JPS60173042A - Resin composition and production of molding therefrom - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which has excellent resistance to heat and chemicals, and moldability and suffers little discoloration during molding, consisting of a polyarylate, an aliph. polyhydric alcohol ester and a metal salt of an org. carboxylic acid. CONSTITUTION:A mixture (a) consisting of terephthalic and isophthalic acids in a molar ratio of 10/0-0/10 is reacted with dihydric alcohols (b) of formulas I and II (wherein X is a bivalent group selected from among a 1-10C alkylene, a 5-10C cycloalkylene, cycloalkylidene, -O-, -S-, -CO- and -SO2-; R1, R2 are each a monovalent group selected from among a 1-20C alkyl, aryl, aralkyl, alkoxyl and arylalkoxyl; m, n are each 0, 1; when m=1, nnot equal to 0; p, q are 0-4) in a molar ratio of 0.1-0.99 to obtain a polyarylate (A). 0.01-1pt.wt. aliph. polyhydric alcohol ester (e.g. glycerol monostearate) and 0.01-1pt.wt. metal salt of an org. carboxylic acid (e.g. magnesium stearate) are blended with 100pts.wt. component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition having excellent heat resistance and moldability, comprising a polyarylate, an aliphatic polyhydric alcohol ester, and an organic carboxylic acid metal salt, and a method for producing a molded product thereof. . In detail, dihydric phenols represented by the following general formula (I), terephthalic acid, isophthalic acid (however, terephthalic acid, isophthalic acid,
Polyarylate 1 consisting of iso=1010~0/10)
00 parts by weight, (wherein,
2- divalent group selected from Rt, Rz; carbon number 1-2
0 alkyl, allyl, aralkyl, alkoxyl,
1 selected from alkoxyl and allyl alkoxyl groups
Value group, m + n; an integer of 0 or 1, provided that when m = 1, n represents an integer of 0.1), QiO ~ 4) aliphatic polyhydric alcohol ester 0.01 to 1 part by weight and organic carboxylic acid The present invention relates to a resin composition comprising 0.01 to 1 ffi parts of a metal salt and having a high heat distortion temperature and improved moldability.

Polyarylates have been known for a long time. The first method for producing it is the interfacial polymerization method, that is, the method of mixing aromatic dicarboxylic acid civalide dissolved in an organic solvent that is incompatible with water and bisphenols dissolved in an alkaline aqueous solution (Japanese Patent Publication No. 4 O-1959). ), and the second is a solution polymerization method, that is, a method in which aromatic dicarboxylic acid halides and bisphenols are reacted together in an organic solvent (Japanese Patent Publication No. 1987-
5599), and the eighth method is a transesterification method in which phenyl esters of aromatic dicarboxylic acids and bisphenols are heated (Japanese Patent Publication No. 88-15247; Japanese Patent Publication No. 4B-28119).
), or a method using a phase transfer catalyst.

The aromatic polyester polymer thus obtained has excellent properties in terms of heat resistance, mechanical properties, and electrical properties, and can be used in a wide range of applications, such as molded products, films, and fibers, either as a melon aggregate alone or as a resin composition. It is something that has.

The polymer used in the present invention can be produced by the various methods described above. However, this polymer has poor moldability from the viewpoint of extrusion or injection molding, and requires high plasticizing temperatures and injection pressures.

Furthermore, coloring during molding cannot be ignored.

Several methods have been proposed to improve the moldability of polyarylates. For example, from the viewpoint of blending with other resins, polypropylene
, ethylene-acetic acid picopolymer (48-51947),
Polyethylene (48-51948), polycarbonate (48-54158), polyethylene terephthalate (48-54159.58-51247), polystyrene (48-51049), polyacrylate (49-21452), polyamide (5O -4146)
, polyethylene oxybenzoate (same 5O-5448
), polytetrafluoroethylene (5O-5444)
, polybutylene terephthalate (5O-84842)
, polyester (5O-64851), polyether ester (5O-82161), etc. In addition, regarding the addition of low molecular weight compounds such as molding aids, trialkyl (aryl) phosphite (48-51047)
,) Realyl phosphate (49-85456)
, phosphite (49-85458.52-165
58.52-100551.52-152954), arylphosphonic acid diester (5l-87145),
Ester compound (49-81449.49-8874
2.49-90848.49-129747゜50-2
2858.51-87146.5l-188740),
Examples include diphenyl sulfone (49-86488), aliphatic amide (5O-51152), and metal salts of organic carboxylic acids (52-152958).

