JPS60245669A - Glass fiber-reinforced resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. having excellent heat resistance, rigidity, tensile strength, etc. and suitable for use as a material for the production of electronic equipment, aircraft parts, automotive parts, etc., by blending a specified glass fiber with a crystalline thermoplastic resin. CONSTITUTION:A glass fiber in which the final coating weight of a bundling agent (a mixture of a bundling component and a surface-treating agent in a ratio of 30:70-70:30) after dry finishing is 0.3wt% or below and average diameter is 10mu or below, fiber length is 1-20mm. and the number of bundled fibers is 100-5,000 is used. 97-20wt% crystalline thermoplastic resin having an m.p. of 160 deg.C (e.g. nylon 6, polybutylene terephthalate or polytetrafluoroethylene) is mixed with 3-80wt% said glass fiber in an extruder or a kneader.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is applicable to resin molding materials, especially electric/electronic equipment,
This invention relates to a glass fiber-reinforced resin composition that has dramatically improved heat resistance, rigidity, tensile elasticity, etc. that can be used in the field of T-industry materials such as aircraft parts and automobile parts.

(Prior Art) Various attempts have been made to improve heat resistance, stiffness, tensile strength, etc. by blending glass fiber with crystalline thermoplastic resin. Among crystalline thermoplastic resins, nylon 6, nylon 66, polybutylene terephthalate, polyethylene terephthalate, polyacetal, polyvinylidene fluoride,
Melting point of polyphenylene sulfuride etc. is 160℃ or higher
A resin blended with glass fiber has been put into practical use mainly in the field of industrial parts as a reinforced resin with an extremely high heat distortion temperature.

In recent years, the need for energy-saving materials has increased, and these highly heat-resistant reinforced thermoplastic resins are lightweight, highly heat-resistant,
Due to its high rigidity and high strength characteristics, it is attracting attention as an alternative material to metals.

(Problems to be solved by the invention) [7] However, conventional glass fiber reinforced thermoplastic resins are insufficient to meet more advanced needs;
There is a strong need for the development of reinforced resins with higher heat resistance, rigidity, and strong friction. (Means for solving the problems) The present inventors have conducted intensive studies based on these circumstances, and have identified specific The present invention was completed based on the discovery that a reinforced resin having extremely high heat resistance, rigidity, and tensile strength, which meets the objectives, can be obtained by blending glass fibers.

That is, according to the present invention, a crystalline thermoplastic resin (a) having a melting point of 160° C. or higher (97 to 20% by weight) and glass fibers (b) having an average diameter of 10 μm or less and a sizing agent adhesion amount of 0.3 μm or less (by weight) 3 This is a glass fiber-reinforced resin composition characterized in that it consists of ~80% by weight.

The crystalline thermoplastic resins having a melting point of 160°C or higher, which is the component (a) used in the present invention, include nylon 6, nylon 66, nylon 11, nylon 12, polyacecool, polyacetal copolymer, polybutylene terephthalate, polyethylene terephthalate. , polyphenylene sulfide, polytetrafluoroethylene, polyvinylidene fluoride, and the like.

Among these, nylon 6, nylon 66, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polytetrafluoroethylene and the like are preferred.

Further, the special glass fiber used in the present invention as the component (b) has an average diameter of 10 μm or less, preferably 2 to 7 μm.
In addition, the final adhesion amount of the binding agent on the surface after dry finishing (including a binding component for the purpose of so-called sizing and a surface treatment agent for the purpose of adhesion and solubility with the resin) is It is preferably 0.3% by weight or less, preferably 0.1 to 0.3% by weight, based on the weight of the glass fibers. 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.1. / % It is heated and softened in a yarn collecting furnace called a bushing, and is flowed down from a number of nozzles on the furnace table, and while this material is stretched with a high degree of bundle, it is dipped in a sizing agent coating device installed in the middle of the process and bundled. The agent is applied, concentrated, dried, and wound up on a rotating drum. At this time, the nozzle, diameter size, take-up speed, take-up atmosphere temperature, etc. are adjusted so that the average diameter is 10 μm or less. At the same time, the concentration, type, coating time, etc. of the sizing agent are adjusted so that the final amount of sizing agent deposited after drying is less than 3 weights of sails. The length of the glass fiber is not specified, so the shape may be roving, chopped strand, strand, etc., but from the viewpoint of mixing with the amorphous thermoplastic resin and cross-wire workability, In particular, chopped strands with a length of about 2 to 8 lengths are preferred.

In this case, the number of condensed wires is usually 100 to 5,000, especially 5.
The number of fibers is preferably in the range of 0.00 to 2,000.6 In addition, if the final length after blending and kneading with a high melting point crystalline thermoplastic resin is 0.2 or more on average, it is considered a so-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 the value observed using an electron microscope or the like, and the amount of sizing agent deposited is the value measured as the loss on burning after burning at 600° C. for 60 minutes.

Those whose average diameter exceeds 10μ, the amount of sizing agent adhered to is 0.
If it exceeds 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.

Although the surface treatment agent in the glass fiber sizing agent may not be used, a coupling agent such as a silane type, an acrylic acid type, or a titanate type is usually used. It is preferable to include a silane coupling agent such as epoxysilane, vinylsilane such as vinyltrichlorosilane, and aminosilane such as γ-aminopropyltriethoxysilane. The final content ratio of the focusing component and the surface treatment agent is not particularly limited, but
~70:30 gives a relatively good balance of physical properties.

