JP2000095948A - Vibration welding resin composition and formed aricle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide welding resin compositions which are proportionately excellent in heat stability, external appearance of molded articles, mechanical strength and vibration weldability and are suitable for hollow products which can be obtained by the vibration welding of two or more molded articles after melt molding. SOLUTION: Vibration welding resin compositions comprise (A) 100 pts.wt. thermoplastic resin and (B) 0.1-50 pts.wt. layer silicate which is a swelling layer silicate and vibration welding resin compositions comprise (A) 100 pts.wt. thermoplastic resin, (B) 0.1-50 pts.wt. layer silicate which is a swelling layer silicate, and (C) 10-150 pts.wt. glass fibers having an average fiber diameter of 5-15 μm. Further, the layer silicate (B) is the one in which exchangeable cationic ions present between layers have been exchanged with organic onium ions, and the thermoplastic resin (A) is at least one resin selected from a polyamide resin, a polyester resin, and a polyphenylene sulfide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a welding resin composition which is excellent in heat resistance, surface appearance of a moldable product, dimensional stability, and vibration welding property, and more particularly to two or more resin compositions after melt molding. The present invention relates to a thermoplastic resin composition suitable for a hollow molded article obtained by vibration welding a molded article.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyamides, aromatic polyesters and polyphenylene sulfides have excellent injection moldability, heat resistance, toughness, oil / gasoline resistance, abrasion resistance, etc. Widely used as injection molded products in the field of machine parts. The development history of thermoplastic resins in the above-mentioned fields is mainly based on the substitution of metal materials, and the commercialization has progressed from parts having many advantages such as weight reduction and rust prevention. More recently, with the advancement of high-performance thermoplastic resin materials and the development of molding techniques, the application of thermoplastic resins to parts that are large and have complex shapes, and which have been considered difficult to convert into resins by conventional techniques, is being studied. It has become. In order to convert such difficult parts into resin, injection molding, extrusion molding, blow molding and other single molding techniques are not enough.It is necessary to combine post-processing techniques such as cutting, bonding and welding. Become. However, the design of the conventional thermoplastic resin material does not consider the applicability to such post-processing. For example, a glass fiber reinforced thermoplastic resin molded product composed of two or more parts is welded by a vibration welding method or the like. At present, when the parts are large in size, the use of the parts is limited due to insufficient strength of the welded portions.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to improve the vibration welding property, which is a problem in the above-mentioned conventional thermoplastic resin, and to further improve the moldability, heat resistance, toughness, oil / gasoline resistance, and the like. An object of the present invention is to obtain a thermoplastic resin composition suitable for vibration welding, which is excellent in balance with inherent properties of the thermoplastic resin such as wear resistance and surface smoothness of a molded article.

[0004]

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, in a thermoplastic resin, a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. It has been found that the object can be achieved by adding glass fibers as needed, and the present invention has been achieved.

That is, the present invention relates to (A) a thermoplastic resin 100
(B) 0.1 to 50 parts by weight of a layered silicate and, if necessary, (C) 10 to 150 parts by weight of glass fiber having an average fiber diameter of 5 to 15 μm, )
An object of the present invention is to provide a resin composition for vibration welding, wherein the layered silicate is a swellable layered silicate.

[0006]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The thermoplastic resin (A) used in the present invention is a resin that can be plastically processed by heating and melting, and examples thereof include polycarbonate resin, polyphenylene ether resin, polystyrene resin, polyamide resin, polyester resin, Examples include polyphenylene sulfide resin, polyacrylate resin, polymethacrylate resin, polyolefin resin, polyacetal resin, and a mixture of these resins. Among these, polyamide resins, polyester resins, and polyphenylene sulfide resins are preferably used.

