JPS6256892B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to improved polyesteramide resin compositions having excellent chemical resistance, hydrolysis resistance, abrasion resistance, adhesion and high temperature properties. The present inventors have discovered that a novel polyester amide made by copolymerizing an amide unit with a butylene terephthalate unit and/or a butylene isophthalate unit has excellent mechanical strength, impact resistance, transparency,
It was discovered that it could be easily produced as a highly polymerized polymer with properties such as flexibility, oil resistance, heat aging resistance, and adhesiveness, and was free from coloration. The application was filed as No. 1983-6214. However, when polyesteramides having such excellent properties are applied to specific applications, further improved performance is required in terms of high temperature properties, hydrolysis resistance, chemical resistance, and the like. For example, applications such as steam hoses and hot water valves require superior hydrolysis resistance and high-temperature properties, while applications such as hydraulic hoses, connectors, gasoline tanks, and electrical wire coatings require oil resistance and resistance. It is necessary to have chemical resistance, wear resistance, and high temperature properties. Therefore, the inventors of the present invention conducted intensive studies to provide polyesteramide with even better performance such as chemical resistance, hydrolysis resistance, abrasion resistance, and high-temperature properties. The inventors have discovered that the above objects can be solved at once by doing the following, and have arrived at the present invention. That is, the present invention comprises (A) 20 to 85% by weight of ester units represented by the following formula () and/or ().
(B) 0.5 to 100 parts by weight of a polyepoxide having two or more functional groups is blended with 100 parts by weight of a polyester amide consisting of 80 to 15% by weight of amide units represented by the following formulas () and/or (). The present invention provides a resin composition comprising: (However, l in formula () is 10 or 11, R in formula () is -(CH ₂ )- _o or a monocyclic aromatic nucleus, m is an integer of 6 to 12, and n is an integer of 6 to 10. ) The polyesteramide used in the present invention is a copolymer consisting of an ester unit represented by the above formula () and/or () and an amide unit represented by the above formula () and/or (). . The ester unit here specifically refers to a butylene terephthalate and/or butylene isophthalate unit, and means a polyester unit produced from terephthalic acid and/or isophthalic acid and 1,4-butanediol by a condensation reaction. This polyester unit can be represented by a polymer unit of the following formula () by integrating the above formulas () and (). Here, when p=0, polybutylene terephthalate, when o=0, polybutylene isophthalate,
When o≠0 and p≠0, a polybutylene terephthalate/polybutylene isophthalate copolymer is obtained. The o:p ratio can be freely selected depending on the purpose and use, but generally when the polyester unit is polybutylene terephthalate alone, it has high crystallinity,
A polyesteramide with a high melting point and high strength is obtained. When the polyester unit is polybutylene isophthalate alone, the resulting amorphous polyester amide is flexible and has a relatively low melting point. Further, when the polyester unit is a polybutylene terephthalate/polybutylene isophthalate copolymer, a flexible polyester amide having the lowest melting point and excellent solubility in solvents can be obtained. Specifically, the amide unit represented by the above formula () and/or (), which is another component of the polyesteramide of the present invention, is 12-aminododecanoic acid, 11-aminoundecanoic acid, and/or
H ₂ N (CH ₂ ) _n NH ₂ diamine component and HOOC−
It means a polyamide unit formed from a dicarboxylic acid component called R-COOH. The diamine components mentioned here include hexamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, and the dicarboxylic acid components include azelaic acid, sebacic acid, decanedicarboxylic acid, terephthalic acid, and isophthalic acid. Can be mentioned. Each of these amide constituents can be used alone or in the form of a copolymer, and may be appropriately selected and used for the purpose of controlling melting point, crystallinity, solubility, heat resistance, chemical resistance, etc. In the polyesteramide of the present invention, it is important to selectively use butylene terephthalate and/or butylene isophthalate as the ester unit and the amide shown in formula () and/or formula () as the amide unit in combination. In this copolymerized polyester amide, there is no problem of monomer distillation out of the system, the polymerization proceeds uniformly without phase separation, and a polymer with a high degree of polymerization without coloration can be obtained, as well as a polymer with a high degree of polymerization. The new copolymer has excellent mechanical strength, impact resistance, transparency,
It is a flexible polymer that has any or all of the following properties: flexibility, oil resistance, solvent resistance, water resistance, heat aging resistance, adhesiveness, solvent solubility, etc. The copolymerization composition ratio of ester units and amide units in polyester amide is 20:80 to 20:80 by weight.
