JPH10231421A - Resin composition for welding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition balanced between moldability and heat resistance and being excellent in suitability for vibration weldability by forming a resin composition containing a nylon resin and a glass fiber having a specified mean particle fiber diameter so that glass fibers having at least a specified fiber length may constitute a specified rate of the entire fiber length. SOLUTION: A nylon resin selected from among nylon 6, nylon 66, a nylon 6 component/nylon 66 component copolymer ((98-80)/2-20)wt.%, etc., in an amount of 100 pts.wt. and 10-150 pts.wt. having a mean fiber diameter of 5-15μm are kneaded once to obtain a mixture in which glass fiber having a weight-average fiber length of 100-400μm and a fiber length of 60μm or below constitutes 10-50wt.% of the entire glass fiber. If necessary, a fibrous or nonfibrous reinforcement such as a carbon fiber, zinc oxide whiskers, kaolin or mica, a discoloration preventive, an antioxidant, a heat stabilizer, etc., may be added to the mixture.

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 nylon resin composition suitable for a hollow molded article obtained by vibration welding a molded article.

[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 the conventional nylon resin material does not consider the applicability to such post-processing. For example, a glass fiber reinforced nylon resin molded product composed of two or more parts is welded by a vibration welding method or the like. At the present time, when used, especially when the parts are large, the strength of the welded portion is insufficient, so that the use is limited at present.

[0003]

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

[0004]

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, by controlling the length distribution of glass fibers contained in the glass fiber reinforced nylon resin to a specific range. The inventors have found that the object is achieved, and arrived at the present invention. That is, the present invention provides (1)
"(A) A resin composition containing (B) 10 to 150 parts by weight of glass fiber having an average fiber diameter of 5 to 15 [mu] m with respect to 100 parts by weight of nylon resin, wherein the weight average of glass fibers in the composition is A resin composition for welding, characterized in that the proportion of glass fibers having a fiber length in the range of 100 to 400 μm and a fiber length of 60 μm or less accounts for 10 to 50% by weight of the total glass fibers. ”, (2) "Average fiber diameter 5 to 15μ
m, a glass fiber having a strand length of 1 mm or more and a glass fiber having an average fiber diameter of 5 to 15 μm and a strand length of 20 to 500 μm, each having a fiber diameter different from each other by at least 2 μm or more.

(3) “The welding resin composition according to any one of (1) and (2) above, wherein the nylon resin is at least one selected from aliphatic nylon resins having a melting point of 200 ° C. or higher.” 4) The welding resin composition according to any one of (1) to (3), wherein the nylon resin is at least one selected from nylon 66, nylon 6, and copolymerized nylon containing these as a main component. (5) “The welding resin composition according to the above (4), wherein the copolymerized nylon is a copolymer composed of a nylon 6 component and a nylon 66 component.”
(6) A copolymer comprising 98 to 80% by weight of a nylon 6 component and 2 to 20% by weight of a nylon 66 component or 98 to 80% by weight of a nylon 66 component and 2 to 20% by weight of a nylon 6 component. The welding resin composition according to claim 5, which is a copolymer. ", (7) a copolymer comprising 97 to 90% by weight of a nylon 6 component and 3 to 10% by weight of a nylon 66 component. Or 97 to 90% by weight of nylon 66 component and nylon 6
(6) which is a copolymer comprising 3 to 10% by weight of a component
The resin composition for welding according to the above. And (8) “(A) 100 parts by weight of nylon resin, (B) 10 to 150 parts by weight of glass fibers having an average fiber diameter of 5 to 15 μm are melt-kneaded. A method for producing a resin composition, wherein the weight-average fiber length of glass fibers in the composition is in the range of 100 to 400 μm and the ratio of glass fibers having a fiber length of 60 μm or less is 1% of all glass fibers.
A method for producing a welding resin composition which accounts for 0 to 50% by weight. (9) The composition according to the above (8), wherein the fiber length distribution of the glass fibers in the composition satisfies the above ratio at the stage of performing the melt-kneading of the component (A) and the component (B) once. A method for producing a resin composition for welding.

