JPH0393855A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent mechanical properties, heat resistance, chemical resistance, luster of molded article and small change of dimension and physical properties by water absorption, comprising a crystalline polyamide, polyphenylene ether and specific amorphous polyamide. CONSTITUTION:(A) 15-98wt.%, preferably 30-80wt.% crystalline polyamide (preferably nylon 66 or nylon 12) having >=1cal/g heat of fusion of crystal (20 deg.C/minute rate of heating) is blended with (B) 1-70wt.%, preferably 10-60wt.% polyphenylene ether [preferably poly(2,6-dimethyl-1,4-phenylene] ether] and (C) 1-50wt.%, preferably 3-40wt.% amorphous polyamide (preferably polycondensate of hexamethylenediamine and terephthalic acid and/or isophthalic acid) having >=100 deg.C glass transition temperature and <1cal/g heat of fusion of crystal to give a resin composition.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention is characterized by mechanical properties and heat resistance. This article relates to a new resin composite that has excellent chemical resistance and gloss of molded products, as well as greatly suppresses changes in dimensions and physical properties due to water absorption. More specifically, the present invention relates to a resin composition comprising (8) crystalline polyamide, (B) polyphenylene ether (hereinafter abbreviated as PPP), and (C) amorphous polyamide having a glass transition temperature of 100° C. or higher.

The resin phase or material of the present invention is used in electrical and electronic applications due to its excellent properties. It is expected to be used in a wide range of fields such as machinery and automobiles.

(Prior art) Boli 72 is tough. It has excellent fatigue resistance, chemical resistance, and moldability, and is currently the most widely used and most commonly used engineering plastic.

However, nylon 6, a typical resin among polyamides,
, nylon 66, nylon 46, etc. have a high water absorption rate, and therefore have the problem that their dimensions and physical properties change due to water absorption.

On the other hand, Pr'E is mechanical force. It is an engineering plastic with excellent electrical properties, heat resistance, and extremely low water absorption, and its use has recently expanded to take advantage of these properties. but. PPE, like general-purpose plastics such as ABS resin, has a major drawback in that it swells or dissolves in common organic solvents such as acetone, toluene, and halogenated hydrocarbons. Also. If oil or gasoline comes into contact with these products due to strain stress, cracks will often develop, and in severe cases, this can lead to catastrophe.

As described above, since polyamide and PPE have very different properties, it is expected that a resin composite made by combining the threads of both will exhibit new properties that complement the properties of roof tiles. Special Publication No. 45-997 includes P P P. It has been proposed to blend polyamide with the aim of improving the moldability of.

However, in this case, only a brittle resin composition with low mechanical properties such as bending strength and impact strength was obtained due to insufficient compatibility between the two components.

Various proposals have been made in attempts to improve the mechanical properties of such resin compositions made of polyamide and PPE. JP-A-56-16525 discloses a method for obtaining a graft copolymer by melt-mixing polyamide and PPE. JP-A-56-26913 discloses a method for obtaining a graft copolymer by melt-mixing polyamide and PPE. Hydrocarbon compounds. Furthermore, resin compositions with compounds having other functional groups are disclosed. JP-A-56-47432 discloses a resin silk composition consisting of boria ξ and PPE. A method is disclosed in which a condensed polymer compound obtained from phenol having an oxysilane ring and shrimp chlorohydrin is blended and melt-mixed. JP-A-56-49753 discloses a resin composition of polyamide, PPE, a rubbery substance, an unsaturated hydrocarbon, and a compound having other functional groups. JP-A-57-36150 discloses a resin composition consisting of a styrenic copolymer containing boriacid, PPE, α,β-monounsaturated dicarboxylic acid anhydride, and an impact strength modifier. ing. JP-A-59-66452 discloses 1,2 i! having a polyamide and a carboxyl group or an acid anhydride structure. ? Resin combinations with PPE modified with substituted olefins are disclosed. Unexamined Japanese Patent Publication 1986-
No. 296061 discloses a resin composition of polyamide, PPE, and oxidized olefin wax. Japanese Patent Publication No. 61-10494 discloses a resin composition comprising boria, PPE, and a liquid polymer.

However, these methods have problems such as a decrease in mechanical properties, especially elastic modulus, and poor gloss on the surface of the molded product. Furthermore, changes in dimensions and physical properties due to water absorption could not be said to be sufficiently suppressed.

(Problems to be Solved by the Invention) In view of the above circumstances, the object of the present invention is to provide a molded product with excellent mechanical properties, heat resistance, chemical resistance, and gloss, while greatly suppressing changes in dimensions and physical properties due to water absorption. The object of the present invention is to obtain a resin composition made of polyamide and PPE. Another object of the present invention is to obtain useful plastic molded articles that can be used in a wide range of fields by using a resin composition having such excellent properties.

