JPS60147465A - Novel polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition of improved solvent resistance and moldability without impairing mechanical strength, by incorporating a polyphenylene ether with a polyester resin and specific phenoxy resin. CONSTITUTION:The objective composition can be obtained by incorporating (A) a polyphenylene ether prepared by polycondensation of at least one sort of monocyclic phenol of formula I (R1 is 1-5C alkyl; R2 and R3 are each H or 1- 3C alkyl) with each 5-95wt%, based on the final composition, of (B) a polyester resin and (C) phenoxy resin of formula II [X1-X8 are each H, lower alkyl or halogen; n>=20(pref. >=70)] in such an amount as to be 1-99wt% based on that of the components (B) plus (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyphenylene ether resin composition having excellent mechanical strength, solvent resistance, and moldability. The present invention relates to a polyphenylene ether-based resin composition containing polyester 111 Jl'B and (c) phenoxy resin.

Polyphenylene ether is a resin with excellent heat resistance, rigidity, electrical properties, etc., and is a polymer material useful as engineering plastics. However, it is well known that polyphenylene ether has major drawbacks such as poor solvent resistance and oil resistance, as well as poor moldability.

For example, US Pat. No. 5,385,435 discloses a technique for improving the moldability of polyphenylene ether by blending polystyrene resin with it. Although blending polystyrene resin does improve moldability to some extent, it does not contribute to improving solvent resistance at all.

On the other hand, JP-A-49-50050 discloses a technique for improving the moldability, that is, melt flowability, of polyphenylene ether by blending polyester m jl with polyphenylene ether. however,
According to studies conducted by experts, the blending of ζ polyester resin certainly improves the melt flowability of polyphenylene ether;
It has become clear that when blended in an amount that accounts for 0% by weight or more, the inherent mechanical strength, especially tensile strength, of polyphenylene ether is significantly impaired. The resin composition obtained at this temperature is not a material that can withstand practical use. Furthermore, when a polyester resin is blended with polyphenylene ether, the solvent resistance of the polyphenylene ether is improved, but the degree of improvement in solvent resistance is proportional to the amount of polyester resin blended. Therefore, if the intention is to impart sufficient solvent resistance, it is necessary to blend a large amount of polyester resin, but such a blend is undesirable because it causes a decrease in the mechanical strength of the resulting resin composition, as described above. It would be dangerous if it would lead to negative results. In any case, the phenomenon that the mechanical strength of polyphenylene ether is impaired when a polyester resin is blended with polyphenylene ether is due to poor compatibility between polyphenylene ether 2 and the polyester resin.

The purpose of the present invention is to improve the solvent resistance and moldability of polyphenylene ether, and to find a resin composition that does not impair the excellent mechanical strength inherent to polyphenylene ether. The object of the present invention is to provide a novel polyphenylene ether resin composition that achieves the above object by interposing a specific resin between polyphenylene ether and polyester resin.

That is, the present invention relates to a polyphenylene ether-based resin composition consisting of polyphenylene ether, (b) a polyester resin, and (c) a phenoxy resin.

As mentioned earlier, polyphenylene ether contains Nl+
When an ester resin is blended, the mechanical strength of polyphenylene ether decreases, but in the polyphenylene ether resin composition of the present invention, extremely unique properties are achieved by blending polyester resin and phenoxy resin together with polyphenylene ether. As a result, the moldability of polyphenylene ether is improved, and the solvent resistance is further improved than when polyester resin is blended alone, and in particular, the decrease in mechanical strength is suppressed. Although the reason why the polyphenylene ether resin composition of the present invention exhibits such a unique effect is not necessarily clear, it is reported in the Journal of Applied Polymer Science (JouruaI3of
Applied Polymer 5science)
Vol. 26, pp. 1645-659 (1J79) reports that when a mixture of a polyester resin and a 7-ethyl/oxy resin is heated and kneaded, a transesterification reaction causes a busy chemical bond between the two resins. Even in this resin composition, chemical bonds are formed between the polyester resin and the phenoxy resin when the resin composition is heated and kneaded.
It is understood that a blend state not seen in conventional compositions was formed between the tophenoxy resin and the resin composition, and as a result, the above-mentioned unique effects were produced in the resin composition of the present invention.

