JPH0449871B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention is a resin molding material, which can be used in the field of industrial materials such as electric/electronic equipment, aircraft parts, and automobile parts, and has dramatically improved heat resistance, rigidity, and tensile strength. The present invention relates to a glass fiber reinforced resin composition. (Prior Art) Various attempts have been made to improve heat resistance, rigidity, tensile strength, etc. by blending glass fiber with crystalline thermoplastic resin. Among crystalline thermoplastic resins, resins with melting points of 160°C or higher, such as nylon 6, nylon 66, polybutylene terephthalate, polyethylene terephthalate, polyacetal, polyvinylidene fluoride, and polyphenylene sulfide, are blended with glass fibers and are subject to thermal deformation. It is put into practical use mainly in the field of industrial parts as a reinforced resin with extremely high temperatures. As the need for energy-saving materials increases in recent years, these highly heat-resistant reinforced thermoplastic resins are attracting attention as metal substitute materials due to their light weight, high heat resistance, high rigidity, and high strength. (Problems to be solved by the invention) However, conventional glass fiber-reinforced thermoplastic resins are insufficient to meet more advanced needs, and reinforced resins with higher heat resistance, rigidity, and strength are needed. Development is desperately needed. (Means for Solving the Problems) As a result of intensive studies based on these circumstances, the present inventors have found that by blending specific glass fibers, extremely high heat resistance, rigidity, and tensile strength can be achieved. The present invention was completed by discovering that a reinforced resin with strength can be obtained. That is, the present invention uses 97 to 20% by weight of a crystalline thermoplastic resin (a) having a melting point of 160°C or higher and an average diameter of 10μ.
This is a glass fiber-reinforced resin composition characterized by comprising 3 to 80% by weight of glass fibers (b) having a sizing agent attachment amount of 0.3% by weight or less. The melting point of the above component (a) used in the present invention is 160°C
The above crystalline thermoplastic resins include nylon 6, nylon 66, nylon 11, nylon 12, polyacetal, polyacetal copolymer, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polytetrafluoroethylene, polyvinylidene fluoride. Examples include. Among these, nylon 6, nylon 66, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polytetrafluoroethylene and the like are preferred. In addition, the special glass fiber used in the present invention, which is the above component (b), has an average diameter of 10μ or less, preferably 2 to 7μ, and has a sizing agent on its surface (this includes a sizing component for the purpose of sizing). (including a surface treatment agent for the purpose of adhesion and compatibility with the resin) after dry finishing, the final adhesion amount is 0.3% by weight or less, preferably 0.1 to 0.3% by weight of the glass fiber weight.
belongs to. The method for manufacturing this glass fiber is, for example, as follows. First, molten glass is formed into glass beads of a predetermined size called marbles, which are heated and softened in a thread-drawing furnace called a pushing, and then flowed down from a number of nozzles on the furnace table to form a material with a high flux. While stretching, the material is immersed in a sizing agent applicator provided midway through the stretching process to apply a sizing agent and bundled, dried, and wound up on a rotating drum. At this time, adjust the nozzle, diameter dimension, take-up speed, take-up atmosphere temperature, etc. to find the average diameter.
Should be 10μ or less. At the same time, the concentration, type, application time, etc. of the sizing agent are adjusted so that the final amount of sizing agent deposited after drying is 0.3% by weight or less. The length of the glass fiber is not specified, so the shape may be roving, chopped strand, strand, etc., but the length is 1 mm from the viewpoint of ease of mixing and kneading with the amorphous thermoplastic resin. Chopped strands with a length of about 20 mm, especially 2 mm to 8 mm are preferred. In this case, the number of focused lines is usually 100 to 5000, especially 500 to 2000.
A range of books is preferred. In addition, the final length after blending and kneading with high melting point crystalline thermoplastic resin is 0.2 on average.
If it is more than mm, it is called milled fiber.