However, in general, blending with other resins may have a certain effect on improving moldability, but it may not improve other physical properties.
For example, there is a significant decrease in heat distortion temperature, transparency, and impact resistance, making it difficult to maintain the original performance of polyarylate. Generally speaking, the amount of a low molecular weight compound used can be smaller than that of a resin blend, but as the amount added increases, moldability is improved, but chemical resistance, heat distortion temperature, etc. are impaired. Therefore, in order to improve moldability, it is desirable to add as little amount as possible.

As a result of intensive research in order to overcome these drawbacks, the present inventors have discovered that additives can be produced by using aliphatic polyhydric alcohol esters and organometallic carboxylic acids together, and by improving their usage methods. The present invention was based on the discovery that the amount of use of can be reduced. The resin composition of the present invention not only maintains the high heat distortion temperature inherent to polyarylate, but also exhibits little coloring during molding and has excellent chemical resistance.

The polyarylate used in the present invention is as described above (IJ
It consists of dihydric phenols represented by the formula and terephthalic acid/isophthalic acid (tere/iso = 1010 to 0/lO molar ratio), but preferably the dihydric phenols have the following (
■) and (IIIJ formula) (However, ■)/([1)+Q[D=0.
1-0.99).

(In the formula, Xp R1* R2+ m y n is the same as above, p.

q is an integer satisfying 1≦p+q≦8). More preferably,
The formula (2) is expressed by the following formula ([V).

R4R6 (In the formula, R3 to R6 are the same +X as R1 and R2, and m is the same as above.) Examples of such dihydric phenols (IN) include bis(4
-hydroxyphenyl)methane, l, 1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, 4,4-dihydroxydiphenyl ether, 4,4-
Examples include dihydroxydiphenyl sulfide. Further, as an example of dihydric phenol (2), 2,2-bis(8,5
-dimethyl-4-hydroxyphenyl)propane, 2.
2-bis(8,6-di-5ec-butyl-4-hydroxyphenyl)propane, 2,2-bis(8,5-sheet t
ert-j thi-4-hydroxyphenyl)propane,
Bis(8,5-dimethyl-4-hydroxyphenyl)methane, 1,1-bis(8,5-dimethyl-4-hydroxyphenyl)ethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl) ) cyclohexane, bis(8
, 5-dimethyl-4-hydroxyphenyl)sulfone,
Bis(8,5-dimethyl-4-hydroxyphenyl)ketone, bis(8,5-dimethyl-4-hydroxyphenyl)ether, bis(8,5-dimethyl-4-hydroxyphenyl)sulfide, 2,2-bis(8,5-dimethyl-4-hydroxyphenyl)ether, bis(8,5-dimethyl-4-hydroxyphenyl)sulfide, ;x.

(a,5->methyl-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(8,5-dimethoxy-4-hydroxyphenyl)propane, bis(8,5-
dimethoxy-4-hydroxyphenyl)methane, 2,2
-bis(8-methoxy-4-hydroxy-5-methylphenyl)propane, bis(8-methoxy-4-hydroxy-5-methylphenyl)methane, bis(8,5-diphenyl-4-hydroxyphenyl)methane, 2,2-bis(8,5-diphenoxy-4-(hydroxyphenyl)propane, bis(8-phenoxy-4-hydroxy-
Examples include 5-methyl)methane, 4,4-dihyethylbiphenyl, and the like.

In addition, condensed polycyclic bisphenols such as dihydroxynaphthalene and dihydroxyanthracene, bisphenols such as alizarin, phenolphthalein, fluorescein, naphthophthalein, thymolphthalein, olin, feu/-rusulfophthalein, and dibromophenolsulfophthalein. Norphthylmethane, 4,4-dihydroxydinaphthyl 1.1' -bis(4-hydroxynaphthyl)-
Dinaphthyl compounds such as 2.2.2-trichloroethane and 2.2-dihydroxydinaphthyl-phenyl-methane can also be used as part of the bisphenols.

Usually, in place of a part of these dicarboxylic acid components and bisphenol components, -functional compounds are used for controlling the molecular weight. For example, phenol, methoxyphenol,
Monophenols such as t-butylphenol, octylphenol, and nonylphenol, monothiophenols, acid chlorides, and amines are used.

