JPH03199253A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyester resin composition without impairing excellent mechanical properties and molding processability and deteriorating physical properties even in use at high temperature for a long period of time by blending a thermoplastic polyester resin with a specific amide-based compound. CONSTITUTION:A resin composition obtained by blending (A) 100 pts.wt. thermoplastic polyester resin, preferably polybutylene terephthalate and a copolymer or mixture consisting essentially thereof with (B) 0.005-10 pts.wt., preferably 0.01-5 pts.wt. amide-based compound expressed by the formula (R is n-functional organic group, preferably containing aromatic group, especially phenylene; X is 2-10C alkylene or substitution product thereof, preferably ethylene or propylene; Y is COOH, OH, SH, H or NH2, preferably COOH or OH; n is 2-4, preferably 2), and as necessary, 0.5-5wt.% (in the composition) antioxidant, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to polyester resin compositions.

More specifically, the present invention relates to a thermoplastic polyester resin composition with improved heat resistance, particularly durability under high temperatures.

[Conventional technology and its issues]

Crystalline thermoplastic polyester resins, such as polyalkylene terephthalate resins, have excellent mechanical properties, electrical properties, and other physical and chemical properties, and are easy to process, so they are used as engineering plastics in automobiles, electrical and electronics. It is used for a wide range of purposes such as parts.

However, with the expansion and diversification of applications, resins are often required to have even higher performance and special properties, and one of these characteristics is durability, especially long-term durability in high-temperature atmospheres. Stability of physical properties (long-term heat resistance) during use is increasingly required.

For example, in the automotive industry, safety requirements require that the physical properties of thermoplastic polyester resins be maintained even at high temperatures and during long-term use.

In order to meet such demands, methods have been proposed in which epoxy resins, polycarbodiimides, etc. are blended with thermoplastic polyester resins.

However, even polyester resins containing these additives still do not have sufficient long-term heat resistance, and a solution to this problem has been desired.

[Means to solve the problem]

In view of such demands, the present inventors have developed excellent mechanical properties,
The present invention has been arrived at as a result of extensive research in order to obtain a polyester resin composition that has durability, especially no deterioration in physical properties even after long-term use at high temperatures, without impairing moldability or the like.

That is, the present invention provides (A) thermoplastic polyester resin 10
The present invention relates to a polyester resin composition in which (B) 0.005 to 10 coulometric parts of an amide compound represented by the following format (1) is blended to 0 parts by weight.

First, the thermoplastic polyester resin (A
) means polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, or these three.
It is a polyester obtained by polycondensation of a polyester mixture, and the present invention is effective on both homopolyester and copolyester.

Examples of dicarboxylic acid compounds used here include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid,
These include known dicarboxylic acids such as diphenyldicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, and sebacic acid, and substituted products thereof. These dicarboxylic acid compounds can also be used in the polymerization in the form of reactive derivatives capable of forming esters, for example lower alcohol esters such as dimethyl ester. 2I1 or higher may also be used.

Examples of dihydroxy compounds constituting the polyester of the present invention include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hydroquinone, resorcinol, dihydroxyphenyl, naphthalene diol, dihydroxy diphenyl ether,
These include dihydroxy compounds such as cyclohexanediol, 2,2-bis(4-hydroxyphenyl)propane, jetoxylated bisfunol, polyoxyalkylene glycols, and substituted products thereof, and they can be used alone or in combination of two or more. can.

Examples of oxycarboxylic acids include oxybenzoic acid, oxynaphthoic acid, diphenyleneoxycarboxylic acid, and substituted products thereof.

Furthermore, derivatives of these compounds capable of forming esters can also be used.

In the present invention, one or more of these compounds may be used.

In addition to these, a polyester having a branched or crosslinked structure containing a small amount of trifunctional heptamer 1, ie, trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, trimethylolpropane, etc., may also be used.

In the present invention, the above compounds are used as monomer components,
Any thermoplastic polyester produced by polycondensation can be used as component (A) of the present invention, preferably polyalkylene terephthalate, more preferably polybutylene terephthalate, and copolymers or mixtures mainly composed of this. be done.

The polyester resin composition of the present invention comprises (A) as described above.
It is characterized by blending an amide compound represented by (B)-Form (1) into a thermoplastic polyester, and the blending of such a compound provides initial superiority for long-term use under high temperatures. This made it possible to maintain the same physical properties as before.

