WO1991011491A1

WO1991011491A1 - Polyarylene sulfide resin composition and preparation thereof

Info

Publication number: WO1991011491A1
Application number: PCT/JP1991/000120
Authority: WO
Inventors: Toshikatsu Nitoh; Toshifumi Nonaka
Original assignee: Polyplastics Co., Ltd.
Priority date: 1990-02-02
Filing date: 1991-01-31
Publication date: 1991-08-08
Also published as: JP2547266B2; JPH03229760A; KR920701365A

Abstract

A polyarylene sulfide resin composition which little causes acidic degradation and is excellent in the control of discoloration and in which a stabilizer can be utilized effectively, said composition comprising 100 parts by weight of a polyarylene sulfide resin and 5 to 400 parts by weight of an inorganic filler having a surface on which 0.01 to 2.5 wt %, based on the filler, of an organic stabilizer has been deposited.

Description

Description Polyarylene sulfide resin composition and preparation method thereof

[Industrial application field]-The present invention relates to a polyolefin sulfate resin composition having an inorganic filler and a method for preparing the same. More specifically, the present invention relates to a poly "lens sulfide resin composition which is less oxidatively degraded during the production of the composition, suppresses discoloration, has high whiteness, and has stable quality and moldability, and a method for preparing the same.

(Prior art).

Polyarylene sulfide (PAS) resin typified by polyphenylene sulfide (PPS) resin is often used as a composition containing an inorganic filler as a composition with excellent mechanical properties, high heat resistance, and heat resistance. chemical resistance, has a flame retardant, also processing productivity _and: in Aimatsu also cost Topafu O over Ma Nsu, in recent years, electric and electronic equipment parts materials and automotive parts material, as the chemical equipment unit product material, market needs Demand is growing because it is well suited to No

In the past, it was difficult to obtain molded products with high whiteness without discoloration, because PAS resin had been actively heated and reacted with oxygen during production to increase its viscosity. The polymerization method has made remarkable progress, and resins with high whiteness have been obtained at the end of polymerization. However, this resin composition is inherently susceptible to oxygen at high temperatures, and in the subsequent process of kneading and extruding with a filler, discoloration proceeds under the influence of heat and oxygen, resulting in low whiteness. At the same time, the change in hue remained a problem.

In addition, there are also problems such as decomposition of the added components during melt-kneading with the filler, which is generated as a gas, and adheres to a mold or the like during molding. In addition, in the electrical and electronic parts industry, which is one of the main demands for this resin, the use of surface mount technology (SMT) for mounting components on wiring boards for the purpose of miniaturizing equipment, streamlining production, and stabilizing. ) Has been developed, and in this process, severe heating is often required due to soldering at the time of component mounting, and under such processing conditions, suppression of discoloration and decomposition is particularly desired.

As a means to solve these problems, the addition of stabilizers such as antioxidants during polymerization or extrusion has been proposed in the past. Decomposition and discoloration are undesirable. Stabilizers proposed by the present inventors, such as Japanese Patent Application Nos. 1-164310 and 1-1644311, are relatively effective, but may not be sufficient.

(Disclosure of the present invention)

The present inventors have developed a method for maintaining excellent heat resistance, solvent resistance, flame retardancy, mechanical properties, and crystallinity of a PAS resin composition, particularly a PPS resin composition, and reducing gas generation during molding. In order to obtain a resin composition that suppresses discoloration, has little discoloration, has high whiteness, and has stable quality, intensive studies have been conducted. During this process, the inorganic filler brings in a large amount of oxygen (air) during the melt extrusion with the filler, and the filler may react at the interface where it comes into contact with the hot resin, causing discoloration. In addition, fillers such as glass fibers are generally treated with various organic surface treatment agents to increase the affinity (adhesion) with the resin, and various organic substances are used as a binder for handling and the like. Assuming that these deposits may decompose at high temperatures and cause problems such as discoloration due to aging, if stabilizers such as antioxidants are concentrated at the interface of the filler, We anticipate that the effect of preventing discoloration will be doubled.As a result of adding a stabilizer etc. to the surface of the filler and adding it, the amount of the added stabilizer will be lower than when adding the stabilizer directly to the blend material. Even if the amount is reduced, it has a sufficient stabilizing effect and remarkable discoloration The present invention was found to improve the generation of decomposed gas and thereby the generation of deposits on a molding die and the like, and to obtain a molded product having a high whiteness.

