JPS63305161A - Flame-retarding polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether resin composition which has an effective flame-retarding effect and is reduced in the heating loss of the flame retardant as a whole, by mixing a polyphenylene ether resin with a vinyl aromatic hydrocarbon resin, a specified metal phosphate and a phosphate compound. CONSTITUTION:This flame-retarding polyphenylene ether resin composition contains a polyphenylene ether resin (a), a vinylaromatic hydrocarbon resin (b), a metal phosphate (c) of formula 1 (wherein M is Ca, Ba or Al, R1, R2, R3 and R4 are each a 1-3C alkyl group, l, m, n and o are each 0 or an integer of 1-5, and p is 0 when M is Ca or Ba and 1 when M is Al) and a phosphate compound (d). The amounts of components (c) and (d) are preferably such that the total of the both is 2-20pts.wt. per 100pts.wt. resin component. The ratio of component (c) to component (d) is desirably 20:80-70:30.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to the Fi-breeding polyphenylene/ether resin composition, and more specifically to the polyphenylene ether resin,
Vinyl aromatic hydrocarbon resin.

The present invention relates to a flame-retardant polyphenylene ether resin composition containing a metal salt of phosphoric acid and a phosphate compound.

[Conventional technology]

Polyphenylene ether has heat resistance, rigidity, and 1! It is a resin with excellent weather properties and is used in a wide range of applications as a useful engineering/engineering plastic. However, polyphenylene ether is inferior in moldability and impact resistance, and furthermore, its flame retardance is not sufficient by itself.

The technology of blending styrene-based resins, elastomer-reinforced water resins, and various types of elastomers for the purpose of improving moldability and impact resistance is now available! ! %
Various documents such as No. 3,585,435 are listed. However, it is well known that the q-flammability of polyphenylene ether is greatly impaired when styrene resins and elastomers are added.

For this reason, when polyphenylene ether or a resin composition consisting of polyphenylene ether and styrene resin and/or elastomer is used in applications that require flame retardancy, it is essential to include a flame retardant. well known. The retarding agents that have been recognized to be effective are mainly phosphorus-containing compounds and halogen-containing compounds.

For example, Japanese Patent Publication No. 49-52947, Japanese Unexamined Patent Publication No. 5
Aromatic 7
The use of Il esters has been proposed.

When phosphoric acid esters are added as a flame retardant to polyphenycin 21-ter, they exhibit excellent flame retardant effects and also improve molding processability due to their plasticizing effect. It is unavoidable that mechanical strength such as heat resistance or tensile strength will be significantly reduced, and furthermore, [the major problem is that these acid esters volatilize from the resin phase during molding, contaminate the metal, Furthermore, the appearance of the molded product is also impaired. This is due to the fact that the molding material containing polyphenylene ether requires a relatively high temperature of 250 to 300° C., which poses a serious problem in practical terms. Taking triphenyl phosphate and tricresyl phosphate as an example,
Even after being kneaded into the resin phase, these substances may evaporate by about 20% when heated to around 300°C. As a technique for solving the problem of volatility of phosphoric acid esters, Japanese Patent Application Laid-Open No. 1189557/1983 proposes the use of an aromatic acid ester/acid ester polymer.

On the other hand, there are many known techniques for cutting off halogen-containing compounds. For example, Japanese Patent Publication No. 48-7945 proposes a method of blending hexabromopense/and antiseptine oxide, and Japanese Patent Publication No. 48-39014 and *m1977-
No. 57255 also discloses a method of adding a similar aromatic halogen compound. Halogen-containing compounds have almost no breathability effect on polyphenylene ether, and when blended with polyphenylene ether, it hardly impairs its heat resistance, which is an excellent feature not found in acid esters. On the other hand, the disadvantage is that moldability is not improved. Furthermore.

When a halogen-containing compound is used as a flame retardant, problems such as blooming due to the migration of the halogen-containing compound to the surface of the molded product and corrosion of molding machines and metal products due to thermal decomposition products of the halogen-containing compound may occur. Rokotohayo (known.

Furthermore, Japanese Patent Publication No. 4B-38768 discloses a method of using a phosphoric acid ester and an aromatic halogen compound in combination, but even in this method, the essential The shortcomings have not been improved yet.

