JPH1129700A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent mechanical strength, dimensional accuracy, dimensional stability and moldability as well as hot-water aging resistance by using a polyphenylene ether resin as an essential resin component. SOLUTION: This thermoplastic resin composition at least contains (A) a polyphenylene ether resin and (B) 1-50 wt.% (based on the resin composition) of glass fiber surface-treated with an aromatic urethane-based binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition comprising a polyphenylene ether-based resin as an essential resin component, and having excellent mechanical strength, dimensional accuracy, dimensional stability and moldability, and also having excellent hot water aging resistance. Things.

[0002]

2. Description of the Related Art A polyphenylene ether-based resin composition comprising a polyphenylene ether-based resin, especially a polystyrene-based resin, has excellent mechanical properties, thermal properties and water resistance. It is used as a material for coin machine chassis of vending machines, water supply and drainage parts, and the like. When rigidity is required for an application, a technique of adding glass fiber to a resin at a ratio according to the purpose is well known. However, when this glass fiber reinforced resin is used in a warm water environment for a long time, there is a problem that the mechanical strength is reduced.

[0003]

Under these circumstances, the problem to be solved by the present invention is to use a polyphenylene ether-based resin as an essential resin component, and to improve mechanical strength, dimensional accuracy,
An object of the present invention is to provide a thermoplastic resin composition having excellent dimensional stability and moldability, and also having excellent hot water aging resistance.

[0004]

That is, the present invention provides a thermoplastic resin composition containing at least the following (A) and (B), wherein the content of (B) in the thermoplastic resin composition is as follows: The present invention relates to a thermoplastic resin composition of 1 to 50% by weight. (A): Polyphenylene ether resin (B): Glass fiber surface-treated with aromatic urethane sizing agent

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention is a polyphenylene ether resin, and a known resin can be used.
The polyphenylene ether-based resin is a general term for a polymer represented by the following general formula, and may be a single polymer or a copolymer of two or more polymers.

[0006]

(Wherein, R _{1 to} R ₄ are each independently
Selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a haloalkyl group or a haloalkoxy group having at least two carbon atoms between the halogen atom and the phenyl ring and containing no tertiary α-carbon. Represents a monovalent substituent and m is an integer representing the degree of polymerization. )

As a preferred specific example of the polyphenylene ether resin, in the above general formula, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ are a hydrogen atom or a carbon atom having 1 carbon atom. And alkyl groups 4 to 4, specifically, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, Poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) Ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether and the like. Examples of the polyphenylene ether-based copolymer include a copolymer in which the above-mentioned polyphenylene ether repeating unit partially contains an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol. Further, a copolymer in which a styrene-based compound is grafted on these PPEs may be used. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing the above-mentioned polyphenylene ether with, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, or the like as a styrene-based compound.

The component (A) of the present invention is a polyphenylene ether-based resin, but a polyphenylene ether-based resin modified with an unsaturated acid such as maleic anhydride is used because it reduces the hot water aging resistance of the resin composition. Do not.

The component (B) of the present invention is a glass fiber surface-treated with an aromatic urethane sizing agent.

Known types of glass fibers can be used, and examples thereof include E glass, C glass, A glass, and S glass. The average diameter of the glass fiber is 5 to 20 μm, preferably 6 to 15 μm
It is.

The component (B) of the present invention is a glass fiber surface-treated with an aromatic urethane sizing agent. As the type of the sizing agent, generally, there are an aromatic urethane type, an aliphatic urethane type, an acrylic type, and the like. In the present invention, an aromatic urethane type sizing agent is used. Other sizing agents do not have good adhesiveness to the resin, so that the mechanical strength of the resin composition decreases.