(Means for Solving the Problem) As a result of extensive research for this purpose, the present inventor has developed a method by blending a specific non-grade boria 5 in a resin composition consisting of boria 5 and PPE. Surprisingly, the inventors found that the surface gloss of molded articles made from such resin compositions was significantly improved, and in addition to improving mechanical strength, changes in dimensions and physical properties due to water absorption were further suppressed, and the present invention was achieved. It is something.

That is, the present invention comprises (A) 15 to 98% by weight of crystalline polyamide and (B) 1 to 70% by weight of polyphenylene ether.
and (C) 1 to 50% by weight of a non-quality polyamide having a glass transition temperature of 100°C or higher.

The crystalline polyamide used as component (A) in the present invention is a polyamide obtained by ring-opening polymerization of lactams such as ε-cappylactam and ω-lauryllactam.
-Agonokaproic acid, 11-aminoundecanoic acid, 1
Polyamides derived from amino acids such as 2-aminododecanoic acid, ethylenediane. Tetramethylene diagonal.
hexamethylene diamine, undecamethylene diamine,
Dodecamethylenediamine, 2,2.4-/2.4.
4- 1-limethylherendia ξane, 1,3-bis(aminomethyl)cyclohexane. 1.4-bis(antanomethyl)cyclohexane, bis(4-antanocyclohexyl)methane, 1-aryan-ξ-3-adannomethyl-3.5.
5-trimethylcyclohexane. Bis(3-methyl-4-anocyclohexyl)methane, 2,2-bis(4
-75nocyclohexyl)propane. Bis(a≧nopropyl)biperazine, bis(aξnoethyl)biperazine and other aliphatic, alicyclic, and aromatic diamines and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid,
Terephthalic acid, isophthalic acid, 2-chloroterephthalic acid.
2-Methylterephthalic acid. 5-Methylisophthalic acid. 5
Boria ξ-does derived from aliphatic, alicyclic, aromatic dicarboxylic acids such as monosodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid 2-diglycolic acid, and copolymerized boriaamides thereof. It is a mixed polyad.

In the present invention, the term "crystalline boria ξ-do" means 1 caf! when measured at a heating rate of 20°C/min using a differential thermal analyzer. ．．
/g or more.

Among these, a particularly preferred crystalline polyamide is nylon 6
, nylon 66, nylon 46, nylon 11, nylon 12, and copolymerized boria≧do or mixed boriaamide containing these as main components.

The PPE used as component (B) in the present invention is known per se, and has the general formula (where R l+ R t+ R 3+ and R4 are hydrogen, halogen, an alkyl group, an alkoxy group, or a combination of a halogen atom and a phenyl ring). Tertiary α in haloalkyl and haloalkoxy groups having at least 2 carbon atoms between them
Indicates a monovalent substituent selected from those containing no one carbon. n
is the number of shots that represents the degree of success. ) is a general term for polymers represented by . The polymer represented by the above general formula may be used alone or in a mixture of two or more. It may also be a copolymer.

In preferred embodiments, R1 and R2 have 1 to 4 carbon atoms.
is an alkyl group, R3, R. is hydrogen or an alkyl group having 1 to 4 carbon atoms.

For example, poly(2,6-dimethyl-1,4-phenylene)
Ether, poly(2,6-diethyl-1,4-phenylene)ether poly(2-methyl-6-ethyl-1.4
-phenylene) ether, poly(2methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, and the like. Particularly preferred PPE is poly(2,6-dimethyl-
1,4-phenylene) ether.

Examples of the PPE copolymer include copolymers containing a portion of alkyl trisubstituted phenol, such as 2,36-trimethylphenol, in the PPE repeating units. It may also be a copolymer in which a styrene compound is grafted onto these PPEs. Styrenic compound-grafted PPE includes styrene-based compounds such as styrene. α-methylstyrene. It is a copolymer obtained by graft polymerization of vinyltoluene, chlorostyrene, etc.

In the present invention, the amorphous boria ξ-do means lcaff/
A substance that does not exhibit a heat of crystal fusion of more than g.

The amorphous BoIJ amide used as component (C) in the present invention has a glass transition temperature of 100° C. or higher in an absolutely dry state. The glass transition temperature can also be determined by measuring at a temperature increase rate of 20'C/min using a differential thermal analyzer. Amorphous polyamides having a glass transition temperature of less than 100° C. are not preferred because they have little effect on improving the properties of the resin compound.