[Problem that the invention seeks to solve]

The present inventors have discovered that polyphenylene ether-based at
As a result of our research to solve the above-mentioned drawbacks that occur when a resin composition of a polyphenylene ether-based AT fat or a polystyrene-based resin is blended with a polystyrene-based resin, we have discovered the following. Heading 1 The resin composition of the present invention has been reached. That is, l) The metal salt of phosphoric acid described below alone does not have a flame retardant effect on polyphenylene resin compositions; n) The combination of the metal salt of phosphoric acid and the phosphate compound produces a synergistic flame retardant effect. Because the effect of oxidation appears.

The amount of phosphate compound used can be reduced compared to when a phosphate compound is used alone.

++1) Since the amount of weight loss on heating of the heptaacid metal salt is smaller than that of ordinary phosphate compounds, the amount of weight loss on heating of the -i fuel as a whole can be reduced by reducing the amount of phosphate compound used in combination. Ru.

[Means for solving problems]

The resin composition of the present invention includes (a) a polyphenylene ether resin, and (b1 a vinyl aromatic hydrocarbon resin).

A metal salt of phosphoric acid represented by the following general formula +11.

and a non-twisted polyphenylene ether resin composition containing a +dl phosphate compound.

M: Ca e Ba + AAI RI In21R31R4: C) - 3 alkyl group 1
+ m * n * O: 0 or an integer p from 1 to 5
:FiO when M is Ca or Ba; 1 when M is AJ; polyphenylene ether resin used as a component in the resin composition of the present invention is a monocyclic phenol H represented by general formula (II); Among them, R5 is a lower alkyl group having 1 to 3 carbon atoms.

R6 and R7 are hydrogen atoms or lower alkyl groups having 1 to 6 carbon atoms; polyphenylene/ether obtained by oxidative polycondensation of one or more of the following; a vinyl aromatic compound is graft-polymerized to this polyphenylene ether; It includes graft copolymers having polyphenylene ether as the base obtained by

This polyphenylene ether may be a homopolymer or a copolymer.

The I# cyclic phenol represented by the general formula (Irl) is 1, for example, 2,6-dimethylphenol.

2.6-diethylphenol, 2.6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-bropylphenol.

2-Ethyl-6-brobylphenol, m-cresonol, 2,3-dimethylphenol, 2゜3-diethylphenol, 2,3-dipropylphenol-2-/chiro-3-ethylphenol. , 2-methyl-5-propylphenol, 2-ethyl-3-methylphenol + 2
-ethyl-3-propylphenol, 2-propyl-3
-Methylphenol, 2-propyl-3-ethylphenol + 2.5.6-drimethylphenol + 2.
Examples include 5.6-dryethyl 7 ethylphenol, 2゜3.6-1-lipropylpher/-l, 2.6-dimethyl-3-ethylphenol, 2.6-dimethyl-3-propylpher/-l, etc. It will be done.

Examples of polyphenylene ethers obtained by polycondensation of one or more of these monocyclic phenols include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2゜6-diethyl-1) ,4-Fenile/
)ether.

Poly(2,6-diprobyl-1,4-phenylene/)ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2-methyl-6-bropylene/)ether
．． 4-) ether-poly(2-ethyl-6-)
Propyl-1,4-phenylene) ether, 2,6-dimethylphenol/2.3.6-)limethylphenol co-11 combination, 2, Is-dimethylphenol/
2-3-6-)! j Ethylphenol copolymer.

2.6-diethylphenol/2.5.6-)limethylphenol copolymer, 2.6-diprobylphenol/2-3-6-)limethylphenol copolymer, poly(
Glareto copolymer obtained by graft polymerizing styrene to 2,6-dimethyl-1゜4-)unicine) ether, 2.6-
Examples include graft copolymers in which styrene is grafted onto a dimethylphenol/2.5.6-)limethylphenol copolymer. ) ether, 2,6-dimethylphenol/2,3-6-dimethylphenol copolymer,
A graft copolymer in which styrene is graft-polymerized to each of the former two is preferable as the polyphenylene ether resin used in the present invention.

In the resin composition of the present invention, the vinyl aromatic hydrocarbon resin of the bl component is used to form a resin composition with the polysunilene ether resin described above (where Rg is a hydrogen atom or a lower alkyl Base.

2 represents a halogen atom or a lower alkyl group, and q is 0
Or a positive integer from 1 to 3. ) refers to a resin containing at least 25% by weight of the neutralized structural unit of the polymer. Examples of such polystyrene-based resins include polystyrene, rubber-modified polystyrene (impact-resistant polystyrene), and poly-p-methyl. Styrene, rubber-modified poly-p-methylstyrene, styrene-butadiene copolymer, styrene-butadiene-7crylonitrile copolymer, styrene-acrylic acid rubber-acrylonitrile copolymer, styrene/-α-methylstyrene copolymer, styrene-butadiene floc copolymer , styrene-maleinoic anhydride copolymer, rubber-modified styrene-maleinoic anhydride copolymer, and the like.