The ratio is 85:15, more preferably 25:75 to 80:20. Polyesteramides having this copolymerization composition include polyesters such as polybutylene terephthalate and polybutylene terephthalate/polybutylene isophthalate copolymers, as well as polyhexamethylene sebamide, polyhexamethylene isophthalamide, and polyhexamethylene dodecanoamide. ,
Polyamides such as polyundecamethylenedodecanoamide, polydodecanamide, and polyundecaneamide have begun to exhibit remarkable new performance that could not be expected from polyamides. The polyesteramide of the present invention comprises (a) a dicarboxylic acid consisting of terephthalic acid and/or isophthalic acid, (b) 1,4-butanediol and (c) an aliphatic diamine _H2N ( _CH2 ) _mNH2 (m is 6 ~12 integers) and aliphatic dicarboxylic acids HOOC ( _CH2 )
Nylon salt from nCOOH (n is an integer from 6 to 10) or aromatic dicarboxylic acid HOOC-Ar-COOH (Ar is a monocyclic aromatic nucleus) and/or ω such as 12-aminododecanoic acid and 11-aminoundecanoic acid. - achieved by melt polymerizing aminocarboxylic acids. An example of a suitable polymerization method is as follows:
An aromatic dicarboxylic acid consisting of terephthalic acid and/or isophthalic acid is first heated at about 150 to 260°C in the presence of a conventional esterification catalyst together with 1.05 to 2.0 times the molar amount of 1,4-butanediol to the aromatic dicarboxylic acid. A polyester prepolymer with an average degree of polymerization of 3 to 8 is prepared under esterification conditions,
This prepolymer and the above aminocarboxylic acid and/or
Alternatively, a polyester amide with a high degree of polymerization that is transparent when melted is obtained by supplying a nylon salt to a polymerization reactor and polycondensing it under reduced pressure of 10 mmHg or less, preferably 1 mmHg or less at 200 to 270°C in the presence of a polymerization catalyst. It can be done. In addition, aromatic dicarboxylic acid, 1,4-butanediol, and the above aminocarboxylic acid or nylon salt are simultaneously present from the initial stage of the esterification reaction, and the temperature is set at 150 to 260°C in an atmospheric pressure reaction system sealed with _N2 . A uniform polyesteramide with a high degree of polymerization can be similarly obtained by carrying out the reaction at high temperature and then carrying out heating polycondensation under the same polymerization conditions as described above. When polymerizing a polyester prepolymer with an aminocarboxylic acid and/or a nylon salt, a lower alkyl ester of terephthalic acid and/or isophthalic acid may be used in advance to prepare the polyester prepolymer. Further, the above-mentioned nylon salt of aminocarboxylic acid or fatty acid diamine and aliphatic dicarboxylic acid or aromatic dicarboxylic acid may be prepared in advance in the form of a prepolymer and subjected to the polymerization reaction. For example, hexamethylene diammonium sebacate (610
salt) with a small amount of sebacic acid to form a nylon 610 prepolymer, which is added during the esterification reaction or subjected to a polymerization reaction with the polybutylene tere(iso)phthalate oligomer after esterification to form a polyester. It can be an amide. Among the amide components used in the present invention, polyamides having good compatibility with polybutylene tere(iso)phthalate, such as polyhexamethylene sebacamide and polydodecanamide, are suitable for their intended use, required performance, and copolymerization. Depending on the composition range, even a high molecular weight product with an average degree of polymerization of 50 or more may be able to be subjected to the polyesteramide polymerization reaction. Titanium-based catalysts give good results in the production of polyesteramides. Particularly preferred are tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal salts of titanium oxalate such as potassium titanium oxalate. Other catalysts include tin compounds such as dibutyltin oxide and dibutyltin laurate, zinc compounds and lead compounds such as zinc acetate and lead acetate. In addition, in the small amount copolymerization range, other dicarboxylic acids such as naphthalene dicarboxylic acid, adipic acid, and cyclohexane dicarboxylic acid, other diol components such as cyclohexanedimethanol, 1,6-hexanediol, m-xylylene diamine, p-xylylene dicarboxylic acid, etc. Nylon salts containing amines, trimethylhexamethylene diamine, etc., and polyfunctional compounds such as trimesic acid, glycerin, pentaerythritol, etc. may be included. In the above-mentioned method for producing polyester amide, the average segment length of the ester units and amide units is generally determined by the copolymerization composition ratio, but it can also be controlled by the reaction conditions, for example at the polyester prepolymer stage. In polymers polymerized by adding nylon salts, the average segment length of each unit is longer than in polymers obtained by reacting all monomers at once, and as a result, the melting point is several degrees Celsius to 20 degrees Celsius higher. Become.
