dioxolane as a cyclic formal was supplied to a polymerization machine at a rate of 1 mol / hour, and dissolved in cyclohexane as a polymerization catalyst. The boron trifluoride di-n-butyl etherate was used in an amount of 10 × 10 ⁻⁵ mol per 1 mol of trioxane,
As a chain transfer agent, a polybutadiene (random copolymer) having hydrogenated hydroxyl groups at both ends represented by the following (formula 6) (Mn =
2330) was continuously fed at 1 × 10 ⁻³ mol per 1 mol of trioxane to carry out polymerization. Except for the above, the same operation as in Example 1 was performed to obtain a pellet (polyacetal copolymer (X1-6)).

[0077]

Embedded image

A part of the polyacetal copolymer (X1-6) thus obtained was taken out, and the terminal hydroxyalkyl group was quantified. Table 1 shows the results. 30 parts by weight of PO-2 used in Example 3 was added to 100 parts by weight of the polyacetal copolymer (X1-6) (2 parts as (A-2) component).
3.1% by weight), and as a heat stabilizer, monopalmitic acid-
ASTM 1
No. dumbbell was obtained (X-6). (X-6) and (Y-
1) was welded in the same manner as in Example 1. Table 1 shows the results.
Shown in

(Example 7) Trioxane containing 4 ppm of water + formic acid was supplied to a polymerization machine at a rate of 40 mol / hour, and at the same time, 1,3-dioxolane as a cyclic formal was supplied at a rate of 2 mol / hour, and dissolved in cyclohexane as a polymerization catalyst. The boron trifluoride di-n-butyl etherate was used in an amount of 10 × 10 ⁻⁵ mol per 1 mol of trioxane,
As a chain transfer agent, a polybutadiene (random copolymer) having hydrogenated hydroxyl groups at both terminals represented by the following (formula 7) (Mn =
3390) was continuously fed at 1 × 10 ⁻³ mol per 1 mol of trioxane to carry out polymerization. Except for the above, the same operation as in Example 1 was performed to obtain a pellet (polyacetal copolymer (X1-7)).

[0080]

Embedded image

A part of the polyacetal copolymer (X1-7) thus obtained was taken out, and the terminal hydroxyalkyl group was quantified. Table 2 shows the results. 50 parts by weight of PO-2 used in Example 3 was added to 100 parts by weight of the polyacetal copolymer (X1-7) (3 parts as (A-2) component).
3.3% by weight), and as a heat stabilizer, monopalmitic acid-
ASTM 1
No. dumbbell was obtained (X-7). (X-7) and (Y-
1) was welded in the same manner as in Example 1. Table 2 shows the results.
Shown in

(Example 8) The polyacetal copolymer (X1-1) used in Example 1 and the polyacetal copolymer (X1-7) used in Example 7 were blended at a ratio of 4: 6. It was fed to a vented twin screw extruder.
(Polyacetal copolymer (X1-8)). A portion of the polyacetal copolymer (X1-8) thus obtained was taken out, and the terminal hydroxyalkyl group was quantified.
Table 2 shows the results. Further, a polyacetal copolymer (X
1-8) 100 parts by weight of PO as component (A-2)
-2, 50 parts by weight, and 10 parts by weight of a polyethylene copolymer (hereinafter referred to as PO-4) obtained by copolymerizing 12% by weight of glycidyl methacrylate of MFR 3.0 ((A-2)
37.5% by weight as a component), and as a heat stabilizer,
The same operation and molding as in Example 1 were carried out except that nylon 6-6 adjusted to an average particle diameter of 4 μ and 0.5 part by weight of nylon 6-6 were obtained to obtain an ASTM No. 1 dumbbell (X-8).
(X-8) and (Y-1) were welded in the same manner as in Example 1. Table 2 shows the results.

