JP3414501B2 - Polyphenylene ether-based flame-retardant resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent flame retardancy, which is obtained by blending two kinds of specific phosphoric acid ester compounds with a polyphenylene ether resin. INDUSTRIAL APPLICABILITY The resin composition of the present invention is free from volatilization of a flame retardant, smoke generation, and bleeding at the time of molding and is excellent in handleability. Molded articles of this resin composition have no discoloration or blistering, and water characteristics do not deteriorate electrical characteristics and the like.

[0002]

2. Description of the Related Art Synthetic resins are generally light, have excellent water resistance, chemical resistance, electrical insulation, mechanical properties, and are easy to mold and process, so they are used as building materials, electrical equipment materials, automotive materials, fibers. Widely used as a material. However, synthetic resins have a drawback that they are more likely to burn than metal materials and inorganic materials. Therefore, many methods for making the synthetic resin flame-retardant have been proposed. Among these conventional flame-retarding methods, the method of blending a halogen compound, a phosphorus compound, an inorganic hydrate or the like with a synthetic resin is most widely used. In particular, organic phosphate compounds such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate and the like are widely used industrially. However, such conventionally used flame retardants have drawbacks such as causing smoke during the molding process, volatilizing, and bleeding on the surface of the molded product.

In order to solve the above-mentioned drawbacks, attempts have been made to put into practical use an organic phosphate compound having a large molecular weight as a flame retardant. For example, European Patent Application Publication No. 74
No. 60, tri (2,6-dimethylphenyl) phosphate compound, European Patent Application Publication No. 129824.
No. 129825, No. 129726, No. 135726, and British Patent Application Publication No. 2043083 disclose resorcinol bisdiphenyl phosphate compounds, and US Pat. No. 4,683,255 discloses tribiphenyl phosphate compounds. . However, these phosphoric acid ester compounds must be used in a large amount to make the resin flame-retardant. In addition, according to our research and analysis, the resin composition flame-retarded by using these phosphate ester compounds may corrode the mold during molding,
The flame retardant may be modified during molding or during long-term use of the molded product, or the molded product may become discolored or blistered, and water absorption may deteriorate the electrical and flame retardant properties of the molded product. Therefore, it was found that the recent severely required characteristics were not satisfied. Further, there is a problem in that handling is deteriorated due to the use of a highly viscous phosphorus compound due to a problem in manufacturing the phosphorus compound.

As described above, conventionally, it has not been possible to provide a resin composition which simultaneously satisfies sufficient flame retardancy, required performance as a product and handleability.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a resin composition which is free from smoke, volatilization and bleeding of a flame retardant at the time of molding and has excellent handleability, and does not cause discoloration, blistering or deterioration of electrical properties of the molded product. Provide things. The present invention not only provides a resin composition having excellent properties, but also achieves flame retardancy of a resin with a halogen-free flame retardant, which has recently been increasing in market demand from the viewpoint of environmental impact and safety. This can contribute to the technical solution of global environmental problems.

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, the phosphoric ester of the component (B) having a specific bond structure with the poniphenylene ether resin The composition in which the compound and the phosphoric acid ester compound of the component (C) having a bond structure different from that of the component (B) are combined does not cause smoke, volatilization or bleeding of the flame retardant during molding and is excellent in handleability. , Found that the discoloration, swelling, and electrical characteristics of the molded product did not deteriorate,
The present invention has been completed.

That is, the present invention comprises 100 parts by weight of (A-1) polyphenylene ether resin, or 10 to 99 parts by weight of (A-1) polyphenylene ether resin and (A-2).
With respect to 100 parts by weight in total of 90 to 1 parts by weight of polystyrene resin, (B) general formula (I)

[0008]

[Chemical 3]

(Here, Q1, Q2, Q3 and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms. R1 and R2 each independently represent a methyl group, and R3 and R4 each independently represent a methyl group or hydrogen. n represents an integer greater than or equal to 1. n1 and n2 are 0 independently.
Represents an integer from 2 to 2. m1, m2, m3, and m4 each independently represent an integer of 0 to 3. ), A phosphoric acid ester compound represented by the formula (C), and (C) the general formula (II)

[0010]

[Chemical 4]

(Here, Q represents a divalent residue corresponding to hydroquinone or resorcinol. Q5, Q6, Q
7 and Q8 each independently represent an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 or more. m5, m6, m7, m8
Each independently represents an integer of 0 to 3. ), The total of (B) and (C) is 0.1 to 0.1.
30 parts by weight, and (B) for the total of (B) and (C)
99 to 20% by weight of component, 1 to 80% by weight of component (C)
A polyphenylene ether-based flame-retardant resin composition comprising

The present invention will be described in detail below. The polyphenylene ether resin used as the component (A-1) of the present invention means the general formula (III-1) and / or (III-
It is a homopolymer or a copolymer having a repeating unit represented by 2).