It may be a pulverized strand product called glass powder, or it may be a continuous single fiber sliver. Although the composition of the raw material glass is not specified, it is preferable to have a low alkali component, and E-glass is a preferable example. Here, the average diameter is a value observed using an electron microscope or the like, and the amount of sizing agent deposited is a value measured as the ignition loss after ignition at 600° C. for 60 minutes. If the average diameter exceeds 10μ or the amount of sizing agent attached exceeds 0.3% by weight, the effect of improving the heat resistance, rigidity, and tensile strength of the composition mixed and kneaded with the high melting point crystalline thermoplastic resin is insufficient. It is. As shown in the examples below, the glass fiber sizing agent contains a film-forming agent such as urethane polymer, acrylic polymer, epoxy polymer, olefin polymer, vinyl acetate polymer, etc. as an essential component, and optionally contains a surfactant and a lubricant. A focusing component with optional ingredients such as a softener, an antistatic agent, etc.
and a surface treatment agent. Here, as the surfactant, sodium alkylbenzene sulfonate, sodium α-olefin sulfonate, alkyl betaine, etc. are well known and are usually blended in an amount of about 10 to 80% by weight. Alkyl polyoxyethylene ether is well known as a lubricant, and is usually blended in an amount of about 10 to 25% by weight. As softeners, polyoxyethylene sodium salts, emulsified oils, etc. are well known and usually have a content of 5 to 50%.
Contains approximately 15% by weight. As antistatic agents, alkylammonium salts, alkyloxy ethers, etc. are well known and are usually blended in an amount of about 4 to 10% by weight. Although the surface treatment agent in the sizing agent may not be included, a coupling agent such as a silane type, acrylic acid type, or titanate type is usually used. Among these, silane coupling agents such as epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, vinylsilanes such as vinyltrichlorosilane, and aminosilanes such as γ-aminopropyltriethoxysilane are preferably included. The final content ratio of the focusing component and the surface treatment agent is not particularly limited, but a ratio of 30:70 to 70:30 provides a relatively good balance of physical properties. The blending ratio of the above components (a) and (b) of the present invention is in the range of 97 to 20% by weight of component (a) and 3 to 80% by weight of component (b). If the amount of component (b) is less than 3% by weight, the effect of improving heat resistance, rigidity, and tensile strength is low;
If it exceeds 80% by weight, the moldability of the composition is poor. The preferred blending ratio is 90 to 50% by weight of component (a) and 10 to 50% by weight of component (b). (Actions and Effects of the Invention) The composition of the present invention has a composition with the same amount of glass fibers compared to a conventional reinforced crystalline thermoplastic resin composition containing ordinary glass fibers (average diameter of about 13 μm). It is characterized by extremely high heat distortion temperature, rigidity, and tensile strength. Even if the crystalline thermoplastic resin has a high melting point, its heat distortion temperature is not very high. Specifically, even if the melting point is 160℃ or higher, the load
The heat distortion temperature below 18.6Kg/ ^cm2 is generally below 100℃,
The highest temperature is 130℃ at most, and the reality is that the high melting point of the resin itself does not provide practical heat resistance. On the other hand, reinforced resin made of crystalline thermoplastic resin mixed with glass fiber has a load of 18.6 kg/cm ²
However, when the specific glass fiber of the present invention is used, the improvement in the heat distortion temperature is extremely remarkable, and even a relatively low concentration of glass fiber can be used to achieve a high heat distortion temperature. can be realized. Furthermore, the composition of the present invention containing a specific glass fiber at a relatively high concentration has a high heat distortion temperature close to the melting point of the resin used, and can also have extremely high rigidity and tensile strength. In addition to these characteristics, the composition of the present invention has the advantage of having a significantly lower specific gravity than metals, so the composition of the present invention is extremely useful as a substitute material for metals in the field of industrial materials such as electrical and electronic equipment, aircraft parts, and automobile parts. . The composition of the present invention may contain various fillers other than glass fiber as additional ingredients, such as calcium carbonate (heavy, light, colloid), talc, mica, silica,
Alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, zinc oxide, zeolite, wollastonite, diatomaceous earth, glass beads, bentonite, montmorillonite, asbestos, hollow glass bulb, graphite, molybdenum disulfide, titanium oxide, carbon fiber In addition to fillers such as , aluminum fiber, stainless steel fiber, brass fiber, aluminum powder, carbon black, wood powder, rice husk, etc.
