JPS6036551A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having improved mold releasability and impact resistance, and high moldability, by compounding a vinyl aromatic hydrocarbon resin and an acrylonitrile-EPDM-styrene graft copolymer resin. CONSTITUTION:The objective composition is obtained by compounding (A) a polyphenylene ether resin, (B) a vinyl aromatic hydrocarbon resin and (C) an acrylonitrile-EPDM-styrene graft copolymer resin. The component B is e.g. polystyrene, and the component C is a copolymer composed of 5-30(wt)% acrylonitrile, 10-60% EPDM (preferably a copolymer of a 3-10C alpha-olefin and 5-10C nonconjugated diene) and 30-80% styrene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition with improved moldability and impact resistance. For more details,
The present invention relates to a polyphenylene ether resin composition with improved moldability and impact resistance, containing a polyphenylene needle resin, a vinyl aromatic hydrocarbon resin, and an acrylonitrile-EPDM-styrene graft copolymer resin.

Polyphenylene ether resin is a resin with excellent +M heat resistance, but it requires molding processing such as extrusion or injection at high temperatures. Molding at high temperatures causes deterioration of the polyphenylene ether resin, and as a result, the excellent performance inherent to the polyphenylene ether resin is impaired. On the other hand, polyphenylene ether resins have low impact strength and are insufficient for use as they are.

A method for alleviating these drawbacks of polyphenylene ether trees [7], for example, U.S. Pat. No. 338
No. 3435 proposes a composition containing polyphenylene ether and a vinyl aromatic hydrocarbon resin, which can be extruded or injected by blending the vinyl aromatic hydrocarbon resin and polyphenylene ether. This makes it possible to lower the temperature to a level suitable for molding. If a rubber-modified polystyrene resin is used as the vinyl aromatic hydrocarbon resin, the impact strength of the resin composition will also be improved. However, although these resin compositions are capable of lowering the temperature to a temperature suitable for molding processes such as extrusion or injection,
No improvements have been made in terms of the separation of the product from the mold at the time of molding, and improvements in impact resistance are insufficient from a practical standpoint.

What is the means to make one molded product come out of the mold as a white ball?
US Pat. No. 3,361,851 discloses a resin composition containing a polyphenylene ether resin and a polyolefin.

Since polyphenylene ether and polyolefin have poor compatibility, the amount of polyolefin blended in the resin composition is limited to 1 to 10% by weight. It is not possible to substantially reduce the temperature to a temperature suitable for molding.

Various resin compositions have been proposed as means for improving +w resistance, for example, US Pat. No. 36605
No. 31 specification 0 is a resin composition containing polyphenylene oxide, polystyrene and rubber; No. 599485
Specification No. 6 describes a resin composition containing polyphenylene oxide, polystyrene, and an A-B-A'ffl block copolymer elastomer; Specification No. 4128602 contains polyphenylene oxide, polystyrene, and rubber;
The maximum average diameter (maxi) of the rubber dispersed in the resin composition
No. 4,128,603 contains polyphenylene oxide and high-impact polystyrene, the high-impact polystyrene containing 22 to 80% by weight of elastomer gel particles. Resin composition;
Publication No. 8139 discloses resin compositions containing polyphenylene ether, polystyrene, and acrylic resin-modified ABS resin. However, in these resin compositions, although the impact resistance is improved, the mold releasability is not improved at the same time, and there is no description suggesting a technique for solving both of the above-mentioned drawbacks at once.

The present inventors have made extensive studies to improve the mold release and impact resistance of a resin composition consisting of a polyphenylene ether resin and a vinyl aromatic hydrocarbon resin without impairing its original performance. As a result, we have arrived at the present invention. That is, the present invention provides polyphenylene ether resin and vinyl aromatic hydrocarbon resin with acrylonitrile-EPD.
This is a polyphenylene ether resin composition which is obtained by blending an M-styrene graft copolymer resin and has good moldability, as well as improved mold releasability from gold enamel and impact resistance.

