JPH10219107A - Resin composition for weld molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. for weld molding which is excellent in heat resistance, molded appearance, dimensional stability, and adhesiveness in weld molding in a good balance by compounding a high-grade nylon resin, glass fibers having a specified average diameter, and a copper compd. SOLUTION: This compsn. contains 100 pts.wt. high-grade nylon resin having the number of carbon atoms per amido group of 7 or higher, 10-150 pts.wt. glass fibers having an average diameter of 5-15μm, and 0.01-2 pts.wt. copper compd. Pref., the high-grade nylon resin is at least one resin selected from among nylon 69, nylon 610, nylon 612, nylon 1010, nylon 1012, nylon 126, nylon 1210, nylon 1212, nylon 11, and nylon 12. The copper compd. is pref. a copper (I) compd., esp. a copper (I) halide; for example, copper (I) acetate and copper (I) iodide are esp. pref.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for welding molding which is excellent in heat resistance, surface appearance of a molded product, dimensional stability, and adhesiveness of a molded product in welding molding such as two-color molding. More particularly, the present invention relates to a nylon resin composition suitable for a hollow molded article obtained by welding and the like.

[0002]

2. Description of the Related Art Nylon resin is widely used as an injection molded product in the fields of automobiles and machine parts because of its excellent injection moldability, heat resistance, toughness, oil / gasoline resistance, and abrasion resistance. It is used for The development process of nylon resin in the above-mentioned fields is mainly based on the substitution of metal materials, and the practical use has been advanced from parts having many advantages such as weight reduction and rust prevention. More recently, with the advancement of the performance and molding technology of nylon resin materials, the application of nylon resin to parts that are large and have complicated shapes, and for which resinization has been difficult with conventional technology, has been studied. 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 conventional nylon resin materials cannot be said to take into account the applicability to such post-processing. For example, a glass fiber reinforced nylon resin molded product composed of two or more parts is represented by a two-color molding method. In particular, when the parts are large in size when they are bonded by an injection welding method, the strength of the bonding part is insufficient with a typical nylon resin such as nylon 66 resin, and the dimensional change due to water absorption with nylon 6 resin. At present, use was limited due to problems such as large size.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to improve the adhesion at the time of welding and the strength of the welded portion at the time of water absorption, which are the problems of the conventional nylon resin described above. An object of the present invention is to obtain a nylon resin composition suitable for a welding molding method which is excellent in the inherent properties of a nylon resin, such as toughness, oil / gasoline resistance, abrasion resistance, and surface smoothness of a molded product.

[0004]

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, have found that a glass fiber reinforced nylon resin uses a specific higher nylon resin as a matrix resin and further contains a copper compound. The inventors have found that the object is achieved, and arrived at the present invention. That is, the present invention provides: (1) “(A) 100 parts by weight of a high-grade nylon resin having 7 or more carbon atoms per amide group,
(B) Glass fibers 10 to 15 having an average fiber diameter of 5 to 15 μm
A resin composition for welding molding, comprising 0 parts by weight and 0.01 to 2 parts by weight of a copper compound (C). (2) “(A) component nylon resin is nylon 69,
Nylon 610, Nylon 612, Nylon 1010,
Nylon 1012, Nylon 126, Nylon 121
0, Nylon 1212, Nylon 11, and Nylon 12. (3) “The welding molding resin composition according to any one of the above, wherein the copper compound is a monovalent copper compound.” (4) “The welding according to claim 3, wherein the monovalent copper compound is cuprous halide. Resin composition for molding. "(5)" (A) 100 parts by weight of a high-grade nylon resin having 7 or more carbon atoms per amide group,
(B) Glass fibers 10 to 15 having an average fiber diameter of 5 to 15 μm
A method for producing a resin composition for fusion molding, comprising mixing 0 part by weight and 0.01 to 2 parts by weight of a copper compound (C). (6) "A method for producing a weld-molded article, characterized in that the resin composition is weld-molded using the resin composition for weld-molding described in any of the above." And a fusion-molded article obtained by fusion-molding using the composition. "

[0005]

