JP2000129125A - Aromatic polysulphone resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polysulphone resin composition including glass fiber, in which adhesion between glass fiber and matrix resin is improved, by blending an aromatic polysulphone with a specific quantity of glass fiber, the surface of which is subjected to specific treatment. SOLUTION: This aromatic polysulphone resin composition comprises (A) 100 pts.wt. aromatic polysulphone resin and (B) 5-240 pts.wt. glass fiber, the surface of which is treated with (i) an alkoxysilane having amino group and (ii) an aromatic polysulphone. It is preferable that the component B has 1-20 μm number average fiber diameter and 25-6,000 μm number average fiber length, and that the treatment quantity of the component i and ii are respectively 0.01-5 pts.wt. and 0.1-10 pts.wt., based on 100 pts.wt. glass fiber. Thus, the aromatic polysulphone resin composition is excellent in adhesion between glass fiber and matrix resin, is expected to have excellent productivity in producing resin molded products and is useful for electronic parts, mechanical ones or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polysulfone resin composition containing glass fibers which is excellent in adhesion between glass fibers and a matrix resin and which is excellent in productivity of a resin molded product.

[0002]

2. Description of the Related Art Aromatic polysulfone resins are suitable materials for electronic parts, mechanical parts and structural materials because of their excellent heat resistance, strength, elastic modulus, creep resistance and the like. In particular, by blending a fibrous material with the aromatic polysulfone resin, it is possible to reduce the molding shrinkage and to improve the strength and the elastic modulus, so that it is expected to be a more industrially suitable material. However, the aromatic polysulfone resin has a disadvantage that adhesion to glass fibers is not good. In general, it is known that in a composite material, sufficient mechanical performance can be exhibited by improving the adhesion between the fibrous filler and the resin matrix (for example, “Chemical Review 8 by the Chemical Society of Japan”). Composite Materials "(1975)). Also,
If the adhesion between the fibrous filler and the resin matrix is poor, the fibers may fall off from the gate portion or the cut portion of the molded product, and the reliability of the product may be significantly impaired. In order to solve these problems, there has been known a method of surface-treating a glass fiber using an alkoxysilane compound in order to adhere the glass fiber to a resin matrix. By the way, the fibrous material tends to be cotton-like, and has a property of significantly impairing workability in handling. In order to avoid such a problem, a surface treatment with a resin such as urethane or epoxy has conventionally been performed. In short, conventionally, when using glass fiber, to improve the adhesion with the resin matrix, and to improve the workability, usually, in combination with a resin such as an alkoxysilane compound and urethane, epoxy, A method of surface treating glass fibers has been used. However, the combined use of the above resins such as urethane and epoxy used for improving the workability hinders the improvement of the adhesion by the alkoxysilane compound, and there is a problem that the intended purpose cannot be achieved.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and provides an aromatic polysulfone resin composition containing glass fibers having excellent adhesion between the glass fibers and the resin matrix without lowering workability. The purpose is to do.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, blended a glass fiber having been subjected to a specific surface treatment with an aromatic polysulfone resin at a specific ratio. As a result, the inventors have found that the above-mentioned object is achieved, and have reached the present invention. That is, according to the present invention, (A) 100 parts by weight of an aromatic polysulfone resin, (B) glass fibers 5 to 2 surface-treated with an alkoxysilane having an amino group and an aromatic polysulfone resin.
An aromatic polysulfone resin composition comprising 40 parts by weight is provided. According to the present invention,
(B) The number average fiber diameter of the glass fiber surface-treated with an alkoxysilane having an amino group and an aromatic polysulfone resin is 1 to 20 μm, and the number average fiber length is 25 to 6000 μm.
m, wherein the aromatic polysulfone resin composition is provided. Furthermore, according to the present invention, there is provided the aromatic polysulfone resin composition wherein the amount of the aromatic polysulfone resin required for the surface treatment of the glass fiber is 0.1 to 10 parts by weight based on 100 parts by weight of the glass fiber. Is done. Still further, according to the present invention, the aromatic polysulfone resin composition wherein the amount of the amino group-containing alkoxysilane required for the surface treatment of the glass fiber is 0.01 to 5 parts by weight based on 100 parts by weight of the glass fiber. Things are provided. Further, according to the present invention, there is provided the aromatic polysulfone resin composition, wherein the aromatic polysulfone resin has a repeating unit represented by the following formula at 80 mol% or more.

