JP3017806B2 - Polyester ester-based thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester ester thermoplastic resin composition. More specifically, the present invention relates to a polyester ester-based thermoplastic resin composition that gives a molded article having excellent heat resistance and moisture resistance.

[0002]

2. Description of the Related Art A polyester ester block copolymer comprising a crystalline aromatic polyester and a lactone is
It has excellent rubber properties, heat resistance and weather resistance.

However, the retention of tensile elongation at break when exposed to high temperatures for a long time (heat resistance and durability) and the retention of tensile elongation at break when exposed to high humidity for a long time (moisture resistance) are sufficient. However, when exposed to high temperature or high humidity for a long time, the tensile elongation at break decreases significantly.

As a method of solving such problems of the polyester ester-based thermoplastic resin, a method of adding a monofunctional or higher epoxy compound (Japanese Patent Application Laid-Open No. 58-162654) is disclosed. A method of adding a metal salt of an aromatic carboxylic acid (JP-A-59-152947), a method of adding a monofunctional or difunctional or bifunctional or more epoxy compound and a trivalent phosphorus compound (JP-A-1-152947)
163259) and the like.

[0005] In a polyester ester-based thermoplastic resin, a polyester ester block copolymer (hereinafter, PET-PL) obtained by reacting polyethylene terephthalate (hereinafter, referred to as PET) with a lactone is PE.
Because T is used, it has a higher crystal melting point and higher Vicat softening temperature than polyester ester block copolymer (hereinafter referred to as PBT-PL) obtained by reacting polybutylene terephthalate with lactones. It is preferred because there is.

By the way, when the method for improving the heat resistance and the humidity resistance is applied to the PET-PL, the heat resistance under the condition of heating at 140 ° C. for 12 days disclosed in the examples of the three publications is applied. The effect is seen, but 170 ℃ x 25
For more high temperature and long-term heat resistance such as days, the above method is carried out using a bifunctional or less epoxy compound.
When applied to PET-PL, tensile elongation at break is sufficiently maintained when a heat and durability test is performed in an environment with low atmospheric humidity, such as winter in Japan. It was found that the tensile elongation at break was not maintained in such an environment with high humidity in the atmosphere.

[0007] Further, with respect to moisture resistance and durability, satisfactory results have not been obtained only by adding an epoxy compound to PET-PL.

When the above-mentioned prior art is applied to PBT-PL, the effect of improving the heat resistance and durability can be seen, but it is not a substitute for PET-PL due to the above-mentioned disadvantage that the Vicat softening point is low.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester ester-based thermoplastic resin composition having excellent heat resistance and durability even in a high humidity environment and having a high Vicat softening point. is there.

[0010]

DISCLOSURE OF THE INVENTION In view of the above prior art, the present inventors have developed a polyester ester block copolymer (PET-PL) obtained by reacting polyethylene terephthalate (PET) with lactones. As a result of intensive studies to improve the heat resistance and humidity resistance, PET-PL is heat resistant and durable when an epoxy compound containing at least one epoxy compound having three or more functional groups, a metal salt of an organic carboxylic acid, and polycarbodiimide are added. The inventors have found that the properties and the moisture resistance and durability are improved, and arrived at the present invention.

That is, according to the present invention, 100 parts (parts by weight, hereinafter the same) of a polyester ester block copolymer obtained by reacting polyethylene terephthalate with a lactone are added with (a) a metal salt of an organic carboxylic acid of 0.05 to 0.05 parts by weight. 5 parts, (b)
0.05 to 10 parts of an epoxy compound containing at least one epoxy compound having three or more functional groups and (c) polycarbodiimide 0.1.
The present invention relates to a polyester ester-based thermoplastic resin composition containing from 0.05 to 10 parts.

[0012]

Action and Examples: Polyester ester block copolymer (PET-PL) obtained by reacting polyethylene terephthalate (PET) and lactones used in the present invention.
Is composed of a polyethylene terephthalate segment and a (poly) lactone segment.