[0013]

[Chemical 5]

(Where R5, R6, R7, R8, R
9 and R10 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, or hydrogen. However, R9 and R10 are not hydrogen at the same time. ) A typical example of a homopolymer of polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene).
Ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-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-isopropyl-1,4-) Examples thereof include phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether.

Among these, poly (2,6-dimethyl-1,
4-phenylene) ether is particularly preferred. The polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. For example,
Copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2,3,6- Examples thereof include copolymers with trimethylphenol and o-cresol.

In the polyphenylene ether-based resin of the present invention, various other phenylene ether units which have been proposed to be present in the polyphenylene ether resin may be used unless they are contrary to the gist of the present invention. It may be included as a partial structure. As an example of what is proposed to coexist in a small amount, JP-A-1-29 is known.
2- (dialkylaminomethyl) -6 described in JP 7428 and JP-A 63-301222.
-Methylphenylene ether unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like.

Further, a polyphenylene ether resin in which a small amount of diphenoquinone or the like is bound in the main chain is also included.
Furthermore, for example, polyphenylene ether modified with a compound having a carbon-carbon double bond, as described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724 and the like. Also includes.

The method for producing the polyphenylene ether resin used in the present invention is not particularly limited, but, for example, according to the method described in Japanese Patent Publication No. 5-13966, in the presence of dibutylamine, 2,6 It can be produced by oxidative coupling polymerization of xylenol. Moreover, the molecular weight and the molecular weight distribution are not particularly limited.

The polystyrene resin used as the component (A-2) of the present invention is a vinyl aromatic polymer or a rubber-modified vinyl aromatic polymer. As the vinyl aromatic polymer, in addition to styrene, nuclear alkyl-substituted styrenes such as o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene, α-methylstyrene,
Polymers of α-alkyl-substituted styrenes such as α-methyl-p-methylstyrene, and copolymers of one or more of these with at least one of other vinyl compounds, and these 2
One or more copolymers may be mentioned. As the compound copolymerizable with the vinyl aromatic compound, methyl methacrylate,
Methacrylic acid esters such as ethyl methacrylate,
Examples thereof include unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and acid anhydrides such as maleic anhydride. Among these polymers, particularly preferred polymers are polystyrene and styrene-acrylonitrile copolymer (AS resin).

Examples of the rubber used for the rubber-modified vinyl aromatic polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber and ethylene-propylene copolymer. You can In particular, polybutadiene and a styrene-butadiene copolymer are preferable, and as the rubber-modified aromatic polymer, rubber-modified polystyrene (HIPS),
Rubber-modified styrene-acrylonitrile copolymer (ABS
Resin) is preferred.

The phosphoric acid ester compound used as the component (B) of the present invention has the general formula (I)

[0022]

[Chemical 6]

(Here, Q1, Q2, Q3 and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms. R1 and R2 each independently represent a methyl group, and R3 and R4 each independently represent a methyl group or hydrogen. n represents an integer greater than or equal to 1. n1 and n2 are 0 independently.
Represents an integer from 2 to 2. m1, m2, m3, and m4 each independently represent an integer of 0 to 3. ). General formula (I)
It is preferable that n1 and n2 are 0 and R3 and R4 are methyl groups.

In the general formula (I), m1, m2,
m3 and m4 are 0, that is, there is no substitution of an alkyl group on the terminal phenyl group, or Q1, Q2, Q3,
Most preferably, Q4 is a methyl group, that is, a terminal phenyl group is substituted with a methyl group. General formula (I)
N is an integer of 1 or more, and the heat resistance and workability differ depending on the number. The preferred range of n is 1 to 1
It is 0. The component (B) may be a mixture of n-mers.

