JPS6241253B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aromatic polyester compositions.
More specifically, the present invention relates to an aromatic polyester composition particularly excellent in long-term heat resistance and moist heat resistance. Aromatic polyesters derived from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid or their ester-forming derivatives and bisphenols or their ester-forming derivatives have been conventionally known. Such aromatic polyesters have, for example, good mechanical properties such as tensile strength, bending strength, impact strength, and bending recovery, high heat distortion temperature and thermal decomposition temperature, excellent heat resistance, and other electrical properties. Due to its excellent flammability, it is expected to be used in a wide variety of molded products. However, the aromatic polyester has a defect in that it is inferior in moist heat resistance and long-term heat resistance, and improvement thereof is desired. The present inventor focused on this point, and determined the mechanical properties, heat distortion temperature, electrical properties, and
As a result of intensive study to improve moist heat resistance and long-term heat resistance without sacrificing excellent properties such as flammability, the objective was achieved by combining and adding specific amounts of oxetane compounds and phosphorus compounds. Based on this knowledge, we have arrived at the present invention. That is, the present invention provides an aromatic polyester having an aromatic dicarboxylic acid as the main acid component and an aromatic dihydroxy compound as the main diol component, and 0.01 to 5% by weight of oxetane represented by the following formula () based on the aromatic polyester. Compound and 0.01~
The present invention relates to an aromatic polyester composition containing 5% by weight of a phosphorus compound represented by the following formula (). formula(): [In the formula, R ₁ and R ₃ are each a hydrogen atom, alkyl, alkoxy, aryloxy, or aryloxyalkyl, R ₂ and R ₄ have the same meaning as R ₁ and R ₃ , or -CH ₂ R′ (-
_CH2X )n (where R' is a diol residue or isocyanuric acid residue, n is 1 or 2, and

[expression] or

[Formula] (R ₅ is the same as R ₁ and R ₃ ), provided that any two of R ₁ to _{R 4} are the above groups other than hydrogen atoms. ] Formula (): [In the formula, m is 0 or 1, R ₆ and R ₇ are each a hydrogen atom, hydroxyl group, alkyl, aryl, alkoxy or aryloxy, and R ₈ is the same as above or