These Fi211 or more may be mixed and used.

The general formula (I) which is the component (e) of the resin composition of the present invention
The metal salt of phosphoric acid represented by l is disclosed in JP-A-59-1452.
It is produced according to the method for producing a phosphate ester partial metal salt disclosed in Japanese Patent No. 24. That is, first, phenols are reacted with phosphorus oxychloride or phosphoric anhydride (at a temperature of 1
After heating at 50 to 200° C. for 2 to 15 hours, hydrolysis is performed to obtain a phosphoric acid ester represented by the formula: Next, according to the synthesis method of 0 ordinary fatty acid metal salts, ! After neutralizing the ester with an alkali (e.g., sodium hydroxide) in an amount equivalent to 1.0 to 1.1 times the amount of both strong acids, inorganic acid metal salts of calcium, barium, and aluminum (e.g., calcium chloride, barium chloride, etc.) are added. The compound represented by the general formula 111 is produced by adding aluminum 411 acid (aluminum 411 acid, etc.) in an equivalent amount of the alkali required for neutralization or a slight excess thereof and metathesis.

In general formula 111, Ih, R2, R3 and R4 are each independent! and 01-3 furkyl group, ie.

There is a methyl group, an ethyl group, a propyl group, an isopropyl group, and +lm, n, and o are each independently 0 or an integer of 1 to 5. Therefore.

Specifically, the phenols used in the production of the metal salt of phosphoric acid represented by the general formula (I) include:

Phenol, cresol, xylenol, trimethylphenol, tetramethylphenol.

P/# Methylphenol, ethylphenol.

Propylphenol, isopropylphenol.

Examples include diethylphenol, triisopropylphenol, and the like, which may be used alone or in combination.

The metals forming the metal salt are calcium, barium, and aluminum, and when the metal is aluminum, one unesterified hydroxyl group must remain.

As the phosphate compound (dl component) of the resin composition of the present invention, those represented by the following general formula (2) are preferred. Specifically, phenyl-bisRIIO/ (Re, RIG-RIIFi .

dichlorofurkyl group, 7lyl group, furkyl-substituted 7lyl group,
7lyl-substituted alkyl group, hydrogen, etc. ) (dodecyl) phosphate, phenyl-bis(neohethyl) phosphate, phenyl-ethyl-hydrodiene phosphate, phenyl-bis(5,5,5-)limethylhexyl) phosphate, ethyl-diphenyl phosphate.

Bis(2-ethylhexyl)-P-)lyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate.

Tri(nonylphenyl)phosphate, phenyl-methyl-hydrogenophosphate, di(dodecyl)-P
- tolyl phosphate, tricresyl phosphate, triphenylphosphinate, tri(impropylphenyl) phosphate, phosphate obtained from a mixture of isopropylphenol and phenol, dibutyl-phenyl phosphate, P-tolyl-bis(2,5,5 -trimethylhexyl) phosphate, 2-ethylhexyl-diphenyl phosphate, diphenyl-hydrodiene phosphate, halogenated triphenyl phosphate, 2-chloroethyl-diphenyl phosphate, tris(β-naphthyl) phosphate, tris(P-phenylphenyl) phosphate, etc. It is. Furthermore, examples of phosphate compounds not represented by the general formula include phosphate polymers having two or more phosphorus atoms in one molecule obtained from a mixture of phenol and resorcinol.

In the resin composition of the present invention, the amount of the metal salt of phosphoric acid and the phosphate compound represented by the general formula (Il) varies depending on the ratio of resin components and/or the degree of flame retardation required for the resin composition. Specifically, the total amount of both is based on 100 parts of the resin component (including the elastomer).

The amount is 1 to 50 parts by weight, preferably 2 to 20 parts by weight. If the lower limit amount is not dropped, a predetermined degree of flammability is achieved, but if the upper limit amount is exceeded, other sexual performance will be impaired. In addition, the ratio (weight ratio) of the metal salt of phosphoric acid and the phosphate compound represented by the general formula (Il) is generally 10/'
10-80720-preferably 2 Q/B O-70/
30-more preferably 40/60 to 65/35.

When the proportion of the compound represented by general formula (I) is high.

If a predetermined degree of flammability is achieved and the proportion of the phosphate compound is high, the amount of volatilization from the resin composition during heating will generally increase.

