JP3500390B2 - Flame retardant resin electric parts - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether-based resin flame-retardant component having excellent low-gas and moisture-heat resistance. More particularly, the present invention relates to a CRT-related high-pressure flame-retardant resin electric component such as a deflection yoke, a magnetic yoke, a flyback transformer, and the like, which are required to have flame retardancy, wet heat resistance, electrical characteristics, and moldability. [0002] The present invention also requires a flame-retardant resin electric component and a relay related to a power supply device such as an AC adapter case, a battery charger, a power transformer, and a power supply box, which require the same characteristics as a CRT-related resin high-voltage electric component. Related to flame-retardant resin electric parts related to relay devices such as main body, relay connector, terminal block, etc., flame-retardant resin electric parts related to display devices such as LED cases and LCD cases, and coin-mechanical parts etc. . [0003] A polyphenylene ether-based resin composition comprising a polyphenylene ether-based resin, particularly a polystyrene-based resin, excels in mechanical properties, thermal properties, moldability, flame retardancy, and electrical properties. From, for example, home appliance parts,
It is widely used as a material for office machine parts, electric and electronic parts, and the like. The main performance requirements for CRT-related flame-retardant resin electrical components are moldability, product appearance, and electrical characteristics under high-temperature and high-humidity conditions. However, with the improvement of industrial technology, the required performance is becoming increasingly severe. At present, there is a tendency that it is difficult to respond in terms of performance with electric parts formed by processing a conventional polyphenylene ether-based flame-retardant resin composition.
An electric part formed by processing a conventional polyphenylene ether-based flame-retardant resin composition has the following performance problems. A conventional polyphenylene ether-based flame-retardant resin composition contains a phosphorus compound or the like as a flame retardant. In particular, organic phosphate compounds such as triphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate and the like are widely used industrially. However, such additives conventionally used are:
During the molding process, smoke and volatilization occur, and the gas causes poor filling and sink marks of the molded product, and the gas trapped in the mold condenses and adheres to the surface of the molded product, and the molded product and mold cavity There was a problem in the formability and product appearance, such as staining the surface of the product and causing the flame retardant to bleed to cause poor appearance. As a method for solving the above-mentioned problem, an organic phosphate compound having a large molecular weight has been adopted as a flame retardant, and development has been attempted. For example, European Patent 7
No. 460 discloses a tri (2,6-dimethylphenyl) phosphate compound, EP 129824, 12982.
No. 5,135,726 discloses a resorcinol bisdiphenyl phosphate compound and the like.
Discloses a tribiphenyl phosphate compound. However, these phosphorus compounds require a large amount of addition for flame retardation of the resin, and electric parts molded with the resin composition flame retarded by these phosphate compounds require a mold during molding. There were drawbacks of poor heat and moisture resistance such as deterioration of electrical properties, flame retardancy and product appearance due to water absorption, modification of the flame retardant, etc. under high temperature and high humidity conditions. As described above, according to the conventional technology, a polyphenylene ether-based resin which can satisfy sufficient flame retardancy, excellent molding processability, product appearance characteristics, and electric characteristics (mainly, dielectric strength) under high temperature and high humidity conditions can be obtained. We could not provide fuel-electric components. SUMMARY OF THE INVENTION The present invention relates to a flame-retardant electric component comprising a polyphenylene ether resin and a polystyrene resin as main components, without impairing its inherent desirable characteristics, and having sufficient flame retardancy and excellent properties. Molding processability, product appearance and excellent electrical properties even under severe conditions of high temperature and humidity,