(10) "The glass fiber to be melt-kneaded is a mixture of glass fiber having an average fiber diameter of 5 to 15 μm and a strand length of 1 mm or more and glass fiber having an average fiber diameter of 5 to 15 μm and a strand length of 20 to 500 μm. Certain methods for producing the welding resin composition according to the above (8) or (9). "And the use of the properties of the resin composition as (11)" A resin according to any one of the above (1) to (7) A molded article obtained by welding a molding material from the composition. "

[0007]

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

The nylon resin used in the present invention is a nylon containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the main components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid, lactams such as ε-aminocaprolactam and ω-laurolactam, tetramethylenediamine, hexamethylene Diamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine Amine, 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)
Aliphatic, alicyclic and aromatic diamines such as methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine, and adipic acid, speric acid, azelaic acid, sebacic acid , Dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, aliphatics such as hexahydroisophthalic acid, Alicyclic and aromatic dicarboxylic acids are mentioned. 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), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene adipamide / polyhexamethylene Terephthalamide copolymer (nylon 66 /
6T), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene Terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene) Terephthalamide) copolymer (nylon 6T / M5)
T), polyxylylene adipamide (nylon XD6), and mixtures or copolymers thereof.
Particularly preferred are nylon 6, nylon 66, nylon 610, nylon 6/66 copolymer,
Nylon 6/12 copolymer, Nylon 6T / 6 copolymer, Nylon 66 / 6T copolymer, Nylon 6T /
Examples include 6I copolymers and nylon 6T / M5T copolymers, and it is also practically preferable to use these nylon resins as a mixture depending on required properties such as moldability, heat resistance, and vibration welding properties.

The degree of polymerization of these nylon 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, particularly 2.0 to 4.0. Those in the range of 0 are preferred.

In the present invention, the glass fiber used as the component (B) is in a state after melt-kneading with a nylon resin,
In particular, the weight average fiber length is 10
It is preferable that the ratio of the glass fiber having a fiber length of 0 to 400 μm and a fiber length of 60 μm or less is controlled to be in a range of 10 to 50% by weight in all the glass fibers. Because the fiber length is 60μ
This is because when a molded product of the nylon resin composition is subjected to vibration welding by the presence of a specific amount of glass fibers of m or less, an extremely high welding strength can be obtained. Although the reason for this is not necessarily clear, it is considered that one of the causes is to affect the orientation behavior of glass fibers in the nylon resin layer melted by frictional heat due to vibration. The preferred weight average fiber length of the glass fiber and the proportion of the glass fiber of 60 μm or less are each 120 to
350 μm and in the range of 15-40% by weight. If the weight average fiber length of the glass fiber is shorter than the above range, the strength of the resin composition tends to decrease, while if it is longer than the above range, the appearance of the molded product and the vibration welding property tend to decrease. On the other hand, if the proportion of the glass fiber having a size of 60 μm or less is less than the above range, the vibration welding property is reduced, and if the proportion is more than the above range, the mechanical strength may be adversely affected. It is preferable in terms of production efficiency to obtain a glass fiber reinforced nylon resin composition having such a fiber length distribution in one melt-kneading step, and as an example of an efficient method for realizing the same, a glass fiber having a strand length of 1 mm or more is used. Fiber length 20-50
A method in which 0 μm glass fiber is used as a raw material as a mixture in an appropriate ratio can be mentioned. 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.

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.

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 contains 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 the raw material nylon resin and glass fiber is prepared by using a single-screw or twin-screw extruder, Banbury. 220 to 330 depending on the melting point of the nylon resin used and supplied to a known melt kneader such as a mixer, a kneader and a mixing roll.
A method of melting and kneading at a temperature of ° C. can be used.

In the melt kneading, in order to realize the specific glass fiber length distribution of the present invention, for example, when melt kneading with a twin screw extruder, a part of the glass fibers is supplied together with a nylon resin from a resin raw material feeder. A method in which the remaining glass fibers are supplied from a side feeder at the tip of the extruder to control the shearing history of the glass fibers, and a method in which glass fibers used as raw materials have different fiber lengths.

