TW492988B - Polyarylene sulfide composition - Google Patents

Abstract

A polyarylene sulfide resin composition excellent in moulding, workability, specially no corrosion or contamination occurring on the metal part such as die upon moulding, and excellent in mechanical properties of its molding articles, characterized in containing 0.05 to 3 parts by weight of (B) zinc oxide whisker based on 100 parts by weight of (A) polyarylene sulfide resin.

Description

I5 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A 7 ......, --——: Description of the Invention (,) The present invention relates to an improved Aryl sulfide resin composition 犓 β __ In other words, it has excellent processability, especially metal parts such as molds during molding are not corroded and contaminated, and the mechanical properties of the molded product are _ 骞 polyaryl Sulfur composition. Typical polyarylene sulfide (hereinafter referred to as PAS) resin, polyphenylene sulfide (hereinafter referred to as PPS) resin, due to its high heat resistance, organic maple ft, chemical resistance, dimensional stability, flame resistance Therefore, it is widely used in electrical and electronic machine parts materials, automotive machine parts materials, chemical lifting machine parts materials, and so on. However, the resin has a sulfur atom in the molecular structure, and the manufacturing raw materials have sulfur or chlorine and an alkali metal such as sodium. When the resin is synthesized, it can generate by-products containing more than 4 sulfur or chlorine, alkali gold, etc. Therefore, there is a lack of corrosion and pollution of metal materials such as molds during forming, and when used as a material of forming parts, defects such as internal metals in the parts or metal plating or evaporation are caused by corrosion and pollution. In order to solve this problem, it is pseudo-proposed that the polymerized P AS resin be deionized and washed with acid or hot water, organic solvents, etc., so that these impurities are reduced to less than 500 PP, preferably 2 (Below QPP®, although it is quite effective, because the PAS resin and its composition are at least 28 ° C in the molding process, even if these impurities can be removed and refined, corrosive gas will be generated during the molding process. In order to solve this problem, the technology to solve this problem is like adding a supplementary substance to the resin, and suppressing corrosiveness and impurities. For example, carbonic acid (please read first) Note on the back, please fill in this page for binding. Φ h This paper size is applicable to Chinese National Standard (CNS) A4 size (X 297 feet) 492988 Kl B7 printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5 'Invention Description (2) (Japanese Patent Laid-Open No. 54-162752), hydrotalcite (Japanese Patent Laid-open No. 6 1 -27 535 3), zinc carbonate, zinc hydroxide (Japanese Patent Laid-Open No. 2-105857), zinc borate (Japanese Patent Laid-open No. Hei. 6-306288 However, the present inventors continued to study the issue that an additive has an anti-ih metal corrosion effect, but it is not sufficient, and it has been found that a small amount of K is added to reduce mechanical properties, etc. In addition, Japanese Patent Laid-Open No. 4 -1 6 4961 reveals the addition of specific zinc oxide, but it is difficult to say that its mechanical properties are sufficient, and it is desired to further improve M. In view of this problem, the present invention provides a mold that can improve the molding of the PAS resin composition. Or the corrosion and pollution of metals during use, and even if a relatively large amount of corrosion inhibitor is used, it does not adversely affect the mechanical properties of tensile strength, impact strength, toughness, etc., and has excellent resistance to metal corrosion and mechanical properties The purpose of the PAS resin composition is to achieve the above-mentioned objective, and as a result of further intensive research, the formulation of the PAS resin by combining specific zinc oxide can not only significantly improve the corrosion and pollution of metals, And the corrosion inhibitor can solve the adverse effect on the mechanical properties, maintain excellent mechanical properties, have both characteristics, and complete the present invention. In other words, the present invention relates to a polyaryl sulfide resin composition, which is characterized in that 100 parts by weight of K (A) polyaryl sulfide resin is 0.05 to 3 parts by weight (B) zinc oxide whiskers. The basic constituents are compounded by K and melt-kneaded. That is, the polyarylate sulfide resin composition of the present invention contains the aforementioned 100 parts by weight (A) and 0.05 to 3 parts by weight (B). -4 -This paper size applies Chinese National Standard (CNS) Α4 specification (210 × 297) (please read the precautions on the back before filling this page), -mouth.Kiss 丨. