JP3397360B2 - Glass fiber reinforced thermoplastic resin composition with excellent ultrasonic weldability - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to heat resistance, mechanical strength,
The present invention relates to a glass fiber reinforced thermoplastic resin composition excellent in low creep property and ultrasonic weldability.

[0002]

2. Description of the Related Art A composition (AS-GF) obtained by blending a styrene-acrylonitrile copolymer with glass fiber has been conventionally used because of its excellent impact resistance, rigidity and dimensional stability.
It has been used for electrical parts such as fan materials.

However, in recent years, various performance requirements for glass fiber reinforced thermoplastic resin compositions have improved, and AS-
Regarding the GF, the conventional composition has a problem that distortion tends to occur with respect to a component under a high load such as a cooler fan material, and the resin composition has excellent ultrasonic weldability and low creep property. Things were strongly requested.

In response to these requirements, a glass fiber reinforced thermoplastic composition having high rigidity and excellent heat resistance and impact resistance by containing a maleimide type copolymer (JP-A-59)
-187046, JP-A-60-47045, JP-A-60-47049) is known, but if a composition having a low creep property and an excellent ultrasonic welding property is to be found? In other words, it has not been sufficient for a component such as a cooler fan material that is subjected to a forming process using ultrasonic welding.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to obtain a glass fiber reinforced excellent in ultrasonic weldability without lowering the low creep property and heat resistance obtained by containing a maleimide copolymer. It is to provide a thermoplastic resin composition.

[0006]

The inventors of the present invention added a graft copolymer containing a rubber-like polymer in a specific amount to obtain a high rigidity and a high rigidity obtained by containing a maleimide copolymer. It has been found that a glass fiber reinforced thermoplastic resin composition having excellent ultrasonic weldability and low creep property can be obtained without lowering heat resistance.

That is, the present invention comprises: (a) component: aromatic vinyl monomer residue 25 to 90% by weight, maleimide monomer residue 10 to 70% by weight, and copolymerizable with these monomers. Vinyl monomer residue 1 to 40% by weight (however, the unsaturated dicarboxylic acid anhydride monomer residue is 1
Maleimide copolymer 1 to 40 parts by weight of a containing al less than 10 wt.%) (B) component: aromatic vinyl monomer residue 60 to 90 wt%, vinyl cyanide monomer residues 10-40 %, And 0 to 20 vinyl monomer residues copolymerizable with these monomers
20-93 parts by weight of copolymer (c) consisting of 10% by weight of rubber-like polymer, 10-70% by weight of aromatic vinyl monomer, 30-90% by weight of aromatic vinyl monomer residue, and 0 of vinyl cyanide monomer residue. To 40 wt% and a graft copolymer consisting of 0 to 20 wt% of a vinyl monomer residue copolymerizable with these monomers 1 to less than 6 parts by weight (d) component: glass fiber 5 to 40 parts by weight Consists of
The proportion of the rubber-like polymer contained in 100 parts by weight of the total amount of the components (a) to (d) is 0.5 to 4.2 parts by weight.
It is in the glass fiber reinforced thermoplastic resin composition characterized by being less than .

The present invention will be described in detail below. The maleimide-based copolymer, which is the component (a) of the present invention, is a copolymer of an aromatic vinyl monomer, a maleimide-based monomer, and a vinyl monomer copolymerizable with these monomers. is there.

Specific examples of the aromatic vinyl monomer used as the component (a) include styrene, α-methylstyrene,
t-Butylstyrene, vinyltoluene, chlorostyrene and the like can be mentioned.

Specific examples of the maleimide-based monomer used as the component (a) include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide and N-cyclohexylmaleimide. -Phenylmaleimide and the like, and N-phenylmaleimide is preferable.

Further, specific examples of the vinyl monomer copolymerizable with the aromatic vinyl monomer or the maleimide-based monomer used as the component (a) include maleic anhydride, methylmaleic anhydride and ethylmaleic anhydride. Acid, unsaturated dicarboxylic acid anhydride such as phenylmaleic anhydride, acrylonitrile,
Examples include vinyl cyanide such as methacrylonitrile, acrylic acid esters such as methyl acrylate, ethyl acrylate and propyl acrylate, methacrylic acid esters such as methyl methacrylate, methyl ethyl acrylate and methyl butyl acrylate, and acrylic acid and methacrylic acid. To be And each monomer can be used individually or in combination.

The maleimide-based copolymer as the component (a) comprises an aromatic vinyl monomer residue of 25 to 90% by weight, a maleimide monomer residue of 10 to 70% by weight, and a copolymer of these monomers. Polymerizable vinyl monomer residues of 1 to 40% by weight are preferred.

