JPH04209649A - Thermoplastic polyesterester resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in the persistence of resistance to heat and humidity and having a high Vicat softening point by compounding a specific polyesterester block copolymer, a metal org. carboxylate, an epoxy compd., and a polycarbodiimide. CONSTITUTION:100 pts.wt. polyesterester block copolymer obtd. by reacting polyethylene terephthalate with a lactone, 0.05-5 pts.wt. metal org. carboxylate, 0.05-10 pts.wt. epoxy compd. contg. at least one trifunctional or higher epoxy compd., and 0.05-10 pts.wt. polycarbodiimide are compounded to give the title compsn. An amt. compounded of the epoxy compd. lower than 0.05 pt.wt. gives insufficient improvement in the persistence of resistance to heat and humidity while an amt. higher than 10 pts.wt. degrades the thermal stability of the compsn. dwelling in a molding machine during molding and elongation at break.

Description

[Detailed description of the invention]

[00011

[Industrial Field of Application] The present invention relates to a polyester ester thermoplastic resin composition. More specifically, the present invention relates to a polyester-based thermoplastic resin composition that provides molded products with excellent heat resistance and moisture resistance. [0002] [Prior Art] A polyester block copolymer composed of a crystalline aromatic polyester and a lactone is
It has excellent rubber properties, heat resistance, and weather resistance. [0003]L However, the retention of tensile elongation at break when exposed to high temperatures for a long time (heat resistance durability) and the retention of tensile elongation at break when exposed to high humidity for a long time (humidity resistance durability) are sufficient. However, when exposed to high temperature or high humidity for a long time, the tensile elongation at break, etc., decreases significantly. [0004] As a method to solve these problems of polyester ester thermoplastic resins, a method of adding an epoxy compound having more than one functional function (Japanese Patent Application Laid-Open No. 16265-1989) has been proposed.
4), a method of adding a monofunctional or more functional epoxy compound and a metal salt of an aliphatic carboxylic acid (JP-A-59-152)
947), and a method of adding a monofunctional, bifunctional, or bifunctional or more functional epoxy compound and a trivalent phosphorus compound (Japanese Patent Application Laid-open No. 1163259). [0005] Among polyester ester thermoplastic resins, polyester ester block copolymers (hereinafter referred to as PUT-PL) obtained by reacting polyethylene terephthalate (hereinafter referred to as PET) and lactones use PET. , is preferable because it has a higher crystal melting point and a higher Vicat softening temperature than a polyester ester block copolymer (hereinafter referred to as PBT-PL) obtained by reacting polybutylene terephthalate and lactones. . [0006] By the way, when the above method for improving heat resistance durability and moisture resistance durability is applied to the PET-PL, the heat resistance durability under the conditions of heating at 140°C for 12 days disclosed in the examples of the three publications mentioned above can be improved. Although there is an effect on
For even higher temperature and long-term heat resistance, such as 170°C x 25 days, if the above method is applied to PET-PL using a bifunctional or lower epoxy compound, it is possible to If a heat resistance durability test is conducted in an environment with low humidity, the tensile elongation at break is sufficiently maintained, but in an environment with high atmospheric humidity, such as in the Japanese summer, the tensile elongation at break is not maintained. I found out. [0007] Furthermore, regarding moisture resistance and durability, PET-P
Simply adding an epoxy compound to L has not yielded satisfactory results. [o o O8] In addition, when the above-mentioned conventional technology is applied to PBT-PL, the effect of improving heat resistance and durability can be seen, but due to the above-mentioned drawback of a low Vicat softening point, PET-PL
- Not a substitute for PL. [0009]

[Problems to be Solved by the Invention] An object of the present invention is to provide a polyester ester thermoplastic resin composition that has excellent heat resistance and durability even in a humid environment and has a high Vicat softening point. be. [00101

