JPH04258622A - Polyphenylene sulfide resin reaction composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in impact resistance or hinge properties by reacting a polyphenylene sulfide resin with a nonblocked polyisocyanate compound and a specified ethylene copolymer. CONSTITUTION:A polyphenylene sulfide resin (A) (desirably a polymer comprising 90mol% or above repeating units of the formula) is made to react with a nonblocked polyisocyanate compound (B) (e.g. 4,4'-diphenylmethane diisocyanate or isophorone diisocyante) and an ethylene copolymer (C) comprising 50-90wt.% ethylene, 5-49wt.% alkyl alpha,beta-unsaturated carboxylate and 0.5-10wt.% maleic anhydride to obtain a resin reaction composition in which component A functions as a sea component and component C as an island component. This composition is excellent in impact resistance and hinge properties.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a polyphenylene sulfide resin composition with improved impact properties, and more specifically, it relates to a polyphenylene sulfide resin composition comprising (A) a polyphenylene sulfide resin, (B) an unblocked polyfunctional isocyanate compound, and ( C) It relates to a polyphenylene sulfide resin reaction composition obtained by reacting with a specific ethylene copolymer.

0002

[Prior Art] JP-A-62-15146 as a composition comprising polyphenylene sulfide resin and elastomer
No. 0 discloses a composition obtained by adding an ethylene copolymer consisting of ethylene, an α,β-unsaturated carboxylic acid alkyl ester, and maleic anhydride as an elastomer to polyphenylene sulfide.

0003

[Problems to be Solved by the Invention] However, in the composition described in the above-mentioned publication, the injection molded piece of the obtained resin composition exhibits a pearl-like luster, and the state of dispersion of the elastomer in the polyphenylene sulfide is non-uniform. and
It was also found that the effect of improving impact resistance was insufficient.

More specifically, as is conventionally known, the molecular chain of polyphenylene sulfide resin has poor reactivity, so even if a highly reactive rubber component such as the copolymer described in the above-mentioned publication is blended, At present, because the adhesion at the interface with the polyphenylene sulfide resin is insufficient, a sufficient effect of improving impact resistance cannot be obtained. Therefore, the inventor of the present invention conducted extensive studies with the aim of improving the adhesion at the interface between polyphenylene sulfide resin and elastomer.

[0005]

[Means for Solving the Problems] That is, the present invention provides (1)
) (A) Polyphenylene sulfide resin (B) Non-blocked polyfunctional isocyanate compound (C) Ethylene 50~
90% by weight, 5 to 49% by weight of α,β-unsaturated carboxylic acid alkyl ester, and 0.5 to 10% by weight of maleic anhydride. , a resin reaction composition in which the component (C) is an island (2) The composition according to the preceding item (1), in which almost no acid anhydride residue is observed in the elastomer extracted with chloroform by an infrared absorption method. thing. (3) The preceding paragraph (including fibrous and/or particulate reinforcing agents)
1) or (2).

The present invention will be explained in more detail below. Polyphenylene sulfide resin (hereinafter referred to as PP) used in the present invention
(referred to as S) has the structural formula:

[0007]

[Chemical formula 1]

A polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by
If the content of the repeating unit is less than 70 mol%, heat resistance will be impaired, which is not preferable. PPS is generally designated as
A polymer with a relatively low molecular weight obtained by the production method typified by Japanese Patent Publication No. 3368, and an essentially linear polymer with a relatively high molecular weight obtained by the production method typified by Japanese Patent Publication No. 52-12240. etc., and the above-mentioned special public interest
In the polymer obtained by the method described in No. 368,
It is also possible to increase the degree of polymerization and use it by heating in an oxygen atmosphere after polymerization, or by adding a crosslinking agent such as a peroxide and heating, and in the present invention, it is possible to use it by increasing the degree of polymerization. It is also possible to use PPS.

[0009] Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula.

0010

[Case 2]

[0011]

[Chemical formula 3]

0012

[C4]

[0013]

[C5]

[0014]

[C6]

[0015]

[C7]

[0016]

[Chemical formula 8]

The melt viscosity of PPS used in the present invention is not particularly limited as long as a molded article can be obtained;
In terms of toughness, S itself is preferably 100 poise or more, and in terms of formability, it is preferably 10,000 poise or less. Particularly preferably 1,000 to 5,000
It is in the range of 0 poise. In the present invention, PPS is present as a sea component.