When the maleimide-based monomer residue is less than 10% by weight, heat resistance and creep properties deteriorate, and when it exceeds 70% by weight, moldability and compatibility with other resins deteriorate.

Further, as the vinyl monomer copolymerizable with the aromatic vinyl monomer or the maleimide type monomer, unsaturated dicarboxylic acid anhydride monomer residues are contained in an amount of 1 to less than 10% by weight. > Get lost.

The maleimide copolymer as the component (a) is prepared by preparing a styrene-maleic anhydride copolymer in advance and preparing a copolymer containing a predetermined amount of maleic anhydride residue as a primary amine. Alternatively, it may be produced by imidization with ammonia, or may be produced by copolymerization of a maleimide monomer and an aromatic vinyl monomer. The polymerization method is generally produced by emulsion polymerization, bulk polymerization, suspension polymerization, or the like.

Next, the copolymer which is the component (b) of the present invention is obtained by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable with these monomers. It was done.

Specific examples of the aromatic vinyl monomer used as the component (b) include styrene, α-methylstyrene,
There are t-butylstyrene, vinyltoluene, chlorostyrene, and the like.

Specific examples of the vinyl cyanide monomer used as the component (b) include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred.

Further, specific examples of the vinyl monomer copolymerizable with the aromatic vinyl monomer or cyanocavinyl monomer used as the component (b) include acrylic acid esters such as methyl acrylate, ethyl acrylate and propyl acrylate. , Methacrylic acid esters such as methyl methacrylate, methyl ethyl acrylate and methyl butyl acrylate, and acrylic acid and methacrylic acid.

The copolymer as the component (b) can be copolymerized with 60 to 90% by weight of aromatic vinyl monomer residues, 10 to 40% by weight of vinyl cyanide monomer residues, and these monomers. It is preferable to use the vinyl monomer residue in the range of 0 to 20% by weight.

When the amount of the aromatic vinyl monomer residue is less than 60% by weight, the compatibility with other resins is lowered, and when the amount of the vinyl cyanide monomer residue is less than 10% by weight, the heat resistance and the chemical resistance are low. , Mechanical strength and the like are reduced.

Next, the graft copolymer which is the component (c) of the present invention is a rubber-like polymer, an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl copolymerizable with these monomers. It is a copolymer of monomers.

Specific examples of the rubbery polymer used in the copolymer of the component (c) include a butadiene polymer, a copolymer of butadiene and a vinyl monomer copolymerizable therewith, and an ethylene-propylene copolymer. Polymer, ethylene-propylene-
Examples thereof include diene copolymers, block copolymers of butadiene and aromatic vinyl, acrylic acid ester polymers, and copolymers of acrylic acid esters and vinyl monomers copolymerizable therewith.

Further, specific examples of the aromatic vinyl monomer, the vinyl cyanide monomer and the vinyl monomer copolymerizable with these monomers as the component (c) include the above-mentioned component (b). It is similar to the one.

The graft copolymer as the component (c) comprises 10 to 70% by weight of a rubbery polymer, 30 to 90% by weight of an aromatic vinyl monomer residue, and 0 to 40 of a vinyl cyanide monomer residue.
It is preferably used in an amount of 0 to 20% by weight and a vinyl monomer residue copolymerizable with these monomers.

When the content of the rubber-like polymer in the component (c) is less than 10% by weight, when the glass fiber reinforced thermoplastic resin composition is used, the ultrasonic weldability of the molded part of the composition can be sufficiently exhibited. However, if it exceeds 70% by weight, the mechanical strength decreases.

The glass fiber which is the component (d) of the present invention is
A fiber having a fiber diameter of 6 to 13 μm and a fiber length of 1.5 to 6 mm is preferable. Regarding the surface treatment of the fibers, those treated with a silane coupling agent are preferable, and aminosilane is more preferably used as the coupling agent.

The respective weight parts of (a), (b), (c) and (d) contained in the glass fiber reinforced thermoplastic resin composition of the present invention are based on the maleimide copolymer of the component (a). The content is 1 to 40 parts by weight, more preferably 15
~ 30 parts by weight. If the content is less than 1 part by weight, the low creep property cannot be sufficiently exhibited, and if it exceeds 40 parts by weight, the mechanical strength decreases.

The amount of the component (b) copolymer is 20 to 93.
Parts by weight, more preferably 40 to 70 parts by weight. If the content is less than 20 parts by weight, the mechanical strength decreases,
If it exceeds 93 parts by weight, the rigidity and heat resistance will be deteriorated, and the low creep property cannot be sufficiently exhibited.

