JPS6281444A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin compsn. which gives moldings having excellent mechanical characteristics, moldabiity and flame retardance, comprising a specified thermoplastic resin, a styrene resin and a phosphorus compd. CONSTITUTION:A resin compsn. comprises 100pts.wt. of the combined quantity of 5-95pts.wt. thermoplastic resin (A) having a m.p. of 150-300 deg.C and at least one polar group selected from among carboxyl, hydroxyl and amino groups at its terminals, 0.01-50pts.wt. styrene resin (B) having epoxy groups, 0-90pts. wt. styrene resin (C) having no epoxy group and 0-90pts.wt. thermoplastic resin (D) having a molecular phase compatible with the resin (C) and a phosphorus compd. (E) in such a proportion that the combined quantity of the components C and D is at least 5pts.wt. As said phosphorus compd., at least one member selected from among compds. of formulas I, II, III (wherein R1, R2, R3 are each an alkyl, a haloalkyl, an aryl, a haloaryl) is used.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a thermoplastic resin composition, and more specifically, it makes thermoplastic resins with poor compatibility compatible with each other by blending a third component, thereby improving the drawbacks of both resins. Another object of the present invention is to provide a thermoplastic resin composition that provides a molded article having excellent mechanical properties, excellent moldability, and flame retardancy. (Prior Art) Conventionally, many attempts have been made to solve the drawbacks of each thermoplastic resin by blending thermoplastic resins having different properties. However, different polymers usually have poor compatibility and do not mix uniformly, forming a so-called "sea-island" structure.
This "sea-island" interface is extremely weak. For this reason, the resulting composition is brittle and has reduced mechanical strength and impact strength. Furthermore, there are other disadvantages of resins that have excellent self-extinguishing properties.For example, when different polymers are blended for the purpose of improving molding processability, the problem arises that although molding processability is improved, self-extinguishing properties are impaired. . (Problems to be solved by the invention) Polyphenylene ether has mechanical properties, electrical properties,
It has excellent properties that are well-balanced in general, such as heat resistance P1, which is excellent, and −=j law stability V1, which is good.
It is used in many applications as engineering plastics because of its high strength, or it has major drawbacks such as poor moldability, impact strength, and chemical resistance. On the other hand, engineering plastics with excellent chemical resistance V1 include thermoplastic polynisder resins (for example, polyethylene terephthalate, polybutylene terephthalate, etc.) and polyamide resins (for example, Nylon 66, Nylon 66, etc.).The former thermoplastic Polyester resin has a high melting point and excellent mechanical strength.
Since the heat deformation temperature under load is extremely low, a large fit glass fiber is usually used as the molding material. However, thermoplastic polyester resins reinforced with glass fibers have poor surface properties, glass fiber orientation occurs during molding, the strong 1α anisotropy v1 of the molded product is extremely large, and the shrinkage rate of the molded product is different. Due to its tropism, it has drawbacks such as warping of the molded product. In order to eliminate these drawbacks of polyphenylene ether and thermoplastic polyester resin, an attempt to melt-mix them has been proposed in Japanese Patent Publication No. 51-21064. However, the resulting composition exhibits typical incompatible properties because the properties derived from the molecular structures of the two (expressed by, for example, S P &4) are greatly increased. That is, the mechanical properties are significantly lower than expected based on both values, and the appearance of the molded product obtained from this composition is also worse than that of the molded product alone. -Improved flow rate of polyphenylene ether-J
It has been proposed in Japanese Patent Publication No. 45-007 to blend a polyamide resin with the following points in mind: 1-1, polyphenylene ether and polyamide are extremely compatible with each other.
