JP2000309707A - Aromatic polysulfone resin composition and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polysulfone resin composition which can improve the adhesion between glass fibers and a matrix resin, and can improve the mechanical characteristics and the reliability of a molding obtained therefrom, and its molded article. SOLUTION: The resin composition is obtained by blending 100 pts.wt. aromatic polysulfone resin at least containing a hydroxylated aromatic polysulfone resin with 5-240 pts.wt. glass fibers having a surface treated with an epoxyalkoxysilane. The molded article is obtained by molding a resin material containing this composition.

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 which can improve the adhesion between glass fibers and a matrix resin and can improve the mechanical properties and the like of the obtained molded article, and electronic and mechanical parts. And a molded article using the above composition, which can be used for various structural materials.

[0002]

2. Description of the Related Art Various resin materials have been used in electronic parts, mechanical parts, various structural materials, and the like. It is also known to mix a matrix resin material with a fibrous material such as glass fiber in order to reduce the molding shrinkage and improve the strength, elasticity, and the like of a molded article obtained from such a resin material. However, depending on the type of resin and the type and form of the fibrous material, the adhesiveness between the matrix resin material and the fibrous material is not good, and the effect expected by blending the fibrous material may be difficult to obtain. is there. For example,
Aromatic polysulfone resin has excellent heat resistance, strength, elastic modulus, and creep resistance.
Although it is a suitable material as a structural material, it does not have good adhesion to glass fibers, and fibers fall off from the gate and cutting surface of the molded product obtained by blending glass fibers, resulting in workability and product reliability. There is a problem that impairs.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an aromatic polysulfone resin composition capable of improving the adhesiveness between glass fiber and a matrix resin, and improving the mechanical properties and the reliability of the obtained molded article. To provide things.
Another object of the present invention is to provide a molded article having excellent mechanical properties and improved interfacial adhesion between glass fiber and matrix resin.

[0004]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the above-mentioned problems. As a result, the aromatic polysulfone resin contains at least an aromatic polysulfone resin having a hydroxyl group, and particularly preferably has a hydroxyl group. A matrix resin material containing at least an aromatic polysulfone resin, using an aromatic polysulfone resin having a hydroxyl equivalent of not more than a specific value, and mixing glass fibers having a specific surface treatment at a specific ratio as glass fibers. The present inventors have found that interfacial adhesion to fibers can be improved, and completed the present invention. That is, according to the present invention, 100 parts by weight of an aromatic polysulfone resin including at least an aromatic polysulfone resin having a hydroxyl group, and a glass fiber 5 surface-treated with an alkoxysilane having an epoxy group are used.
There is provided an aromatic polysulfone resin composition characterized by comprising 240 parts by weight. Further, according to the present invention, there is provided a molded article obtained by molding a resin material containing the aromatic polysulfone resin composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention is surface-treated with an aromatic polysulfone resin containing at least an aromatic polysulfone resin having a hydroxyl group (hereinafter referred to as aromatic polysulfone resin A) and an alkoxysilane having an epoxy group. And glass fibers mixed at a specific ratio. The aromatic polysulfone resin A used in the composition of the present invention may be composed of an aromatic polysulfone resin having a hydroxyl group, or may be composed of an aromatic polysulfone resin having a hydroxyl group and an aromatic polysulfone resin having no hydroxyl group. The aromatic polysulfone resin is a polyarylene compound containing an arylene unit, an ether bond and a sulfone bond as essential constituent units. The aromatic polysulfone resin having a hydroxyl group further has a hydroxyl group at a terminal and / or an arylene unit. Is a compound added to The arylene unit may be located randomly or orderly with ether and sulfone bonds. Typical examples of the aromatic polysulfone resin A include compounds having a repeating unit represented by the following formulas (1) to (3). However, formulas (2) and (3) include a random copolymer.

[0006]

Embedded image (In the formulas (1) to (3), R represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, a phenyl group, a halogen atom or a hydroxyl group, and each R on the same or different nucleus is P is a positive number from 0 to 4, and each p may be different from each other.
In (3), m and n indicate the average number of repeating units, and m / n is 0.001 to 10,000. Also, the formula
In (3), q is a positive number of 1 to 3. )

In the above formulas (1) to (3), p is preferably 0, and in the formula (3), q = 1 or 2 is preferable. Further, in the formula (2) or (3), (m / m + n)>
It is preferably 0.8. As a more preferred aromatic polysulfone resin, a compound having 80 mol% or more of a repeating unit in which p = 0 in the formula (1) is desirable. Examples of the aromatic polysulfone resin having a hydroxyl group in the aromatic polysulfone resin A include a resin having a hydroxyl group added to an appropriate R position or a terminal in the repeating unit represented by the formulas (1) to (3). No. Preferably,
A polysulfone resin having a hydroxyl group at a terminal is preferable.

[0008] In the aromatic polysulfone resin A, the hydroxyl group content is 400,000 g in terms of hydroxyl equivalent (OH equivalent).
/ Eq or less is preferable. The hydroxyl equivalent is 400,000 g /
Exceeding eq is not preferred because good adhesion to glass fibers may not be sufficiently exhibited.

In producing an aromatic polysulfone resin having a hydroxyl group, a method for introducing a hydroxyl group into the aromatic polysulfone resin is not particularly limited. For example, as a method for introducing a hydroxyl group to the terminal of an aromatic polysulfone resin, a dihydric phenol such as 4,4′-dihydroxydiphenylsulfone or bisphenol A is reacted with potassium carbonate or sodium hydroxide to obtain a hydroxyl group. Upon desalting and polycondensation of a divalent phenolate and a dichloro compound such as 4,4'-dichlorodiphenylsulfone, an excessive amount of a divalent phenolate is charged, and the terminal group is converted to a phenolate. And a method of adding a hydroxyl group to the terminal. The adjustment of the hydroxyl equivalent of the aromatic polysulfone resin A can be adjusted in the manufacturing process such as the above method, and also, the aromatic polysulfone resins having different hydroxyl equivalents are mixed with each other, or the aromatic polysulfone resin having no hydroxyl group is mixed. It may be adjusted by the following. As the aromatic polysulfone resin A, a commercially available product can be used. For example, the product name is “SUMICA EXCEL PES”
5003P ”,“ 3600P ”,“ 4100P ”
(Above, manufactured by Sumitomo Chemical Co., Ltd.) and the like, but are not limited thereto.

[0010] In the glass fiber used in the composition of the present invention and surface-treated with an alkoxysilane having an epoxy group, the glass fiber is obtained by processing glass containing silicate as a main component into a fibrous form. Glass types include 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, and E glass is particularly preferred.
The production of glass fiber can be performed by a general method of spinning glass in a molten state (1300 ° C. or higher). The fiber diameter and fiber length of the glass fiber are not particularly limited. For example,
Number average fiber diameter is preferably 1-20 μm, 5-15 μm
Is more preferred. If the number average fiber diameter is less than 1 μm, the sizing effect at the time of spinning becomes insufficient, and as a result, it is difficult to mix with the aromatic polysulfone resin A, which is not preferable. On the other hand, if the number average fiber diameter exceeds 20 μm, it is not preferable because the strand take-up property becomes unstable during melt granulation of the composition of the present invention. On the other hand, the fiber length is preferably 25 to 6000 μm in number average fiber length, and 30 to 3000 μm.
m is more preferred. When the number average fiber length is less than 25 μm,
It is not preferable because the reinforcing effect by the glass fiber may be reduced. On the other hand, if the number average fiber length exceeds 6000 μm, the take-up of strands during melt granulation of the composition of the present invention becomes unstable, and the surface state of the obtained molded article may be further deteriorated. .

As the alkoxysilane having an epoxy group for surface-treating the glass fiber, an alkoxysilane represented by the formula (4) can be mentioned.

[0012]

Embedded image (In the formula, R ¹ is an alkylene group having 1 to 4 carbon atoms, R ²
Represents an alkyl group having 1 to 4 carbon atoms, a methoxy group or an ethoxy group, and R ³ represents an alkyl group having 1 to 5 carbon atoms.
X represents a functional group having an epoxy group. m is 1
An integer of 3 and n is an integer of 0 to 2 and m + n ≦ 3
It is. In the formula (4), examples of the functional group having an epoxy group as X include a functional group represented by the following formula (5) or (6). However, in the functional group represented by the formula (6), the formula (4)
Examples of the site that binds to R ¹ include the positions 2 to 5 in the formula (6).

[0013]

Embedded image

The alkoxysilane represented by the formula (4) includes, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane and the like.

As a method for surface-treating a glass fiber with an alkoxysilane having an epoxy group, for example,
A dry method in which an aqueous solution of an alkoxysilane having an epoxy group or an organic solvent solution is added to a glass fiber at a high speed with a mixer capable of high-speed stirring, and the mixture is uniformly dispersed and dried; an aqueous solution of an alkoxysilane having an epoxy group Or after immersing the glass fiber in an organic solvent solution, filtered,
An immersion method for drying; a spray method for spraying an alkoxysilane having an epoxy group after drying a glass fiber; an alkoxy group having an epoxy group when melt-kneading a resin material containing an aromatic polysulfone resin A and glass fiber. Examples include an integral blend method in which silane is directly added, but the method is not limited thereto.

In the glass fiber surface-treated with the alkoxysilane having an epoxy group, 0.05 to 2 parts by weight of the alkoxysilane having an epoxy group is added to 100 parts by weight of the glass fiber. It is preferred to have it in a ratio of 5 to 1 part by weight. If the proportion of the alkoxysilane having an epoxy group is less than 0.05 part by weight, the effect of improving the interfacial adhesion between the matrix resin material and the glass fiber may not be sufficient, which is not preferable. On the other hand, when the proportion of the alkoxysilane having an epoxy group exceeds 2 parts by weight, the decomposition gas of the alkoxysilane having an epoxy group increases, and as a result, the thermal stability at the time of molding may be impaired. Absent. In order to adjust the proportion of such an alkoxysilane having an epoxy group, the glass fiber can be adjusted by a surface treatment method using the alkoxysilane having an epoxy group. The ratio of the alkoxysilane having an epoxy group to the glass fiber, that is, the surface treatment amount is, for example, J
It can be determined by the ignition loss measurement specified in ISR3420. Glass fibers surface-treated with an alkoxysilane having an epoxy group used in the composition of the present invention,
For example, it may be further treated with a sizing agent such as a thermosetting resin or a thermoplastic resin.

In the composition of the present invention, the mixing ratio of the glass fiber surface-treated with the alkoxysilane having an epoxy group is 5 to 240 parts by weight based on 100 parts by weight of the aromatic polysulfone resin having a hydroxyl group. Yes,
Preferably it is 10 to 160 parts by weight. 24
If the amount exceeds 0 parts by weight, the biteability of the screw during granulation and the like becomes poor, and plasticization during subsequent molding becomes unstable. It is not preferable because the appearance is deteriorated.
On the other hand, when the amount is less than 5 parts by weight, the mechanical strength of a molded article obtained from the composition becomes insufficient.

In the composition of the present invention, if necessary, in addition to the above essential components, for example, a thermoplastic resin or a thermosetting resin other than the aromatic polysulfone resin A; silica-alumina fiber, alumina fiber, Fibrous or needle-like reinforcing materials such as carbon fibers and aluminum borate whiskers; inorganic fillers such as talc, mica, clay and glass beads; release improvers such as fluororesins and metal soaps; dyes and pigments One or more ordinary additives such as a coloring agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, and a surfactant can be added in an appropriately determined mixing ratio. Examples of other thermoplastic resins include polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and modified products thereof, and polyetherimide. Examples of the thermosetting resin include a phenol resin, an epoxy resin, and a polyimide resin. These can be used alone or in combination of two or more.

In the composition of the present invention, there is no particular limitation on the means of compounding each component to prepare a molding material. For example, an aromatic polysulfone resin A, glass fibers surface-treated with an alkoxysilane having an epoxy group, and, if necessary, the above-mentioned other components and the like are mixed using a Henschel mixer, a tumbler or the like, and then extruded. It is common to melt-knead the mixture into a molding material such as a pellet. At this time, as the melt-kneading method, all the raw materials may be fed to an extruder after being mixed at once,
If necessary, a reinforcing material such as a fibrous material or an inorganic filler may be fed separately from the raw material mainly composed of resin. Melt kneading conditions can be appropriately selected and performed.

The fiber diameter and fiber length of the glass fiber after mixing the above-mentioned raw materials to form a molding material, that is, the fiber diameter and fiber length of the glass fiber in the composition, when the fiber diameter is the number average fiber diameter Is preferably 1 to 20 μm, more preferably 5 to 15 μm. If the number average fiber diameter is less than 1 μm, the bunching effect at the time of spinning becomes insufficient, and as a result, the adhesiveness to the aromatic polysulfone resin A may be insufficient, which is not preferable. When the number average fiber diameter exceeds 20 μm,
It is not preferable because the strand take-up property during melt granulation becomes unstable. On the other hand, in the case of the fiber length, the number average fiber length is preferably 25 to 6000 μm, and 30 to 300 μm.
0 μm is more preferred. If the number average fiber length is less than 25 μm, the reinforcing effect of the glass fibers is undesirably reduced. On the other hand, if the number average fiber length exceeds 6000 μm, the strand take-up property during melt granulation becomes unstable, and the surface condition of a product molded from the obtained composition is undesirably deteriorated. In order to measure the number average fiber diameter and number average fiber length of the glass fibers in such a composition, an aromatic polysulfone resin A and a glass fiber surface-treated with an alkoxysilane having an epoxy group are biaxially measured. A pellet can be obtained by using an extruder, the obtained pellet is fired at 600 ° C., and an optical microscope image of the residual glass fiber can be photographed and then analyzed by image analysis for measurement.

The molded article of the present invention is obtained by molding a resin material containing the composition of the present invention. Molding is, for example, molding a molding material such as a pellet containing the composition of the present invention into a desired shape as an electronic component, a mechanical component or various structural materials by ordinary compression molding, extrusion molding, injection molding, or the like. Can be done by The molding conditions at that time can be appropriately selected and performed.

[0022]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. Incidentally, the measurement of various physical properties in the examples, the measurement of the number average fiber length and the number average fiber diameter of the glass fibers in the composition (after blending), and the determination of the quality of the adhesion between the matrix resin material and the glass fibers is The procedure was as follows. (1) Flexural strength, modulus of elasticity The composition of the present invention was 127 m long using an injection molding machine.
m, a test piece having a width of 12.7 mm and a thickness of 6.4 mm were molded and measured in accordance with ASTM D790. (2) Izod impact strength The composition of the present invention was prepared using an injection molding machine to a length of 64 m.
m, a width of 12.7 mm, a thickness of 6.4 mm, and a test piece having a notch having a tip radius of 0.25 mm and a depth of 2.7 mm at the center were measured in accordance with ASTM D256. (3) Hydroxy group equivalent The aromatic polysulfone resin A was dissolved in dimethylformamide, and the amount of hydroxyl group was measured with a potentiometric titrator using a 0.05 mol / l potassium methoxide / toluene / methanol solution as a titration reagent. The equivalent was calculated. Further, in Examples in which two or more aromatic polysulfone resins A having known hydroxyl equivalents were mixed to adjust the hydroxyl equivalent, the hydroxyl equivalents of both were calculated from the mixing ratio. (4) Number average fiber length and number average fiber diameter of glass fibers in the composition Powder of aromatic polysulfone resin A (trade name “SUMICA EXCEL PES4100 manufactured by Sumitomo Chemical Co., Ltd.)
P "," 5003P "), and a glass fiber surface-treated with an alkoxysilane having an epoxy group, using a twin-screw extruder (trade name" PCM-30 ", manufactured by Ikegai Iron Works Co., Ltd.) The pellet obtained by granulating at a cylinder temperature of 340 ° C. was fired at 600 ° C., and an optical microscope image of the residual glass fiber was photographed and analyzed by image analysis. (5) Determining the quality of interfacial adhesion (adhesion between matrix resin material and glass fiber) The fracture surface of the test piece after the Izod impact strength test was examined using a scanning microscope (trade name "S-2300" manufactured by Hitachi, Ltd.). (Hitachi Scanning Microscope) and visually evaluated whether or not the interface between the matrix resin material and the glass fiber was separated. ○ indicates that the adhesion between the matrix resin and the glass fiber is good, and x indicates that it is poor.

Production Examples 1 to 3 Glass fiber ( manufactured by Central Glass Co., Ltd., trade name "EFH7")
5-01 ", not surface-treated) with a Henschel mixer at a high speed (up to 1500 rpm), and a 5% by weight aqueous solution of an alkoxysilane having an epoxy group.
(Toray Dow Corning Silicone Co., Ltd., trade name "S
H6040 "and ion-exchanged water)
Was added intermittently, and at the same time as the addition was completed, stirring was performed while heating to 130 ° C., followed by drying to prepare a surface-treated glass fiber. The amount of the alkoxysilane having an epoxy group adhered to the glass fiber, that is, the surface treatment amount (glass fiber 10
(Amount relative to 0 parts by weight) was adjusted by the amount of the alkoxysilane-containing aqueous solution used. Table 1 shows the results.

[0024]

[Table 1]

Examples 1 to 5, Comparative Examples 1 and 2 As a powder of the aromatic polysulfone resin A, "Sumica Excel PES410" manufactured by Sumitomo Chemical Co., Ltd.
0P "(hydroxyl equivalent 432,000 g / eq)," 500
3P "(hydroxyl equivalent: 9000 g / eq), and using the surface-treated glass fibers obtained in Production Examples 1 to 3 as glass fibers, in a mixing ratio shown in Table 2 and a twin-screw extruder (Ikekai Iron Works ( Granulation was performed at 340 ° C. cylinder temperature using a trade name “PCM-30” (trade name, manufactured by Co., Ltd.) to obtain pellets. The obtained pellets are injected into an injection molding machine (PS4 manufactured by Nissei Plastic Industry Co., Ltd.).
(0E5ASE) under the conditions of a cylinder temperature of 360 ° C. and a mold temperature of 150 ° C., and the bending strength, bending elastic modulus, Izod impact strength and interfacial adhesion were measured. Table 2 shows the results. Table 2 also shows the hydroxyl equivalents of the aromatic polysulfone resin A powder used in each example.

[0026]

[Table 2]

[0027]

The aromatic polysulfone resin composition of the present invention contains the aromatic polysulfone resin A and the glass fiber having been subjected to a specific surface treatment in a specific ratio, so that the matrix resin material and the fibrous material are mixed. Adhesion can be improved. Further, since the molded article of the present invention uses the composition, the interfacial adhesion between the matrix resin material and the fibrous material is improved, the mechanical performance of the molded article is excellent, and it is extremely suitable for electronic parts, mechanical parts and various structural materials. Useful.

Continued on the front page (72) Inventor Hiroshi Nakamura 6 Kitahara, Tsukuba-shi, Ibaraki F-term (reference) 4F072 AA02 AA08 AB09 AB14 AB15 AC06 AD46 AF24 AK15 AL11 AL16 AL17 4J002 CN031 DL006 FA046 FB136 FD016

Claims (6)

[Claims] 1. A glass fiber surface-treated with an alkoxysilane having an epoxy group in an amount of 5 to 240 parts by weight based on 100 parts by weight of an aromatic polysulfone resin containing at least an aromatic polysulfone resin having a hydroxyl group. An aromatic polysulfone resin composition comprising: 2. The aromatic polysulfone resin composition according to claim 1, wherein the number average fiber diameter of the glass fibers in the composition is 1 to 20 μm and the number average fiber length is 25 to 6000 μm. 3. The aromatic polysulfone resin composition according to claim 1, wherein the hydroxyl equivalent of the aromatic polysulfone resin is not more than 400,000 (g / eq). 4. The glass fiber surface-treated with an alkoxysilane having an epoxy group has 0.05 to 2 parts by weight of the alkoxysilane having an epoxy group with respect to 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 6. A molded article obtained by molding a resin material containing the aromatic polysulfone resin composition according to any one of claims 1 to 5.