JPH01193360A - Polyphenylene sulfide composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene sulfide composition suitable as electronic and electric parts, having water-vapor resistance and mechanical characteristics, by blending a polyphenylene sulfide with a specific ureidosilane. CONSTITUTION:(A) 100 pts.wt. polyphenylene sulfide containing >=70 mol% repeating unit shown by formula I is blended with (B) 5-400 pts.wt. filler (e.g., glass fibers) and (C) 0.05-10wt.% based on the filler of a ureidosilane (e.g., gamma-ureidomethyltriethoxysilane) shown by formula II (R<1> is 1-15C alkylene; X is 2-10C alkoxy or halogen) and/or formula III [R<2> and R<3> are 1-14C alkylene; Y is -NR<4>- (R<4> is H, etc.), -S-, etc.; Z is 1-10C alkoxy or halogen].

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyphenylene sulfide composition containing a ureido silane compound, and more specifically, by containing the ureido silane compound, it has excellent mechanical properties, The present invention relates to a polyphenylene sulfide composition having moisture resistance.

[Conventional technology]

Polyphenylene sulfide resin (hereinafter abbreviated as PPS) has excellent heat resistance, chemical resistance, flame retardancy, etc., but has the drawback of being brittle. For this reason, various reinforcing materials and fillers such as glass fiber are usually added to improve mechanical properties and heat resistance for practical use. Taking advantage of its characteristics, PPS containing these fillers is widely used in electronic and electrical applications such as connectors, printed wiring board substrates, and electronic component encapsulating materials, automobile applications, and office equipment applications.

However, since the adhesion between these fillers and PPS is not good, there is a drawback that the electrical properties are deteriorated when moisture is absorbed, and there is also a problem that the mechanical properties are not sufficiently developed. The use of various coupling agents has been proposed for the purpose of improving these drawbacks. For example, amide and sulfamide-based silanes (JP-A-62-27459), perfluoroalkyl-based silanes (JP-A-61-296063), silanes having a double bond and an amine group (JP-A-61-296063),
285255), polysilane compounds (Japanese Unexamined Patent Publication No. 1983)
-206463), halosilane (JP-A-59-6)
837 ()), mercaptosilane (Unexamined Japanese Patent Publication No. 1983-
31503), aminosilane, 3-ureidopropyltrimethoxysilane (Japanese Patent Application Laid-open No. 58-65750), titanate coupling agents (Japanese Patent Application Laid-open No. 56-10)
2004 Publication).

[Problems to be Solved by the Invention] By using the above-mentioned coupling agent, the electrical properties and mechanical properties upon moisture absorption are improved to some extent, but they have not yet reached a satisfactory level.

[Means for solving problems]

As a result of intensive study, the inventors of the present invention found that, in place of the already known 3-ureidopropylsilane,
In the ureidosilane represented by 2C0NHRSi We have found that this can be improved, and have arrived at the present invention. That is, the present invention.

A, a polyphenylene sulfide resin B, a filler, and a ureido silane represented by a and/or b shown below as essential components.

a, NHi CNHR' S i
X3 (where R1 represents an alkylene group having 1 to 15 carbon atoms, and X represents an alkoxy group having 2 to 10 carbon atoms or a halogen group).

b, NH, -C-NH-R2-Y-R3-3i (where R2 and R3 are alkylene groups having 1 to 14 carbon atoms, Y is -NR'-1-S-1-SO-1-802 - or -〇-1R4 represents H or an alkyl group having 1 to 10 carbon atoms, and Z represents an alkoxy group having 1 to 10 carbon atoms or a halogen group). Polyphenylsulfide (hereinafter referred to as PPS) used in the present invention has the structural formula ←-Q-8-1→
It is a polymer containing 70 mol % or more, more preferably 90 mol % or more of the repeating unit represented by the following. If the repeating unit is less than 70 mol %, heat resistance will be impaired, so it is not preferable. Generally, pps is a polymer with a relatively small molecular weight obtained by a production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by a production method typified by a production method typified by Japanese Patent Publication No. 52-12240. There are relatively high molecular weight polymers, etc., and in the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, by heating in an oxygen atmosphere after polymerization or by crosslinking with peroxide etc. It is also possible to increase the degree of polymerization and use it by adding an agent and heating it, and in the present invention, it is possible to use PPS obtained by any method. Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula.