The method for producing such PET-PL is not particularly limited, and any method can be employed. For example, PE
It can be obtained by a method of reacting T and a lactone batchwise or continuously.

Polyethylene terephthalate (PET) used in PET-PL is composed of ethylene terephthalate units in an amount of 70 mol% or more of all the structural units. In addition, for example, glycols such as butanediol, hexamethylenediol and cyclohexanedimethanol are used. And esters containing dicarboxylic acids such as isophthalic acid, adipic acid and sebacic acid as components may be copolymerized.

Lactones include, for example, ε-caprolactone, methyl-ε-caprolactone, dimethyl-
ε-caprolactone, trimethyl-ε-caprolactone, β-propiolactone, pivalolactone, γ-valerolactone, enantholactone, caprylolactone, and the like. Among them, ε-caprolactone is most preferred. Such lactones may be used alone or in combination of two or more in the reaction with the polyethylene terephthalate.

In the production of PET-PL, the composition ratio (weight ratio, hereinafter the same) of PET and lactone is 90/10 to 10/90.
And preferably 80/20 to 30/70. If the ratio of PET exceeds 90/10 in such a composition ratio, the obtained PE
The tensile elongation at break of T-PL is reduced, and the flexibility is reduced.
On the other hand, if it is less than 10/90, the crystallization speed becomes slow and the formability becomes poor.

The metal salt of an organic carboxylic acid used in the present invention acts as a crystal nucleating agent and promotes crystallization of PET-PL to improve moldability and the like. For example, stearic acid, sebacic acid, Metal salts such as palmitic acid, montanic acid, dimer acid, trimer acid, and benzoic acid are included. Of these, the organic carboxylic acid is preferably an aliphatic carboxylic acid, and the metal is a metal of Group IA or IIA of the periodic table, for example, sodium,
This is the case for potassium and calcium. Particularly preferred is the sodium salt of montanic acid. These metal salts of organic carboxylic acids may be used alone or in combination of two or more.

The amount of the metal salt of the organic carboxylic acid added is
0.05-5 parts, preferably 0.1-3 parts per 100 parts PET-PL
Department. When the addition amount is less than 0.05 part, crystallization is not sufficiently promoted and moldability is deteriorated. If the amount exceeds 5 parts, the obtained molded product has a remarkable decrease in tensile elongation at break, resulting in poor moisture resistance and durability.

The epoxy compound used in the present invention is PE
The T-PL-containing composition is added to improve the heat resistance and the moisture resistance of the composition.

The structure of the trifunctional or higher epoxy compound in the present invention is not particularly limited, but it is preferable that the compound has three or more epoxy groups in the molecule and has an epoxy equivalent in the range of 70 to 1,000. Among them, a trifunctional or tetrafunctional epoxy compound is preferable.

Specific examples of the epoxy compound having three or more functional groups include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and pentaerythritol polyglycidyl ether.

The above trifunctional or higher epoxy compounds may be used alone or in combination of two or more.

In the present invention, when it is necessary to further increase the initial tensile elongation at break than when only epoxy compounds having three or more functions are used, it is preferable to use epoxy compounds having two or less functions together. . Even more favorable results can be obtained by using a bifunctional or less epoxy compound in combination for improving the moisture resistance and durability.

Specific examples of the epoxy compound having two or less functional groups include phenyl glycidyl ether, polyethylene glycol monophenyl monoglycidyl ether, ethylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and bisphenol A diglycidyl ether.

The combination ratio of the trifunctional or higher functional epoxy compound to the bifunctional or lower functional epoxy compound cannot be determined unconditionally because it varies depending on the epoxy equivalent of the epoxy compound. However, the weight ratio is in the range of 95/5 to 45/55. It is common to use. The ratio of epoxy compounds having three or more functional groups is 95/5
If the ratio exceeds 50, the initial tensile elongation at break tends to be insufficient, and if it is less than 45/55, the heat resistance tends to be insufficient.