The amount of the graft copolymer as the component (c) is 1 to
It is less than 6 parts by weight. Furthermore, (a) component- (d) component 1
Rubbery polymer is 0.5 in 00 parts by weight 4.2 parts by weight Not
It must be fully included. If the content of the graft copolymer is 1 part by weight, or if the proportion of the rubber-like polymer in all the components is less than 0.5 part by weight, the ultrasonic weldability is not sufficiently exhibited, and the content of the graft copolymer is When 10 parts by weight or the ratio of the rubber-like polymer in all components exceeds 4.2 parts by weight, the rigidity is largely reduced and the creep property is also deteriorated.

The amount of the glass fiber as the component (d) is 5 to 40.
If it is less than 5 parts by weight, rigidity, mechanical strength and dimensional stability are poor, and if it exceeds 40 parts by weight, fluidity is lowered.

The glass fiber reinforced thermoplastic resin composition of the present invention can be obtained by using various known mixing methods. Specifically, there is a method in which each raw material is uniformly mixed in advance with a mixer such as a tumbler or a Henschel mixer, supplied to a single-screw or twin-screw extruder, melt-kneaded, and then adjusted as pellets.

Further, the glass fiber reinforced thermoplastic resin composition of the present invention may contain a colorant, a stabilizer, a lubricant and other auxiliaries, if necessary.

The glass fiber reinforced thermoplastic resin composition of the present invention can be molded into a desired molded product by a molding method such as injection molding, compression molding and extrusion molding.

The glass fiber reinforced thermoplastic resin composition according to the present invention has not only excellent low creep property and heat resistance but also rigidity, dimensional stability and mechanical strength as a glass fiber reinforced resin. Since it is also excellent in ultrasonic weldability, a plastic product produced by ultrasonically welding a part formed by molding this glass fiber reinforced thermoplastic resin composition is extremely excellent in practical use, and its representative An example is a cooler fan.

Further, the glass fiber reinforced thermoplastic resin composition according to the present invention can be used as a preferable material for various electric parts as well as cooler fan parts.

[0037]

EXAMPLES Examples and comparative examples will be given to explain the present invention in more detail, but the present invention is not limited to these examples. In addition, "part" described below
Are all based on weight.

(A) Method for producing maleimide-based copolymer Component 60 parts of styrene and 50 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and then the internal temperature was raised to 85 ° C. did. Separately, a solution of 40 parts of maleic anhydride and 0.15 part of benzoyl peroxide dissolved in 250 parts of methyl ethyl ketone was prepared, and this solution was continuously added into the system over 8 hours. After the addition was completed, the reaction was continued at 85 ° C for 3 hours. When a part of the reaction solution was sampled and the polymerization rate was quantified by gas chromatography, both styrene and maleic anhydride were 99% or more. Next, 36 parts of aniline and 0.3 part of triethylamine were added to the system, and the temperature was adjusted to 140 ° C.
The stirring was continued for 7 hours. After cooling, the content was supplied to a co-rotating twin-screw extruder with a vacuum vent having a deliquoring function, deliquoring, devolatilizing and pelletizing, and this polymer was used as a maleimide-based copolymer. The imidation ratio at this time was 96%. This maleimide-based copolymer is referred to as polymer A.

(B) Component Copolymer Production Method In an autoclave equipped with a stirrer, 100 parts of pure water and a third
Add 0.6 parts of calcium phosphate and stir at 150 rpm, then 44 parts of styrene, 24 parts of acrylonitrile, tertiary butyl peroxy 3 ・ 5 ・ 5 trimethylhexanoate
0.05 part, tertiary butyl peroxyacetate 0.05
Part, 0.35 parts of tertialed decyl mercaptan,
After that, the mixture was stirred with nitrogen gas for 15 minutes, and then sealed. From the time when the temperature started to rise to 100 ° C., 32 parts of styrene monomer was added at a constant rate over 5 hours. After the addition of styrene was completed, the temperature was raised to 120 ° C. and kept for 2.5 hours, then cooled, neutralized, dehydrated and dried in the usual manner. The polymerization rate at this time is
It was 98%. The polymer thus obtained is referred to as polymer B.

