JPS6143654A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition having improved heat resistance and molding properties, obtained by blending an aromatic polyester consisting of an aromatic dicarboxylic acid and a bihydric phenol with a specific modified polyalkylene terephthalate composition. CONSTITUTION:(A) 100pts.wt. aromatic polyester consisting of a phenol shown by the formula I (X is 1-10C alkylene, -O-, etc.; R1 and R2 are 1-2C alkyl, etc.; m is 0, 1, or 9; q is 0-4) and an aromatic dicarboxylic acid is blended with (B) 0.1-50pts.wt., preferably 0.1-10pts.wt. modified polyalkylene terephthalate composition comprising B1: a polyalkylene terephthalate polymer(PET, etc.), and B2: a polyoxyalkylene compound shown by the formula II (R1 is H, etc.; R2 is 2- 4C aliphatic hydrocarbon; l is 0, or positive integer; R3 is H, etc.; m is 1-6), containing one ore more alkaline(earth) metallic salts of carboxylic acid, having 200-20,000 molecular weight, wherein an amount of metal is 0.001-2wt% based on total amounts of the components B1 and B2.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a novel polyester with excellent heat resistance and moldability, which is made of an aromatic polyester made of an aromatic dicarboxylic acid and a dihydric phenol, and a modified polyalkylene terephthalate composition. The present invention relates to a resin composition. In detail, dihydric phenols represented by the following general formula (1) and terephthalic acid, isophthalic acid (
However, for 100 parts by weight of an aromatic polyester consisting of tele/iso=1010 to 0/10, group, -0-t-8-, -00-2-Boz-, 几1 + R2 is an alkyl, allyl, aralkyl, alkoxyl, alkoxyl and allylalkoxyl group having 1 to 20 carbon atoms; a monovalent group selected,
ml n is an integer of O or 1j1, however, when m=1, neo,
p and q represent integers of 0 to 4) (a) a polyalkylene terephthalate polymer; and (b) at least one carboxylic acid metal salt in one molecule (however, the metal is an alkali metal or alkaline earth metal); A modified polyalkylene terephthalate composition 0 containing a polyoxyalkylene compound that grows R), and the amount of the metal is 0.001 to 2.0% by weight based on the total amount of (a) and (b). .1 to 60 parts by weight.

(Conventional technology) Aromatic polyesters have been known for a long time.

The first manufacturing method is an interfacial polymerization method, that is, a method in which aromatic dicarboxylic acid cybaride dissolved in an organic solvent that is incompatible with water is mixed with bisphenols dissolved in an alkaline aqueous solution (Japanese Patent Publication No. 40-1959). ), 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 (vj Kosho 87-5599), and the eighth is a method in which phenyl esters of aromatic dicarboxylic acids and bisphenols are reacted together. Transesterification method by heating
Several methods are known, such as 119) 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 articles, films, and fibers, either 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.

In order to improve the moldability of aromatic polyester,
Several methods have been proposed. Polyethylene terephthalate (JP 48-54159.58-5124
7), polyethylene oxybenzoate (same 5O-54
48), polyethylene terephthalate (5O-848)
42), polyester (5O-64851), polyether ester (5O-82161), and other resin blends.

(Problems to be Solved by the Invention) The present invention provides a novel method that has a greater effect with a small amount of addition, a higher heat distortion temperature, and superior mechanical strength than the above-mentioned disclosed technology in terms of moldability improvement. A resin composition is provided.

(Means for Solving the Problems) That is, the present invention provides for 100 parts by weight of an aromatic polyester comprising an aromatic dicarboxylic acid and a divalent phenolic compound, (a) a polyalkylene terephthalate polymer,
b) A polyoxyalkylene compound having at least one alkali metal salt or alkaline earth metal salt of carboxylic acid in one molecule, and the amount of the metal is (a) and (b).
b) A modified polyalkylene terephthalate composition of o, ooi to 2.0% by weight based on the total amount of
The contents include a resin composition containing 60 parts by weight.

The aromatic polyester used in the present invention is as described above (
1) Dihydric phenols and terephthalic acid/isophthalic acid (however, terephthalic acid/isophthalic acid (tere/iso 41010-0710)
(molar ratio), but preferably dihydric phenols are a mixture of those represented by the following α) and formula 0 (provided that 1)/(I)+(2)=0.1 ~0.
99).

