JPS59122543A - Polyphenylene ether resin composition having excellent colorability - Google Patents

Abstract

PURPOSE:To provide the titled composition having lightened resin color without deteriorating the heat deformation temperature and mechanical characteritics, and having improved colorability, by compounding magnesium hypophosphite and an organic phosphonite compound. CONSTITUTION:The objective resin composition is prepared by compounding (A) 100pts.wt. of a polyphenylene ether resin with (B) 0.05-20pts.wt., preferably 0.2-5pts.wt. of magnesium hypophosphite, and (C) 0.05-10pts.wt., preferably 0.1-5pts.wt. of an organic phosphonite compound (e.g. 10-desiloxy-9,10-dihydro- 9-oxa-10-phosphaphenanthrene). The polyphenylene ether resin is preferably a mixture of 20-80wt% of polyphenylene ether and 80-20wt% of a styrene polymer. The polyphenylene ether is poly (2,6-dimethyl-1,4-phenylene) ether and the styrene polymer is high-impact polystyrene. The compounding is carried out by melting and kneading the resin with the magnesium hypophosphite and the phosphonite compound at 230-330 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition having excellent colorability. More specifically, the present invention relates to a polyphenylene ether-based mJ fat composition containing magnesium hypophosphite and an organic phosphonite compound.

In general, polyphenylene ether-based monomer resins are thermoplastic resins that have a high heat distortion temperature and excellent mechanical and electrical properties, and are often used in home appliances, office equipment, etc. It has the disadvantage that the color of ether is poor, and furthermore, the color changes due to heat and light, making it difficult to color it in vivid colors.

Thermoplastic resins are used in many applications because of their good moldability and ease of coloring, and their color characteristics are important for their marketability.

As a result of various studies conducted by the present inventors on reducing the color of polyphenylene ether resin and improving its coloring property, the present inventors have found that the high heat distortion temperature and good mechanical properties of polyphenylene ether resin can be reduced without impairing the high heat distortion temperature and good mechanical properties of polyphenylene ether resin. All improvements in coloring properties have been achieved.

The present invention provides a resin composition comprising magnesium hypophosphite, an organic phosphonite compound, and a polyphenylene ether resin.

Conventionally, phosphite was added to polyphenylene ether resin for the purpose of stabilizing it.
No. 9751, Special Publication No. 13938, Special Publication No. 1973
-40589, etc. However, the color improvement effect of the phosphorous esters described in these publications is not sufficient, and when a large amount of the phosphorous esters are added to polyphenylene ether resins, I% Kosho 51-
As described in No. 33938, the physical properties of the resin, especially the heat distortion temperature, are significantly reduced.

The most important feature of polyphenylene ether resin, which is that it has a high heat distortion temperature, is lost.

On the other hand, the present inventors added primary magnesium hypophosphite to PoIJ.
It was discovered that adding magnesium hypophosphite to phenylene ether resin had a very large color improvement effect, but adding magnesium hypophosphite drastically reduced the fluidity of polyphenylene ether 61 resin, and furthermore, the surface of the molded product became shark-skin-like. This is undesirable because the appearance of the pattern becomes uneven, and the product value is significantly impaired.

The inventors of the present invention have conducted intensive studies and found that 1. By blending the magnesium hypophosphite and organic phosphonite compound described in the present invention into polyphenylene ether-based resins, the color improvement effect is further improved, and the fluidity is further improved. The effect was great, and the shark skin pattern on the surface of the molded product was eliminated. Furthermore, there was hardly any decrease in heat distortion temperature or Izot impact strength, and surprisingly, a good resin composition was obtained with almost no thermal discoloration.

Although there are various gold silk hypophosphite salts, the magnesium salt of hypophosphorous acid is most suitable for use in combination with the organic phosnenite compound of the present invention. When sodium or barium salts of hypophosphorous acid are used, flash occurs during molding (same as silver streaks, but flash is defined as a phenomenon in which a thick mark that looks like a flash of light running in the flow direction of the resin on the surface of the molded product appears white) ) occurs. Calcium salts of hypophosphorous acid have major drawbacks such as insufficient color tone improvement effect and cannot be put to practical use. 1 to be combined with an organic phosphonite compound
It is essential that it be a magnesium hypophosphite salt.

Magnesium hypophosphite used in the present invention is a compound represented by the following chemical formula. Jiyarin Town (HzPO*
) x Magnesium oxide is generally manufactured industrially mainly for export, such as as a nutritional supplement for livestock farming.

The organic phosphonite compound used in the present invention is an allylphosphonite compound having one or more phosphonites in the molecule.