[Means for Solving the Problems] In view of the above-mentioned conventional technology, the present inventors have discovered that polyethylene terephthalate (PET)
) and lactones to improve the heat resistance and moisture resistance of polyester block copolymer (PET-PL).
We have discovered that the heat resistance and humidity resistance of PET-PL can be improved by adding an epoxy compound containing at least one trifunctional or higher functional epoxy compound, a metal salt of an organic carboxylic acid, and a polycarbodiimide, and have arrived at the present invention. . [00111 That is, in the present invention, 100 parts (monomeric parts, the same shall apply hereinafter) of a polyester ester block copolymer obtained by reacting polyethylene terephthalate and lactones, (a) 0.00 parts of a metal salt of an organic carboxylic acid are added. 05-5
(b) at least one trifunctional or higher functional epoxy compound;
The present invention relates to a polyester-based thermoplastic resin composition containing 0.05 to 10 parts of a seed-containing epoxy compound and 0.05 to 10 parts of (C) polycarbodiimide. [0012] [Function and Examples] A polyester block copolymer (P
ET-PL) consists of polyethylene terephthalate segments and (poly)lactone segments. [0013] There is no particular limitation on the method for producing PET-PL, and any method can be adopted. For example, it can be obtained by reacting PET and lactones batchwise or continuously. [0014] Polyethylene terephthalate (PET) used in PET-PL consists of 70 of the total constituent units.
More than mol% of the esters are composed of ethylene terephthalate units, and other components include glycols such as butanediol, hexamethylene diol, and cyclohexane dimetatool, and dicarboxylic acids such as isophthalic acid, adipic acid, and sebacic acid. It may be polymerized. [0015] Lactones include, for example, ε-caprolactone, methyl-ε-caprolactone, and dimethyl ε-caprolactone.
- caprolactone, trimethyl-ε-caprolactone,
Examples include β-propiolactone, pivalolactone, γ-valerolactone, enantolactone, cabrylolactone, 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. [0016] PE in producing PET-PL
The composition ratio (weight ratio, same below) of T and lactones is 90
/10 to 10/90, preferably 80/20 to 3
It is 0/70. If the ratio of PET exceeds 90/10 in such a composition ratio, the tensile elongation at break of the resulting PET-PL will decrease and the flexibility will decrease. If it is less than 10/90, the crystallization rate will be slow and the moldability will be poor. [0017] The metal salt of an organic carboxylic acid used in the present invention functions as a crystal nucleating agent, promotes crystallization of PET-PL, and improves moldability, etc., and includes, for example, stearic acid, sebacic acid, Examples include metal salts of palmitic acid, montanic acid, dimer acid, trimer acid, benzoic acid, and the like. Among these, preferred is the case where the organic carboxylic acid is an aliphatic carboxylic acid, and the metal is a metal of Group IA or Group IIA of the periodic table, such as sodium, potassium, calcium, etc. 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. [0018] The amount of the metal salt of organic carboxylic acid added is 0.05 to 5 parts, preferably 0.1 to 3 parts, based on 100 parts of PET-PL. If the amount added is less than 0.05 part, crystallization will not be sufficiently promoted and moldability will deteriorate. Moreover, if the amount exceeds 5 parts, the tensile elongation at break of the resulting molded product will decrease significantly, and the moisture resistance and durability will deteriorate. [00191 The epoxy compound used in the present invention is P
It is added to improve the heat resistance durability and humidity resistance durability of the ET-PL containing composition. [00201 The trifunctional or higher functional epoxy compound in the present invention is not particularly limited in its structure, but it preferably has three or more epoxy groups in the molecule and has an epoxy equivalent in the range of 70 to 1000. Among these, trifunctional or tetrafunctional epoxy compounds are preferred. [00211 Specific examples of the epoxy compound having 3 or more functionalities include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and the like. [0022] The trifunctional or higher functional epoxy compound may be used alone or in combination of two or more. [00231 In the present invention, if it is necessary to further increase the initial tensile elongation at break than in the case where the epoxy compound is composed only of a trifunctional or higher functional epoxy compound, it is preferable to use a difunctional or lower functional epoxy compound in combination. Even more favorable results can be obtained when an epoxy compound having less than two functional groups is used in combination in improving the moisture resistance and durability. [0024] Specific examples of the epoxy compound having two or more functional groups include phenyl glycidyl ether, polyethylene glycol monophenyl monoglycidyl ether, ethylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and the like. [0025] The combined ratio of the trifunctional or higher functional epoxy compound and the bifunctional or lower functional epoxy compound cannot be further determined because it varies depending on the epoxy equivalent of the epoxy compound, but it is preferable to use it in the range of 9515 to 45155 in terms of weight ratio. Common. If the ratio of the trifunctional or higher functional epoxy compound exceeds 9515, the initial tensile elongation at break tends to be insufficient, and if it is less than 45155, the heat resistance durability tends to become insufficient. [00261 PE of epoxy compound used in the present invention
The amount to be added to T-PL cannot be precisely determined because it varies depending on the epoxy equivalent of the epoxy compound to be added, but it is usually 0.0 parts per 100 parts of PET-PL.
5 to 10 parts, preferably (11 to 5 parts, more preferably 0.2 to 3 parts). If the amount added is less than 0.05 parts, the effect of improving heat resistance durability and moisture resistance durability is small. In addition, if it exceeds 10 parts, the retention stability during molding deteriorates, and furthermore, the tensile elongation at break decreases. Polycarbodiimide is added to improve this. Such polycarbodiimide is a compound having at least two carbodiimide groups per molecule, and there are no particular limitations on its structure. Specific examples of such polycarbodiimide include: For example, expression: % expression %]