(Example 9) 100 parts by weight of the polyacetal copolymer (X1-8) used in Example 8 was added to (A-2)
As a component, 50 parts by weight of a maleic anhydride-modified high-density polyethylene polymer having a MFR of 3.0 and a maleic anhydride modification rate of 0.3% (hereinafter referred to as PO-5) ((A-
2) The same operation as in Example 1 except that 33.3% by weight as a component) and 0.5 part by weight of nylon 6-6 adjusted to an average particle diameter of 4 μm as a heat stabilizer were respectively added. It was molded to obtain ASTM No. 1 dumbbell (X-
9). (X-9) and (Y-1) were welded in the same manner as in Example 1. Table 2 shows the results.

Example 10 100 parts by weight of the polyacetal copolymer (X1-8) used in Example 8 was added to (A-
2) As components, 50 parts by weight of PO-5 and PO-
72.2 parts by weight (15.0 parts by weight as component (A-2)), and 0.5 parts by weight of nylon 6-6 adjusted to an average particle size of 4 μ as a heat stabilizer were added. Except for the above, the operation and molding were performed in the same manner as in Example 1;
No. 1 dumbbell was obtained (X-10). (X-10) and (Y-1) were welded in the same manner as in Example 1. Table 2 shows the results.

(Example 11) 100 parts by weight of the polyacetal copolymer (X1-8) used in Example 8 was added with (A-
2) As components, 50 parts by weight of PO-5 and PO-
1 was added in an amount of 100 parts by weight (60.0% by weight as the component (A-2)), and 0.5 parts by weight of nylon 6-6 adjusted to an average particle size of 4 μm as a heat stabilizer were added. The same operation and molding as in Example 1 were performed, and ASTM1
No. dumbbell was obtained (X-11). (X-11) and (Y
-1) was welded in the same manner as in Example 1. Table 2 shows the results.

Example 12 100 parts by weight of the polyacetal copolymer (X1-8) used in Example 8 was added with (A-
2) As components, 50 parts by weight of PO-5 and PO-
15.7 parts by weight (65.0 as component (A-2))
AST), and the same procedure as in Example 1 was carried out, except that 0.5 parts by weight of nylon 6-6 adjusted to an average particle size of 4 μ and 0.5 parts by weight were added as heat stabilizers.
An M1 dumbbell was obtained (X-12). (X-12) and (Y-1) were welded in the same manner as in Example 1. Table 2 shows the results.

(Example 13) 100 parts by weight of the polyacetal copolymer (X1-8) used in Example 8 was added with (A-
2) As components, 50 parts by weight of PO-5 and PO-
1 in 183.3 parts by weight (70.0% as component (A-2))
AST), and the same procedure as in Example 1 was carried out, except that 0.5 parts by weight of nylon 6-6 adjusted to an average particle size of 4 μ and 0.5 parts by weight were added as heat stabilizers.
An M1 dumbbell was obtained (X-13). (X-13) and (Y-1) were welded in the same manner as in Example 1. Table 3 shows the results.

(Example 14) 100 parts by weight of the polyacetal copolymer (X1-8) used in Example 8 was added with (A-
2) As components, 50 parts by weight of PO-5 and PO-
1 was added in an amount of 350 parts by weight (80.0% by weight as the component (A-2)), and nylon 6-6 adjusted to an average particle size of 4μ and 0.5 part by weight were added as heat stabilizers. ASTM1 is operated and formed in the same manner as in Example 1.
No. dumbbell was obtained (X-14). (X-14) and (Y
-1) was welded in the same manner as in Example 1. Table 3 shows the results.

(Comparative Example 1) 100 parts by weight of the polyacetal copolymer (X1-1) used in Example 1 was used as a heat stabilizer to adjust the average particle size of nylon 6-6, 0.5
Parts by weight and uniformly mixed, then supplied to a twin-screw extruder and melt-kneaded again as in Example 1, and pelletized (Z1-
1) was obtained. After drying the pellet at 80 ° C. for 24 hours,
ASTM No. 1 dumbbell was formed using a SH-75 molding machine manufactured by Sumitomo Heavy Industries, which was adjusted to a cylinder temperature of 200 ° C. and a mold temperature of 70 ° C. (Z-1). (Z-1) and (Y-
1) was welded in the same manner as in Example 1. Table 3 shows the results.
Shown in

