JPS5937300B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyarylate composition with improved moldability of a polyester (hereinafter referred to as polyarylate) comprising an aromatic dicarboxylic acid and a divalent phenolic compound (hereinafter referred to as bisphenols). It is something.

Polyarylates produced from aromatic dicarboxylic acids or functional derivatives thereof and bisphenols or functional derivatives thereof have been well known for a long time.

As a method for producing such polyarylates, so-called interfacial polymerization (W, M, Earecks
on, J., Poly. Sci, XL3991959,
Japanese Patent Publication No. 40-1959) Solution polymerization in which aromatic dicarboxylic acid chloride and bisphenols are reacted in an organic solvent (A, Conix, Ind, Emg, c'm)
■1471959, Special Publication No. 37-5599),
Melt polymerization by heating aromatic dicarboxylic acids and bisphenols in the presence of acetic anhydride, Melt polymerization by heating phenyl esters of aromatic dicarboxylic acids and bisphenols (Japanese Patent Publication No. 38-15247), Aromatic dicarboxylic acids and bisphenols Methods such as melt polymerization (Japanese Patent Publication No. 38-26299) are known, in which a compound is heated in the presence of a diaryl carbonate. It is also well known that polyarylates 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 temperature, and electrical properties such as specific resistance, dielectric breakdown, arc resistance, dielectric constant, and dielectric loss. It maintains excellent properties in terms of physical properties, flammability, dimensional stability, and chemical resistance, and for this reason, general molded products, films, etc. made by injection molding, extrusion molding, press molding, or various other molding methods. Fibers and coated materials are expected to have a wide range of applications. As mentioned above, polyarylate has many excellent properties and is of great utility value, but its major drawback is poor moldability.

In general, for polymers, and plastics in particular, moldability plays an important role in the evaluation of the polymer, and even if the material itself has excellent properties, if the moldability is poor, it will not be possible 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 making a product by injection molding using a polymer with a high softening temperature and high melt viscosity, a high plasticizing temperature, high injection pressure, and high mold temperature are required, which only causes high costs. In addition, high plasticization temperatures induce thermal decomposition of the polymer, high injection pressures cause distortion in the product, and failure to comply with such severe conditions can lead to fatal appearance defects such as shots, sink marks, and flow marks. This causes defects and the mechanical properties are also significantly reduced. Polyarylates also have such high softening temperatures and high melt viscosity, and have poor moldability, limiting their uses. Therefore, improvement of its moldability has been desired for a long time. Furthermore, although polyarylate itself has excellent impact resistance, it has been desired to further improve it. In order to improve moldability, there is a conventional method of using various plasticizers or lubricants, and these plasticizers or lubricants include esters of aliphatic or aromatic carboxylic acids, chlorinated hydrocarbons, epoxy compounds, These include glycerol derivatives, phosphates or phosphoric acid esters, phosphites or phosphite esters.

However, all of these often reduce the molecular weight of the polyarylate during molding, resulting in a reduction in the performance of the molded product, particularly the impact strength. Therefore, an object of the present invention is to improve the moldability of polyarylate while maintaining its excellent properties.

The present inventors have arrived at the present invention as a result of intensive research to improve the above-mentioned drawbacks of round polyarylate.
Not only was the moldability improved, but most of the advantages of the original polyarylate were retained.

That is, the novel resin composition of the present invention is 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 is represented by the general formula Bisphenols (
However, -X- is 1O-, -S-, -SO2-, -CO-
selected from the group consisting of an alkylene group or an alkylidene group, R1, R2, R3, R4, RI. R2, orbital and R'4 are selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group) and 0.1 to 10% by weight of a polyarylate of the general formula R5-0-C-0- R
6 (wherein R5 and R6 are groups selected from the group consisting of aliphatic and aromatic groups).

The polyarylate used in the present invention is produced from terephthalic acid, isophthalic acid, or functional derivatives thereof, and bisphenols, and any of interfacial polymerization, solution polymerization, or melt polymerization is adopted as the production method. It can also be used.

The polyarylate of the present invention using a mixture of terephthalic acid groups and isophthalic acid groups as the acid component is a copolymer, in which case the molar ratio of terephthalic acid groups to isophthalic acid groups is 9.
:1 to 1:9 is preferable. The bisphenols used in the present invention are represented by the general formula, where -X- is -0-, -S-, -SO2-, -1-, an alkylene group or an alkylidene group (the alkylene group or alkylidene group is optional). If so, it may be substituted with one or more hydrocarbon groups, halogen atoms, or halogenated hydrocarbon groups).

