JPH0255764A - Glass fiber-reinforced resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in appearance such as surface gloss and mechanical strengths by mixing a glass fiber-reinforced nylon 46 resin composition with a specified copolymer nylon. CONSTITUTION:This glass fiber-reinforced resin composition is obtained by mixing nylon 46 (A) [desirably, of a relative viscosity of 1.5-5.5, especially, 2.0-4.5 (in 96% sulfuric acid in a concentration of 1g/dl at 25 deg.C)] with a copolymer nylon (B) of nylon 6 with nylon 66 (5-70 mol%) [desirably of a relative viscosity of 1.5-6.0, especially, 2.0-5.0 (in 96 % sulfuric acid in a concentration of 1g/dl at 25 deg.C)], a glass fiber (C) (desirably of a diameter of 3-20mum) in a mixing ratio of B/(A+B)<=0.5, B/(B+C)>=0.1, and 0.05<=C/(A+B+C)<=0.7.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a glass fiber-reinforced resin composition, and more specifically to a glass fiber-reinforced resin composition with improved appearance and mechanical strength as represented by surface gloss. The present invention relates to a nylon 46 resin composition.

The resin composition of the present invention has excellent heat resistance, mechanical properties, and appearance, and can be molded by injection molding, etc., and is suitable as useful parts for electrical machinery, automobiles, and the like.

(Conventional technology) Nylon 46 is an already known polyamide.

For example, Japanese Patent Publication No. 8248-8248 and Japanese Patent Publication No. 60-8248
No. 28843 discloses a method for producing nylon 46. It is also known that nylon 46 has excellent properties as an engineering plastic, particularly excellent heat resistance.

For example, its melting point is 295°C, which is nylon 6
0220°C, which is not only higher than 260'C of nylon 66, but also higher than 285°C of polyphenylene sulfide. The degree of crystallinity is high, and the unreinforced heat distortion temperature (18.6 kg/coil load) is 220°C, the highest value among engineering plastics.

It also has excellent sliding properties, fatigue resistance, and rigidity.

Glass fiber reinforced resin compositions of nylon 46 are also known. For example, JP-A-61-64751 discloses glass fiber reinforcement of a blend of nylon 46 and nylon 6 or nylon 66. JP-A-61-1
No. 88455 discloses glass fiber reinforcement of a blend of nylon 46 and aliphatic nylon. JP-A-61-188457 discloses a resin composition comprising nylon 46, a lubricant, and glass fiber. Other JP-A-62-185746 and JP-A-62
JP-201964 also discloses a resin composition containing nylon 46 and glass fiber.

However, although resin compositions made of nylon 46 and glass fibers have extremely good heat resistance, they are significantly inferior in appearance, typified by surface gloss, compared to glass fiber reinforced resin compositions such as nylon 6 and nylon 66. The mechanical strength was also not necessarily satisfactory compared to that of nylon 6 and nylon 66.

However, despite the widespread demand for attempts to solve these problems with glass fiber reinforced nylon 46 resin compositions, the reality is that very few attempts have been made.

(Problems to be Solved by the Invention) Therefore, two objects of the present invention are to provide glass fiber reinforced nylon 46 with improved appearance and mechanical strength, represented by surface gloss.
The objective is to obtain a resin composition.

(Means for Solving the Problems) As a result of extensive research to solve the above problems, the present inventors have surprisingly achieved something by including a specific copolymerized nylon in a glass fiber-reinforced nylon 46 resin composition. The present invention has been achieved by discovering that all of the above problems can be achieved.

That is, the present invention is a glass fiber-reinforced resin composition consisting of the following three components A, 'B and C, the weight blending ratio of which is within a range that satisfies the formulas [1), (III and (I[r)] [However, (A), (B) and (C
) represents the weight mixing ratio of each component. ] A: Nylon 46 B: Copolymerized nylon consisting of nylon 6 component and nylon 66 component, with 5 mol% to 7 mol% of nylon 66 component
Nylon 46, which is used as component A in the present invention, is a fiber obtained by a condensation reaction using adipic acid or a functional derivative thereof as an acid component and tetramethylene diamine or a functional derivative thereof as an amine component. It is a high-molecular-weight polyamide.

Nylon 46 used in the present invention may contain other copolymer components within a range that does not significantly impair its heat resistance. Their copolymerized components include 6-aminocaproic acid, 11
-aminoundecanoic acid, 12-aminodo'decanoic acid, ε
-caprolactam, ω-lauryllactam, hexamethylene diamine, undecamethylene diamine, metaxylylene diamine, adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid and the like.

The method for producing nylon 46 used in the present invention is arbitrary. For example, Japanese Patent Publication No. 60-28843, Japanese Patent Publication No. 60-28843,
The method disclosed in JP-A-8248, JP-A-58-83029, and JP-A-61-43631, that is, first, a prepolymer with a small amount of cyclic terminal groups is produced under specific conditions, and then Particularly preferred are those obtained by solid phase polymerization in a steam atmosphere to prepare high molecular weight nylon 46, or those obtained by heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone.

Although there is no particular restriction on the degree of polymerization of nylon 46 used in the present invention, the relative viscosity was determined using 96% sulfuric acid at a concentration of 1 g/
When measured at d1.25℃, 1.5 to 5.5 and even 2
．． Nylon 46 in the range 0 to 4.5 is preferred. 5
．． When using nylon 46 having a relative viscosity of more than 5, not only does the fluidity of the composition deteriorate.