The purpose of the present invention is to impart wet heat resistance that maintains the appearance. The present inventors have made intensive studies to achieve the above object, and as a result, have found that a polyphenylene ether-based resin composition containing a specific phosphoric ester compound as a flame retardant The flame-retardant electric parts molded from the product have excellent molding processability and product appearance without smoke, volatilization, and bleed due to the flame retardant during molding, and have excellent electrical properties even under severe conditions of high temperature and high humidity. The present inventors have found the performance of maintaining the physical characteristics and product appearance, and have reached the present invention. That is, the flame-retardant electric component of the present invention is obtained by molding and processing a polyphenylene ether-based resin composition using, as a flame retardant, a phosphate compound having both a bonding structure of bisphenols and a terminal structure of an alkyl-substituted monofunctional phenol. It is a flame-retardant electrical component obtained by: That is, the present invention relates to a resin composition comprising a polyphenylene ether-based resin and a polystyrene resin as main components, and a compound represented by the general formula (I):
And / or general formula (II): (Where Q1, Q2, Q3, and Q4 are
Represents a tyl group or hydrogen, and m1, m2, m3, and m4 are
Indicates 1 or 2. n shows 1-3. [0011] [Chemical formula 4] (Where Q1, Q2, Q3, and Q4 are
Represents a tyl group. n shows 1-3. By molding the resin composition comprising the phosphate ester compound represented by the formula (1), there is no smoke, volatilization, or bleeding during the molding process, and there is no deterioration in the electrical properties due to discoloration, blistering, and water absorption of the molded product. Excellent CR that can withstand long-term use and recycling
A high-pressure flame-retardant resin electric part for T is provided. Hereinafter, the present invention will be described in detail. First, the polyphenylene ether-based resin used in the present invention will be described. As typical examples of the polyphenylene ether resin constituting the present invention, general formula (III): III-1, III-2, Embedded image Wherein R5, R6, R7, R8, R9,
R10 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, and hydrogen, and R9 and R10 are not simultaneously hydrogen. ) Is a repeating unit, and the structural unit is (III-
A homopolymer or a copolymer composed of 1) and (III-2) can be used. Representative examples of the homopolymer of the polyphenylene ether resin include 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-phenylene) ether,
And homopolymers such as poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether. Of these, particularly preferred is poly (2,6-dimethyl-1,4-phenylene) ether. The polyphenylene ether copolymer is a polyphenylene ether copolymer containing polyphenylene ether monomer units as a main component, such as a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol or a copolymer of o-cresol. Polymer or 2,3,6
-A copolymer with trimethylphenol and o-cresol. As the polystyrene resin constituting the present invention, a vinyl aromatic polymer or a rubber-modified vinyl aromatic polymer is used. As the vinyl aromatic polymer, in addition to styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, alkyl-substituted styrene such as p-tert-butylstyrene, α-methylstyrene, α-methyl-p-
Examples include polymers such as α-alkyl-substituted styrenes such as methylstyrene, copolymers of one or more of these with at least one of other vinyl compounds, and copolymers of two or more of these. Examples of the compound copolymerizable with the vinyl aromatic compound include methyl methacrylate, methacrylic acid esters such as ethyl methacrylate, acrylonitrile, unsaturated nitrile compounds such as methacrylonitrile, and acid anhydrides such as maleic anhydride. . Among these polymers, particularly preferred polymers are polystyrene and styrene-acrylonitrile copolymer (AS resin).
