JP3110496B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention has good moldability,
The present invention relates to a resin composition which has excellent heat resistance and heat aging properties, has excellent mechanical properties even after a heat history, does not yellow, and does not cause uneven gloss.

[0002]

2. Description of the Related Art A resin composition comprising an aromatic polyester and a polyamide has excellent moldability, chemical properties, mechanical properties, electrical properties, heat deformation resistance and heat aging resistance. It has a very wide range of uses for electrical components, mechanical components and others. Needless to say, as its applications have expanded and better properties have been demanded in general for the above properties, in particular, moldability,
Particularly, heat aging resistance is required.
However, they are not always supplied with satisfactory ones.

That is, as the shape of a molded article becomes more complicated and thinner, it is necessary to increase the fluidity of the molding material (decrease the melt viscosity) and increase the resin temperature during molding. It has to be. However, the conventional resin composition has a melting temperature of 26.
If the temperature exceeds 0 ° C., the performance is greatly reduced, and molding at a high temperature is difficult. In addition, various properties such as durability (heat aging resistance) of the molded product when used in a high temperature atmosphere are essential requirements for engineering plastics which are supposed to be used at high temperatures. Attempts to improve the quality have been widespread.

Further, the conventional resin composition changes its color to yellow when it is melt-kneaded, so that it is difficult to color the molded product in white or light color, which has been a major obstacle in use. In order to solve these problems, various heat stabilizers have been proposed in the past. For example, Tokiko Sho 60
No. 37141 discloses the use of cuprous chloride or cuprous chloride and 2-mercaptobenzimidazole. However, although these heat stabilizers exhibit a certain heat stabilizing effect, they also have a problem in that the gloss of the molded article is deteriorated as a side effect, causing uneven gloss.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, it is an object of the present invention to provide excellent moldability, excellent heat resistance and heat aging resistance, and hence excellent mechanical properties even after a heat history. And without yellowing
An object of the present invention is to provide a resin composition free from uneven gloss.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on the above problems and found that the above problems can be achieved by adding a specific phosphite compound to a resin composition comprising an aromatic polyester and a polyamide. And found the present invention.

That is, the gist of the present invention is as follows:
It comprises the components (B) and (C), and the component (A)
70 parts by weight, 90 to 30 parts by weight of component (B), and 0.001 to 1.0 part by weight of component (C) based on 100 parts by weight of the total of components (A) and (B). A composition.

(A) Terephthalic acid and / or isophthalic acid or a functional derivative thereof (provided that the molar ratio of terephthalic acid residues to isophthalic acid residues is from 7: 3 to 0: 1)
Aromatic polyester copolymer obtained from 0) and a bisphenol represented by the general formula [1]. (B) Polyamide. (C) A phosphite compound represented by the general formula [2].

Hereinafter, the present invention will be described in detail. Generally, a resin composition comprising an aromatic polyester and a polyamide has significantly lower thermal stability as compared with a single resin. For example, terephthalic acid / isophthalic acid = 50/5
0 (molar ratio) and 2,2-bis (4-hydroxyphenyl)
Aromatic polyesters consisting of propane (bisphenol A) are practically stable up to 400 ° C, and polycaprolactam (nylon 6) is practically stable up to 300 ° C. However, the resin composition consisting of 50 parts by weight of each of them starts thermal decomposition when the temperature exceeds 260 ° C. It is unclear why this phenomenon occurs, but it is thought that the two resins promote thermal decomposition with each other.

On the other hand, as a result of various studies, when the phosphite compound represented by the general formula [2] is added to a resin composition comprising an aromatic polyester and a polyamide, the heat resistance temperature is greatly improved, and It turned out that the effect was exhibited. Such an effect on the thermal stability of the phosphite compound was quite unexpected.

