JPS608359A - Polyphenylene sulfide resin composition having improved whiteness - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent color tone, and high mechanical strength and productivity, and capable of giving clear white color and various other colors easily, by compounding a specific uncrosslinked PPS with an epoxy resin, a white pigment and a reinforcing material. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.wt. of an uncrosslinked polyphenylene sulfide resin (PPS) having a melt flow rate of >=20g/10min according to ASTM D-1238 using an orifice of 2.09mm. diameter and 31.74mm. length at 315.6 deg.C under 345g load with (B) 0.1-30pts.wt., preferably 1-25pts.wt. of an epoxy resin, (C) 0.1-150pts.wt., preferably 1-120 pts.wt. of a white pigment, and (D) 5-150pts.wt., preferably 10-120pts.wt. of a reinforcing material. The component B is e.g. bisphenol A glycidyl ether, etc., and the component C is e.g. titanium oxide, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition, and particularly to a resin composition that has improved color tone and mechanical strength, and also has good productivity during manufacturing.

Polyphenylene sulfide resin (hereinafter referred to as PPS)
is a resin with extremely good heat resistance, chemical resistance, flame retardancy, and mechanical strength, but generally linear PPS is thermally crosslinked with air to make it partially three-dimensional. . Such resins are originally pale yellow in color during heat treatment in the thermal crosslinking process.
It is a molding material that is extremely difficult to whiten and adjust to various colors because PS changes color and a mixture obtained by uniformly kneading various reinforcing materials has the same color tone. That is, although white pigments such as titanium oxide, zinc sulfide, etc. are blended into crosslinked pps, even if the white pigments are added to the extent that the physical properties do not deteriorate, satisfactory whiteness cannot be obtained, and of course, a large amount of white pigments cannot be obtained. Addition of a white pigment causes a decrease in physical properties, especially a decrease in mechanical strength, making it difficult to call it a practical engineering plastic.

As a result of intensive research, the present inventors have discovered a PPS composition that improves the above-mentioned drawbacks of PPS, such as whitening and difficulty in various color toning, and also has less deterioration in physical properties accompanying it.
That is, the present invention is non-crosslinked and conforms to ASTM D123.
In the melt flow rate measurement method of 8, the diameter is 2.09
using an orifice with a length of 31.75 tnx,
．． ppsio with a melt flow rate of 20& or more/10 minutes measured under a temperature condition of 6°C and a load of 645g
To provide a white-modified polyphenylene sulfide resin composition, which is composed of 0.1 to 30 parts by weight of an epoxy resin, 0.1 to 150 parts by weight of a color pigment, and 5 to 150 parts by weight of a reinforcing material, based on 0 parts by weight of an epoxy resin. .

The PPS used in the present invention is uncrosslinked and has the above melt flow rate value (hereinafter abbreviated as uncrosslinked PPS). Such PPS preferably contains 90 mol% or more of the structural unit represented by the general formula +S-. Polymerization methods for this polymer include a method in which p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, a method in which p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, and a method in which p-dichlorobenzene is polymerized in the presence of sodium sulfide, sodium bisulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Examples include self-condensation of p-chlorothiophenol, and the reaction of sodium sulfide and p-dichlorobenzene in an amide solvent such as mi-N-methylpyrrolidone or dimethylacetamide, or a sulfonic solvent such as sulfolane. An appropriate method is to At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. 10 bonds c -Q-o -Q-s as copolymerization components
-), sulfone bond (-G-8Q2-G-8-), biphenyl bond (-OΣ-Q-s-), substituted phenyl sulfide bond -9°- (, where R is alkyl, nitro, feral, alkoxy trifunctional phenyl sulfide group), trifunctional phenyl sulfide The copolymerization component is preferably 5 mol % or less, although it may be within a range that does not significantly affect the condensation property. Especially trifunctional or higher functional phenyl,
When biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or more. As a typical example, Rydon v-1 manufactured by Philips Vetroleum, Inc. in the United States is commercially available.