(C) Component Copolymer Production Method In an autoclave equipped with a stirrer, 100 parts of polybutadiene latex (solids content 50%, average particle size 0.35μ, gel content 90%), sodium stearate 1 part , Sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetic acid 0.03 part,
After adding 0.003 parts of ferrous sulfate and 200 parts of water and heating to 65 ° C, 50 parts of a monomer mixture consisting of 30% by weight of acrylonitrile and 70% by weight of styrene, 0.3 part of t-dodecyl mercaptan, cumene hydroperoxide. 0.2 part was continuously added over 4 hours, and after the addition was completed, polymerization was carried out at 65 ° C. for 2 hours. The polymerization rate was 96%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a white powdery polymer. The polymer thus obtained is referred to as polymer C.

The glass fiber has a fiber length of 3 mm and a fiber diameter of 13 μ.
And the one using aminosilane as the coupling agent was used.

Examples 1 to 3 , Comparative Examples 1 to 3, 6 Polymer A, Polymer B, Polymer C and glass fiber were blended in the ratio of parts by weight shown in Table 1 and pelletized by an extruder. . The pellets were molded by an injection molding machine, test pieces were prepared, and each physical property was evaluated. The results are shown in Table 1.

Each physical property was determined according to the following measuring methods. Tensile strength: ASTM D-638 Flexural modulus: ASTM D-790 Heat distortion temperature: ASTM D-648 (Thickness 1/4 inch, load
18.6 kg / cm ² ) Thermal creep characteristics: Test machine, Toyo Seiki Seisakusho Co., Ltd. “Creep 200”, temperature 70 ℃, load 350 kg / cm ²
Measured under the conditions of ultrasonic weldability: Cut a dumbbell with a rib at a predetermined position and use an ultrasonic welder machine, Seidensha Electronics Co., Ltd. "1201B / P46A", amplitude 25μ, air pressure 2kg / cm
^2. Ultrasonic welding under conditions of welding time 0.7sec, ASTM D-6
Measure tensile strength according to 38

[0044]

[Table 1]

Example 5, Comparative Examples 4 to 5 The components were blended in the proportions shown in Example 1, Comparative Example 1 and Comparative Example 2, pelletized by an extruder, and then the pellets were molded by an injection molding machine as shown in FIG. The molded product shown in FIG. 2 is molded, and a plurality of these products are ultrasonically welded to each other to form the mold shown in FIG.
A fan was prepared. Table 2 shows the results of observing the state of the curler fan rotated at a high speed in a thermostatic chamber at 70 ° C.

[0046]

[Table 2]

[0047]

As described above, the graft copolymerization is performed on the glass fiber reinforced thermoplastic resin composition containing the maleimide-based copolymer so that the content of the rubber-like polymer is 0.5 to 5% by weight. As a glass fiber reinforced resin composition with improved ultrasonic weldability and excellent low creep property, heat resistance and rigidity, the addition of coalesced products, such as electrical parts such as cooler fan materials, various industrial parts It is useful for.

[Brief description of drawings]

FIG. 1 is a component of a cooler fan molded by an injection molding machine.

FIG. 2 is a part of a cooler fan molded by an injection molding machine.

FIG. 3 is a graph obtained by ultrasonically welding the components of FIGS. 1 and 2;
I'm Rahfan

─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-60-47045 (JP, A) JP-A-5-279544 (JP, A) JP-A-6-122797 (JP, A) JP-A-6- 122798 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (3)

(57) [Claims] 1. Component (a): Aromatic vinyl monomer residue 25
~ 90 wt%, maleimide monomer residue 10 to 70 wt%, and vinyl monomer residue copolymerizable with these monomers
1 to 40% by weight (however, unsaturated dicarboxylic acid anhydride monomer
1-40 parts by weight of maleimide-based copolymer consisting of 1 to less than 10% by weight of residues ) (b) Component: aromatic vinyl monomer residue 60-90% by weight, vinyl cyanide monomer residue Group 10 to 40% by weight, and vinyl monomer residue 0 to 20 copolymerizable with these monomers
20 to 93 parts by weight of copolymer (c) consisting of 10% by weight of rubber-like polymer 10 to 70% by weight, aromatic vinyl monomer residue 30 to 90% by weight, vinyl cyanide monomer residue 0 To 40 wt% and a graft copolymer consisting of 0 to 20 wt% of a vinyl monomer residue copolymerizable with these monomers 1 to less than 6 parts by weight (d) component: glass fiber 5 to 40 parts by weight Consisting of (a)
The glass fiber reinforced thermoplastic resin composition, wherein the proportion of the rubber-like polymer contained in 100 parts by weight of the total amount of the components (d) to (b) is 0.5 to less than 4.2 parts by weight. 2. A plastic article molded article was prepared by ultrasonic wave welding consisting claim 1 Glass fiber-reinforced thermoplastic resin composition. 3. The plastic product according to claim 2, wherein the molded product is a cooler fan.