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

The nylon resin used as the component (A) in the present invention is a high-grade nylon resin having 7 or more carbon atoms per amide group, and a lactam or amino acid having 7 or more carbon atoms, and a diamine and a dicarboxylic acid. Among the combinations with an acid, it is a higher nylon resin containing a structural unit derived from a polyamide-forming component such as a substantially equimolar salt which satisfies the above-mentioned amide group concentration requirement as an essential component.
Examples of these polyamide-forming components include amino acids such as 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, enantholactam,
lactams such as ω-laurolactam, tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- /
2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, meta-xylenediamine,
P-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-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, etc. Aliphatic, alicyclic, aromatic diamines and adipic acid, spearic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, Aliphatic, alicyclic, such as methyl isophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid,
And aromatic dicarboxylic acids. Specific examples of particularly useful high-grade nylon resins include nylon 6.9, nylon 6.10, nylon 6.12, nylon 10.10, nylon 10.12, nylon 11.
6, nylon 11/10, nylon 11/12, nylon 12.6, nylon 12/10, nylon 12.1
2, nylon 12T, nylon 11, nylon 12, nylon 6T / 6I copolymer, nylon 6T / M-5T copolymer, and mixtures and copolymers thereof.

The degree of polymerization of the nylon resin used here 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. ~
Those having a range of 4.0 are preferably used.

In the present invention, the use of the above-mentioned high-grade nylon resin as a matrix resin is intended to obtain a product having a high adhesive strength at the time of injection welding such as two-color molding, and to perform welding when the welded product absorbs water. It is important to keep the part strength high. Although it is not clear why high-grade nylon can be used to obtain a product with high adhesive strength during welding, the solidification and crystallization behavior of the resin composition is slower than that of nylon 46 resin or nylon 66 resin. Is presumed to be effective in increasing the miscibility of the bonded part of the molded article.

In the present invention, the glass fiber used as the component (B) is a glass fiber having an average fiber diameter of 5 to 15 μm, and the fiber length is not particularly limited. Usually, a glass fiber having a strand length of 3 mm having a high extrusion kneading workability can be used. However, a glass fiber having a strand length of 1 mm or more and a glass fiber having a fiber length of 20 to 500 μm can also be used as a raw material as a mixture. When two or more types of glass fibers having different strand lengths are used in combination, it is also a preferable method to use glass fibers having different average diameters of 2 μm or more.

[0010] 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 nylon resin.

Specific examples of the copper compound used as the component (C) in the present invention include cuprous chloride, cupric chloride, and the like.
Cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, cupric nitrate, copper phosphate, cuprous acetate,
Cupric acetate, cupric salicylate, cupric stearate,
Complex compounds of cupric benzoate and the above-mentioned inorganic copper halide with xylylenediamine, 2-mercaptobenzimidazole, benzimidazole and the like can be mentioned. Of these, monovalent copper compounds, particularly monovalent copper halide compounds, are preferred, and cuprous acetate, cuprous iodide and the like can be exemplified as particularly suitable copper compounds. The addition amount of the copper compound is an amount sufficient to improve the strength of the welded portion when the molded article of the resin composition to be formed is adhered by the two-color molding method. 0.01 to 2 parts by weight, more preferably 0.015 to 1 part by weight. If the addition amount of the copper compound is less than 0.01 part by weight, the strength of the welded portion during welding and molding, such as two-color molding, tends to be insufficient. The liberation of metallic copper occurs and the coloring reduces the value of the product. In the present invention, it is also possible to add an alkali halide in a form used in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide, and potassium iodide, iodine Sodium chloride is particularly preferred.

In the present invention, it is also possible to add a fibrous / non-fibrous inorganic reinforcing material in addition to the above specific glass fibers. Specific examples of such reinforcing agents include carbon fiber, potassium whisker, titanate, and the like. Zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber,
Fibrous fillers such as metal fibers, wallastenite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide Metal compounds such as titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide; Examples include non-fibrous fillers such as glass beads, ceramic beads, boron nitride, silicon carbide, and silica. These may be hollow, and two or more of these fillers may be used in combination. 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.

