KR20000029411A - Polypenylene sulfide resin composite material - Google Patents

Abstract

PURPOSE: Polyphenylene sulfide(PPS) resin complex material is given to provide a proper process ability, mechanical strength and dimension exactness, as well as a removement or minimization of the glitter caused by any processing. CONSTITUTION: A material is characterized by composing of (A) 100 part by weight of resin complex material of 60 to 95wt% of PPS resin and 40 to 5wt% of polyphenylene ether(PPE) resin; (B) 0.3 to 5 part by weight of epoxy silane compound; (C) fibrous filler, inorganic filler or a mixture thereof. The PPS resin complex material includes preferably PPS resin having 300 to 3000 poise of melting viscosity and PPE resin having 500 to 50000 poise of melt viscosity, at 500sec-1 of shear velocity and 300°C. The PPS resin includes 70% or more of a structural unit represented by the formula 1. The PPE resin is a homopolymer having a repeated structural unit represented by the formula 2.

Description

Polyphenylene sulfide resin composite material {POLYPENYLENE SULFIDE RESIN COMPOSITE MATERIAL}

The present invention relates to a polyphenylene sulfide resin composite material having suitable processability such as injection molding, no flash phenomenon occurring during the molding process, or minimal and excellent mechanical strength and heat resistance.

Diecst metals such as aluminum and zinc have been used in precision parts such as optical parts, electronic and electrical parts, and automotive parts. However, the recent rise in product prices due to processes involving dimensional precision and fixed form has led to the replacement of these metal parts with thermoplastics, mainly reinforced plastics. Some of the more complex forms can be mass-produced by injection molding, which reduces production costs. In addition, a plurality of parts can be unified, so that the total number of parts can be reduced. Among many thermoplastic resins having excellent heat resistance, dimensional stability, chemical resistance, flame retardancy and processability, polyphenylene sulfide resin (PPS) is a suitable resin for use in such a case. If extreme strength or dimensional stability is required, the PPS is filled with high concentrations of fibrous, granular or plate-shaped inorganic fillers.

PPS has a disadvantage in that glare occurs during the molding process. The reason for this is that the shear rate dependence of the PPS melt viscosity is very small, which can be traced to the fact that the melt viscosity is very low, such as the edge of the cavity, or in the micro voids of the mold where the shear rate of the resin is low. A common method of removing glare from molded PPS is to include a blasting process, such as blasting small nylon beads at high speed. The cost increase associated with this cannot be ignored. Molding processes combined with metal foils in order to reduce the additional cost of parts are a recent trend that has been actively pursued. Therefore, it is necessary to avoid the blasting process, or to eliminate or at least minimize the generation of PPS flashes in order to remove the damage done to the metal foil.

Many methods have been studied to minimize PPS flashes. For example, polyamide is added, or liquid crystal polymers or special polyester compounds are added to improve the flowability of the PPS. However, this is not enough to reduce the occurrence of glare and significantly reduce the strength of the material. In particular, the addition of polyamides poses a significant problem, in which case the material's water absorption capacity is increased and PPS dimensional stability is lost. Another proposal is a composite with polyphenylene ether (PPE) added. By adding PPE, it is possible to reduce glare, but a large amount of PPE is required to significantly reduce or eliminate glare generation, thus significantly reducing the processability and mechanical strength of the material.

The present invention relates to a PPS resin composite material having a moderate processability and mechanical strength and dimensional precision while minimizing the flash shape generated in the PPS molding process. This kind of resin composite material can be used in electrical and electronic precision components such as connectors or electrical sealing components, or optical components such as light pick up.

The present invention provides a PPS resin composite material which has excellent processability, strength and dimensional stability while eliminating or minimizing the generation of flash after processing. The present invention (a) 100 parts by weight of a resin composite material consisting of 60 to 95% by weight of polyphenylene sulfide resin and 5 to 40% by weight of polyphenylene ether resin, (B) 0.3 to 5 parts by weight of epoxy silane compound, and ( C) Polyphenylene sulfide resin composite material comprising 10 to 400 parts by weight of fibrous fillers, inorganic fillers, or mixtures thereof.