Therefore, the optimum method for producing the polymer should be selected depending on the intended use. The polyepoxide having two or more functionalities used in the present invention is represented by the following general formula () and/or (), and is a polyepoxide having two or more functionalities. (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 and is combined with R' to form a 5- to 6-membered ring. Useful in the compositions of the present invention are polyepoxide compounds () obtained by epoxidation of olefins () or polyglycidyl compounds () obtained by reaction of epihalohydrin with active hydrogen compounds. Typical polyepoxides () obtained by this process include vinylcyclohexene dioxide, bis(2,3-epoxycyclobenzyl)ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis(3-epoxycyclohexanecarboxylate).・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, tinphenol A, tetrabromobisphenol A, resorcinol, hydroquinone, pyrogallol, cresol, 4,4'-methylenebisphenol, 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. . (Here, x = 0 to 5, y = 1 to 6) In addition, epichlorohydrin and aliphatic compounds having 2 to 6 alcoholic hydroxyl groups, such as ethylene glycol, butanediol, poly(alkylene oxide glycol), glycerin, and pentaerythritol, Polyglycidyl esters of polycarboxylic acids such as adipic acid, succinic acid, phthalic acid, and trimellitic acid are also included in the polyepoxide of the present invention. These polyepoxides are used in amounts of 0.5 to 100 parts by weight of polyesteramide.
It is blended in a proportion of 100 parts by weight, preferably 1 to 75 parts by weight, but the blending amount can be determined as appropriate depending on the intended use and performance. For example, if the purpose is to improve the hydrolysis resistance of polyesteramide, adding a small amount of polyepoxide (0.5 to 10 parts by weight) is sufficient. For this purpose 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 polyesteramide and polyepoxide, but it is also possible to heat-form a resin composition in which polyesteramide powder is impregnated with or adhered to polyepoxide liquid or powder in a mold. It is. Melt blends of polyesteramide and polyepoxide are generally prepared using rubber rolls, Banbury mixers,
The mixing can be carried out using a kneading device such as a kneader, a single-screw extruder, or a multi-screw extruder, but in the case of blending a small amount of polyepoxide, the mixing can also be carried out in a polyesteramide polymerization machine. Melt-kneading of polyesteramide and polyepoxide is usually carried out at a temperature of 100-250°C, but a low temperature should be selected within the range allowed by the melting point of the polyesteramide in order to avoid local reaction runaway. Further, mixing of polyesteramide and polyepoxide can also be carried out in a solution state, for example, chloroform, trichlene, m
- According to the method of adding polyepoxide to a solution of cresol, o-chlorobenzene, tetrahydrofuran, etc., it can be mixed at a relatively low temperature of room temperature to 100°C, so there is no risk of gelation, and a considerable amount of polyepoxide can be mixed. It is possible to stably mix polyepoxides of 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 polyesteramide composition of the present invention may be added with stabilizers such as antioxidants, thermal decomposition stabilizers, and light stabilizers, and coloring at any time during polymerization, after polymerization, and kneading, or before molding the kneaded resin composition. Additives such as additives, flame retardants, reinforcing materials, fillers, various molding aids, and plasticizers can be optionally mixed and used. In addition, the resin composition comprising polyesteramide and polyepoxide of the present invention includes aliphatic secondary amine,
Epoxy catalysts such as aliphatic tertiary amines and organic acid metal salts, aromatic, alicyclic and aliphatic polyamines,
Epoxy curing agents such as acid anhydrides can also be used in combination, making it possible to obtain even better performance, particularly 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 1 166 parts of terephthalic acid, 1,4-butanediol
135 parts and 129 parts of 12-aminododecanoic acid were placed in a reaction vessel along with 0.09 parts of titanium tetrabutoxide;
45 for 3 hours at a temperature of 230 °C under stirring after purging with _N2
The mixture was heated for 1 minute to react, and 62.5 parts of a mixture of water, tetrahydrofuran and 1,4-butanediol was distilled out of the system. The reaction mixture was then transferred to a polymerization reaction vessel, and 0.18 parts of titanium tetrabutoxide and 0.33 parts of "Irganox" 1010 were added, and then the reaction mixture was reacted for about 1 hour.