Embedded image

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The aromatic polysulfone resin composition of the present invention comprises an aromatic polysulfone resin as the component (A) and a glass fiber surface-treated with an alkoxysilane having an amino group as the component (B) and an aromatic polysulfone resin. , In a specific blending ratio.

The aromatic polysulfone resin used for the component (A) and the component (B) used in the present invention is a constituent unit in which an arylene unit, an ether bond and a sulfone bond are essential, and the arylene unit is an ether and a sulfone. It is defined as a polyarylene compound that is located randomly or orderly with bonding. Representative examples include those having the following repeating units, but are not limited thereto.

[0007]

Embedded image (In the formula, R ₁ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, a phenyl group or a halogen atom, and p is a positive number of 0 to 4. q, m, n represents the average number of repeating units, q is a positive number from 1 to 3, and m / n is from 0.001 to 10000. Each R ₁ on the same or different nucleus may be different from each other. Also, each p may be different from each other, provided that equation (2)
The compound represented by (3) includes a random copolymer. ). In the repeating unit represented by the formula (2) or (3), it is preferable to use an aromatic polysulfone resin having a repeating unit in which (m / m + n) is 0.8 or more. Further, q in the structural unit of the formula (3) is preferably 1. Among these, those having a repeating unit of the formula (1) or (2) are preferred, and more preferred are aromatic polysulfone resins having a repeating unit of the formula (1) of 80 mol% or more. As an example of a commercially available product, as a product having a repeating unit represented by the formula (1), “Sumika Excel PES3600P, 41
00P ”or the like having a repeating unit represented by the formula (2), a product name“ UDEL P-1 ”of AMOCO.
700 "and the like, but are not limited thereto. The terminal structures of these repeating units are determined according to the production method of each resin. For example, Cl, OH, O
R (R is an alkyl group) and the like are exemplified, and among these, Cl and / or OH are preferable.

In the present invention, the component (B) is, as described above, a glass fiber surface-treated with an alkoxysilane having an amino group and an aromatic polysulfone resin. The aromatic polysulfone resin used for the component (B) is the same as the component (A) as described above, but the type thereof may be the same as or different from the component (A). The glass fiber in the component (B) is obtained by processing glass containing silicate as a main component into a fibrous form. As the type of glass, alkali glass for general use (A
Glass), acid-resistant glass for chemical use (C glass), low-density glass (D glass), borosilicate glass (E glass), and the like. In the present invention, E glass is preferable.
For producing glass fibers, a method of spinning glass in a molten state (1300 ° C. or higher) is generally used. The alkoxysilane having an amino group in the component (B) is represented by the formula
And the like.

[0009]

Embedded image (Wherein R ′ is an alkylene group having 1 to 4 carbon atoms or N-
represents a β-aminoethyl group, R ″ represents an alkyl group having 1 to 4 carbon atoms, a methoxy group or an ethoxy group, and R ″ ″ represents an alkyl group having 1 to 5 carbon atoms. m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n ≦ 3. Examples of the alkoxysilane having an amino group represented by the formula (4) include γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β- ( (Aminoethyl) -γ-aminopropylmethyldimethoxysilane.

In order to produce the component (B) used in the present invention, (a) a glass fiber is surface-treated in advance with the above-mentioned amino-containing alkoxysilane, and further surface-treated with an aromatic polysulfone resin. And a method in which a mixture of (b) an alkoxysilane having an amino group and an aromatic polysulfone resin is prepared in advance and glass fibers are surface-treated with this mixture. In the above method (a), examples of a method of surface-treating a glass fiber with an alkoxysilane having an amino group include the following methods. Dry method: A method in which an aqueous solution of an alkoxysilane having an amino group and an organic solvent solution are added to a glass fiber with high-speed stirring using a mixer capable of high-speed stirring, uniformly dispersed, and then dried. A method in which glass fibers are immersed in an aqueous solution of an alkoxysilane having an organic solvent, filtered, and dried. Spray method: A method in which the glass fibers are dried and then an alkoxysilane having an amino group is sprayed. Next, in the method (a), the surface treatment with the aromatic polysulfone resin is performed using an organic solvent solution of the aromatic polysulfone resin in the same manner as in the dry method, the immersion method, or the spray method. Can be. On the other hand, in the method (b), a mixed organic solvent solution of an alkoxysilane having an amino group and an aromatic polysulfone is prepared in advance, and the dry method, the dipping method, or the spraying method is performed using the mixed organic solvent solution. Processing can be performed in the same manner as in the method. The organic solvent used in each of the above methods is not particularly limited. For example, N, N′-dimethylformamide,
N, N'-dimethylacetamide, N-methylpyrrolidone, methylene chloride, chloroform and the like are preferred.