The polyphenylene ether resin used in the resin composition of the present invention is a polyphenylene ether 2 formed by polymerizing one or more monocyclic phenols represented by the general formula (11), and this polyphenylene ether 7- i (Here, 几1 is an alkyl group having 1 to 3 carbon atoms, 1% 2 and 几5 are hydrogen atoms or carbon atoms of 1 to 3
In the lower alkyl group of 6, there must be a lower alkyl substituent at the ortho position of at least one of the hydroxyl groups. ) A graft copolymer having a polyphenylene ether as its backbone is obtained by grafting together a vinyl aromatic compound. This polyphenylene polymer may be a homopolymer or a copolymer. Furthermore, the definition of polyphenylene ether resin in () of the present invention refers to the above-mentioned polyphenylene ether and other *+
It also includes a composition obtained by mixing a bit component and/or an elastomer component (details of these components will be described later).

Examples of the monophenol represented by the general formula (1) include 2,6-dimethylphenol, 2,6-
Dinitylphenol, 2,6-dipyruphenol, 2-methyl-6-ethylphenol, 2-methyl-
6-propylphenol, 2-ethyl-6-propylphenol, m-rusol, 2. -Dimethylphenol, 2゜6-diethylphenol, 2. Ro-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-6-methylphenol, 2-ethyl-ro-propylphenol,
2-furopyru-6-methylphenol, 2-propyl-
5-ethylphenol, 2.3, 6-i-dimethylphenol, 2,3.6-driethylphenol, 2 and 6
．． 6-Driprovirphenol 2.6-dimethyl-5-ethyl-7enol, 2.6-dimethyl-ro-propylphenol, and the like. Examples of polyphenylene ether obtained by polycondensation of one or more of these phenols include poly(2,6-dimethyl-1,4-phenylene) ether and poly(2,6-ethyl-1,4-phenylene) ether. , poly(2,6-
Diprobyl-1,4-7 enylene) ether, poly(2
-Mesou-6-nityl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2-ethyl-6-furopylene) 1.
4-phenylene) ether, 2,6-dimethylphenol/2.3.6-dorimedylphenol copolymer, 2.
6-dimethylphenol/2. s, 6-driethylphenol copolymer, 2,6-ethylphenol/2,3
．． 6-) Styrene graph on dimethylphenol copolymer, 2,6-cyf-ropylphenol/2,3,6-drimethylphenol copolymer, poly(2,6-dimethyl-1°4-phenylene)ether 1-polymerized graft copolymer, 2,6-dimethylphenol/2,3
, a graft copolymer obtained by graft-polymerizing styrene onto a 6-dolimethylphenol copolymer, and the like. especially,
Poly(2,6-dimethyl-1,4-phenylene)ether, 2,6-dimethylphenol/2,3.

A 6-dolimethylphenol copolymer and a graft copolymer obtained by graft-polymerizing styrene to each of the former two are preferred as the polyphenylene ether resin used in the present invention.

The vinyl aromatic hydrocarbon resin in the resin composition of the present invention refers to a monomer structural unit represented by the following general formula (11),
The polymer 4 (here, R4 is a hydrogen atom or an accidental alkyl group, Z
represents a halogen atom or a paper alkyl group, and p is 0 or a positive genus of 1 to 3. ) is a resin having at least 2 s in it,
For example, polystyrene, rubber-modified polystyrene (impact-resistant polystyrene), styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-acrylic acid rubber acrylonitrile copolymer, styrene-α-methylstyrene copolymer, styrene-butadiene block copolymers, etc., and these i
'! , 2 ftmlu + - was used as a base material (bar), and the acrylonitrile-EPDM-styrene graft copolymer resin used in the resin composition of the present invention (
Hereinafter, AES resin (hereinafter abbreviated as AES resin) refers to a resin obtained by graft copolymerizing EPDMi, styrene, and acrylonitrile. Here, styrene refers to styrene itself, α-methylstyrene, vinyltoluene, α-
Includes methylvinyltoluene and similar compounds. Furthermore, styrene and its analogous compounds may be used in combination of two or more.