Puni Puta ο

That is, in the present invention, in the preparation of a composition in which an inorganic filler is blended with a polyolefin sulfide resin, an organic stabilizer is previously added to the surface of 100 to 100 parts by weight of the polyolefin sulfide resin. 5% by weight (对 inorganic filler) A method for preparing a polyarylene sulfide resin composition comprising 5 to 400 parts by weight of an inorganic filler adhered thereto, and a method for preparing the same. It relates to the obtained resin composition.

The base resin used in the composition of the present invention is mainly composed of a PAS resin, and is mainly composed of a repeating unit "(~ Ar-S) ~ (where Ar is an arylene group). Examples of the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p, diphenylene sulphone group, p, p, A biphenylene group, a p, p'-diphenylene ether group, a p, p, a diphenylenecarbonyl group, a naphthalene group, and the like can be used.

In this case, a polymer using the same repeating unit, that is, a homopolymer can be used among the arylene sulfide groups composed of the above-mentioned arylene group, and from the viewpoint of the processability of the composition, different types are used. Copolymers containing repeat units may be preferred.

As the homopolymer, those having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group are particularly preferably used.

As the copolymer, two or more different combinations of arylene sulfide groups composed of the above-mentioned arylene groups can be used. Among them, p-phenylene sulfide group and m-phenylene sulfide group are preferred. Or a combination containing a thio group. Among them, those containing 50 mol% or more, preferably 70 mol% or more of p-phenylene sulfide group are suitable in terms of physical properties such as heat resistance, moldability, and mechanical properties. . A copolymer containing 5 to 50 mol%, particularly 10 to 25 mol% of m-phenylene sulfide group is preferable as a copolymer. -In this case, those in which the repeating units of the components are contained in a block form (for example, those described in JP-A-61.14228) are more excellent in processability than those in a random form, and Excellent in heat resistance and mechanical properties, preferred Can be used well. -..

Among them, a polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly containing a bifunctional halogen aromatic compound can be particularly preferably used. -In addition to polymers having linear structures, polymers that partially form cross-linked structures by using a small amount of a cross-linking agent such as a polyaromatic compound having three or more halogen substituents during condensation polymerization are also used. It is also possible to use a polymer in which the linear polymer described above is heated at a high temperature in the presence of oxygen at a high temperature to increase the melt viscosity and thereby improve the formability. Kasori Borima that high-temperature heating is one 1. purpose of the present invention for coloring brown, high resin composition whiteness can not be obtained. _t However, the resin stabilization effect was some. Me, molding This is effective in obtaining a resin composition in which gas generation at the time, deposits on the mold and the like are reduced and physical properties are hardly reduced.

The melt viscosity (temperature 310, shear rate 1200 / sec) of the polyolefin resin as a base resin used in the present invention is 10 or more: preferably L0000 poise. Those having a melt viscosity in the range of 5000 vise are particularly preferred because of their excellent balance between mechanical properties and fluidity, and melt viscosity less than 10 vise is not preferred because of insufficient mechanical strength. However, when the melt viscosity exceeds 10,000 voids, it is not preferable because the flowability of the resin composition is poor at the time of injection molding and the molding operation becomes difficult. Further, as the base resin of the present invention, the resin is in a range not adversely affected. Other thermoplastic resin besides arylene sulfide resin ί It is also possible to use a small amount together.