The phosphoric acid ester compound of the component (B) of the present invention has a binding structure with a specific bifunctional phenol and a terminal structure with a specific monofunctional phenol. Examples of the bifunctional phenol include 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, Bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-
Examples include, but are not limited to, bisphenols such as bis (4-hydroxyphenyl) ethane. Bisphenol A is particularly preferable.

As the monofunctional phenol, unsubstituted phenol, monoalkylphenol, dialkylphenol and trialkylphenol can be used alone or as a mixture of two or more kinds. Especially phenol, cresol,
Dimethylphenol (mixed xylenol), 2,6-dimethylphenol and trimethylphenol are preferred.
The phosphoric acid ester compound as the component (B) is greatly suppressed in volatility and is excellent in stability and hydrolysis resistance.
Further, it does not cause a problem such as gelation by causing a reaction with the polyphenylene ether resin, does not accelerate decomposition of the polyphenylene ether resin, and does not corrode metal parts such as a molding machine. .

In the present invention, the component (C) general formula (II) is used in combination with the above-mentioned component (B) phosphate ester compound.

[0028]

[Chemical 7]

(Here, Q represents a divalent residue corresponding to hydroquinone or resorcinol. Q5, Q6, Q
7 and Q8 each independently represent an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 or more. m5, m6, m7, m8
Each independently represents an integer of 0 to 3. ), The phosphoric acid ester compound represented by can be used. General formula (I
In I), m5, m6, m7 and m8 are 0, that is, there is no substitution of the alkyl group on the terminal phenyl group, or Q5, Q6, Q7 and Q8 are methyl groups, that is, the terminal phenyl group is substituted with a methyl group. Is preferable.

In the general formula (II), n is an integer of 1 or more, and heat resistance and workability vary depending on the number.
The preferable range of n is 1 to 10. The component (C) may be a mixture of n-mers. (C) of the present invention
The phosphoric acid ester compound as a component has a binding structure with a specific bifunctional phenol and a terminal structure with a specific monofunctional phenol.

As the bifunctional phenol, hydroquinone or resorcinol can be used. As the monofunctional phenol, the constituent monofunctional phenol of the phosphoric acid ester compound as the component (B) can be similarly used. Particularly, phenol, cresol, dimethylphenol (mixed xylenol), 2,6-dimethylphenol and trimethylphenol are preferable.

When the phosphoric acid ester compound of the component (B) is used in combination with the phosphoric acid ester compound of the component (C), the flame retardancy is not impaired as compared with the case where each of them is used alone, and the molding process is effectively performed. It is possible to reduce smoke generation and bleeding. Generally, both the component (B) and the component (C) are liquid substances at around room temperature, but the component (B) is a viscous liquid having an extremely high viscosity, and the handleability during metering and mixing is poor, but the viscosity is By using the low component (C) together, the viscosity of the mixed phosphoric acid ester compound is lowered and the handling becomes easy. Further, the component (C) has a drawback that it is inferior in hydrolysis resistance to the component (B), but in the resin composition of the present invention used in combination with the component (B), the component (C) is simply added. It is possible to improve the hydrolysis resistance more effectively than to reduce the amount, and to suppress discoloration or blistering of the molded product or dielectric breakdown due to water absorption that occurs in the exposure test under high temperature and high humidity conditions.

The phosphoric acid ester compound as the component (B) and the component (C) can be obtained by reacting the above-mentioned bifunctional phenol and monofunctional phenol with phosphorus oxychloride, but the production method is not restricted at all. There is no such thing.
The resin composition of the present invention comprises 100 parts by weight of the polyphenylene ether resin as the component (A-1), or 10 to 99 parts by weight of the polyphenylene ether resin as the component (A-1) and (A-
2) Component polystyrene-based resin 90 to 1 parts by weight in total 1
With respect to 00 parts by weight, the total amount of the phosphoric acid ester compound as the component (B) and the phosphoric acid ester compound as the component (C) is 0.1 to 30 parts by weight, and the total of (B) and (C) is (B) component is 99 to 20% by weight, and (C) component is 1 to 8
0% by weight, more preferably 90 to 35% by weight of the component (B) and 10 to 65% by weight of the component (C). If the blending ratio of the component (B) and the component (C) is too small, that is, less than 0.1 parts by weight to 100 parts by weight of the resin, the flame retardancy is insufficient, and if too much, that is, 100 parts by weight of the resin is added. On the other hand, when the amount is 30 parts by weight or more, the heat resistance of the resin is impaired. Also, for the sum of (B) and (C), (C)
If the amount of the component is too large, the hydrolysis resistance is impaired, and if the amount of the component (C) is too small, the handleability is not sufficiently improved.

