JPS59223753A - Polyphenylene sulfide resin molding material - Google Patents

Abstract

PURPOSE:To provide PPS having improved flow characteristics and weld strength, by using two kinds of polyphenylene sulfide resins (PPS) having specified melt flow rates in combination and incorporating a reinforcing material or an inorg. filler therein. CONSTITUTION:A polyphenylene sulfide (PPS) resin molding material is prepared from 95-30wt% resin (PPS-A) whose melt flow index is adjusted to 5-100 by a thermal crosslinking and 5-70wt% resin (PPS-H) whose melt flow index is adjusted to 5-200 by a synthetic reaction. The melt flow rate is measured according to ASTM D1238-70T at 300 deg.C under a load of 5kg. A reinforcing material and/or an inorg. filler are/is incorporated in the PPS resin molding material. Pref. said material consists of 90-35wt% PPS resin composed of 95-30wt% PPS-A resin and 5-70wt% PPS-H resin and 10-65wt% reinforcing material and/or inorg. filler.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene sulfide resin molding material, in particular a melt flow rate consisting of a resin prepared by thermal crosslinking and a resin prepared by a synthetic reaction, and a reinforcing agent and/or an inorganic resin. The present invention relates to a polyphenylene sulfide resin molded material that contains a filler, has excellent moldability, and has good strength so that the molded product does not break during secondary processing.

Although polyphenylene sulfide (hereinafter referred to as PPS) resin is a thermoplastic resin, it has the properties of a thermosetting resin that can be crosslinked by heating, etc. Polycarbonate, nylon, saturated polyester, and other engineering materials Extremely high rigidity compared to plastic
Heat resistance, chemical resistance! It is known as an engineering plastic with excellent chemical properties. .

PPS resin can be molded by compression molding, injection molding, extrusion molding, etc. However, since PPB resin alone has low elongation and is brittle, it is necessary to use reinforcing agents and/or inorganic fillers as a molding material. , glass fiber, asbestos, glass beads, fine silica powder, etc. are mixed in to strengthen the material. Currently, the molding material made of PPEI resin is in the form of pellets containing glass fiber, and the molded product obtained by molding is made of PPEI resin.
In addition to the properties of S resin, it has improved strength and is suitable for electrical and electronic equipment.

Used in office machinery, chemical machinery, other machinery, and their parts.

Among PPS resin molding materials, those containing large amounts of reinforcing agents and/or inorganic fillers have advantages such as excellent arc resistance and low cost, but on the other hand, moldability decreases. However, it also has drawbacks such as poor appearance of the molded product obtained. In molding by molding, compression molding, injection molding, etc., the distribution of the resin, reinforcing agent, and inorganic filler in the molding material tends to be uneven, especially at the confluence point of the flow of the molding material in the molding die. Fusion is incomplete at the weld portion, and as a result, the weld strength of the molded product is low, and there is a problem that the molded product is easily broken from the weld portion due to thermal stress or mechanical stress during secondary processing of the molded product.

Conventionally, to deal with such a decrease in weld strength,
Measures have been taken to avoid these drawbacks by improving the design of the molds used for compression molding and injection molding to improve the flow of molding. However, P
The excellent properties of PS resins require support for molded products of more diverse and complex shapes, and it is no longer possible to overcome these problems by improving molds to avoid defects. On the other hand, the synthesis method of pps resin has been improved, and molding materials with high weld strength and improved fluidity during molding are commercially available as pp resin molding materials, but due to the characteristics of such molding materials, It takes a long time to cool the molded product, and if the molding cycle is accelerated, the molded product deforms.Moreover, even though the weld strength of the molded product molded by this molding phase is improved, the non-weld part is There is a problem that the strength decreases. Furthermore, on the side of improving molding materials, there is a proposal to improve weld strength by reducing the diameter of glass fibers used as reinforcing agents in PrS resin molding compounds, but the diameter of glass fibers is There are limitations from the viewpoint of fiber production, and no significant effect on improving weld strength has been observed.