The present invention also provides 100 parts by weight of a resin composite material consisting of (A) 60 to 95% by weight of polyphenylene sulfide resin and 5 to 40% by weight of polyphenylene ether resin, (B) 0.3 to 5 parts by weight of epoxy silane compound, (C) 10 to 400 parts by weight of a fibrous filler, an inorganic filler or a mixture of the two, and (D) kaolin having an average particle diameter of 0.05 to 0.5 µm and attapulgite having an average particle diameter of 0.02 to 0.2 µm, or a combination thereof It provides a polyphenylene sulfide resin composite material consisting of 10 to 150 parts by weight of the mixture.

The preferred polyphenylene sulfide resin composite material is from 300 ℃, the shear rate at 500sec ^-1, a melt viscosity of 300 to 3000 and a polyphenylene sulfide resin having a poise, 300 ℃, shear rate 500sec ^-1 at a melt viscosity of 500 to 50,000 poise It is to include a polyphenylene ether resin having.

Among the more desirable the resin composite material is from between 290 and 350 ℃ ℃, and a shear rate of 6000sec ^-1, a melt viscosity of 2000 poise or less, a shear rate of 20sec ^-1 and 6000sec ^-1, the melt viscosity ratio is not less than 10.

The present invention is a PPS resin containing 70% or more of the structural unit represented by the following formula (1).

No more than 70 mole percent of the unit structure can produce composites of significant properties. Suitable polymerization methods of PPS resins require sodium sulfide and p-dichlorobenzene to be reacted in N-methylpyrrolidone, a sulfone solvent such as sulfolane, or an amide solvent such as dimethylacetoamide. The degree of polymerization is controlled by addition of alkali metal salts of alkali acids such as carboxylic acids or sulfonic acids and alkali hydroxides, alkali metal carbonates and alkaline earth metal oxides. Compounds such as meta-phenylene sulfide, ortho-phenylene sulfide, phenylene sulfide ether, phenylene sulfide sulfone, biphenyl sulfide, and substituted phenylene may contain up to 30 mol%, preferably up to 10 mol% of the structural units. It may be included as a copolymerization component, where the substituents may be substituted with alkyl, nitro, phenyl, alkoxy and carboxylic acid groups, or metal salt groups of carboxylic acids.

PPS resins are generally used after adjusting the melt viscosity by thermal bridge formation in the presence of oxygen at 200 to 250 ° C. A suitable melt viscosity of the PPS of the present invention is 300 to 3000 poise at a temperature of 300 ° C. and a shear rate of 500 sec ⁻¹ , but preferably 600 to 2500 poise. If the melt viscosity is less than 300 poises, it causes the occurrence of glare, and if the melt viscosity is larger than 3000 poises, workability is significantly reduced. Therefore, it is preferable to use a filler having a relatively low viscosity, considering that workability and mold formation are excluded when mixing a high concentration of filler within the above range.

The PPE resin used in the present invention is a hoco polymer having a repeating unit represented by the following Chemical Formula 2, wherein at least one of R1 and R2 is a straight chain or a primary or secondary branched chain, and has an alkyl group, allyl group, and halogen having 1 to 4 carbon atoms. Atom or hydrogen atom.

The PPE resin is the same as or different from each other, and a copolymer consisting of the repeating unit of Formula 2 and the repeating unit of Formula 3 below, wherein in Formula 3, R3, R4, R5, and R6 are straight chain, primary, or secondary It is a branched chain, and is an alkyl group, an allyl group, a halogen atom, or a hydrogen atom having 1 to 4 carbon atoms. The compounds are the same or different from each other, provided that R3 and R4 in formula (3) may not be hydrogen supported at the same time, or are graft copolymers polymerized with styrene into the homopolymer or copolymer.

