JPS581144B2 - Jyushiso Saibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid and isophthalic acid is 9:1 to 1:9) and bisphenols represented by the general formula [ However, -X- is -O-
, -S-, -SO2-, -CO- or an alkylene group, or an alkylidene group (BV) If necessary, the alkylene group or alkylidene group may be substituted with one or more hydrocarbon groups, halogen atoms, or halogenated hydrocarbon groups. R1, R2, R3, R4, R'2, R'3, R'4,
is selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups] and bis fatty acid amides, or ester waxes, metal soaps, or 2 selected from these groups. The invention relates to a resin composition containing one or more species.

Aromatic polyesterne copolymers produced from terephthalic acid, isophthalic acid, or functional derivatives thereof, and divalent phenolic compounds (hereinafter referred to as bisphenols) or functional derivatives thereof have been known for a long time.

A method for producing such a copolymerized polyarylate is a so-called interfacial polymerization (W.M. Eareckson J.Poly.Sc
i. XL, 399, 1959, Special Publication 1977-195
9), solution polymerization in which dichloride of terephthalic acid and isophthalic acid and bisphenols are reacted in an organic solvent (A. Co-nix, Ind. Eng. Chem.
51, 147, 1959 Special Publication No. 37-5599). Melt polymerization by heating terephthalic acid, isophthalic acid, and bisphenols in the presence of acetic anhydride; Melt polymerization by heating terephthalic acid, phenyl ester of isophthalic acid, and bisphenols (Japanese Patent Publication No. 38-15247) Tenorophthalic acid, isophthalic acid, and bisphenols Methods such as melt polymerization (Japanese Patent Publication No. 38-26299) in which bisphenols are heated in the presence of diallyl carbonite are known.

It is also known that aromatic polyester copolymers obtained by such methods have many excellent properties.

In other words, mechanical properties such as tensile strength, bending strength, bending recovery rate and impact strength, thermal properties such as heat distortion temperature and thermal decomposition, and electrical properties such as specific resistance, insulation fracture, arc resistance, dielectric constant and dielectric loss. General molded products, films, and fibers made by injection molding, extrusion molding, press molding, or various other molding methods. and coating materials are expected to have a wide range of uses.

As mentioned above, aromatic polyester copolymers have excellent properties, have great utility value, and have good moldability, allowing them to be molded into ordinary injection molded products or extrusion molded products.

However, for polymers in general and plastics in particular, moldability occupies an important position in the evaluation of the polymer.
It is always desired to have better moldability.

The present inventors conducted extensive research to improve the moldability and processability of aromatic polyester copolymers while maintaining their excellent transparency, colorability, and mechanical properties. Metallic soaps or a mixture of two or more selected from these groups (hereinafter referred to as ``lubricant'').

) has been found to significantly improve the moldability and processability of the aromatic polyester copolymer while maintaining its transparency, colorability, and mechanical properties.

That is, the purpose of the present invention is to lower the melt viscosity and molding temperature of aromatic polyester copolymers, and to improve mechanical properties such as transparency, colorability, tensile temperature, tensile elongation, and impact strength of aromatic polyester copolymers. The purpose of this invention was to provide a resin composition that maintained a high level of properties, and this objective was achieved by adding a lubricant to an aromatic polyester copolymer.

The lubricant can be mixed with the aromatic polyester copolymer by various methods.

(1) A method of directly adding a lubricant to an aromatic polyester copolymer; (2) A method of dissolving or swelling-infiltrating the aromatic polyester copolymer in a low boiling point solvent such as alcohol, ketone, or saturated hydrocarbon, and adding a lubricant to this. A method of impregnating or adhering a lubricant to an aromatic polyester copolymer by stirring and mixing after dissolving and distilling off the solvent, (3) Before or during polymerization in the production process of interfacial polymerization method and solution polymerization method. A method in which a lubricant is added to an organic solvent for polymerization, (4) a method in which a lubricant is added to an aromatic polyester copolymer solution after completion of polymerization in the production process of an interfacial polymerization method and a solution polymerization method, and a concentration solidification method or a solvent strip method is used. They can be mixed by a method of obtaining a lubricant-containing aromatic polyester copolymer powder.

In the present invention, the bis fatty acid amides added to improve the moldability of the aromatic polyester copolymer include methylene bis stearamide, ethylene bis stearamide, methylene bis lauryl amide, ethylene bis lauryl amide, and methylene bis oleyl. amide, ethylene bisoleyl amide, etc.

Examples of ester waxes include Montanixiad ester wax, cetyl ester, myricyl ester, and the like.

Examples of metal soaps include barium stearate, barium laurate, barium ricinoleate, calcium stearate, calcium laurate, calcium ricinoleate, calcium benzoate, and magnesium stearate.

Furthermore, mixtures of these lubricants are also effective in improving the moldability of aromatic polyester copolymers, and combinations of different types of lubricants are particularly effective as they exhibit a synergistic effect.