Any other thermoplastic resin may be used as long as it is stable at high temperatures. For example, aromatic polyesters composed of aromatic dicarboxylic acids such as polyolefin (co) polymers, poly (ethylene terephthalate), polybutylene terephthalate and diols or oxycarboxylic acids, polyamide polymers, polyamides, etc. Examples thereof include carbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, and fluorine resin. These thermoplastic resins can be used as a mixture of two or more kinds.

As the inorganic filler used in the composition of the present invention, any filler generally used for thermoplastic resins can be used, and fibrous, granular, and plate-like fillers are used. .

Among them, fibrous fillers include glass fiber, aspect fiber, carbon fiber, silicon fiber, silica / alumina fiber, zirconium fiber, boron nitride fiber, silicon nitride fiber, boron fiber, Titanic acid fibers and inorganic and fibrous materials such as stainless steel, aluminum, titanium, copper, brass and other metal fibrous materials. Particularly typical fibrous fillers are glass fibers or carbon fibers. High melting point organic fibrous substances such as polyamides, fluororesins, and acrylic resins can also be used.

On the other hand, powdered particulate fillers include carbon black, silica, and quartz powder. Powder, glass beads, glass powder, calcium silicate, aluminum silicate, silicates such as kaolin, talc, clay, diatomaceous earth, wollastonite, iron oxide, titanium oxide, Oxides of metals such as zinc oxide and alumina, and carbonates of metals such as carbonated magnesium and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and other silicon carbide, silicon nitride and nitride Boron, various metal powders, and the like.

In addition, examples of the plate-like filler include my strength, glass flake, various metal foils, and the like.

These inorganic fillers can be used alone or in combination of two or more. The amount of the inorganic filler to be used is 5 to 400 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the polystyrene sulfide resin. If the amount is less than 5 parts by weight, the mechanical strength is not sufficient. If the amount is too large, molding work becomes difficult.

These fillers are preferably subjected to a surface treatment or a convergence treatment with a functional compound such as an epoxy compound, an isocyanate compound, a silane compound, a titanate compound or a polymer.

A feature of the present invention resides in that an organic stabilizer is previously attached to such an inorganic filler and added to the resin.

Organic stabilizers that adhere to the surface of inorganic fillers include phenolic, amine, zeolite, and linoleic organic compounds that are generally used to prevent the oxidation of resin and rubber. .

Among these, organic phosphorus-based stabilizers and phenolic antioxidants are particularly effective in suppressing discoloration and produce less gas during molding.]: Is preferred. ·

As the organic phosphorus-based stabilizer, for example, phosphite-based and phosphonite-based organic compounds described in Japanese Patent Application Nos. 11-164310 and 11-164431 are preferable. Triaryl phosphite, such as it, tri (nonyl phenyl), phosphite, etc., Jisteria J Lepenta erythritol disulfide, cyclic neopentente Tris-bis (2,4-di-tert-butylphenylene phosphite), G- (2,6-di-tert-butyl-14-methyl phenyl) Penta erythritol diphenyl phosphite Heat-resistant phosphites such as butyl ether, tetrakis (2,4-di-t-butylphenyl) —4,4-biphenylene phosphonite and other phosphonite compounds Etc. can be cited as a typical example. However, inorganic phosphorus-based compounds, such as hypophosphorous acid or salts thereof, have a low heat-resistant temperature and are easily decomposed, and the inclusions tend to affect the crystallinity of PAS and lower the crystallinity. Not good.