The nylon resin composition of the present invention thus obtained is excellent in heat resistance, molded product surface appearance, dimensional stability, and vibration welding property, and is excellent in injection molding, extrusion molding, It is particularly useful when the molded product obtained by blow molding is 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 an automobile, a water inlet,
It can be suitably used for cooling system parts such as water outlets, fuel injection parts such as fuel injection pipes and fuel delivery pipes, and hollow parts such as oil tanks. In particular, since the nylon resin composition of the present invention has good surface smoothness of a molded product, when used for an intake system component such as an intake manifold, the nylon resin composition exhibits low resistance when passing a gas and exhibits high efficiency.

[0019]

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 vibration welding strength were performed by the following methods. [Fiber length distribution] Approximately 1 g of the resin composition was burned in an electric furnace to remove the resin component, the obtained glass fiber was photographed with a micrograph, and the length of each glass single fiber was measured. Was. [Material strength] Measured according to the following standard method. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 [Fluidity] Using a spiral flow measurement mold having a spiral shape with a width of 10 mm, a thickness of 2 mm and a total length of 600 mm,
Injection molding temperature 250 ° C, injection molding pressure 30kgf / cm
^{2. When} a material was injection-molded at a mold temperature of 80 ° C., the flow distance in the mold was measured and used as an index of fluidity.
The longer the flow length, the better the fluidity. [Surface Smoothness] A square plate of 80 × 80 × 3 mm was injection-molded, and the sharpness of the reflected image of a fluorescent lamp was visually observed on the surface of the obtained molded product, and was used as an index of smoothness. A: A reflected image of a fluorescent lamp is clearly observed. ：: 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 Vibration Welding Strength] Surface shape shown in FIG.
m was molded by injection molding, and the two molded pieces were welded under the following conditions using a Branson 2850 type vibration welding apparatus, and then subjected to a tensile test to measure the strength of the welded portion. Frequency: 240Hz Pressure: 70kgf Amplitude: 1.5mm Welding allowance: 1.5mm

Example 1 Melting and kneading of a nylon resin and glass fiber was carried out by T
This was performed using an EX30 type twin screw extruder. 70% nylon 6 resin with relative viscosity 2.70 and fiber diameter 13μ
m, and 10% glass fiber with a strand length of 1.5 mm are dry-blended and supplied to the feeder of an extruder operating at a cylinder temperature of 250 ° C. and a screw rotation speed of 150 rpm. Melt kneading was performed by supplying 20% of glass fiber having a diameter of 9 μm and a strand length of 3 mm, and the extruded gut was cooled and pelletized with a pelletizer.

The weight average fiber length of the glass fibers in the resin composition obtained here is 290 μm, and the ratio of the glass fibers having a fiber length of 60 μm or less is 20% of the total glass fibers, and this is injected into various test pieces. The results of measuring the fluidity, surface smoothness, material strength, welding strength, and the like after molding were as shown in Table 1.

[0023]

[Table 1]

Comparative Example 1 The glass fiber used was 9 μm in fiber diameter and 3 mm in strand length.
, And kneading, pelletizing, injection molding, and measuring physical properties were performed in exactly the same manner as described in Example 1 except that only glass fibers were supplied from the side feeder. The results are as shown in Table 1. The composition obtained here has an inadequate glass fiber length distribution, and thus has higher fluidity, welding strength and surface smoothness than the composition of the present invention shown in Example 1 Was inferior.

Examples 2 to 4 Melt kneading, pelletizing, and injection were performed in exactly the same manner as in Example 1 except that the types and amounts of the nylon resin and glass fiber used were changed as shown in Table 2. The molding and physical properties were measured, and the results shown in Table 1 were obtained. The composition obtained here was also excellent in fluidity, surface smoothness and welding strength and of high practical value.

[0026]

[Table 2]

Example 5 65% of a nylon 6/66 copolymer having a melting point of 217 ° C. and a relative viscosity of 2.65 was supplied to a feeder of an extruder operating at a cylinder temperature of 250 ° C. and a screw rotation speed of 150 rpm. From the side feeder at the tip of the extruder, 20% of glass fiber having a fiber diameter of 9 μm and a strand length of 3 mm and a fiber diameter of 13 μm and a strand length of about 0.2
A mixture of 15% of milled glass fiber of 15 mm was supplied and melt-kneaded. The extruded gut was cooled and pelletized by a pelletizer.