[0008] The polyamide resin used in the present invention is:
It is a nylon made mainly of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid; lactams such as ε-caprolactam and ω-laurolactam; tetramethylenediamine; Melenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, meta-xylylenediamine, para Xylylenediamine, 1,3
-Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane,
Bis (4-aminocyclohexyl) methane, bis (3-
Methyl-4-aminocyclohexyl) methane, 2,2-
Aliphatic (alicyclic, aromatic) diamines such as bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid; Aliphatic, alicyclic, aromatic, such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, a particularly useful nylon resin is a nylon resin having a melting point of 200 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexa Methylene dodecamide (nylon 612), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipa Mid /
Polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T /
6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6
T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene) terephthalamide copolymer (nylon 6T / M5T), polyhexamethylene terephthalamide / polyhexamethylene sebacamide / polycaproamide copolymer (nylon 6T / 610 /
6), polyhexamethylene terephthalamide / polydodecaneamide / polyhexamethylene adipamide copolymer (nylon 6T / 12/66), polyhexamethylene terephthalamide / polydodecaneamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 12
/ 6I), polyxylylene adipamide (nylon XD
6) and mixtures or copolymers thereof.

Particularly preferred are nylon 6, nylon 66, nylon 6/66 copolymer, nylon 610 and also nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 6 copolymer, nylon 6T / 12/66 copolymer. , Nylon 6
Copolymers having hexamethylene terephthalamide units, such as T / 12 / 6I copolymer, can be mentioned. Further, these nylon resins can be used as a mixture according to required properties such as moldability, heat resistance, toughness and surface properties. It is practically preferable to use it.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 5.0, especially 2.0 to 4.0. 0
Are preferred.

Examples of the polyester resin include thermoplastic polyesters having an aromatic ring in a chain unit of a polymer. Usually, an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) are used. And / or a polymer or copolymer obtained by a condensation reaction containing hydroxycarboxylic acid as a main component. These may be liquid crystalline or non-liquid crystalline.

Specific examples of preferred polyesters in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate,
Polyalkylene terephthalate such as polycyclohexane dimethylene terephthalate and polyhexylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (phenoxy) ethane- In addition to 4,4′-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene-4,4′-dicarboxylate / terephthalate,
Non-liquid crystalline polyesters such as poly (ethylene terephthalate / cyclohexane dimethylene terephthalate).

As the liquid crystalline polyester, an anisotropic molten phase comprising a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an ethylenedioxy unit and the like is formed. Polyester can be mentioned.

Examples of the aromatic oxycarbonyl unit include, for example, p-hydroxybenzoic acid, 6-hydroxy-2-
Structural units generated from naphthoic acid, aromatic dioxy units include, for example, 4,4′-dihydroxybiphenyl, hydroquinone, structural units generated from t-butylhydroquinone, and aromatic dicarbonyl units include, for example, terephthalic acid, Examples of the structural unit generated from isophthalic acid and 2,6-naphthalenedicarboxylic acid and the aromatic iminooxy unit include a structural unit generated from 4-aminophenol. Specific examples include liquid crystalline polyesters such as p-oxybenzoic acid / polyethylene terephthalate and p-oxybenzoic acid / 6-oxy-2-naphthoic acid.

Particularly preferred are polybutylene terephthalate, polyethylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate. These polyester resins can be used to obtain necessary properties such as moldability, heat resistance, toughness, and surface properties. Accordingly, it is practically preferable to use it as a mixture.

Although the degree of polymerization of these polyesters is not limited, polybutylene terephthalate has an intrinsic viscosity measured at 25 ° C. in a 0.5% o-chlorophenol solution.
It is preferably in the range of 0.80 to 1.9, particularly preferably in the range of 1.0 to 1.5. In the case of polyethylene terephthalate, the intrinsic viscosity measured under the same conditions as described above is 0.36 to
Those having a range of 1.60, particularly 0.52 to 1.35 are preferred. The polyphenylene sulfide resin used in the present invention has the following structural formula

Embedded image Is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by Further, less than 30 mol% of the repeating unit can be constituted by a repeating unit having the following structural formula.