Regarding the amount of these lubricants added, if they are used in an amount of 10% by weight or more, the heat distortion temperature will be significantly lowered, and mechanical properties such as impact strength will also be reduced. In order to improve fluidity without deteriorating mechanical properties, the content is preferably 1% by weight or less.

The aromatic polyester copolymer used in the present invention is produced by the above-mentioned known method, and the aromatic dicarboxylic acid groups are terephthalic acid groups and isophthalic acid groups, and the ratio thereof is 1:9 to 1:9. The ratio is 9:1.

Furthermore, the properties of the composition of the present invention can be improved by adding other types of pomers, and the properties can be improved by adding additives such as plasticizers, antioxidants, heat resistant agents, or glass fibers. can also be improved.

The present invention will be explained in more detail below with reference to Examples, but the Examples are merely examples and the present invention is not limited thereto.

In addition, in the examples, "%" indicating the amount of lubricant added means "% by weight".

Example 1 An aromatic polyester copolymer was produced by an interfacial polymerization method using a methylene chloride solution of a mixed acid dichloride having a molar ratio of terephthalic acid dichloride/isophthalic acid dichloride of 5/5 and an alkaline aqueous solution of bisphenol A.

The logarithmic viscosity of this in phenol/tetrachloroethane (6/4, weight ratio) at 25°C was 0.65.

To this aromatic polyester copolymer powder, 0.3 wt% each of ethylene bis stearamide, ethylene bis lauryl amide, or ethylene bis oleyl amide was added to the aromatic polyester, and the mixture was mixed for 5 minutes in a nitrogen stream using a super mixer, and then extracted. I turned it into a chip using Ruder.

Using this chip, various test pieces were molded using an injection molding machine and various physical property values were measured.

Table 1 shows the melt viscosity, molding conditions, and physical properties of these lubricant-containing aromatic polyester copolymers.

(1) Melting temperature 300℃, shear stress 9.0×106d
yne/cm2 (2) Melting temperature 320℃ Load 216
0g (3) Izod impact strength For aromatic polyester copolymers with no lubricant added,
Melt viscosity is as high as 4.3 x 104 at 300℃, molding temperature 3
Severe molding conditions are required: 60°C and an injection pressure of 155kg/cm2.

However, when 0.3% each of ethylene bisstearoamide, ethylene bis lauryl amide, or ethylene bis oleyl amide was added to an aromatic polyester copolymer, the melt viscosity decreased significantly as shown in Table 1, making it difficult to mold. performance has been greatly improved.

Moreover, the excellent mechanical properties of the aromatic polyester copolymer are maintained.

All of these molded products are transparent.

Example 2 An aromatic polyester copolymer was produced by an interfacial polymerization method using a methylene chloride solution of mixed acid dichloride with a molar ratio of terephthalic acid dichloride/isophthalic acid dichloride of 7/3 and an alkaline aqueous solution of bisphenol A.

The logarithmic viscosity of this in phenol/tetrachloroethane (614, weight ratio) at 25°C was 0.63.

This aromatic polyester copolymer powder was added with Hoechstwax-E (manufactured by Hoechst Japan) and Hoechstwax-E (manufactured by Hoechst Japan).
0.3% of each OP (manufactured by Hoechst Japan) was added, mixed for 5 minutes in a nitrogen stream using a super mixer, and then chipped using an extruder.

Using this chip, various test pieces were molded using an injection molding machine and various physical property values were measured.

Table 2 shows the melt viscosity, molding conditions, and physical properties of these lubricant-containing aromatic polyester copolymers.

(1) Melting temperature 300℃, shear stress 9.0×10
6dyne/cm2 (2) Melting temperature 320℃, load
2160g (3) Izod impact strength The moldability of aromatic polyester copolymers containing notched Hoechstwax-E and Hoechstwax-OP is significantly improved, and the excellent mechanical properties of aromatic polyester copolymers are also maintained. has been done.

All of these molded products are transparent.

Example 3 Terephthalic acid dichloride/Isophthalic acid dichloride-3
An aromatic polyester copolymer was produced from a methylene chloride solution of mixed acid dichloride No. 17 and an alkaline aqueous solution of bisphenol A by an interfacial polymerization method.

The logarithmic viscosity of this was 0.63. Magnesium stearate, barium laurate, and calcium stearate were added to this aromatic polyester copolymer powder at zero concentrations.
．． 3% was added, mixed for 5 minutes in a nitrogen stream using a super mixer, and then chipped using an extruder.

Using this chip, various test pieces are molded using an injection molding machine.
Various physical property values were measured.

Table 3 shows the performance of these lubricant-containing aromatic polyester copolymers.

(l) Melting temperature 300℃, shear stress 9.0×106d
yne/cm2 (2) Melting temperature 320℃, load 2
160g (3) Izod impact strength Notch As shown in Table 3, the moldability of these lubricant-containing aromatic polyester copolymers is significantly improved, and their excellent mechanical properties are maintained.