When the reaction conditions were brought to 245°C and 0.1 mmHg or less, and the polymerization reaction was continued for an additional 1 hour and 35 minutes, a transparent viscous polymer was obtained. The obtained polyesteramide had a weight composition ratio of polybutylene terephthalate:polydodecanamide of 65:35, and exhibited a relative viscosity of 1.50 and a polymer melting point of 158°C. The polyepoxide represented by the formula () ["Epicord" 815 (manufactured by Ciel Chemical Co., Ltd., epoxy equivalent: about 185]] was blended with the polyester amide thus obtained in the amount shown in Table 1, and heated to 165-170°C. The mixture was kneaded for 5 minutes on a rubber roll machine and collected as a sheet. Next, it was press-molded into a 2 mm thick sheet at 230°C, and then 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 being treated with boiling water for 2 hours were determined. These results are shown in Table 1. Sample 1-D in this example is a polyesteramide containing no polyepoxide and serves as a comparative sample.

[Table] Example 2 3.00 parts of isophthalic acid, 1,4-butanediol
In the same manner as in Example 1, except that 2.93 parts and 3.00 parts of hexamethylene diammonium sebacate were used as starting materials, the weight ratio of the constituent units of polybutylene isophthalate:polyhexamethylene sebaamide was 60:
40, a relative viscosity of 1.45, and a melting point of 132°C. To 100 parts of this polyesteramide, 20 parts of a polyepoxide represented by the above formula () ["Epikoat" 1001 (manufactured by Ciel 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.

[Table] Example 3 200 parts of terephthalic acid, 133 parts of isophthalic acid, 1.
Using 325 parts of 4-butanediol and 241 parts of 12-aminododecanoic acid as starting materials, in the same manner as in Example 1, the structural unit weight ratio of polybutylene terephthalate: polybutylene isophthalate: polydodecaneamide was 40:27: 33 polyesteramides were prepared. The melting point of this polyesteramide is 101℃,
The relative viscosity was 1.41. Dissolve 100 parts of the above polyesteramide in a mixed solvent of chlorobenzene/methanol (80/20) and
% solution. A separately prepared 75% xylene solution of bisphenol type epoxy resin "Epicote" 1001 was added to this at the solid content ratio shown in Table 3 to form a uniform transparent solution. These solutions were cast onto a glass plate and incubated at 50°C for 2 hours and at 100°C for 24 hours.
Table 3 shows the results of examining the film properties and resistance to various solvents at 80°C after drying by heating for a period of time.

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Claims (1)

[Scope of Claims] 1 (A) 20 to 85% by weight of ester units represented by the following formula () and/or () and the following formula ()
and/or () amide unit 80
A resin composition comprising 0.5 to 100 parts by weight of (B) a polyepoxide having two or more functional groups to 100 parts by weight of a polyesteramide comprising 15% by weight. (However, l in formula () is 10 or 11, R in formula () is -(CH ₂ )- _o or a monocyclic aromatic nucleus, m is an integer of 6 to 12, and n is an integer of 6 to 10. )