[0018]

Embedded image

The swellable layered silicate (B) used in the present invention is a sheet crystal layer in which tetrahedral silica sheets are superposed on and under an octahedral sheet containing an element selected from aluminum, magnesium, lithium and the like. Has a 2: 1 type structure and has exchangeable cations between layers of the plate-like crystal layer. The size of the single plate-like crystal is usually 0.05 to 0.5 μm in width and 6 to 15 Å in thickness. Further, the cation exchange capacity of the exchangeable cations is 0.2 to 3 meq / g,
Preferably, the cation exchange capacity is 0.8 to 1.5 meq /
g.

Specific examples of the layered silicate include various clay minerals such as smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and sauconite, vermiculite, halloysite, kanemite, keniyaite, zirconium phosphate, and titanium phosphate. And swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc., and may be natural or synthesized. . Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferred.

The layered silicate of the present invention is preferably a layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions.

Examples of the organic onium ion include an ammonium ion, a phosphonium ion and a sulfonium ion. Among these, ammonium ions and phosphonium ions are preferable, and ammonium ions are particularly preferably used. As ammonium ions,
Any of primary ammonium, secondary ammonium, tertiary ammonium and quaternary ammonium may be used.

The primary ammonium ion includes decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

The secondary ammonium ion includes methyl dodecylammonium, methyloctadecyl ammonium and the like.

Examples of the tertiary ammonium ion include dimethyldodecylammonium and dimethyloctadecylammonium.

The quaternary ammonium ion includes benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium and benzyldimethyloctadecylammonium; trioctylmethylammonium; trimethyloctylammonium; trimethyldodecylammonium , Alkyltrimethylammonium ions such as trimethyloctadecylammonium, dimethyldioctylammonium, dimethyldidodecylammonium,
And dimethyldialkylammonium ions such as dimethyldioctadecylammonium.

In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine,
-Aminocaproic acid, 11-aminoundecanoic acid, 12
-Ammonium ions derived from aminododecanoic acid and the like.

Of these ammonium ions, trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, ammonium ions derived from 12-aminododecanoic acid and the like are preferred.

In the present invention, the layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions,
It can be produced by reacting a layered silicate having an exchangeable cation between layers with an organic onium ion by a known method. Specific examples include a method based on an ion exchange reaction in a polar solvent such as water, methanol and ethanol, and a method based on directly reacting a liquid or molten ammonium salt with a layered silicate.

In the present invention, the amount of the organic onium ion with respect to the layered silicate is determined based on the dispersibility of the layered silicate, thermal stability during melting, gas generation during molding, and suppression of generation of odor. Typically 0.4 for cation exchange capacity
The range is from 2.0 to 2.0 equivalents, but preferably from 0.8 to 1.2 equivalents.

These layered silicates are used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound or an epoxy compound, in addition to the above-mentioned organic onium salt. You may.

Preferred coupling agents are organic silane compounds, and specific examples thereof are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4- Epoxy-containing alkoxysilane compounds such as epoxycyclohexyl) ethyltrimethoxysilane, mercapto-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ
-Ureidopropyltrimethoxysilane, γ- (2-
Ureido group-containing alkoxysilane compounds such as ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyl Isocyanato group-containing alkoxysilane compounds such as diethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyl Amino group-containing alkoxysilane compounds such as dimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxyp Ropirtrimethoxysilane,
hydroxyl-containing alkoxysilane compounds such as γ-hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ
-Alkoxysilane compounds containing a carbon-carbon unsaturated group such as -aminopropyltrimethoxysilane / hydrochloride. In particular, a carbon-carbon unsaturated group-containing alkoxysilane compound is preferably used.