The ad compound (B) blended for this purpose is represented by the following format (1).

Any amide compound added as component (B) is effective as long as it has the structure represented by formula (1).

In the formula (1), R is an n-valent, that is, a di- to tetravalent organic group, such as an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a cycloalkylene group having 5 to 12 carbon atoms. ,
Examples include an aralkylene group having 8 to 20 carbon atoms. More specifically, the alkylene group includes methylene, ethylene, propylene, butylene, pentylene, hexamethylene, octamethylone, nonamethylene, decamethylene,
Examples include dimethylmethylene, arylene groups include phenylene, naphthylene, diphenylene, etc., and cycloalkylene groups include cyclohexylene. Among these, R is preferably one containing an aromatic group, particularly a phenylene group.

In the formula, χ is a C2-C1° alkylene group or a substituent thereof, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a cycloalkyl group having 5 to 12 carbon atoms. group, and an aralkyl group having 8 to 20 carbon atoms. More specifically, examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexamethyl, octamethyl, nonamethyl, decamethyl, dimethylmethyl, etc., and examples of aryl groups include phenyl, naphthyl, diphenyl, etc. An example of cycloalkyl is cyclohexyl. Of these, X
As such, ethylene group and propylene group are preferable.

In the formula, Y is -COOI+, -011, -3H, -I+
, -NHa, and among these, -COO
I+, -OH are preferred.

Further, n is an integer of 2 to 4, preferably 2.

Specific examples of the amide compound (B) represented by general formula (1) include N,N'-bis(2-carboxyethyl)malonamide, N,N'-bis(2-carboxyethyl)
Succinamide, N, N'-bis(2-carboxyethyl)glutaramide, N.

N'-bis(2-carboquinethyl)adipinamide,
N,N'-bis(2-carboxyethyl)isophthalamide, N,N''-bis(2-carboxyethyl)terephthalamide, N,N'-bis(3carboxypropyl)
Malonamide, N,N'-bis(3-carboxypropyl)succiamide, N,N'-bis(3-carboxypropyl)glutaramide, N,N'-bis(3-carboxypropyl)adipinamide, N,N' −Bis(
3-carboxypropyl)isophthalamide, N, N'
-bis(3-carboxypropyl)terephthalamide,
N, N'-his(2-hydroxyethyl)malonamide, N, N'-bis(2-hydroxyethyl)succiamide, N, N'-bis(2-hydroxyethyl)glutarate, N, N'-bis (2-Hydroxyethyl)adipinamide, N,N''-bis(2-hydroxyethyl)isophthalamide, N,N'-bis(2-hydroxyethyl)terephthalamide, N,N'-bis(3-hydroxypropyl)malona Kudo, N, N'-bis (3
-hydroxypropyl)succiamide, N, N'-bis(3-hydroxypropyl)glutaramide, N,N
'-bis(3-hydroxypropyl)adipinamide,
N,N'-bis(3-hydroxypropyl)isophthalamide, N,N'-bis(3-hydroxypropyl)
Terephthalamide, N,N',N''-tris(2-hydroxyethyl)trimesinamide, 3.3'.

Examples include 5.5'-tetrakis(2-hydroxyethylaminocarbonyl)biphenyl. These compounds may be used alone or in combination of two or more.

Among these compounds, N, N'bis(2-carboxyethyl)isophthalamide, N, N
'-Bis(3-carboxypropyl)isophthalamide, N,N'-bis-(2-carboxyethyl)terephthalamide, N,N'-bis(3-carboxypropyl)terephthalamide, N,N'-bis( 2-hydroxyethyl)isophthalamide, N,N'-bis-(2-
Hydroxypropyl〉Isophthalamide, N, N'-
Bis-(2-hydroxyethyl)terephthalamide, N
, N'-bis(2-hydroxypropyl)terephthalamide.

The amount of amide compound (B) added is based on the polyester resin (^
) 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight. Amide compounds have a strong affinity based on hydrogen bonds with each other or with polyester resin, so they have almost no sublimation property.
Since there is no volatilization during heating, it has the characteristic that it is effective when added in a very small amount, but if it is less than 0.005% by weight, the effect is small, and if it is too much, it has the disadvantage of reducing the excellent physical properties of polyester resin. occurs.