The epoxy compound used in the present invention, PET-
The amount to be added to the PL can not be determined unconditionally because it depends on the epoxy equivalent of the epoxy compound to be added, but usually 0.05 to 10 parts, preferably 100 parts by weight of PET-PL, preferably
0.1 to 5 parts, more preferably 0.2 to 3 parts. When the amount is less than 0.05 part, the effect of improving the heat resistance and the moisture resistance becomes small. On the other hand, if it exceeds 10 parts, the retention stability during molding becomes poor, and the tensile elongation at break is further reduced.

In the present invention, polycarbodiimide is added to further improve the moisture resistance and durability of the PET-PL composition. Such a polycarbodiimide is a compound having at least two carbodiimide groups per molecule, and its structure is not particularly limited. Specific examples of such a polycarbodiimide include, for example, a compound represented by the formula:

[0028]

Embedded image

And Stabacol P (carbodiimide group content, 13.5% or more) manufactured by Bayer AG.

The amount of the polycarbodiimide added is PE
0.05 to 10 parts, preferably 0.1 to 5 parts per 100 parts of T-PL
Parts, more preferably 0.3 to 3 parts. 0.05 added
If the amount is less than 10 parts, the effect of improving the moisture resistance and durability is small. If the amount exceeds 10 parts, the excellent properties inherent in PET-PL are impaired, and the heat resistance and durability are reduced.

The polyester ester-based thermoplastic resin composition of the present invention is obtained by mixing the PET-PL with the metal salt of the organic carboxylic acid, an epoxy compound containing a tri- or more functional epoxy compound, and polycarbodiimide. Can be

The mixing method is not particularly limited as long as each component is uniformly mixed. For example, a method in which the above additives are dry-blended into PET-PL chips, and then heated and melted and mixed using an extruder, PET-PL
A method of blending the above additives and melt-mixing them before dispensing at the time of polymerization may be employed.

In the present invention, when PET-PL is mixed with an additive, other well-known additives other than the above-mentioned additives, such as a heat stabilizer, a weather resistance stabilizer, and a water resistance stabilizer, may be used. Agents, catalyst deactivators, lubricants, fillers, pigments, plasticizers, thermoplastic resins, and the like.

The thus obtained polyester ester-based thermoplastic resin composition of the present invention is obtained by improving the heat resistance and moisture resistance of PET-PL, and is suitable for use as a molding material, film, fiber and the like. Can.

Next, the polyester ester-based thermoplastic resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

The physical properties of the polyester ester-based thermoplastic resin compositions in Production Examples, Examples and Comparative Examples were measured according to the following methods.

(Logarithmic viscosity (dl / g)) The polyester ester block copolymer or the polyester ester-based thermoplastic resin composition was mixed with phenol / 1,1,1,
Dissolve in a 2,2-tetrachloroethane mixed solvent (weight ratio 1: 1) to a concentration of 0.5 g / dl, measure at 25 ° C. using an Ubbelohde viscometer, and calculate the logarithmic viscosity according to the formula: logarithmic viscosity = [ln (Viscosity of solution / viscosity of solvent)] / concentration.

(Crystal Melting Point) The crystalline melting point of the polyester ester block copolymer or the polyester ester-based thermoplastic resin composition was measured by using DSC7 manufactured by Perkin-Elmer (heating rate: 20 ° C./min).

(Tensile Elongation at Break) A polyester ester-based thermoplastic resin composition chip was molded into a No. 3 dumbbell-type test piece (thickness: 3 mm) by an injection molding machine, and subjected to a tensile test in accordance with JIS K 6301 to carry out tensile elongation at break. The degree was measured.