The treatment of the phyllosilicate with these coupling agents can be carried out in a polar solvent such as water, methanol or ethanol.
Alternatively, a method of adsorbing the coupling agent to the layered silicate in these mixed solvents or a method of dropping and adsorbing the coupling agent solution while stirring the layered silicate in a high-speed stirring mixer such as a Henschel mixer, Further, any method may be used, in which a silane coupling agent is directly added to the layered silicate and mixed and adsorbed in a mortar or the like. When treating a layered silicate with a coupling agent,
It is preferable to simultaneously mix water, acidic water, alkaline water and the like in order to promote the hydrolysis of the alkoxy group of the coupling agent. Further, in order to enhance the reaction efficiency of the coupling agent, water such as methanol or ethanol and an organic solvent which dissolves both the coupling agent may be mixed in addition to water. The reaction can be further promoted by heat-treating the layered silicate treated with such a coupling agent. When the layered silicate and the thermoplastic polyester are melt-kneaded without using a layered silicate with a coupling agent in advance, a so-called integral blending method of adding these coupling agents may be used.

The order of the treatment of the layered silicate with the organic onium ion and the treatment with the coupling agent is not particularly limited. However, it is preferable to first treat the layered silicate with the organic onium ion and then treat with the coupling agent.

In the present invention, the content of the layered silicate (B) is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, particularly preferably 1.20 parts by weight as an inorganic ash content relative to 100 parts by weight of the thermoplastic resin. The range is 5 to 10 parts by weight. If the ash content is too small, the effect of improving the physical properties is small, and if the ash content is too large, the toughness may decrease. The inorganic ash content is a value obtained by incinulating 2 g of the resin composition in an electric furnace at 500 ° C. for 3 hours.

The glass fiber (C) used in the present invention has an average fiber diameter of 5 to 15 μm, and can be blended by any method such as chopped strand or roving.

The total glass fiber content in the resin composition of the present invention is in the range of 10 to 150 parts by weight, more preferably 20 to 80 parts by weight, per 100 parts by weight of the thermoplastic resin.

Specific examples of the olefin compound having a carboxylic acid anhydride group in the molecule or a polymer of these olefin compounds used as the component (D) used in the present invention include maleic anhydride, itaconic anhydride and glutacon anhydride. Examples thereof include acids, citraconic anhydride, aconitic anhydride, and polymers of these substituted olefin compounds. In the olefin compound polymer, olefins other than the olefin compound having a carboxylic anhydride group in the molecule, such as styrene, isobutylene, methacrylic acid ester, and acrylic acid ester, are copolymerized within a range that does not impair the effects of the present invention. Although it does not matter, it is preferable that the polymer is substantially composed of a polymer of an olefin compound having a carboxylic anhydride group in the molecule. The polymerization degree of the olefin compound polymer is preferably 2 to 100, more preferably 2 to 50, and most preferably 2 to 20. Among these, maleic anhydride and polymaleic anhydride are most preferably used because they have high ductility and rigidity-imparting effects. Examples of polymaleic anhydride include, for example, J. Macromol. Sci.-Revs. Ma
Cromol. Chem., C13 (2), 235 (1975) and the like can be used. These olefin compounds having a carboxylic acid anhydride group in the molecule or a polymer of these olefin compounds can be mixed in advance with a layered silicate and melt-kneaded with a polyamide.

The addition amount of these olefin compounds or polymers of these olefin compounds is from 0.05 to 10 parts by weight per 100 parts by weight of the thermoplastic resin, the effect of improving ductility,
It is preferable from the viewpoint of fluidity of the composition, more preferably in the range of 0.1 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight.

The olefin compound having a carboxylic acid anhydride group in the molecule or a polymer of these olefin compounds used here may have an anhydride structure substantially when melt-kneaded with a thermoplastic resin. The olefin compound or a polymer of the olefin compound is hydrolyzed and subjected to melt-kneading in the form of a carboxylic acid or an aqueous solution thereof, followed by a dehydration reaction by heating during the melt-kneading, and a thermoplastic resin substantially in the form of an acid anhydride. May be melt-kneaded.