Based on recognition of this problem, the present inventors have determined that the weld strength decreases tJ: Because the solidification temperature is high based on the characteristics of PPs resin, assimilation occurs before the molding material reaches the weld part during molding, and the fluidity Focusing on the fact that the fusion is incomplete because the bonding is performed in a state where the bonding temperature is reduced, various studies were conducted on improving the fluidity and weld strength of PPEI resin molding materials. . the result,
PPS resin has a melt flow rate of 5 due to thermal crosslinking.
5-20 by synthetic reaction with resin prepared to ~100
PPS resin molding materials containing gold as a reinforcing agent and/or inorganic filler have improved fluidity during molding and improved weld strength of molded products, and have without sacrificing its unique characteristics.
The present invention has been completed by discovering that the above problems can be solved.

The object of the present invention is to provide a PPS resin molding material in which the melt flow rate is composed of a resin prepared by thermal crosslinking and a resin prepared by a synthetic reaction, and contains a reinforcing agent and/or an inorganic filler gold. The object of the present invention is to provide a pps flt4 resin molding material which has excellent mechanical strength, and which also provides a molded product with high weld strength, and which does not break from the weld part during secondary processing.

That is, the present invention provides a polyphenylene sulfide resin molding material for compression molding or injection molding, in which the polyphenylene sulfide resin in the molding material has a 't1-melt flow rate of 5 due to thermal crosslinking, as measured under the following conditions. Resin prepared to H-1, OO 95-30
The present invention is a polyphenylene sulfide resin molding material, characterized in that it contains 5 to 70% by weight of a resin prepared by a synthetic reaction with a weight ratio of 5 to 200, and a filler, a reinforcing agent, and/or an inorganic filler.

Measurement method: ASTM D1238-70T temperature
Temperature: 300'C Load: 5# In the present invention, a resin (hereinafter referred to as PP5-A) whose melt flow rate is adjusted to 5 to 100 by thermal crosslinking is used.
) can be obtained by heat treatment in the presence of oxygen at a temperature below the melting point of the currently commercially available uncrosslinked pps resin or partially crosslinked pps resin '1 pps resin, for example 230 ° C. . However, p
Since ps-A resin is commercially available, it can be used without heat treatment. For example, it can be used for "P-4" and "p-6" (both in powder form) manufactured by Phillips Petroleum Company in the United States.

In addition, the melt flow rate is 5 to 20 depending on the synthesis reaction.
FJ to 0! The produced resin (hereinafter referred to as Pr5-H) is disclosed in Japanese Patent Publication No. 12240/1986 and Japanese Patent Publication No. 53-2 (1983), which are disclosed as a method for producing a high molecular weight PPS polymer.
It can be produced by changing the reaction conditions, such as changing the reaction time, reaction source degree, and catalyst, according to the method described in Japanese Patent No. 5589, US Pat. No. 3,354,129, and the like. That is, according to Japanese Patent Publication No. 52-12240, a high molecular weight pps polymer is produced by completely mixing and reacting at least one of a sulfur source, paradihalobenzene, an alkali total carboxylic acid salt, and an organic amide. A combination was obtained, and also
According to Publication No. 89, a first composition is entirely formed by contacting N-alkyl-2-pyrrolidone, lithium acetate, and water, and after dehydration, it is contacted with a second composition containing water and alkali gold sulfide H4. A pps polymer is obtained by reacting to completely form the third composition, and then contacting and reacting with para-dihalobenzene after dehydration.

In the present invention, the melt flow rate is ASTM, D
The value was measured using a melt indexer specified in 1238-70T at a temperature of 300°C and a load of 5 Alv.
EI-H resin is 5-200 (f/10 min). As is clear from the comparison between the Examples and Comparative Examples shown later, the molding material containing all the PPS resins with melt flow rate within this range has a high processability during molding, that is, the molding material. Since the fluidity is improved and the resin is completely melted in the weld area, it is possible to improve the mechanical strength such as the weld strength of the molded product, as well as the effects of the reinforcing agent and inorganic filler. Moreover, in the secondary processing of molded products, it is possible to eliminate defects caused by breakage during ultrasonic welding, for example. A molding material made by blending two types of PPEI resins having melt flow rates within the above range has a lower viscosity during melting and a lower solidification temperature (crystallization temperature) during molding. The weld strength of the molded product depends on whether the resin is fused at the weld part just before cooling or whether it is cooled after the fusion is completed.
It is thought that there will be a large difference in the residual stress of the molded product. A molded article made of a molding material made of a pps resin whose melt flow rate deviates from the above range in either a large or small direction does not show improvement in mechanical strength such as weld strength. Further, the mechanical strength of molded products made of molding materials made of PP5-A or Pr5-H resins having melt 70-rates within the above-mentioned ranges is not improved.