R1, R2, R3, R4, B. ,R? , R'3 and R
'4 is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Examples of such bisphenols include 4,4'-dihydroxy-diphenyl ether, 4,4'-dihydroxy-2,2'-dimethyl-diphenyl ether, 4,45-dihydroxy-3,3
'-dichlorodiphenyl ether, 4,45-hydroxy-diphenyl sulfide, 4,4'-dihydroxy-diphenyl sulfone, 4,4'-dihydroxy-diphenyl ketone, 4,4'-dihydroxy-diphenyl rumethane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 1●1-bis(4-hydroxyphenyl)-n-butane, bis( 4-hydroxyphenyl)-cyclohexyl-methane, 1,1-bis(4-hydroxyphenyl)
Examples include -2,2,2-trichloroethane,
Of course, it is generally produced, and the representative one is called 2,2-bis(4-hydroxyphenyl)propane, that is, bisphenol A.

If desired, mixtures of the bisphenols mentioned above or mixtures of bisphenols with small amounts of other divalent compounds can be used. In general, in order to lower the softening point of polyarylate in order to improve moldability, X is preferably a relatively large group such as propyl, isopropyl, butyl or isobutyl. General formula R5-0- blended to improve the moldability of polyarylate in the present invention
The compound represented by C-0-R6 is a type of carbonate compound, and typical examples thereof include the following.

Namely, dioctyl carbonate, didecyl carbonate, didodecyl carbonate, dioctadecyl carbonate, distearyl carbonate, di-3-dimethyldecyl carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate) bis( 4-t
-butylphenyl carbonate, dinaphthyl carbonate, didodecylphenyl carbonate, etc. These carbonate compounds to be blended are preferably present in the polyarylate as much as possible when the polyarylate is heated and melted during injection or extrusion molding, and therefore those with low volatility are suitable. Therefore, it is preferable to use carbonates having a large molecular weight. The carbonate compound used is 0.1 to polyarylate.
10% by weight is used, preferably 0.5-5% by weight. The carbonate compound may be incorporated into the polyarylate by any method. For example, a carbonate compound may be added or added to polyarylate pellets or powder and mixed using a mixing roll, a Banbury mixer, an extruder, or the like. A preferred method is to melt the polyarylate using an extruder, blend it therein, and then pelletize it. Alternatively, the above-mentioned carbonate compound may be mixed with polyarylate pellets or powder and molded directly using the mixture. Also,
Another method may be to mix the carbonate compound into the polyarylate solution and then evaporate the solution to disperse the carbonate compound in the polyarylate. Conventionally, various plasticizers and lubricants have often been used to improve moldability.

However, in these cases, it is often observed that the molecular weight of the polyarylate decreases during thermoforming such as injection molding and extrusion molding. The mechanical properties of polyarylates are significantly dependent on their molecular weight, with lower molecular weights resulting in lower impact strength in particular. However, the blending of carbonate in the present invention not only improves the flow during melting and improves moldability, but also reduces the molecular weight drop during thermoforming as described above, and therefore maintains good mechanical properties. It will be done. In order to improve the heat resistance, light resistance, and oxidation resistance of the composition of the present invention, a thermal decomposition inhibitor, an antioxidant, or an ultraviolet absorber may be present in the composition.

In that case, benzotriazole compounds, phosphorus compounds, phenolic compounds, benzophenone derivatives, etc. are used. Further, other polymers such as polyethylene terephthalate, polycarbonate, polyethylene, and polypropylene may be mixed and composited. In addition, other plasticizers, pigments, lubricants, etc. can also be used in the composition of the present invention, and glass fibers can also be added to strengthen the composition. The composition of the present invention can be made into various useful products using commonly known plastic molding methods such as press molding, injection molding, and extrusion molding using powder, chips, or other forms.

Examples of such products include gears, bearings, electrical parts, insulating material containers, and a wide range of other products, which are used in a wide range of applications as products that require high performance as engineering plastics. Furthermore, the properties of the molded product can be further improved by heat treatment. Next, examples of the present invention will be shown.

Note that "parts" in the examples are "parts by weight." Example 1 A copolymerized polyarylate was produced from a methylene chloride solution of a mixed acid chloride having a ratio of terephthalic acid dichloride/isophthalic acid dichloride of 7:3 and an alkaline aqueous solution of bisphenol A by an interfacial polymerization method.