[0018] The PPS used in the present invention also contains ordinary additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, and colorants, and small amounts thereof, to the extent that the effects of the present invention are not impaired. Other resinous or rubbery polymers can be added. Furthermore, for the purpose of controlling the degree of cross-linking of PPS, a normal peroxide-based cross-linking agent and JP-A-59-13
Crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A No. 1650, or dialkyltin dicarboxylates and amino acids described in JP-A-58-204045 and JP-A-58-204046, etc. It is also possible to incorporate a crosslinking inhibitor such as triazole.

The unblocked polyfunctional isocyanate compound in the present invention includes an isocyanate compound having two or more unblocked isocyanates in one molecule, and has the general formula: R-(N=C=O)n or R-(N=C=S)n (wherein, R is an organic group composed of elements such as carbon, hydrogen, sulfur, phosphorus, nitrogen, oxygen, etc., and n is an integer of 2 or more.) Unblocked polyfunctional isocyanate represented by
Alternatively, there are isothiocyanate compounds.

The general types are roughly divided into aliphatic type and aromatic type, and modified type is dimeric type,
Although there are trimer type (isocyanurate type), multimer type, etc., any isocyanate compound can be used in the present invention. However, block-type isocyanates (also called mask-type isocyanates), i.e., blocks in which isocyanates are reacted in advance with acidic sodium sulfite, phenol, cresol, lactams, heterocyclic compounds, hydrocyanic acid, sulfites, etc., and then regenerated at high temperatures. Type isocyanate compounds are not included because they have little effect for this purpose.

Examples of specific compounds include 4,4'
-diphenylmethane diisocyanate, 4,4'-diphenylpropane diisocyanate, naphthylene 1,5-
Diisocyanate, toluene diisocyanate, dimerized toluene diisocyanate, hexamethylene diisocyanate, trimerized hexamethylene diisocyanate, pentamerized hexamethylene diisocyanate, heptamerized hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate, phenylene diisocyanate, 3,3
'-Dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, 3,3'-bitolene-4,4'-diisocyanate, xylene diisocyanate.

Isophorone diisocyanate, triphenylmethane triisocyanate, lysine diisocyanate, dicyclohexyldimethylmethane diisocyanate,
Diethyl fumarate diisocyanate, triisocyanate benzene, triisocyanate naphthalene, bis(
4-isocyanate phenyl) ether, bis (4-isocyanate phenyl) thioether, bis (4- isocyanate phenyl) sulfone, tris (4- isocyanate phenyl) phosphite, tris (4- isocyanate phenyl) phosphate, and the corresponding iso There are compounds with thiocyanate and unblocked polyfunctional isocyanate compounds such as the above-mentioned aromatic isocyanate compounds to which water is added.

[0023] The quantitative ratio of the non-blocked polyfunctional isocyanate compound to PPS is 90 to 99% relative to the total amount of PPS and the above-mentioned isocyanate compound.
．． 9, preferably 95 to 99.8% by weight, and the non-blocked polyfunctional isocyanate compound to 0.1 to 10, preferably 0
．． It is 2 to 5% by weight. If the weight percent of the isocyanate compound is too small, impact resistance may not be sufficient.
Also, if there is too much, it may become difficult to process.

The ethylene copolymer used as component (C) in the present invention is an excellent alloy type elastomer, and contains 50 to 90% by weight of ethylene, 5 to 49% by weight of α,β-unsaturated carboxylic acid alkyl ester, and anhydrous Maleic acid 0.5~
It is an ethylene copolymer (hereinafter simply referred to as ethylene copolymer) consisting of 10% by weight. In the present invention, component (C) exists in the composition in the form of an island component, and is dispersed in the sea component formed by component (A), PPS. The average particle size of the island component is preferably 0.3 μm or less. If it is too large, impact resistance may not be sufficient.

The ethylene copolymer used in the present invention is
Its monomer components consist of tyrene, α,β-unsaturated carboxylic acid alkyl ester, and maleic anhydride, and ethylene is 50 to 90% by weight, preferably 60 to 85% by weight, α,β-unsaturated carboxylic acid Acid alkyl ester is 5~
49% by weight, preferably from 7 to 45% by weight, and maleic anhydride from 0.5 to 10% by weight, preferably from 1 to 8% by weight.

α,β-Unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example,
Alkyl esters such as acrylic acid and methacrylic acid, including methyl acrylate, ethyl acrylate, n-propyl acrylate, isoropyl acrylate, n-butyl acrylate, t-butyl acrylate, and acrylic acid. Isobutyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-methacrylate
Examples include butyl and isobutyl methacrylate, and among these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferred.