In the present invention, the blending ratio of PP5-A resin and PP5-H resin, which have been subjected to melt flow rate 'fAM, is
There is a preferable range in which the molding material made of S resin has excellent moldability and improves the mechanical strength such as the weld strength of the molded product.

That is, 95 to 30% by weight of pps-A resin and PP5-
Preferably, the composition comprises 5 to 70% by weight of H resin. A molding material having such a blending ratio has a lower melt viscosity and a lower assimilation temperature during molding. Moreover, the cooling time required for demolding after molding is the same as the molding time of conventional molding materials made of PP5-A resin alone, and there is an advantage that there is no need to change the molding cycle. If the blending ratio of pps-a resin is 5 mN% or less, the fluidity during molding will not change, and no improvement effect will be observed in terms of the weld strength of the molded product or breakage during secondary processing. do not have. On the other hand, 70
If the weight percentage is exceeded, the weld strength of the molded product or fracture during secondary processing will be improved, but the mechanical strength of non-welded parts will decrease and the cooling time required for demolding after molding will become significantly longer. However, since the molding cycle becomes longer, it is also unfavorable from the viewpoint of productivity.

The pps resin molding material of the present invention is composed of melt flow rate prepared pps-hll/ll fat and Pre-H resin, and contains a reinforcing agent and/or an inorganic filler. Any fibrous material such as glass fiber or carbon fiber, potassium titanium, wollastonite, asbestos, or silicon carbide that is used as a reinforcing agent for thermoplastic resin B'Q can be used. Further, such a reinforcing agent may be surface-treated with a silane coupling agent such as vinylsilane, aminosilane, mercaptosilane, or epoxy, a titanium-based coupling agent, or a sizing agent. The form used is chopped strands.

It may be in any form such as roving or milled phyno (-).The inorganic filler is not particularly limited, but it does not decompose or smoke when heated during molding, and it does not cause hygroscopicity or changes over time. It is preferable to use an inorganic filler that does not affect the molded product. Examples of such inorganic fillers include OaOo3, MgOog, Ba5o4,
Carbonates such as 0aSo4, sulfates, OuO+ Z
Metal oxides such as nO+ TiO2r hlgor A12os, silica, graphite, boron nitride, graphite, molybdenum disulfide, talc, clay, etc. can be used in the form of finely ground powder, Alternatively, a scaly filler is preferable in terms of fluidity and mechanical strength.The inorganic filler is not limited to one type, and two or more types may be used in combination, and furthermore, it may be used in combination with the above-mentioned reinforcing agent. You can also do it.

The blending ratio of the reinforcing agent and/or inorganic filler to the PPS resin consisting of PP5-A resin and PP5-H resin is not particularly limited, but it depends on the fluidity of the molding material during compression molding or injection molding. There is a preferable range from the viewpoint of the mechanical strength of the molded product. That is, it is preferable that the Pre resin resin is 90 to 5 to 65 weight percent, which is composed of 95 to 30 weight percent of PP5-A resin and 5 to 70 weight percent of PPB-H resin. The reinforcing agent and the inorganic filler may be blended individually or in combination. When used in combination, the mixing ratio of the two is not particularly limited, but from the viewpoint of cost, it is preferable to use a small amount of fibrous material such as glass fiber or carbon fiber in the reinforcing agent and a large amount of the inorganic filler. On the other hand, in terms of melt flowability during molding, it is preferable to use a large amount of fibrous reinforcing agent and a large amount of inorganic filler.

In either case, it is desirable not to exceed the necessary and sufficient %tk in relation to the required strength of the molded product.

In the present invention, a known method can be used for mixing the PP5-A resin, PP8-H resin, reinforcing agent and/or inorganic filler. For example, PP5-A resin and Pre
-H resin is mechanically homogeneously mixed using a mixer such as a Henschel mixer to form a premix, and then the premix and the reinforcing agent and/or inorganic filler are dispersed using a mixer. The mixture is put into a twin-screw kneading extruder and heated to 300 to 400°C to melt and cross-mix, then cooled and pelletized using a pelletizer to form cylindrical pieces.