(In the formula, X, 几1.几2.m, n are the same as above, p・q
l, tl≦p+q≦8). More preferably, the formula (1) is represented by the following formula (2).

(In the formula, Ra to Re are Rt, the same as R2, X+m
is the same as above) Examples of such dihydric phenol (II) include bis(4
-hydroxyphenyl)methane, 1.1-bis(4-hydroxyphenyl)ethane, 2.2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, 4.4'-dihydroxydiphenyl ether, 4.4
'-dihydroxydiphenyl sulfide, etc. In addition, as an example of dihydric phenol 0, 2,2-bis(8,6
-dimether-4-hydroxyphenyl)propane, 2,
2-bis(a,5-di-5ea-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dit
art-)-F Ru 4-hydroxyphenyl)propane, bis(8,5-dimethyl-4-hydroxyphenyl)methane, 1,1-bis(8,5-dimethyl-4-hydroxyphenyl)ethane, 1,1 -bis(8,5-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)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-5-methyl)methane, 4,4'-dihydroxy-8,8C5,
5'-tetramethylbiphenyl, 4,4'-dihydroxy-a, 8', 5. Examples include gi-tetraethyl biphenyl.

Other condensed polycyclic bisphenols such as dihydroxynaphthalene and dihydroxyanthracene, bisphenolic pigments such as alizarin, phenolphthalein, fluorescein, naphthophthalein, thymolphthalein, ollin, phenolsulfophthalein, and dibromophenolsulfophthalein. , 2,2'-dihydroxy-1
, 1'-dinaphthylmethane, 4,4-dihydroxydinaphthyl-1゜1.2,2-dihydroxydinaphthyl-1
,1,1,1-bis(4-hydroxynaphthyl) -2
, 2,2-trichloroethane, 2,2-dihydroxydinaphthyl-phenyl-methane and other dinaphthyl compounds,
It can also be used as part of 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 mainly used.

The preferred molecular weight of the polymer is an intrinsic viscosity of 0.50 to 0.7.
It is in the range of 0dl/I (82°Q, in Ri00ho71zA).

In the present invention, the polyalkylene terephthalate polymer (a) is a dicarboxylic acid component in which at least 60 mol% is terephthalic acid, and at least 90 mol% is ethylene glycol, propane- 1
, 3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1゜6-diol, cyclohexane-1,4-dimetatool. , obtained by polycondensation. From an industrial standpoint, polyethylene terephthalate and polybutylene terephthalate are particularly preferred.

O of the dicarboxylic acid component of polyalkylene terephthalate
~10 monov% of other aromatic dicarboxylic acids having 6 to 14 carbon atoms, aliphatic dicarboxylic acids having 4 to 8 carbon atoms, or 8 carbon atoms
to 12 alicyclic dicarboxylic acids. Examples of such dicarboxylic acids include phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and the like. In addition, 0 to 10 mol% of the diol component is other aliphatic diol having 8 to 10 carbon atoms, other alicyclic diol having 6 to 16 carbon atoms, or 6 to 6 carbon atoms.
-12 aromatic diols.

Examples of such diols include 2,2-dimethylpropane-1,8-diol, 2,2-bis-(4'-hydroxycyclohexyl)-propane, 2,2-bis-
Examples include (4'-hydroxyphenyl)propane and hydroquinone. Furthermore, an oxycarboxylic acid such as ε-oxycaproic acid, hydroxybenzoic acid, etc. may be copolymerized in an amount of 10 mol % or less of the dicarboxylic acid component and diol component. Of course, the polyalkylene terephthalate may be branched with an octahydric or tetrahydric alcohol or an octabasic or tetrabasic acid. Examples of suitable branching agents include trimesic acid, trimellitic acid, trimethylolpropane, pentaerythritol, and the like.