Examples of homopolymer PPEs include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl -1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) Ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6 -Chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxymethyl-1,4-phenylene) ether and poly (2-methyl-6-chloroethyl-1,4-phenylene ) Ether.

PPE copolymers include polyethylene ether copolymers, which are mainly o-cresols, polyphenylene ether structures copolymerized with phenols substituted with alkyl groups, such as 2,3,6-trimethylphenol, and represented by the following formula (4): It includes. R3, R4, R5, and R6 of Formula 4 have the same definition as in Formula 3 above.

The preferred melt viscosity of the PPE used in the present invention is 5000 to 50,000 poise at 300 ° C. and shear rate 500 sec ⁻¹ , more preferably 10,000 to 30,000 poise. At 5000 poise or less, the effect of flash reduction is very small, and when it is larger than 50,000 poise, workability is reduced.

Preferred composition ratios of the copolymers are 60 to 95% by weight PPS and 40 to 5% by weight PPE. More preferred composition ratios are 70 to 95% by weight of PPS and 30 to 10% by weight of PPE. The glare reduction effect is negligibly small when the weight ratio of PPE is less than 5, and the workability and the rP strength are reduced when the PPE weight ratio is greater than 40.

Epoxysilane compounds used in the present invention are needed to improve mechanical strength and reduced glare. γ-glycidoxypropyltrimethoxysilane is most preferred over other of the epoxysilane compounds. The amount of the epoxy silane compound is 0.3 to 5 parts by weight, more preferably 0.5 to 3 parts by weight based on 100 parts by weight of the resin composite material composed of PPS and PPE. If it is less than 0.3 part by weight, the mechanical strength or the flashing phenomenon are not reduced, and if it is larger than 5, the workability will be reduced.

Kaolin used in the present invention is a fine white clay inorganic material, generally represented by 2SiO ₂ · Al ₂ O ₃ · 2H ₂ O, an average particle diameter of 0.05 to 0.5㎛, preferably 0.1 to 0.4㎛. If the average particle diameter is less than 0.05 mu m, it will cause a problem of mold formation, and if the average particle radius is larger than 0.5 mu m, the flash reduction effect will be small.

Aterpulzite used in the present invention is a very fine needle-shaped filler, generally represented by Si ₈ O ₂₀ Mg ₅ (OH ₂ ) (OH ₂ ) 4H ₂ O, the average particle diameter is 0.02 to 0.2 ㎛, preferably Is 0.05 to 0.1 mu m. If the average particle diameter is less than 0.02 mu m, a problem of casting is caused, and if the average particle diameter is larger than 0.2 mu m, the glare reduction effect is reduced.

Kaolin and attapulgite can be used individually or together. With respect to 100 parts by weight of the resin composite material including PPS and PPE resin, the mixing amount of kaolin and / or attapulgite is 10 to 150 parts by weight, preferably 20 to 130 parts by weight. If it is less than 10 parts by weight, there is no effect of reducing glare, and if it is 150 parts by weight or more, the moldability will be lowered. If smoothness of the resulting material is required, it is better to use kaolin separately.

The fibrous fillers used in the present invention are glass, carbon, asbestos, silica, silica-aluminum, aluminum, zirconia, boron nitride, boron, silicon nitride, or titanic acid in addition to fibers of metals such as stainless steel, aluminum, titanium, copper or brass. It is an inorganic fiber material containing calcium fiber. Other inorganic fillers include carbon black, silica, quartz powder, glass beads, glass powder, glass flakes, calcium silicate, aluminum silicate, talc, clay, mica, diatomaceous earth, wollastonite silicate, iron oxide, titanium oxide, zinc oxide, (like aluminum) Metal oxides, calcium carbonate, metal carbonates (such as magnesium), calcium sulfate, metal sulfates (such as barium), as well as metal powders such as silicon carbonate, silicon nitride and boron nitride. Multiple fillers can be used simultaneously. In addition, it is preferable to use a surface treatment compound to improve the particle surface. Examples of the surface treating agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds and titanate compounds. The surface of the filler can be treated with these compounds before use, and these compounds can be added directly to the mixture when the materials are mixed. The blending amount of the filler with respect to 100 parts by weight of the material (A) is 10 to 400 parts by weight, preferably 50 to 300 parts by weight. If it is less than 10 parts by weight, it has an insufficient effect in many respects, and if it is 400 or more, workability will decrease.