All of these molded products were transparent.

Example 4 An aromatic polyester copolymer was produced by an interfacial polymerization method using a methylene chloride solution of mixed acid dichloride having a molar ratio of terephthalic acid dichloride/isophthalic acid dichloride of 5/5 and an alkaline aqueous solution of bisphenol A.

The logarithmic viscosity of this in phenol/tetrachloroethane (614, weight ratio) at 25°C was 0.65.

To this aromatic polyester copolymer powder, 0.3% each of ethylene bisstearamide, Hoechstwax-OP, or a 1:1 mixture thereof was added and mixed for 5 minutes in a nitrogen stream using a super mixer, followed by an extruder. It was made into a chip.

Using this chip, various test pieces are molded using an injection molding machine.
Various physical property values were measured.

Table 4 shows the melt viscosity, molding conditions, and physical properties of these lubricant-containing aromatic polyester copolymers.

(1) Melting temperature 300℃, shear stress 9.0×106d
yne/cm2 (2) Melting temperature 320°C.

Load: 2160g (3) Izod impact strength As shown in Table 4 with a notch, a mixture of different lubricants has a greater lubricating effect than a single substance, and the moldability of aromatic polyester copolymers to which mixed lubricants are added is significantly improved. Moreover, the excellent mechanical properties of aromatic polyester copolymers are maintained.

Such a tendency was also observed in other combinations.

Example 5 An aromatic polyester copolymer was produced by an interfacial polymerization method using a methylene chloride solution of mixed acid dichloride with a molar ratio of terephthalic acid dichloride/isophthalic acid dichloride of 5/5 and an alkaline aqueous solution of bisphenol A.

The logarithmic viscosity of this in phenol/tetrachloroethane (614, weight ratio) at 25°C was 0.65.

The aromatic polyester copolymer was mixed with varying amounts of ethylene bis stearamide in a nitrogen stream for 5 minutes using a super mixer, and then chipped using an extruder.

Using this chip, various test pieces were molded using an injection molding machine and various physical property values were measured.

The results are shown in Table-5.

(1) Melting temperature 300℃, shear stress 9.0×10
6 dyne/cm2 (2) Load 18.6 kg/cm2 (3) Izod impact strength Notched Example 6, Comparative Example 1 The aromatic polyester copolymer powder used in Example 1 was coated with the examples shown in Table 6. Each of the various lubricants used in 1 to 3 was added in an amount of 0.3 wt%, and the mixture was chipped at 330°C using a vented extruder.

Using this chip, the melting temperature was 330℃ and the mold temperature was 120℃.
After injection molding a test piece with a diameter of 50 mm and a thickness of 1/8 inch at ℃, its parallel light transmittance was measured in order to evaluate the transparency of the obtained test piece.

In addition, using this chip, the melting temperature was 320℃ and the load was 21℃.
The melt index at 60 g was measured.

The results are shown in Table-6. For comparison, Sunwax 131P (manufactured by Sanyo Chemical Industries, Ltd.), a low molecular weight polyethylene polymer that is generally well known as a lubricant, was used.
average molecular weight 3500] or Hoechstwax PA-
190 (manufactured by Hoechst Japan Co., Ltd., average molecular weight 9000), a test similar to the above case was conducted.

The results are shown in Table-6.

As shown in Table 6, in the case of the comparative example, the transparency was significantly impaired, whereas in the case of the present invention, the excellent transparency of the aromatic polyester copolymer was maintained.

Comparative Example 2 Polyethylene terephthalate [in phenol/tetrachloroethane (1/1, weight ratio) mixed solvent, concentration 0.5 g
/dl, with a logarithmic viscosity of 0.7 measured at 20°C] and 0.3 wt of each of the various lubricants used in Example 6.
% at a time and use a vented extruder to
It is made into chips at 0℃, and the melting temperature is 270℃ using this chip.
A test piece with a diameter of 50 mm and a thickness of 1/8 inch was injection molded at a mold temperature of 120°C.

When the parallel light transmittance of the obtained test pieces was measured, it was 3% for all test pieces.

Note that the parallel light transmittance of polyethylene terephthalate alone was also 3%.

Claims (1)

[Scope of Claims] 1. A mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid and isophthalic acid is 9:1 to 1:9) and bisphenols represented by the general formula [where -X is -O-,
-S-, -SO2-, -CO- or alkylene or alkylidene groups (if necessary, the alkylene or alkylidene groups may be substituted with one or more hydrocarbon groups, halogen atoms or halogenated hydrocarbon groups) selected from the group consisting of R
1, R2, R3, R4, R'1, R'2, R'3, R'
4 is selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups] and bis fatty acid amides, or ester waxes, or metal soaps, or selected from these groups. A resin composition containing a mixture of two or more types.