1 was poor, and the resulting resin composition had a significant deterioration in mechanical V1 quality, and no characteristic properties other than improved fluidity were obtained. Furthermore, polyphenylene ether resin alone has a T
Since the ratio of 1/1 is extremely poor, in order to improve the ratio, a styrene resin is actually used as proposed in Japanese Patent Publication No. 17812/1983. Alternatively, it is used by blending it with various resins to improve the molding process f/I. Therefore, the self-extinguishing f
Polyphenylene ether resin has the disadvantage that it has a low flame retardancy and is significantly more flammable than polyphenylene ether resin alone, and therefore it is desired to improve its flame retardance. (Means for Solving the Problems) In a blend of thermoplastic resins with different properties and poor compatibility, the present inventors have made the two components compatible by blending a third component, and have achieved the superiority of both resins. As a result of intensive studies to improve the shortcomings of both resins without reducing their properties, we have developed a combination of thermoplastic resins (such as thermoplastic polyvarnish-chill resins and polyamide resins) and styrene resins that do not contain epoxy groups and/or The compatibility of the entire system is improved by blending a styrene-based resin impregnated with epoxy resin as a third component into a thermoplastic resin that has good molecular compatibility with the styrene-based resin, and then a phosphorus compound is further blended. The present inventors discovered the very interesting fact that flame retardancy can be imparted, moldability can be improved, and a resin composition with excellent performance can be obtained, and the present invention has been completed.That is, the present invention is a thermoplastic resin (A) having at least one polar group selected from carbotyl group, hydroxyl group and amino group at the terminal and having a melting point of 150 to 300°C (A) 5 to 95
Part by weight, styrenic resin containing epoxy group (n)O
, 11 parts of old ~50tTi, 0 to 90 parts by weight of a styrenic resin (C) that does not contain epoxy, and 0 to 90 parts by weight of a thermoplastic resin (D) that has molecular compatibility with the styrene resin (C).
Combine 90 parts by weight! [00 parts by weight, the total amount of (C) and (D) is 5 parts by weight or more, and a phosphorus compound (
It is a thermoplastic resin composition characterized by containing IC). The thermoplastic resin (A) in the present invention has at least one type of polarity Jλ selected from carboxyl group, hydroxyl group, and amino group at the terminal and has a melting point of 150 to 300°C.
Thermoplastic resins such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane 7 dimethylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, polyester constituents and other acid components and/or or glycol components, such as acid components such as inphthalic acid, P-oxybenzoic acid, adipic acid, sebacic acid, geltaric acid, diphenylmethanedicarboxylic acid, dimer acid, hexamethylene glycol, diethylene glycol, neopentyl glycol, bisphenol A1 neopentyl glycol Polyesters copolymerized with glycol components such as alkylene oxide adducts, aromatic polyester/polyether block copolymers, aromatic polyester polylactone block copolymers, polyesters in a broad sense such as polyarylates, nylon 6, and polyester 6 , 6, Nai 11 6. )), nylon 6.10, nylon 0,12, nylon 11 6/G
, 6. Polyxylylene adipamide, polyhexamethylene terephthalamide, polyphenylene phthalamide, polyxylylene adipamide/hexamethylene adipamide, polyester amide elastomer, polyether amide elastomer, poly ether ester amide elastomer,
Polyamides such as dimer acid copolymerized polyamides are exemplified, and resins may be used alone or in blends of multiple resins or copolymers thereof. In particular, those having a melting point of 200°C or higher are preferred from the viewpoint of heat resistance. Usually, it is preferable that the polyester resin mentioned above has an L-1 stroke of 11 degrees of 0.4 or more, more preferably 0.
Particularly preferably 5 or more. In addition, polyamide usually has a relative viscosity (JIS 6810-
(measured in 98% sulfuric acid according to 1970) is preferably 1.8 or more, and particularly preferably 20 or more. In addition, as the styrene resin (11) containing an epoxy group in the present invention, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, hydroquine alkyl (meth)
Glycidyl ether of acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate,
Examples include polystyrene copolymerized or graft copolymerized with an epoxy group-containing copolymerizable unsaturated monomer such as glycidyl itaconate, styrene-containing polymers such as acrylonitrile-styrene copolymer, and styrene/butadiene copolymer. be done. The content of the epoxy group-containing copolymerizable unsaturated monomer is usually 0.5 to 30% by weight based on the resin (11).