As a guideline for the molecular weight of the ethylene copolymer,
It is given as a melt index value at 190°C and under a load of 2.16 kg. The melt index value of the ethylene copolymer used is in the range of 0.1-1000, preferably 0.2-500, more preferably 1-100. These ethylene copolymers are commercially available from Sumitomo Chemical Co., Ltd. under the name "Bondine", for example.

[0028] The amount of these ethylene copolymers to be blended into PPS is based on the total amount of PPS and ethylene copolymer.
70 to 99% by weight of PPS and 30 to 1% by weight of ethylene copolymer are suitable; if PPS exceeds 99% by weight and the ethylene copolymer is less than 1% by weight, the desired brittleness can be improved. The effect of this is insufficient. Also, PPS is 7
If the ethylene copolymer content is less than 0% by weight and exceeds 30% by weight, there is a risk that the strength, rigidity, and heat resistance of PPS will be impaired, and gelation will occur during melt-kneading, impairing extrusion stability and moldability. PPS 70~
97% by weight, preferably 30-3% by weight of ethylene copolymer, more preferably 75-95% by weight of PPS, 25-5% by weight of ethylene copolymer, especially PPS80
-90% by weight, the range of 20 to 10% by weight of the ethylene copolymer can be preferably selected.

The reaction of PPS, isocyanate compound, and ethylene copolymer is carried out by a melt-kneading method, and the mixing order does not matter, but the most preferable method is to
This is a reaction method in which PPS and an isocyanate compound are melt-kneaded and then the ethylene copolymer is kneaded. To simplify the process, a method may be adopted in which PPS, an isocyanate compound, and this ethylene copolymer are mixed at the same time.

In the present invention, fibrous and/or granular reinforcing agents are not essential components, but if necessary, 3 parts by weight of PPS and this ethylene copolymer may be added.
It is possible to blend in an amount not exceeding 0.00 parts by weight, and usually in a range of 10 to 300 parts by weight, it is possible to improve strength, rigidity, heat resistance, dimensional stability, etc.

Such fibrous reinforcing agents may be either organic or inorganic fibers, including inorganic fibers such as glass fibers, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers; Examples include carbon fiber. The granular reinforcing agent may be either organic or inorganic filler, such as silicates such as wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate; alumina, silicon oxide, magnesium oxide, Metal oxides such as zirconium oxide and titanium oxide; carbonates such as calcium carbonate, magnesium carbonate, and dolomite;
Sulfates such as calcium sulfate and barium sulfate; glass and
Examples include beads, boron nitride, silicon carbide, Saroyan, silica, etc., and these may be hollow (porous).

Two or more of these reinforcing agents can be used in combination, and if necessary, the reinforcing agent can be pretreated with a coupling agent such as a silane type or titanium type before use. There are no particular limitations on the means for preparing the resin reaction composition of the present invention, but PPS and isocyanate are melt-kneaded and reacted, then the ethylene copolymer is melt-kneaded and reacted, and the reinforcing agent is added at a temperature above the melting point of PPS. A typical method is to melt and knead in an extruder and then pelletize.

[0033] The melt-kneading temperature is 280°C to 340°C.
is preferable; if it is less than 280°C, the melting of PPS may become insufficient, and if it exceeds 340°C, the ethylene copolymer may undergo thermal deterioration and gelation, so care must be taken. Note that another reaction method includes a method of simultaneously melt-kneading PPS, an isocyanate, and an ethylene copolymer to obtain a resin reaction composition, which is useful as a simplified method.

[0034] The melt-kneading in the present invention can be carried out using a known device such as a kneader, a roll mill, or an extruder, which is normally used for kneading resin melts. Types of extruders include single-screw, twin-screw, co-kneader, etc., and the composition of the present invention can be obtained using any of these extruders. The kneading temperature is higher than the melting point of the polyphenylene sulfide resin, and is 280 to 340, which is usually used.
It can be sufficiently kneaded up to ℃.

[0035]

[Examples] The present invention will be explained in more detail with reference to Examples below, but these are not intended to limit the present invention.

[0036]

[Comparative Example 1] PPS powder (manufactured by Toprene Co., Ltd., Toprene T
-4) at 150°C for 3 hours, lowered the temperature to 50°C, mixed with a Henschel mixer, and then processed with a Werner Friedler ZSK40 twin-screw extruder at a cylinder temperature of 290-300°C and nitrogen. Pelletized in atmosphere.