The composite materials of the present invention are generally plastic resins which can be heated or known substances which are added to thermosetting resins, for example stabilizers (for example antioxidants and ultraviolet absorbers), antistatic agents, flame retardants or colorants such as pigments or pigments. And lubricants added on demand.

The processing method of the composite material of the present invention has no requirements. For example, an appropriate proportion of the mixture is mixed in a blender or a mixer and then melted, kneaded and pelletized in an extruder. A predetermined amount of fiberglass is fed through the side feeder prior to the kneading and pelleting process. The resulting pellet molding material is subjected to mold apparatuses such as thermoplastic mold apparatuses, injection molding apparatuses, injection press molding apparatuses and the like, which are widely used for molding into desired shapes.

Preferred PPS resin composite materials of the present invention have a melt viscosity of less than 2000 poise at a shear rate of 6000 sec ⁻¹ at 290 to 350 ° C., and a melt viscosity ratio of at least 10 at shear rates of 6000 sec ⁻¹ and 20 sec ⁻¹ . This effectively reduces the occurrence of glare during the injection molding process. It is desirable to have high fluidity at high shear rates immediately after injection, or to have low fluidity at low shear rates, when touching the mold edges. Therefore, the greater the melt viscosity ratio between high and lower shear rates, and the lower the melt viscosity at high shear rates, the less glare generation. Typical PPS molding temperature of 290 ℃ and 350 ℃ between the shear rate melt viscosity of 2000 poise or less at 6000sec ^-1 help, 6000sec ^-1 of shear rate of 20sec ^-1, and when the melt viscosity ratio is 10 or more, the glare generated decreases effectively.

Example

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Next, each component used for the Example and comparative example of this invention is shown.

PPS Resin (PPS-1): Toplain Company Limited

LV-3, Melt Viscosity 1000 Poise (300 ° C, 500sec-1)

PPS Resin (PPS-2): Topplane Company Limited

T-1, Melt Viscosity 300 Poise (300 ° C, 500sec-1)

PPE resin (PPE): Melt viscosity 18000 poise (300 ℃, 500sec-1)

Silane Compound: γ-Glycidoxypropyltrimethoxysilane

Nippon Unicar Company Limited

A-187

Kaolin: Angelhard (US) Company

ASP200 average particle diameter 0.4㎛

Etherpulgite: Angel Hard (USA) Company

ATTAGEL # 50 average particle size 0.1㎛

Fiberglass: Nippon Plate Glass Company Limited

Company Limited) Product Name RES03-TP29

Calcium Carbonate: Shiraishi Calcium Company Limited

Whiten P-30

The components are mixed in the compositions described in Tables 1-6 below, followed by melting and kneading using a dual shaft kneader to pelletize. The molded material was dehumidified at 140 ° C. for 5 hours. The test model was manufactured at an injection molding machine (Toshiba Machine, IS80EPN) at a cylinder temperature of 300 ° C., an injection pressure of 1200 kg / cm 2, an intermediate injection speed, and a molding temperature of 140 ° C. Each model is tested for tensile strength, tensile elongation, bending strength, bending modulus, Izod impact strength and molding shrinkage by ASTM test method.

The flash characteristics are evaluated by measuring the length of the flashes generated at the gaps (length 5 mm, depth 20 µm) generated around the pupil when molding each material at the minimum molding filling speed. In addition, the melt viscosity of each material is measured by capturography (Capirography, Toyo Seiki, 310 ° C., shear rate 20 and 6000 sec ⁻¹ ).