It is. Examples of the rubber used for the rubber-modified vinyl aromatic polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, ethylene-propylene copolymer and the like. Can be. In particular, polybutadiene and styrene-butadiene copolymer are preferable, and rubber-modified aromatic polymers include rubber-modified polystyrene (HIPS),
Rubber-modified styrene-acrylonitrile copolymer (ABS
Resin) is preferred. In addition, a thermoplastic elastomer is blended with a resin composition containing a polyphenylene ether resin and a polystyrene resin as main components for the purpose of improving mechanical properties as long as the properties of the flame-retardant resin electric component of the present invention are not impaired. It is also possible. As a thermoplastic elastomer,
Styrene-butadiene block copolymer, styrene-butadiene block copolymer partially or entirely hydrogenated, ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer, thermoplastic polyester elastomer, ethylene-based Examples thereof include an ionomer resin and a rubber-like core-shell polymer. Particularly, a styrene-butadiene block copolymer and a styrene-butadiene block polymer in which a part or all of a butadiene portion is hydrogenated are preferable. The ratio of the polyphenylene ether resin to the polystyrene resin in the resin composition constituting the flame-retardant resin electric component of the present invention is preferably 20 to 600 parts by weight of the polystyrene resin per 100 parts by weight of the polyphenylene ether resin. More preferably, it is 100 to 500 parts by weight. Hereinafter, the phosphate compound used in the present invention will be described. The phosphate ester compound used in the present invention is represented by the general formula (I) and the general formula (II): (Where Q1, Q2, Q3, and Q4 are
Represents a tyl group or hydrogen, and m1, m2, m3, and m4 are
Indicates 1 or 2. n shows 1-3. ), [Formula 8] (Where Q1, Q2, Q3, and Q4 are
Represents a tyl group. n shows 1-3. ). In the general formula (I), n is 1 to 3. Further, the phosphoric ester may be a mixture of n-mers. The phosphate compound, which is a component of the present invention, has a bonding structure by "specific bifunctional phenol" and a terminal structure by "specific monofunctional phenol". Examples of the “specific bifunctional phenol” include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, and bis (4-hydroxyphenyl). Bisphenols such as phenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane;
It is not limited to this. Particularly, bisphenol A is preferred. As the "specific monofunctional phenol", monoalkylphenol, dialkylphenol and trialkylphenol can be used alone or as a mixture of two or more. Particularly preferred are cresol, dimethylphenol (mixed xylenol), 2,6-dimethylphenol, and trimethylphenol. The phosphate compound as a component of the present invention is a compound comprising two or more phosphate esters.
Bifunctional phenols, which are linked by bisphenols, which greatly reduce volatility. Moreover, conventional polyphosphates, such as those linked with resorcinol or hydroquinone, cannot achieve the following. Specifically, the flame-retardant electric parts molded with the resin composition constituting the present invention are the same as those of the conventional flame-retardant electric parts molded with the resin composition using polyphosphate. It is possible to suppress discoloration, blistering, or dielectric breakdown due to water absorption that occurs in an exposure test under conditions, and to use a monoalkylphenol, a dialkylphenol, or a trialkylphenol as the “monofunctional phenol”. Flame-retardant electrical components molded from resin compositions are unsubstituted monofunctional phenols. The thermal stability and hydrolysis resistance of the monofunctional phenol are further improved as compared with the case of using a phosphate compound having a terminal structure according to the formula (I). The effect was particularly remarkable in terms of improvement in hydrolysis resistance, and could not be expected at all simply from the change in the acidity of the alkyl-substituted monofunctional phenol. And the terminal structure of the alkyl-substituted monofunctional phenol at the same time, and the flame-retardant resin electric component obtained by molding the resin composition using this phosphate compound was in contact with moisture in a heated atmosphere. In this case, the compound exhibits excellent properties for maintaining the initial electrical characteristics and appearance. Flame-retardant electrical components molded with resin compositions using lucinol polyphosphate, hydroquinone polyphosphate, etc. have poor thermal stability during molding, and the reaction between the phosphate compound and the polyphenylene ether-based resin is poor. As a result, the resin composition could not be processed at a high temperature without loss due to problems such as gelation, and the acid component such as phosphoric acid generated by the decomposition of the phosphate compound decomposed the resin. Is promoted, resulting in a decrease in molecular weight and physical properties, resulting in a lack of practicality and long-term stability.In addition, the acidic component generated by the decomposition of the phosphate ester causes the resin composition of the molding machine to come into contact with the resin composition. Metal parts such as barrels and screws, mold surfaces, and metal parts of products that come into contact when molded products are used. There is a problem that is eating. On the other hand, the flame-retardant electric component of the present invention has not only no hydrolyzability in a high-temperature and high-humidity environment, but also has excellent thermal stability at the time of molding, and emits smoke, volatilizes at the time of molding.