Comparative Example 2 100 parts by weight of the polyacetal copolymer (X1-1) used in Example 1 was added to (A-2)
A pellet was obtained in the same manner as in Example 1, except that 11.2 parts by weight of PO-1 was added as the component (10.1% by weight as the component (A-2)). After drying the pellets at 80 ° C. for 24 hours, the cylinder temperature was 200 ° C. and the mold temperature was 7
Using a Sumitomo Heavy Industries SH-75 molding machine adjusted to 0 ° C,
It was formed into an ASTM No. 1 dumbbell (Z-2). (Z
-2) and (Y-1) were welded in the same manner as in Example 1. Table 3 shows the results.

(Comparative Example 3) To 100 parts by weight of the polyacetal copolymer (X1-4) used in Example 4, 0.04 parts by weight of calcium monopalmitate-monostearate was added as a heat stabilizer, and the mixture was uniformly mixed. After mixing, the mixture was supplied to a twin-screw extruder and melt-kneaded again as in Example 1 to obtain pellets. The pellets were dried at 80 ° C. for 24 hours, and then formed into ASTM No. 1 dumbbells using a SH-75 molding machine manufactured by Sumitomo Heavy Industries, which was adjusted to a cylinder temperature of 200 ° C. and a mold temperature of 70 ° C. (Z-3). (Z-3) and (Y-1) were welded in the same manner as in Example 1. Table 3 shows the results.

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

Example 15 100 parts by weight of the polyacetal copolymer (X1-6) used in Example 6 was added with (A-
2) As a component, 50 parts by weight of PO-2 and PO-
15.7 parts by weight (65.0 as component (A-2))
Wt.%), And 0.5 parts by weight of nylon 6-6 adjusted to an average particle size of 4 μm as a heat stabilizer, respectively, and uniformly mixed. The mixture was kneaded to obtain a pellet. The pellets are placed at 80 ° C for 2
After drying for 4 hours, cylinder temperature 200 ° C, mold temperature 70
Using a SH-75 molding machine manufactured by Sumitomo Heavy Industries adjusted to
It was molded into an STM1 dumbbell (X-15).

Further, a polyacetal copolymer (X1-6)
100 parts by weight of PO-2 as the component (A-2)
0 parts by weight, and 72 parts by weight of PO-1 (55.0% by weight as the component (A-2)).
After adding 0.5 parts by weight of nylon 6-6 adjusted to an average particle size of 4 μm and mixing uniformly, the mixture was supplied to the twin-screw extruder and melt-kneaded again to obtain pellets. After drying the pellets at 80 ° C. for 24 hours, the cylinder temperature was 200
ASTM No. 1 dumbbell was formed using an SH-75 molding machine manufactured by Sumitomo Heavy Industries, Ltd., which was adjusted to 70 ° C. and a mold temperature of 70 ° C. (X-16). Also, a polyacetal resin (trade name: Tenac-CHC450) manufactured by Asahi Kasei Kogyo Co., Ltd. is molded into an ASTM No. 1 dumbbell using a SH-75 molding machine manufactured by Sumitomo Heavy Industries, which has been adjusted to a cylinder temperature of 200 ° C. and a mold temperature of 70 ° C. Processed (Z-4).

The ASTM No. 1 dumbbell (X
-15), (X-16), (Z-4), and Example 1
(Y-1) used in Nos. 15 to 15 was heated for 30 seconds by a contact heating method using a hot plate adjusted to a surface temperature of 250 ° C. in the range shown in FIG.
A length of 1.5 mm was welded in the longitudinal direction, and each melted portion was cooled for 90 seconds after welding. afterwards,
As shown in FIG. 2, a test piece having a total length of 120 mm was cut out from the center of the welded portion, and the welding strength was measured. Table 4 shows the measurement results. Combinations; (Z-4) to (X-16) (X-16) to (X-15) (X-15) to (Y-1)