The addition of an alkoxysilane having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group to the nylon resin composition of the present invention is performed by mechanical Strength,
It is effective in improving toughness and the like. Specific examples of such compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
epoxy group-containing alkoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
-Mercapto group-containing alkoxysilane compounds such as mercaptopropyltriethoxysilane; ureide group-containing such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane Alkoxysilane compound, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane;
Amino-containing alkoxysilane compounds such as -aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ- Examples include a hydroxyl group-containing alkoxysilane compound such as hydroxypropyltriethoxysilane.

Further, the nylon 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 and the like. Additives such as antioxidants, heat stabilizers, lubricants, UV inhibitors, colorants, etc. can be added.

The method for preparing the nylon resin composition of the present invention is not limited to a specific method. As a specific and efficient example, a mixture of a raw material nylon resin, a glass fiber and a copper compound is extruded in a single screw or a twin screw. Depending on the melting point of the nylon resin to be supplied to a known melt kneader such as a mixer, a Banbury mixer, a kneader, and a mixing roll.
A method of melting and kneading at a temperature of 0 to 330 ° C. can be used.

In the present invention, the addition of a copper compound which is effective for improving the adhesive strength at the time of fusion molding may be carried out in any of the above-mentioned melt-kneading processes. Further, it may be added in advance during the polymerization of the raw material nylon resin. The nylon resin composition of the present invention thus obtained is excellent in heat resistance, molded product surface appearance, dimensional stability, and adhesion at the time of fusion molding, and is usually used as two-color molding. As in the molding method of simultaneously injecting or extruding two or more types of molten resin, a molded product obtained by injection molding, extrusion molding, or blow molding is inserted into an injection molding die, and then a new injection molding is performed. It is particularly useful when the two are bonded together, and taking advantage of this advantage, for example, intake system components such as an intake manifold of an automobile, cooling system components such as a water inlet and a water outlet, fuel injection, fuel delivery pipes and the like. It can be suitably used for hollow parts such as system parts and containers such as oil tanks. That.

[0017]

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 by weight.

In the following examples, evaluations of material strength, fluidity, surface smoothness of molded products, and welding strength were performed by the following methods. [Material strength] Measured according to the following standard method. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 [Surface smoothness] A square plate of 80 × 80 × 3 mm is injection-molded, and the sharpness of the reflected image of a fluorescent lamp is visually observed on the surface of the obtained molded product. did. ：: The reflected image of the fluorescent lamp is observed although it is unclear. Δ: The reflected image of the fluorescent lamp cannot be observed. [Measurement of Adhesive Strength] A test piece having a surface shape shown in FIG. 1 and a thickness of 10 mm was obtained by halving a test piece for measuring bending fatigue, and a resin composition obtained by a method described below was subjected to an injection molding method. Molded. One of the molded pieces is inserted into a bending fatigue test piece mold, and the remaining portion is newly injection-molded with the same resin composition, and a molded product having a shape shown in FIG. I got The molded product was subjected to a tensile test, and the breaking strength was defined as the value of the adhesive strength 1.

A test piece 2 having the shape of FIG. 1 obtained separately.
Insert the pieces into the mold so that sides A are in contact with each other,
As shown in FIG. 3, an additional band-shaped portion B having a thickness of 1 mm and a width of 10 mm was injection-molded using the same resin composition with the side A as a center line, and the adhesion test was performed by the band-shaped portion B. I got a piece. The bending strength of the obtained test piece was measured, and the value was defined as adhesive strength 2.

Example 1 Melting and kneading of a nylon resin, glass fiber and a copper compound were performed using a TEX30 type twin screw extruder manufactured by Japan Steel Works. 0.05 parts by weight of iodide 1 to 100 parts by weight of nylon 610 and nylon resin having a relative viscosity of 2.80
Dry blending of copper and 0.2 parts by weight of potassium iodide, cylinder temperature 280 ° C, screw rotation speed 150r
pm, fed to the feeder of the extruder in operation, fed from the side feeder at the tip of the extruder, fed 50 parts by weight of glass fiber with a fiber diameter of 10 μm and a strand length of 3 mm, melt-kneaded, and cooled the extrusion gut Thereafter, the mixture was pelletized with a pelletizer.