Acrylonitrile includes not only acrylonitrile itself but also methacrylonitrile and similar compounds thereof. Acrylonitrile and its A-lower compounds may be used in combination of two or more types. EPDM is a general term for rubbery copolymers of monoolefin and polyene crystals, and includes those made from ethylene, α-ol/fins, and polyenes. Preferred copolymers of this type have 10 to 90 molar proportions of ethylene, 10 to 90 molar proportions of α-olefins having 5 to 16 carbon atoms, and 4 to 20 carbon atoms, non-conjugated cyclic or It is obtained from a monomer mixture containing 0.1 to 10 moles of polyeno, which is a chain diene. Particularly preferred are 3 to 1 carbon atoms.
It is a copolymer obtained from a monomer mixture comprising an α-ole/fin having 0 and a nonconjugated cyclic or chain diene having 5 to 10 carbon atoms. Acrylonitrile in AES resin is 5-60% of the three components, IF d,
, styrene is 60 to 80 weight liters! , L'rimo and E P
]) It is preferable that 1 occupies 10 to 60 M3 qlo. Such A E 8 < b + B words have already been sold as commercial products, for example, [product name r-J 81 (from 1 Honsei Rubber Co., Ltd.)].

ABS 110" Each H, 1 product number of Sonoike is on sale.

The proportion of the kBB resin in the polyphenylene ether resin composition of the present invention varies depending on the proportion of the polyphenylene ether resin composition, but generally speaking, the proportion of the kBB resin in the polyphenylene ether resin composition of the present invention is determined by setting the total amount of the six components to 100 parts by weight. Ether resin is 1
0 to 89 parts by weight, 10 to 8 parts by weight of vinyl aromatic hydrocarbon resin
The AES resin is blended in an amount of 1 to 20 parts by weight, preferably 10 to 88 parts by weight of a polyphenylene ether resin and 10 to 88 parts by weight of a vinyl aromatic hydrocarbon resin. be. If the content of AES resin is below the lower limit, the AES resin will not be able to contribute much to improving the mold releasability and impact resistance, and if it is above the upper limit, the original performance of the polyphenylene ether resin will be impaired.

The resin composition of the present invention may further contain an elastomer component, if desired. The elastomer component used here is an elastomer in the -y sense, for example, as described in "Propert" by A. V. Tobolsky.
ies and 5 structures of pol
y-mcrS” (John Wiley &.5o
ns, Inc., 1960) Pages 71-78 1 The adopted definition of elastomer is 10-109dynes/i (0
, 1 to 1020%). Specific examples of elastomers include A-B-A' elastomeric block copolymer, A-13-A' elastomeric block copolymer in which the double bond of the polybutadiene portion is hydrogenated, polybutadiene, polyisobutyl Copolymers of diene compounds and vinyl aromatic compounds, nitrile rubber, propylene copolymer, ethylene-propylene-diene copolymer (EPDM), thiol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, Examples include graft products of butyl rubber and polyethylene, polyester elastomers, and the like. Particularly desirable is an AB-A' dispersed elastomer block copolymer. The terminal blocks A and A' of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, B is a polymerized conjugated diene block,
It is desirable that the molecular weight of the B block is larger than the sum of the molecules of the A and A' blocks. The terminal blocks A and A' may be the same or different, and the block is a thermoplastic homopolymer or copolymer derived from a vinyl aromatic compound in which the aromatic moiety may be monocyclic or polycyclic. . Examples of such vinyl aromatic compounds are styrene,
Examples include α-methylstyrene, vinyltoluene, vinylxylene, vinylxylene, vinylnaphthalene and mixtures thereof. The central block B is a conjugated diene hydrocarbon, such as 1,6-butadiene, 2.
An elastomeric assembly derived from 6-dimethylbucdiene, isoprene and 1,6-pentadiene and mixtures thereof. Each end block A2 and A'
preferably has a molecular weight of about 2000 to about ioooooo
while the molecular weight of central block B preferably ranges from about 25,000 to about 1,000,000. Further, the dihedral bond portion of the central block r3 may be hydrogenated. Blend 1 of these elastomers is polyphenylene ether resin, vinyl aromatic hydrocarbon resin
Based on the total amount of 100 parts by weight of 6 and NTCS resins, it is added in an amount of 1 to 25 parts by weight.