This is not preferable because it increases the variation in mechanical and thermal properties. On the other hand, a relative viscosity lower than 1.5 has the disadvantage that the mechanical strength of the composition decreases.

The copolymerized nylon used as component B in the present invention is composed of nylon 6 component and nylon 66 component, and contains 5 mol% to 70 mol% of nylon 66 component. Here, the nylon 6 component refers to a repeating unit represented by the following formula (TV), and the nylon 66 component refers to a repeating unit represented by the following formula [■].

The copolymerized nylon used in the present invention may contain other copolymerized components as necessary. These copolymerized components include 11-aminoundecanoic acid, 12-aminododecanoic acid, ω-lauryllactam, undecamethylene diamine, metaxylylene diamine, trimethylhexamethylene diamine, azelaic acid, sebacic acid, isophthalic acid. Acids, terephthalic acid, etc. can be mentioned.

Copolymerized nylon can be manufactured by a known method.

The most common method is to heat ε-caprolactam and nylon 66 salt while mixing them in the presence of water, distill off the water under pressure, and then polymerize under reduced pressure.

There is no particular restriction on the degree of polymerization of the copolymerized nylon used in the present invention, but 96% sulfuric acid is used and the concentration is 1 g/d.
R, the relative viscosity at 25°C is 1.5 to 6.0, and even 2.
Those in the range of 0 to 5.0 are preferred. Relative viscosity6.
If it exceeds 0, the melt viscosity becomes too high and the fluidity of the resin composition deteriorates, which is not preferable. Conversely, if the relative viscosity is 1.
If it is less than 5, it gives only low mechanical strength and is not preferable.

The glass fiber used as component C in the present invention is generally used as a reinforcing material for thermoplastic resins and thermosetting resins, and there are no particular restrictions on the shape of the glass fiber.
From long fiber type (glass roving) to short fiber type (
Any shape can be used, including chopped strands, milled fibers, and glass flakes.

Among these, glass fibers having a diameter of about 3 to 20 μm are preferred because they provide particularly good appearance and mechanical strength.

In the present invention, the weight mixing ratio of nylon 46 as component A and copolymerized nylon as component B satisfies formula (1).

However, A) and (B) represent the weight blending ratio of component A and component B, respectively. When formula (1) is not satisfied, that is, when the weight ratio of nylon 46 as component A is smaller than that of the copolymerized nylon as component B, the heat resistance of the resin composition is undesirably reduced.

In the present invention, the weight mixing ratio of the copolymerized nylon as component B and the glass fiber as component C satisfies 2 [■].

However, C) represents the weight blending ratio of component C. If formula (II) is not satisfied, that is, if the weight blending ratio of copolymerized nylon as component B is less than 10% of the total weight blending ratio of copolymerized nylon as component B and the weight blending ratio of glass fiber as component C, it is typical for surface gloss. The effect of improving the appearance is insufficient.

In the present invention, the weight blending ratio of glass fiber as component C is determined by the formula (
1) is satisfied.

When the weight blending ratio of glass fiber as component C in the resin composition is less than 5%, heat resistance and mechanical properties are insufficient. On the other hand, if it exceeds 70%, the appearance, typified by surface gloss, will be greatly reduced, and mechanical properties will also be reduced.

The resin composition of the present invention may optionally contain an antioxidant, an ultraviolet absorber, a colorant, and
Other inorganic reinforcing agents can be included.

As a method for obtaining the resin composition of the present invention, a method of melt-mixing using an extruder, roll mixer, panburi mixer, kneader mixer, etc. can be used.

The resin composition of the present invention can be used in various forms 1, such as various molded products,
It can be formed into sheets, tubes, etc. and used.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to this.

〔Example〕

Examples 1-4. Comparative Example 1.2 Copolymerized nylon 46 with a relative viscosity of 4.0 (KS400, manufactured by DSM, Netherlands) and copolymerized nylon with a relative viscosity of 2.8, containing 7.5 mol% of nylon 66 components (C10, manufactured by Unitika)
30) and chopped glass fiber strands (T289 manufactured by Nippon Electric Glass Co., Ltd.) with a diameter of 13 μm were mixed in the proportions shown in Table 1, vacuum-dried at 90°C for 16 hours, and then melt-mixed using a twin-screw press ratio machine. , this was cut to obtain a beret.

The obtained pellets were molded using an injection molding machine to create test pieces.

Using this test piece, surface gloss, heat distortion temperature, tensile strength, and tensile modulus were measured. The results are also listed in Table 1.

(Effect of the invention) In the glass fiber reinforced resin composition of the present invention.

By including a specific amount of copolymerized nylon, the surface gloss is significantly improved compared to the comparative example, and the heat resistance and mechanical properties represented by the heat distortion temperature are maintained as they are. Moreover, it is noteworthy that a higher value than expected was obtained for the tensile strength.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Claims] (1) A glass fiber reinforced resin composition consisting of the following three components A, B and C, the weight blending ratio of which is within a range that satisfies formulas [I], [II] and [III]. [However, (A), (B) and (C) represent the weight blending ratio of each component. ] (B)/{(A)+(B)}≦0.5 [I]0.1≦
(B)/{(B)+(C)}[II]0.05≦(C)/
{(A)+(B)+(C)}≦0.7 [III] A: Nylon 46 B: Copolymerized nylon consisting of 6 nylon components and 66 nylon components, with 5 mol% of nylon 66 components 7
C containing 0 mol%: glass fiber