In the case of a conventional resin composition containing no phosphite compound, the resin temperature during injection molding and extrusion molding is 2
When the temperature exceeds 60 ° C., discoloration and deterioration of physical properties occur. On the other hand, the resin composition of the present invention containing a phosphite compound can not only be melt-molded up to a resin temperature of 300 ° C. without practical problems, but also has mechanical properties and Particularly, the toughness such as impact strength and elongation at break is significantly improved. Also, on the surface of the molded article of the resin composition containing no phosphite compound, uneven gloss of glossy portion and cloudy portion occurs on the surface, and this is emphasized as uneven coloring in the case of colored products as well as non-colored products. Although it was difficult to obtain a good appearance, the surface of the molded article of the resin composition to which the phosphite compound was added was uniformly shiny, and the appearance was good even for colored products as well as non-colored products. was gotten. Also, with respect to the heat aging resistance, the retention of toughness was better than that of the resin composition containing no phosphite compound.

The aromatic polyester used in the present invention is terephthalic acid and / or isophthalic acid or a functional derivative thereof (provided that the molar ratio between terephthalic acid residues and isophthalic acid residues is from 7: 3 to 0:10). And the bisphenols represented by the general formula [1]. When the terephthalic acid residue exceeds 70 mol%, the melting temperature of the aromatic polyester becomes too high, and the resin composition of the present invention is It becomes difficult to prepare.

The derivatives of terephthalic acid and isophthalic acid include, for example, halides of these acids such as dichloride and diesters of alkyl and aryl. Further, the phenylene group of terephthalic acid, isophthalic acid and derivatives thereof used in the present invention may be substituted with a halogen atom or an alkyl group.

Specific examples of bisphenols represented by the general formula [1] include 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-2-methylphenyl)-
Ether, bis (4-hydroxy-3-chlorophenyl) -ether, bis (4-hydroxyphenyl) -sulfide, bis (4-hydroxyphenyl) -sulfone, bis (4-hydroxyphenyl) -ketone, bis ( 4-hydroxyphenyl) -methane, bis (4-hydroxy-3-methylphenyl) -methane, bis (4-hydroxy-3,5-dichlorophenyl) -methane, bis (4-hydroxy-3,5-dibromo Phenyl) -methane, bis (4-hydroxy-3,5-difluorophenyl) -methane, 1,1-bis (4-hydroxyphenyl)
-Ethane, 2,2-bis (4-hydroxy-3-methylphenyl) -propane, 2,2-bis (4-hydroxy-3,
3-dimethylphenyl) -propane, 2,2-bis (4-
(Hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) -propane, 1,1-bis (4-hydroxyphenyl) -n-butane, bis (4-hydroxyphenyl)
-Phenylmethane, bis (4-hydroxyphenyl)-
Diphenylmethane, bis (4-hydroxyphenyl)-
4-methylphenylmethane, 1,1-bis (4-hydroxyphenyl) -2,2,2-trichloroethane, bis (4-
(Hydroxyphenyl) -4-chlorophenyl-methane,
1,1-bis (4-hydroxyphenyl) -cyclohexane, bis (4-hydroxyphenyl) -cyclohexylmethane, 2,2-bis (4-hydroxynaphthyl) -propane, 1,1-di (4-hydroxy Phenyl) -1-phenylethane and the like, and the most typical one is
2,2-bis (4-hydroxyphenyl) -propane (bisphenol A). If necessary, a mixture of the bisphenols or a mixture of the bisphenols and a small amount of another divalent compound, for example, dihydroxynaphthalene such as 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, hydroquinone, Resorcinol, 2,
Mixtures of 6-dihydroxytoluene, 2,6-dihydroxychlorobenzene, 3,6-dihydroxytoluene and the like can be used.

The aromatic polyester used in the present invention is synthesized by any method such as an interfacial polymerization method, a melt polymerization method, and a solution polymerization method. The logarithmic viscosity of the aromatic polyester [25 ° C, phenol / tetrachloroethane = 6 /
4 (weight ratio) measured in a mixed solvent] is preferably 0.4 to 0.8. If the logarithmic viscosity is less than 0.4, the mechanical strength of the resin composition of the present invention, particularly the toughness and the heat distortion temperature, tend to decrease. If the logarithmic viscosity exceeds 0.8, the resin temperature must be extremely high during melt-kneading. And tend to yellow during melt-kneading.