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 492988 A7 B7 5. Description of the invention (3) The constituent elements of the present invention will be described in detail in the following paragraph. The PAS resin of the component (A) of the composition of the present invention is composed mainly of K- (Ar-S)-(Ar is aryl) as the repeating unit. Examples of the aryl group include p-phenylene, m-phenylene, o-phenylene, substituted phenylene,? ≫, 0'-diphenylenesulfonyl,? >,? ) '-Diphenylene, 0' ^ 'diphenylene ether, ρ, ρ'-diphenylenecarboxyl, naphthyl and the like. At this time, in the aryl sulfide group composed of the above-mentioned aryl group, in addition to the polymer (ie, homopolymer) using the same repeating unit, in terms of the processability of the composition, the composition contains different repeating units. Copolymers are also preferred. Homopolymers use p-phenylene as the aryl group, especially those where p-phenylene sulfide is the repeating unit. In addition, the copolymer system can use two different aryl sulfide groups composed of aryl sulfide groups on M, but especially M contains p-phenylene sulfide group and m-phenylene sulfide group. Ether groups are more preferred for M combinations. Among them, in terms of heat resistance, formability, mechanical properties, and the like, K contains 70 moles: The p-phenylene sulfide group on M is preferably, and more preferably 80 moles on K. In addition, in these PAS resins, it is more preferable to use a high-molecular-weight polymer having a substantially linear structure obtained by polycondensation of a monopolymer mainly composed of a functionalized aromatic compound. In addition to the PAS resin M with a straight structure, a small amount of a monopolymer such as a polyhalogenated aromatic compound having 3 halogen substituents on the K is used during condensation polymerization to form a partially branched structure or a crosslinked structure. The polymer can also be used, and low molecular weight mullion structure polymer can be used. In the presence of oxygen or oxidant, κ high temperature heating increases the melt viscosity by oxidative cross-linking or thermal cross-linking κ, improving -5-paper size Applicable to Chinese National Standard (CNS) Α4 gauge Taiwan (210X 297 male) -Ii -----------_ 1T ------ IP (Please read the precautions on the back before filling this page) 492988 ΑΊ Β7 V. Description of the invention (Polymer with processability. In addition, the PAS resin of component (A) is the straight PAS (31010, viscosity of 10 ~ 300Pa's at a shear rate of UOOsec · 1) as above Body, head. Portion (1 ~ 30 weight:!:, Preferably 2 ~ 25 weight: U is higher (300 ~ 3000Pa's), preferably 500 ~ 200Pa's), or a mixture of branched or crosslinked PAS resin is also applicable. And the purpose is that after polymerization, the PAS resin used in the present invention is subjected to acid cleaning and hot water. Deionization treatments such as washing, organic solvent washing (or a combination thereof), etc. remove byproduct impurities, so that the chlorine content and the alkali metal content are each 500 ppmM, preferably 300ρρηιM. Second, this The average fiber diameter (short diameter) of the acicular portion of the zinc oxide whisker used in the component (B) of the invention measured by a microscope method is 0.1 to 5 μm, and the average fiber length (long diameter) is 2 to 100 / iin. The average aspect ratio is preferably 5 M. The commercially available zinc oxide is a three-dimensional tetragonal shape. The whisker with the above shape is a suitable compound, but it is not limited by this.事 太 # is 10, which is the best for the right amount, and the weight is _) 3 (Β 二 解 05 上 ο The weight of the sulphur-based aromatic polymer of the tree is as high as ο The weight is heavy ο Central Bureau of Standards, Ministry of Economic Affairs Printed by Employee Consumer Cooperative