The weight-average fiber length of the glass fibers in the resin composition obtained here was 380 μm, and the ratio of glass fibers having a fiber length of 60 μm or less was 30% of the total glass fibers. Injection molding into test pieces of fluidity,
The results of measuring the surface smoothness, material strength, welding strength, and the like are as shown in Table 1.

Examples 6-8 Melt kneading, pelletizing, and injection were performed in exactly the same manner as described in Example 5, except that the types and amounts of the nylon resin and glass fiber used were changed as shown in Table 2. The molding and physical properties were measured, and the results shown in Table 1 were obtained. The composition obtained here was also excellent in fluidity, surface smoothness and welding strength and of high practical value.

[0030]

As described above, the resin composition of the present invention is excellent in heat resistance, surface appearance of a molded product, dimensional stability and vibration welding property, and is excellent in injection molding, extrusion molding, It is particularly useful when the molded product obtained by blow molding is used by welding by the vibration welding method, etc., taking advantage of this advantage, for example, for intake system parts such as automobile intake manifolds, hollow parts such as oil tanks, etc. Can be suitably used. In particular, since the nylon resin composition of the present invention has good surface smoothness of a molded product, when used for an intake system component such as an intake manifold, the nylon resin composition exhibits low resistance when passing a gas and exhibits high efficiency.

[Brief description of the drawings]

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

Claims (10)

[Claims] (A) 100 parts by weight of nylon resin, (B) glass fiber having an average fiber diameter of 5 to 15 μm.
A resin composition containing 150 parts by weight, wherein the weight average fiber length of the glass fibers in the composition is 100 to 400 μm
Wherein the proportion of glass fibers having a fiber length of 60 μm or less accounts for 10 to 50% by weight of all glass fibers. 2. A glass fiber having an average fiber diameter of 5 to 15 μm and a strand length of 1 mm or more and a glass fiber having an average fiber diameter of 5 to 15 μm and a strand length of 20 to 500 μm are different from each other by at least 2 μm. Item 1
The resin composition for welding according to the above. 3. The welding resin composition according to claim 1, wherein the nylon resin is at least one selected from aliphatic nylon resins having a melting point of 200 ° C. or higher. 4. The nylon resin is nylon 66 or nylon 6.
The resin composition for welding according to any one of claims 1 to 3, wherein the resin composition is at least one selected from the group consisting of copolymerized nylons containing these as a main component. 5. The welding resin composition according to claim 4, wherein the copolymerized nylon is a copolymer comprising 6 components of nylon and 66 components of nylon. 6. The copolymerized nylon is a nylon 6 component of 98-8.
The welding resin according to claim 5, which is a copolymer comprising 0% by weight and 2 to 20% by weight of a nylon 66 component or a copolymer comprising 98 to 80% by weight of a nylon 66 component and 2 to 20% by weight of a nylon 6 component. Composition. 7. The copolymerized nylon is a nylon 6 component 97-9.
The welding resin according to claim 6, which is a copolymer comprising 0% by weight and 3 to 10% by weight of nylon 66 component or a copolymer comprising 97 to 90% by weight of nylon 66 component and 3 to 10% by weight of nylon 6 component. Composition. 8. A glass fiber having an average fiber diameter of 5 to 15 .mu.m with respect to (A) 100 parts by weight of a nylon resin.
A method for producing a welding resin composition in which 150 parts by weight is melt-kneaded, wherein the glass fiber in the composition has a weight average fiber length in a range of 100 to 400 μm and a fiber length of 60.
The ratio of the glass fiber of μm or less is 10 to 5 of the total glass fiber.
A method for producing a welding resin composition which accounts for 0% by weight. 9. The melt kneading of the component (A) and the component (B) is carried out in one step.
9. The method for producing a welding resin composition according to claim 8, wherein the fiber length distribution of the glass fibers in the composition at the stage of performing the above operations satisfies the above ratio. 10. A glass fiber to be melt-kneaded has an average fiber diameter of 5 to 15 μm, a glass fiber having a strand length of 1 mm or more, an average fiber diameter of 5 to 15 μm, and a strand length of 20 to 5 μm.
The method for producing a welding resin composition according to claim 8 or 9, which is a mixture with a glass fiber of 00 µm.