The polyamide used in the present invention is represented by the general formula [3] or [4].

[0017]

Embedded image

[0018]

Embedded image (In the formula, R ₁₁ , R ₁₂ and R ₁₃ represent an alkylene group.
N represents a natural number. )

The polyamide used in the present invention is:
Any of the above general formulas may be used.
For example, polycaprolactam, polyhexamethylene adipamide, polytetramethylene adipamide, polyhexamethylene sepacamide, polyaminoundecanoic acid, polylaurolactam, and the like are preferable. Among them, polycaprolactam and polyhexamethylene are particularly preferable. Adipamide and polytetramethylene adipamide. Such a polyamide is formed by a self-condensation reaction of an amino acid, a polymerization reaction of a lactam or a condensation reaction of a diamine and a dibasic acid, and has a relative viscosity of 2.0 to 8.0 measured by JIS K 6810, particularly
Those which are 2.2 to 7.0 are preferred. If the relative viscosity is less than 2.0, the mechanical strength of the resin composition tends to be low, and 8.
If it exceeds 0, the moldability tends to be significantly deteriorated.

The phosphite compound used in the present invention is a phosphite compound represented by the general formula [2].

The mixing ratio of the aromatic polyester (A) and the polyamide (B), which are the components of the resin composition of the present invention, is as follows:
The component (A) is 10 to 70 parts by weight and the component (B) is 90 to 3 parts by weight.
0 parts by weight, preferably 30 to 60 parts by weight of the component (A) and 70 to 40 parts by weight of the component (B). (A) Component is 1
If the amount is less than 0 parts by weight, the heat deformation resistance of the resin composition is remarkably impaired. If the amount of the component (B) is less than 30 parts by weight, the chemical resistance is remarkably impaired. I do.

The amount of the phosphite compound represented by the general formula [2] is determined by the amount of the component (A) and the component (B).
0.001 to 1.0 part by weight, preferably 0 part by weight, preferably
It is 0.01 to 0.5 parts by weight. If the amount is less than 0.001 part by weight, the effect on heat resistance is not exhibited. If the amount is more than 1.0 part by weight, the resin composition is decomposed rather.

In order to improve the heat resistance, weather resistance, oxidation resistance and the like of the resin composition, a thermal decomposition inhibitor, an ultraviolet absorber or an antioxidant may be present in the resin composition. These additives include hindered phenol compounds, amine compounds, phosphorus compounds, benzotriazole compounds and the like. These additives may be present in each resin before mixing, or may be added when each component is mixed. In addition, plasticizers, dyes and pigments, lubricants and nucleating agents, inorganic fillers and the like can be used in common with the resin composition of the present invention. In addition, glass fiber, inorganic silicate, silica, quartz, carbon fiber, asbestos, clay,
A reinforcing material such as talc, mica, wollastonite or a filler may be contained, and if necessary, a flame retardant or a flame retardant auxiliary may be used in combination. Furthermore, the resin composition of the present invention may contain EP rubber, EPDM, ethylene
Low-elastic materials such as vinyl acetate copolymers and ethylene / (meth) acrylate copolymers, as well as maleic anhydride, adducts of anhydrous himic acid and adducts of glycidyl groups can be added.

The resin composition of the present invention is usually used in a melt-kneaded state. Further, each component may be used in a state of being simply mechanically mixed, or each component may be separately melt-kneaded and used. The resin composition of the present invention may be molded by any method, and a melt molding method such as injection molding or extrusion molding is generally suitable. As the form of the resin composition when performing the melt molding, it is preferable that the resin composition is previously melt-kneaded and molded into a chip or the like.

[0025]

The present invention will be described more specifically with reference to the following examples. In addition, each characteristic value was measured as follows.

(1) Logarithmic viscosity of resin composition Using an Ubbelohde viscometer, phenol and 1,1,2,
The measurement was performed at 25 ° C. using a mixed solvent of 2-tetrachloroethane [50/50 (weight ratio)].