[Formula] (where R ₆ , R ₇ , m are the same as above, R″ is alkylene). However, R ₆ to _{R 8} are all hydrogen atoms or hydrogen atoms and alkyl having 3 or less carbon atoms. The aromatic polyester used in the present invention is a dicarboxylic acid (or an ester-forming derivative thereof) mainly consisting of an aromatic dicarboxylic acid and a diol (or an ester-forming derivative thereof) mainly consisting of an aromatic dihydroxy compound. It is a homopolymer or copolymer derived from. Examples of the aromatic dicarboxylic acids constituting the main acid component include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, etc. These can be used alone or in combination of two or more. Among these, terephthalic acid and isophthalic acid are preferred, and in particular, terephthalic acid and isophthalic acid are used in a molar ratio of 1:9 to 1:9. It is preferable to use them in combination so that the ratio is 9:1. Examples of acid components other than aromatic dicarboxylic acids include aliphatic or alicyclic dicarboxylic acids such as hexahydroterephthalic acid, sebacic acid, adipic acid, etc. The content of these aliphatic or alicyclic dicarboxylic acids is preferably 40 mol% or less, more preferably 30 mol% or less of the total acid component.Also, as the aromatic dihydroxy compound constituting the main diol component of the aromatic polyester,
For example, 2,2-bis(4-hydroxyphenyl)
Propane [bisphenol A], 1,1-bis(4-hydroxyphenyl)cyclohexane [bisphenol Z], 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4' -dihydroxydiphenylketone, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-
Examples include hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxyphenylmethane, hydroquinone, and 4,4'-dihydroxydiphenyl. These can be used alone,
Moreover, two or more types can also be used in combination.
Among these, bisphenol A is particularly preferred. Examples of diol components other than aromatic dihydroxy compounds include ethylene glycol,
Examples include aliphatic or alicyclic dihydroxy compounds such as trimethylene glycol, tetramethylene glycol, and the like. The content of these aliphatic or alicyclic dihydroxy compounds is preferably 40 mol% or less, more preferably 30 mol% or less, of the total diol component. The aromatic polyester may be produced by conventionally known methods, such as interfacial polymerization, solution polymerization, and melt polymerization. The degree of polymerization of aromatic polyester is 0.3 when the reduced specific viscosity is measured at 35°C at a polymer concentration of 1.2 g/dl in a mixed solvent of phenol/tetrachloroethane (60/40: polymerization ratio).
It is preferably 0.4 or more, particularly 0.5 or more. In the present invention, the oxetane compound to be blended into the aromatic polyester is an oxetane compound represented by the above formula (), and is a group that reacts with the aromatic polyester under the melting conditions of the aromatic polyester and has an adverse effect such as a decrease in molecular weight. For example, it does not have a hydroxy group, a carboxyl group, an ester group, etc. In the above formula (), alkyl is methyl, ethyl, etc., alkoxy is butoxy, aryloxy is phenoxy, orthochlorophenylphenoxy, orthophenylphenoxy, etc., and aryloxyalkyl is phenoxymethyl, Preferred examples can be given for each. Further, R' is a diol residue or an isocyanuric acid residue, and preferred examples of the diol include ethylene glycol and bisphenol A. Specifically, preferred oxetane compounds include, for example, 2-ethyl-
2-phenoxymethyloxetane, 3-ethyl-
3-phenoxymethyloxetane, 2-ethyl-
2-(orthochlorophenylphenoxy)oxetane, 3-methyl-3-butoxyoxetane, 2
-ethyl-2-phenoxyoxetane, 2-ethyl-2-orthophenylphenoxyoxetane,
Ethylene glycol bis(3-methyl-3oxetanemethyl) ether, ethylene glycol bis(2-ethyl-2oxetanemethyl) ether,
Bisphenol A bis(2-ethyl-2oxetanemethyl)ether, tris(2-ethyl-2oxetanemethyl)isocyanurate, tris(3
-methyl-3oxetane methyl) isocyanurate, and the like. These oxetane compounds are
It is preferable that the polyester has a boiling point higher than the melting temperature of the polyester. These oxetane compounds can be used alone or in combination of two or more. The amount of the oxetane compound used is 0.01 to 5% by weight, preferably 0.05 to 3% by weight, particularly preferably 0.05 to 3% by weight based on the aromatic polyester.
It is 0.1 to 2% by weight. If the amount of the oxetane compound used is too small, the effect of the present invention will not be fully exhibited, and if it is too large, decomposition, coloring, etc. will occur during molding, which is not preferable. Further, the phosphorus compound used in the present invention is a compound represented by the above formula (). In the above formula (), alkyl is methyl, ethyl, butyl, etc., aryl is phenyl,
Preferred examples of alkoxy include methoxy, butoxy, 2-ethylhexyloxy, stearyloxy, lauryloxy, etc., and preferred examples of aryloxy include phenoxy, cresyloxy, etc. Preferred examples of the alkylene for R'' include pentaerythritylene. Examples of such phosphorus compounds include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphousulfonous acid, phosphinous acid, phosphin, and phosphin oxide. Or these derivatives include triphenyl phosphite, tributyl phosphite, tris-2-ethylhexyl phosphite, trisstearyl phosphite, triphenyl phosphate, tristearyl phosphate, trimethyl phosphate. , tributyl phosphate, phenylfuosfunic acid, dilauryl phosufinate, diphenyl phosufinate, diphenyl ethyl phosufinate, dimethyl methyl phosufonate, dicresyl phosufonate, diphenyl phosufonate, diphenyl phosufonate, phenyl phosufonate Examples include distearyl acid, pentaerythrityl bis(methyl phosphite), triphenyl phosphin, tributyl phosphin, etc.These may be used alone or in a mixture of two or more.The amount of the phosphorus compound depends on the aromatic polyester. Against
It is 0.01 to 5% by weight, preferably 0.05 to 3% by weight, particularly preferably 0.1 to 2% by weight. The polyester composition of the present invention may optionally include glass fiber, carbon fiber, asbestos, talc,
Fillers such as potassium titanate, carbon black, etc.; various additives such as flame retardants, antioxidants, heat stabilizers, lubricants, antistatic agents, colorants, etc.; or other polymers such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate,
polystyrene, polyethylene, polypropylene,
Can be blended with AS, ABS, rubber, etc. Any conventionally known method can be used to produce the composition of the present invention. For example, an aromatic polyester, an oxetane compound, a phosphorus compound, and if necessary other additives, V
Mix with a mold blender, mixer, kneader, etc.
Direct injection molding method: These can be manufactured by melt extrusion using an extruder. The composition of the present invention can be prepared by conventional molding methods such as injection molding,
It can be easily formed into molded products such as plastics, films, fibers, pulp, etc. by extrusion molding, press molding, etc. The molded article made of the composition of the present invention not only has the excellent properties inherent to aromatic polyester, but also
Excellent long-term heat resistance and moist heat resistance. The present invention will be explained below with reference to Examples, in which all "parts" indicate parts by weight. Examples 1 to 3 and Comparative Example 1 203 parts of terephthalic acid dichloride and 203 parts of isophthalic acid dichloride were dissolved in 5000 parts of methylene chloride, while 456 parts of bisphenol A, 168 parts of sodium chloride, 5 parts of P-t-butylphenol and trimethyl 2.5 parts of benzyl ammonium chloride was dissolved in 10,000 parts of water, and then both solutions were vigorously mixed and stirred using a mixer for about 6 hours. Next, the organic layer was separated, thoroughly washed with water, dried, and concentrated to obtain a polymer. The reduced specific viscosity of this polymer was 0.72. Next, 100 parts of this polymer were mixed with predetermined amounts of an oxetane compound and a phosphorus compound shown in the table below, and a sheet having a thickness of about 1 mm was formed by melt extrusion.
Reduced specific viscosity of the obtained sheet, the sheet was heated to 170℃
The table shows changes in physical properties when the sheet was left in a gear aging tester for 200 hours and the occurrence of glaze when the sheet was left in steam at about 90°C for 100 hours.