The epoxy resin used in the present invention has two epoxy groups.
It can be liquid or solid. For example, bisphenol A rsorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 113j5-)IJ hydroxybenzene, bisphenol S,) lyhydroxydiphenyldimethylmethane, 4°4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew 7 Enol, 2, 2,
5. Glycidyl ether of bisphenol such as 5-tetrakis(4-hydroxyphenyl)hexannat, norogenated bisphenol instead of bisphenol, glycidyl ether type such as diglycidyl ether of butanediol, glycidyl ester type such as phthalic acid glycidyl ester, N- Glycidyl epoxy resins such as glycidylamine type glycidyl aniline, epoxidized polyolefins, linear types such as epoxidized soybean oil, and cyclic non-glycidyl epoxy resins such as vinyl cyclohexene dioxide and synchropentadiene dioxide, novolac type epoxy Examples include resins and those substituted with nitrogen.

As the white pigment, various types such as titanium oxide and zinc sulfide can be used.

Reinforcing materials include glass fiber, Merck, walastenite, gypsum, gypsum fiber, rock wool, white mica, calcium carbonate, aluminum hydroxide, silica, silica powder,
Various materials can be used that do not adversely affect the pale color tone of aluminum oxide.

In the resin composition of the present invention, 0.1 to 6 parts by weight of epoxy resin is blended per 10 parts by weight of uncrosslinked pps. If the epoxy resin exceeds 30 parts by weight, gelation will progress during melt processing, resulting in poor productivity. The preferred amount is 1 to 2.
5 parts by weight.

In addition, melt flow rate of uncrosslinked PPs)
In the case of t4/10 minutes, thickening and gelation due to the addition of epoxy are significant, making molding impossible. Crosslinked pp that can be used
s has a low viscosity with a melt flow rate of 209 or more/10 minutes, preferably 25 to 120 Ji+/10 minutes.

The amount of white pigment to be blended is 0.1 to 150 parts by weight based on 8100 parts by weight of uncrosslinked PP, and if the amount exceeds 150 parts by weight, the mechanical strength decreases so much that it is not practical.

The preferred amount is 1 to 120 parts by weight. Similarly, the blending amount of the reinforcing material is 5 to 150 parts by weight, and if it exceeds 150 parts by weight, productivity will be poor. The preferred amount is 10 to 120 parts by weight.

The composition of the present invention can be applied to polystyrene resin, styrene copolymer resin, rubber, polyamide resin, polyester resin, olefin resin, polyphenylene oxide resin, polysulfone resin for the purpose of improving moldability or other physical properties. , polyether sulfone resin, polyimide resin, polyetherimide resin, etc. may be blended to the extent that the basic physical properties of the composition are not significantly changed.

In addition, pigments, plasticizers, antioxidants, weather resistance improvers, etc. may be added to the composition of the present invention for the purpose of improving whiteness, moldability, oxidation stability, weather resistance, or other purposes.

One of the features of the present invention is the use of uncrosslinked pps, which results in a composition with greatly improved color tone. However, when using uncrosslinked pps, white pigment, and reinforcing material without blending epoxy resin, the resin viscosity during melting is extremely low, and the pps, white pigment, and reinforcing material separate during melt processing, resulting in extremely poor productivity. Therefore, it is practically impossible to manufacture. This drawback can be overcome by using uncrosslinked linear PPS, which has a high molecular weight and a melt flow rate lower than 20 g/10 minutes, but its physical properties, especially mechanical strength, are inferior to crosslinked PPS. This is also inconvenient because the cost becomes extremely high.

In the present invention, by blending an uncrosslinked PP5K multifunctional epoxy resin with a specific melt flow rate value,
It is possible to increase the viscosity of an uncrosslinked pps resin during melting to a level that allows production, and to obtain a pps composition with good color tone that greatly reduces the deterioration in physical properties caused by the use of uncrosslinked pps and white pigments. . Also, the addition of a white pigment, which was conventionally required to whiten cross-linked PPS! Not only is it possible to greatly reduce the amount of pigment to 7, but also it is possible to achieve clear whitening and toning by using various pigments in combination, which was previously considered impossible with PPS.