These results are shown in Tables 1-6. The melt viscosity ratio of the table is the ratio of melt viscosity measured at a shear rate of 20sec ^-1 and 6000sec ^-1.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PPS-1PPE Silane Compound Glass Fiber 85150.565 85151.065 85151.565 85152.065 85153.065 60403.065 Tensile Strength (MPa) 148 155 157 166 171 158 Tensile Elongation (%) 1.75 1.8 1.85 2.0 2.2 2.1 Bending strength (MPa) 191 195 215 210 230 200 Izod impact strength (J / m) 99 100 113 125 128 118 Mold Shrinkage (%) MDTD 0.220.55 0.220.55 0.200.55 0.200.55 0.200.55 0.200.50 Flash length (㎛) 40 30 20 10 0 0 Melt viscosity, 300 ℃ 20sec ^-1 6000sec ^-1 210001380 225001400 263001550 286001580 361001630 454001890 Melt viscosity ratio 15.2 16.0 16.9 18.1 22.1 24.0

Example 7 Example 8 PPS-1PPE Silane Compound Glass Fiber 90103.065 9553.065 Tensile Strength (MPa) 170 175 Tensile Elongation (%) 2.2 2.2 Bending strength (MPa) 220 235 Izod impact strength (J / m) 139 141 Mold Shrinkage (%) MDTD 0.220.51 0.220.52 Flash length (㎛) 30 30 Melt viscosity, 300 ℃ 20sec ^-1 6000sec ^-1 258001620 246001280 Melt viscosity ratio 15.9 19.2

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PPS-1PPE Silane Compound Glass Fiber 10065 851565 703065 1003.065 50503.065 Tensile Strength (MPa) 120 110 98 156 136 Tensile Elongation (%) 1.1 1.2 1.0 2.2 1.6 Bending strength (MPa) 170 160 150 210 165 Izod impact strength (J / m) 98 92 88 146 89 Mold Shrinkage (%) MDTD 0.220.53 0.200.54 0.200.53 0.220.51 0.180.53 Flash length (㎛) 500 160 188 120 0 Melt viscosity, 300 ℃ 20sec ^-1 6000sec ^-1 103001680 150001700 163001750 176001880 630002200 Melt viscosity ratio 6.1 8.8 9.3 9.3 28.6

Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 PPS-2PPE Aterpulzite Silane Compound Fiberglass Calcium Carbonate 90103028570 90102028570 90101028570 90103018570 90103038570 80203028570 Bending strength (MPa) 158 160 162 157 163 150 Bending Factor (GPa) 16.7 17.0 17.4 16.0 15.7 13.5 Flash length (㎛) 25 30 35 40 10 10 Melt viscosity, 300 ℃ 20sec ^-1 6000sec ^-1 360001520 325001500 303001550 296001480 364001630 384001690 Melt viscosity ratio 23.7 21.7 19.5 20.0 22.3 22.7

Example 15 Example 16 Example 17 Example 18 PPS-2PPEAterpulzitekaolinsilane Compound Glass Fiber Calcium Carbonate 70303028570 90103028570 90102028570 90101028570 Bending strength (MPa) 158 158 157 150 Bending Factor (GPa) 16.7 16.7 16.0 15.7 Flash length (㎛) 5 10 25 30 Melt viscosity, 300 ℃ 20sec ^-1 6000sec ^-1 330001720 330001620 300001580 290001480 Melt viscosity ratio 19.2 20.4 19.0 19.6

Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 PPS-2PPE Kaolin Atterite Silane Compound Glass Fiber Calcium Carbonate 1008570 90108570 100308570 9010308570 10028570 50502528570 Bending strength (MPa) 160 157 160 160 160 100 Bending Factor (GPa) 15.7 15.5 16.0 16.7 16.7 11.0 Flash length (㎛) 500 150 180 100 100 0 Melt viscosity, 300 ℃ 20sec ^-1 6000sec ^-1 53001020 98001220 65001080 69001180 89001100 570002000 Melt viscosity ratio 5.2 8.0 6.0 5.8 8.1 28.5

The polyphenylene sulfide resin composite material according to the present invention has excellent processability, strength and dimensional stability, while eliminating or minimizing the occurrence of glare after processing.