Although the composition of the present invention is not essential, further effects can be obtained by using in combination one or more types of antioxidants such as hindered phenol type, phosphorus type, and thioether type antioxidants.

Here, as hindered phenol antioxidants,
2.2'-methylenebis(4-methyl-6-1-butylphenol), hexamethylene glycolbis(3,5
-di-t-butyl-4-hydroxyhydrocinnamate), tetrakis[methylene (3,5-di-t-butyl-
4-hydroxyhydrocinnamate)] methane, triethylene glycol bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate, 1
．． 3.5-)limethyl-2,4,6-)lis(3,5-)
di-t-butyl-4-hydroxybenzyl)benzene,
n-octadecyl-3-(4'-hyFroquin-3',
5'-di-t-butylphenol) propionate, 4
．． 4'-methylenebis(2,6-di-t-butylphenol), 4.4°-butylidenebis(6-t-butyl-
3-methylphenol), 2.2'-thiodiethylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionate, distearyl-3,5-di-t
-butyl-4-hydroxybenzylphosphonate, 2-
Examples include t-butyl-6-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenylacrylate.

In addition, the phosphorus antioxidant is represented by the following formula (2), where R+ and Rt are selected from an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkoxy group. , each of which may be the same or different, among which RI R1 is an alkyl group having 6 or more carbon atoms, a substituted alkyl group, an alkoxy group, or an aryl group or a substituted aryl group that has stability during processing. Favorable from this point of view.

Particularly preferred is the case where R8R1 is an aryl group or a substituted aryl group. Examples of these include phenyl group,
Naphthyl group, diphenyl group, etc. or alkyl thereof,
These include hydroxy and/or alkoxy substituted products. Examples of specific compounds include bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,
Bis(nonylphenyl)pentaerythritol diphosphite, 4-phenoxy-9-α-(4-hydroxyphenyl)-p-cumenyloxy-3.5,8.10-tetraoxa-4,9-diphosphaspiro(5,5)undecane etc.

In addition, examples of thioether antioxidants include dilauryl thiodipropionate, simiristyl thiodipropionate, distearyl thiodipropionate, laurylstearyl thiodipropionate, and tetrakis[methylene-
Examples include 3-(dodecylthio)propionate comethane and dialkyl(C1,~+5)-3,3-thiodipropionate.

The amount of these antioxidants added is 0.05 to 5% by weight (in the composition), preferably 0.1 to 3% by weight.

The resin composition of the present invention may also be supplemented with a small amount of other thermoplastic resin as long as the purpose is not impaired. The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures.

Examples include boria chloride, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, and fluororesin.

Moreover, these thermoplastic resins can also be used in combination of two or more types.

In order to impart desired characteristics to the composition of the present invention according to its purpose, known substances generally added to thermoplastic resins, thermosetting resins, etc., such as stabilizers such as ultraviolet absorbers, antistatic agents, etc. Of course, it is also possible to incorporate flame retardants, flame retardant aids, colorants such as dyes and pigments, lubricants, plasticizers, crystallization promoters, crystal nucleating agents, inorganic fillers, and the like.

Examples of inorganic fillers include glass fiber, carbon fiber, ceramic fiber, boron fiber, potassium titanate fiber, general inorganic fiber such as asbestos, calcium carbonate, highly dispersed silicate, aluminum, aluminum hydroxide, and talc. , clay, mica, glass flakes, glass powder, glass peas, quartz powder, silica sand, wollastonite, carbon black, barium sulfate, calcined gypsum, silicon carbide, alumina, boron nitride, silicon nitride, etc. powder and granular materials, plates inorganic compounds,
Includes whiskers, etc.

These inorganic fillers can be used singly or in combination of two or more, if necessary.

There are no particular restrictions on the preparation of the composition of the present invention, and it can be easily prepared using known equipment and methods that are generally used for the preparation of conventional resin bottoms.

For example, i) a method of mixing each acid component, then kneading and extruding it using an extruder to prepare pellets, and then molding;
- A method of first preparing pellets with different compositions, mixing a predetermined amount of the pellets, applying the mixture to a bottom shape, and obtaining a molded product with the desired composition after molding; ii) A method of directly charging one or more of each component into a molding machine, etc. , any of them can be used. Further, adding a part of the resin component as a fine powder by mixing it with other acid components is a preferable method for uniformly blending these components.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

The measurement method for evaluating physical properties shown in the following examples is as follows.

