JPH07188535A - Polymer alloy - Google Patents

Abstract

PURPOSE:To provide a polymer alloy holding the excellent characteristics of a thermoplastic polyester and a polyamide as such and simultaneously highly improved in compatibility, mechanical strength, molded product appearance, etc., by adding a specific compatibilizing agent to the thermoplastic polyester and the polyamide. CONSTITUTION:This polymer alloy comprises (A) 95-5 pts.wt. of a thermoplastic polyester (preferably polybutylene terephthalate having a number-average mol.wt. of 10000-50000), (B) 5-95 pts.wt. of a polyamide (preferably nylon 6 having a number-average mol.wt. of 10000-50000), and (C) a compound of the formula (R<1>, R<2> are hydroxyl, uts Na salt; R<3> to R<6> are H, 1-8C alkyl) [preferably bis(4- hydroxy-3,5-dimethylphenyl)ether] as a compatibilizing agent in an amount of 0.3-10 pts.wt. per 100 pts.wt. of the components A and B. The polymer allay is obtained usually by, if necessary, preliminarily kneading the components A, B and C and, if necessary, a filler, a reinforcing material, etc., and subsequently melt-kneading the mixture with a kneader, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to polymer alloys composed of thermoplastic polyesters and polyamides with improved compatibility.

[0002]

2. Description of the Related Art Thermoplastic polyesters typified by polybutylene terephthalate and polyamides typified by nylon are used as engineering plastics in various industrial fields. The thermoplastic polyester is excellent in heat resistance, chemical resistance and electrical properties, and the polyamide is tough and is a resin excellent in lubricity, abrasion resistance, chemical resistance and oil resistance. However, thermoplastic polyesters have the drawbacks of low heat distortion temperature, and polyamides have the drawbacks of poor dimensional stability and electrical properties.

In recent years, in order to solve the drawbacks of both resins of thermoplastic polyester and polyamide, and further to develop new applications, research and development of polymer alloys composed of both resins have been conducted. However, both resins have poor compatibility, and problems such as a large decrease in mechanical strength and deterioration of the appearance of molded products occur, and practical application cannot be expected with simple polymer alloys.

[0004]

An object of the present invention is to provide a polymer alloy composed of a thermoplastic polyester and a polyamide in which the above problems have been solved, which polymer alloy has excellent mechanical strength and retains a good morphology. To do.

[0005]

The above object of the present invention is achieved by adding a specific compound to a polymer alloy of thermoplastic polyester and polyamide.

That is, the present invention comprises (A) 95 to 5 parts by weight of a thermoplastic polyester resin and (B) a polyamide resin of 5 to 5.
95 parts by weight and 100 parts by weight of (A) and (B) in total, (C) a compound of the following structural formula (I) 0.3 to
10 parts by weight

[0007]

[Chemical 2]

(Wherein R ¹ and R ² each represent a hydroxyl group or a sodium salt thereof, and R ³ , R ⁴ and R
⁵ and R ⁶ are the same or different groups and each represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. ) Is provided.

The present invention will be described in more detail below. The thermoplastic polyester used in the present invention is a polymer having an ester bond as a main bonding unit,
Specifically, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, α, β
-Bis (4-carboxyphenoxy) ethane, adipic acid sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cis-hexanedicarboxylic acid, dicarboxylic acids and other ester-forming derivatives thereof, and ethylene glycol, propylene Glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis (4-hydroxyethoxyphenyl) propane, xylylene glycol, polyethylene ether Glycols such as glycols, polytetramethylene ether glycols, and aliphatic polyester oligomers having hydroxyl groups at both ends or their ester-forming properties. It is a thermoplastic polyester to the body component.

Glycolic acid as a comonomer component,
Hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, hydroxycarboxylic acid such as naphthyl glycolic acid, lactone compound such as propiolactone, butyrolactone, valerolactone, caprolactone or trimethylolpropane within a range capable of retaining thermoplasticity, It may contain a polyfunctional ester-forming component such as trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid. Further, aromatic compounds such as dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, tetrachloroterephthalic acid, 1,4-dimethylol tetrabromobenzene, tetrabromobisphenol A, and tetrabromobisphenol A ethylene oxide adduct. It also includes a thermoplastic polyester resin obtained by copolymerizing a halogen compound having a halogen compound such as chlorine or bromine as a substituent in the nucleus and having an ester-forming group. Furthermore, a liquid crystalline polyester that exhibits optical anisotropy when melted,
Specifically included are (all) aromatic polyesters.