In the present invention, the polyoxyalkylene compound (b) refers to the general formula α) (wherein 1 is hydrogen or an m-valent organic group, R2 is C2-0
4 aliphatic hydrocarbon group, l is 0 or a positive integer, R8 is a group containing hydrogen or a carboxylic acid metal salt, m is a positive integer of 1 to 6). Such a polyoxyalkylene compound is, for example, an ester of a monofunctional or polyfunctional alcohol of substantially polyoxyalkylene with a polyhydric carboxylic acid anhydride;
It can also be obtained by neutralizing with an alkali metal hydroxide or an alkali metal alcoholade, and for example,
1. Reacting a monofunctional or polyfunctional alcohol of substantially polyoxyalkylene with a monocarboxylic acid containing an alkali metal carboxylate or an ester-forming derivative thereof.
It can be obtained by Here, "substantially"
means that a part of the molecule may contain other elements or organic groups. Specific examples of such polyoxyalkylene compounds include mono- and di-:l-succinic acid ester sodium salts, mono- and di-fumaric acid ester potassium salts of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer, etc. , mono- and di(tetrabromo)phthalic acid ester sodium salts, mono- and di-trimellitic acid ester sodium salts, mono- and dichlorendic acid ester lithium salts, mono-trimellitic acid of monomethoxypolyethylene glycol, etc. Examples include ester sodium salt and mono(tetrabromo)phthalic acid ester sodium salt.

Furthermore, mono-, di-, tri-, or tetraphthalic acid ester sodium salts of glycerin-alkylene oxide adducts, trimethylolpropane-alkylene oxide adducts, and pentaerythritol-alkylene oxide adducts, and mono-, di-, tri-, or tetraphthalic acid ester sodium salts. (Tetra Pro)
Preferred compounds include phthalic acid ester sodium salts.

These alkali metal bases have the general formula (to)-6-X+
000M) n@ (However, X is a halogenated or non-halogenated aliphatic, alicyclic or aromatic hydrocarbon group, M is an alkali metal, n
is a positive integer from 1 to 5). When an alkaline earth metal salt is used instead of an alkali metal salt, it is natural that the carboxylic acid metal salt is represented by -00014.

Of course, the polyoxyalkylene compound is not limited to those exemplified above.

These may be used alone or in combination of two or more. Further, these can be used in combination with polyoxyfulkylene itself such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.

The molecular weight range of the polyoxyalkylene compound is 200~
20,000, particularly preferably 200 to 6,000 from the viewpoint of compatibility with polyalkylene terephthalate. The polyoxyalkylene compound nail has a metal content of o, ooi to 2,0% by weight based on polyalkylene terephthalate.
, preferably in an amount of 0.01 to 1.0% by weight.

The amount of the polyoxyalkylene compound used varies depending on its type, molecular weight, etc., but is usually 0.1 to 40% by weight, preferably 1 to 20% by weight, based on the modified polyalkylene terephthalate composition.

Copolymerization and/or mixing of such polyoxyalkylene compounds can be carried out by adding the polyoxyalkylene compound during the production of polyalkylene terephthalate and reacting or mixing it, or by mixing it with polyalkylene terephthalate in a mixing device such as an extruder. This can be achieved by a method of further performing a melt polycondensation reaction after mixing. Furthermore, it is also possible to subsequently subject the copolymer or mixture to a solid-phase polycondensation reaction.

The polyalkylene terephthalate polymer composition can be used in an amount of 0.1 to 60 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the aromatic polyester. Furthermore, if a higher heat distortion temperature is desired, it is preferable to use 0.1 to 8 parts by weight, but as shown in the examples, even such a small amount can significantly reduce the molding pressure during injection molding. In addition, the injection speed can be varied over a wide range, which is a very desirable effect in obtaining a molded body.

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 resin composition of the present invention.

Furthermore, in the present invention, flame retardancy can be further improved by incorporating a flame retardant.

Examples of the flame retardant to be used include compounds containing elements of Groups (1), (2), Ma, and (2) of the periodic table, with halogen compounds, phosphorus compounds, and antimony compounds being particularly preferred.

These can be used alone or in combination of two or more. Specific examples of the flame retardant include tetrabromobisphenol A or its derivatives, decabromodiphenyl ether, tetrabromophthalic anhydride, perchlorcyclopentadiene derivatives, triphenyl phosphate, and antimony trioxide. The blending amount of the flame retardant is 0 to 10 parts by weight per 100 parts by weight of the composition.