[1] Stavaxol P (carbodiimide group content, 13.5% or more), manufactured by Bayer, represented by [0029] and the like can be mentioned. [00301 The amount of polycarbodiimide added is P
The amount is 0.05 to 10 parts, preferably 0.1 to 5 parts, and more preferably 0.3 to 3 parts per 100 parts of ET-PL. If the amount added is less than 0.05 parts, the effect of improving moisture resistance and durability is small, and if it exceeds 10 parts, PET-PL
In addition to impairing the excellent properties originally possessed by the metal, the heat resistance and durability are also reduced. [0031] The polyester ester thermoplastic resin composition of the present invention can be produced by mixing the PET-PL with the metal salt of the organic carboxylic acid, an epoxy compound containing a trifunctional or higher functional epoxy compound, and polycarbodiimide. It will be done. [0032] Such a mixing method is not particularly limited and may be employed as long as it allows each component to be mixed uniformly. For example, a method in which the additives are triblended into PET-PL chips and then heated and melted using an extruder to mix;
A method may be adopted in which the additives are blended and melt-mixed before the PET-PL balls are combined and discharged. ro 033] In the present invention, PET-PL
In addition to the above-mentioned additives, commonly known additives such as heat stabilizers, weathering stabilizers, water-resistant stabilizers, catalyst deactivators, lubricants, fillers, and pigments may be used when mixing with additives. , a plasticizer, a thermoplastic resin, etc. may be blended. [0034] The polyester ester thermoplastic resin composition of the present invention thus obtained has improved heat resistance durability and moisture resistance durability of PUT-PL, and is suitable for use as, for example, molding materials, films, fibers, etc. Shitsuru. [0035] Next, the polyester thermoplastic resin composition of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples. [0036] The physical properties of the polyester thermoplastic resin compositions in the Production Examples, Examples, and Comparative Examples were measured according to the method shown below. [0037] (Logistic viscosity (dl 7g)) The polyester ester block copolymer or polyester ester thermoplastic resin composition was dissolved in a mixed solvent of phenol/1,1°2.2-tetrachloroethane (weight ratio 1:1)
The solution was dissolved at a concentration of 0.5 g/d1 and measured at 25°C using an Ubbelohde viscometer, and the logarithmic viscosity was calculated using the formula logarithmic viscosity = [ln (viscosity of solution/viscosity of solvent) 1 part concentration. did. (0038] (Crystal melting point) The crystal melting point of the polyester ester block copolymer or polyester ester thermoplastic resin composition was measured using DSC7 (temperature increase rate 20° C./min) manufactured by PerkinElmer. (0039) ( Tensile elongation at break) A polyester ester thermoplastic resin composition chip was molded into a No. 3 dumbbell-shaped specimen (thickness 3 mm) using an injection molding machine, and a tensile test was conducted according to JIS K 6301 to determine the bow 1 tensile elongation at break. (00401 (Heat resistance and durability)) The dumbbell-shaped test piece was placed in a gear oven kept at 170°C, and air containing an average of 20 g/'m'' moisture was flowed at a rate of 13 m3/hr. After holding for 25 days,
The tensile elongation at break was measured, and the retention rate with respect to the initial value was calculated using the formula: elongation retention rate (%)=(tensile elongation at break after test/tensile elongation at break before test)×100. (00411 (Moisture Resistance Durability) The dumbbell-shaped test piece was kept in a constant temperature chamber kept at 80°C x 95% for 12 days, then the tensile elongation at break was measured, and the retention rate with respect to the initial value was calculated using the formula elongation. Retention rate (%) =: (
Tensile elongation at break after test/Tensile elongation at break before test)
Calculated using 00. [0042] (Moldability) The mold releasability when 30 shots of the previous dumbbell-shaped test piece were injection molded was evaluated according to the criteria shown below, and was defined as moldability. ○: Of the injection-molded test pieces, 95% or more of the test pieces were automatically released from the mold. Δ: Of the injection-molded test pieces, 70% or more of the test pieces were automatically released from the mold. ×: Of the injection-molded test pieces, less than 70% of the test pieces were automatically released from the mold. [0043]