Preferred thermoplastic polyesters are, more specifically, polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, poly (ethylene / butylene terephthalate), poly (butylene). -Tetramethylene terephthalate) and the like, and these can be used alone or as a mixture. A particularly preferred thermoplastic polyester is polybutylene terephthalate. Preferred polybutylene terephthalate here is terephthalic acid as an acid component,
The glycol component contains 1,4-butanediol as a main basic component, and an acid component or a glycol component, which can be appropriately copolymerized, is copolymerized as necessary. The copolymerizable acid component and glycol component can be selected from those described above.

The number average molecular weight of these thermoplastic polyesters may be 8,000 or more, more preferably 1
It is in the range of 50,000 to 50,000.

The polyamide used in the present invention is a polymer having an acid amide bond (-CONH-) as a repeating unit.

The polyamide which can be used in the present invention is obtained by polymerizing amino acid, lactam or diamine and carboxylic acid as monomers. Specific examples of the monomer include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and para-aminomethylbenzoic acid, ε-caprolactam, ω-
Lactams such as laurolactam, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4
4-trimethylhexamethylenediamine, 5-methylnonamelenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino- 3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis Diamines such as (aminopropyl) piperazine and aminoethylpiperazine, adipic acid,
Suberic acid, azelaic acid, sebacic acid, dodecanenic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydro Some are combined with dicarboxylic acids such as isophthalic acid and diglycolic acid.

Examples of polyamides obtained from these monomers include nylon 3, nylon 4, nylon 4-6, nylon 6, nylon 6T, nylon 6-6,
Nylon 6-10, Polyamide 6-12, Nylon 7,
Nylon 8, Nylon 9, Nylon 11, Nylon 1
2, polyamide MXD6, and copolyamides thereof. These can be used alone or as a mixture.

Preferred polyamides for the present invention are nylon 6, nylon 6-6, nylon 6-10, nylon 11 and nylon 12, with nylon 6 being particularly preferred. The number average molecular weight of these polyamides is 8.0
00 or more, and more preferably 10,000 to 5
It is in the range of 10,000.

(C) of the composition of the present invention is a compound having the following structural formula (I) and acting as a compatibilizing agent between the thermoplastic polyester and the polyamide.

[0018]

[Chemical 3]

(Wherein R ¹ and R ² each represent a hydroxyl group or a sodium salt thereof, and R ³ , R ⁴ and R
⁵ and R ⁶ are the same or different groups and each represent a hydrogen atom or a C _{1 to} C ₈ alkyl group. )

Specific examples of the alkyl group represented by R ³ , R ⁴ , R ⁵ and R ⁶ in the structural formula (I) include methyl,
Alkyl groups such as ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, hexyl, heptyl, n-octyl, 2-ethylhexyl, tert-octyl and the like can be mentioned. . In addition, R ¹ and R ^2, and R ³ , R ⁴ , R ⁵ and R ⁶ in the structural formula (I) may be the same or different substituents.

Specific examples of the above compound include 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-diethylphenyl) ether, Bis (4-hydroxy-3,5-dipropylphenyl) ether, bis (4-hydroxy-3,5-di-n-butylphenyl) ether, bis (4-hydroxy-3,5-)
Diisobutylphenyl) ether, bis (4-hydroxy-3,5-di-sec-butylphenyl) ether,
Examples thereof include bis (4-hydroxy-3,5-di-tert-butylphenyl) ether, and a sodium salt obtained by neutralizing one or both of the hydroxyl groups of these compounds with sodium. These can be used alone or as a mixture. Preferably,
Bis (4-hydroxy-3,5-dimethylphenyl) ether.

The thermoplastic polyester (A) and the polyamide (B) are blended in a proportion of 95 to 5 parts by weight of the thermoplastic polyester and 5 to 95 parts by weight of the polyamide per 100 parts by weight of the total amount of both. Further, the addition amount of the component (C) is 0.3 to 10 parts by weight based on 100 parts by weight of the total amount of the thermoplastic polyester and the polyamide. This amount is 0.
If it is less than 3 parts by weight, the effect is small, and if it exceeds 10 parts by weight, the effect does not change so much, which is economically disadvantageous.

In addition to the above components, the composition of the present invention also comprises
The following fillers, reinforcing agents, additives and the like can be added within a range that does not impair the effects of the present invention. Such fillers include inorganic fibrous fillers such as glass fibers, carbon fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, metal fibers and silicon nitride; barium sulfate, calcium sulfate, bentonite, sericite, zeolite. , Mica, mica, talc, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass powder, glass balloon Examples of the filler include inorganic powder particles such as quartz and quartz glass, or plate-like or flake-like fillers; organic fillers such as aramid fibers. Further, a small amount of a releasing agent, a coupling agent, a colorant, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a foaming agent, a flame retardant, a flame retardant auxiliary agent such as antimony trioxide, etc. may be appropriately added.