and preferably 1 to 20% by weight. In addition, as the epoxy group-free styrene resin (C) in the present invention, homopolymers such as polystyrene, polychlorostyrene, and polyα-methylstyrene, styrene liptadiene copolymers, and styrene/isoprene copolymers are used. , styrene/acrylic nitrile copolymer, styrene/
Acrylonitrile fist acrylate copolymer, styrene,
Acrylic tolyl-butadiene copolymer, methyl-1-non-butadiene rubber-modified polystyrene, El) DMM) / mu-modified polystyrene, acrylic rubber-modified styrene / acrylonitrile copolymer, styrene-maleic acid copolymer,
Examples include polystyrene thermoplastic elastomers such as hydrogenated styrene-butadiene block copolymers. Furthermore, as the thermoplastic resin (D>) in the present invention,
Molecular compatibility with styrene resin Rrl (C) (compatible on the molecular order, changing the Tg of styrene resin (C) +B
-Tg), and a specific example thereof is a polyphenylene ether resin. Examples of the polyphenylene ether resin include resins having the Q1-position represented by the general formula. Here, R, R, R, and R4 are hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, cyano group, alkoxy group, phenoxy group, or nitro group, and n does not indicate the degree of polymerization. Specific examples of R,, R,, R3 and R4 include hydrogen, chlorine, bromine, iodide, methyl, ethyl,
Allyl, phenyl, pencil, methylbenzyl, ri'1
Examples include groups such as methyl, bromethyl, cyanoethyl, cyan, methoxy, ethoxy, pheno-Y-cy, and 2)Fl. Specifically, for example, poly-2,6-dimethyl-1. /I-phenylene ether, poly-2,6
-diethyl-11/1-phenylene needle, poly-2
, B-dipropyl-1,11-phenylene ether, poly-2,6-simethoxy 1,4-phenylene ether, poly-2, [; , 6-dipromemethyl-1.
4-phenylene ether, poly-2,6-diphenyl-
1,4-phenylene; l-zyl, poly-2,6-dydolyl-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether and poly-2,
5-dimethyl-1+4-phenylene ether, poly-2
, 0-dibenzyl-1,4-phenylene ether and the like. A preferred polyphenylene ether resin is a polymer in which R1 and R4 in the general formula represent an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and n is usually 50 or more and 1-
Or preferable. Component (C) and component (1)) may be obtained by polymerizing the monomer of one of the components in the presence of the IJmer of the other component. Furthermore, in the present invention, in order to obtain flame retardancy and excellent moldability, it is necessary to contain a phosphorus compound (E). The phosphorus compound (E) in the present invention contains one or more compounds selected from the group consisting of compounds represented by the following general formulas (a) to (c). R101' OR5 --- (a) OR. R10-P-OR3... (b) OR. R+ OI'ORa..."...(C
) (However, in the formula, R, R, and R3 are the same or different alkyl, haloalkyl, aryl, and haloaryl JI (not shown). Specific examples of the compound represented by the general formula (a) include trimethyl phosphate,
triethyl phosphate, triphenyl phosphate,
Tricresyl phosphate, talesyl diphenyl phosphate, diphenyloctyl phosphate, tributyl phosphate, tris(3-chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(
Examples thereof include bromochloropropyl phosphate, tris(2-boomethyl) phosphate, trioctyl phosphate, and tryptoxyethyl phosphate. Specific examples of the compound represented by the general formula (b) include trimedelphosphite, triethylphosphite, tris(2-chloroethyl)phosphite, triphenylphosphite, and the like. Specific examples of the compound represented by the general formula (C) include dimethyl phenylposboxate, phenylphosphonbutydiethyl, diptyl phenylbosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, and bis(hydroxyethyl)benzylphosphonate. , bis(2-bromoethyl) 2-promoedyl phosphonate, and the like. One or two of the compounds represented by the general formulas (a) to (c) may be used simultaneously. Furthermore, the composition of the present invention includes a catalyst for promoting the reactivity between the epoxy group in component (B) and component (A), or for improving the affinity with component (A) by ring opening of the epoxy group. It is preferable to use Although the reaction between component (A) and the epoxy group is effective even without a catalyst, the reaction is significantly accelerated when a catalyst is used. As the catalyst, it is generally preferable to blend amines, phosphorus compounds, metal salts of monocarboxylic acids and/or dicarboxylic acids having 10 or more carbon atoms in Group I-a or IT-a of the Periodic Table of Elements, and the like. Particularly preferred are trivalent phosphorus compounds such as tributylphosphine and triphenylphosphine, and metal salts of stearic acid such as calcium stearate and sodium stearate. When using these catalysts, they may be used alone or in combination of two or more. Further, the effect remains the same whether the above catalyst is added all at once or divided into parts. Its composition h

[There is no particular limitation, but
Component (A) It is usually 3 parts by weight or less, preferably 0.03 to 2 parts by weight, per 1 part of Inn City 1i. ”-components (A), (TI), (C), (1))
The blending ratio of and (l) can be changed as appropriate depending on the desired physical properties, purpose, cost, etc.