[Production Example 1] Polyethylene terephthalate consisting of 100% ethylene terephthalate units (logarithmic viscosity 1.1 d
32 parts of ε-caprolactone were added to 68 parts of ε-caprolactone and dissolved at 240°C, followed by polymerization for 1 hour to obtain a polyester ester copolymer which is a polyethylene terephthalate-(poly)caprolactone copolymer. The copolymer has a logarithmic viscosity of 1.05 dl/g and a crystalline melting point of 2.
The temperature was 30°C. [0044] Hereinafter, this copolymer will be referred to as copolymer (2). [0045]

[Example 1] To 0,100 parts of the copolymer obtained in Production Example 1, 0.2 parts of sodium montanate, bifunctional and trifunctional mixed epoxy compounds (trimethylolpropane diglycidyl ether and trimethylolpropane triglycidyl ether) were added. Approximately 50:50 (weight ratio) mixture with glycidyl ether, 1.4 parts of epoxy equivalent (145), 0.5 part of polycarbodiimide (Stavaxol P, manufactured by Bayer), Irganox 1010 (antioxidant, manufactured by Ciba Geigy) ,Product name)
After tri-blending 0.1 part of triphenyl phosphate, 25+nn+ co-directional twin screw extruder was used.
Melt mixing was performed at 55° C. to obtain a polyester ester thermoplastic resin composition. The obtained composition was evaluated for moldability, tensile elongation at break, heat resistance durability, and humidity resistance durability. The results are shown in Table 1. [00461

[Example 2] The epoxy compound was converted into a trifunctional epoxy compound (glycerol triglycidyl ether, epoxy equivalent: 155 (manufactured by Chomen Kasei Co., Ltd., Bunacol EX-421)) 0.7
A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1, except that the composition was changed to The results are shown in Table 1. [0047] [Example 3] The epoxy compound was converted into a tetrafunctional poxy compound (pentaerythritol tetraglycidyl ether, epoxy equivalent: 23
1 (manufactured by Chomen Kasei Co., Ltd., Bunacol EX-411)
A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1, except that the amount was changed to 2.2 parts. The results are shown in Table 1. [00481