The polyphenylene ether used in the resin composition of the present invention is a polyphenylene ether obtained by polycondensing one or more monocyclic phenols represented by the general formula (υ): The lower alkyl groups in ~3, I2 and R5 are hydrogen atoms or lower alkyl groups having 1 to 6 carbon atoms, and a lower alkyl substituent must always be present at the ortho position of at least one of the hydroxyl groups. .) Includes graft copolymers having polyphenylene ether at the core obtained by graft polymerizing a vinyl aromatic compound to L/7 ether.This polyphenylene ether may be a homopolymer or a copolymer. Good too.

Examples of the monocyclic phenol represented by the general formula (1) include 2.6-dimethylphenol, 2.6-dinitylphenol, 2.6-dipropylphenol, 2-
Methyl-6-nitylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,6-dimethylphenol, 2゜6-dinitylphenol, 2,3-dipropyl Phenol, 2-methyl-6-ethylphenol, 2-methyl-
6-propylphenol, 2-ethyl-6-methylphenol, 2-nigel-5-propylphenol, 2-
7' lobi-6-methylphenol, 2-propyl-6
-ethylphenol, 2,5.6-drimethylphenol, 2,5.6-driethylphenol, 25.6-)
Dipropylphenol, 2,6-dimethyl-3-ethyl-phenol, 2,6-dimethyl-3-propylphenol and the like can be mentioned. Examples of polyphenylene ether obtained by polycondensation of one or more of these 72/-l include poly(2,6-cymethyl-1,4-
phenylene) ether, poly(2,6-ethyl-1.
4-) unilene) ether, poly (2,,6-diprobyl-1,4-7 enylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6- Broby-ether, poly(2-ethyl-6-propyl-1,4-
phenylene) ether, 2,6-dimethylphenol/
2,5: 6-drimethylphenol t&(L 2,
is-dimethylphenol/2, 3. 6-) 11-functional tylphenol copolymer, 2,6-dinitylphenol/2,5. 6-) Limethylphenol copolymer, 2,
6-di7'a pyruphenol/2,5.6-)limethylphenol copolymer, poly(2,6'-dimethyl-1).

Graft copolymer of styrene grafted to 4-phenylene) ether, 2,6-dimethylphenol/2
, a graft copolymer obtained by graft-polymerizing styrene onto a 5,6-dorynotylphenol copolymer, and the like. In particular, poly(2,6-dimethyl-1,4-7enylene) nityl, 2,6-dimethylphenol 72*5m j6
-dolimethylphenol copolymer and a graft copolymer in which styrene is graft-polymerized to each of the former two are preferred as the polyphenylene ether resin used in the present invention.

The polyester resin used in the resin composition of the present invention refers to a high molecular weight thermoplastic resin having an ester bond in the main chain of the molecule. Polycondensation products obtained from a dicarboxylic acid or its derivative and a cyclic ether compound; Polycondensation products obtained from a metal salt of a dicarboxylic acid and a dihalogen compound; Polycondensation products obtained from a dicarboxylic acid or a derivative thereof and a dihalogen compound; Examples include ring-opening polymers. Here, the dicarboxylic acid derivative refers to an acid anhydride, an esterified product, or an acid chloride. The dicarboxylic acid may be aliphatic or aromatic, and examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrephthalic acid, and p-carboxyfurane acid. Phenylacetic acid, p-phenylene diacetic acid, m-phenylene diglycolic acid, p-phenylene diglylic acid, diphenylethane, diphenyl-p
.

p'-dicarboxylic acid, diphenyl-m,m'-dicarboxylic acid, diphenyl-4,4'-diacetic acid, di723methane-p,p'-dicarboxylic acid, diphenylethane-m,
Bodicarboxylic acid, stilbene dicarboxylic acid, penzoferne-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-dicarboxylic acid
1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2I7-dicarboxylic acid, p-carboxyphenol cyacetic acid, p-carboxyphenoxybutyric acid, 1.

2-diphenoxypropane-p,v-dicarboxylic acid, 1
, 5-diphenoxypropane-p,p'-dicarbonate iLi. s-diphenoxybutane-p+ p'-dicarboxylic acid, 1,5-diphenoxypentane-p,p'
-dicarboxylic acid, 1,6-difninoxypentane-p:
p'-dicarboxylic acid, P-(1)-carboxyphenoxy)benzoic acid, 1,2-bis(2-methoxyphenoxy)-2-p,p'-dicarboxylic acid, i,s-bis(2-methoxyphenoxy) ) Propane -p, +f/-
dicarboxylic acid, 1,4-bis(2-methoxyphenoxy)-butane-p,p'-dicarboxylic acid, 1,5-bis(
2-methoxyphenoxy)-3-pentane-p,
Examples of aliphatic dicarboxylic acids include p'-dicarboxylic acids, such as oxalic acid, succinic acid,
Adipic acid, corkic acid, gelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, fumaric acid, etc. are mentioned.