(Examples 16 and 17, Comparative Example 4) Example 1
(X-15), (X-16), (Y-1) and (Z-4) used in Example 5 were combined with the following two in FIG.
Using a hot plate adjusted to a surface temperature of 250 ° C., using a contact heating method, the range shown in (1) was heated for 30 seconds, and 1.5 mm of the margin was welded in the longitudinal direction. Cooled for 90 seconds. Thereafter, as shown in FIG. 2, a test piece having a total length of 120 mm was cut out centering on the welded portion, and the welding strength was measured. Tables 5 and 6 show the measurement results. Combination (Example 16); (Z-4) to (X-1)
5) Combinations of (X-15) to (Y-1) (Example 17); (Z-4) to (X-1)
6) Combinations of (X-16) to (Y-1) (Comparative Example 4); (Z-4) to (Y-)
1)

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

(Embodiment 18) FIG. 4 shows that 22 outermost layers
According to STM-D1238, 190 ° C, 21.60 kg
Example 8 was integrated with a 21-car fuel tank blow-molded with 4 types and 6 layers made of polyethylene having an MFR of 7.0 measured at a load of 1 by a hot plate welding method of directly contacting a hot plate. Polyacetal copolymer (X1-
8) 100 parts by weight of PO-5 as a component (A-2)
Was mixed with 50 parts by weight (33.3% by weight as the component (A-2)) and 0.5 parts by weight of nylon 6-6 adjusted to an average particle size of 4 μ as a heat stabilizer (A). The example of the product of the tube which formed the component and was arrange | positioned at 24 recirculation lines is shown.

Example 19 FIG. 5 shows the polyacetal copolymer composition (Z1-1) used in Comparative Example 1.
The polyacetal copolymer (X1-8) 10 used in Example 8 was added to a float valve arranged in the 36 vent line.
0 parts by weight, as a component (A-2), 50 parts by weight of PO-5 and 135.7 parts by weight of PO-1 ((A-2)
(65.0% by weight as a component), and further, as a thermal stabilizer, 0.034 parts by weight of monopalmitic acid-calcium monostearate are mixed, and a 34 intermediate layer composed of the component (A) is brought into direct contact with a hot plate. The parts integrated by the hot plate welding method and the 32 outermost layers are ASTM-D1
Hot plate welding for directly contacting a hot plate with 31 automotive fuel tanks blow-molded with 4 types and 6 layers of polyethylene having an MFR of 7.0 measured at 190 ° C under a load of 21.60 kg according to 238 An example of a product integrated by the method is shown.

(Example 20) In FIG. 6, the 42 outermost layers
As the component (A-1), 20% by weight of the polyacetal copolymer (X1-8) used in Example 8, and as the component (A-2), according to ASTM-D1238, at 190 ° C., 21.
0.04 parts by weight of monopalmitic acid-calcium monostearate was used as a heat stabilizer with respect to 100 parts by weight of the resin composition with polyethylene having an MFR of 7.0 measured under a load of 60 kg. 41 composed of the component (A) blended and blow-molded in 4 layers and 6 layers
The product example of a 44 fuel inlet tube made of the polyacetal copolymer (Z1-1) used in Comparative Example 1 and integrated with an automotive fuel tank and a hot plate welding method of directly contacting a hot plate is shown. .

(Example 21) FIG. 5 shows that a polyacetal copolymer (Z1-1) used in Comparative Example 1 and a float valve arranged in a 36 vent line were used for the polyacetal copolymer used in Example 8. 100 parts by weight of the combined (X1-8), 50 parts by weight of PO-4 as the component (A-2) (33.3% by weight as the component (A-2)), and monopalmitin as the heat stabilizer Hot plate welding in which a 39 intermediate layer composed of the component (A) and 0.037 parts by weight of acid-calcium monostearate respectively and a 37 vent line tube composed of 6-6 polyamide are brought into direct contact with a hot plate. An example of a product integrated by the method is shown.