), (13), (C) and (+)), the total d1 amount is 10
0 parts, 5 to 95 parts by weight of component (A), preferably 20 to 80 parts, component (f() is 0.01 parts)
~50,0001 iL parts, preferably 0.05 to 30 parts by weight, and 0 to 90 parts by weight of component (C), preferably 0 to 75 parts! 11 parts and component (I)) or 0~OOiTj itt
parts, preferably 0 to 80 parts by weight, and the total amount of component (C) and component (D) is 5 parts by weight or more, and component (E) is the total amount of components (A) to (D). It is contained in an amount of 0.5 to 30 parts by weight, preferably 1 to 15 parts by weight, per 100 parts by weight. If the amount of component (A) added is too small, disadvantages such as decreased chemical resistance may occur, and component (C) and/or (D)
If the amount is too low, molding shrinkage will increase and the molded product will have scratches.
This results in warpage and deterioration of surface properties. Furthermore, when the amount of component (Il) is too small, the compatibility between component (A) and component (C) and/or component (D) is poor, resulting in a disadvantage that physical properties are deteriorated. If the amount of component (E) is too small, flame retardancy and moldability will be reduced. The composition of the present invention may further include ingredients (
A) Crystal nucleating agent such as talc, mica, titanium oxide,
Carbon black, etc., crystallization promoting Wl+, for example, when the component (A> is an ethylene terephthalate polyester, a polyoxyalkylene compound compatible with the polyester, a polyhydric alcohol derivative, a higher fatty acid ester, a higher fatty acid metal salt) , polyhydric carboxylic acid ester, polymer may include aliphatic polycarboxylic acid salt, polyhydric alcohol ester, etc. The amount of the crystal nucleating agent is usually up to 50% by weight of the composition, The amount of the crystallization accelerator is preferably up to about 10% by weight based on the composition. In addition, antioxidants, ultraviolet absorbers, stabilizers such as hydrolysis resistance improvers, plasticizers, lubricants, flame retardants, flame retardants, etc. Auxiliary agents, antistatic agents, colorants, conductivity imparting agents, sliding properties improvers (solid lubricants, liquid lubricants), multifunctional bridging agents, impact resistance improvers (for example, Tg is 0°C or less, preferably is a rubber-like material (more preferably a reactive group-containing rubber), I
Inorganic optical lI agents and mechanical reinforcement agents other than those listed in Z (e.g., glass fibers, carbon TA fibers, graphite fibers, silicon carbide fibers, silicon nitride fibers, boron nitride fibers, potassium titanate whiskers, heat-resistant AM fibers) , additives such as conductivity imparting agents (for example, metal fibers, polyacetylene fibers, metal powders, iron phosphorus, carbon black, organic conductive polymers, etc.) may be added. When blending inorganic fillers and inorganic fibers, silane couplers, titanium couplers, zircoaluminate couplers, etc. may be used in combination. Additionally, other resins may be blended to any extent and type without detracting from the objectives of the present invention. The method for producing the composition of the present invention is not particularly limited, and any method may be used. For example, they can be blended by mechanical kneading using an extruder, roll mill, Banbury mixer, or the like. Multi-stage kneading may be used, such as kneading component (A) and component (11) and then kneading other components. The composition of the present invention can be widely used for forming molded products such as various molded parts, films, sheets such as plates, IIA fiber products, pipe products, containers, etc., and can also be used as an antiseptic agent and an adhesive. It can also be used as a sealant, a modifier for other resins, etc. Further, it can be formed into a film, fiber, etc., and further stretch-molded, or a secondary molded product. (Function) The composition of the present invention has a component (A) due to the presence of component (II).
