JPS5920352A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having improved moldability as well as improved transparency, consisting of a polyarylate and a specified ester oligomer. CONSTITUTION:A resin compsn. consists of a polyarylate (e.g. one obtd. from a mixture of terephthalic acid and isophthalic acid or their functional derivatives and bisphenol A or its functional derivative) and an ester oligomer obtd. by reacting a dihydric phenol or its functional derivative with a carbonate precursor, such as one obtd. reacting P-t-butylphenol-blocked bisphenol A with carbonic acid. While retaining excellent properties such as heat resistance, etc. inherent to the polyarylate, the moldability and transparency are improved and hence, the compsn, is useful as a molding material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an ester oligomer with improved moldability that is obtained by reacting (A) a polyarylate, (B) a dihydric phenol or a functional derivative thereof, and a carbonate precursor. This invention relates to a resin composition.

It is widely known that polyarylates have excellent performance as molding materials. That is, mechanical properties such as tensile strength 1 bending strength 1 bending @ J modulus, impact strength, and thermal properties such as heat distortion temperature and thermal decomposition.

It maintains excellent properties in terms of specific resistance, dielectric breakdown, arc resistance, dielectric constant and dielectric loss, flammability, one-dimensional stability, and chemical resistance, and is therefore suitable for injection molding, extrusion molding, and pressing. BACKGROUND OF THE INVENTION General molded articles, films, fibers and coated materials made by molding or other various molding methods are expected to have a wide range of uses.

As mentioned above, polyarylates have many excellent properties and are of great utility value, but their major drawback is poor moldability. In general, when it comes to polymers and especially plastics, moldability plays an important role in the evaluation of the material itself.

Even if the material itself has excellent properties, if the moldability is poor, not only will it be impossible to economically manufacture the product, but the product will not be able to fully utilize its excellent properties. For example, when manufacturing products by injection molding using polymers with high softening temperatures and high melt viscosity, high plasticizing temperatures, high injection pressures, and high mold temperatures are required, which causes high costs. Not only that, the high plasticizing temperature will cause the thermal decomposition of the polymer, the high injection pressure will cause distortion in the product, and the appearance of short shot "sink marks", flow marks etc. This results in the above fatal drawback, and the mechanical properties are also significantly low. Polyarylates also have such high softening temperatures, high melt viscosity, and poor moldability, and their uses have been limited. 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, and chlorinated fatty acid esters, have poor heat resistance and poor compatibility and miscibility. Polyarylates that have been plasticized with some loss of color lose the excellent transparency and coloring properties of polyarylates, and have the disadvantage of significantly lowering mechanical properties. development was desired.

The inventors have demonstrated the excellent heat resistance of polyarylates.

As a result of extensive research, we have developed an ester oligomer obtained by reacting polyarylate with a dihydric phenol or its functional derivative and a carbonate precursor in order to improve its moldability without impairing its transparency and mechanical properties. The inventors of the present invention have found that the addition of V not only achieves the above objectives, but also surprisingly improves transparency significantly.

This is a resin composition with improved moldability consisting of a chill oligomer.

The polyarylate which is one component of the resin composition of the present invention is
It is obtained from aromatic cicafreponic acid or a functional derivative thereof and dihydric pheno-I or a functional derivative thereof.

The aromatic dicarboxylic acid used in the preparation of the polyarylate may be any aromatic dicarboxylic acid as long as it reacts with dihydric phenol to give a satisfactory polymer, and may be used alone or in combination of two or more. Preferred aromatic dicarboxylic acids include prephthalic acid, isophthalic acid, and isophthalic acid, and mixtures thereof are particularly preferred in terms of melt processability and overall performance.

After the mixing, the mixing ratio is not limited, but prephthalate/L' acid/isophthalic acid = 97
1 to 1/9 (molar ratio) is preferred, especially melt processability.

In terms of performance balance, 775 to 3/7 (7l ratio) and Shijokoha 1/1 (molar ratio) are desirable.

