JPS603099B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic polyester copolymer composition, and more particularly to a method for preventing craze of an aromatic polyester copolymer molded article composed of terephthalic acid, isophthalic acid, and bisphenols. The present invention relates to an aromatic polyester copolymer composition containing an organic carboxylic acid metal salt and a phosphite compound.

Mixtures of terephthalic acid, isophthalic acid, or their functional derivatives (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is 1:9, 9:1) and bisphels represented by the following general formula ( However, 1X- is -01, 1S-, 1SO1, 1SQ-, 1CO1, alkylene group,
selected from the group consisting of alkylidene groups, R,, R2, R
3, R4, R',, R'2, R'3, R'4 are selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group)
Aromatic polyester copolymers consisting of these have been well known for a long time.

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

In other words, good mechanical properties such as tensile strength, bending strength, bending recovery rate, and impact strength, high thermal deformation temperature and thermal decomposition temperature, and electrical properties such as specific resistance, insulation breakdown, arc resistance, and dielectric properties. General molded products, films, fibers, and coated materials made by injection molding, extrusion molding, press molding, or other molding methods are excellent in terms of physical properties, combustion sacrifice, dimensional stability, and chemical resistance. It is expected to have a wide range of uses. Aromatic polyester copolymers have such excellent properties and are of great utility value, but their drawback is that crazes occur in molded products when they are left in hot water or steam for a long time.
The craze phenomenon has already been reported in the literature and elsewhere, and when aromatic polyester copolymers are treated with hot water or steam, turbidity occurs in part or the entire molded article. Although the reason for this phenomenon is not clear, it not only causes the molded product to lose its transparency, but also causes the molded product to form arms, resulting in lower impact strength, reduced elongation at break, and bending stress. This leads to the molded product being destroyed. Several methods are already known for preventing craze generation in aromatic polyester copolymers.

That is, polyethylene terephthalate is mixed and melted,
A method for making molded products (Hakama Sekisho 49-2 grade required publication, Tsubaki Sekisho 50-1 Ima No. 34), a method for making molded products by mixing and melting polybutylene terephthalate (Bō Kaisho 50-1 I 342)
(Japanese Patent No. 49-61244), or a method of mixing and melting an organic phosphorus compound and molding it (Japanese Patent Publication No. 49-61244). However, in either case, there was a drawback that the flame retardancy of the aromatic polyester copolymer was somewhat reduced. Furthermore, the present applicant has previously proposed an aromatic polyester copolymer composition containing a specific phosphite compound as Tsubaki Gansho 50-Mushihiragi No. 0P.

Molded articles obtained from this product are excellent in coloration prevention and craze resistance, but have the drawbacks of somewhat reduced flame retardancy and tensile impact strength. The present inventors have discovered that it is possible to create a molded product that maintains the mechanical strength and flame retardant properties of aromatic polyester copolymers, has little coloration, and has excellent craze resistance. Although the addition of a metal salt of an organic carboxylic acid causes some thermal decomposition of the aromatic polyester copolymer at high temperatures during melt extrusion and molding, resulting in coloring of the molded product, it has been found that it has an excellent effect in preventing craze. As a result of repeated studies, we found that all of the above-mentioned drawbacks of aromatic polyester copolymers could be overcome by using the above metal salt of an organic carboxylic acid in combination with the above-mentioned phosphite compound. , and arrived at the present invention.

That is, the present invention provides a combination of isophthalic acid and terephthalic acid or functional derivatives thereof (provided that the molar ratio of isophthalic acid groups to terephthalic acid groups is not 1:9, but 9:1), and -
Bisphenols represented by general formula (1) (however,
1×1 is -0-, 1SO2-, 1SO1, 1S1, 1C
O1, transparent from the group consisting of an alkylene group consisting of 1 to 4 carbon atoms, an alkylidene group, R,, R public R3, R4
, R',, R'2, R'3, R'4 are selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, and an alkyl group having 1 to 4 carbon atoms). 'B' is a metal salt of an organic carboxylic acid consisting of 2 to 4 carbon atoms (the metal is selected from the metals of groups 1, 2, 3 and 4 of the short periodic table), and [C' general A phosphite compound represented by formula (0) (wherein R5 and R6 are each independently a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, a polyhydric phenol residue, or a polyhydric alcohol group) Indicates a group in which a hydroxyl group remains, or a group in which at least one of the hydroxyl groups in these groups is a phosphite ester)
Therefore, the content of 'B' component is 0.0 with respect to the square component.
1 to 3.0% by weight, and the content of the 'C' component is 0.01 to 2.0% by weight relative to the component (■). % by weight of the resin composition.