(2) Color Tone The pellets of the obtained resin composition were visually judged.

(3) Izod impact strength Measured according to ASTM D256.

(4) Tensile properties Measured according to ASTM D638.

(5) Heat distortion temperature Measured according to ASTM D648.

(6) Unevenness of gloss Visual judgment was made.

Examples 1-5, Comparative Examples 1 and 2 By an interfacial polymerization method, a methylene chloride solution of terephthalic acid dichloride and isophthalic acid dichloride (molar ratio = 1: 1) and an aqueous solution of bisphenol A in an alkaline solution were prepared.
An aromatic polyester copolymer was produced. The logarithmic viscosity of this aromatic polyester copolymer was 0.70 [measured in a mixed solvent of phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.].

This aromatic polyester copolymer was mixed with a polycaprolactam having a relative viscosity of 2.6 (measured at 25 ° C. in 98% sulfuric acid at a concentration of 1%) at a weight ratio of 1: 1. Parts, a phosphite compound represented by the general formula [5] (Mark PEP-36, manufactured by Adeka Argus Chemical Co., Ltd.)

[0034]

Embedded image

Was added at the ratio shown in Table 1 and mixed uniformly.
Vacuum dried at 100 ° C for 8 hours, and then a twin-screw extruder (cylinder temperature: 280 ° C, PC;
M-30) to obtain a pellet. Table 1 shows the logarithmic viscosity and color tone of the obtained pellets.

Next, test pieces were obtained from the obtained pellets at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS-80) to obtain various characteristic values. Table 1 shows the results.

[0037]

[Table 1]

As is apparent from Table 1, Mark PE
By adding P-36, the logarithmic viscosity, color tone,
It is clear that characteristics such as toughness and gloss unevenness of the molded product are greatly improved.

Examples 6 to 9, Comparative Examples 3 and 4 The aromatic polyester and polycaprolactam used in Example 1 were mixed in the proportions shown in Table 2, and 100 parts by weight of the obtained mixture was used in Example 1. Mark PEP-3
6 was added in an amount of 0.2 part by weight, and a test piece was molded in the same manner as in Example 1 to obtain each characteristic value. Table 2 shows the results. In Comparative Examples 3 and 4, the resin component was out of the range specified in the present invention.

[0040]

[Table 2]

Comparative Examples 5 and 6 The aromatic polyester and polycaprolactam used in Example 3 were mixed at a weight ratio of 50:50, and 100 parts by weight of the obtained mixture was mixed with cuprous chloride and 2-mercapto. A test piece was molded in the same manner as in Example 3 except that benzimidazole was added, and each characteristic value was obtained. Table 3 shows the results.

[0042]

[Table 3]

[0043]

The resin composition of the present invention has the above-mentioned composition, has good moldability, and has excellent heat resistance and heat aging resistance. With no yellowing and no gloss unevenness.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/08 C08L 77/00 C08K 5/524

Claims (1)

(57) [Claims] 1. A composition comprising the following components (A), (B) and (C), wherein component (A) is 10 to 70 parts by weight, component (B) is 90 to 30 parts by weight, and component (C) is 0.001 to 1.0 with respect to 100 parts by weight of the total of the component (A) and the component (B).
A resin composition which is part by weight. (A) Terephthalic acid and / or isophthalic acid or a functional derivative thereof (provided that the molar ratio of terephthalic acid residues to isophthalic acid residues is from 7: 3 to 0:10) and represented by the following general formula [1]: An aromatic polyester copolymer obtained from bisphenols. Embedded image (Wherein, -X- is -O -, - S -, - SO 2 -, - CO
—, Selected from the group consisting of an alkylene group and an alkylidene group, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are a group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Selected from. (B) Polyamide. (C) A phosphite compound represented by the following general formula [2]. Embedded image (In the formula, R ₉ and R ₁₀ are selected from the group consisting of a hydrogen atom and a hydrocarbon group.)