(Heat resistance) The dumbbell type test piece was placed in a gear oven maintained at 170 ° C., and air containing an average of 20 g / m ³ of water was blown at 13 m ³ / hr.
After holding for 25 days by flowing at a rate of, the tensile elongation at break is measured, and the retention rate relative to the initial value is calculated by the formula: Elongation retention rate (%) = (tensile elongation at break after test / tensile elongation at break before test) ) × 100.

(Moisture resistance / durability) After holding the dumbbell type test piece in a thermo-hygrostat kept at 80 ° C. × 95% RH for 12 days, the tensile elongation at break was measured, and the holding ratio to the initial value was calculated by the following formula. Elongation retention (%) = (tensile rupture elongation after test / tensile rupture elongation before test) × 100.

(Moldability) The mold releasability when 30 shots of the dumbbell-shaped test piece were injection-molded was evaluated according to the following criteria, and the moldability was determined. ：: Of the injection-molded test pieces, 95% or more of the test pieces were automatically released from the mold. C: 70% or more of the injection-molded test pieces were automatically released from the mold. ×: Of the injection-molded test pieces, only less than 70% of the test pieces were automatically released from the mold.

[0043]

[Production Example 1] Polyethylene terephthalate composed of 100% ethylene terephthalate unit (logarithmic viscosity 1.1 dl / g) 68
To this part, 32 parts of ε-caprolactone was added and dissolved at 240 ° C., followed by polymerization for 1 hour to obtain a polyester ester copolymer which was a polyethylene terephthalate- (poly) caprolactone copolymer. The logarithmic viscosity of the copolymer is
The crystal melting point was 1.05 dl / g and the crystal melting point was 230 ° C.

Hereinafter, this copolymer is referred to as a copolymer.

[0045]

Example 1 100 parts of the copolymer obtained in Production Example 1 was mixed with 0.2 part of sodium montanate and a bifunctional / trifunctional mixed epoxy compound (trimethylolpropane diglycidyl ether and trimethylolpropane triglycidyl ether). Of a mixture of about 50:50 (weight ratio), 1.4 parts of an epoxy equivalent of about 145), 05 parts of polycarbodiimide (manufactured by Bayer, Starvacol P), 10 parts of Irganox 1010
After dry blending 0.1 part of triphenyl phosphate (trade name, manufactured by Ciba Geiger), 25 mm
Melt and mix at 255 ° C using a co-rotating twin screw extruder,
A polyester ester-based thermoplastic resin composition was obtained. The obtained composition was evaluated for formability, tensile elongation at break, heat resistance, and moisture resistance. Table 1 shows the results
Shown in

[0046]

Example 2 An epoxy compound was a trifunctional epoxy compound (glycerol triglycidyl ether, epoxy equivalent
155 (Denacol EX-421, manufactured by Nagase Kasei KK) A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount was changed to 0.7 part. Table 1 shows the results.

[0047]

Example 3 An epoxy compound was a tetrafunctional epoxy compound (pentaerythritol tetraglycidyl ether, epoxy equivalent 231 (Denacol EX-41, manufactured by Nagase Kasei KK)
1) A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount was changed to 2.2 parts. Table 1 shows the results.

[0048]

Example 4 An epoxy compound was a tetrafunctional epoxy compound (Denacol EX-411, manufactured by Nagase Kasei Co., Ltd.), 1.1 parts, a bifunctional epoxy compound (1,6-hexanediol glycidyl ether, epoxy equivalent: 150 (Nagase Chemical Co., Ltd.) ), Denacol EX-212)) A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount was changed to 0.7 part. Table 1 shows the results
Shown in

[0049]

Comparative Example 1 A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount of sodium montanate was changed to 7 parts. Table 1 shows the results.

[0050]

Comparative Example 2 A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount of sodium montanate was changed to 0.01 part. Table 1 shows the results.