In the molding material of the present invention, other thermoplastic resins or fc may be used for PPS resin without departing from the purpose of the present invention.
can be used in combination with a thermosetting resin or the like. Examples of such resins include polyenalene, polypropylene,
polystyrene.

polyvinyl chloride, polymethacrylate, polyurethane,
polyamide, polycarbonate, polyamide-imide,
Fluorine-containing resin, epoxy resin.

Known resins such as silicone resins may be used.

Furthermore, lubricant, lubricant 2 coloring agent 2 foaming agent, mold release agent.

A heat stabilizer, a combination inhibitor, a stiffness improver, etc. can be used in combination.

Since the molding material of the present invention has good fluidity during molding, it does not cause maldistribution of reinforcing agents, fillers, or compounding agents, which have conventionally caused various problems. Therefore, the mechanical strength such as weld strength of the molded product molded with the uninvented molding material has a strength that is not found in the conventional pps resin molding material, as is clear from the comparison between the examples and comparative examples shown later. It is something that can be destroyed.

The molding material of the present invention can be molded by conventional compression molding, injection molding, or extrusion molding. The molding conditions are not particularly limited, and the molding material of the present invention can be used to mold products with complex shapes, which conventionally had low mechanical strength and made it difficult to use PPS resin molding materials, especially molded products made by ultrasonic welding etc. It enables the production of molded products that require subsequent processing. Furthermore, it can be used in a wide range of applications as engineering plastics for vehicle equipment, electrical machinery, electrical machinery, office machinery, chemical machinery, and their parts, such as plates, rods, tubes, containers, gears, etc. .

The present invention will be explained in detail below using all Examples, but the present invention is not limited to these Examples.

In addition, in the examples, the evaluation method of the molding material.

The molding conditions and test methods for the test molded product are as follows.

Molding conditions for the molded product: Molding was performed using an injection molding machine under the following conditions.

Cylinder temperature -340℃ Injection pressure = 1000Wcd (resin pressure exchange n) Mold temperature: 1
20° C. Flowability test of molding material: Molding was performed under the above molding conditions using a spiral flow mold with a radius of 3.2 centimeters, and the flow length was measured.

Measurement of the shortest cooling time during molding: After injecting a rectangular parallelepiped of 6.3 sn x 6.3 m x 63.5 m under the above molding conditions, measure the shortest cooling time without deforming or breaking the molded product with a molded product ejection bin when demolding. did.

Measurement of mechanical strength of molded product: The molded product molded under the above molding conditions was prepared into a test piece according to J.K. S-7113, and the tensile strength of the welded part and the tensile strength of the non-welded part were tested by the "Tensilon" tensile test. It was measured using a machine (manufactured by Toyo Baldwin).

Secondary processing test for molded products - Circular cups 1 and 2 with a diameter of 40 mm, a height of 10 gourds, and a wall thickness of 3.2 mm as shown in FIG. 1 were molded using a three-point pinpoint gauge under the above molding conditions. The ultrasonic welded joints 3 and 3' in the form of a bead joint, shown enlarged in Fig. 2, were welded using an ultrasonic welding machine (manufactured by Seidensha Denshi Kogyo Co., Ltd.) at a frequency of 25 μm, as shown in Fig. 3. After creating the cup 4, an air pressure of 3.0 to 9/ca was applied to the cup, and the cup was immersed in water to check the weldability from the presence or absence of air leakage.

Example 1 50ii parts of "Rydon pps P-4" (melt flow rate 50.0) as PP resin and PP
Paradichlorobenzene and sodium disulfide were used as raw materials for the B-H resin, lithium acetate was used as a catalyst, N-methyl-2-pyrrolidone was used as a reaction solvent, and the reaction temperature was 27.
10 parts by weight of melt flow rate 38.8 (1) PPF3 resin obtained by reacting at 5°C for 3 hours was blended and mixed in a Henschel mixer, and then chopped strands of glass fibers having a length of 3-3 were mixed. "C8-MA-497" (
40 parts by weight (manufactured by Asahi Fiberglass Co., Ltd.) were added and mixed and dispersed using a v-mixer to obtain a premix. This premix was extruded at a total screw rotation of 50 revolutions/min to form a pellet. The pellets were processed in an injection molding machine according to the molding conditions described above, and each sample was subjected to fluidity tests of molding materials, measurements of the shortest cooling time during molding, mechanical strength measurements of molded products, and secondary processing tests of molded products. was molded.