The blending ratio of the above (a) component and (b) component of the present invention is (a
) component is 97 to 20% by weight and component (b) is 3 to 80% by weight.
% by weight. (b) If the composition of the component is less than 3% by weight, the effect of improving heat resistance, stiffness, and tensile strength is low;
If it exceeds 80% by weight, the acid form processability of the composition is poor.

A 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 can be applied to ordinary glass fibers (having an average diameter of 13
Compared to conventional reinforced crystalline thermoplastic resin compositions prepared by acetic acid bonding, the composition has significantly higher heat deformation temperature, stiffness, and tensile strength in the same glass-fiber composite. Crystalline thermoplastic resin has a high melting point, and its electrothermal deformation temperature is not very high. Specifically, even if the melting point is 160°C or higher, the heat distortion temperature under a load xs of 6 kg/- is generally below ioo'c, and even if it is high, it is at most 130°C.5 The high melting point of the resin itself makes it practical heat resistance. The reality is that it is not tied to gender. On the other hand, reinforced resin made of crystalline thermoplastic resin mixed with glass fiber has a load of 18.6 kg.
/ tyl+ The lower heat distortion temperature tends to improve and approach the melting point of 7, but the increase in the upper heat distortion temperature using the specific glass fiber of the present invention is extremely remarkable, and with a relatively high concentration of glass fiber A high heat deformation temperature can be achieved by heating.

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 can be used as a L2 substitute material for metals in the field of industrial materials such as electrical and electronic equipment, aircraft parts, and automobile parts. Extremely useful.

The composition of the present invention may contain various fillers other than glass fiber as additional ingredients, such as calcium carbonate (heavy, light, colloid), zurku, mica, silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, oxidized Zinc, zeolite, wollastonite, clay, glass peas, bentonite, montmorillonite, asbestos, hollow glass bulb, graphite, molybdenum disulfide, titanium oxide, carbon m, m, aluminum fiber, stainless steel fiber, brass fiber, aluminum In addition to fillers such as powder, carbon black, wood flour, and rice grain, thermoplastic resins other than component (a) such as polypropylene and polyethylene (
high density, medium density, low density dust, linear low density), polystyrene, polycarbonate, modified polyphenylene oxide, propylene/ethylene block or random copolymer, maleic anhydride modified polyolefin, rubber or ID
Latex components such as ethylene/propylene copolymer rubber, styrene/butadiene rubber, styrene/butadiene/styrene block copolymer, hydrogenated derivatives of styrene/butadiene/styrene block copolymer, polybutadiene, polyisobutylene, thermosetting resins, etc. Epoxy resin, melamine resin, phenolic resin, unsaturated polyester resin; Antioxidant (phenol type, sulfur type, etc.); Lubricant; Various organic and inorganic pigments; Ultraviolet absorber: Antistatic agent; Dispersant: Medium Combination additives: foaming agents: plasticizers; copper damage inhibitors; flame retardants; crosslinking agents; flowability improvers and the like.

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 for 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 screw extruder, twin screw extruder, Banbury mixer, roll, Prabender Plastograph, or kneader.

Usually, it is kneaded with an extruder etc. to make a pellet-like compound and then subjected to processing, but in special cases, component (a) and (
It is also possible to directly supply the b'l component to various molding machines 7 and mold it while kneading it in the molding machine. ! ! In addition, component (b) was kneaded in advance to a high concentration to make a masterbatch7, and it was mixed with (
It is also possible to perform blend comparison or molding while diluting with component a).

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 and glass fibers with an average diameter of 4μ and a sizing agent adhesion of 0.12% by weight and 6μ and 0.15% by weight [all Fiber length: 3
聰、Number of bundles: i, o o o pieces, Surface treatment agent: γ-glycidoxypropyl trimethoxysilane, Composition of binding components: surfactant, lubricant, softener, antistatic agent, film forming agent, etc. , surface treatment agent/focusing component ratio = 50:50
] were mixed in the proportions shown in Table 1, and then 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 1o in Table 1.

For comparison, the average diameter is 13μ and the amount of sizing agent attached is 15.
Heavy hydrogen, average diameter 6μ, sizing agent adhesion amount 0.4% by weight
A similar experiment was conducted using glass fibers (in each case, the fiber length, number of bundles, type of surface treatment agent, and ratio of surface treatment agent to bundle component were the same as in the example). The result is N11l in Table 1.
1 to 18.

As is clear from the table, the heat distortion temperature, rigidity, and tensile strength of the examples are significantly higher than those of the comparative examples using the same resin and the same amount of glass fiber. Regarding the measurement method of physical properties, heat distortion temperature is JIS
K-7207 (18.6Kg/rfl load), bending elastic modulus and bending strength are in accordance with JIS K-6720, and tensile strength is in accordance with JIS K-7113.

(Left below) (Application example) Using pellets with the composition of Example Nn7, the mold clamping pressure was 40.
A distributor cap was molded using a 0 ton injection molding machine at a molding temperature of 250°C. A distributor t-yap with extremely excellent performance such as heat resistance and mechanical strength and an extremely lightweight candle was obtained.

Patent applicant Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa Agent: Patent Attorney Masahisa Nagatani

Claims (1)

[Claims] Crystalline thermoplastic resin (a) 97~ with a melting point of 160°C or higher
Glass fibers (b) 3 to 8 having an average diameter of 20% by weight, an average diameter of 10μ or less, and a sizing agent adhesion amount of 0.3% by weight or less
0 weight! A glass fiber reinforced resin composition comprising: