JPH0343452A - Polyphenylene sulfide resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyphenylene sulfide resin composition that has excellent mechanical properties such as strength and impact resistance, and has improved weld strength.

<Conventional technology> Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has properties suitable for engineering plastics, such as excellent heat resistance, flame retardance, rigidity, and electrical insulation properties, and is mainly used for injection molding. Used in various electrical parts, mechanical parts, automobile parts, etc.

However, PP5I! J-type resin has drawbacks such as being brittle and having low impact resistance, and low weld strength especially in reinforced products reinforced with glass 1IJl fibers, etc., so it is particularly difficult to use in applications such as small precision parts that require these properties. Its use is restricted.

In view of this situation, PP5t! Several studies have been made to improve the Wi impact resistance and weld strength of I-type fats. For example, a method using glass fibers having a diameter within a specific range (for example,
3591) and a method of using two types of PPS resins having different viscosities together (for example, Japanese Patent Publication No. 63-67503) have been proposed.

<Problem to be solved by the invention> However, the former method requires the use of expensive glass fibers with a specific diameter, and the use of such glass fibers causes problems such as a decrease in fluidity. There's a problem.

On the other hand, in the latter method, the weld strength of the composition obtained is at most 550 kt f/d, and it cannot be said that sufficient improvement has been made.

Therefore, the object of the present invention is to obtain a polyphenylene sulfide resin composition that has excellent strength and impact resistance, and has improved weld strength.

As a result of intensive studies in order to solve the above problems, the present inventors found that by blending a specific silane compound and glass fiber into PP5tll fat having a specific molecular weight distribution and melt flow rate retention rate. The present inventors have discovered that a composition with specific improvements in strength, impact resistance, and weld strength can be obtained, and have completed the present invention.

Means for Solving the Problems> That is, the present invention provides (A) the ratio of the number average molecular weight (〒) to the weight average molecular weight (Mw) determined by gel permeation chromatography using 1-chloronaphthalene as a solvent; has a molecular weight distribution that satisfies the following formula (1), and ASTM
The retention rate of the melt flow rate value specified in D1238-86 (315.5℃, 5.0OOf load) is as follows (
2) To provide a PPS resin composition comprising 100 parts by weight of a PPS resin satisfying the formula, FB) 0.01 to IO parts by weight of a ureido silane compound, and (C) 10 to 250 parts by weight of glass LA fiber. It is something.

Mw/Mn<20 (1) 50<
MF5/MFISX100<150 (2) (where MFs and MF+s are residence times of 5 minutes and 15 minutes, respectively)
The PP5vfJ fat (A) used in the present invention is 1-
It has a molecular weight distribution in which the ratio of number average molecular weight (Mn) to weight average molecular weight (Mw) determined by gel permeation chromatography using chloronaphthalene as a solvent satisfies the following formula (1), and ASTM D1238-86 (31
In order to achieve the object of the present invention, it is extremely important that the retention rate of the melt flow rate value set at 5.5° C.

Mw/M n< 20 (1) 5
0<MFs/MF+sX 100<150!
2) (Here, M F s and M P +s represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively.) PP5v that does not satisfy the above two conditions! Even if the ureido silane compound (B) is added to the J resin (A), hardly any improvement in impact resistance or weld strength can be obtained.

Examples of PPS resins that satisfy these conditions include M2888 and M2588 manufactured and sold by Toshi-Philips Vetroleum.

Next, the ureidosilane compound (B) used in the present invention is an alkoxysilane or halosilane having one or more ureido groups in the molecule, such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, etc. Examples include silane and γ-(2-ureidoethyl)aminopropyltrimethoxysilane, and two or more of these can also be used in combination.

In the present invention, these ureidosilane compounds (
B) has a remarkable effect of improving the hardness and weld strength, and the same improvement effect cannot be obtained even if other typical organic silane compounds, such as unsaturated silane compounds, are used.

The amount of the ureidosilane compound (B) to be blended with respect to 10.0 parts by weight of the PPS resin (A) is preferably in the range of 0.01 to 10 parts by weight, particularly 0.1 to 5 parts by weight.

If the amount added is less than 0.01 part by weight, the effect of improving 81i9 resistance and weld strength will not be sufficiently exhibited, and if it exceeds 10 parts by weight, the fluidity of the composition will be significantly impaired, which is not preferable.

The glass fiber (C) used in the present invention has a diameter of 5 to
Examples include 15 um commonly available commercially available glass fibers or chopped glass strands for reinforcing plastics. The blending amount of the glass fiber (C) with respect to 10,011 parts by weight of the PPS resin (A) is selected to be in the range of 10 to 250 parts by weight. If the amount is less than 10 parts by weight, the mechanical strength of the composition will be insufficient, and if it exceeds 250 parts by weight, fluidity will be impaired, which is not preferable.

In addition to the glass 1a fibers, other fillers can be blended as long as they do not impair the effects of the present invention.

Such fillers other than glass fibers include inorganic fibers such as alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers, fibrous fillers such as carbon fibers, wollastenite, sericite, and kaolin. , mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon chloride, metal compounds such as magnesium oxide, zirconium oxide, titanium oxide, carbonates such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate , sulfates such as barium sulfate, glass beads, boron nitride, non-fibrous fillers such as silicon carbide and silica,
These may be hollow, and it is also possible to use two or more of these fillers in combination.

The PPS resin composition of the present invention may also contain conventional additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, and flame retardants, to the extent that they do not impair the effects of the present invention. and small amounts of other polymers can be added.

The method for preparing the composition of the present invention is not particularly limited, but PPS
A method of tri-blending the resin, glass fiber, and ureido silane compound and then melt-kneading the resin, glass fiber, and ureido silane compound in an extruder at a temperature higher than the melting point of the PPS resin (i.e., 280 to 380°C), or a method of tri-blending the resin, glass fiber, and ureido silane compound, or mixing the PPS resin, glass fiber, or PP5f! l
A typical method is to tri-blend a fat and a ureido silane compound, melt-knead the mixture, and then melt-knead this and the remaining one.

The present invention will be further explained below with reference to Examples.

<Example> Tensile strength, bending strength, flexural modulus, isot impact strength, weld strength,
Melt flow rate, molecular weight and molecular weight distribution were each measured according to the following methods.

Tensile strength/ASTM-D638 Bending strength: STM-D790 Bending modulus: ASTM-D790 Izot impact strength: ASTM-D256 Measurement of weld strength Has a gate at both ends and a weld line near the center of the test piece An ASTM No. 2 dumbbell piece with
This was done under conditions between.

Melt flow rate: ASTM-D 1238-86
(315.5°C, 5.0OOr load) Measurement of molecular weight and molecular weight distribution: Using a gel permeation chromatography device manufactured by Waters, Polymer Journal Vol. 44 (1987) 2
The experiment was carried out according to the method disclosed on pages 139 to 141 of the issue.

Reference Examples> The PPS resin logs used in the present examples and comparative examples are shown below, and their characteristic values are shown in Table 1.

PP5-1: Manufactured by Toshi Phillips Petroleum Co., M2588 PPS-2: Manufactured by Toshi Phillips Petroleum Co., Ltd.
M2888 PPS-3: Manufactured by Toshi Phillips Vetrolilum Co., Ltd.
M2100 PPS-4: Manufactured by Toshi Phillips Vetroleum Co., Ltd.
M2900 Example 1 After tri-blending PP5-1, γ-ureidopropyltriethoxysilane and glass fiber in the proportions shown in Table 2, the mixture was melt-kneaded using a screw extruder set at a temperature of 300 to 310°C and then pelletized. did. The obtained pellet was used to mold a test piece for evaluating mechanical properties.

Tensile strength and bending strength measured on the obtained test piece,
The flexural modulus, Izot impact strength and weld strength are shown in Table 3.

Example 2 PPS-2, γ-ureidopropyltriethoxysilane, and glass fiber were triblended in the proportions shown in Table 2, and then melt-kneaded using a screw extruder set at a temperature of 300 to 310°C and then pelletized. . The obtained pellet was used to mold a test piece for evaluating mechanical properties.

The physical property values measured in the same manner for the obtained test piece were
Shown in the table.

Example 3 After tri-blending PPS-1, γ-glycidoxypropyltrimethoxysilane and glass fiber in the proportions shown in Table 2, the mixture was melt-kneaded using a screw extruder set at a temperature of 300 to 310°C. Pelletized. The obtained pellet was used to form a test piece for evaluating the characteristics at llll.

The physical property values measured in the same manner for the obtained test piece were
Shown in the table.

Example 4.5 After dry-blending pps-i, γ-ureidopropyltriethoxysilane, and glass fiber in the proportions shown in Table 2, the mixture was melt-kneaded using a screw extruder set at a temperature of 300 to 310°C. It was then pelletized. The obtained pellet was used to mold a test piece for evaluating mechanical properties.

The physical property values measured in the same manner for the obtained test piece were
Shown in the table.

Comparative Example 1 A test piece for evaluation was prepared by kneading and molding in exactly the same manner as in Example 1 except that γ-ureidopropyltriethoxysilane was not used.

The physical property values measured in the same manner for the obtained test piece were
Shown in the table.

Comparative Example 2 A test piece for evaluation was prepared by kneading and molding in the same manner as in Example 2 except that γ-ureidopropyltriethoxysilane was not used.

The physical property values measured in the same manner for the obtained test piece were
Shown in the table.

Comparative Examples 3-4 PPS-3 (Comparative Example 3) and PP5-4 (Comparative Example 4)
A test piece for evaluation was prepared by kneading and molding in exactly the same manner as in Example 1, except that .

The physical property values measured in the same manner for the obtained test piece were
Shown in the table.

Comparative Examples 5 to 6 Test pieces for evaluation were prepared by kneading and molding in exactly the same manner as in Example 1, except that various organic silane compounds shown in Table 2 were used instead of γ-ureidopropyltriethoxysilane. It was created.

The physical property values measured in the same manner for the obtained test piece were
Shown in the table.

Table 1 Table 2 Table 5I-1: γ-ureidopropyltriethoxysilane: γ-ureidopropyltrimethoxysilane: γ-methacryloxypropyltrimethoxysilane: γ-vinyltrimethoxysilane l-4 I I-2 Table <Effects of the Invention> The polyphenylene sulfide resin composition of the present invention has a
It has excellent mechanical properties such as impact resistance and weld strength, and is particularly suitable for injection molding applications.

Claims (1)

[Scope of Claims] (A) The ratio of the number average molecular weight (Mn) to the weight average molecular weight (@Mw@) determined by gel permeation chromatography using 1-chloronaphthalene as a solvent is expressed by the following formula (1). It has a molecular weight distribution that meets ASTM D1238-86 (
100 parts by weight of a polyphenylene sulfide resin that satisfies the following formula (2), and 0.01 to 10 parts by weight of (B) a ureido silane compound, whose retention rate of the melt flow rate value determined at 315.5° C. and 5,000 g load) satisfies the following formula (2). and (C) a polyphenylene sulfide resin composition comprising 10 to 250 parts by weight of glass fiber. @Mw@/@Mn@<20(1) 50<MF_5/MF_1_5×100<150(2)
(Here, MF_5 and MF_1_5 represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively.)