[Example 4] The epoxy compound was mixed with 1.1 parts of a tetrafunctional poxy compound (Bunacol EX-411, manufactured by Chomen Kasei Co., Ltd.), and 1 part of a bifunctional poxy compound (1,6-hexanediol glycidyl ether, epoxy equivalent). A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1, except that the amount was changed to 0.7 parts. The results are shown in Table 1. [00491 Comparative Example 1] A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1 except that the amount of sodium montanate added was changed to 7 parts. The results are shown in Table 1. [00501 Comparative Example 2] A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1, except that the amount of sodium montanate added was changed to 0.01 part. The results are shown in Table 1. [00511 [Comparative Example 3] The epoxy compound was converted into a monofunctional engineered poxy compound (epoxy equivalent: 351 (manufactured by Chomen Kasei Co., Ltd., Bunacol EX-192).
”) 1.2 parts, bifunctional engineered poxy compound (diethylene glycol dignosidyl ether, epoxy equivalent weight 154
(Bunacol EX-851, manufactured by Chomen Kasei Co., Ltd.)
A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1, except that the amount was changed to 0.6 parts. The results are shown in Table 1. [0052] [Comparative Example 4] A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the epoxy compound was changed to 15 parts of a bifunctional and trifunctional mixed epoxy compound (the one used in Example 1). Well, I evaluated it. The results are shown in Table 1. [0053]

[Comparative Example 5] A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the epoxy compound was changed to 0.01 part of a bifunctional and trifunctional mixed epoxy compound (the one used in Example 1). ,evaluated. The results are shown in Table 1. [0054]

[Comparative Example 6] The epoxy compound was converted into a tetrafunctional poxy compound (Bunacol E
Example 1 except that the amount was changed to 11 parts (X411) and 15 parts of a bifunctional engineered poxy compound (Bunacol EX-212)
A thermoplastic resin composition was prepared and evaluated in the same manner as described above. The results are shown in Table 1. [0055]

Comparative Example 7 A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1, except that the amount of polycarbodiimide added was changed to 15 parts. The results are shown in Table 1. [0056]

Comparative Example 8 A thermoplastic resin composition was prepared and evaluated in the same manner as in Example 1, except that the amount of polycarbodiimide was not added. The results are shown in Table 1. [0057]

[Table 1] [0058]

[Example 5] Regarding the sample obtained in Example 1, the moisture content in the air in the heat resistance durability test was increased from an average of 20 g/m3 to an average of 6 g/m3.
The heat resistance and durability were evaluated in the same manner as in Example 1 except that the following was changed. The results are shown in Table 2. [0059] * *

[Comparative Example 9] Regarding the sample obtained in Comparative Example 3, the moisture content in the air in the heat resistance durability test was increased from an average of 20 g/m3 to an average of 6 g/m3.
The heat resistance and durability were evaluated in the same manner as in Comparative Example 3, except that the temperature was changed to . The results are shown in Table 2. [00601

[Table 2] [00611 From the results in Tables 1 and 2, the polyester ester thermoplastic resin compositions of the present invention obtained in Examples 1 to 4 were superior to any of the compositions obtained in Comparative Examples 1 to 8. When compared, it can be seen that the heat resistance durability and moisture resistance durability are significantly improved in a well-balanced manner. [0062] [Effects of the Invention] The polyester ester thermoplastic resin composition of the present invention has better heat resistance and moisture resistance than conventional polyester ester thermoplastic compositions, and is suitable for molding materials, It can be suitably used as a film, fiber, etc. inventor

Claims (4)

[Claims] Claim 1: To 100 parts by weight of a polyester block copolymer obtained by reacting polyethylene terephthalate and lactones, (a) 0.05 to 5 parts by weight of a metal salt of an organic carboxylic acid; (b) 3 parts by weight; A polyester ester thermoplastic resin composition containing 0.05 to 10 parts by weight of an epoxy compound containing at least one functional or higher epoxy compound and (c) 0.05 to 10 parts by weight of polycarbodiimide. 2. The polyester ester thermoplastic resin composition according to claim 1, wherein the epoxy compound comprises one or more trifunctional or more functional epoxy compounds. 3. The epoxy compound comprises one or more trifunctional and/or tetrafunctional epoxy compounds, and two or more trifunctional and/or tetrafunctional epoxy compounds.
2. The polyester ester thermoplastic resin composition according to claim 1, which comprises one or more types of subfunctional epoxy compounds, and the weight ratio of the two is from 95/5 to 45/55. 4. The organic carboxylic acid in the metal salt of an organic carboxylic acid is an aliphatic carboxylic acid, and the metal forming the metal salt is a metal of Group IA or Group IIA of the Periodic Table of the Elements. polyester ester thermoplastic resin composition.