Further, as the phenol-based antioxidant, a series of phenol derivatives, which is generally referred to as hindered phenol, is effective. Among them, high heat resistant high molecular weight type compounds have a good balance between moldability and resin stabilization. Compounds of this type include, for example, pentaerythritol tetrakis [3- (3,5-di-t-butyl-14-hydroxy-4-phenyl) probionate] and triethylene glycol Le-bis [3- (3-t-butyl-1-5-methyl-1-4-hydroxyphenyl) propionate] is a typical example. In order to attach these organic stabilizers to the surface of the inorganic filler, a solution obtained by dissolving or dispersing the stabilizer in a solvent is spray-stirred and dispersed in an inorganic filler in a Henschel mixer _: After that, the method of evaporating the solvent, including the method of performing the sizing treatment and adhering to the sizing treatment, by adding a stabilizer to the sizing agent when the inorganic filler is collected, and the like. Any method can be applied as long as it can be uniformly attached to the surface of the filler, and the method is not limited to the method of attachment.

The amount of the stabilizer to be attached to the surface of the inorganic filler is preferably 0.01% to 2.5% by weight, and more preferably 0.02% to 1% by weight. The effect of the invention, such as improvement in whiteness, is not sufficient. If the effect is large, odor or gas is generated during processing, which is not preferable.

Further, the organic stabilizer of the present invention may be used as a mixture of two or more kinds.

The composition of the present invention further includes known substances generally added to thermoplastic resins and thermosetting resins, that is, coloring agents such as antistatic agents, flame retardants, dyes and pigments, lubricants and crystallization. Accelerators, crystal nucleating agents, etc. can also be added as appropriate according to the required performance.

The polyarylene sulfide resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. That is, necessary components can be mixed, kneaded using a single-screw or twin-screw extruder, and extruded into a pellet for a ^ -shape. The method in which the fat component is added in the middle of melting is less likely to damage the fibrous filler, and the effect of the present invention is sufficiently exhibited. It is. --As is clear from the above description and Examples, the PAS resin composition produced by the method of the present invention has little discoloration in processing such as extrusion and molding, and a molded article with high stability and whiteness can be obtained. In addition, the generation of gas during processing is small, the generation of deposits on the mold tends to be suppressed, and expensive stabilizers are used because they are effective even in a small amount compared to the usual method of using stabilizers. It also has the advantage of minimizing the rise in cost, and can be expected as a material for various functional components, especially electronic components assembled using surface-mount technology.

〔Example〕 '

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 15 and Comparative Examples 1 to 13

The commercially available organic stabilizers shown in Tables 1, 2, and 3 are included in sizing agents or binders and adhered to inorganic fillers, and sizing is performed as shown in Tables 1-3. Then, it was mixed with polyphenylene sulfide resin (Kureha Chemical Industry Co., Ltd., trade name "Photo KP") for 30 seconds in a blender. Next, this mixture was melt-kneaded with an extruder having a cylinder temperature of 310 * C to prepare a pellet of a polyolefin sulfide resin composition. .

Using this pellet, an ASTM test piece was molded using an injection molding machine at a cylinder temperature of 320 and a mold temperature of 150, and the tensile strength and tensile elongation were measured. In addition, the gas generated from the nozzle during extrusion and molding is used to remove the odor during molding. The degree of adhesion was determined from the surface state of the mold after repeated detection and detection by air and visual observation.

Also, under the same molding conditions, a flat plate of 80 mm X 80 cm X 3 mm is formed, and the hue (whiteness L value) of the flat plate is measured using a color difference meter Z-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. did. The results are shown in Tables 1, 2 and 3.

For comparison, when no stabilizer was present, the same test was carried out on pellets extruded by mixing the same amount of the same stabilizer with resin without adhering to the filler by the usual method. Was. Table 1 shows the results.

2 and 3 show.