In general, when using two or more types of additives in combination, it is difficult to even achieve an effect according to the mixing ratio, but molded products made of such resin compositions maintain flame retardancy, improve coloring during molding, and can be used with steam or hot water. It is surprising that not only does it not cause crazes and maintain good transparency even after being left to stand for a long period of time, but its mechanical strengths such as tensile strength, bending strength, and elongation at break are higher than when the phosphite compound is added alone. It is.

The method for producing the aromatic polyester copolymer used in the present invention is a so-called interfacial polymerization process in which aromatic dicarboxylic acid dichloride dissolved in an organic solvent incompatible with water and bisphenols dissolved in an alkaline aqueous solution are mixed and reacted. legal, solution polymerization method in which aromatic dicarboxylic acid chloride and bisphenols are reacted in an organic solvent, melt polymerization method in which aromatic dicarboxylic acid and bisphenols are heated in the presence of acetic anhydride, phenyl polymerization method of aromatic dicarboxylic acid Melt polymerization method of heating stell and bisphenols;
Examples include a melt polymerization method in which aromatic dicarboxylic acid and bisphels are heated in the presence of diaryl carbonate.

The molar ratio of the terephthalic acid group and the isophthalic acid group, which are the phthalic acid components of the aromatic polyester hollyhock polymer in the present invention, can be selected from a range of 9:1 to 1:9, preferably 7:3, none, to 3 The ratio is 7 to 7, more preferably 1 to 1.

In addition, as the dihydric phenol component, pisphenols represented by the general formula (1) are used, and the typical ones are 2,2-bis(4-hydroxyphenyl)-propane, 4,4'-propane, Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4
'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2-bis(4-hydroxy-3,5-dibromophenyl)-propane, 2.2
-bis-(4-hydroxy-3,5-dichlorophenyl)-propane, and these may be used alone or in combination of two or more.

The metal salt of organic carboxylic acid used in the present invention has 2 carbon atoms.
It is a metal salt of an organic carboxylic acid consisting of pine or pine and a metal belonging to Groups 1 to 4 of the short periodic table. The organic carboxylic acid used in the present invention refers to a polybasic acid having 1 to 4 carboxyl groups and up to 4 basic acids.

Typical organic carboxylic acids include acetic acid, monobasic acid,
Propionic acid, n-monobutyric acid, isobutyric acid, n-Pare IJ anoic acid, trimethylacetic acid, caproic acid, n-heptanoic acid, cabrylic acid, belargonic acid, lauric acid, stearic acid,
Fluoroacetic acid, Ch. chloroacetic acid, bromoacetic acid, dichloroacetic acid, trichloroacetic acid, chlorobropionic acid, glyulic acid, lactic acid, methoxyacetic acid, glyoxylic acid, acrylic acid,
Examples include phenylacetic acid, benzoic acid, toluic acid, chlorobenzoic acid, probenzoic acid, salicylic acid, cinnamic acid, naphthalene monocarboxylic acid, pyridine carboxylic acid, and quinoline carboxylic acid. Examples of dibasic acids include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. Examples of tribasic acids include trimellitic acid, and tetrabasic acids include pyromellitic acid. As the metal constituting the metal salt of the organic carboxylic acid used in the present invention, metals of Groups 1, 2, 3 and 4 of the short periodic table are used.
Particularly preferred metals include alkali metals such as lithium, sodium, and potassium, magnesium, calcium,
Examples include alkali metals such as barium, as well as zinc, cadmium, tin, and lead. 1st, 2nd, 3rd and 4th
In the case of metals other than the group metals, they have little effect on preventing craze and also cause thermal decomposition when melting the polymer, which is disadvantageous. All of the carboxyl groups of the polybasic organic carboxylic acid may be bonded to metals, or some of them may remain as carboxyl groups without forming a disk. In order to exhibit the effects of the present invention, the amount of the metal salt of the organic carboxylic acid contained in the aromatic polyester copolymer composition of the present invention is 0.01 to 34% relative to the aromatic polyester copolymer. A weight % range of 0.1 to 1.0 weight % is preferred.

By using such a small amount, craze prevention can be sufficiently achieved. Further, the use of a large amount is not preferable because rather than bringing about a significant improvement in craze prevention, it causes the properties of the molded article, particularly decomposition and coloring during molding, a decrease in heat resistance and durability, and a decrease in mechanical strength due to a decrease in molecular weight. On the other hand, if it is less than 0.01% by weight, it is not preferable because the craze prevention effect is poor. When such an aromatic polyester copolymer hybrid containing a metal carboxylate is melt-extruded into chips and then molded by injection molding or the like, the molded product is formed by thermal decomposition compared to a case where the metal carboxylate is not included. The degree of coloration is the same or somewhat greater.