FIG. 2 shows a schematic diagram of a scanning electron microscope (SEM) photograph of the notched Izod fracture surface structure of the injection molded piece of Comparative Example 1. Then, the obtained pellets and ethylene copolymer pellets consisting of 67% ethylene, 30.5% ethyl acrylate, and 2.5% maleic anhydride and having a melt index value of 2.0 were dried in a weight ratio of 80:20. The mixture was blended, supplied to a twin-screw kneading extruder, melt-kneaded at 310°C, extruded into strands, and cut to obtain pellets of the composition.

The pellets were injection molded at 290 to 320°C using an injection molding machine to obtain test pieces for measuring physical properties. The injection molded pieces exhibited a pearly appearance and a lustrous appearance. For the impact resistance evaluation of the obtained test piece,
The Izod impact strength was measured according to the ASTM D-256 method and was 5 kg·cm/cm, which was insufficient as an impact strength. Also, the obtained molded piece was heated to 180
When it was bent, it broke after one bend, and the hinge properties were also insufficient.

When the infrared absorption spectrum of the resin composition obtained here was taken, strong absorption at 1734 cm -1 was observed due to >C=O of the ester bond of the ethylene copolymer. Also, 1780 based on >C=O of maleic anhydride
Absorption at cm-1 was also observed. This is shown in Figure 4. The average particle diameter of the elastomer of the island component was determined to be 2.5 μm from the injection molded test piece obtained here.

In addition, chloroform extraction was carried out from the thin section of the injection molded piece to extract the elastomer. Eighty percent of the charged elastomer was extracted by chloroform extraction. When the infrared absorption spectrum of the chloroform-extracted elastomer was taken, absorption at 1734 cm-1 due to >C=O of the ester was strongly observed, and absorption at 1780 cm-1 due to >C=O of the acid anhydride was also observed. The same was observed, and it showed the same infrared absorption spectrum as the ethylene copolymer used as the raw material. This is shown in Figure 3.

[0041]

[Example 1] PPS powder (Toprene T-4) at 150%
After drying at ℃ for 3 hours, lower the temperature to 50℃, 4.
4' diphenylmethane diisocyanate PPS100
2 parts by weight were mixed in a Henschel mixer in a nitrogen atmosphere for 30 seconds, and then pelletized in a nitrogen atmosphere using a Werner Friedler ZSK40 twin-screw extruder at a cylinder temperature of 290 to 300°C. .

Then, the obtained pellets and 67% ethylene
, 30.5% ethyl acrylate, and 2.5% maleic anhydride, and were dry blended with ethylene copolymer pellets with a melt index value of 2.0 at a weight ratio of 80:20, and then twin-screw kneaded. Feed to the extruder, 310
Melt and knead at ℃, extrude into strands, cut,
Pellets of the composition were obtained.

The pellets were injection molded at 290 to 320°C using an injection molding machine to obtain test pieces for measuring physical properties. For the evaluation of impact resistance, the Izod impact strength (notched) of the obtained test pieces was measured according to ASTM
When measured according to D-256 method, 85 kg・cm
/cm, indicating extremely high impact strength. In addition, the obtained molded piece was bent 180 degrees, returned to its original shape, and folded again.
A hinge characteristic test of 80° bending was conducted 50 times, but the hinge did not break and exhibited high hinge characteristics.

FIG. 1 shows a schematic diagram of a SEM photograph of the notched Izod fracture surface of the injection molded piece of Example 1. Although the magnification is the same as in Comparative Example 1, it can be seen that the particle size of the island component is smaller. In addition, when taking an infrared absorption spectrum of the resin composition obtained here, strong absorption at 1734 cm-1 was observed due to >C=O of the ester bond of the ethylene copolymer, but >C═O-based absorption at 1780 cm −1 was only slightly observed. Also, no absorption at 2294 cm-1 due to -N=C=O of 4,4 diphenylmethane diisocyanate was observed. These measurement results indicate that the acid anhydride in the ethylene copolymer is involved in the reaction to create a new resin composition.

[0045] The average particle diameter of the elastomer of the island component was determined from the injection molded test piece obtained here, and was found to be 0.2.
It was μm. In addition, chloroform extraction was performed from a thin section of the injection molded piece to extract the elastomer. 15% of the charged elastomer was removed by chloroform extraction.
was only extracted. In addition, when taking an infrared absorption spectrum of the chloroform-extracted elastomer, a strong absorption at 1734 cm-1 based on >C=O of the ester was observed, but an absorption at 1780 cm-1 based on the >C=O of the acid anhydride was observed.
Almost no absorption at cm-1 was observed, which was different from the infrared absorption spectrum of the ethylene copolymer used as the raw material.