Examples of preferred dicarboxylic acids are aromatic dicarboxylic acids, and more preferred are terephthalic acid, isophthalic acid, and phthalic acid.

Examples of dihydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol, butane-1,5-diol, butane-1,4-diol,
2,2-dimethylpropane-1,6-diol, cis
-2-butysor 1,4-' diol, tra@5-2-butene-1
, 4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol and the like. Examples of preferred dihydric alcohols are ethylene glycol, propylene glycol, trimethylene glycol, butane-1,4-diol or butane-1,5-diol, more preferably ethylene glycol and butane-1 ,4
- diols may be mentioned. Examples of dihydric phenol compounds include hydroquinone, resorcinol,
Bisphenol A and the like can be mentioned.

Examples of the cyclic ether compound include ethylene oxide and propylene oxide, and examples of the cyclic ester compound include δ-varep lactone and ε
-kabu-lactone r. The dihalogen compound to be reacted with the dicarboxylic acid metal salt is the above-mentioned 2.
It refers to a compound obtained by replacing two hydroxyl groups of a hydrofluoric acid or dihydric phenol compound with a halogen atom such as chlorine or bromine.

The polyester resin used in the resin composition of the present invention may be manufactured by a known method using the above-mentioned raw materials.
Methods taught in Japanese Patent No. 15998, Japanese Patent No. 54-2594, and other known documents are employed.

Furthermore, the phenoxy resin, which is another component used in the resin composition of the present invention, refers to a polycondensate of epichlorohydrin and bisphenol A or its nuclear substituted product, and has the following general formula % formula % (in the formula % 1, which is a positive integer of 20 or more) Phenoxy resins and resins preferably used in the present invention are:
A more preferred phenoxy resin is a polymer in which n in the formula (value) is 70 or more, and a more preferred phenoxy resin is a polymer derived from shrimp coolhydrin and bisphenol A, and in which n in the formula (value) is 70 or more.

Such phenoxy resin can be produced by condensing bisphenol A or its nuclear substituted product with epichlorohydrin in the presence of an alkali such as caustic soda. ，
No. 602゜075 or Ai 1, No. 5,505,528 Specification (1) teaches this, and these are cited as references.

In the resin composition of the present invention, 6) polyphenylene ether, (b) polyester resin, and (C) phenoxy resin can be easily mixed in any ratio, but in order to achieve the object of the present invention, polyester resin and phenoxy resin should be blended in an amount that in total accounts for a proportion in the range of 5 to 95 i% by weight in the resin composition of the present invention. The phenoxy resin should be used in an amount ranging from 1 to 99% by weight of the total amount of polyester resin and 7-enoxy resin.

In order to prepare the polyphenylene ether resin composition of the present invention, any known method may be used to mix the composition components, polyphenylene ether, polyester resin, and phenoxy resin, such as roll milling, Examples include a method of melt-kneading using a Banbury Mixer 1 extruder or the like. In addition, the order in which these three components are mixed may be either mixed at the same time, or mixed in advance and then mixed with the remaining one component. However, polyester resin It is more preferable to premix the polyphenylene ether and the phenoxy resin, and then mix the mixture with the polyphenylene ether.

The resin composition of the present invention may optionally contain other resins; elastomers; various additives such as flame retardants, flame retardant aids, stabilizers, ultraviolet absorbers, plasticizers, and lubricants; pigments, fillers, Other ingredients may be added as appropriate.

Examples of other resins include polystyrene resin,
Examples include polyamide, polycarbonate, polysulfone, and the like.

To explain polystyrene resin in more detail, it is a resin containing at least 25% by weight or more of a structural unit represented by the following general formula (Ill) in its polymer, (a+t*1gK-f*tst*m* yh+hH
, '2 represents a halogen atom or a lower alkyl group, p
is 0 or a positive integer from 1 to 5. ) For example, polystyrene, high impact polystyrene, styrene-butadiene copolymer, styrene-butadiene acrylonitrile copolymer, styrene-7crylonitrile copolymer, styrene-α-methylstyrene copolymer,
Styrene/maleic anhydride copolymer, kJfjBM
styrene/maleic anhydride/copolymer, poly-p-
Examples include methylstyrene and impact-resistant poly-p-methylstyrene. Here, the impact-resistant polystyrene includes rubber-modified polystyrene modified with a rubber component such as polybutadiene, butadiene-styrene copolymer rubber, or EPDM.