The logarithmic viscosity of this product measured in phenol/tetrachloroethane (6:4 weight ratio) at a concentration of 1 p/A at 25°C was 0.
It was 73. 0.5 part of distearyl carbonate was added to 99.5 parts of this polyarylate powder and mixed in a mold blender. After drying, this was extruded at 280° C. using a 65 mmφL/D=24 extruder and cut to obtain chips. The logarithmic viscosity of this chip was 0.65, which was the same as without the addition of distearyl carbonate. In order to measure the flow of the polymer during melting, a melt index was measured using a Koka type flow tester. At 330°C, the composition of the present invention weighed 13 grams, compared to 7 grams without distearyl carbonate. 10 again? Dyne/Cd, 3
The melt viscosity at 30°C was 2000 poise with the addition of distearyl carbonate and 2500 poise without the addition. It is clear from the melt index and melt viscosity results that the composition of the present invention has significantly improved fluidity during melting. In order to measure the moldability more specifically, the spiral flow length was measured.
T1L, and the effect of adding distearyl carbonate was remarkable. Next, using the above chip, the cylinder temperature was 330°C and the injection pressure was 7001°C in an injection molding machine.
When molding a molded article with a length of 10 inches, a width of 1/2 inch, and a thickness of 1/16 inch under the conditions of <g/Cd, in the case of the composition of the present invention, the composition was completely filled, There was no "sink" in the molded product, but in the case of the product without distearyl carbonate, the polymer was not completely filled,
It became a short shot. The logarithmic viscosity of the molded product is determined by the addition of
Both without additives are 0.60, and the impact strength is 4 in both cases.
There was no difference at 00 kg/Cd (tensile impact ASTM-D-1822). On the other hand, when dioctyl phthalate was used as a plasticizer, the moldability improved, but the logarithmic viscosity of the molded product decreased to 0.54 and the impact strength was low. Example 2 Diphenyl terephthalate/diphenyl isophthalate (1
:1 molar ratio) and bisphenol A by a melt polymerization method.

Immediately after being discharged from the polymerization kettle, it was cut into chips. 99 parts of this chip and 1 part of didodecyl phenyl carbonate were mixed in a super mixer, and then 4011! φLA)=1
The mixture was extruded using a No. 8 extruder to obtain strands, which were cut to obtain pellets. Injection molding was carried out using this pellet, but the cylinder temperature of the injection molding machine was 30
Molding was possible at 0°C and mold temperature of 120°C, but when didodecyl phenyl carbonate was not used, good molded products were obtained under the above conditions even though the logarithmic viscosity of the pellet was 0.04 lower than that of the additive. I couldn't get it. Example 3 99 parts by weight of the polyarylate used in Example 1 and 1 part by weight each of the carbonates shown in Table 1 were mixed, dried, and chipped in the same manner as in Example 1.

Using the obtained chip, the spiral flow length was measured in the same manner as in Example 1. The results are shown in Table 1, and it is clear that the addition of carbonate significantly increases the spiral flow length. The longer the spiral flow length, the better the moldability, so the effect of improving moldability by adding carbonate was remarkable. Further, using the above chip, a molded article having a length of 10 inches, a width of 1/2 inch, and a thickness of 1/16 inch was molded using an injection molding machine in the same manner as in Example 1. In the case of the composition of the present invention, It was possible to mold the molded product without any short shot or "sink mark", and the impact strength of the molded product obtained was no different from that without carbonate. Example 4 99 parts by weight of the polyarylate used in Example 1 and 1 part by weight each of the carbonates shown in Table 2 were mixed, dried, and chipped in the same manner as in Example 1.

Using the obtained chip, the spiral flow length was measured in the same manner as in Example 1. The results are shown in Table 2, and it is clear that the addition of carbonate significantly increases the spiral flow length.

Claims (1)

[Claims] 1. A mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups and isophthalic acid groups is 9:1 to 1:9) and general formulas ▲ mathematical formulas, chemical formulas, tables, etc. There are bisphenols represented by ▼ (however, -X- is -O-
, -S-, -SO_2-, -CO-, an alkylene group or an alkylidene group, R_1, R
_2, R_3, R_4, R'_1, R'_2, R'_3
and R'_4 is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group) and the general formula ▲ mathematical formula, chemical formula, table, etc. There is ▼ (R_5 in the formula
and R_6 is a group selected from the group consisting of an aliphatic group and an aromatic group.