[0051]

Comparative Example 3 An epoxy compound was converted to a monofunctional epoxy compound (epoxy equivalent: 351 (Denacol EX manufactured by Nagase Kasei Co., Ltd.)
-192)) In the same manner as in Example 1, except that the amount was changed to 0.6 parts, 1.2 parts, a bifunctional epoxy compound (diethylene glycol diglycidyl ether, epoxy equivalent: 154 (Denacol EX-851, manufactured by Nagase Kasei Co., Ltd.)) A plastic resin composition was obtained and evaluated. Table 1 shows the results.

[0052]

Comparative Example 4 A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the epoxy compound was changed to 15 parts of a bifunctional / trifunctional mixed type epoxy compound (used in Example 1). did. Table 1 shows the results.

[0053]

Comparative Example 5 A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the epoxy compound was changed to 0.01 part of a bifunctional / trifunctional mixed type epoxy compound (used in Example 1). did. Table 1 shows the results.

[0054]

Comparative Example 6 A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the epoxy compound was changed to 1.1 parts of a tetrafunctional epoxy compound (Denacol EX-411) and 15 parts of a bifunctional epoxy compound (Denacol EX-212). And evaluated. Table 1 shows the results.

[0055]

Comparative Example 7 A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the addition amount of polycarbodiimide was changed to 15 parts. Table 1 shows the results.

[0056]

Comparative Example 8 A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount of polycarbodiimide was not changed. Table 1 shows the results.

[0057]

[Table 1]

[0058]

Example 5 The sample obtained in Example 1 was found to have an average moisture content in the air of 20 g / m ³ to 6 g / m in the heat resistance test.
the exception that the m ³ was evaluated heat resistance in the same manner as in Example 1. Table 2 shows the results.

[0059]

[Comparative Example 9] With respect to the sample obtained in Comparative Example 3, the moisture in the air in the heat resistance test was 20 g / m ³ on average to 6 g / m ² on average.
the exception that the m ³ was evaluated heat resistance in the same manner as in Comparative Example 3. Table 2 shows the results.

[0060]

[Table 2]

From the results shown in Tables 1 and 2, the polyester ester thermoplastic resin compositions of the present invention obtained in Examples 1 to 4 can be compared with any of the compositions obtained in Comparative Examples 1 to 8. It can be seen that the heat resistance and the humidity resistance are significantly improved in a well-balanced manner.

[0062]

Industrial Applicability The polyester ester thermoplastic resin composition of the present invention has better heat resistance and moisture resistance than conventional polyester ester thermoplastic compositions, and can be used for molding materials, films and fibers. It can be suitably used as such.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 63:00 79:04) (72) Inventor Masahiro Asada 8-1-1 Yokoo, Suma-ku, Kobe-shi, Hyogo 45-102 (56 References JP-A-2-276853 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 67/00

Claims (4)

(57) [Claims] 1. A metal salt of (a) an organic carboxylic acid is added to 100 parts by weight of a polyester ester block copolymer obtained by reacting polyethylene terephthalate with a lactone.
0.05 to 5 parts by weight, (b) 0.05 to 10 parts by weight of an epoxy compound containing at least one epoxy compound having three or more functional groups, and
(c) A polyester ester-based thermoplastic resin composition comprising 0.05 to 10 parts by weight of polycarbodiimide. 2. The polyester ester-based thermoplastic resin composition according to claim 1, wherein the epoxy compound comprises one or two or more epoxy compounds having three or more functional groups. 3. An epoxy compound comprising one or more of trifunctional and / or tetrafunctional epoxy compounds,
The polyester ester thermoplastic resin composition according to claim 1, comprising one or more of bifunctional or less functional epoxy compounds, and the ratio of both is 95/5 to 45/55 by weight. 4. The method according to claim 1, wherein the organic carboxylic acid in the metal salt of the organic carboxylic acid is an aliphatic carboxylic acid, and the metal forming the metal salt is a metal belonging to Group IA or IIA of the periodic table. Polyester ester thermoplastic resin composition.