The preferred molecular weight of the polymer is an intrinsic viscosity of 0.50 to 0.7.
0 de/f (at 82° C. in chloroform).

Aromatic polyester coated with such a groove structure (
2)) The component represented by the formula is, compared to conventional commercially available products,
Provides superior properties in terms of water resistance and alkali resistance. However, despite having a high heat distortion temperature, the melt fluidity during molding is low, resulting in coloring of the molded product.

The aliphatic polyhydric alcohol ester compound used in the present invention is preferably one in which the polyhydric alcohol component is selected from ethylene glycol, propylene glycol, chrycerin, neopentyl glycol, pentaerythritol, and sorbitol. In addition, the acid component has 2 or more carbon atoms.
Selected from 80 aromatic or aliphatic carboxylic acids.

Specifically, benzoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, melisic acid,
Examples include montanic acid. More specific examples include glycerin monostearate, glycerin tristearate, hydroxystearic acid triglyceride, neopentyl glycol dibenzoate, glycerin tribenzoate, pentaerythritol tetrabenzoate, ethylene glycol monostearate, and the like. The amount of aliphatic polyhydric alcohol ester to be used is 0.01 to 1 part by weight per 100 parts of polyarylate.・.

The carboxylic acid gold g4 salt used in the present invention has 10 carbon atoms.
It is a metal salt of 80 aliphatic carboxylic acids and gold scrap belonging to Groups 2 to 4 of the short periodic table. Specific examples of preferred carboxylic acids include uric acid, myristic acid,
Examples include palmitic acid, stearic acid, cerotic acid, melisic acid, and montanic acid. Preferred metals include magnesium, calcium, barium, zinc, lead, tin, and cadmium. The amount of carboxylic acid metal salt used in the present invention is 0.01 to 1 part by weight per 100 parts by weight of polyarylate.

Next, the present invention also relates to a compounding method for effectively utilizing the effects of these compounds. That is, first, when extruding polyarylate into chips, an aliphatic polyhydric alcohol ester is melt-mixed. Next, the chip and the organometallic carboxylate are melt-mixed when forming a molded article by injection molding, extrusion molding, or the like. By using such a method, compared to the case where all the components are melt-mixed when forming extrusion chips, the amount of each additive used can be reduced, or even more if the amount used is the same, as shown in the examples. We have found that polymers with a certain molecular weight can be used.

Generally, the smaller the amount of additives added to the polyarylate molded article, and the higher the polymer molecular weight, the better the properties such as heat resistance and chemical resistance. Although the mechanism of action is not necessarily clear, it is thought that aliphatic polyhydric alcohol esters act on polyarylates in an internally lubricating manner, and organic carboxylic acid metal salts act in an externally lubricating manner.

The addition of these compounds to the polyarylates of the present invention
Therefore, it is done in stages. For blending with aliphatic polyhydric alcohol ester, polyarylate granules or powder are used in a U-type blender, Henschel mixer, super mixer, kneader, etc. Next, a ribbon blender or the like is used to blend the melt-extruded chips with the organic carboxylic acid metal salt.

In order to further improve heat resistance, weather resistance, oxidation resistance, etc., a small amount of antioxidant, anti-aging agent, and light stabilizer may be added to the aromatic polyester polymer composition of the present invention. If it is desired to impart flame retardancy, various conventionally known flame retardants can be added. Further, it can be reinforced by adding inorganic fibers such as glass fibers and metal whiskers, carbon fibers, organic fibers, and the like.

It goes without saying that coloring can be done by adding dyes, pigments, etc., and it is also possible to use inorganic fillers.

Furthermore, it is also possible to create compositions with various characteristics by blending them with other resins.

The aromatic polyester composition of the present invention thus produced has a wide range of uses as molded articles, films, and sheets for mechanical parts, electrical parts, etc. by various molding methods.

Hereinafter, the present invention will be explained by examples, but it is not limited only by these examples.

Reference example 1 Production of boary arylate -Tetramethylbisphenol F124.57f.

Paramethoxyphenol 9.9'lf, sodium hydrosulfide 2.64F, 4N-NaOH96
0d and 1660 g of water were mixed in an 81 flask in a N2 atmosphere and cooled to 2°C to prepare an alkaline aqueous solution of bisphenol. Meanwhile, in another 81 flask, 274.05 F of terephthalic acid chloride.