The resin composition obtained here is injection-molded and weld-molded into various test pieces to obtain surface smoothness, material strength,
The results of measuring the adhesive strength and the like are as shown in Table 1.

[0022]

[Table 1]

Comparative Example 1 Kneading, pelletizing, injection molding and measurement of physical properties were carried out in exactly the same manner as described in Example 1, except that nylon 66 having a relative viscosity of 2.80 was used instead of nylon 610 as the nylon resin. Was. The results are as shown in Table 1,
The composition obtained here was insufficient in adhesive strength as compared with the composition of the present invention shown in Example 1.

Comparative Example 2 Kneading, pelletizing, injection molding, and measurement of physical properties were performed in exactly the same manner as described in Example 1 except that nylon 6 having a relative viscosity of 2.80 was used instead of nylon 610 as the nylon resin. Was. The results are as shown in Table 1. The composition obtained in this example had a particularly high adhesive strength when absorbing water.
The composition was insufficient compared with the composition of the present invention shown in FIG.

Comparative Example 3 Kneading, pelletizing, injection molding and measurement of physical properties were carried out in exactly the same manner as described in Example 1 except that cuprous iodide and potassium iodide were not added. The results are as shown in Table 1. The composition obtained here was insufficient in adhesive strength as compared with the composition of the present invention shown in Example 1.

Examples 2 to 4 Except that the types and amounts of the nylon resin, glass fiber and copper compound used were changed as shown in Table 2, melt kneading and pelletizing were carried out in exactly the same manner as described in Example 1. ,
Injection molding and measurement of physical properties were performed, and the results shown in Table 1 were obtained. The composition obtained here was also excellent in surface smoothness and welding strength and of high practical value.

[0027]

[Table 2]

[0028]

As described above, the nylon resin composition of the present invention is excellent in heat resistance, molded product surface appearance, dimensional stability, and adhesion at the time of fusion molding.
As in the conventional molding method of simultaneously injecting or extruding two or more types of molten resin as welding molding, the molded product obtained by injection molding, extrusion molding, or blow molding is inserted into an injection molding die, and then a new molding is performed. It is particularly useful when both are bonded and used by injection molding.

[Brief description of the drawings]

FIG. 1 is a plan view showing a shape of a test piece before two-color molding used in an example.

FIG. 2 is a plan view of a test piece whose tensile strength is measured in Examples.

FIG. 3 is a plan view and a side view of a test piece whose bending strength is measured in an example.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI B29K 105: 06

Claims (7)

[Claims] (A) 100 parts by weight of a high-grade nylon resin having 7 or more carbon atoms per amide group,
(B) Glass fibers 10 to 15 having an average fiber diameter of 5 to 15 μm
A resin composition for welding molding, comprising 0 parts by weight and 0.01 to 2 parts by weight of a copper compound (C). 2. The nylon resin of the component (A) is nylon 6
9, nylon 610, nylon 612, nylon 101
0, nylon 1012, nylon 126, nylon 12
10, nylon 1212, nylon 11, nylon 12
The resin composition for welding molding according to claim 1, which is at least one member selected from the group consisting of: 3. The copper compound is a monovalent copper compound.
3. The resin composition for fusion molding according to any one of claims 1 to 2. 4. The resin composition according to claim 3, wherein the monovalent copper compound is cuprous halide. 5. A (A) 100 parts by weight of a high-grade nylon resin having 7 or more carbon atoms per amide group,
(B) Glass fibers 10 to 15 having an average fiber diameter of 5 to 15 μm
A method for producing a resin composition for fusion molding, comprising mixing 0 part by weight and 0.01 to 2 parts by weight of a copper compound (C). 6. A method for producing a weld-molded article, wherein the resin composition is weld-molded using the resin composition according to claim 1. 7. A weld-molded article formed by welding using the resin composition for weld-molding according to claim 1.