In the present invention, mechanical strength, heat resistance, and dimensional stability can be further improved by incorporating a granular or plate-like inorganic filler. Examples of the granular or plate-like inorganic fillers used include mica, kaolin, clay,
Examples include talc, asbestos, calcium silicate, calcium sulfate, and calcium carbonate, with mica and talc being particularly preferred. These may be used alone or in combination of two or more. The blending amount is 0 to 200 parts by weight per 100 parts by weight of the resin composition, and preferably 10 to 50 parts by weight when considering mechanical strength, heat resistance, and fluidity.

In the present invention, an LA# reinforcing agent can also be added to further improve heat resistance under high loads, strength at high temperatures, and dimensional accuracy. Examples of the fibrous reinforcing agent used include glass fiber, mineral fiber, carbon fiber, silicon carbide fiber,
Examples include boron carbide fibers, potassium titanate fibers, gypsum lam, etc., with glass fibers and mineral fibers being particularly preferred. In order to improve affinity with the aromatic polyester and modified polyalkylene terephthalate, an M-shaped reinforcing agent whose surface has been treated with a silane coupling agent or the like is preferably used. The blending amount of these m male enhancers is as follows: resin composition 1
0 to 200 parts by weight, heat resistance,
When considering strength, fluidity, etc., preferably 5 to 150
Parts by weight.

Conventionally known blending methods can be used for these blends.

(Effects of the Invention) The resin composition of the present invention thus produced is particularly preferred for injection molding, but can also be suitably used for extrusion molding and other various molding methods, and can be used for mechanical parts, electrical parts, etc. It has a wide range of uses as molded bodies, films, and sheets.

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

Reference Example 1 Production of polyarylate Bisphenol A44 o, t 5 y, s, s',
5.5'-Tetramethylbisphenol It' 247
．． 10 (1, para-t-butylphenol 81.2'
l, sodium hydrosulfide 5.28F, 4N
-1920 liters of NaOH scraps and 8820 liters of water were mixed in a 61 flask in a N2 atmosphere and cooled to 2°C to prepare an alkaline aqueous solution of bisphenol. Meanwhile, another 61
In a flask, add 548.1f of terephthalic acid chloride and 60.9f of isophthalic acid chloride to 500% of methylene chloride.
0al! Then, it was dissolved in a N2 atmosphere and cooled to 2°C.

151 In a separable flask, 2000 at of water and 0.9 benzyltributylammonium chloride as a catalyst.
41 was placed under a N2 atmosphere and cooled in the same manner.

While vigorously stirring the mixture, the above two liquids were added continuously using a pump for 800 seconds each. Six hours after the completion of the addition, 8.41' of benzoyl chloride was added to the system in which 8.41' of benzoyl chloride was dissolved in 100 ar of 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 neutralized with a small amount of hydrochloric acid while stirring. After repeated desalting by washing with water, the same amount of a7ton 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 = 0.60 (0.82 dt/f in chloroform at 82°C).

Reference Example 2 Production of modified polyalkylene phthalate composition In a 41 autoclave equipped with a stirrer, dimethyl terephthalate) 1942F (10 mol), ethylene glycol 18
66N (22 mol) and 2f of zinc acetate as a transesterification catalyst were added, and the transesterification reaction was carried out by heating and stirring at 160 to 210°C for 2 hours under a nitrogen atmosphere. After the theoretical amount of methanol has been distilled out, polyethylene with an average molecular weight of 870 is produced! J-5-iv-yltil:
c:x5-tv tool rfjX22.2 Of(0,06
mol) and triphenyl phosphate 2.1j as heat stabilizer
0.7y of antimony trioxide was added as a F% polycondensation catalyst. Subsequently, a polycondensation reaction was carried out at 270°C and 1<1 Torr.

The intrinsic viscosity of the obtained polymer was 0.60 dt/f (25°
C1 phenol/tetrachloroethane = l/12
1X amount ratio).