(RIIRIO here independently represents a hydrogen group, a halogen group, an alkyl group having 1 to 18 carbon atoms, an allyl group, and a halogen group having 1 to 18 carbon atoms.
alkoxy group, allyloxy group, Q has 1 to 1 carbon atoms
Residues of alcohols, phenols, and naphthols having 8 alkyl groups, allyl groups, and 2 or more hydroxyl groups, p is an integer of 1 or more, and y is an integer of 0 to 4. ) is a compound represented by Also, the general formula (where Re,
Q is the same as above. 2 represents an integer between θ and 5. ) Also included are compounds represented by

Representative examples of the organic phosphonite compounds used in the present invention include 1o-desyloxy-9,1o-dihydro-9-oxa-10-phos7a-7enanthrene, 1°-lauryloxy-9,10-dihydro-9-oxa -10-phosphaphenanthrene, lo-stearyloxy-9,10-
Dihydro-9-oxa-10-phosphaphenanthrene, 10-phenoxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, 10-(2-te
rt-butylphenoxy)-9゜O-dihydro-9-
Oxa-10-bos7 afuenanthrene, 1G-(2,
4-di-tert-butylphenoxy)-9,10-dihydro-9-oxa-10-phosphaphenanthrene,
10-, (2,6-tert-butylphenoxy)
-9,10-dihydro-9-oxa-10-phos7a7-enanthrene, 10-(2,6-dimethylphenoxy)-9,10-dihydro-9, -oxa-10-phosphaphenanthrene, (4,4 '.

6.6'-tetra-tert-butyl-2,2'-
biphenylene) phenylphosphonite, (4,4',6
．． 6'-tetra-tert-amyl-2,2'-biphenylene)phenylphosphonite, (4,4', 6,
'6'-tetratert-octyl-2,2'-biphenylene)phenylphosphonite, 0-(2,6-tert-butylphenyl)-0'-(2,4-di-tert-butylphenyl)phenylphosphonite night,
0-(2,6-dimethylphenylene/l/) -0'-
(2-tert-buty/l/7 x = A/)
Phenylphosphonite, ,0-(2,4-diter
tert-butylphenyl) -0'-(2,4,6-)di-tert-butylphenyl) phenylphosphonite, o
, o'-bis(2,6-tertgyl-4-methylphenyl)phenylphosphoney), 0.0'-bis(
2,4-di-tert-7'-tylphenyl) phenylphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphonite, tetrakis(2-tert-butylphenyl) -4,4'biphenylene diphosphonate), 14,3
-) IJ Su(2-methyl-4-(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
-yl-oxy) -5-tert-butylphenyl]
Close the lid, etc.

A particularly preferred organic phosphonite compound for use in the compositions of the invention is lO-desyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene.

The polyphenylene ether resin of the present invention has the general formula (where R□, R2, R3, R4, R5, R are the same or different alkyl groups with 4 to 4 carbon atoms, excluding tert-butyl groups, aryl A homopolymer consisting of [I] or CI) and (II) as repeating units, and the constituent units are [I] or CI) and (II). Alternatively, copolymers and graft copolymers obtained by graft-polymerizing styrene or the like onto the polymers may be mentioned.

Representative examples of homopolymers of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, and poly(2,6-dimethyl-1,4-phenylene) ether. -diether-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(
2-Methyl-6-n-butyl-1,4-phenylene)ether, poly(2-ethyl-6-improvil-1,4-
phenylene)ether, poly(2-methyl-6-diC1)
Homopolymers such as 1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether Can be mentioned.

The polyphenylene ether copolymer has the general formula (here K
R3+ R4+ R5+ R6 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, an aryl group, halogen, or hydrogen, and R5° and R6 are not hydrogen at the same time. ) Including polyphenylene ether copolymers mainly composed of a polyphenylene ether structure obtained by copolymerizing with an alkyl-transformed phenol such as 2,3,6-drimetherphenol. Alternatively, a graft copolymer of a monomer copolymerizable with styrene may be used.

Examples of monomers that can be copolymerized with styrene include α-methylstyrene, methylstyrene, dimethylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, and esters of methacrylic acid.

Means for grafting these monomers onto polyphenylene ether are not limited to lips, but for example, Japanese Patent Publication No. 52-3
0991, Japanese Patent Publication No. 52-38596, and Japanese Patent Publication No. 52-142799, etc., that is, heating styrene alone or the above monomers to polyphenylene ether in the presence of a peroxide. A method of performing a graft reaction can be used.

In addition, the polyphenylene ether resin used in the present invention includes polyphenylene ether graft copolymers alone and other resins such as styrene resins, polycarbonates, polyamides, styrene-butadiene block copolymers, etc. Mixtures of can also be used. Among these, the resin to be mixed with polyphenylene ether is preferably a styrene resin, especially impact-resistant polystyrene, from the viewpoint of mechanical properties, etc., and the blending ratio is 20-80% polyphenylene ether and 80-20% impact-resistant polymethylene ether. A weightman is best.