The elastomeric component is an elastomer in the general sense, for example A, V,'; Tobolsky
'4- Properties and 5truct
ures of Polymers” (John
Wiley & Sonm, Inc., 196
0) You can cite the definition adopted on pages 71-78,
Elastomer has a Young's modulus of 105 to 1 at room temperature.
Ro'dynes/c+a snow (0-1~1 0 2
0 kg/Cr1L'). Specific examples of elastomers include A-B-A' type elastomeric block copolymers, A-B-x type elastomeric block copolymers in which the double bond in the polybutadiene portion is hydrogenated, and polybutadiene , polyisoprene, copolymer of diene compound and vinyl aromatic compound, nitrile rubber, ethylene-a-pyrene co-mq, ethylene-propylene-diene copolymer (EPDM), thiocol rubber,
Examples include polysulfide rubber, acrylic acid rubber, polyurethane rubber, a graft product of butyl rubber □ and polyethylene, polyester elastomer, polyamide elastomer, and the like. In particular, AB-* type elastomeric block copolymers are preferred.

The terminal blocks A and N of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block or a conjugated diene block in which most of the double bonds are hydrogenated. It is desirable that the molecular weight of the B block is larger than the combined molecular weight of the A and N blocks. The terminal bootsks A and S may be the same or different, and the bootsks are thermoplastic homopolymers or copolymers derived from vinyl aromatic compounds in which the aromatic portion may be monocyclic or polycyclic. Examples of such vinyl aromatic compounds include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof. Central block B is an elastomeric polymer derived from conjugated diene hydrocarbons such as 1,5-butadiene, 2,5-dimethylbutadiene, isoprene and 1,6-pentadiene and mixtures thereof. The molecular weight of each terminal block A and N preferably ranges from about 2,000 to about 100,000, while the molecular weight of central block B preferably ranges from about 25,000 to about 1.000. ooo, n.

It is in the range of O.

Examples of the various additives mentioned above include flame retardants such as
Phosphates such as triphenyl phosphate, tricresyl phosphate, phosphates obtained from mixtures of isopropylphenol and phenol, phosphates obtained from difunctional phenols such as benzohydroquinone or bisphenol A and other alcohols or phenols. Esters; Brominated compounds represented by decabromo biphenyl, pentabromotoluene, thecaboomobiphenyl ether, hexabromobenzene, brominated polystyrene, etc.; nitrogen-containing compounds such as cyanuric acid derivatives, melamine derivatives, etc. can. Combustion aids may be used, examples of which include antimony, boronate, zinc or iron compounds. In addition, other additives include stabilizers such as sterically hindered phenols and phosphite compounds; salicilate compounds,
Ultraviolet absorbers exemplified by oxalic acid diamide compounds and stereographic amine compounds; lubricants exemplified by polystyrene wax, polypropylene wax, and paraffin. Furthermore, titanium oxide, zinc sulfide,
Pigments exemplified by zinc oxide; exemplified by glass fiber, glass peas, asbestos, wollastonite, mica, talc, clay, carbonaceous, magnesium hydroxide, silica, potassium titanate fiber, diatomaceous earth, rock wool,
Mineral fillers; inorganic fillers typified by flakes of aluminum or zinc, or fibers of metals such as brass and aluminum zinc; and organic fillers typified by carbon fibers.

The polyphenylene ether resin composition of the present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 2,6-dimethylphenol/2,5. ．． 6. -) Limethyl 7w-nol copolymer (:21516.-)! + The ratio of methylphenol is 5 moles) to 1 part by weight of 25% polyethylene terephthalate) (melting point measured by DSC is 260%)
"C" manufactured by Toyobo Co., Ltd., grade name rRE5o
o'') 80 weight 1 kg6 and phenoxy resin (a condensate of bisphenol A and epichlorohydrin, solid content concentration 40
wt% MEK solution, the solution viscosity measured in the liquid is approximately 5,5
It has a molecular weight of approximately 29°000. Product name: "Phenoxy resin" from Union Carbide Co., Ltd.
It is commercially available under the grade name rPKHH. )20
% by weight and melted at about 3oooC using an extruder,
75 parts by weight of the pellets obtained by mixing were blended, and the mixture was melt-kneaded again at 500°C using an extruder. As a result, the composition was polyphenylene ether/polyethylene terephthalate/phenoxy resin = 25/60/1 in weight ratio.
5) and extrude to obtain pellets.

Using an injection molding machine, the pellets thus obtained are molded into 1/
Test specimens 8 inches thick were molded and tensile strength was measured.