Formed — 麵麵 Hi

So-called

Stabilizer

Polyfeneren jwili f & 10 m Pull 31? Length 3 Width sulphide resin Adhesive

Acknowledgment + addition) ⁺ change of state

隨麵翻翻麵〕翻翻%%%%%%%% 値値 L L 値% L L 値麵麵麵値麵 1.4 L

■ mum 100 power 'Rashuaiaha' one 70 Λ n 1

U. 丄 74.5 Almost none 丄 * 0

Column 3 100 Rasfipa 70 n U, j 76.2

Woman M 100 power 'Rasphino,' 70 Λ 11. n U 77.0 i iQ n • 1 丄, 7 ί

B Example 5 100 Forces 'Las Phino,' One n

70 (J.1 73.9 Almost none Almost none 丄 loin 1.0

Crane example 6.100 strength * Lasfino, '70 and U. 丄 73.1 1 7

m n 1

100 power 'Las Fino,' one n n

70 U U, 丄 73.2 丄 i ΰoΰ on 1 7

υ

n

Lord | J8 100, power 'Las Fino,' one 10 10n 1

U. 丄 71.4 t 0 c. U

t bell J 9 100; ga Rasuf Aino 200 Λ 0.1 75.1 1

丄 J r.Jr.Un 1 1

丄, 1

比蛟例 1 100 Power 'Lasphino,' one 70 63.9 small St small iy u 1 above. Ϋ́ R

Ratio 2 100 force 'Las Phino, '70 A 0.1 66.2 Fine 盘 Fine loon 1 0

Ratio 删 3 100 Glass fiber 70 Λ 1.0 73.8 Multi si Low 1750 1.6

Fig. 4 100 Glass fiber 70.A 0.005 66.5 Fine m Fine 1940 1.8

侧 5 100 Glass fiber 70 Λ 4,0 79.5

! 11 M 1520 1.4

Relative shelf 6 100 Force 'Rashuaja' 1 10 65.1 Fine Fine M • 830 5.2

Ratio f fine 7 100 Glass fino, '1 200 ■ 61,0 Small Fine 1550 1.1

Note: Λ; MARK PBP-8 made by Adeka Gas Co., Ltd. Distearyl pentaerythritol diphosphite

B; Adeka Gas Co. Thigh MARK PEP-36, di (2,6-tbutyl 4-methylphenyl) pentaerythritol diphosphite

C; Adeka gas belly MARK 2112, Tri (noyulphenyl) phosphite

D; Ciba gigineilgafos P-EPQ FF, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenephosphonite

*; GL% in each case

• P; Chino, 'Gygi-I®® Irganox 245, triethyleneglycol-> bis [3- (3-1-buty-5-methyl-4-hydroxyphenyl) propionate] *; Against

Composition white fe ^ gas continuous — energetic essence stabilizer

Polyphenylene 鹂, etc. 麵 Surface toughness, drawer width, Sulfide 11115 With surface IJ

(Amount of appreciation + addition)) Female changes

("Rare part" [translator%] broom%] threshold [kgf / cni] [%] 鵷 Example 14 100 Calcium carbonate 70 A 0.1 '77.0 Almost none Almost none 1150 2.4 Haze line 15 100 Talc 70 Λ 0.1 79.9 970 970 1.7-comparison 2 100 Calcium 70 6 0.1 68.2 fine fine 1150 2.4 · comparison 3, 100 talc 70 Λ 0.1 71.1 fine fine 960. 1.7 Note: Λ; T deca Gas ^ ® MARK PGP-8, distearyl pentaerythritol diphosphite

*;, The deviation is also flM%

Claims

Scope of Claims In preparing a composition in which an inorganic filler is blended with a polysulfide resin, 100 parts by weight of a polysulfide resin is added to an organic surface in advance. 0.01 to 2.5% by weight of a stabilizer (based on inorganic filler) 5 to 400 'parts by weight of an inorganic filler to which a stabilizing agent is applied is used. Preparation method.

2. The method for preparing a polyarylene sulfide resin composition according to claim 1, wherein the organic stabilizer is a phosphite-based and Ζ- or phosphonite-based organic compound.

2. The method for preparing a polyarylene sulfide resin composition according to claim 1, wherein the organic stabilizer is a phenolic antioxidant.

The method for preparing a polyethylene sulfide resin composition according to claim 6, wherein the inorganic filler is glass fiber.

A resin composition obtained by the preparation method according to claim 1.