The amount of magnesium hypophosphite in the resin composition of the present invention is as follows:
The content is preferably 0.05 to 20 parts by weight per 00 parts by weight. Furthermore, from the viewpoint of improving the color tone, it is preferable to use 0.2 to 5 parts by weight, most preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyphenylene ether resin.
It is a proportion of parts by weight.

If the amount of magnesium hypophosphite added is too small, the effect of improving the color tone will not be large, and if the amount added is too large, the mechanical properties of the resin composition will deteriorate, which is not preferable.

On the other hand, the amount of the organic phosphonite compound is preferably 0.05 to 10 parts by weight per 100 parts by weight of the polyphenylene ether resin. The most preferable ratio is 0.1 to 5 parts by weight based on ioo parts by weight of the polyphenylene ether resin.

Further, in order to increase the stabilizing effect, a phenolic antioxidant may be further added to the resin composition of the present invention. A sterically hindered phenol is used as the phenolic antioxidant.

The method for producing the resin composition of the present invention is not particularly limited. For example, resin and additives are mixed in a conventional extruder, kneader 1, etc.
A method of kneading using a heating roll, a Banbury mixer, etc. can be adopted. Further, the kneading temperature is 230°C depending on the content of polyphenylene ether in the resin composition of the present invention.
It is preferable to carry out at a temperature of ~330°C. The temperature of the melting wire and sufficient mixing are effective in improving the color tone, and preferably the shear rate (shear rate) is 50 sec.
``It is preferable to mix the wires by melting at or above.

Other additives conventionally known to the compositions of the invention, such as plasticizers, colorants, flame retardants, stabilizers, mold release agents and glass fibers,
It is of course possible to add fillers such as glass peas, calcium carbonate, and talc to the fibrous reinforcing agent such as carbon fiber.

The resin composition obtained by the present invention has good color tone and little discoloration due to heat, so it is a polyphenylene ether resin composition that can be produced in five bright colors, and has good mechanical properties, heat It is extremely useful industrially because it has a high deformation temperature.

Examples are shown below, but it goes without saying that the present invention is not limited to the following examples.

Parts indicate parts by weight.

Examples 1 to 3 Intrinsic viscosity measured at 30°C after dissolving in chloroform is 0
．． 64dllt of poly(2,6-dimethyl-phenylene-1,4-ether), rubber-reinforced polystyrene (Stein 402...manufactured by Asahi Kasei Industries, Ltd.), magnesium hypophosphite (Daido Pharmaceutical Co., Ltd. #), 10- Desyloxy-9,1
o-dihydro-9-oxa-10-phosphaphenanthrene (DC...manufactured by Sangensha), octadecyl-3-(3
, 5-ditertiary-butyl-4-hydroxyphenyl) flobionate (Irganox 1076, manufactured by Ciba Geigy) were uniformly mixed in a blender in the proportions shown in Table 1, and heated to 290 °C using a 30mm twin-screw extruder. The mixture was melt-mixed to obtain a pellet-shaped resin composition. 72o7 test method and Izod impact strength were measured based on the JIS-K 7110 test method. Also, the gloss level is JIS-Z
It was measured based on the test method of 8741. The appearance was determined by visual observation of the appearance of shark skin patterns.

The physical property measurement results are shown in Table IK. By using magnesium hypophosphite and an organic phosphonite compound, the color improvement effect was further improved, and surprisingly, the fluidity improvement effect was large, and the shark skin pattern on the surface of the molded product was eliminated. Further, there is almost no decrease in heat distortion temperature and Izot impact strength, and more surprisingly, it is clear that there is almost no thermal discoloration.

Comparative Example 3 Intrinsic viscosity measured at 30'C after dissolving in chloroform is 0.64 del? poly(2,6-dimethyl-phenylene-1,4-ether), rubber-reinforced polystyrene (
Styron ■402 (manufactured by Asahi Kasei Industries, Ltd.) Also, resin compositions in which magnesium hypophosphite and organic phosphonite compounds among the above components were not used were obtained for comparison (Comparative Examples 1 and 2).

The resin composition thus obtained was molded at 290° C. using a 5-ounce injection molding machine and subjected to a test.

Whiteness is determined by object color filj measurement color measurement color difference measurement W
(Lab) values are shown.

The color tone was determined by visually observing a test piece molded using an injection molding machine.