Isophthalic acid chloride 80.45F to methylene chloride 2
500+++/ in an N2 atmosphere and cooled to 2°C.

81 In a separable flask, 1000 g of water/.

Benzyltributylammonium chloride as catalyst 0
．． 47f was placed in an N2 atmosphere and cooled in the same manner. While stirring this vigorously, add 800% each of the above two liquids.
Addition was made continuously by pump over a period of seconds. Six hours after the completion of the addition, 4.22 g of benzoyl chloride was added to the system dissolved in 100 g/methylene chloride. After 20 minutes, stirring was stopped, and after about 10 minutes, the mixture was separated into a methylene chloride solution containing the polymer and an aqueous solution containing common salt and sodium hydroxide. After decanting the aqueous layer, the same amount of water was added and the mixture was neutralized with a small amount of hydrochloric acid while stirring. After repeated desalination by water washing, the same amount of acetone was gradually added to the methylene chloride solution to precipitate the polymer to obtain a powder. The molecular weight of the polymer was ηsp/c=0.70 (0.82 dl/1/ in chloroform at 82°C).

Examples 1 to 2, Comparative Examples 1 to 8 100 parts by weight of the polyarylate prepared in the same manner as in Reference Example 1 and the aliphatic polyhydric alcohol ester shown in Table 1 were blended in a Henschel mixer, and then melted at 880°C. Extrusion was performed to obtain pellets. Next, the organic carboxylic acid metal salts shown in Table 1 were uniformly blended into the pellets, and the mixture was heated at 860°C.
A test piece (dumbbell No. 1) was obtained by injection molding.

As is clear from Table 1, Examples 1 and 2 of the present invention require a smaller total amount of additives than the comparative example, have a higher heat distortion temperature, and are less colored during molding. On the other hand, a sufficient molded article could not be obtained unless 1 part by weight of glycerin monostearate alone and 0.7 part by weight of magnesium stearate alone were used.

Table 1 (Note) a) Measurement conditions Based on ASTM 648, load was 18.6 #/d.

Claims (1)

[Scope of Claims] (1) A resin composition containing 0.01 to 1 part by weight of aliphatic polyhydric alcohol ester and 0.01 to 1 part by weight of organic carboxylic acid metal salt per 100 parts by weight of polyarylate. thing. (2) A patent claim in which the polyarylate is a polymer consisting of a dihydric phenol represented by the following general formula (I), terephthalic acid, and isophthalic acid (however, tere/iso = 1010-0/10 molar ratio) The composition according to item 1. (In the formula, , R1゜R
2i Monovalent group selected from alkyl, allyl, aralkyl, alkoxyl, alkoxyl and allylalkoxyl groups having 1 to 20 carbon atoms, m, fi; Q or an integer of 1, provided that when m = 1, nAO1p, qRing 0~
Indicates an integer of 4. ) (3) The dihydric phenol component is a mixed component of the following general formulas (II) and (2) (however, the molar ratio (
The resin composition according to claim 2, wherein II)/(II)+ side -〇, 1 to 0.99). (In the formula, X + R1+ R2+ m, n is the same ip as above, Q is l≦1) and represents an integer of 10Q≦8. )(4
) The resin composition according to claim 8, wherein the dihydric phenol (2) is represented by the following general formula (IV). (In the formula, R3-R6 are R, R2 are the same + The composition according to claim 1, which is an ester consisting of a selected alcohol. (6) The aliphatic polyhydric alcohol ester has 2 to 8 carbon atoms.
The composition according to claim 1, which is an ester consisting of a carboxylic acid selected from zero aromatic or aliphatic carboxylic acids. (7) The composition according to claim 1, wherein the carboxylic acid used in the organic carboxylic acid metal salt is an aliphatic carboxylic acid having 10 to 80 carbon atoms. (8) The composition according to claim 1, wherein the metal used in the organic carboxylic acid metal salt belongs to Groups 2 to 4 of the short periodic table. (9) After uniformly melt-kneading 100 parts by weight of polyarylate and 0.01 to 1 part by weight of aliphatic polyhydric alcohol ester, the mixture is extruded into pellets, and then 0.01 to 1 part by weight of an organic carboxylic acid metal salt is melt-kneaded. A method for producing a molded article using a resin composition, characterized in that O1-1 Jushabu is blended with the pellets.