JPS582975B2 - 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 groups to isophthalic acid groups is 9:1 to 1:9) and bisphenol represented by the general formula. [However, -X1 is -0-
, -S-, -SO2-, -CO-, an alkylene group, or an alkyritene group (if necessary, the alkylene group or alkyritene group is substituted with 1 or more hydrocarbon groups, halogen atoms or halogenated hydrocarbon groups) R1, R2,
R3, R4, R'1, R'2, R'3, and R/4 are selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups. aromatic esters (Y, Y' are selected from aryl groups or condensed polycyclic hydrocarbon groups)
The present invention relates to a resin composition containing 0% by weight or less.

Aromatic polyester 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.

As a method for producing such an aromatic polyester copolymer, a so-called interfacial polymerization method (W. M. Eareckson. J. Poly.
Sci. XL 399 1959, special public service 40-19
59), a solution polymerization method in which aromatic dicarboxylic acid chloride and bisphenols are reacted in an organic solvent (
A. Conix. Ind. Eng. Chem. 51 1
47 1959, Japanese Patent Publication No. 37-5599), Melt polymerization method of heating aromatic dicarboxylic acid and bisphenols in the presence of acetic anhydride, Melt polymerization method of heating phenyl ester of aromatic dicarboxylic acid and bisphenols (
Japanese Patent Publication No. 38-15247), a melt polymerization method in which aromatic dicarboxylic acid and bisphenol are heated in the presence of diaryl carbonate (Japanese Patent Publication No. 38-26299)
Methods such as these are known.

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

In other words, it has excellent mechanical properties such as tensile strength, bending strength, bending recovery rate, and impact strength, especially recovery characteristics, thermal properties such as heat distortion temperature and thermal decomposition temperature, specific resistance value, dielectric breakdown,
It also maintains excellent electrical properties such as arc resistance and dielectric properties, flammability, dimensional stability, and chemical resistance, making it suitable for injection molding, extrusion molding, press molding, and various other molding methods. The general molded articles, films, fibers and coating materials produced are expected to have a wide range of uses.

As mentioned above, aromatic polyester copolymers have excellent properties and are of very high utility value, but their major drawback is poor moldability.

In general, when it comes to polymers and plastics, moldability plays an important role in the evaluation of the product, and even if the material itself has excellent properties, if the moldability is poor, it is difficult to manufacture the product economically. Not only is it impossible to do so, but its excellent properties are not fully demonstrated in the product.

For example, when a product is made by injection molding using a polymer with a high softening temperature and high melt viscosity, the plasticization temperature is high,
High injection pressure and high mold temperature are required, which not only causes high costs, but also high plasticization temperature induces oxidative decomposition and thermal decomposition of the polymer, and high injection pressure causes distortion in the product. Furthermore, when such severe conditions are violated, fatal defects in appearance such as short shots, sink marks, and flow marks occur, and the mechanical properties are also significantly degraded.

Aromatic polyester copolymers also have such high softening temperatures and high melt viscosity, have poor moldability, and have limited uses.

Therefore, improvement of its moldability has been desired for a long time.

However, conventionally used general plasticizers such as low molecular weight fatty acid esters such as butyl laurate and butyl stearate, as well as chlorinated fatty acid esters, have poor heat resistance and have some problems with compatibility and miscibility. If the aromatic polyester copolymer is plasticized by chipping, it loses the excellent transparency and coloring properties of the aromatic polyester copolymer, and furthermore, the mechanical properties are significantly reduced. It was hoped that a drug would emerge.

The present inventors have conducted intensive research to improve moldability and processability while maintaining the excellent transparency, colorability, and mechanical properties of aromatic polyester copolymers. Discover esters (where Y and Y' are selected from aryl groups or condensed polycyclic hydrocarbon groups) (hereinafter these compounds will be referred to as aromatic ester plasticizers), and add 20% of such aromatic ester plasticizers by weight. It has been found that the moldability and processability of the aromatic polyester copolymer can be significantly improved while maintaining the transparency, colorability and mechanical properties of the aromatic polyester copolymer.

That is, the purpose of the present invention is to lower the melt viscosity and molding temperature of aromatic polyester copolymers, and to improve the mechanical properties such as transparency, colorability, tensile strength, tensile elongation, and impact strength of aromatic polyester copolymers. The objective was to provide a resin composition that maintained a high level of properties, and this objective was achieved by adding 20% by weight or less of an aromatic ester plasticizer to an aromatic polyester copolymer.

Examples of such aromatic plasticizers include diphenyl terephthalate, but the aromatic ester plasticizers used in the present invention are not limited thereto.

The aromatic ester plasticizer can be mixed and added to the aromatic polyester copolymer by various methods.

