JPH0250955B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyether ester amide resin composition that has excellent oil resistance, chemical resistance, hydrolysis resistance, abrasion resistance, mechanical strength at high temperatures, creep resistance, and adhesiveness. Polyether ester amide is a well-known material that has polyamide repeating units, polyether repeating units, and ester bonds in the polymer main chain, and like polyether ester or polyester amide, it has excellent impact resistance and rubber elasticity, making it a new material in the elastomer field. has been attracting attention in recent years. In particular, polyether ester amide has excellent lightness, transparency, and low-temperature impact resistance, and is less likely to cause burrs or sink marks during molding, making it promising for various molding applications. There is still room for improvement in terms of gender, etc.
For example, applications such as steam hoses and hot water valves require excellent hydrolysis resistance and high-temperature properties, while applications such as hydraulic hoses, connectors, gasoline tanks, and electrical wire coatings require additional oil and chemical resistance. It is necessary that the material has properties such as durability, abrasion resistance, and high-temperature properties. Therefore, the object of the present invention is to provide polyetheresteramide with oil resistance, chemical resistance, hydrolysis resistance, abrasion resistance, and excellent high temperature properties. That is, the present invention provides polyether ester amide (A)
A resin composition containing 0.5 to 100 parts by weight of polyepoxide (B) having two or more functional groups per 100 parts by weight. Polyether ester amide (A) in the present invention
is an aminocarboxylic acid with 6 or more carbon atoms, a lactam, or a salt of a dicarboxylic acid with 6 or more carbon atoms and a diamine with 6 or more carbon atoms, number average molecular weight
300 to 6000 poly(alkylene oxide) glycol (b) and dicarboxylic acid having 4 to 20 carbon atoms
(c) and is a polymer having amide bonds, ether bonds, and ester bonds in the molecular chain. As an aminocarboxylic acid having 6 or more carbon atoms, ω
-aminocaproic acid, ω-aminoenanthate, ω
-aminocaprylic acid, ω-aminopergonic acid, ω
-aminocapric acid, 11-aminoundecanoic acid,
Among 12-aminododecanoic acids, those having 11 or more carbon atoms are preferred. Lactams having 6 or more carbon atoms include caprolactam, enantlactam, capryllactam, laurolactam, etc. Among them, those having 10 or more carbon atoms are preferred. Salts of dicarboxylic acids having 6 or more carbon atoms and diamines having 6 or more carbon atoms include adipic acid-hexamethylene diamine salts, sebacic acid-hexamethylene diamine salts,
There are isophthalic acid-hexamethylene diamine salts, among others, dicarboxylic acids having 10 or more carbon atoms are preferred. In addition, these compounds are used for purposes such as lowering the melting point of polyether ester amide and increasing adhesiveness.
These compounds can be used in combination, and other amide-forming components can also be used in small amounts as copolymerization components. The poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6000 in the present invention includes polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol,
Poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc., among others, have excellent heat resistance and water resistance. Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether esteramide, such as mechanical strength, elastic recovery, etc. The number average molecular weight of poly(alkylene oxide) glycol can be used in the range of 300 to 6000, but a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low-temperature properties and mechanical properties is selected, and this optimum molecular weight range is selected. varies depending on the type of poly(alkylene oxide) glycol. For example, in the case of polyethylene glycol, it is 300 to 6000, particularly preferably 1000 to
When 4000 is poly(propylene oxide) glycol, it is preferably 300 to 2000, particularly preferably 500 to 1200, and in the case of poly(tetramethylene oxide) glycol, it is preferably 500 to 2500, particularly preferably 500 to 1500. It will be done. Dicarboxylic acid (c) having 4 to 20 carbon atoms in the present invention
Examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 5-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid alicyclic dicarboxylic acids such as acids, and succinic acid,
Mention may be made of aliphatic dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid and dodecanedic acid. In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. On the other hand, the polyepoxide (B) having two or more types of functional groups used in the present invention is represented by the following general formula () and/or (), and is a polyepoxide having two or more functional groups. [However, in the formula, n is 2 to 10, R is H or lower alkyl, and R' is a polyvalent group that can contain an aromatic ring, even if it is combined with R to form a 5- to 6-membered ring. good. Polyepoxide compounds () obtained by the following or polyglycidyl compounds () obtained by reaction of epihalohydrin with an active hydrogen compound are useful in the compositions of the present invention. Typical polyepoxides obtained by epoxidizing olefins include vinylcyclohexene dioxide, bis(2,3-epoxycyclobenzyl)ether, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3-(3,4-epoxy-cyclohexane)-
8,9-epoxy-dioxaspiro[5,5]-
Examples include undecane, epoxidized butadiene, and epoxidized natural oils. Polyglycidyl compounds () derived from epihalohydrin and active hydrogen compounds include epichlorohydrin and bisphenol A, tetrabromobisphenol A, resorcinol, hydroquinone, pyrogallol, cresol, 4,4'-methylenebisphenol and phenol, or cresol and aldehyde. Polyphenols derived from (novolac)
Diglycidyl ether of bisphenol A of the following formula () and polyglycidyl ether of phenol-formaldehyde novolacs of the following formula () are particularly preferred. . Also, reaction products of epichlorohydrin and aliphatic compounds having 2 to 6 alcoholic hydroxyl groups, such as ethylene glycol, butanediol, poly(alkylene oxide glycol), glycerin, and pentaerythritol, adipic acid, succinic acid, phthalic acid, and trimeric acid. Also included in the polyepoxides of this invention are polyglycidyl esters of polycarboxylic acids such as acids. The method for polymerizing polyether ester amide (A) is not particularly limited, and any known method can be used. For example, salts of aminocarboxylic acids, lactams (a) or dicarboxylic acid-diamines and dicarboxylic acids (C)