The ratio of the polyphenylene ether resin to the vinyl aromatic aspect ratio hydrogen resin in the resin composition of the present invention (with respect to the heavy ratio, m is generally 799 to 99/1 - preferably 10/90 to 90,710, more preferably 20/80
~80/20.

Other components such as various additives, fillers, and elastomers may be added to the resin composition of the present invention depending on the purpose. For example, sterically hindered phenols, organic phosphites, phosphonites, phosphonasic acids, cyclic phosphonite dihydrazine derivatives, amine derivatives, carbamate derivatives, thioethers, phosphoric triamides.
Stabilizers such as benzoxazole derivatives and metal sulfides;
Pe/citriazole derivatives.

Pe/siphenon derivatives, salicylate derivatives.

Ultraviolet absorbers such as sterically hindered amines and oxalic acid diamide derivatives; Olefins/waxes as lubricants such as polyethylene wax and polypropylene/wax; decabromo biphenyl.

Pe/Tab Kumotoluene. J4 cord type S refueling agent represented by decabromo biphenyl ether, brominated polyethylene, etc.;
Ceraminaceae represented by titanium oxide, zinc oxide, carbon black, etc.; Glass fiber.

glass peas, asbestos, and wollastonite.

Inorganic fillers such as mica, talc, clay, calcium carbonate, silica, etc.: copper, nickel.

Metal flakes represented by aluminum, zinc flakes, etc.; aluminum #jI fibers, aluminum alloy fibers,
Examples include metal fibers typified by brass fibers and stainless steel fibers, carbon fibers, filter fillers typified by aromatic polyamide fibers, and the like.

Further, the elastomer is an elastomer in a general sense.
tures of I”olmers”
(John WILEY & Songs Inc.
+ 1960) Please cite the definition adopted on pages 71-78.

Elastomer has a Young's modulus of 105 to 10 at room temperature.
'dynes/a11 (0, 1~1020KP/C
11). Specific examples of elastomers include +A-B-Niya elastomeric block copolymer, and A in which the double bond in the polybutadiene portion is hydrogenated.
-B-A' type elastomeric block copolymer, polybutadiene, polyisopre/, copolymer of diene compound and vinyl compound, radial teleblock copolymer, nitrile rubber, ethylene-propylene copolymer, ethylene-
Propylene-diene copolymer (EPDM).

Examples include thiocol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber, graft copolymer of butyl rubber and polyethylene, polyester elastomer, polyamide elastomer, polyurethane elastomer, and the like. In particular, A-B-A'fi elastomeric block copolymers. The terminal blocks A and A' 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. , the molecular weight Fih of the B block and A'
It is desirable that the molecular weight is larger than the combined molecular weight of the blocks. The terminal blocks A and A' may be the same or different, and the block is made of a vinyl aromatic hydrocarbon in which the aromatic moiety may be monocyclic or polycyclic. A derived thermoplastic homopolymer or copolymer. Examples of such vinyl aromatic hydrocarbons are styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene,
Mention may be made of vinylnaphthalene and mixtures thereof.

The central block B is a conjugated diene hydrocarbon, for example lf,
Elastomeric polymers derived from 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pe/tadiene and mixtures thereof. The molecular weight of each end block A and A' is preferably about 2.
000 to about 100,000, - should the molecular weight of the central block B preferably range from about 25,000 to about 1
．． The range is 000.000.

When preparing the polyphenylene ether resin composition of the present invention, any conventionally known method may be used. For example, after mixing each component with a high-speed mixer such as a turnpull mixer or a shell/shell mixer, A mixing method using a Banbury mixer or the like is appropriately selected.

〔Example〕

Hereinafter, the resin composition of the present invention will be specifically explained using reference examples, examples, and comparative examples. Note that 1 part means 1 part by weight unless otherwise specified.

Reference Example The following metal salts of phosphoric acid synthesized according to the method described above were measured for weight loss upon heating.

Measurement conditions Equipment R: TG-8110 (ffJ Gakutm) In:
10° C./ml Mouth atmosphere: pressurized air The weight loss n of each of the above substances until the temperature was raised from room temperature to 500° C. was as follows. For comparison, values for triphenyl phosphate are also shown.

TPP 79% A) q, 4% B) /), q% C) 9, a% D) s, 9% As is clear from the above results, 1. The metal phosphoric acid used in the resin composition of the present invention The reduction in the amount of salt on heating is much smaller than in the case of hitherto known triphenyl phosphate.