Claims (11)

(A) 100 parts by weight of the resin composite material consisting of 60 to 95% by weight of polyphenylene sulfide resin and 40 to 5% by weight of ether resin of polyphenylene, (B) 0.3 to 5 parts by weight of epoxy silane compound, and (C) A polyphenylene sulfide resin composite material comprising a fibrous filler, an inorganic filler, or a mixture thereof (C). (A) 100 parts by weight of a resin composite material consisting of 60 to 95% by weight of polyphenylene sulfide resin and 40 to 5% by weight of ether resin of polyphenylene, (B) 0.3 to 5 parts by weight of epoxy silane compound, (C) fibrous 10 to 400 parts by weight of a filler, an inorganic filler, or a mixture thereof, and (D) kaolin having an average particle diameter of 0.05 to 0.5 µm, and attapulgite having an average particle diameter of 0.02 to 0.2 µm, or a mixture thereof 10 to 150 Polyphenylene sulfide resin composite material consisting of parts by weight. The polyphenylene sulfide resin composite material according to claim 1, wherein the polyphenylene sulfide resin has a melt viscosity of 300 to 3000 poise at 300 ° C. and a shear rate of 500 sec ⁻¹ . The polyphenylene sulfide resin composite material according to claim 1, wherein the polyphenylene ether resin produces a melt viscosity of 500 to 5000 poise at 300 ° C. and a shear rate of 500 sec ⁻¹ . 2. The polyphenylene sulfide resin composite material according to claim 1, wherein the polyphenylene sulfide resin composite material has a melt viscosity of not more than 2000 poise at a shear rate of 6000 sec ⁻¹ between 290 ° C. and 350 ° C., and a melting point between shear rates of 6000 sec ⁻¹ and 20 sec ⁻¹ . A polyphenylene sulfide resin composite material having a dobby of 10 or more. 3. The polyphenylene sulfide resin composite material according to claim 2, wherein the polyphenylene sulfide resin has a melt viscosity of 300 to 3000 poise at 300 ° C. and a shear rate of 500 sec ⁻¹ . 3. The polyphenylene sulfide resin composite material according to claim 2, wherein the polyphenylene ether resin has a melt viscosity of 500 to 50,000 poise at 300 ° C. and a shear rate of 500 sec ⁻¹ . The polyphenylene sulfide resin composite material according to claim 3, wherein the polyphenylene ether resin has a melt viscosity of 500 to 50,000 poise at 300 ° C and a shear rate of 500 sec ^-1 . The method of claim 2, wherein the polyphenylene sulfide resin in a composite material between 290 and 350 ℃ ℃, at a shear rate 6000sec ^-1, a melt viscosity of 2000 poise or less, between a shear rate of 20sec ^-1 and 6000sec ^-1, the melting point A polyphenylene sulfide resin composite material having a dobby of 10 or more. The method of claim 3 wherein the polyphenylene sulfide resin between composite material is 290 ℃ and 350 ℃, at a shear rate 6000sec ^-1, a melt viscosity of 2000 poise or less, the melt viscosity at a shear rate of between ^-1 and 6000sec ^-1 20sec ratio A polyphenylene sulfide resin composite material having 10 or more. The method of claim 4, wherein the polyphenylene sulfide resin in a composite material between 290 and 350 ℃ ℃, at a shear rate 6000sec ^-1, a melt viscosity of 2000 poise or less, between a shear rate of 20sec ^-1 and 6000sec ^-1, the melting point A polyphenylene sulfide resin composite material having a dobby of 10 or more.