The effect of E (combination, inhibition, and discoloration) can be used to reduce the weight of the aging effect. The amount of anti-corrosive 3-corrosion super-corrosion is the same as that of foreign gold. It is the least WEK alkyl oxygen ring when it is filled. Μ The surface of the whisker is prepared in advance. The composition of the zinc oxide and oxygen machine is the same as the phase} (B holds the guarantee, when the external machine is separated into a neutral machine and the machine is dispersed, it is divided into 1 alkane, silicon base. Oxyalkane silyl oxocycloalkane. Gigadamine is better than or equal to ^ mesh \, and the basic oxygen species holding alkane to protect silicon. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 male f) 492988 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Λ 7 _____—— —] V. Description of the Invention (r) Any one of the silane compounds with more than one alkoxy group and 2 or 3 alkane groups All are effective, such as y-cyclopropoxypropyltrimethoxysilicone, y-glycidoxypropyltriethoxysilane, etc. Aminoalkoxysilicone has 1 値 or more in one molecule Amine compounds with 2 or 3 hydrazone oxygen are effective, for example, y-aminopropyltrimethoxysilicon, y ~ Fluorenylpropyltriethoxysilane, aminoethyl) ~ y-aminopropyltrimethoxysilane, etc. The amount of these oxaloxaroxanes is based on the zinc gasification of the component (B) In terms of whiskers, 0.05 to 5 weight χ is preferred. When phosphoric acid or hypophosphorous acid or a salt thereof as the component (C) is further added in the present invention, the long-term humidity and heat resistance can be improved, so it is assumed that (C) Phosphoric acid or hypophosphorous acid or salts thereof used herein are, for example, at least one or two or more spikes selected from the group consisting of phosphoric acid hypophosphate, calcium phosphate sodium phosphate, zinc hypophosphite hypophosphite, Sodium hypophosphite and other salts of zinc, osmium metal, or soil test gold, preferably, calcium hypophosphite, 1 phosphonium hypophosphite, and zinc hypophosphite 81. The compounding amount of the component (C) to parts by weight U) The sulfuric acid-based resin is 0.05 to 2 parts by weight, and more preferably 0.1 to 1 part by weight. _When the amount is too small, the long-term humidity and heat resistance 6¾¾S effect cannot be obtained. When the amount is too large, gas contained in the molding is generated, so it is not desirable. H & $ ± $ (e) The component coexists with the (B) component, which will not unexpectedly hinder the anti-corrosive effect on metals and the pollution resistance when Λ $ is used. ^ 1 Know both The interaction can improve long-term humidity and heat resistance. In particular, the direct combination of (c) ingredients is still effective, but part of this paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)-Install · ,-mouth