A method of reacting in approximately equimolar ratio to create a polyamide prepolymer having carboxylic acid groups at both ends, and reacting this with poly(alkylene oxide) glycol under vacuum, or (a), (b), and (c) ) is charged into a reaction tank and reacted under pressure at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, followed by polymerization under normal pressure or reduced pressure. It has been known. There is also a method in which the compounds (a), (b), and (c) are simultaneously charged into a reaction tank, melt-mixed, and then polymerized all at once under high vacuum; this method is preferable since it causes less coloring of the polymer. The polyepoxide of the present invention is blended in an amount of 0.5 to 100 parts by weight, preferably 1 to 75 parts by weight, with respect to 100 parts by weight of the polyether ester amide, but the blending amount may be determined as appropriate depending on the intended use and performance. You can choose and decide. For example, when the purpose is to improve the hydrolysis resistance of polyether ester amide, it is sufficient to add a small amount of polyepoxide (0.5 to 10 parts by weight), and it is also effective to improve the chemical resistance and high temperature properties of polyether ester amide. For the purpose of improving the polyepoxide, it is necessary to add relatively large amounts of polyepoxide, from 20 to 100 parts by weight. Melt blending or solution blending is preferred as a method for mixing polyether ester amide and polyepoxide, but a resin composition in which polyether ester amide powder is impregnated with or adhered to polyepoxide liquid or powder is heated and molded in a mold. It is also possible to do so. Melt blending of polyether ester amide and polyepoxide can generally be carried out using kneading equipment such as rubber rolls, Banbury mixers, kneaders, single-screw or multi-screw extruders, but when blending a small amount of polyepoxide, polyether ester It is also possible to mix in an amide polymerizer. Melt-kneading of polyether ester amide and polyepoxide is usually carried out at a temperature of 100 to 250°C, but a low temperature should be selected within the range allowed by the melting point of the polyether ester amide to avoid local reaction runaway. Mixing of polyether ester amide and polyepoxide can also be carried out in a solution state, for example, by adding and mixing polyepoxide into a solution of polyether ester amide in chloroform, tricrene, m-cresol, o-chlorobenzene, tetrahydrofuran, etc. According to room temperature~
Since it can be mixed at a relatively low temperature of 100°C, there is no risk of gelation, and it is possible to stably mix a considerable amount of polyepoxide. The resin composition solution thus obtained can be directly cast into a film and dried by heating, or the powder obtained by reprecipitation in a poor solvent can be heated and molded in a mold. The polyether ester amide composition of the present invention contains stabilizers such as antioxidants, thermal decomposition stabilizers, and light stabilizers during polymerization, after polymerization, and kneading, or at any time before molding the kneaded resin composition. , colorants, flame retardants, reinforcing materials, fillers, various molding aids,
Additives such as plasticizers can be optionally added. In addition, the resin composition comprising the polyether ester amide and polyepoxide of the present invention may contain epoxy ring-opening catalysts such as aliphatic secondary amines, aliphatic tertiary amines, organic acid metal salts, aromatic, alicyclic, aliphatic, etc. Epoxy curing agents such as polyamines and acid anhydrides can also be used in combination, making it possible to obtain even better performance, especially in terms of chemical resistance and high temperature properties. The present invention will be explained below with reference to Examples. In the examples, all "parts" or "%" are expressed as weight ratios. Further, the relative viscosity is a value measured in orthochlorophenol at 25° C. and a concentration of 0.5%, and the melting point is also the melting peak temperature measured by DSC (Perkin Elmer DSC-1B) unless otherwise specified. Example 1 54.57 parts of ω-aminododecanoic acid, dodecanedioic acid,
13.42 parts and 38.68 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 663 determined by the end group determination method were mixed with 0.2 parts of "Irganox" 1098 (antioxidant) and 0.05 parts of tetrabutyl titanate catalyst using a helical ribbon stirring blade. The mixture was charged into a reaction vessel equipped with N ₂ purge, heated and stirred at 220°C for 30 minutes to obtain a homogeneous clear solution, and then brought to polymerization conditions of 250°C < 1 mmHg in 30 minutes according to a temperature increase and pressure reduction program. When the reaction was carried out under these conditions for 5 hours and 25 minutes, a viscous colorless and transparent molten polymer was obtained which exhibited a stirring torque of 5.0 Kg·cm at 22 rpm, and when this polymer was discharged into water as a gut, it crystallized and turned white. The polyether ester amide obtained had a relative viscosity (ηr) of 1.87 when measured in orthochlorophenol at 25°C at a concentration of 0.5%, and a crystal melting point (Tm) of 154°C by DSC. (In the following examples, ηr and Tm are also determined by this method). The thus obtained polyether ester amide (A-1) was blended with the polyepoxide represented by the above formula () [“Epikoat” 815 (manufactured by Ciel Chemical, epoxy equivalent: about 185)] in the amount shown in Table 1, and
The mixture was kneaded for 5 minutes on a rubber roll machine heated to 170°C and collected as a sheet. Then 2mm at 230℃
After press-molding into a thick sheet, it was heat-treated at 100°C for 16 hours. A suitably shaped test piece was cut from this sheet and its mechanical properties and chemical resistance were examined. In addition, the mechanical properties at 100°C and after 24 hours of treatment with boiling water were determined. These results are shown in Table 1. Sample 1-D in this example is a polyether ester amide containing no polyepoxide,
This is a comparative sample.