In the component (B), the surface treatment amount of the glass fiber with the alkoxysilane having an amino group is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the glass fiber. Parts are desirable. On the other hand, the surface treatment amount of glass fiber by aromatic polysulfone is 0.05 to 10 parts by weight with respect to 100 parts by weight of glass fiber.
It is preferably 0.1 parts by weight, more preferably 0.1 to 3 parts by weight.
All of these surface treatment amounts can be determined by ignition loss measurement specified in JISR3420. Surface treatment amount by alkoxysilane having an amino group,
If the amount is less than 0.01 part by weight, the mechanical performance of the obtained molded article may be insufficient. If the amount exceeds 5 parts by weight, the decomposition gas of the surface treatment agent itself increases, and as a result, It is not preferable because thermal stability may be impaired. On the other hand, if the surface treatment amount with the aromatic polysulfone resin is less than 0.05 parts by weight, it is difficult to converge the glass fibers, and if it exceeds 10 parts by weight, the glass fibers are difficult to spread during production. It is not preferable because productivity is reduced.

If the component (B) is a fiber, its size and the like are not particularly limited, but the number average fiber diameter is 1 to 20 μm.
Is preferably, and more preferably 5 to 15 μm. When the number average fiber diameter is less than 1 μm, the convergence effect at the time of spinning becomes insufficient, and as a result, it becomes difficult to mix the component (A), which is not preferable. On the other hand, if the number average fiber diameter is larger than 20 μm, it is not preferable because the strand take-up property becomes unstable during melt granulation of the composition. On the other hand, the number average fiber length of the component (B) is preferably 25 to 6000 μm, and 30 to 3000 μm.
m is more preferred. If the number average fiber length is less than 25 μm, the reinforcing effect of the glass fiber is reduced, which is not preferable. If the number average fiber length is more than 6000 μm, the take-off property of the strand during melt granulation of the composition becomes unstable, and further molding from the obtained composition It is not preferable because the surface condition of the product is deteriorated.

The component (B) may be used after being treated with a sizing agent. Examples of the sizing agent include a thermosetting resin and a thermoplastic resin.

In the present invention, the blending ratio of the above-mentioned component (B) is 100% for the aromatic polysulfone resin 100 which is the component (A).
The amount is 5 to 240 parts by weight, preferably 10 to 160 parts by weight based on parts by weight. If the compounding ratio is more than 240 parts by weight, the biting property to the screw during granulation becomes worse, and the plasticization at the time of molding becomes unstable. May occur. If the amount is less than 5 parts by weight, the mechanical strength of the molded product becomes insufficient.

In the composition of the present invention, the component (A)
In addition to the component (B), if necessary, for example, a fibrous or acicular reinforcing material other than the component (B) such as silica alumina fiber, alumina fiber, carbon fiber, aluminum borate whisker, etc .; talc, mica, Inorganic fillers such as clay and glass beads; release improvers such as fluororesins and metal soaps; coloring agents such as dyes and pigments; antioxidants; heat stabilizers; ultraviolet absorbers; And the like can be added. In addition, a small amount of thermoplastic resin, for example, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and modified products thereof, polyetherimide and the like, and a small amount of thermosetting resin, for example, phenol resin, epoxy resin , A polyimide resin or the like, or two or more kinds.

The means for blending each component in the composition of the present invention is not particularly limited. For example, a method in which the components (A) and (B), if necessary, an inorganic filler, a release improver, a heat stabilizer, and the like are mixed using a Henschel mixer, a tumbler and the like, and then melt-kneaded using an extruder. Is common.
At this time, as a melt-kneading method, all the components may be mixed and supplied to the extruder after being mixed together, or if necessary.
A component such as a reinforcing material such as the component (B) or an inorganic filler may be supplied separately from the component mainly comprising the component (A).

[0017]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples.