The dihydric phenol used for the preparation of polyarylate has the following general formula (I), (I[) or ([)
The following can be mentioned.

The above general formula [where R□+R1! g R3*
R4+ R1' + RXR3', R4' is a hydrogen atom, a halogen atom, or a hydrocarbon group.

selected from the group consisting of halogenated hydrocarbon groups, X is O
, S, SO, CO, an alkylene group or an alkylidene group (if necessary, the alkylene group or alkylidene group may be substituted with one or more halogen atoms). Specific examples of preferred dihydric phenols include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-6
,5-diglomophenytL/) y”lopane,2,2-
bis(4-hydroxy-1,5-5)chlorophenyl)
Globan, A, 4'-hydroquine diphenyl lephon, 4, 4'-dihydroxydiphenyl ether/
L', 4.4'-dihydroxydiphenyl sulfuride, 4.4'-dihydroxydiphenylketone, 4.4'-dihydroxydiphenylmethane,
2.2'-bis(4-hydroxy-6,5-dimethylphenyl)globan, 1,1-bis(4-hydroxyphenylated/I/)ethane, 1.1-bis(4-hydroxyphenylated/I) /) cyclohexane, 4,4'-dihydroxydiphenyl, benzoquinone, etc. These may be used alone or in combination of two or more. Furthermore, although these divalent phenols are substituted products, other isomers may also be used. Furthermore, these divalent phenols! It may also be used in combination with ethylene glyco-A/7'robilene glyco-I. The most typical dihydric phenol is 2,2-bis(4-hydroxyphenyl)propane, commonly referred to as bisphenol-A, which is most preferred from the viewpoint of overall physical properties.

Therefore, 1 Boria in the present invention! The most preferred IL/-) are terephthalic acid, isophthalic acid, or a mixture of these functional derivatives (provided that

The molar ratio of the trefuglylic acid group and the isophthalic acid group is 9:
1 to 1:9. Especially 7:3 to 3 near) and general formula (
Ill), particularly bisphenol A or its functional derivative. In the first aspect of the present invention, polyarylates having a number average degree of polymerization of 5 U to 150 are preferably used.

The ester I rheooligomer, which is a component of the resin composition of the present invention, is produced by the reaction of divalent phenol or a functional derivative thereof with a carbonate precursor such as phosgene, a halogenated formate, or a carbonate ester. The sea urchin phenol obtained by the above general formulas (I), (n) and (
Iff) can be mentioned. Specific examples of preferred divalent phenols include those exemplified as those used in the preparation of polyarylates. These may be used alone or in combination of two or more. In addition, although these divalent phenol-I are para-substituted isomers, other isomers may also be used,
Furthermore, ethylene glyco-7 is added to these dihydric pheno-I,
Propylene glycol or the like may be used in combination. The most typical divalent phenol is 2.2-bis(4-hydroxyphenol)furopane, commonly called bisphenol A. Therefore, in the present invention, and △ It is also preferable to use a carbonate precursor and a dihydric phenol of the general formula ([), especially a bisphenol.
/L/A or its functional derivative.

The ester oligomer used in the present invention 1 preferably has a functional group at the end of its molecular chain capped by reaction with a monofunctional end capping agent. The reason is 1. For example, if a hydroxyl group is present at the end of an oligomer, when it is melt-mixed with a polyarylate, the hydroxyl group will react with the polyarylate, lowering the molecular weight of the polyarylate, and therefore affecting the mechanical properties of the resin composition. This is because it tends to deteriorate.

Examples of such terminal capping agents include pt-butylphene-1, P-methoxyphenol, 0-phenylphenol, β-naphthol, P-cumylphenol, methanol, butanol, methylcaptan phthalimide, and the like. However, any substance that blocks the functional groups at the ends of the oligomer may be used. The number average degree of polymerization of the ester oligomer used in the present invention is preferably 5 to 80. 1 more, preferably 4~
70. The most preferred range is 5-50. On the other hand, if the degree of polymerization is too low, oligomers tend to bleed out from the resin composition and the thermal stability of the dressing composition tends to decrease.