In the present invention, it is also possible to add a fibrous / non-fibrous inorganic reinforcing material in addition to the above-mentioned glass fibers. Specific examples of such reinforcing agents include carbon fiber, potassium whisker, zinc oxide and zinc oxide. Whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, fibrous filler such as metal fiber, etc., walasteinite, zeolite, sericite, kaolin, mica, clay, pyro Silicates such as fillite, bentonite, asbestos, talc and alumina silicate, metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, and sulfuric acid Sulfates such as calcium and barium sulfate, and hydroxyl Magnesium, calcium hydroxide,
Examples include hydroxides such as aluminum hydroxide, glass beads, ceramic beads, non-fibrous fillers such as boron nitride, silicon carbide and silica, which may be hollow, and furthermore, two kinds of these fillers. These can be used together. Further, it is more excellent to pre-treat and use these fibrous / non-fibrous fillers with coupling agents such as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds and epoxy compounds. It is preferable from the viewpoint of obtaining high mechanical strength.

Further, the thermoplastic resin composition of the present invention includes a nucleating agent such as talc, kaolin, an organic phosphorus compound, polyetheretherketone, a coloring inhibitor such as hypophosphite, a hindered phenol, a hindered amine. Additives such as antioxidants, heat stabilizers, UV inhibitors, coloring agents, copper compounds (such as copper halides such as copper iodide), and alkali metal halides (such as potassium iodide) can be added. it can.

The method for producing the resin composition of the present invention is not particularly limited. When (B) a layered silicate is blended with (A) a thermoplastic resin, (A) a polymerization system of the thermoplastic resin may be mixed with (A). B) A method in which a layered silicate is present may be used, but a method in which both are melt-kneaded is preferred. There is no particular limitation on the method,
It is sufficient that mechanical shearing can be performed in a molten state of the thermoplastic resin. The processing method may be either a batch method or a continuous method, but a continuous method capable of continuous production is preferable from the viewpoint of working efficiency. The specific kneading apparatus is not limited, but an extruder, particularly a twin-screw extruder, is preferable in terms of productivity. It is also preferable to provide a vent for the purpose of removing water and low-molecular-weight volatile components generated during melt-kneading. When a twin-screw extruder is used, a layered silicate in which (A) a thermoplastic resin and an exchangeable cation existing between layers (B) have been exchanged with an organic onium ion is previously mixed in a blender or the like, and then mixed. And the supply of (A) component from the upstream feed port of the extruder and the (B) component from the downstream feed port. No restrictions. The screw arrangement of the extruder is not particularly limited, but a kneading zone is preferably provided in order to finely disperse the layered silicate.

Further, even when (C) an olefin compound having a glass fiber and / or (D) a carboxylic anhydride group in a molecule or a polymer of these olefin compounds is further compounded, there is no limitation on the method of addition. (A) a thermoplastic resin, (B) a layered silicate and (D) an olefin compound having a carboxylic anhydride group in a molecule or a method of dry-blending a polymer of these olefin compounds followed by melt-kneading; A method in which (B) is added during melt-kneading, and the like.

The resin composition of the present invention can be formed into a molded product by a known method. There is no limitation on the method, and it is sufficient that each part for obtaining a final molded product by the vibration welding method is obtained. At that time, the resin composition of the present invention may be used in the form of a master batch. That is, as an example, a method of blending (A) a part of a thermoplastic resin, (B) a masterbatch pellet made of a layered silicate, and (A) a pellet of the remaining thermoplastic resin, and melt-molding to directly form a molded article. And the like.

The resin composition of the present invention thus obtained is excellent in heat resistance, surface appearance of the molded product, dimensional stability and vibration weldability, and is excellent in injection molding, extrusion molding, blow molding, and the like. It is particularly useful when the molded product obtained by molding is welded by a vibration welding method or the like, and taking advantage of this advantage, for example, an intake system component such as an automobile intake manifold, or a cooling system component such as a water inlet or a water outlet. , Fuel injection, fuel delivery parts such as fuel delivery pipes,
It can be suitably used for hollow parts such as containers such as oil tanks.

[0047]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the blending ratios shown in Examples and Comparative Examples are all parts by weight.