Thermoplastic resins other than component (a) such as polypropylene, polyethylene (high density, medium density, low density, linear low density), polystyrene, polycarbonate,
Modified polyphenylene oxide, propylene/ethylene block or random copolymer, maleic anhydride modified polyolefin, rubber or latex components such as ethylene/propylene copolymer rubber, styrene/butadiene rubber, styrene/butadiene/styrene block copolymer, Hydrogenated derivatives of styrene-butadiene-styrene block copolymers, polybutadiene, polyisobutylene, thermosetting resins such as epoxy resins, melamine resins, phenolic resins, unsaturated polyester resins; antioxidants (phenolic, sulfur, etc.);
Lubricants; various organic and inorganic pigments; ultraviolet absorbers;
Antistatic agent; Dispersant; Neutralizing agent; Foaming agent; Plasticizer;
Copper damage inhibitors; flame retardants; crosslinking agents; flowability improvers and the like can be mentioned. The addition of these additional ingredients improves the physical property balance, molded product surface characteristics (surface scratch resistance, gloss, weld appearance, silver streaks, flow marks, etc.), printability, paintability, adhesion, plating performance, moldability,
It is effective in improving durability, etc. These additional components can also be added in combination. The composition of the present invention can be produced using a conventional kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a Brabender Plastograph, or a kneader. Usually, it is kneaded with an extruder etc. to make a pellet-like compound and then subjected to processing, but in special cases
Components (a) and (b) can also be directly supplied to various molding machines and molded while being kneaded by the molding machine. Also,
It is also possible to knead component (b) in advance to a high concentration to form a masterbatch, and then dilute it with component (a) for blend compounding or molding. The composition of the present invention can be molded using a conventional molding machine for thermoplastic resins. That is, it can be applied to injection molding, extrusion molding, blow molding, thermoforming, etc. (Example) Various crystalline thermoplastic resins with a melting point of 160°C or higher, an average diameter of 4μ, a sizing agent deposit of 0.12% by weight, and the same
Each glass fiber is 6μ and 0.15% by weight [fiber length: 3mm, number of bundled fibers: 1000, surface treatment agent: γ-
Glycidoxypropyltolyltoxysilane, focusing components: 40 parts by weight of surfactant (sodium alkylbenzenesulfonate), 20 parts by weight of lubricant (alkyl polyoxyether), 8 parts by weight of softener (polyoxyethylene sodium salt), electrostatic charge Composed of 7 parts by weight of inhibitor (alkyltrimethylammonium salt), 25 parts by weight of film-forming agent (linear polyurethane), etc., surface treatment agent/focusing component ratio = 50:50] in the ratio shown in Table 1. After mixing, the mixture was kneaded and granulated using a single-screw extruder at a temperature of 270°C. The obtained pellets were molded using an injection molding machine to prepare test pieces, and the rigidity and tensile strength were measured. The results are shown in Nos. 1 to 10 in Table 1. For comparison, the average diameter is 13μ and the amount of sizing agent attached is
0.15% by weight, average diameter 6μ, sizing agent coverage 0.4
A similar experiment was carried out using glass fibers of % by weight (fiber length, number of bundles, type of surface treatment agent, and ratio of surface treatment agent to bundle component were the same as in Examples).
The results are shown in Nos. 11 to 18 of Table 1. As is clear from the table, the examples have significantly higher heat distortion temperatures, stiffness, and tensile strength than the comparative examples using the same resin and the same amount of glass fiber. Regarding the measurement method of physical properties, the heat distortion temperature is
JIS K-7207 (18.6Kg/ ^cm2 load), bending elastic modulus and bending strength are JIS K-6720, tensile strength is JIS K-
Compliant with 7113.

[Table] (Application example) Distributor caps were molded using pellets having the composition of Example No. 7 at a molding temperature of 250°C using an injection molding machine with a mold clamping pressure of 400 tons. Heat-resistant,
A distributor cap with extremely excellent performance such as mechanical strength and extremely lightweight was obtained.

Claims (1)

[Claims] 1 Crystalline thermoplastic resin (a)97 with a melting point of 160℃ or higher
Glass fiber (b) 3 with ~20% by weight, an average diameter of 10μ or less, and a sizing agent adhesion amount of 0.3% by weight or less
A glass fiber reinforced resin composition comprising ~80% by weight.