If desired, stabilizers such as ft1j are added to the resin composition of the present invention, and examples thereof include triphenyl phosphite, tricresyl phosphite, tridecyl phosphite, and tri(nonylphenyl) phosphite. , hydrogenated bisphenol A phosphite resin, and the like; 2,6-tert-butyl-p-ri1/sol, 2,2'-methylenebis( 4-methyl-6-tert-butylphenol), 1.3.5
--Tris(4-tert-buna-3-hydroxy-
2,6-dimethylbenzyl)isocyanuric acid, pentaerythrityl-tetrakis[3-(3,5-di-tert)
-phthyl-4-hydroxyphenyl)propionate]
Sterically hindered phenols such as exemplified by; thermooxidative stabilizers known for other polyphenylene ether resins; 2-(
2'-hydroxy-57-methylphenyl)benzotriazole, 2-(2'-hydroxy-5''-tert
-butylphenyl)benzotriazole, 2-(2'-
Hydroxy-3',5'-di-tert-ptylph 1
benzotriazole-based ultraviolet absorbers exemplified by 2.4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2.27-dihydroxy-4-methoxybenzophenone, etc. Benzophenone ultraviolet absorber;
2.2. ．． A sterically hindered amine type ultraviolet absorber such as sepatic acid diester of 5゜6-tetramethyl-4-hydroxypiperidine; and other known ultraviolet absorbers may be blended.

The resin composition of the present invention may further contain other components such as various additives and fillers depending on the purpose.

For example, olefin wax as a lubricant such as polyethylene wax or polypropylene wax; phosphate flame retardants such as triphenyl phosphate, tricresyl phosphate, or phosphate obtained from a mixture of isopropylphenol and phenol. Plasticizer ↓ Brominated flame retardant represented by decabromo biphenyl, pestabromotoluene al or decabromo biphenyl ether; Pigment represented by p-titanium zinc sulfide or zinc oxide; Glass fiber, asbestos, wollastonite. , mica, talc, copper, aluminum or nickel flakes, or stainless steel fibers; and organic fillers such as carbon fiber or carbon black. The amount of these additions varies depending on the compound, but
It must be within a range that does not impair the heat resistance of the resin composition of the present invention.

Hereinafter, the resin composition of the present invention will be specifically explained with reference to Examples and Comparative Examples. However, the usage amount and relationship of each constituent component of the resin composition are expressed on a weight basis unless otherwise specified. .

Example 1 and Comparative Example 1 2,6-dimethylphenol/2,3 with an intrinsic viscosity of 1,52 parts g/r (25°C, OD in form).

60 parts of 6-trimethylphenol copolymer (the proportion of 2,3゜6-trimethylphenol is 5 mol g),
Impact-resistant polystyrene (intrinsic viscosity of polystyrene matrix measured in chloroform at 25 °C
-89de/9, gel-containing f''k16,5t sample analyzed using methyl ethyl ketone as solvent, Coulter
Weight average rubber particle size measured by counter 6.6μ
) 29 parts, AES&F fat [Product name 1-JSRAE
Slloj, manufactured by Japan Synthetic Rubber @] 8 parts, polystyrene-polybutadiene-polystyrene block copolymer (weight ratio of polystyrene part to polybutadiene part is 30)
/70, and 2 using a Brookfield model RVT viscometer of a 20-titoluene solution of the copolymer.
(viscosity measured at 5°C is 1500 cps) 2 parts, ethyl/propylene copolymer (reduced specific viscosity measured at 165°C at a concentration of 0.1 r/100 cps using decalin as a solvent, glass transition point -49°C) 1 part, triphenyl 7 phosphate 6 parts, titanium oxide (rutile type, average particle size Ojμ) 7 m, hydrogenated bisphenol A phosphite resin 0.4 part and 2,2'-methylene-
0.6 part of bis(4-methyl-6-tert-butyl) was thoroughly mixed using a Henschel mixer. The resulting mixture was heated to a maximum cylinder temperature of 290℃.
It was extruded into pellets using an As-60 twin-screw extruder (manufactured by Nakagama Kikai Seisakusho) set at ) was used to mold a test piece under an injection pressure of 1°50 mm. At this time, the mold release agent was first sprayed onto the mold surface, and then the number of shots of the test piece molded before it became necessary to spray the mold release agent was measured. This was used as a measure of E-shape performance.Izot impact strength was measured using a molded test piece.

The above procedure was repeated except that 67 parts of gJ-resistant polystyrene was used without using the Fi8 resin in the above operation (ratio example 1).

Izot impact strength and Bl, JL, l! are shown below. Demonstrate performance.

Table 1 It is clear from the results in Table 1 that the use of AES resin improves the isot impact strength and the release performance.