The method for producing the polymer alloy of the present invention is not particularly limited and may be a conventionally known method. Usually, (A) a thermoplastic polyester resin, (B) a polyamide resin, (C) a compound having the structural formula (I) and, if necessary, the above-mentioned fillers, additives, etc., either simultaneously or each in 2 or 3 components. It is possible to employ a method of pre-mixing or without pre-mixing and supplying the mixture to an ordinary melt-kneading processing apparatus such as a single-screw or multi-screw extruder, a Banbury mixer, a kneader and the like to perform melt-kneading.

In addition to the above, there is also a method of post-adding (C) the compound represented by the structural formula (I) among the compounding ingredients of the present invention. This means that, for example, the thermoplastic polyester resin (A) of the present invention, the polyamide resin (B) of the present invention and the above-mentioned filler as a dispersant are charged from a supply port of an extruder, and then the constituent C of the present invention is charged. There is also a method. That is, the thermoplastic polyester and the polyamide are charged at the same time as the filler from the supply port to bring the thermoplastic polyester and the polyamide into a mixed and dispersed state to some extent, and then the compound of the structural formula (I) is charged. Further, it is possible to further uniformly mix and disperse, and to stabilize and fix the dispersion structure. This charging method may improve the extrudability, injection moldability, and various physical properties of the molded product. Further, in the adjusting method in which no filler is blended, the thermoplastic polyester resin (A) and the polyamide resin (B) of the present invention are melted in advance, and (C) the compound having the structural formula (I) in a molten state. There is also a method of kneading. When this method is used, the thermoplastic polyester or polyamide is affected by the compatibilizing agent of the constituent C, and may be in a good mixed / dispersed state, and the dispersed structure thereof may be stabilized / fixed.

The polymer alloy of the present invention has the characteristics that each resin has, that is, the heat resistance, chemical resistance and electrical properties of thermoplastic polyester, the toughness of polyamide,
The compatibility is remarkably improved without impairing various excellent properties such as lubricity, wear resistance, chemical resistance and oil resistance, and various properties such as mechanical strength such as tensile strength are remarkably improved. To do.

Therefore, the polymer alloy of the present invention is
Molded products with excellent physical properties can be obtained by subjecting to molding used for ordinary thermoplastic resins such as injection molding, extrusion molding, blow molding, compression molding, and various automotive parts, mechanical parts, electric / electronic parts It is useful as general sundries. For example, various building and aircraft / automobile interior parts, switches, connectors, printed circuit boards, coil bobbins, housing and other electrical / electronic parts, bearings, gears, bearing rivets, nuts and other general mechanical parts, OA equipment parts, etc. Precision parts such as camera parts and watch parts, tennis rackets, skis, golf clubs,
Leisure and sports equipment such as fishing rods, daily sundries, paints,
It can be used as an insulating agent.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples. The compositions shown in Table 1 were mixed with a Henschel mixer and kneaded with a twin-screw extruder to obtain each composition. Next, a test piece was prepared from them by an injection molding machine, and mechanical properties were measured. The test methods for the measured physical properties and evaluation criteria are shown below. The results are also shown in Table 1. Composition is the amount of polymer that is most easily evaluated for compatibilization, 50:50 and 6
It was set to 0 to 40. Bis (4-hydroxy-) as C component
3,5-Dimethylphenyl) ether was used. Table 1
From the results, the effect of the C component as a compatibilizing agent was clearly recognized, and this was confirmed by morphological observation of the composition by a scanning electron microscope.

1) Tensile Strength It was measured according to ASTM D-638. (Unit MPa) 2) Notched Izod impact strength Measured according to ASTM D-256. The measurement used the test piece of thickness 1/8 inch. (Unit: kg · cm / cm) 3) Appearance of molded product Compatibility evaluation; visual judgment and morphological observation with a scanning electron microscope ○… Excellent compatibility, good appearance ×… Poor compatibility, poor appearance

[0030]

[Table 1]

[0031]

[Effect] The polymer alloy of the present invention has been improved in the conventional drawbacks such as compatibility, drastic reduction in mechanical strength, and deterioration of appearance of molded articles. That is, according to the present invention, there is provided a resin composition in which various properties such as mechanical strength such as tensile strength and appearance of a molded product are remarkably improved while maintaining the excellent properties of thermoplastic polyester and polyamide.

Claims (1)

[Claims] 1. (A) thermoplastic polyester 95 to 5 parts by weight, (B) polyamide 5 to 95 parts by weight and (C)
0.3 to 10 parts by weight of a compound having the following structural formula (I) relative to 100 parts by weight of (A) and (B) in total: (However, R ¹ and R ² each represent a hydroxyl group or a sodium salt thereof, and R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different groups, and each is a hydrogen atom or C ₁
An alkyl group -C _8. ) Is a polymer alloy.