[Table] Example 2 65.48 parts of ω-aminododecanoic acid, dodecanedioic acid
Polyamide hard segment/polyether ester soft segment was prepared in the same manner as in Example 1 except that 30.95 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 663 were used as the starting material. ), ηr=1.77,
Tm=162.5℃ polyether ester amide (A
-2) was adjusted. To 100 parts of this polyether ester amide (A-2), 20 parts of a polyepoxide represented by the above formula () ["Epicote" 1001 (manufactured by Shell Chemical Co., Ltd., epoxy equivalent: about 500]] was melt-kneaded.
Chemical resistance (24°C at 70°C) due to polyepoxide formulation
Table 2 shows the results of a test to see how the immersion time (immersion time) changed. Furthermore, the polyepoxide compound is
After heat treatment at 100°C for 24 hours, it was subjected to a chemical resistance test. Also, put the test piece in an autoclave with water,
Table 3 shows the results of examining hydrolysis resistance.

【table】

【table】

[Table] Example 3 43.65 parts of ω-aminododecanoic acid, dodecanedioic acid
Using 16.10 parts and 46.42 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 663 as starting materials, a polyamide hard block/polyether ester block of 40/60 was prepared in the same manner as in Example 1.
(weight ratio), ηr=1.99, and Tm=143°C, polyetheresteramide (A-3) was prepared. 100 parts by weight of the above polyether ester amide was dissolved in a mixed solvent of chlorobenzene/methanol (80/20) to prepare a 20 solution. Bisphenol type epoxy resin “Epicoat” 1001 prepared separately from this
A 75% xylene solution of was added at the solid content ratio shown in Table 4 to form a homogeneous solution. These solutions were cast onto a glass plate and heated at 50°C for 2 hours and at 100°C.
Table 4 shows the results of examining the film properties, resistance to various solvents, and hydrolysis resistance at 80° C. after heating and drying for 24 hours.

【table】

【table】

Claims (1)

[Claims] 1 Polyepoxide having two or more functional groups per 100 parts by weight of polyether ester amide (A)
(B) A resin composition containing 0.5 to 100 parts by weight.