←◎昂o, -os+ In addition, the PPS used in the present invention may contain antioxidants, heat stabilizers, lubricants, crystal nucleating agents,
Conventional additives such as UV inhibitors, colorants, and other types of polymers can be added, and in addition, for the purpose of controlling the degree of crosslinking of PPS, conventional peroxidants and JP-A-59-
Crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A No. 131650 or JP-A-58-204045
It is also possible to incorporate crosslinking inhibitors such as dialkyl dicarboxylates and aminotriazoles described in Japanese Patent Application Laid-open No. 58-204046 and the like. The filler used in the present invention may be either inorganic or organic, and its form may be fibrous, granular, or any other form. Examples of such fillers include glass fiber, glass fiber, carbon fiber, silica fiber, asbestos fiber, silica/carmina fiber, alumina fiber, silicon carbide fiber, boron nitride fiber, silicon nitride fiber, zirconia fiber, and boron fiber. , gypsum fiber,
Silicon carbide whiskers, potassium titanate whiskers, calcium silicate fibers, various other ceramic fibers, various metal fibers, aramid fibers, polybenzthiazole fibers, polybenzimidazole fibers, silica, mica, glass peas, talc, clay, Bentonite, wollastenite, selinite, kaolin, asbestos, alumina silicate, calcium silicate, montmorillonite, alumina, silicon chloride, element, magnesium oxide, zirconium oxide, titanium oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate , boron nitride, silicon carbide, Saroyan, etc., and these may be hollow. These fillers are one or two types.
Used in mixtures of more than one species.

In the composition of the present invention, there is no particular restriction on the amount of these fillers added, but it is usually preferably 5 to 400 parts by weight based on 3100 parts by weight of PP. If it is less than 5 parts by weight, it is difficult to obtain the effect of improving mechanical strength and heat resistance, and if it exceeds 400 parts by weight, melt flowability is reduced, moldability is impaired, and mechanical strength is also reduced. The ureidosilane used in the present invention is a, -"maximum NH, -C-NI-I-N
F(-R1-31-X3 (where R1 has 1 carbon number
~15 alkylene group, X represents an alkoxy group having 2 to 10 carbon atoms or a halogen group) and/or b, -
MaximumNH2CNHR'-Y-R3Si Z3 (
However, R2 and R3 are alkylene groups having 1 to 14 carbon atoms, and Y is NR', -3-1-SO-1-SO, -
or -〇-1R4 is a compound represented by H or an alkyl group having 1 to 10 carbon atoms, and Z represents an alkoxy group having 1 to 10 carbon atoms or a halogen group). Examples of the ureidosilane used in the present invention include γ-ureidomethyl 1-ethoxysilane, γ-ureidoethyltriethoxysilane, γ-ureidopropyltriethoxysilane,
7--Ureidopropyltrichlorosilane, γ-ureidobutyltrimethoxysilane, γ-(ureidomethyl)
Aminopropyltrimethoxysilane, γ-(2-ureidoethyl)aminopropyltrimethoxysilane, γ-(
Examples include 2-ureidoethyl)aminopropyltriethoxysilane, γ-2-ureidoethylaminopropyltrimethylsilane, and γ-3-ureidopropyl)aminopropyltrimethylsilane. These ureidosilanes may be used alone or in combination of two or more. It is also possible to use it in combination with other silane compounds such as aminosilane, epoxysilane, vinylsilane, and halosilane. There are no particular restrictions on the amount of these ureidosilanes used in the present invention, but the appropriate amount is usually 0.05 to 10% by weight based on the filler. If it is less than 0.05% by weight, it is difficult to obtain the desired effect, and if it exceeds 10% by weight, the improving effect reaches saturation, which is not only economically disadvantageous, but also impairs the fluidity of the composition, which is not preferable. There are no particular limitations on the method of blending these ureidosilanes, but for example, - constant pH
A method of immersing the filler in a ureido silane solution (aqueous solution, organic solvent solution, water/organic solvent solution) prepared in Examples include methods of mixing and blending materials. There are no particular limitations on the means for preparing the composition of the present invention, and for example, the filler and PPS that have been treated with ureido silane in advance, or the three components of ureido silane, filler, and PPS are mixed in a ribbon blade type mixer or a drum type rotary mixer. Examples include a method of mixing using a machine and then melt-kneading using a single-screw extruder, a multi-screw extruder, a kneader, or the like. Additionally, chopped fibers, chopped fiber mats, continuous fiber mats, woven fabrics, knitted fabrics, etc., which are fibrous fillers treated with ureido silane, may be sprayed with PPS powder, PPS slurry, or PPS slurry.
It is also possible to directly produce a sheet-like molded product or a three-dimensional shaped product by laminating the PS sheets 1 to 1 and bonding them together under heat and pressure. The fibrous filler-reinforced PPS sheet thus obtained is useful as a base material for a printed wiring board to which metal foil such as copper foil is laminated.