Examples 1-3 2.6-dimethylphenol/2°3.6 with an intrinsic viscosity of 0.47 dl/jl (25°C, in chloroform)
Itto! j Methylphenol copolymer (2゜3.6-) The proportion of methylphenol is 5 mol%) 50 parts, II impact-resistant polystyrene/(Boristyrene/matrix measured at 25°C using chloroform as a solvent) Intrinsic viscosity 0
．． 80dA! /! ! , gel content 22.4% by weight obtained using benzene as a solvent) 46 parts, polystyrene/-polybutadiene-polystyrene block copolymer (weight ratio of polystyrene part and polybutane part is 50/70)
and the viscosity of a 20% tolueno solution of the copolymer was 1500 cps as measured at 25°C using a Brookfield Model R, VT viscometer), 5 parts of ethylene-propylene copolymer (concentration using decalin as solvent) 0゜1
y/1 o od, reduced specific viscosity measured at a temperature of 135°C 2.0. Glass transition point -49°C) 1 part.

Tetrakis (2,4-di-tart-butylphenyl)
414'-biphenylene range 7 osphonite 0.4
parts, 2,6-tert-butyl-P-cresol 0
．． 3 parts, titanium oxide 5 parts, partially oxidized polyethylene wax (Sanyo Chemical: trade name rE 250pJ) 1.5 parts,
The weight parts of triphenyl phosphate (TPP) and the metal salt of phosphoric acid of the reference example shown in Table 1, respectively, were taken out of the Labo Plastomill (Toyo Seiki) at a kneading tank temperature of 27 and heated to 290°C. Using a mold, pressure 2
001 for 10 minutes to produce a sheet with a thickness of 1/16". N" x s" strip-shaped test pieces were cut from this sheet and used to perform a baking test according to UT and 94 standards. The results are shown in Table 1.

Comparative Examples 1 to 4 In Examples 1 to 5, instead of the combined use of triphenyl phosphate and a metal salt of phosphoric acid, tri-1-enyl phosphate or Su/a! The operations of Examples 1 to 3 were repeated except that each of the metal salts was used individually in the parts by weight shown in Table 1.

The results are shown in Table 1.

From the results in Table 1, it is clear that although a large amount of metal salt of phosphoric acid alone (Comparative Example 2.3.4) has no flame retardant effect, even a small amount of metal salt of phosphoric acid has no flame retardant effect. When used in combination with a small amount of tri-7enyl phosphate, the flame retardant effect becomes apparent. Note that the ri flame retardant effect is not observed with only a small amount of triphenyl phosphate (ratio FF example 1).

Example 5 In Example 1, reference example A) was used as the metal salt of phosphoric acid.
s, sN, 1 part, triphenyl phosphate 8.
The procedure of Example 1 was repeated except that a quadruple joint was used.

The average burning time was 4.9 seconds. Incidentally, the average combustion time Fi was 8.5 seconds when only triphenyl phosphate was used in the 8.4-layer base.

Example 6 In Example 3, reference example C) was used as the metal salt of sulphur/acid.
The operation of Example 3 was repeated except that K was replaced with D) in an amount of 8.5 parts by weight, and triphenyl phosphate was used in an amount of 6.0 parts by weight. The average burning time was 5.8 seconds. On the other hand, when only 12.6 parts by weight of D) in Reference Example was used, drops occurred.

〔Effect of the invention〕

The amount of weight loss on heating of the metal salt of the oxide/acid, which is a component of the resin composition of the present invention, is small, and therefore, the weight loss of the metal salt of the anolyte/acid, which is a component of the resin composition of the present invention, is small, and therefore, the weight loss of the metal salt of the anolyte/acid, which is a constituent component of the resin composition of the present invention, is small. The amount of volatilization is lower than in the case of a resin composition containing only a corresponding phosphate compound in a large amount.

Furthermore, the combined use of a metal salt of phosphoric acid and a Boss 7ite compound has an effective flame retardant effect on polyphenylene ether resin compositions.

Claims (1)

[Claims] Contains (a) a polyphenylene ether resin, (b) a vinyl aromatic hydrocarbon resin, (c) a metal salt of phosphoric acid represented by the following general formula (I), and (d) a phosphate compound. Flame retardant polyphenylene ether resin composition▲Mathematical formulas, chemical formulas, tables, etc.▼(I) M: Ca, Ba, Al R_1, R_2, R_3, R_4: Alkyl groups of C_1_ to_3 l, m, n, o : 0 or an integer from 1 to 5 p: 0 when M is Ca or Ba 1 when M is Al