JPS5936948B2 - Aromatic polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to two types of aromatic polyesters, namely, an aromatic polyester having 2,2-bis(4-hydroxyphenyl)propane as its dihydric phenol component as a main component, and a 1,1- The present invention relates to a resin composition comprising an aromatic polyester containing bis(4-hydroxyphenyl)cyclohexane as a main component.

Aromatic polyester (hereinafter referred to as bisphenol A) synthesized from a dihydric phenol whose main component is 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) or its derivative, and an aromatic dibasic acid or its derivative. APC (referred to as APC) has superior properties over existing plastics, such as a high heat distortion temperature, excellent mechanical properties, electrical properties, and transparency, and can be molded by injection, extrusion, blow molding, etc. There are great expectations for its application to a wide range of applications, including electronics, electrical parts, mechanical parts, architectural parts, and lighting equipment.

Due to the high water vapor permeability of water vapor, its application to aqueous solutions and containers for foods and medicines containing aqueous solutions has been limited due to lack of performance. Generally, in order to compensate for the shortcomings of resins, it is a method to blend resins with opposite properties, for example, a resin with good processability for a resin with poor processability, and a resin with a low heat distortion temperature. A method of blending a resin with a high heat distortion temperature is used, but in this case, there is usually a significant sacrifice in mechanical properties, surface gloss, transparency, etc.
The present inventors conducted research to find a resin that has good compatibility with the APC and good water vapor permeability, and found that 1,1-bis(
Aromatic polyester (hereinafter referred to as APZ) synthesized from dihydric phenol whose main component is 4-hydroxyphenyl)cyclohexane (hereinafter referred to as bisphenol Z) or its derivative and aromatic dibasic acid or its derivative is extremely resistant. It has been found that it has excellent water vapor permeability and good compatibility with APC.

That is, by blending APZ with APC, AP
We have discovered that it is possible to obtain a composition that significantly improves water vapor permeability, which is a drawback of APC, without reducing the transparency, mechanical strength, and heat resistance, which are the characteristics of APC, and arrived at the present invention. On the other hand, APZ is inferior to APC in mechanical properties, especially impact strength and processability, especially blow moldability.
It has also been found that impact strength and processability are significantly improved by blending PC.

APC used as a component of the composition of the present invention is an aromatic polyester synthesized from a dihydric phenol component whose main component is bisphenol A or its derivative, and an aromatic dibasic acid or its derivative. Moreover, APZ is an aromatic polyester synthesized from a dihydric phenol component whose main component is bisphenol Z or a derivative thereof, and an aromatic dibasic acid or a derivative thereof.

Both APC and APZ may be copolymerized aromatic polyesters in which part of the divalent phenol is replaced with another divalent phenol.

Examples of the second component of the dihydric phenol include bis(4-hydroxyphenyl)-methane, bis(4-hydroxy-3-methylphenyl)-methane, and bis(4-hydroxy-3,5-dichlorophenyl). -methane, bis(4-hydroxy-3,5-dibromophenyl)-methane, bis(4-hydroxy-3,5-difluorophenyl)-methane, bis(4-hydroxyphenyl)-ketone, bis(4- hydroxyphenyl)-sulfide,
Bis(4-hydroxyphenyl)-sulfone, 4,4
'-dihydroxydiphenyl ether, 1,1-bis(
4-Hydroxyphenynotri-ethane, 2,2-bis(4
-hydroxy-3-methylphenyl)propane, 2,2
-bis(4-hydroxy-3-chlorophenyl)-propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)-propane, 2,2-bis(4-hydroxynaphthynolypropane, 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'chlorophenynolymethane, bis(4-hydroxyphenyl)-cyclohexylmethane, 4,4'-dihydroxydiphenyl,
These include dihydroxynaphthalenes such as 2,2'-dihydroxydiphenyl and 2,6-dihydroxynaphthylene, hydroquinone, resorcinol, 2,6-dihydroxytoluene, 2,6-dihydroxychlorobenzene, and 3,6-dihydroxytoluene. Specifically, the divalent phenol derivative is a diester of the divalent phenol such as alkyl or phenyl. A mixture of these may also be used. The aromatic dibasic acid is represented by the following general formula. In the above formula, Ar' represents an arylene group such as o-phenylene group, m-phenylene group, p-phenylene group and naphthylene group, and these arylene groups may be substituted with an alkyl group or a halogen atom.