) is modified, and the -compatibility v1 of component (A) and component (C) and/or component (I)) is improved, resulting in a uniform blend and a molded product with excellent mechanical properties. At the same time, the molding shrinkage of component (A) is reduced, so problems such as sink marks and warpage can be solved to provide a molded product with excellent surface properties, and the durability of component (C) and/or (1') is It has features such as improved chemical properties, and furthermore, by containing component (E), it has flame retardancy and excellent moldability. (Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Note that the percentages in the examples are based on weight. In addition, various measurements in the examples were carried out by the following methods. (1) Bending test Measured according to ASTM-079n. (2) Molding processability Using the snake flow mold shown in No. 1M, the mold temperature was 70.
℃, cylinder temperature 290℃, injection pressure 1n (10kg
The flow length was measured at /cj and the moldability was evaluated. (3) Gai Moe vl “Te5ts for Flammability o
f Plastic materials U I, -0
Flame retardancy was evaluated based on 4".Fllll + was determined and moldability was evaluated. Examples 1 to 8, Comparative Examples 1 to 4 Polyethylene terephthalate with [η] of 0.63 or [ η] or 1.2 polybutylene terephthalate powder, epoxy-based styrene resin, styrene resin that does not contain epoxy groups, [η] is 0.58 (measured in Jroform at 30°C) poly-2,6-cymethyl-1.4
- Phenylene ether and a predetermined amount of a phosphorus compound not shown in Table 1 are combined with each other in Bure/Goo, and 30 Dragon φ
Using a twin-screw extruder (PCM-30, manufactured by Ikei Tekko Co., Ltd.), the mixture was kneaded and extruded into pellets at a cylinder temperature of 295°C. The obtained pellets were dried at 120°C for 5 hours in an air dryer, and then placed in an injection molding machine (Metsuki Resin Kogyo?l, FS-75).
mold) into a molded product. At this time, the cylinder lagoon I "is 2B
The mold temperature was 70°C. The results are shown in Table 1. In Table 1]) Polyethylene terephthalate 2) Styrene copolymer copolymerized with 30 mol% glycidyl methacrylate 3) Hydrogenated styrene-butadiene block copolymer 4) Poly-2,6-dimethylphenylene-1,4 -Ether 5) Triphenyl phosphate 6) Styrene copolymer copolymerized with 10 mol % glycidyl methacrylate 7) High impact polystyrene 8) Acrylonitrile Ruthenium 17 J copolymerized with 10 mol % glycidyl methacrylate (Polymer 9) Glycidyl methacrylate Polybutylene terephthalate As is clear from Table 1, the composition of the present invention containing an epoxy-modified styrene resin and an organic phosphoric acid ester exhibits excellent bending strength and is also flame retardant. It can be seen that it has excellent moldability. Note that this composition was found to have advantages such as excellent chemical resistance. Examples 10 and 11, Comparative Example 5.6 Molding was performed in the same manner as in Example 1 except that the polyester in Example 1 was replaced with nylon 6 with a relative viscosity of 9-7 and the cylinder temperature was 260°C. We evaluated the characteristics of The results are shown in Table 2. As is clear from Table 2, the compositions of the present invention exhibit excellent bending strength, as well as flame retardancy and excellent moldability. Additionally, this composition was also recognized to have excellent chemical resistance.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of the molding die used in the fluidity evaluation. , shows a snake flow mold with a thickness of 2 mm, and A is a film gate. Patent applicant: Toyobo Co., Ltd. W-1 Figure 2ul

Claims (1)

[Claims] It has at least one polar group selected from carboxyl group, hydroxyl group and amino group at the terminal and has a melting point of 150 to 30
0°C thermoplastic resin (A) 5 to 95 parts by weight, epoxy group-containing styrene resin (B) 0.01 to 50 parts by weight, epoxy group-free styrene resin (C) 0 to 90 parts by weight , and 0 to 90 parts by weight of a thermoplastic resin (D) having molecular compatibility with the styrene resin (C), with a total of 100 parts by weight, and the total amount of (C) and (D) is 5 parts by weight or more. A thermoplastic resin composition characterized in that it further contains a phosphorus compound (E).