Reference Example 8 In place of polyethylene glycol sodium phthalate in Reference Example 2, polypropylene glycol trimellitic acid ester disodium salt 19.68F (with an average molecular weight of 656) was used.
A polymer having an intrinsic viscosity of 0.65 was obtained in the same manner as in Example 1 using 0.03 mol).

Examples The polymers of Reference Examples 1 to 8 were blended in the proportions shown in Table 1 using a Henschel mixer, and then melt-extruded at 290 to 880°C to obtain pellets. Then injection molded at 860°C,
A test piece was obtained. For comparison, polyethylene terephthalate (PE'l'), polybutylene terephthalate (P
B'l' ), polyethyleneoxybenzoate (PE
Tables 1 and 2 show the results of blending OB').

According to the present invention, by blending only one part of the modified polyalkylene terephthalate composition, the molding pressure was significantly lowered compared to Comparative Example 1 without blending, and the injection speed was also able to be increased by 80%. On the other hand, Comparative Examples 2 and 8.4 and Example 1.6 in which 10 parts each of PFtT, PBT, and PROB were combined.
Comparing the above, the comparative example requires a higher injection pressure, and the mechanical strength of the test piece has a lower impact value and
It can be seen that there is a significant decrease in the heat distortion temperature.

(Margin below)

Claims (1)

[Scope of Claims] (1) Based on 100 parts by weight of an aromatic polyester consisting of an aromatic dicarboxylic acid and a dihydric phenolic compound, (a)
It contains a polyalkylene terephthalate polymer and (b) a polyoxyalkylene compound having at least one alkali metal salt or alkaline earth metal salt of carboxylic acid in one molecule, and the amount of the metal is (i) A resin composition containing 0.1 to 50 parts by weight of a modified polyalkylene terephthalate composition in an amount of 0.001 to 2.0% by weight based on the total amount of (b). (2) The resin composition according to claim 1, which contains 0.1 to 10 parts by weight of the modified polyalkylene terephthalate composition based on 100 parts by weight of the aromatic polyester. (3) The resin composition according to claim 1, which contains 0.1 to 8 parts by weight of the modified polyalkylene terephthalate composition based on 100 parts by weight of the aromatic polyester. (4) The aromatic polyester is a polymer consisting of dihydric phenols represented by the following general formula (I), terephthalic acid, and isophthalic acid (however, tere/iso = 10/0 to 0/10 molar ratio). A resin composition according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, A divalent group selected from -CO-, -SO_2-, R_1 and R_2 are monovalent groups selected from alkyl, allyl, aralkyl, alkoxyl, allyloxyl and allyl alkoxyl groups having 1 to 20 carbon atoms,
m and n are integers of 0 or 1, however, when m=1, n≠o, p
, q represents an integer of 0 to 4. ) (5) The dihydric phenol component is a mixed component of the following general formulas (II) and (III) (however, molar ratio (II) / (II) + (III) = 0.1 to 0.99
) The resin composition according to claim 4. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, X, R_1, R_2, m, n are the same as above, p
, q represents an integer of 1≦p+q≦8. )(6) The resin composition according to claim 5, wherein the dihydric phenol (III) is represented by the following general formula (IV). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R_3 to R_6 are the same as R_1 and R_2, X,
(m is the same as above) (7) The resin composition according to claim 1, wherein 60% by weight or more of the polyalkylene terephthalate polymer is polyalkylene terephthalate. (8) The resin composition according to claim 7, wherein the polyalkylene terephthalate is selected from polyethylene terephthalate, polybutylene terephthalate, copolymers thereof, and mixtures thereof. (9) The polyoxyalkylene compound has the general formula (V)R
_1-[-(OR_2)-_lOR_3]_m(V)(
Here, R_1 is hydrogen or an m-valent organic group, R_2 is C
_2 to C_4 are aliphatic hydrocarbon groups, l is 0 or a positive integer, R_3 is a group containing hydrogen or a carboxylic acid metal salt, and m is a positive integer of 1 to 6. ) The resin composition according to claim 1. (10) The molecular weight of the polyoxyalkylene compound is 200
9. The resin composition according to claim 9, which has a molecular weight of 20,000 to 20,000. (11) The resin composition according to claim 1, wherein a polyoxyalkylene compound is copolymerized with a polyalkylene terephthalate.