Examples 2, 6 and 4 In Example 1, 4 parts of AES resin, 63 parts of high-impact polystyrene (Example 2), and 2 parts of AES f'aJ resin were added.
part and 65 parts of high-impact polystyrene (Example 3), A
ESvL[B all 14.13. ! =iiUt impact 11 Folystyrene 23F='JI (Example 4) The procedure of Example 1 was repeated except that the blending amount was changed.

Table 2 shows the measurement results of the Izot impact strength and radial performance.

Table 2 Example 5 and Comparative Example 2 Example 1 (2,6-dimethylphenol/2,3.6-dolimethylphenol copolymer used in C) 6
0 parts, 62 parts of the impact-resistant polystyrene used in Example 1 and 8 parts of the AES resin used in Example 1 were used as the same fat components, and the other components were the same as in Example 1. The operation was repeated.

In the above, the above Ll was produced and repeated except that the AES resin was not used and the impact-resistant polystyrene was changed to 407;B (Comparative Example 2).

Izont conquest j3 to 1; strong route and ll;; l bar tree 1
・Ig fi's 8 (1) fixed five results are shown in Table 5.

Table: Example 6 and Comparative Example 6 60 parts of 2,6-dimethylphenol/2,5.6-h-limethylphenol copolymer used in Example 1, impact-resistant polystyrene used in Example 1 6
4 parts of the AES 4N resin used in Example 1, and 2 parts of the polystyrene-bolybutadiene-volistinumbronok copolymer used in Example 1 were used as resin components, and for other components: The same procedure as in Example 1 was repeated.

The above operation was repeated except that the AES resin was not used and the impact-resistant permanent polystyrene was changed to 68 parts (Comparative Example 6).

The results are shown in Table 4.

Table 4 Example 7 and Comparative Example 4 60 parts of the 2,6-dimethylphenol/2,5.6-)limethylphenol copolymer used in Example 1, used after washing in Actual Mft Example 1 735 parts of high-impact polystyrene, 6 parts of the AES resin used in Example 1, and 1 part of the egulene-propylene copolymer used in Example 1 were used as resin components, and the other components were the same as in Example 1. The procedure of Example 1 was repeated.

The above operation was repeated except that the AES resin was not heated for one month and the impact-resistant polystyrene was changed to 69 parts (Comparative Example 4).

The results are shown in Table 5.

Table 5 Example 8 and Comparative Example 5 Poly-2,6-dimethyl-1,4-phenylene/ with intrinsic viscosity 0.53d4/V (25°C, in RiII-roform)
40 parts of ether, 745.5 parts of high-impact polystyrene used in Example 1, AI! used in Example 1! : S resin 10 parts, polystyrene-polybutadiene-polystyrene block copolymer used in Example 1 6.5 parts, ethylene-propylene copolymer used in Example 1 1 part, titanium oxide used in Example 1 7 Miyako, hydrogenated bisphenol A phosphite resin o, 4 parts and 2 parts
,2'-methine-bis(4-methyl-6-tert
Example 1 was repeated, except that 0.6 part of phenol-butylphenol was used.

The same procedure as described above was repeated without using the AES resin and using 55.5 parts of high-impact polystyrene (Comparative Example 5). Table 6 shows the lees.

Table 6 Comparative Example 6 2,6-dimethylphene 7- used in Example IVL
/l/2,5.6-)limethylfuconol copolymer
60 parts of Example 1, 2 parts of high-impact polystyrene used in Example 1, 65 parts of AES resin used in Example 1
2 parts of the polystyrene-bolybutazinine-polystyrene block copolymer used in Example 1 and Example 1
One part of the ethylene-propylene copolymer used in Example 1 was used as the resin component, and the components of the song were the same as in Example 1, and the procedure of Example 1 was repeated. The results are shown in Table 7. () The mold performance is improved, but the impact strength is low.

Table 7 F------,-,,-,,:,,,-,,,----
,,,,−,,,−,,,,,−,,,,−,−,,,,
,,-□ t'1llll t! ! gender, f]I

Claims (1)

[Claims] A polyphenylene ether resin composition with improved moldability and impact resistance, containing a polyphenylene ether resin, a vinyl aromatic hydrocarbon resin, and an acrylonitrile-EPDM-styrene graft copolymer resin.