In the following examples, evaluation of material strength, fluidity, and vibration welding strength was performed by the following methods. [Material strength] Measured according to the following standard method. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 [Measurement of Vibration Welding Strength] The shapes of the test pieces used for evaluating the welding strength are as shown in FIGS. A rib 1 having a width of 1.5 mm and a height of 2.5 mm is provided on the welding surface of the test piece shown in FIG. 1, and the rib 1 is melted and joined by friction during welding. A test piece having the shape shown in FIGS. 1 and 2 was formed and welded under the following conditions using a 2850 type vibration welding apparatus manufactured by Branson. Frequency: 240 Hz Pressure: 70 kgf Amplitude: 1.5 mm Welding allowance: 1.5 mm FIG. 3 shows the shape of a hollow molded product obtained by welding.
The obtained hollow molded article was filled with water, an internal pressure was applied to the hollow molded article in a water tank, and the pressure at the time of burst was defined as the welding strength.

Reference Example 1 Na-type montmorillonite (Kunimine Industries: Knipia F,
100 g of a cation exchange capacity (120 meq / 100 g) was stirred and dispersed in 10 liters of warm water, and 2 L of warm water in which 48 g (equivalent to the cation exchange capacity) of trioctylmethylammonium chloride was dissolved, and stirred for 1 hour. . The resulting precipitate was separated by filtration and washed with warm water. This washing and filtration operations were performed three times, and the obtained solid was vacuum-dried at 80 ° C. to obtain a dried organically modified layered silicate (B-1). When the amount of inorganic ash in this organically modified layered silicate was measured, the proportion of inorganic ash was 67% by weight. The inorganic ash content is a value obtained by incinulating 0.1 g of layered silicate in an electric furnace at 500 ° C. for 3 hours.

Reference Example 2 To the dried organically modified layered silicate obtained in Reference Example 1, 8 g of γ-methacryloxypropyltrimethoxysilane (Toray Dow Corning Silicone: SZ6030) was added to the inorganic ash content of 100 g. Mix in a mortar for 20 minutes. Further, a mixed solution of 2 g of a 500 ppm hydrochloric acid aqueous solution and 6 g of methanol was added, mixed in a mortar for 30 minutes, and dried to obtain an organically modified layered silicate (B-2). Inorganic ash content is 6
It was 6% by weight.

REFERENCE EXAMPLE 3 100 g of montmorillonite and 30.2 g of 12-aminododecanoic acid hydrochloride (equivalent to the cation exchange capacity) as in Reference Example 1 were used as raw materials, and the organically modified layered silicate was prepared in the same manner as in Reference Example 1. B-3) was obtained. The inorganic ash content was 75% by weight.

Examples 1 to 3 In concentrated sulfuric acid, the relative viscosity measured at 25% at a concentration of 1% was 2.
Nylon 6 resin (N6) and the layered silicate manufactured in Reference Example 1 or 2, maleic anhydride powder (MA
H), 10 μm diameter chopped glass fibers were blended at the ratios shown in Table 1, and melt kneading was performed with a twin screw extruder (Nippon Steel Works: TEX-30) having a cylinder temperature set at 250 ° C. at a screw rotation speed of 200 rpm. did. After drying the obtained pellets, cylinder temperature 250 ° C, mold temperature 80 ° C
To obtain a test piece for evaluating physical properties and a molded piece for evaluating vibration welding strength. Table 1 shows the evaluation results. The amount of inorganic ash in the composition was determined by cutting a piece of about 2 g from the molded piece.
It was determined by incineration for 3 hours in an electric furnace at 00 ° C.

Comparative Examples 1-2 The same nylon 6 as used in Example 1 and kaolin (B-4) having an average particle size of 1.4 μm or non-swellable layered silicate were used in Example 1 or as kaolin (B-4). The same glass fibers were blended at the ratio shown in Table 2 to obtain a resin composition in the same manner as in Example 1. The results of the molding and evaluation were as shown in Table 2.