Not only does it not cause problems such as deterioration of electrical characteristics due to water absorption, but also solves the problem that the decomposability of the resin composition is remarkably suppressed, and the metal parts of the molding machine and the metal parts with which the molded products come into contact are corroded. ing. The phosphate compound as a component of the present invention can be obtained by reacting "specific bifunctional phenol" and "specific monofunctional phenol" with phosphorus oxychloride. It will not be done. The mixing ratio of the polyphenylene ether-based resin composition and the phosphate compound of the flame-retardant resin electric component of the present invention is not particularly limited as long as the effects of the present invention can be sufficiently exerted, but the mixing ratio of the phosphate compound is not limited. If the content is too small, the flame retardancy is insufficient, and if it is too large, the heat resistance is impaired. The phosphoric acid ester compound is preferably 1 to 100 parts by weight of the polyphenylene ether-based resin composition.
It is 200 parts by weight, more preferably 1 to 100 parts by weight. The method for producing the resin composition of the flame-retardant resin electric component of the present invention can be carried out by kneading using a generally known kneading machine such as an extruder, a heating roll, a kneader, a Banbury mixer and the like. . Further, the resin composition of the flame-retardant resin electric component of the present invention may contain other flame retardants, for example, decabromodiphenyl ether, tetrabromobisphenol A, hexabromobenzene, as long as the effects of the invention are not impaired.
Known organic halogen compounds such as hexabromocyclododecane and perchlorocyclodecane; halogen-containing inorganic compounds such as ammonium bromide; organic or inorganic phosphorus compounds such as red phosphorus, polyphosphoric acid, and ammonium phosphate; and tris (halopro Pill) phosphate,
Halogen-containing such as tris (haloethyl) phosphate
Phosphorus compounds, phosphonitrile chloride derivatives, nitrogen-containing phosphorus compounds such as phosphonoamides, melamine, uric acid, methylol melamine, dicyandiamide, melamine formaldehyde resin, uric acid formaldehyde resin, nitrogen compounds such as triazine compounds, magnesium hydroxide,
Inorganic hydrates such as aluminum hydroxide and dawsonite,
Antimony oxide, antimonate barium metaborate,
Inorganic compounds such as zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate, tin oxide, and anti-dripping agents such as polytetrafluoroethylene and siloxane compounds are used in combination. It doesn't matter. Further, other additives such as a plasticizer, a mold release agent, an ultraviolet absorber, an antioxidant, and a light stabilizer may be added to the resin composition of the flame-retardant resin electric component of the present invention as long as the effects of the present invention are not impaired. In addition to the addition of a stabilizer such as an agent, or the amount of face dyeing, glass fiber, glass chips, glass beads, carbon fiber, wollastonite, calcium carbonate, talc, etc. And fillers such as mica, wood flour, slate flour, and fibrous asbestos. EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
Table 1 shows the phosphoric ester compounds used in the examples. [Table 1] Example 1 Poly 2,6-dimethyl-1,4 having an intrinsic viscosity [η] of 0.52 measured in chloroform at 30 ° C.
-Phenylene ether (hereinafter abbreviated as PPE) 70
15 parts by weight of impact-resistant polystyrene (hereinafter abbreviated as HIPS) containing 10 parts by weight and 10% by weight of a polybutadiene component, 5 parts by weight of polystyrene (hereinafter abbreviated as GPPS), octadecyl-3- (3-5-di) -T-butyl-4
-Hydroxyphenyl) propionate and 13 parts by weight of phosphoric ester A (mixture of n = 1 to 3) (bisphenol A / polycresyl phosphate) in 0.3 part by weight of PCM-30 The mixture was melted and kneaded with a shaft extruder (manufactured by Ikegai Iron Works Co., Ltd.) to obtain pellets. Using the pellets, injection molding was performed at a cylinder temperature of 280 ° C. to obtain a 1/16 inch combustion test piece.