Example 22 FIG. 7 shows that 100 parts by weight of the polyacetal copolymer (X1-8) used in Example 8 was
(A-2) 50 parts by weight of PO-5 as a component, and
135.7 parts by weight of PO-1 (6% as component (A-2))
5.0% by weight).
Example 8: 55 intermediate layers consisting of component (A) to which 0.5 parts by weight of nylon 6-6 adjusted to μ were added.
100 parts by weight of the polyacetal copolymer (X1-8) used in (1), 50 parts by weight of PO-5 and 72.2 parts by weight of PO-1 as the component (A-2) ((A-2)). (55.0% by weight as a component), and further, as a heat stabilizer, nylon 6-6 adjusted to an average particle size of 4 μm and 0.5 part by weight of each of the components (A) were added, and a 56 intermediate layer was pressed. A resin joined body integrated by using a molding machine and a polyacetal resin (trade name; Tenac-, manufactured by Asahi Kasei Corporation)
CHC450) and tubes placed in a 54 recirculation line, and 52 outermost layers are made of AS
According to TM-D1238, each of the 51 automotive fuel tanks blow-molded with four types and six layers of polyethylene having an MFR of 7.0 measured at 190 ° C. under a load of 21.60 kg is brought into direct contact with the hot plate. An example of a product integrated by a hot plate welding method is shown.

[0107]

Conventionally, the joining structure of a polyacetal resin and another thermoplastic resin represented by polyethylene has not been at a level that can withstand practical use. The joining structure comprising the thermoplastic resin composition and the mixture of the polyacetal copolymer composition and the polyolefin resin composition of the present invention has excellent welding strength between resins, and is suitable for automobile parts, electric / electronic equipment parts, and OA-related parts. It is useful for parts and various industrial miscellaneous parts.

[Brief description of the drawings]

FIG. 1 is a front view of an ASTM No. 1 dumbbell used in Examples 1 to 17 and Comparative Examples 1 to 4 of the present invention.

FIG. 2 is a front view of a tensile test piece used in Examples 1 to 17 and Comparative Example 2 of the present invention.

FIG. 3 is a conceptual diagram of an automobile fuel tank and valves, tubes, flanges, and the like using the joint structure found in the present invention.

FIG. 4 is a conceptual cross-sectional view of a tube disposed on a recirculation line integrated with a fuel tank for an automobile, using a joint structure found in the present invention shown in Example 18.

FIG. 5 is a conceptual cross section of a float valve and a vent line tube arranged in a vent line integrated with an automobile fuel tank, using the joint structure found in the present invention shown in Examples 19 and 21. FIG.

FIG. 6 is a conceptual cross-sectional view of a fuel inlet tube integrated with an automobile fuel tank, using the joint structure found in the present invention shown in Example 20.

FIG. 7 is a conceptual cross-sectional view of a tube arranged in a recirculation line integrated with a fuel tank for an automobile, using the joint structure found in the present invention shown in Example 22.

[Explanation of symbols]

A: Total length of ASTM No. 1 dumbbell (180 mm) B: Width of both ends of ASTM No. 1 dumbbell (20 mm) C: In Examples 1 to 17 and Comparative Examples 1 to 4, distance from end of portion where resin is melted (1. 5 mm) D: Overall length of the specimen used for the welding strength test (120 mm) 1: ASTM1 used in Examples 1 to 17 and Comparative Examples 1 to 4
No. dumbbell (thickness: 3.2 mm) 2: welding margin for melting resin in Examples 1 to 17 and Comparative Examples 1 to 3: AS used for welding test in Examples 1 to 17 and Comparative Example 2.
TM1 dumbbell part 4: welded part 5: direction in which force acts during welding strength test 11: automotive fuel tank formed by multilayer blow molding with outermost layer made of polyethylene 12: integrated with automotive fuel tank Pressure relief valve 13: Flange for fuel sender module integrated with fuel tank for automobile 14: Float valve arranged on vent line integrated with fuel tank for automobile 15: Integrated with fuel tank for automobile 16: Fuel injection tube integrated with fuel tank for automobile 17: Drain valve integrated with fuel tank for automobile 18: Swirling tank integrated with fuel tank for automobile 21: A self-formed member formed by blow molding of four types and six layers in which the outermost layer is polyethylene Car fuel tank 22: Polyethylene layer as outermost layer of car fuel tank 23: Welded part 24: Tube made of component (A) of the present invention disposed on recirculation line 31: Four kinds and six layers of outermost layer made of polyethylene Automotive fuel tank formed by blow molding 32: Polyethylene layer as outermost layer of automotive fuel tank 33: Welded part 34: Intermediate layer 35: Welded part 36: Float valve made of polyacetal resin composition arranged in vent line 37 : Vent line tube made of polyamide resin 38: Welded part 39: Intermediate layer 40: Welded part 41: Fuel tank for automobiles formed by blow molding of four types and six layers whose outermost layer is the component (A) of the present invention 42: (A) component layer of the outermost layer of the fuel tank for automobiles 43: welded part 44: polyacetal resin Injection tube made of a material 51: Automotive fuel tank formed by blow molding of 4 types and 6 layers whose outermost layer is polyethylene 52: Polyethylene layer of the outermost layer of automotive fuel tank 53: Welded part 54: To recirculation line A tube composed of the component (A) of the present invention disposed 55: an intermediate layer 56: an intermediate layer