[Table] Example 4 and Comparative Example 2 In Example 1, the amount of terephthalic acid dichloride was
A polymer was obtained in exactly the same manner except that the amount of isophthalic acid dichloride was changed to 162.4 parts and 243.6 parts. The reduced specific viscosity of the polymer was 0.78. Next, 1.5 parts of tris(2-ethyl-2oxetanemethyl)isocyanurate and 0.2 parts of triphenyl phosphate were mixed with 100 parts of this polymer, and the mixture was melt-extruded and formed into cylindrical chips with a diameter of about 1 mm and a length of about 2 mm. did. The reduced specific viscosity of the composition thus obtained was 0.75. Next, this chip was heated to 140°C using an autoclave.
The reduced specific viscosity was measured after being immersed in water at ℃ for 1 day and the reduced specific viscosity was 0.71. For comparison, the same treatment as above was carried out without adding any oxetane compound or phosphorus compound.
The reduced specific viscosity of the chips decreased from 0.76 to 0.42. Examples 5 to 9 and Comparative Example 3 318 parts of diphenyl terephthalate, 318 parts of diphenyl isophthalate, 479 parts of bisphenol A, and 0.07 part of titanium tetrabutoxide were charged into a reactor equipped with a stirrer, and the phenol produced by the reaction was removed from the system. Heated to 320℃ while distilling it off to 30℃ under normal pressure.
minutes, then the pressure in the system was gradually reduced to about 0.5 mmHg in absolute pressure after 10 minutes, and the reaction was further carried out under this pressure for 60 minutes to obtain a polymer with a reduced specific viscosity of 0.73. Next, predetermined amounts of the oxetane compound and phosphorus compound shown in the table below were added and mixed to 100 parts of this polymer.
Chips were obtained by melt extrusion. Heat this chip to 140℃
The chips were immersed in warm water for one day, and changes in reduced specific viscosity of the chips were measured. The results are shown in the table below. Further, for comparison, the same procedure as in the above example was carried out except that the oxetane compound and the phosphorus compound were not used. The results are also shown in the table below.

【table】

Claims (1)

[Scope of Claims] 1. An aromatic polyester containing an aromatic dicarboxylic acid as the main acid component and an aromatic dihydroxy compound as the main diol component, which is expressed by the following formula () in an amount of 0.01 to 5% by weight based on the aromatic polyester. An aromatic polyester composition containing an oxetane compound represented by the formula (2) and 0.01 to 5% by weight of a phosphorus compound represented by the following formula (). formula(): [In the formula, R ₁ and R ₃ are each a hydrogen atom, alkyl, alkoxy, aryloxy, or aryloxyalkyl; R ₂ and R ₄ have the same meaning as R ₁ and R ₃ or -CH ₂ R′ (-CH ₂ X) n (where R' is a diol residue or an isocyanuric acid residue, n is 1 or 2,
X is [Formula] or [Formula] (R ₅ is the same as R ₁ and R ₃ ): However, any two of R ₁ to R ₄ are the above groups other than hydrogen atoms. ] Formula (): [In the formula, m is 0 or 1, R ₆ and R ₇ are each a hydrogen atom, a hydroxyl group, alkyl, aryl, alkoxy, or aryloxy; R ₈ has the same meaning as above or [Formula] (where R ₆ and R ₇ are Same as above, R″ is alkylene). However, R ₆ to _{R 8} are not all hydrogen atoms or hydrogen atoms and alkyl having 3 or less carbon atoms.]