-AW 492988 B1 V. Description of the invention (b) or all inorganic or organic filler materials with 箸 (D) components, so that the method of mixing with other components is also effective. There is no particular limitation on the method for attaching the component (C). For example, a solution containing a scissor compound is sprayed on the filling material to be adhered, or when glass fiber is used, the scissor solution can be applied to the fiber by a stick coating method. To attach. In addition, it can be treated together with epoxy resin, urethane resin stripping agent, or coupling agent such as amine silane, epoxy silane, etc. as a surface treatment agent for glass fibers. The inorganic or organic filling material of the component (D) used in the present invention is not an essential component, but is used to obtain a molded product having excellent properties such as mechanical strength, heat resistance, dimensional stability (concave and convexity, deformation), and electrical properties. It is better to cooperate, these can use fibrous, powder, or plate-like filling materials or their mixtures depending on their purpose. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out) (This page) Examples of fibrous fillers include glass fibers, long and short diameter fibers, sulfonic fibers, silica fibers, silica, alumina fibers, chromium fibers, boron nitride fibers, silicon nitride fibers, boron fibers, and phthalic acid. In addition to potassium acid fibers, there are inorganic fibrous substances such as stainless steel pins, fibrous objects such as aluminum, titanium, copper, and brass. Particularly typical fibrous fillers are glass fibers, sulfon fibers, or potassium phthalate fibers. In addition, organic fibrous materials such as aromatic polyamines, acrylic resins, and fluororesins can also be used. In addition, powdery fillers include, for example, black, black lead, silicon dioxide, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite. Silicate, iron oxide, oxygen-8. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 492988 Printed by the Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives A7 B7 5. Invention Description (7) Metal oxides of titanium and alumina, such as metal carbonates of calcium carbonate and magnesium carbonate, such as metal sulfates of calcium sulfate and barium sulfate, and other metal powders such as sulfonated silicon and silicon nitride. Typical examples are carbon black, silicon dioxide, glass beads or glass powder, calcium carbonate, talc, and the like. Examples of the plate-shaped filler include mica, glass flakes, and various metal foils. These filler materials may be used in combination of one or two kinds of M. When a fibrous filler (especially glass fiber or carbon fiber) is used in combination with a powdery or plate-shaped filler, it can have both mechanical strength and dimensional accuracy, electrical properties, etc., which is a better combination. In addition, when using these fillers, a bundler or a surface-treated surface is applied to the M surface-treating agent or bundled as necessary. Examples of the treatment agent include functional compounds such as epoxy-based compounds, isocyanate-based compounds, silane-based compounds, and phthalate-based compounds. The compounding amount of the upper (D) component is 1 to 75% by weight, and more preferably 3 to 70% by weight, based on the total composition. If it is too much, in addition to the difficulty of forming operation, the mechanical strength of the formed product will also be a problem. In addition, the molded article composition used in the present invention is a conventional substance added to a thermoplastic resin, that is, a stabilizer such as an antioxidant or an ultraviolet absorber, a flame retardant, a dye, a pigment, and the like, a lubricant, and a crystal. A chemical accelerator, a crystallization nucleating agent, etc. may be appropriately added depending on the required performance. The preparation of the resin composition of the present invention can be performed by the equipment and method used in the preparation of the general synthetic resin composition. Generally speaking, it is necessary to mix -9-This paper size is applicable to the Chinese National Standard (CNS) Α4 Regulation 彳 210X29? Public dark) Please read the notes on the back d • Fill in the items. Packing-: Write this page 、 11 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 492988 Λ '. _ H?---— &Quot; 1 Ⅰ. 一 ·-—— ——— 一 — 一 岛 ―' · ， ——- -———— — Five (#) copies of the invention description, and melt-kneaded using a 1-axis or 2-axis extruder, and scooped out into pellets for forming. In addition, in the process of melting and extruding the resin component, it is better to add and mix inorganic components such as glass fiber. 〇 The material pellets thus obtained can be used for injection molding, extrusion molding, hollow molding, compression molding, etc. The conventional thermoplastic resin molding method is used for molding, and the best method is injection molding. Examples The present invention is specifically described in the following examples and comparative examples, but the present invention is not limited thereto. Examples 1 to 14 and Comparative Examples 1 to 10 100 parts by weight (A) of a substantially linear polyphenylene sulfide resin (manufactured by Wu Yu Chemical Industry Co., Ltd., "KPS", viscosity 50? &Amp;, (3 10 ° € :, 120086 (1-1), add the component (B) shown in Table 1 ~ 2 and mix with a manual mixer for 20 minutes ^ additional addition The components (C) and (D) in the amounts shown in Tables 1 to 2 were mixed in a mixer for 30 seconds. They were kneaded with an extruder with a cylinder temperature of 31 () ° C to make polyphenylene sulfide. The pellets of the resin composition were determined to have the metal's corrosiveness, mechanical specificity, and long-term humidity and heat resistance. The results are shown in Tables 1 to 2. Example 1 5 Except for the use of (!)) Components, For glass fibers, a solution of a (C) calcium hypophosphite solution dissolved in a solvent in the proportion shown in Table 2 is applied, and once it is fully dried and pre-attached, the rest are prepared under the same conditions as in the above examples. And evaluate the results. The results are shown in Table 2. -1 0-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling this page)