A high-temperature and high-humidity exposure test was performed using this test piece to evaluate the flame retardancy. The results are shown in Table 2. The flame retardancy was evaluated using a 1/8 inch test piece according to the vertical combustion test method specified in UL-94, and was ranked. Also, assuming a flyback transformer case of a high-pressure flame-retardant resin electric part for CRT as a representative example of the flame-retardant resin electric part using the pellets, a simple model, and injection molding of the cylindrical product of FIG. 1 at a cylinder temperature of 280 ° C. 10,000 shots were continuously molded at the same time, and the volatility of the resin composition was evaluated.The amount of smoke generated from the nozzle part of the injection molding machine when purging the resin composition was visually observed and the appearance of the surface of the molded product and the mold cavity. An evaluation was performed. Next, a high-temperature and high-humidity exposure test was performed on the molded product, and changes in appearance, weight, and dielectric strength were examined. Table 3 shows the results. The high-temperature and high-humidity exposure test was performed by exposing the test piece at 120 ° C. under 2 atm saturated steam for 96 hours. Dielectric strength is JIS C2110
The measurement was carried out by the short-term method according to the opposite method in accordance with the above. The upper electrode is 20
mmφ spherical electrode, 25mmφ spherical electrode
AC50Hz in silicon oil at 0 ° C, pressure rise rate 1KV / s
It measured on condition of ec. Example 2 The procedure of Example 1 was repeated except that the phosphate ester A in Example 1 was replaced with phosphate ester B (a mixture of n = 1 to 3) (bisphenol A / polyxylenyl phosphate). Evaluation was performed in the same manner, and the results are shown in Tables 2 and 3. Example 3 The procedure of Example 1 was repeated except that the phosphoric acid ester A was replaced by a phosphoric acid ester C (a mixture of n = 1 to 3) (bisphenol A / poly (2,6-xyenyl) phosphate). Evaluation was performed in the same manner as in Example 1, and the results are shown in Tables 2 and 3. Example 4 The procedure of Example 1 was repeated, except that the phosphate ester A in Example 1 was replaced with phosphate ester D (a mixture of n = 1 to 3) (bisphenol A / polydiphenyl phosphate). The evaluation was performed, and the results are shown in Tables 2 and 3. Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that the phosphoric acid ester A in Example 1 was replaced with a phosphoric acid ester E (a mixture of n = 1 to 3) (resorcinol / polyphenyl phosphate). Table 2 shows the results.
The results are shown in Table 3. Comparative Example 2 Evaluation was performed in the same manner as in Example 1 except that the phosphate ester A in Example 1 was replaced with phosphate ester F (a mixture of n = 1 to 3) (hydroquinone / polyphenyl phosphate). Table 2 shows the results.
The results are shown in Table 3. Comparative Example 3 Evaluation was performed in the same manner as in Example 1 except that the phosphoric acid ester A in Example 1 was replaced with a phosphoric acid ester G (triphenyl phosphate [trade name: TPP], manufactured by Daihachi Chemical Co., Ltd.). The results are shown in Tables 2 and 3. [Table 2] [Table 3] The flame-retardant electric parts made of a polyphenylene ether-based resin of the present invention have a sufficient flame retardancy without impairing the inherently preferable characteristics as compared with the conventional flame-retardant electric parts made of a polyphenylene ether-based resin. , Excellent molding processability, appearance characteristics, and excellent electrical characteristics even under high temperature and high humidity conditions, and moisture and heat resistance maintaining the appearance. It meets the required performance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a simplified model assuming a flyback transformer case used in an embodiment.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 71/12 C08L 25/04-25/14 C08K 5/521-5/523 CA (STN)

Claims (1)

(57) [Claim 1] A resin composition containing a polyphenylene ether resin and a polystyrene resin as main components and a general formula (I)
And / or general formula (II) ( Wherein Q1, Q2, Q3, and Q4 represent a methyl group, or
Represents hydrogen, and m1, m2, m3, and m4 represent 1 or 2
You. n shows 1-3. ) (In the formula, Q1, Q2, Q3, and Q4 represent a methyl group.
n shows 1-3. A high-pressure flame-retardant resin electric part for CRT, comprising a resin composition comprising a phosphate compound represented by the formula (1).