Dia ξ constituting the amorphous polyamide used in the present invention
Typical examples include ethylene diane and tetramethylene diane. Hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine 2 2.4 −/
2,4.4-trimethylhexamane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane. Bis(4-anocyclohexyl)methane 1-amino-3-aminomethyl-3.5
．． 5-}rimedylcyclohexane, bis(3-methyl-4-anocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane. Bis(antanopropyl)piperazine. Examples include bis(aminoethyl)piperazine.

Typical examples of dicarboxylic acids constituting the non-standard polyamide used in the present invention include adipic acid and suberic acid. Azelaic acid, sebacic acid, dodecanniic acid, terephthalic acid,
・Isophthalic acid, 2-chloroterephthalic acid. 2-methylterephthalic acid, 5-methylisophthalic acid. Examples include 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

Typical examples of the amino acids and lacums constituting the non-grade polyamide used in the present invention include 6-anocaproic acid, 11-anoundecanoic acid, 12-anododecanoic acid, p-aminomethylammonium, Amino acids such as aromatic acid,
ε one-turnip lactam. Mention may be made of lactams such as ω-lauryllactam.

Examples of the most suitable non-grade boria≧de for use in the present invention include 2,2.4-/2,4.4-}limethylhexyl-4-notylenedia≧terephthalic acid and/or isophthalic acid. Polycondensate, hexamethylenedia ξ
Polycondensates of hexamethylene diamine bis(4-aminosyl-hexyl)methane terephthalic acid and isophthalic acid. Hexamethylene diane bis(3-methyl-4-aminocyclohexyl)methane terephthalic acid F:. and/or polycondensates of isophthalic acid. Polycondensate of ε-cabrolactam/bis(4-aminocyclohexyl)methane/terephthalic acid and/or isophthalic acid. ε monolactam bis(3-methyl-4-
aminocyclohexyl)methane terephthalic acid and/
Or isophthalic acid condensate, ω-lauryllactam bis(4-aξnonchlorohexyl)methane terephthalic acid and/or isophthalic acid polycondensate, ω-
Examples include polycondensates of lauryl lactam bis(3-medy-4-aminosichexyl)methane terephthalic acid and/or isophthalic acid.

The content of crystalline polyamide as component (A) in the resin composition of the present invention is 15 to 98% by weight, more preferably 3% by weight.
It is 0 to 80% by weight. The combination of crystalline boria ξ is I
If it is less than 5% by weight, mechanical strength and chemical resistance will deteriorate. On the other hand, if the amount of crystalline polyamide added exceeds 98% by weight, heat resistance will decrease and changes in dimensions and physical properties due to water absorption will increase.

The content of PPE (TI) in the resin composition of the present invention is from 1 to 70% by weight, more preferably from 10 to 60*
It is a condolence%. If the amount of PPE blended is less than 1% by market weight, the heat resistance will be low and the changes in dimensions and physical properties due to water absorption will be large. On the other hand, if the amount of PPP added exceeds 70% by weight, the chemical resistance will decrease.

The blending amount of (C) a certain non-quality polyamide in the resin composition of the present invention is 1 to 50% by weight, more preferably 3 to 50% by weight.
It is 40% by weight. When the amount of non-quality polyad is less than 1%, the gloss of a certain shaped article of the resin composition decreases,
Dimensions and physical properties change significantly due to water absorption. On the other hand, if the blend exceeds 50% by weight, the heat resistance will decrease.

In the resin composition of the present invention, other polymers may be blended as necessary, as long as the properties thereof are not significantly impaired.

In this case, the blending amount is preferably 30% by weight or less. Other such polymers include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone, polysulfone polyether sulfone, polyether ketone, polyether ether ketone, polyetherimide polyphenylene sulfide, ABS, PMMA polypropylene, polyethylene 1 Examples include phenoxy resin liquid crystal polymers and rubbery polymers.

Furthermore, the resin composition of the present invention includes: As long as it does not impair its precepts and physical properties. Pigments, heat stabilizers, antioxidants. Weathering agent, flame retardant, OK! v! It is possible to add a mold release agent, a mold release agent, a reinforcing material, and the like.

Glass fiber is used as a reinforcing material. Metal fiber. Potassium titanate whiskers, carbon 1a iff, i61l El-like reinforcements such as ara≧do fibers, talc. Calcium carbonate mica There are filler reinforcement materials such as glass flakes and metal flakes. In particular, glass fiber carp having a diameter of 3 to 20 μm is preferable because it further improves the strength, control rate, and heat resistance of the e-bonding product.

Method for producing a resin composition of the present invention or resin IF of the present invention
Any method can be used to obtain various molded products from I-bomono.

For example, each component of the resin composition of the present invention may be mixed with a Banbury mixer. Mix in a tumbler or other method and then inject directly. It can be molded into various insert molded products by methods such as extrusion molding and blow molding. Also, mix each portion with a Banbury mixer. After mixing using a tumbler or other method, melting and blending with an extruder, etc., and cutting to obtain 1.0 mm and 1.0 mm,
This can be shaped by injection molding, extrusion molding, blow molding, etc. to make various spectacular products.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these. The measurement methods and raw materials used in Examples and Comparative Examples are as follows.