〔Example〕

The present invention will be described in more detail below using examples. Note that the values of parts and % used in the examples indicate parts by weight and % by weight, respectively, unless otherwise specified. In addition, each physical property measurement in the examples was performed according to the following method.

Bending strength AST) f 079
0 Izot impact strength (with notch) ASTH [) 256
Insulation resistance ASTHD257 [Practical Examples 1 to 3 ■ Comparative Examples 1 to 4] Cleardon PR-06 (pps manufactured by Fili-Nbusvetroliarm Co., Ltd.) - Glass fiber, calcium carbonate (Example 3), and silane compound After mixing in the proportions shown in Table 1, melt kneading into pellets using an extruder at a temperature of 2.
80°C to 320°C). Subsequently, the obtained pellets were placed in an injection molding machine (molding temperature: 280°C to 320°C, mold temperature: 150°C).
), and the physical properties were measured, and the results shown in Table 1 were obtained. As is clear from the results in Table 1, the compositions of Examples 1 to 3 containing ureido silane are different from those of Comparative Example 1 containing other silane coupling agents.
It has better moisture resistance (water absorption rate after pressure coating, insulation resistance) than the compositions No. 4 to 4.

[Examples 4 to 6] <Rydon V-1@> (PP5 manufactured by Phillips Petroleum), glass fiber, fused silica, and ureido silane were mixed in the proportions shown in Table 2, and then mixed in the same manner as in Example 1. A test piece was prepared by melt mixing M/injection molding, and the physical properties were measured, and the results shown in Table 2 were obtained. As can be seen from Table 2, the compositions of the present invention have excellent moisture resistance (water absorption rate after pre-shackling treatment, insulation resistance) and mechanical properties [Examples 7-8 Comparative Examples 5-7] The PPS powder of Example 1 was uniformly sprinkled on a glass fiber continuous strand mat treated with an alcohol-diluted aqueous solution of the silane compound shown in Table 3, and the mat was supplied into a mold heated to 320°C and compression molded. After that, it was cooled to 150° C. to produce a plate-shaped molded product. The insulation resistance of this test piece under normal conditions and after being boiled in water for 2 hours was determined according to JIS
When measured based on C6481, the results shown in Table 3 were obtained. As is clear from Table 3, by treating the glass fibers with ureidosilane, the electrical insulation properties during moisture absorption are significantly improved.

Notes to Table 3 a) γ-ureidopropyltriethoxysilane manufactured by Toshi Silicone Co., Ltd. b) γ-(2-ureidoethyl)aminopropyltrimethoxysilane manufactured by Toshi Silicone Co., Ltd. c) Vinyltrichlorosilane manufactured by NUC Corporation d) Methyltrimethoxysilane manufactured by Toshi Silicone Co., Ltd. [Effects of the invention] The polyphenylene sulfide composition of the present invention has excellent moisture resistance and mechanical properties, and is used in various applications including electronic and electrical parts. Suitable for use in various applications.

Claims (1)

[Scope of Claims] A polyphenylene sulfide composition comprising A, a polyphenylene sulfide resin B, a filler, and C, a ureidosilane represented by a and/or b below as essential components. a, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where R^1 represents an alkylene group having 1 to 15 carbon atoms, and X represents an alkoxy group or halogen group having 2 to 10 carbon atoms). b, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where R^2 and R^3 are alkylene groups with 1 to 14 carbon atoms, Y is -NR^4-, -S-, -SO-,
-SO_2- or -O-, R^4 represents H or an alkyl group having 1 to 10 carbon atoms, and Z represents an alkoxy group having 1 to 10 carbon atoms or a halogen group).