Production Examples 1 to 3 Glass fibers ("CS03JAPx-1", manufactured by Asahi Fiber Glass Co., Ltd.) having the blending amounts shown in Table 1 were spread on trays and placed in an electric furnace at 600 ° C. for 5 hours. The organic matter adhering to was removed. Next, the mixture was cooled to room temperature, and an amino group-containing alkoxysilane aqueous solution (adjusted using “AY43-059” manufactured by Dow Corning Toray Silicone Co., Ltd. and ion-exchanged water) was added in the amount shown in Table 1. For 30 minutes. The obtained glass fiber was filtered and dried by heating at 80 ° C. × 8 hours to obtain a glass fiber treated with an amino group-containing alkoxysilane. Subsequently, the amino group-containing alkoxysilane-treated glass fiber was treated in the same manner as described above,
After immersion in an aromatic polysulfone / N, N'-dimethylformamide (DMF) solution having the composition shown in Table 1,
After drying under reduced pressure at 30 ° C. for 8 hours, a glass fiber surface-treated with an aromatic polysulfone resin in addition to the amino group-containing alkoxysilane treatment was obtained. In addition, each surface treatment amount is JIS
It was determined from the heat loss according to R3420. The results are shown in Table 1.

[0019]

[Table 1]

Examples 1 and 2 and Comparative Examples 1 and 2 Aromatic polysulfone resin powder ("Sumika Excel PES4100P", manufactured by Sumitomo Chemical Co., Ltd.) and the surface-treated glass fibers produced in Production Examples 1 to 3 are shown in Table 1. 2, the twin screw extruder (PCM manufactured by Ikegai Iron Works Co., Ltd.)
-30 "), and granulated at a cylinder temperature of 340 ° C to obtain aromatic polysulfone resin pellets. On this occasion,
The workability in the feed was evaluated. Good workability was evaluated as ○, and workability poor was evaluated as ×. The obtained pellets were fired at 600 ° C., and after taking an optical microscope image of the residual glass fiber, image analysis was performed to measure the number average fiber diameter and the number average fiber length. Table 2 shows the results. Subsequently, the obtained aromatic polysulfone resin pellets were injected into an injection molding machine (“PS40E5” manufactured by Nissei Resin Industry Co., Ltd.).
ASE ”) at a cylinder temperature of 360 ° C. and a mold temperature of 150 ° C., a length of 64 mm, a width of 12.7 mm, a thickness of 6.4 mm, a tip radius of 0.25 mm at the center, and a depth of 2.7 mm. A test piece having a notch was formed. Subsequently, the test piece was broken with a hammer, and the cross section was observed with a scanning electron microscope, and the adhesion was evaluated based on the amount and state of adhesion of the matrix resin to the glass fibers. A sample having good adhesion was evaluated as “O”, and a sample having poor adhesion was evaluated as “X”. Table 2 shows the results
Shown in The “commercial glass fiber” in Table 2 is “CS03JAPx-1” manufactured by Asahi Fiber Glass Co., Ltd. The surface treatment agent for this glass fiber is an amino-containing alkoxysilane and a urethane resin. The surface treatment amount obtained in accordance with the above was 0.3 pph in total for the amino group-containing alkoxysilane and the urethane resin. From the results in Table 2, it was clarified that Examples using the aromatic polysulfone resin composition of the present invention had excellent adhesion between the glass fibers and the resin matrix.

[0021]

[Table 2]

[0022]

Industrial Applicability The aromatic polysulfone resin composition of the present invention contains an aromatic polysulfone resin and a glass fiber surface-treated with an alkoxysilane having an amino group and an aromatic polysulfone resin in a specific blending ratio. The adhesion between the glass fiber and the matrix resin can be improved without lowering the workability at the time. Therefore, it is extremely useful for electronic parts, mechanical parts, structural materials and the like.

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Claims (5)

[Claims] (1) 100 parts by weight of an aromatic polysulfone resin, (B) 5-240 parts by weight of glass fibers surface-treated with an alkoxysilane having an amino group and an aromatic polysulfone resin. Aromatic polysulfone resin composition. 2. A glass fiber surface-treated with (B) an alkoxysilane having an amino group and an aromatic polysulfone resin having a number average fiber diameter of 1 to 20 μm and a number average fiber length of 2
The aromatic polysulfone resin composition according to claim 1, which has a thickness of 5 to 6000 µm. 3. The aromatic polysulfone resin according to claim 1, wherein the amount of the aromatic polysulfone resin required for the surface treatment of the glass fiber is 0.1 to 10 parts by weight based on 100 parts by weight of the glass fiber. Composition. 4. The amount of the alkoxysilane having an amino group required for surface treatment of the glass fiber is 0.01 to 5 parts by weight based on 100 parts by weight of the glass fiber.
The aromatic polysulfone resin composition according to any one of claims 1 to 3. 5. The aromatic polysulfone resin composition according to claim 1, wherein the aromatic polysulfone resin has a repeating unit represented by the following formula at 80 mol% or more. Embedded image