This phenomenon is thought to be due to the fact that thermal decomposition is somewhat accelerated by the presence of carboxylic acid metal salts. The phosphite compound used in the present invention, which prevents this thermal decomposition, improves the color tone of the molded product, and also has a craze prevention effect without impairing the flammability and transparency of the molded product, is represented by general formula (0). . The structural formula of the representative compound is shown below. These compounds are mainly produced by the method shown in Synthesis Example 1. Synthesis Example 1 3 cycles of pentaerythritol, tristearylphosphite scales. After 4 days, 0.1% by weight of potassium carbonate was mixed with the total weight of the above two components as a catalyst, and the mixture was heated at 135°C.
I boiled it for 3 hours.

The main reaction component had the following structural formula, and the phosphorus content in the entire reaction mixture was 0.8%. Furthermore, as shown in Synthesis Example 2, a polymer such as a random copolymer consisting of two types of difunctional phenols, bentaerythritol and phosphate ester may also be used.

Synthesis Example 2 1240% of triphenyl phosphite, 272% of bentaerythritol, 110% of hydroquinone, 8% of 2,2-pis(4-hydroxyphenyl)-propane, and the total weight of the above four components as a catalyst. Yo.

To the solution, 0.1% by weight of potassium carbonate was added and heated at 135° C. for 3 hours. Furthermore, the phenol was removed under reduced pressure, and the theoretical amount of triphenylphosphite was approximately 100%.
% of phenol was recovered. This material is a polymer randomly containing the following structures [a} and 'b}, and the phosphorus content based on the total weight of the polymer is 17.2% by weight. The polymer structure has the following bonded structure'a
} and 'b- randomly. These phosphite compounds may be used alone or in combination of two or more.

When such a phosphite compound is used without the above-mentioned metal salt of organic carboxylic acid, it shows an effect of preventing coloring and preventing craze, but it causes a decrease in the mechanical strength of the molded product, and when used in a large amount, it becomes difficult. This results in a decrease in flammability.

Molded articles made from aromatic polyester copolymer compositions that use a combination of the anti-craze effect and flame retardancy due to the metal salt of organic carboxylic acid, and the anti-craze effect and anti-coloration effect due to the phosphite compound have little discoloration. It maintains flame retardancy, significantly reduces the occurrence of crazes, and has almost no decrease in mechanical strength. Among these, the ability to maintain mechanical strength was particularly unexpected. The amount of the phosphite compound contained in the aromatic polyester copolymer composition of the present invention is determined by the coloring prevention effect, craze prevention effect, and reduction in flame retardance.
0.01 to 2.0 for aromatic polyester copolymer. % by weight, especially from 0.05 to 1. A range of % by weight is preferred.

The method of adding the metal salt of organic carboxylic acid and the phosphite compound to the aromatic polyester copolymer is not particularly limited, and they can be added in various steps.

For example, aromatic polyester copolymer is mixed with methylene chloride,
A solution of a phosphite compound dissolved in an organic solvent and a solution of a metal salt of an organic carboxylic acid dissolved in water or an organic solvent are mixed and concentrated into a solution dissolved in an organic solvent such as chloroform or benzene, and then the organic solvent or water is added. A method of heating and distilling, or a method of adding an organic carboxylic acid metal salt and a phosphite compound before or during melt extrusion, and a method of adding an organic carboxylic acid metal salt and a phosphite compound to aromatic polyester copolymer chips after melt extrusion. There are methods such as adding a compound. In order to impart heat resistance, weather resistance, and oxidation resistance to the composition comprising the aromatic polyester copolymer of the present invention, an organic carboxylic acid metal salt, and a phosphite compound, thermal decomposition inhibitors, ultraviolet absorbers, antioxidants, etc. may be made to exist as appropriate.

For these purposes, phosphorus compounds, benzotriazole compounds, benzophenone compounds, phenolic compounds, etc. are used. Furthermore, plasticizers, pigments, lubricants, etc. can also be used, and glass fibers can also be added to strengthen the material. In addition, the composition of the present invention can be applied to polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, polyethylene oxybenzoate, polycarbonate, polyethylene,
Contains one or more polymers such as polypropylene, polyamide, polyurethane, polystyrene, ABS, 8VA, polyacrylic acid ester, polytetrafluoroethylene methyl methacrylate, polyphenylene sulfide, rubber, etc. depending on the purpose. It may be something.

That is, in the present invention, a mixture of the aromatic polyester copolymer and the other polymers mentioned above can be used, and even in this case, the organic carboxylic acid metal salt and phosphite compound used in the present invention have a remarkable Show effectiveness. - The aromatic polyester copolymer composition of the present invention has excellent stability and moldability while retaining the advantages of conventional aromatic polyester copolymers. The molded article obtained from the resin composition of the present invention is 50 to 1
Even when exposed to hot water or water vapor at 00°C for a long time, craze generation is significantly prevented, molecular weight and mechanical strength are less reduced, and transparency is maintained.