Evaluation tests and measurements were performed on each sample according to the methods described above.

The results are shown in Table 1.

Examples 2 to 4 M pieces were prepared by changing the blending ratio of PPe-A resin and PP5-H resin in Example 1 to the blending ratio shown in Table 1. We created them and conducted evaluation tests and measurements on them.

The results are shown in Table 1.

Comparative Examples 1 to 4 Pellets and all test samples were prepared in the same manner as in Example 1, except that the blending ratio t of PP5-A resin and PPe-H resin in Example 1 was changed to the one shown in Table 1. We created them, and conducted evaluation tests and measurements on them.

The results are shown in Table 1.

Example 5 The blending ratio of the PP5-A resin and PP8-H resin in Example 1 was changed, and further, chopped strands of glass fiber with a length of 3 cm and talc were added as an inorganic filler.
A pellet and each test sample were prepared in the same manner as in Example 1, and their evaluation tests and measurements were performed. The results are shown in Table 2.

Comparative Example 5 Pellets and test samples were prepared in the same manner as in Example 5, except that the PP5-H resin in Example 5 was not blended and the PPB resin was replaced with PP5-A resin, and their evaluation was Tests and measurements were carried out. The results are shown in Table 2.

Example 6 "Rydon-PPS-P 4" as PPS-A resin
(Melt flow rate 50.0) and PP5-H resin using Balajichlorobenzene and sodium disulfide as raw materials, lithium acetate as a catalyst, and N- as a reaction solvent.
Methyl-2-pyrrolidone kumquat, PP with a melt flow rate of 70 obtained by reacting at a reaction temperature of 270°C for 3 hours, resin and glass fiber were mixed in the proportions shown in Table 3, and the same as in Example 1 was prepared. All pellets and test samples were prepared using the method, and their evaluation tests and measurements were conducted.

The results are shown in Table 3.

Examples 7-8 Example 60 PP5-H resins with melt flows of 1/ite of 150 and 10 were obtained by changing the reaction conditions in the PPB-H resin synthesis reaction. These were mixed with PPEI-A resin and glass fiber, and pellets and test samples were prepared in the same manner as in Example 6, and their evaluation tests and measurements were performed.

The results are shown in Table 3.

Comparative Examples 6-7 The reaction conditions in the ppB-H resin synthesis reaction of Example 6 were completely changed to produce melt flow rates of 250 and 1.
A 5-H resin was obtained. These were completely blended with PP5-A resin and glass fiber, and pellets and test samples were prepared in the same manner as in Example 6, and their evaluation tests and measurements were performed.

The results are shown in Table 3.

1

[Brief explanation of the drawing]

FIG. 1 is a perspective view of a circular cup in a secondary processing test of a molded product using the molding material of the present invention. FIG. 2 is an enlarged cross-sectional view taken along line A-A of the ultrasonic welded joint of the circular cup. FIG. 3 is a cross-sectional view taken along the line A-A after the joint portion of the circular cup is ultrasonically welded. 1.2...Secondary machining circular cup. 3.3'... Ultrasonic welding joint of circular cup. 4 ・Cup after curved ultrasonic welding

Claims (1)

[Scope of Claims] 1. In a polyphenylene sulfide resin molding material for compression molding or injection molding, the polyphenylene sulfide resin in the molding material has a melt flow rate of 5 to 5 as measured under the following conditions due to thermal crosslinking. 100
K RAM resin 95 to 30 weight blocks and resin prepared from 5 to 200 weight blocks by synthetic reaction, 5 to 70 weight blocks, containing 7111 toughener and/or inorganic filler. Polyphenylene sulfide resin molding material with % characteristics. Measurement method: ASTM D1238-70T Temperature: 300℃ Load: 5 to 72, characterized by a total content of 90 to 35% by weight of polyphenylene sulfide resin and 10 to 65% by weight of reinforcing agent and/or inorganic filler A polyphenylene sulfide resin molding material according to claim 1.