Examples 4-6, Comparative Examples 3-6 Relative viscosities measured in concentrated sulfuric acid at a concentration of 1% at 25 ° C.
Nylon 66 resin (N66), a polybutylene terephthalate resin (PB) having an intrinsic viscosity of 1.2 in o-chlorophenol solution at a concentration of 0.5% at 25 ° C.
T) A polyphenylene sulfide resin (PPS) having a melt flow rate measured at 315 ° C. and a load of 500 g of 600 g / 10 min, the layered silicate produced in Reference Example 1 or 3, and the same glass fiber as in Example 1. Compounded at the ratio shown in Table 1 or 2, 280 ° C for N66, PBT
Was melt-kneaded in the same manner as in Example 1 using a twin-screw extruder set at 250 ° C. and PPS at 310 ° C. to obtain a resin composition. The results of the molding and evaluation were as shown in Table 1 or 2.

[0055]

[Table 1]

From Examples 1 to 6 and Comparative Examples 1 to 6, the compositions of the present invention show superior welding strength to the compositions of Comparative Examples having the same inorganic ash content, and are of high practical value as vibration welding materials. It is.

[0057]

As described above, the resin composition of the present invention has excellent mechanical strength and vibration-welding properties, and is excellent in molding obtained by injection molding, extrusion molding, or blow molding. It is particularly useful when used by welding by a vibration welding method or the like, and taking advantage of this advantage, for example, an intake system component such as an intake manifold of a car, a cooling system component such as a water inlet and a water outlet,
It can be suitably used for fuel injection parts, fuel parts such as fuel delivery pipes, hollow parts such as containers such as oil tanks, and the like.

[Brief description of the drawings]

FIG. 1 is a plan view showing the shape of a test piece for measuring welding strength used in an example.

FIG. 2 is a plan view showing the shape of a test piece for measuring welding strength used in Examples.

FIG. 3 is a plan view showing a shape of a hollow molded product obtained by welding a test piece.

[Explanation of symbols]

 1. Rib of test piece for welding strength measurement

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 67/00 C08L 67/00 77/00 77/00 81/02 81/02 F-term (reference) 4F071 AA02 AA36 AA43 AA54 AA63 AA78 AB26 AB28 AC09 AD01 AF05 AF45 AF54 AG11 AH19 BA01 BB13 BC07 4J002 BB001 BB092 BB212 BC021 BN052 CB001 CF001 CF161 CG001 CH071 CL001 CN011 DJ006 DL007 FA047 FB097 FB137 FB147 FB147

Claims (8)

[Claims] 1. A blend of (B) 0.1 to 50 parts by weight of a layered silicate with respect to 100 parts by weight of a thermoplastic resin, wherein (B) the layered silicate is a swellable layered silicate. A resin composition for vibration welding. 2. (A) 100 to 100 parts by weight of a thermoplastic resin, (B) 0.1 to 50 parts by weight of a layered silicate, and (C)
A vibration welding resin composition comprising 10 to 150 parts by weight of glass fiber having an average fiber diameter of 5 to 15 μm, wherein (B) the layered silicate is a swellable layered silicate. 3. The resin for vibration welding according to claim 1, wherein (B) the layered silicate is a layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions. Composition. 4. The vibration welding according to claim 1, wherein (A) the thermoplastic resin is at least one resin selected from a polyamide resin, a polyester resin and a polyphenylene sulfide resin. Resin composition. (B) The layered silicate is a layered silicate in which exchangeable metal ions existing between layers are ion-exchanged with an organic onium salt and further treated with a coupling agent having a reactive functional group. The resin composition for vibration welding according to any one of claims 1 to 4, wherein: 6. The vibration welding resin composition according to claim 1, further comprising (D) an olefin compound having a carboxylic anhydride group in the molecule or a polymer of the olefin compound. 7. A molded article for vibration welding comprising the resin composition for vibration welding according to claim 1. 8. A molded product obtained by vibration welding a molded product comprising the resin composition for vibration welding according to claim 1.