Thermochromic property is the difference in color tone between a test piece molded under normal conditions and a test piece molded in an injection molding machine at a temperature of 290°C with the resin staying in the molding machine for 10 minutes longer than usual. ΔE (Lab) measured with a color difference meter for measuring object color
It is shown as the value of

Fluidity is determined by melt flow index (25°℃1
oK9 load), injection molded product (JIS-6871) The minimum injection pressure to obtain a tensile test piece that fully satisfies JIS-6871 was measured.The heating deformation temperature was a,s-ditertiary-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Geigy) was blended in the proportions shown in Table 1 and evaluated using the methods of Examples 1 to 3.The results are shown in Table 1. -1.

Although the calcium salt of hypophosphorous acid has a small shark-skin appearance, it is clear that the color tone improvement effect is not sufficient and it cannot be put to practical use. Therefore, in order to be used simultaneously with an organic phosphonite compound, it is essential to use a magnesium salt of hypophosphorous acid.

The following is a margin of N-1m.Properties and physical properties of the fat composition) Color tone; Appearance showing the order of Osu... × Good Poor); Company Procedures Amendment (Voluntary) February S, 1980 Director General of the Patent Office Kazuo Wakasugi 1, Indication of Case Patent Application No. 227665 of 1988
No. 2, Name of the invention: Polyphenylene/tech-chill resin composition with excellent coloring property a Relationship with the case of the person making the amendment Patent applicant: 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture, subject of the amendment 5. Contents of amendment (L) The general formula on page 7, line 7 of the specification will be corrected.

(2) Page 16, line 18, “A composition was obtained.” and “
Insert the following sentence between "Test method of 7207."

(Examples 1 to 3) Resin compositions in which magnesium hypophosphite and organic phosphonite compounds among the above components were not used were also obtained for comparison (Comparative Examples 1 to 2).

The resin composition thus obtained was molded using a 5-ounce injection molding machine at 290°C and subjected to testing.

The whiteness is W(La) measured using a colorimeter for measuring object color.
b) values are shown.

The color tone was determined by visually observing a test piece molded using an injection molding machine.

Thermochromic property was ゛C1 for test pieces molded under normal conditions.
△E (Lab) The difference in color tone from a test piece molded with an injection molding machine at a temperature of 290°C and with the resin staying in the molding machine for 10 minutes longer than usual was measured using a color difference meter for object color measurement.
It is shown as the value of

Fluidity is determined by melt flow index (250℃
1 OKf load), and the minimum injection pressure to obtain an injection molded product (tensile test piece satisfying JIS-6871) was measured. In addition, the heating deformation temperature is JIS-K.'' (3) The text from page 17, line 15 to page 18, line 13, ``Also, among the above components...・
・Delete JIS-Kl for heating deformation temperature.

(4) In the bottom column of the physical properties column of Table 1 on page 20, [most recent injection pressure to obtain a molded product (xy/c++!G)J] is [minimum injection pressure to obtain a molded product (Kfl-〇)J] to correct.

that's all

Claims (1)

[Scope of Claims] 1. A resin composition with excellent coloring property characterized by comprising magnesium hypophosphite, an organic phosphonite compound, and a polyphenylene ether-based four-stick resin (2. Polyphenylene ether in the resin composition, lI fat 1
0.05 parts by weight of magnesium hypophosphite
Furthermore, an organic phosphonite compound is added in a proportion of ~20 parts by weight.
．． Resin composition 1 according to claim (1) containing 0.05 to 10 parts by weight of magnesium hypophosphite per 100 parts by weight of polyphenylene ether resin in the resin composition. The resin composition according to claim (1), further comprising 0.1 to 5 parts by weight of an organic phosphonite compound. ,10-
The resin composition according to claim (1), which is dihydro-9-oxa-10-phosphaphenanthrene, and the polyphenylene ether-based resin composition, which is a mixture of polyphenylene ether and styrene polymer. Resin composition according to range item (1) & 20 to 80% by weight of polyphenylene ether and 80% of tostyrene polymer
~207t % of claim No. (
Resin composition 7 according to item 5), wherein the polyphenylene ether is poly(2,6 dimethyl-1,4-phenylene) ether,
Resin composition 8 according to Claim 8, Resin composition 9 according to Claim 5 or 6, wherein the polyphenylene ether is styrene kraft poly(2,6 dimethyl-1,4-phenylene) ether. , the resin composition 10 according to claim (5) or (6), wherein the styrenic polymer is made of impact-resistant polystyrene, and the resin composition according to claim (1), which is made of phenol. A polyphenylene ether resin composition 11 containing a polyphenylene ether antioxidant is obtained by completely melting and intermixing a polyphenylene ether resin, magnesium hypophosphite, and an organic phosphonite compound at a temperature of 23o~330°G. Claim No. (
Method for producing a resin composition according to item 1) lλ A method for producing a resin composition according to claim <11), characterized in that the shear rate at the time of melt mixing 9 is 505 ec-1 or more