[0046]

[Example 2] PPS powder (Toprene T-4) at 150%
After drying at ℃ for 3 hours, lower the temperature to 50℃, 4.
4'-diphenylmethane diisocyanate PPS10
After mixing 2 parts by weight with 0 parts by weight in a Henschel mixer in a nitrogen atmosphere for 30 seconds, a mixture consisting of this PPS powder, 67% ethylene, 30.5% ethyl acrylate, and 2.5% maleic anhydride was prepared. , and ethylene copolymer pellets with a melt index value of 2.0 at a weight ratio of 80:20, and supplied to a ZSK40 twin-screw kneading extruder manufactured by Werner Friedler.
The mixture was melt-kneaded at 310°C, extruded into strands, and cut to obtain pellets of the composition.

[0047] The pellets were injection molded at 290 to 320°C using an injection molding machine to obtain test pieces for measuring physical properties. For the evaluation of impact resistance, the Izod impact strength (notched) of the obtained test pieces was measured according to ASTM
When measured according to D-256 method, 80 kg・cm
/cm, indicating extremely high impact strength.

When the infrared absorption spectrum of the resin composition obtained here was taken, a strong absorption at 1734 cm-1 due to >C=O of the ester bond of the ethylene copolymer was observed, but maleic anhydride >1780c based on C=O
Only a very slight absorption of m-1 was observed. Also, -N= of 4,4 diphenylmethane diisocyanate
Absorption at 2294 cm −1 due to C=O was also not observed. These measurement results indicate that the acid anhydride in the ethylene copolymer is involved in the reaction to create a new resin composition.

[0049] The average particle diameter of the elastomer of the island component was determined from the injection molded test piece obtained here, and was found to be 0.2.
It was μm. In addition, chloroform extraction was performed from a thin section of the injection molded piece to extract the elastomer. 10% of the charged elastomer was removed by chloroform extraction.
was only extracted. In addition, when taking an infrared absorption spectrum of the chloroform-extracted elastomer, a strong absorption at 1734 cm-1 based on >C=O of the ester was observed, but an absorption at 1780 cm-1 based on the >C=O of the acid anhydride was observed.
Almost no absorption at cm-1 was observed, which was different from the infrared absorption spectrum of the ethylene copolymer used as the raw material.

[0050]

[Examples 3 to 9] The procedure was carried out in the same manner as in Example 1, and PPS powder and 4,4'-diphenylmethane diisocyanate (MD
I) was blended, extruded, dry blended with an ethylene elastomer, and further extruded using a twin-screw kneading extruder. The obtained pellets were injection molded, and the Izod impact strength (notched) was measured, and the results are shown in Table 1. Note that the average particle diameter of the elastomer obtained from the injection molded piece was 0.
It was 3 μm or less.

Table 1 also shows the physical properties of the glass fiber reinforced material containing glass fibers.

[0052]

[Table 1]

[0053]

EFFECTS OF THE INVENTION According to the present invention, a polyphenylene sulfide resin reaction composition having excellent impact resistance or hinge properties was obtained.

[Brief explanation of the drawing]

FIG. 1 shows a schematic view modeling the observation results of a scanning electron microscope (SEM) photograph of a fractured surface of an injection molded resin piece of Example 1.

FIG. 2 is a schematic diagram modeling the observation results of a scanning electron microscope (SEM) photograph of a fractured surface of an injection molded resin piece of Comparative Example 1.

FIG. 3 is a schematic diagram modeling the observation results of a scanning electron microscope (SEM) photograph of the fractured surface of the injection molded resin piece of Example 1.

FIG. 4 shows an infrared absorption spectrum of an elastomer extracted with chloroform from a thin section of an injection molded piece of Comparative Example 1.

Claims (1)

[Claims] Claim 1: (A) Polyphenylene sulfide resin (B) Non-blocked polyfunctional isocyanate compound (C)
50-90% by weight of ethylene, 5-49% by weight of α,β-unsaturated carboxylic acid alkyl ester and 0% of maleic anhydride.
．． A resin reaction composition obtained by reacting an ethylene copolymer containing 5 to 10% by weight, wherein the component (A) is a sea, and the component (C) is an island.