If the degree of polymerization is too high, the effect of improving moldability tends to decrease.

The content of the ester oligomer in the resin composition is preferably 1 to 50% by weight based on the total amount of the polyarylate and the ester oligomer, but a molding material with well-balanced heat resistance, moldability, and transparency can be obtained. 5-40 for
More preferably it is 5 to 30% by weight, especially 5 to 30% by weight.

The ester oligomer can be mixed with the polyarylate in various ways.

(1) Adding the ester oligomer directly to the polyarylate powder; (2) Dissolving or swelling the polyarylate powder in a low-boiling solvent such as alcohol, ketone, or saturated hydrocarbon, and then dissolving the ester oligomer therein. After that, a method of impregnating or adhering the ester oligomer to the polyarylate powder by stirring and mixing and distilling off the solvent (
3) In the production process of interfacial polymerization method and solution polymerization method, 1 method of adding Fleako Esthe I Reoligomer to an organic solvent before or during polymerization and polymerizing it, (4) Production process of interfacial polymerization method and solution polymerization method In this case, the ester oligomer is added to the polyarylate solution after the polymerization is completed, and the polyarylate powder containing the ester I rheooligomer can be obtained by a concentration solidification method or a bath agent stripping method.

Depending on the purpose, the resin composition of the present invention may contain weathering (light) agents, heat resistant agents, flame retardants, molding process improvers (various additives such as mold release agents and lubricants, and filler reinforcing agents such as glass fiber and inorganic powder). The resin composition of the present invention has the advantage of improved moldability and transparency while retaining the excellent properties of polyarylate such as heat resistance, and is useful as a molding material. It is something.

The present invention will be explained in more detail below with reference to Examples.

Examples 1-5. Comparative Example 1 A polyarylate (molecular weight approximately 25,000) obtained from a mixed dicarboxylic acid with a molar ratio of prephthalic acid and isophthalic acid of 1:1 and bisphenol/l/A was end-capped with pt-butylphenol. Ester oligomer obtained from bispheno-IV A and carbonic acid (molecular weight approximately 5.1100
) were mixed in various ratios shown in Table 1 and pelletized using a melt extruder. Using these pellets, various test specimens were made using an injection molding machine, and the heat distortion temperature, perflow length, and Izotsu impact strength were measured.

Total light transmittance and yellow in glass were measured.

The results are shown in Table 1.

As is clear from Table 1, the resin composition of the present invention has significantly improved moldability and transparency without substantially impairing the heat resistance of polyarylate.

Table 1 (2) ASTM D256. -4-'With thick notch (
3) ASTM D100 3.2m thickness (4) AS
TM D1925.2 Thickness Examples 6-9. Comparative example 2 7% molar ratio of terephthalic acid and isophthalic acid is 4:6
A polyarylate obtained from a combined dicarboxylic acid and bisphenol A (molecular weight approximately 30,000) and an ester oligomer end-capped with P-cumylphenol and having various degrees of polymerization shown in Table 2 were mixed in a 9:1 (weight ratio). ), and the mixture was mixed using an F8 melt extruder and pelletized using a trowel. Using the pellets, various test specimens were made using an injection molding machine, and their heat deformation temperature, 1<-flow length, Izot impact strength, total light transmittance, and yellow in glass were measured. The results are shown in Table 21.

As is clear from Table 2, the resin composition of the present invention has significantly improved moldability and transparency without substantially impairing the heat resistance of polyarylate.

<1) Thickness 1ag, molding conditions (cylinder temperature 340
°C, pressure 1400 kgM) (2) ASTM D
256. ('With thick notch +3) ASTM Dl
003, 2 tm thickness (4) ASTM D1925.
2fi thickness patent applicant Unitika Co., Ltd.

Claims (1)

[Claims] (1) (At polyarylate and (B) divalent phenol)
A resin composition with improved moldability comprising a Varnish 7-1v oligomer obtained by reacting Varnish 7-1v or a functional derivative thereof with a carbonate precursor.