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) // B29K 59:00 B29K 59:00 F term (reference) 4F211 AA03 AA04E AA22 AA23A AA23F AA23J AH17 AH55 AH56 TA01 TC01 TC06 TD07 TD11 TN07 TN28 TN81 TQ01 4J002 AC11W BB00W BB03W BB04W BB05W BB06W BB07W BB08W BB12W BB14W BB15W BB17W BB20W BB20Y BB22W BB23W BP02W CB00X FD010 FD040 FD060 FD070 FD090 FD170 GN00 GQ00 4J032 AA02 AA04 AA05 AA34 AA35 AA36 AA47 AB06 AB22 AB31 AB35 AC14 AC16 AC19 AF08

Claims (21)

[Claims] 1. A thermoplastic resin bonded structure composed of two or more types of resin components, wherein at least one of the following two components is a component (A) and a component (B): A thermoplastic resin bonded structure characterized by having the above. Component (A): 5 to 80% by weight based on the total weight of component (A) (hereinafter referred to as component (A-1)) and 20 to 95% by weight based on the total weight of component (A) %
A resin composition selected from the group consisting of a polyolefin resin, an olefin-based elastomer, and a hydrogenated butadiene-based elastomer (hereinafter, referred to as a component (A-2)). Component (B): thermoplastic resin 2. The composition according to claim 1, further comprising at least one structure obtained by bonding a polyacetal resin as the component (C) in the order of the component (C), the component (A), and the component (B). The thermoplastic resin bonded structure according to the above. 3. In a structure joined in the order of component (C) -component (A) -component (B), a joined structure comprising two or more components (A) and different components (A) having different compositions. The thermoplastic resin bonded structure according to claim 2, comprising: 4. The component (A) which is directly bonded to the component (C).
4. The component according to claim 3, wherein the concentration of the component (A-1) in the component is higher than the concentration of the component (A-1) in the other component (A) directly joined to the component (B). Thermoplastic resin joint structure. 5. The polyacetal resin as the component (A-1) contains a hydroxyalkyl group at a molecular terminal and the concentration of the hydroxyalkyl group terminal is at least 5 × 10 ⁻⁵ mol per mol of oxymethylene unit. 2. A polyacetal copolymer according to claim 1.
5. The thermoplastic resin bonded structure according to any one of items 4 to 4. 6. The polyacetal resin of the component (A-1) is copolymerized by using water or an aliphatic alcohol having 10 or less carbon atoms as a chain transfer agent and, if necessary, in combination with formal. The thermoplastic resin bonded structure according to any one of claims 1 to 5, further comprising a polyacetal copolymer as one of its constituent components. 7. The polyacetal resin as the component (A-1) has a molecular weight of 500 having at least one hydroxyl group.
Using a polymer that is 10,000 to 10,000 as a chain transfer agent,
The polyacetal block copolymer obtained by copolymerizing a cyclic acetal and a cyclic ether and / or a cyclic formal is contained as one of the constituent components thereof, according to any one of claims 1 to 6, The thermoplastic resin bonded structure according to the above. 8. The polyacetal resin as the component (A-1) has a number average molecular weight of 10,000 represented by the following (formula 1).
The thermoplastic resin bonded structure according to any one of claims 1 to 7, wherein the thermoplastic resin-bonded structure comprises (1) a polyacetal block copolymer of up to 500,000 as one of its constituent components. Embedded image (Wherein, except for A (hereinafter referred to as B block), m = 2
98 mol%, n = 2 to 98 mol%, n + m = 100 mol%, and the units in parentheses of m exist randomly or in blocks with respect to the units in parentheses of n, and have a number average molecular weight of 500 to 10, 000 is a hydrogenated liquid polybutadiene residue whose both ends are hydroxyalkylated.