In addition to the phosphoric acid ester as the component (B) and the component (C) used in the present invention, a phosphoric acid ester generally used within a range that does not impair the effects of the present invention, such as triphenyl phosphate and tricre. Contains phosphoric acid esters such as dil phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with various substituents, various condensation type phosphoric acid ester compounds, etc. You may have.

Other additives to the resin composition of the present invention, such as plasticizers, other flame retardants, etc., within the range that does not impair the effects of the present invention,
It is possible to add stabilizers such as antioxidants and ultraviolet absorbers, release agents, dyes and pigments, or fibrous reinforcing agents such as glass fibers and carbon fibers, and fillers such as glass beads, calcium carbonate and talc. it can. The method for producing the composition of the present invention is not particularly limited, and it can be produced by kneading using a kneader such as an extruder, a heating roll, a kneader, a Banbury mixer.

[0036]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
The composition was evaluated by the following methods and conditions.・ Flame resistance: 8 based on UL standard 94 vertical combustion test method
It was performed and rated using a 1-inch test piece.

Amount of smoke generated: The amount of smoke generated from the nozzle of the injection molding machine when purging the resin composition was visually observed. -Handlability: The viscosity of the mixed phosphate ester compound was used as an index of handleability. The viscosity of the phosphoric acid ester compound was calculated by measuring the flowing time using an Ubbelohde viscometer at 25 ° C., multiplying this by the constant of the viscometer to determine the kinematic viscosity, and further multiplying the kinematic viscosity by the density of the sample.

Hydrolyzability of composition: Gloss change ΔG (gloss before test-gloss after test) of the test piece after hot water immersion test (80 ° C., 10 hr) was evaluated. The gloss was measured based on JIS-Z8741 using a dumbbell test piece at an incident angle of 60 °. The impact-resistant polystyrene resin used in Examples and Comparative Examples was prepared by the following manufacturing method.

(Production Example 1: Preparation of partially hydrogenated conjugated diene rubber
Construction) The partially hydrogenated conjugated diene rubber used in the examples is
It was produced by the method described. A stirrer with an internal volume of 10 liters,
Using a jacketed autoclave as a reactor,
Butadiene / n-hexane mixture (butadiene concentration 20
%) At 20 liters / hr, n-butyllithium / n
-Hexane solution (concentration 5%) 70 ml / hr
And continuous polymerization of butadiene at a polymerization temperature of 110 ° C.
Carried out. Deactivate the obtained active polymer with methanol and separate
Stirrer with internal volume of 10 liters, reaction with jacket
Transfer 8 liters of polymer solution to the machine and add water at 60 ° C.
Di-p-tolyl-bis (1-cyclopenta) as an addition catalyst
Dienyl) titanium / cyclohexane solution (concentration 1.
2 millimoles / liter) 250 ml, n-bu
Chill lithium solution (concentration 6 mmol / l) 50m
Liter and 0 ℃, 2.0kg / cm²Under hydrogen pressure of
Add a mixture, hydrogen partial pressure 3.0 kg / cm ²At
The reaction was carried out for 60 minutes. The partially hydrogenated polymer solution obtained was acid
2,6-di-t-butylhydroxytate as an antioxidant
Add 0.5 parts of Ruene per polymer to remove solvent
It was Partial hydrogenation obtained by sampling after deactivation of methanol
The analytical values of the conjugated diene rubber are shown in Table 1.

[0040]

[Table 1]

Production Example 2: (Production of Impact-Resistant Polystyrene Resin) The impact-resistant styrene resin used in the examples was produced by the bulk polymerization method: 10 parts of the partially hydrogenated conjugated diene rubber of Production Example 1 and 90 parts of styrene. And ethylbenzene dissolved in 8 parts of benzene, and further added with 0.05 part of benzoyl peroxide and 0.10 part of α-methylstyrene dimer with respect to styrene, and heated at 80 ° C. for 4 hours and 110 ° C. for 4 hours. 15
Polymerization was carried out at 0 ° C. for 4 hours with stirring. Further, heat treatment was carried out at around 230 ° C. for 30 minutes, and then unreacted styrene and ethylbenzene were removed in vacuum to obtain a high impact polystyrene resin. The content of partially hydrogenated polybutadiene in the obtained impact-resistant polystyrene resin was 11%,
The average particle size of the partially hydrogenated polybutadiene containing the dispersed particles of polystyrene was 1.3 μm. Also,
The reduced viscosity measured at 30 ° C. in toluene was 0.65.