The mixed wire of the composition of the present invention is mechanically melt-kneaded using an extruder or other kneading device at a high enough temperature to melt the PPS.

The resin composition of the present invention also has excellent moldability, and practical molded products can be easily obtained by methods such as injection molding and compression molding.

Next, the present invention will be explained with reference to Examples. Note that parts in the examples are based on weight.

Reference Example-1 (Synthesis of PPS) In a 50A scale autoclave, N-methylpyrrolidone was added at a molar ratio of 70, sodium sulfide nonahydrate was added at o, 99,
Sodium benzoate 0601 Sodium hydroxide 0.
15 mol"'Q (50 mol scale) was heated to 210'C in a nitrogen stream and dehydration was carried out to a dehydration rate of 110%. After cooling the system to 100°C, p-dichlorobenzene was added at a molar ratio of 1.0. After charging and sealing, the internal pressure was increased to 2.5 A with nitrogen.The heat generated by polymerization was controlled by controlling the heating temperature, and the temperature was raised to 270'C, and polymerization was carried out with stirring for 5 hours. The internal pressure had risen to 9/crt? at 17. After cooling the system, the pressure was released and the contents were poured into a large amount of water to collect the flaky polymer. The polymer was washed repeatedly with hot water and acetone. The final yield was 70% in the form of white flakes.

The resulting PPS had an intrinsic viscosity of 0.14 and a melt flow rate of 7 i/10 min as measured by the method described in the text.

Example-1 For 5100 parts of PP synthesized in Reference Example-1, 10 parts of bisphenol-type epoxy resin (Evicron ■7050, manufactured by Dainippon Ink & Chemicals ■) and 80 parts of titanium oxide (Tiebake ■R-680, manufactured by Ishiya Sangyo Co., Ltd.) ■Toughness), glass fiber (Glaslon ■C8-03+-MA497, manufactured by Asahi Fiberglass ■) was mixed in a ■ type tumbler, and a homogeneous mixture was mixed in a cylinder with a temperature of 660℃.40 parts m
The mixture was melted and kneaded uniformly using a zl-shaft extruder, pulled out into strands, and cut with a pelletizer to produce pellets with a diameter of 3 mm and a length of 3 mm.

This pellet is placed in a cylinder at a temperature of 360℃ and a mold temperature of 14℃.
Various test pieces were made using a 6-oz injection molding machine set at 0° C., injection pressure 1000 kg A1171, and medium injection speed. Further, under the same conditions, the fluidity during molding was measured using a spiral flow mold with a 5 mrn semicircular cross section and a mold temperature of 140°C.

As a result, a molded product with a white and glossy appearance was obtained, and when various physical properties were measured, the tensile strength (hereinafter referred to as T-8
) 980 kg/d, Notched Izot impact strength (hereinafter abbreviated as Notched ■・I) 5.0 Yu・Crr
L/ari, spiral flow 36cm, and as a result of measuring the color of the molded product with a color machine, Lfti
It showed u76, s, a value -2.0, b value 94, and white discoloration 74.7.

Example 2 Example except that the amount of titanium oxide was changed to 60 parts
Table 1 shows the results obtained in the same manner as in 1.

Example-6 White pigment was changed from titanium oxide to zinc sulfide (Sactris L,
Example-1 except for changing to (manufactured by West German Saktorben)
Table 1 shows the results obtained in the same manner as above.

Example 4 The same procedure as in Example 1 was performed except that the epoxy resin was changed to a novolak type epoxy resin (Evicron ■N-695, manufactured by Dainippon Ink & Chemicals ■). The results are shown in Table 1.

Example-5 From adding 100 parts of glass fiber to reinforcing material, glass fiber/talc (Talc 5P-44, manufactured by Fuji Talc ■) = 60 parts/
Table 1 shows the results obtained in the same manner as in Example 1 except that the addition amount was changed to 60 parts.