Next, the present invention will be explained by examples.

Example 1 203 parts by weight of terephthalic acid dichloride and 2030 parts by weight of isophthalic acid dichloride were added to 6500 parts by weight of methylene chloride.
It was dissolved in 0 parts by weight at 20°C.

On the other hand, 456 parts by weight of 2,2-bis-(4-hydroxyphenyl)-propane, 1 part by weight of caustic soda, 6 parts by weight of para-tertiary butylphenol, and 2 parts by weight of trimethylbenzylammonium chloride were added to 1000 parts by weight of water.
00 parts by weight at 20°C. Both solutions were placed in a reaction vessel equipped with a homomixer and mixed vigorously at 20°C for 5 hours. The rope was stopped and the methylene chloride phase was separated, washed with ion-exchanged water until the washing water became neutral, and then acetone was added and dried to obtain a flaky polymer. Logarithmic viscosity of this polymer (25°C, phenol/tetrachloroethane 6/4 weight ratio mixed solvent, polymer concentration 1/d
') was 0.65. Various metal salts of organic carboxylic acids and phosphite compounds shown in Table 1 are added and mixed to the bound polymer flakes, and the mixture is melt-extruded to form chips.
Furthermore, a molded article was molded by injection molding.

The color tone and Fujiburn property of this molded article were examined, and the molded article was boiled for 24 hours in hot water at 10 pi, and the occurrence of crazes, changes in average molecular weight expressed by logarithmic viscosity, and changes in mechanical strength were examined before and after the boiling treatment. The results were as shown in Table 1.
In addition, the phosphite compound is represented by the following abbreviations.

The structural formula or content of each is as follows. P--1 P--2 P--3 P-Ko-4 P-5 Pentaerythritol 2. Random copolymer consisting of 2-bis-(4-hydroxyphenyl)-propane hydroquinone triphenyl phosphite (see Synthesis Example 2) ) Table 1 Here, the molded product color tone represents the degree of coloration by numerical rank, and the larger the number, the greater the degree of coloration.

The unit of tensile strength is k9'.
The flammability was determined by the flammability of a 1/16 inch thick molded article measured by Underwriters Laboratories Subject 94. All amounts added are weight % based on the aromatic polyester copolymer. No. As shown in No. 1, when no additive is included, significant craze occurs during hot water treatment.

When metal salts of organic carboxylic acids are added, NO. 2.No.
10, No. 25, NO. As shown in No. 30, it has the effect of preventing craze, maintaining mechanical strength, and maintaining flame retardancy, but the color tone of the molded product is the same or slightly worse than that without additives. On the other hand, the addition of phosphorus compounds was No. As seen in No. 4, the color tone of the molded article is improved, but the mechanical strength and flame retardance are reduced. Compared to using a metal salt of an organic carboxylic acid or a phosphorus compound alone, using both together can improve craze while maintaining flame retardancy and mechanical strength, and improve the degree of coloration of molded products. Compete based on most of the results in Table 1. However, No. ONo. 21,
No. As shown in Fig. 23, as the amount of organic carboxylic acid metal salt added increases, the coloring of the molded article changes.

Claims (1)

[Scope of Claims] 1 (A) A mixture of isophthalic acid and terephthalic acid or their functional derivatives (provided that the molar ratio of isophthalic acid groups to terephthalic acid groups is 1:9 to 9:1) and the general formula (I ) Bisphenols represented by ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (However, -X- is -O-, -SO_2-, -SO-, -
selected from the group consisting of S-, -CO-, an alkylene group having 1 to 4 carbon atoms, and an alkylidene group, R_1, R_
2, R_3, R_4, R'_1, R'_2, R'_3,
R'_4 is hydrogen atom, chlorine atom, bromine atom, carbon number 1-
(B) an aromatic polyester copolymer consisting of an alkyl group (selected from the group consisting of 4 alkyl groups), and (B) a carbon number of 2
a metal salt of an organic carboxylic acid consisting of ~22 (the metal is selected from metals of Groups 1, 2, 3, and 4 of the short periodic table), and (C) a phosphite compound represented by general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_5,
R_6 each independently represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, a polyhydric phenol residue, or a polyhydric alcohol residue with a remaining hydroxyl group, or a residue thereof. At least one of the hydroxyl groups in the group is a phosphite ester), the content of component (B) is 0.01 to 3.0% by weight relative to component (A), and (
The content of component C) is 0.01 to 2.0 relative to component (A).
% by weight of the resin composition.