In addition, in order to determine the solvent resistance, the pellets were subjected to chloroform extraction using a Soxhlet extractor, and the chloroform-insoluble content was determined.

The results are shown in Table-1.

As can be seen from the table, the amount of nails insoluble in chloroform was greater than the amount of polyester resin used.

Since components other than the polyester resin are soluble in chloroform, the above result can be understood to mean that a chemical bond was formed between the polyester resin and the phenoxy resin.

Comparative Example 1 In Example 1, the phenoxy resin was replaced with impact-resistant polystyrene (having a polystyrene matrix with an intrinsic viscosity of 0.89 d, 13/g as measured at 25° C. using chloroform as a solvent, and a gel portion content of Example 1 was repeated by substituting 16% iIi%). The results are in the table-
Also listed in 1.

Example 2 50% each of the polyphenylene ether, polyethylene terephthalate and phenoxy resin used in Example i
Parts by weight, 40 parts by weight and 10 parts by weight were used, and these were simultaneously melted and kneaded at 500°C in an extruder. The tensile strength and chloroform-insoluble content were measured using the same method as in Example 1. The results are shown in Table 11C.

Comparative Example 2 Example 2 was repeated except that the phenoxy resin in Example 2 was replaced with the high-impact polystyrene used in Comparative Example 1.

The results are also listed in Table-1.

Example 6 In Example 1, polyphenylene ether was added from 25 parts by weight to 75 parts by weight, and polyethylene terephthalate was added to 60 parts by weight.
20 parts by weight K from the heavy lid part.

Then, Example 1 was repeated with the composition changing the phenoxy resin from 15 parts by weight to 5 parts by weight.

The results are shown in Table-1.

Comparative Example 3 Example 5 was repeated except that the phenoxy resin in Example 6 was replaced with the high impact polystyrene of Comparative Example 1.

The results are also listed in Table-1.

Example 4 In Example 1, polyphenylene ether copolymer
Poly(2) having an intrinsic viscosity of 0.50 (dWg) measured at 25°C using polyproform as a solvent
,6-dimethyl-14-phenylene)ether 50i
lf parts, and the use of polyethylene terephthalate and phenoxy resin was changed to 45 parts by weight and 5 parts by weight, respectively.
Example 1 was repeated except that the part weight was changed.

The results are shown in Table-1.

Comparative Example 4 Example 4 was repeated except that the phenoxy resin in Example 4 was replaced with the high-impact polystyrene used in Comparative Example 1.

The results are also listed in Table IK.

Example 5 Each of the polyphenylene ether, polyethylene terephthalate and phenoxy resin used in Example 1 was
Parts by weight, 54 parts by weight, and 6 parts by weight were used, and 20 parts by weight of the high-impact polystyrene used in Comparative Example 1 were further mixed therewith, and the mixture was melt mixed at about 300°C in a simultaneous trap extruder. . The tensile strength and chloroform-insoluble content were measured in the same manner as in Example 1.

The results are shown in Table-1.

Comparative Example 5 Example 5 was repeated except that 6 parts by weight of the phenoxy resin was removed and the impact-resistant polystyrene was changed from 20 parts by weight to 26 parts by weight.

The results are also listed in Table-1.

Example 6 To 40 parts by weight of the polyphenylene ether used in Example 1 and 20 parts by weight of the high-impact polystyrene used in Comparative Example 1, polyethylene terephthalate and 7-enoxy resin used in Example 1 were added in advance at a weight ratio of 80:20. Benz obtained by melt-mixing using an extruder) 40ffi
j[, and the mixture is heated again at about 600℃ using an extruder.
The mixture was melted and kneaded. Tensile strength and chloroform insoluble content are
It was measured by the same method as Example-1.

The results are shown in Table-1.

Comparative Example 6 Example 6 was repeated except that the phenoxy resin was removed from the composition of Example 6, the impact-resistant polystyrene was changed from 20 parts by weight to 28 parts by weight, and each component was simultaneously melt-kneaded in an extruder. .

The results are also listed in Table 1.

Comparative Example 7 In Comparative Example 6, polyethylene terephthalate was
From the amount of fi to 40 parts by weight, impact-resistant polystyrene 2
Comparative Example 6 was repeated with the composition changed from 8 parts by weight to 20 parts by weight.

The results are also listed in Table-1.

Claims (1)

[Claims] (a) Polyphenylene ether and false] A polyphenylene ether resin composition consisting of a polyester resin and (C) a phenoxy resin.