Example 6 Example 1 except that the pigment was changed from adding 80 parts of titanium oxide to adding 40 parts and 15 parts of titanium oxide/blue face family (Dairen Blue P-194, manufactured by Dainippon Ink & Chemicals). Table 1 shows the results obtained in the same manner as above. In addition, when the color of the molded product was measured using a color machine, the b1 direction was -33.
, 2, which was large in the negative direction and had a clear blue color.

Comparative example-1 Cross-linked pps (Light 7P-4, intrinsic viscosity 0.6
) was carried out in the same manner as in Example-1, except that no epoxy resin was added. Table 2 shows the results of Example-1.
Compared to No. 1, the mechanical strength was extremely low, and the color of the molded product was pale yellow.

Comparative Example 2 Table 2 shows the results obtained in the same manner as in Example 6 except that PPS was replaced with Rydon P-4 and no epoxy was added.

Note that the mechanical strength is extremely low compared to Example-6.
The color of the molded product was an unclear blue.

Comparative Example 3 The same procedure as in Example 1 was carried out except that no epoxy resin was added. As a result, no epoxy resin was caught during extrusion and extrusion was impossible.

Comparative Example 4 The same procedure as in Example 1 was carried out except that the amount of epoxy resin added was increased from 10 parts to 35 parts. As a result, the viscosity increased during extrusion, and gelation occurred due to retention, making extrusion impossible at all.

Comparative Example-5 Table 2 shows the results of the same procedure as in Example-1 except that the amount of white pigment added was increased from 80 parts to 170 parts. Although the color was whiter compared to Example-1, the strength was significantly lower.

Comparative Example-6 The same procedure as in Example-1 was carried out except that the amount of reinforcing agent added was increased from 100 parts to 170 parts. As a result, the raw material did not accumulate at all during extrusion, and extrusion was impossible.

Comparative Example-7 An uncrosslinked product synthesized in the same manner as Reference Example 1 except that the polymerization time was changed to 10 hours, and the stress melt flow rate was 5 g/10
A composition was obtained using the linear polymer 1jkPPs with the formulation shown in Table 2. The resulting composition had low strength, increased viscosity, and significantly gelled, making it unsuitable as a molding material.

Comparative Example-8 Table 2 shows the results of the same procedure as in Example-1 except that PPS was changed to Rydon P-4. In addition, the viscosity increased during extrusion, gelation was significant, and the strength of the composition was low (unsuitable as a molding material).

The symbols in the table are as shown below.

1) Blue pigment Dyren ■ Blue DP-394 manufactured by Dainippon Ink & Chemicals ■ 2) Bisphenol type epoxy resin Ebiclone ■ 7050 manufactured by Dainippon Ink & Chemicals ■ 5)
Titanium oxide tiebake ■R-680 made by Ishiya Sangyo ■4 glass fiber glassron ■O8-03-MA497 made by Asahi Fiberglass @5) Zinc sulfide Sactris ■L made by Sucuttlepen, West Germany 6) Novolac type epoxy resin Evicron N- 695 manufactured by Dainippon Ink & Chemicals ■ 7) Merck Merck 5P-44 manufactured by Fuji Talc ■ 8) Productivity evaluation 0: Raw materials were well incorporated and there were no problems at all.

Δ: Kneading is possible by force feeding due to poor penetration of raw materials.

×: No mixing of raw materials and no crosstalk possible.

9) Rydon ■P-4 Manufactured by Philip Vetroleum Thermal crosslinking pps intrinsic viscosity 0.3 Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Scope of Claims] 0.1 to 60 parts by weight of an epoxy resin and 0.1 to 60 parts by weight of a white pigment per 100 M parts of an uncrosslinked polyphenylene sulfide resin having a melt flow rate of (I) below.
A whitening-modified polyphenylene sulfide resin composition comprising 150 parts by weight and 5 to 150 parts by weight of a reinforcing agent. (II ASTM D-1238 melt flow rate measurement method, diameter 2.09 mm, length 31.75
Using a 315 mm orifice. (Melt flow rate measured at 345I under temperature condition of 5℃ is 20g.
More than 10 minutes.