A mixture of these may also be used. The derivatives of aromatic dibasic acids are cyclolades or diesters of alkyl, phenyl, etc. of the aromatic dibasic acids.

A mixture of these may also be used. APC and APZ used as components of the composition of the present invention can be prepared by any method such as interfacial polycondensation method, solution polycondensation method, melt polycondensation method, etc. It is synthesized by the following method.

The degree of polymerization of the APC and APZ was at 25°C in chloroform.
Intrinsic viscosity measured from 0.35dj/9 to 1.50d
1/9 is preferable.

The composition of the present invention is APCl~99wt? and APZ99~
The composition consists of 1% by weight.

If the APC is more than 99% by weight, the effect of improving water vapor permeability is insufficient, and if the APC is less than 1%, the APC
The effect of improving impact resistance and blow moldability of PZ is insufficient.
In particular, when the amount of APC mixed is 10 to 90% by weight, a composition with excellent moisture permeability, transparency, impact strength, and processability can be obtained, which is useful.

In producing the composition of the present invention, a commonly used mixing method is used.

Examples include a solution blending method and a method using a so-called general kneading machine such as a kneading roll, an extruder, and a Banbury mixer. The compositions of the invention may contain dyes, pigments, fillers, heat-light stabilizers and other additives conventionally added to plastics. The present invention will be explained below with reference to Examples, but these are merely illustrative and can be modified as appropriate within the scope of the present invention.

Example 1 An aromatic polyester (abbreviated as APC) having a basic structure of 50 mol%, m substitution of 50 mol%, and an intrinsic viscosity of 0.65 d1 measured at 25°C in cucaroform, and a basic structure of p The substitution is 50 mol %, the m substitution is 50 mol %, and the intrinsic viscosity measured at 25° C. in cucaroform is 0.60 d1/9.

) with various blends of aromatic polyester (abbreviated as APZ) were melt-blended using an extruder, and the resulting blend was press-molded at 310°C to measure various physical properties. Container molding was carried out.

The water vapor permeability of the film was determined by press molding to create a film with a thickness of approximately 200μ, and according to JIS ZO2O8, at 40°C.
90%R. H. It was calculated from the weight increase of dry calcium chloride due to water vapor passing through the sample film in the atmosphere of

The water vapor permeability of the container was determined by filling a 15-gold container (average wall thickness 0.6511) obtained by blow molding with water, sealing the container, and heating the container at 20° C. with a temperature of 65% R. H.

The weight loss was measured after being left in the atmosphere for 14 days and expressed as a percentage of the weight before being left. The results are shown in Table 1, and the water vapor permeability of the film is plotted against the blend ratio in FIG.

Comparative Example 1 Used in Example 1 1. Various experiments were conducted on APC and APZ as in the examples.

The results are shown in Table 1 and FIG.

APZ had a large screw rotation load during molding, and a good blow molded product was obtained.

From Table 1 and FIG. 1, the composition of the present invention has water vapor permeability,
It has excellent impact strength, heat resistance, transparency, and blow moldability, and especially the water vapor permeability, which is the value normally expected from a blend of the two (the value that satisfies the additivity of both - the broken line in Figure 1).
This is a surprising and unexpected performance.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between the water vapor permeability and the mixing ratio of a film made from a mixture of aromatic polyesters APC and APZ.

Claims (1)

[Claims] 1 1 to 9.9% by weight of an aromatic polyester synthesized from a dihydric phenol component containing 2,2-bis(4-hydroxyphenyl)propane or a derivative thereof as a main component and an aromatic dibasic acid or a derivative thereof; , from 99 to 1% by weight of an aromatic polyester synthesized from a dihydric phenol whose main component is 1,1-bis(4-hydroxyphenyl)cyclohexane or its derivative, and an aromatic dibasic acid or its derivative. A resin composition.