The component (B) of the present invention is preferably surface-treated with both an aromatic urethane sizing agent and a silane coupling agent. The silane coupling agent has an organic functional group that reacts with the resin, and examples of the organic functional group include an amino group, an epoxy group, a methacryl group, a vinyl group, and a mercapto group. Preferred are an amino group and an epoxy group. . It is preferable that the treatment amount of the silane coupling agent is large. If the amount is small, the hot water aging resistance is undesirably reduced.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition containing at least the above components (A) and (B), wherein (B)
Is a thermoplastic resin composition having a content of 1 to 50% by weight, preferably 10 to 40% by weight. If the content of the component (B) is too small, the rigidity (mechanical strength) is not sufficient, while if the content is too large, the moldability is significantly reduced.

The thermoplastic resin composition of the present invention contains (C) a polystyrene resin in addition to (A) and (B),
(A) The content of (C) per 100 parts by weight is 1900
It may be a thermoplastic resin composition of not more than part by weight.

As the component (C) polystyrene-based resin of the present invention, known resins can be used, and a repeating structural unit derived from an aromatic vinyl compound represented by the following general formula:
Those having at least 25% by weight or more in the polymer are preferred.

[0017]

(Wherein R ₅ is a hydrogen atom or a group having 1 carbon atom)
And Z represents a halogen atom or a substituent that is an alkyl group having 1 to 4 carbon atoms.
Which is an integer of 5)

As such a styrene polymer, styrene or a derivative thereof (for example, p-methylstyrene,
homopolymers of α-methylstyrene, α-methyl-p-methylstyrene, chlorostyrene, bromostyrene, etc.) and, for example, polybutadiene, styrene-butadiene block copolymers, partially hydrogenated products thereof, and styrene-isoprene block copolymers. Styrene-based copolymers obtained by modifying an elastomeric substance such as coalesce, partially hydrogenated product thereof, polyisoprene, butyl rubber, EPDM, ethylene-propylene copolymer, natural rubber alone or a mixture thereof, and furthermore, styrene-based copolymer Examples of the union include styrene-butadiene random and block copolymers, partially hydrogenated products thereof, styrene-isoprene random and block copolymers, partially hydrogenated products thereof, styrene-acrylonitrile copolymer (SAN), and styrene-methyl methacrylate. Copolymer (MS resin), styrene- Methyl methacrylate-butadiene copolymer (MBS), styrene-acrylonitrile-butadiene copolymer (ABS) and the like can be mentioned.

The amount of (C) used is 1900 parts by weight or less per 100 parts by weight of (A), preferably 5 to 1000 parts by weight.
Parts by weight, more preferably 10 to 500 parts by weight. By using (C) in this range, moldability can be improved. If the amount of (C) used is excessive, the heat resistance decreases.

[0021] The thermoplastic resin composition of the present invention may contain an elastomer for the purpose of imparting impact resistance. The elastomer is a natural and synthetic rubbery material that is elastic at room temperature. Specific examples thereof include natural rubber, butadiene polymer, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, and acrylic acid ester. Polymer, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, thioco-
Rubber, polysulfide rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide, etc.), epichlorohydrin rubber, styrene-butadiene copolymer having a styrene content of less than 25% by weight, partially hydrogenated product thereof, styrene-isoprene copolymer Examples thereof include polymers and partially hydrogenated products thereof. These rubbery substances can be produced by any polymerization method (eg, emulsion polymerization, solution polymerization), any catalyst (eg, peroxide, trialkylaluminum, lithium halide,
(Nickel-based catalyst). Further, those having various degrees of crosslinking and those having various proportions of microstructure (for example, cis structure, trans structure, vinyl group, etc.) are also used. As the copolymer, any of various copolymers such as a random copolymer, a block copolymer, and a graft copolymer can be used. Further, a partially modified rubber-like substance can be used, and examples thereof include hydroxy or carboxy-terminal modified polybutadiene.

The thermoplastic resin composition of the present invention may contain, in addition to the above-mentioned components, other additives commonly used in kneading and molding the resin according to the purpose, as long as the physical properties thereof are not impaired, for example, Flame retardants, pigments, dyes, reinforcing agents (such as carbon fiber), other fillers, heat-resistant agents, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, flow improvers, antistatic agents, stabilizers Etc. can be added. The stabilizer is not particularly limited, and includes all conventional stabilizers. The stabilizer includes a heat stabilizer, an antioxidant, a light stabilizer, and a polymerization inhibitor.