■ Tensile strength and elongation ^ST? The initial strength and elongation and the elongation after heating at 120° C. for 500 hours were measured according to I 0-638 (test piece ^ STM type ■ type: thickness 1 vw).

■ Izot impact strength ^ Notched izot impact strength was measured in accordance with STM D-256.

Examples 1 to 7 and Comparative Examples 1 to 2 As the thermoplastic polyester (A), polybutylene terephthalate (A-1) with an intrinsic viscosity of 0.8 and (B) as the acid content, various aido-based compounds shown in Table 1 were used. The compounds were added and mixed in the proportions shown in Table 1, and pellets were obtained using an extruder.The pellets were then used to prepare test pieces by injection molding, and the above-mentioned physical properties were evaluated. For comparison, pellets were prepared in the same manner as in the example for polybutylene terephthalate (A-1) without adding the acid component (B) and with an epoxy compound added and mixed in place of component (8). The above evaluation was performed.

The results are also shown in Table 1.

Example 8 and Comparative Example 3 Characteristics were evaluated in the same manner as in Example 2, except that polybutylene terephthalate (A-2) with an intrinsic viscosity of 1.0 was used as the thermoplastic polyester (A). As a comparative example (B)
I'li, with minutes omitted, was also evaluated. The results are shown in Table 1.

Example 9 and Comparative Example 4 Component (A) of Example 2 was replaced with a mixed polymer of polybutylene terephthalate and polyethylene terephthalate (A-3
) was tested and evaluated in the same manner as in Example 2, except that

The results are shown in Table 1.

On the other hand, as a comparative example, a product in which component (B) was omitted was tested and evaluated in the same manner as in the example. The results are also shown in Table 1.

Notes to Table 1: Polybutylene terephthalate with an intrinsic viscosity of 0.8 Polybutylene terephthalate with an intrinsic viscosity of 1.0 75 parts by weight of polybutylene terephthalate (A-1) and 25 parts by weight of polyethylene terephthalate (with an intrinsic viscosity of 0.7) Mixed polymer N, N'-bis(2-hydroxyethyl)isophthalamide N, N'-bis(2-hydroxypropyl)isophthalamide N, N'-bis(2-hydroxyethyl)terephthalamide N, N'-bis (2-carboxyethyl)isophthalamide bisphenol^ type jepoxy compound [Effects of the invention] As is clear from the above explanation and examples, the polyester resin of the present invention has better heat resistance stability than conventional polyester resins, especially under high temperatures. The object of the present invention is to provide a resin that has significantly improved durability and exhibits little decrease in tensile elongation even when placed under high temperatures for long periods of time.

As mentioned above, the polyester resin of the present invention has little deterioration in toughness due to thermal history, so it is suitable for mechanical materials and parts used for long periods in high-temperature environments in automobiles, electrical equipment, etc.
For example, it is suitably used for connectors, coil bobbins, switches, relays, etc.

Claims (1)

[Claims] 1 (A) For 100 parts by weight of thermoplastic polyester resin, (B) The following general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (I) R represents an n-valent organic group , X is an alkylene group of C_2 to C_1_0 or a substituted product thereof, Y is -COOH, -OH,
-SH, -H, -NH_2, and n represents an integer of 2 to 4. A polyester resin composition containing 0.005 to 10 parts by weight of an amide compound represented by: 2. The polyester resin composition according to claim 1, wherein R in the formula (I) representing the amide compound (B) contains an aromatic group. 3 (B) Claim 1 in which X in formula (I) representing an amide compound is ethylene or propylene or a substituted product thereof.
Or the polyester resin composition according to 2. 4 (B) Y in formula (I) representing an amide compound is -C
The polyester resin composition according to any one of claims 1 to 3, which is OOH. 5 (B) Y in formula (I) representing an amide compound is -O
The polyester resin composition according to any one of claims 1 to 3, which is H. 6. The polyester resin composition according to any one of claims 1 to 5, wherein the thermoplastic polyester resin (A) is polybutylene terephthalate and a copolymer or mixture mainly composed of polybutylene terephthalate.