(Phosphoric acid ester compound) Table 2 shows the phosphoric acid ester compound used in Examples and Comparative Examples.

[0043]

[Table 2]

[0044]

Example 1 Poly-2,6-dimethyl-1,4 having an intrinsic viscosity [η] of 0.52 measured at 30 ° C. in chloroform.
-65 parts by weight of phenylene ether (hereinafter abbreviated as PPE), 23 parts by weight of high impact polystyrene resin (hereinafter abbreviated as HIPS) prepared in Production Example 2, polystyrene resin [Asahi Kasei Polystyrene 68: Asahi Kasei Polystyrene 68]
5] (hereinafter, abbreviated as GPPS) 12 parts by weight of the resin composition is added to 100 parts by weight of the phosphoric acid ester A in an amount of 6 parts by weight.
6 parts by weight of phosphoric acid ester C and octadecyl-3- (3,5-di-t-butyl-4) as a stabilizer.
0.3 parts by weight of -hydroxyphenyl) propionate was mixed and melt-kneaded with a twin-screw extruder set to a cylinder temperature of 300 ° C to obtain pellets. The pellets were injection-molded and evaluated. The results are shown in Table 3.

[0045]

Examples 2 to 4 and Comparative Examples 1 to 3 Each component was mixed in the composition shown in Table 3 and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0046]

[Table 3]

[0047]

EFFECTS OF THE INVENTION The polyphenylene ether flame retardant resin composition of the present invention is free from smoke, volatilization and bleeding of the flame retardant at the time of molding and is excellent in handleability as compared with the conventional flame retardant resin composition. It is possible to provide a non-halogen flame-retardant resin composition which is free from discoloration, blistering, deterioration of electrical characteristics and the like.

Claims (5)

(57) [Claims] 1. With respect to 100 parts by weight of (A-1) polyphenylene ether resin, (B) general formula (I): (Here, Q1, Q2, Q3, and Q4 independently have 1 carbon atom.
Represents an alkyl group from 6 to 6. R1 and R2 are methyl groups,
R3 and R4 independently represent a methyl group or hydrogen. n is 1
Represents the above integers. n1 and n2 each independently represent an integer of 0 to 2. m1, m2, m3, and m4 each independently represent an integer of 0 to 3. ) And a phosphoric acid ester compound represented by the formula (C) and a general formula (II): (Here, Q represents a divalent residue corresponding to hydroquinone or resorcinol. Q5, Q6, Q7, and Q8 each independently represent an alkyl group having 1 to 6 carbon atoms. N represents an integer of 1 or more. M5, m6, m7, and m8 each independently represent an integer of 0 to 3), and the phosphoric acid ester compound represented by (B) and (C) is 0.1 to 30 parts by weight, And the component (B) is 99 to 20 with respect to the total of (B) and (C).
A polyphenylene ether flame-retardant resin composition comprising 1% to 80% by weight of component (C). 2. (A-1) 100 parts by weight of polyphenylene ether resin, (A-1) 10 to 99 parts by weight of polyphenylene ether resin and (A-2) polystyrene resin 9
The polyphenylene ether flame-retardant resin composition according to claim 1, which is a total of 100 parts by weight of 0 to 1 part by weight. 3. In the general formula (I) representing the phosphoric acid ester compound as the component (B), n1 and n2 are 0, and R3 and R
4. The polyphenylene ether flame-retardant resin composition according to claim 1, wherein 4 is a methyl group. 4. In the general formula (I) representing the phosphoric acid ester compound as the component (B), m1, m2, m3 and m4 are
The polyphenylene ether flame-retardant resin composition according to claim 1 or 2, which is 0. 5. In the general formula (I) representing the phosphoric acid ester compound of the component (B), Q1, Q2, Q3 and Q4 are
The polyphenylene ether flame-retardant resin composition according to claim 1 or 2, which is a methyl group.