Namely, (1) a method in which aromatic polyester copolymer powder is added directly; (2) aromatic polyester copolymer powder is dissolved or swollen immersed in a low boiling point solvent such as alcohol, ketone, or saturated hydrocarbon; A method for impregnating or adhering a plasticizer to an aromatic polyester copolymer powder by dissolving a group ester plasticizer, stirring and mixing, removing the solvent, and (3) in the production process of an interfacial polymerization method and a solution polymerization method. , a method of polymerizing by adding an aromatic ester plasticizer to an organic solvent before or during polymerization, (4
) In the manufacturing process of the interfacial polymerization method and the solution polymerization method, an aromatic ester plasticizer is added to the aromatic polyester copolymer solution after polymerization, and the plasticizer-containing aromatic polyester copolymer is added by the concentration solidification method or the solvent strip method. The mixture can be carried out by a method of obtaining a polymer powder.

Regarding the amount of aromatic ester plasticizer added, as the amount of plasticizer increases, the moldability is significantly improved, but as already mentioned, the colorability, transparency, and Additions of up to 20% by weight of plasticizer can be employed in order to maintain a high degree of various mechanical properties.

More preferably, it is effective to use 5% by weight or less in order to maintain high flame retardancy.

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 9. :l.

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

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

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 weight 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 kg/dl at 25°C in phenol/tetrachloroethane (6/4 weight ratio) is 0.63.
Met.

5% by weight of di-β-naphthyl terephthalate was added to this aromatic polyester copolymer powder, mixed for 5 minutes in a super mixer nitrogen stream, and then pelletized using an extruder.

Using this pellet, 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 property values of these plasticizer-containing aromatic polyester copolymers.

In this way, 5% by weight of di-β-naphthyl terephthalate
The moldability of the added aromatic polyester copolymer is significantly improved, and 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 a mixed acid dichloride having a weight ratio of terephthalic acid dichloride/inphthalic acid dichloride of 5/5 and an alkaline aqueous solution of bisphenol A.

The logarithmic viscosity of this in methylene chloride at 25° C. kg/dl was 0.65.

Bis(p-(1-methyl-l-phenylethyl)phenyl) terephthalate was added to the methylene chloride solution of this aromatic polyester copolymer in an amount of 5 wt% based on the polymer, and a plasticizer was added by a concentration solidification method using a continuous nitrate. An aromatic polyester copolymer powder was obtained.

This powder was pelletized using an extruder.

Using this pellet, 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 property values of these plasticizer-containing aromatic polyester copolymers.

An aromatic polyester copolymer to which no plasticizer is added has a high melt viscosity of 4.3×104 at 300°C, and requires severe molding conditions such as a molding temperature of 360°C and an injection pressure of 1550 kg/cm2.

However, the melt viscosity of the plasticizer-containing aromatic polyester copolymer obtained in this example was significantly reduced;
Formability is greatly improved.

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

All of these molded products are transparent.

Example 3 Aromatic polyester copolymer (phenol/tetrachloride) obtained by interfacial polymerization from a methylene chloride solution of mixed acid dichloride with a weight ratio of terephthalic acid dichloride/isophthalic acid dichloride of 5/5 and an alkaline aqueous solution of bisphenol A. kg/dl at 25°C in ethane (6/4 weight ratio)
2.5% by weight of di-(para-tert-butylphenyl) isophthalate and 2.5% by weight of di-(para-tert-butylphenyl) terephthalate were added to powder (with a logarithmic viscosity of 0.65), and the mixture was mixed with a super mixer in a nitrogen stream. After mixing for 5 minutes, it was pelletized using an extruder.

Using this pellet, a molding test was conducted using a spiral mold in an injection molding machine.

Molding temperature: 320℃, mold temperature: 120℃, injection pressure: 126℃
The injection was carried out at a weight of 0 kg/cm2 and an injection time of 10 seconds.

The results are shown in Table 3.

It can be seen that the plasticizer-containing copolymer according to the present invention has significantly improved moldability.

Claims (1)

[Scope of Claims] 1. A mixture of terephthalic acid and inphthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9) and bisphenols represented by the general formula [ However, -X- is -0-
, -S-, -SO2-, -CO-, an alkylene group or an alkylidene group (if necessary, the alkylene group or alkylidene group is substituted with 1 or more hydrocarbon groups, halogen atoms or halogenated hydrocarbon groups) R1, R2, R
3, R4, R'1, R'2, R'3, and R'4 are selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups. Aromatic esters represented by (Y, Y' are selected from aryl groups or condensed polycyclic hydrocarbon groups)
A resin composition containing 0% by weight or less.