The method for producing the thermoplastic resin of the present invention is not particularly limited, and an ordinary method can be used, but a melt kneading method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include, in particular, an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously.
The order of mixing the components is not particularly limited, but it is generally preferable to mix the glass fibers after mixing the components other than the glass fibers.

The method for producing a molded article from the PPE resin composition of the present invention includes, for example, injection molding, extrusion molding, blow molding, press molding and the like, but is not limited to these methods.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
The following compounds were used in the examples. (A) Component PPE: intrinsic viscosity (chloroform, 25 ° C.) 0.46 d
1 / g poly (2,6-dimethyl-1,4-phenylene) ether (B) component GF-1: glass fiber treated with aromatic urethane sizing agent, fiber diameter 10 μm, trademark TP35, Japan GF-2: glass fiber treated with an aliphatic urethane sizing agent, fiber diameter 10 μm, trademark TP64, manufactured by Nippon Sheet Glass GF-3: glass fiber treated with an acrylic sizing agent,
Fiber diameter 10 μm, trademark TPA0814, Nippon Sheet Glass Co., Ltd. (C) component HIPS: high impact polystyrene, trademark Sumibrite M588, Sumitomo Chemical Co., Ltd. MAH: maleic anhydride

Each evaluation test was performed as follows. (1) Impact strength According to ASTM D256, Izod impact strength at room temperature was measured using a 1 / 8-inch thick notched test piece. (2) Flexural properties Flexural strength (FS) was measured using a 1/4 inch thick test specimen in accordance with ASTM D790. (3) Tensile Properties According to ASTM D638, tensile strength (YS) was measured using a 1/4 inch thick test piece. (4) Hot water aging resistance The test pieces for the above (1) to (3) were aged in a hot water autoclave at 110 ° C. for 1500 hours, and the retention from the strength before aging (strength after aging for 1500 hours / aging) Pre-strength).

Example 1 and Comparative Examples 1 to 5 In the formulations shown in Table 1, the components excluding component (B) were introduced from the first input port of the twin-screw extruder, and component (B) was supplied from the second input port. The mixture was fed and melt-kneaded at a set temperature of 280 ° C. to form pellets. Using these pellets, set temperature 290 ℃,
Injection molding was performed under the condition of a mold temperature of 80 ° C. The obtained molded articles were evaluated in the above (1) to (4). Table 1 shows the results.

The following can be seen from the results. In a system in which PPE was modified with MAH for the purpose of reacting with a coupling agent (Comparative Examples 3 to 5), the initial strength was high but the hot water deterioration was remarkable. In the MAH unmodified system, the initial strength is low and the hot water aging resistance is not good except for the aromatic urethane sizing agent (Comparative Examples 1 and 2). By using glass fibers surface-treated with an aromatic urethane sizing agent, sufficient initial strength and hot water aging resistance are exhibited even when MAH is unmodified (Example 1).

[0029]

[Table 1]

The numerical values in the formulation column are parts by weight. The immersion conditions “before immersion” and “after immersion” in the evaluation column are as follows.
Immerse in hot water for 1500 hours

[0031]

As described above, according to the present invention, a polyphenylene ether-based resin is used as an essential resin component, and is excellent in mechanical strength, dimensional accuracy, dimensional stability and moldability, and also excellent in hot water aging resistance. A thermoplastic resin composition could be provided.

Claims (2)

[Claims] 1. A thermoplastic resin composition containing at least the following (A) and (B), wherein the content of (B) in the thermoplastic resin composition is 1 to 50% by weight. Resin composition. (A): Polyphenylene ether resin (B): Glass fiber surface-treated with aromatic urethane sizing agent 2. In addition to (A) and (B), it contains the following (C), and the content of (C) per 100 parts by weight of (A) is 1
The thermoplastic resin composition according to claim 1, wherein the amount is 900 parts by weight or less. (C): polystyrene resin