Condolences, degree and elongation at break ASTM D638.1 Dumbbell Izod 1・'! - Hayabusa P ASTM D256, 3.2mm PfJ. Processed for 165 hours under the conditions of 65° C. and 95% RH.

Length 12.5cm, Width 1.25cm, f'j-mi 0
．． The dimensional change in the length direction of a 32 cm test piece was measured.

A certain gloss level ASTM D523. A No. 1 dumbbell with an incident angle of 60 degrees was immersed in toluene at room temperature for 165 hours, and changes in appearance and weight were observed.

Nylon 6: Manufactured by Unitika, A1030BRL Nylon 66: Manufactured by IC1, ^125 Nylon 46: Manufactured by Unitika, F5000PPE: C
; Manufactured by E Plastics Japan Co., Ltd., PPO534J Non-quality polyamide PA-1: Reference example 1. Glass transition temperature: 150°C Trogamide T: manufactured by Dynamite Nobel, glass transition temperature: 14
8°C, 2,2.4-/2,4.4-trimethylhexamethylenediamine/terephthalic acid polycondensate X-2 1: Manufactured by Mitsubishi Chemical Corporation. Glass transition temperature 125℃
, Hexamethylene diane ξ-terephthalic acid-isophthalic acid polycondensate TR55: Manufactured by EMS, glass transition temperature 152°C, polycondensation of ω-lauryllactam bis(3-methyl-4-anocyclohexyl)methane-isophthalic acid Material reference example 1: Amorphous polyamide (PA-1) 45 mol% of isophthalic acid, 5 mol% of terephthalic acid, 45 mol% of hexamethylenediamine, 5 mol% of bis(4-ano-3-methylcyclohexyl)methane 10 h of the raw materials were charged into a reaction tank along with 8 h of pure water, and the air in the reaction tank was purged several times with nitrogen. After the temperature was raised to 90°C and the reaction was carried out for about 5 hours, the reaction temperature was gradually raised to 280°C over 10 hours while stirring the tank under pressure (18 bar).

Then, the pressure was released and the pressure was lowered to atmospheric pressure, followed by polymerization at the same temperature for 6 hours. After the reaction was completed, the polymer was discharged from the reaction vessel and cut into pellets.

This copolyamide has no melting point. Its glass transition temperature was 150'C. P
It shall be A-1.

Practical Can Examples 1 to 3, Comparative Examples 1 to 3 After mixing the respective raw materials in a tumbler at the compounding ratio shown in Table 1, vacuum drying was performed at 90° C. for 16 hours. Then, using a twin-screw extruder (manufactured by Ikeyo Tekkosu Co., Ltd., PCM45),
The mixture was melted and kneaded at the temperature listed above, and then cut to obtain a berent made of resin. The pellets were molded using an injection molding machine (JIOOS manufactured by Nippon Steel Corporation) at the temperatures shown in Table 1 to obtain test pieces.

The test piece was subjected to various physical property measurements.

Table 1 shows the results of physical property measurements. As shown in Table 1, the resin compositions of the Examples had better mechanical properties such as tensile strength and Izod impact strength, as well as better surface gloss than the Comparative Examples. Moreover, there is little change in dimensions or physical properties due to water absorption.

Examples 4 to 10 Pellets of resin compositions having the compositions listed in Table 2 were obtained in exactly the same manner as in Examples 1 to 3, and test pieces were formed using the pellets. The results of those performance evaluations are listed in Table 2. As specifically shown in Table 2, the resin compositions of the examples have good mechanical properties. Heat resistance, chemical resistance, gloss of the molded product, and changes in dimensions and object 1+ due to water absorption are also reduced.

(Effects of the Invention) The resin assembly or proboscis of the present invention is... (A) Crystalline polyad 15~
98% by weight, (B) ~70% by weight of PPPI, and (C)
Consists of 1 to 50% by weight of amorphous boria with a glass transition temperature of 100°C or higher, crystalline polyad and PPE.
The gloss of the surface of the molded product is greatly improved compared to the resin composition made of effectively suppressed. Furthermore, the resin composition of the present invention maintains the properties of a resin composition made of crystalline polyamide and PPE in terms of heat resistance and chemical resistance.

Claims (1)

[Claims] (1) (A) 15 to 98% by weight of crystalline polyamide;
B) 1 to 70% by weight of polyphenylene ether; and (C)
A resin composition comprising 1 to 50% by weight of an amorphous polyamide having a glass transition temperature of 100°C or higher.