However, B block may be those having the following unsaturated bond iodine value 20g-I ₂ / 100g. k = 2-6
And two k's may be the same or different. R is hydrogen, an alkyl group,
It is selected from a substituted alkyl group, an aryl group, and a substituted aryl group, and each may be the same or different. A
Is a polyoxymethylene copolymer residue represented by the following (Formula 2). Embedded image (R ₁ is selected from hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group.
Also, they may be different. j is an integer selected from 2 to 6. x = 95 to 99.9 mol%, y = 5 to 0.1 mol%, x + y = 100 mol%, the unit in parentheses of y is x
Exists randomly for units in parentheses. ), (Formula 1), the average number average molecular weight of the two A blocks is 5,000 to 250,000. ) 9. The composition according to claim 1, wherein the component (A-2) is selected from a polyethylene homopolymer, a polyethylene copolymer, a block copolymer, and an ionomer containing ethylene as a main component.
A resin composition comprising at least one kind of resin composition.
9. The thermoplastic resin bonded structure according to any one of items 8 to 8. 10. The thermoplastic resin bonded structure according to claim 1, wherein the component (A-2) is a modified α-olefin polymer. 11. The composition according to claim 1, wherein the component (A-2) is composed of at least one resin selected from polyethylene homopolymers, polyethylene copolymers, block copolymers and ionomers containing ethylene as a main component and a modified α-olefin polymer. The thermoplastic resin bonded structure according to any one of claims 1 to 8, which is a mixed composition with at least one selected resin. 12. The thermoplastic resin bonded structure according to claim 1, wherein the thermoplastic resin (B) is a polyolefin resin. 13. A thermoplastic resin as the component (B), wherein the thermoplastic resin is mainly composed of ethylene, such as a polyethylene homopolymer, a polyethylene copolymer, a block copolymer, an ionomer,
The thermoplastic resin bonded structure according to any one of claims 1 to 11, wherein the thermoplastic resin bonded structure is one selected from a mixture of two or more thereof. 14. The thermoplastic resin as the component (B) is a modified α
-An olefin-based polymer.
12. The thermoplastic resin bonded structure according to any one of items 11 to 11. 15. The thermoplastic resin bonded structure according to claim 1, wherein the thermoplastic resin (B) is a polyacetal resin. 16. The thermoplastic resin bonded structure according to claim 7, wherein the thermoplastic resin (B) is a polyamide resin. 17. The thermoplastic resin bonded structure according to claim 1, wherein the component (A) and the component (B) are integrated by welding. . 18. The component (A) and the component (B) are composed of two or more kinds of different material injection molding, resin insert injection molding, two or more layers of different material co-extrusion molding, and two or more layers of multilayer lamination blow. The thermoplastic resin bonded structure according to any one of claims 1 to 16, wherein the thermoplastic resin bonded structure is integrated by a molding method selected from molding. 19. In a thermoplastic resin joined structure continuously joined in the order of component (C) -component (A) -component (B), two or more types of welds are formed between each resin component by welding. The material is integrated by one or more molding methods selected from material injection molding, resin insert injection molding, co-extrusion molding of two or more layers of different materials, and multilayer lamination blow molding of two or more layers. 17. The thermoplastic resin bonded structure according to any one of 2 to 16. 20. An automobile part using the thermoplastic resin bonded structure according to claim 1. Description: 21. The vehicle component according to claim 20, wherein the component is a vehicle fuel-circulating component.