492988 A7 B7 V. Description of the invention (9) Moreover, the evaluation method is as follows. [Corrosion resistance] Add 4g pellets on the bottom of the test tube with an inner diameter of 18raa and a height of 160inffl, and hang a test piece (SKD-11) of iron, chromium and carbon as the main component at a predetermined position ( 15X 16〇x. After plugging the upper part of the test tube and heating it at 320 ° C for 3 hours, the test piece was taken out, and the corrosion state was observed by visual inspection and a microscope, and the relative grade of the following 视 was classified according to the corrosion state.

ABCDE (Read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Corrosive, Low Corrosive [Tensile Strength] K injection molding machine, at a cylinder temperature of 320 ¾, mold temperature The tensile test piece was formed at 150 t !, and the test piece was measured for tensile strength and elongation according to AS TM D-6 38. [Long-term Moisture and Heat Resistance] Μ injection molding machine, forming a tensile test piece at a cylinder temperature of 320Π and a mold temperature of 150¾, and processing the test piece in hot water at 95 < c for 500 hours, according to ASTM D -638 was used as a reference to measure tensile strength. -11-

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、 1T _12_ This paper size is applicable to Chinese national standard (€?) 8 size 4 (210 '/ 297 gong) 492988 kl B7 V. Description of the invention (U) Printed by the Central Standards Bureau of the Ministry of Standards and Consumer Affairs Cooperative! CJ1 ΓΤ s 1 I rr draw nr 1 rr 1 rr S snow rr 21 1 m 1 rr surface rr snow 5 1 8 ϊ 8 Y 8 8 8 § f— 8: 8 8 § § IB S | 8 Is 1 Ϊ 1 S5, ? fO is > 8 ω 8 jj s country cx? 1 cin T 1 1 I a logic s I i δ 1 OS 1 o hr O In O In 丨 ⑺ O in ο bi 1 IMl division i £ £ 1 1 1 1 1 I ; 1 1 1 1 1 Bianjia; e I 〇Ιο 1 1 1 1 1 1 1 1 1 1 1 1 1 m 1 1 | 1 S up to Iw II 1 雠 1 1 haze w 1 m 1 a ί Xinjiang; IS 'Contains δ § Volume UmH _ I o CR3 1 -..... σσ > zt > > D > ra 1 igi Hk 2 特 j ί— 2 zsf sincere — CO «D CO • Private — -1 1 HA k 'H-Jk 〇〇— CO 3 ►—A — ss δ ΟΟ! I 8 ill esil < 5iS m (Please read the precautions on the back before filling this page) -13- This paper size applies to Chinese national standards (CNS) A4 specification (210X29? F) 492988 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 ΙΓ 5. Description of the invention (^) Note:

(A) PPS

(A_l): PPS (B) corrosion inhibitor (B-1) manufactured by Panasonic, manufactured by Panasonic Amtic, zinc oxide whiskers (epoxysilane-treated), average fiber diameter (short diameter) ) = 0 · 3 # β, average fiber length (long diameter) = 4 // m (B-2) manufactured by Panasonic Amtic (transliteration) company, vaporized zinc whiskers (aminosilane treatment), average fiber Diameter (short diameter) = 0.3 Affi, average fiber length (long diameter) = 4 // 51 (B-3) made by Panasonic Amtic (Zincin), zinc oxide whisker (untreated), average fiber Diameter (short diameter) = 0.3 // β, average fiber length (long diameter (B-4) manufactured by Sanwa Metal Mining Co., gasification zinc (dry method), average particle size = 0 · 7 # 班 (B -5) Jie chemical company, zinc chloride (dry method), average particle size = 0.07 // si (B-6) Jie chemical company, zinc oxide (wet method), average particle size = 0.02 // in (C) Ingredient (C-1) Calcium hypophosphite. -14- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 cm) p pack— 丨 (Please read the precautions on the back before filling this page ) Order

Claims (1)

i. Announcement VI. The scope of the patent application No. 8 7 1 1 6 〇 8 9 "Polyaryl sulfide resin composition" is prepared (91 VI. The scope of patent application: Amendment 丨 February 5th, repair, j— .._. Ί A polyaryl sulfide resin composition containing 100 parts by weight of (A) polyaryl sulfide resin and 0.0 5 to 3 parts by weight of (B) zinc oxide whiskers. It is characterized in that (A) the polyaryl sulfide resin is deionized after polymerization, and the chlorine content and the alkali metal content are each 500 ppm or less; (B) the average fiber diameter (short diameter) of the needle-like portion of the zinc oxide whisker of the component ) Is 0 · 1 ~ 5 // m, the average fiber length (long diameter) is 2 ~ 100 // m, and the average aspect ratio is 5 or more. (B) The surface of the zinc oxide whisker of the component is at least 1 in advance. The species is selected from the group consisting of epoxidized alkoxysilane and amine alkoxysilane treatment. 2. The composition according to item 1 of the scope of patent application, wherein for 100 parts by weight of (A) polyarylsulfide resin In addition, it contains 0.05 ~ 2 parts by weight of (C) at least one selected from the group consisting of phosphoric acid, hypophosphorous acid, and the like. 3. The composition according to item 2 of the scope of patent application, wherein (C) is It is hypophosphite. 4. The composition according to item 1 or 2 of the scope of patent application, wherein (D) component which additionally contains 1 to 75% by weight (for the total amount of the composition) is selected from the component (B) Inorganic or organic filler materials made of fibrous filler materials, powdery filler materials, plate-shaped filler materials, and mixtures thereof. 5. The composition according to item 4 of the scope of patent application, which contains 3 ~ 70% by weight of the component (D) is glass fiber or carbon fiber.