JPS5849575B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition, more specifically a mixture of terephthalic acid and isophthalic acid or their functional derivatives (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9) and bisphenols (hereinafter referred to as polyarylate copolymer) and polyarylene polyether, improvements in the molding ratio and chemical and physical properties. The present invention relates to a resin composition prepared by the present invention.

Polyarylate copolymers produced from terephthalic acid, isophthalic acid, or functional derivatives thereof, and bisphenols or functional derivatives thereof have been well known for a long time.

As a method for producing such a polyarylate copolymer, so-called interfacial polymerization (W.M.Ear.
eckson. J, Poly, Sci. XL,
3 9 91959, Japanese Patent Publication No. 40-1959), Solution polymerization in which aromatic dicarboxylic acid chloride and bisphenols are reacted in an organic solvent (A. Cont)
(,Ind, Eng. Chom, ,5 1]
4 7-1 9 5 9, Special Publication No. 37-5599),
Melt polymerization of aromatic dicarboxylic acids and bisphenols in the presence of acetic anhydride, melt polymerization of phenyl esters of aromatic dicarboxylic acids and bisphenols (
Methods such as Japanese Patent Publication No. 38-15247) and melt polymerization of aromatic dicarboxylic acids and bisphenols in the presence of diaryl carbonate (% Japanese Publication No. 43-28] 19) are known.

It is also well known that polyarylate copolymers obtained by such methods have many excellent properties.

In other words, mechanical properties such as tensile strength, bending strength, bending recovery rate, and sanitary strength, thermal properties such as heat distortion temperature and thermal decomposition temperature, specific resistance value, dielectric breakdown, arc resistance, dielectric constant, and dielectric loss, etc. General molded products that have excellent electrical properties, flammability, dimensional stability, and chemical resistance, and are made by injection molding, extrusion molding, press molding, or various other molding methods. Film, fiber and coating materials are expected to have a wide range of applications.

As mentioned above, polyarylate copolymers have many excellent properties, have great utility value, and have good moldability, allowing ordinary injection molding and extrusion molding.

However, in general, when it comes to polymers, especially plastics, moldability occupies an important position in the evaluation of the polymer itself.
It has always been desired to have better moldability.

The present inventors have arrived at the present invention as a result of intensive research to further improve the moldability of polyarylate copolymers, and the composition of the present invention can be used in scales with improved moldability. In addition, while retaining most of the advantages of the original polyarylate copolymer, the defects of polyarylate copolymer, which are the stress cracks and small cracks caused by harsh environments, are significantly improved, and the high hardness and good transparency are improved. It has the advantage of retaining gloss and gloss, and this fact is far superior to what would be expected from the single component constituting the composition.

The term "severe environmental stress cracks and cracks" refers to the types of organic solvents, such as acetone or carbon tetrachloride, which are accelerated by the presence of such solvents when the solvent is brought into contact with stressed parts made of polyarylate copolymers. means the destruction of

The novel resin composition of the present invention is a mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is from 9:1 to 9:9).
Bisphenols represented by the general formula (where -x-ito-
, -s -, -so2-, -co- and an alkylene group, an alkylidene group, and R1 y R2
p R3 y R4 s R'1 t R'2 t
R'3 and R'4 are each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group) and polyarylene polyether, and the polyarylate copolymer is 10 parts by weight of polyarylene polyether per 100 parts by weight of polymer
The composition has a composition ratio of 0 parts by weight or less.

Therefore, the first objective of the present invention is to improve the moldability of polyarylate copolymers, and the second objective is to prevent environmental stress cracks and small cracks while maintaining the excellent properties of polyarylate copolymers. The goal is to make it even more resistant.

In order to improve this resistance to environmental stress cracking, the present inventors have conducted various studies and hereby present a method for improving the resistance to environmental stress cracking without deteriorating the desirable properties of polyarylate copolymers. They discovered this.

Moreover, it is surprising that other properties of polyarylate are simultaneously improved by this method.

The polyarylate copolymer used in the present invention is
It is produced from terephthalic acid and isophthalic acid, or their functional derivatives, and bisphenols, and either interfacial polymerization or melt polymerization can be used as the production method.

In the present invention, in which a mixture of terephthalic acid groups and isophthalic acid groups is used as the acid component, the molar ratio of terephthalic acid groups to isophthalic acid groups is in the range of 9:1 to 1:9.

The bisphenols used in the present invention are represented by the general formula -X1 is 10-, -S--so2-, -co-, or an alkylene group or an alkylidene group.

R1 t R2 t R3 y R4 y R'1 +
Spots, R′3 and Fe41″i hydrogen atoms, halogen atoms,
selected from the group consisting of hydrocarbon groups.

Examples of such bisphenols include 4,4/1-dihydroxy-diphenyl ether, 4,4'dihydroxy-2,2'-dimethyl-diphenyl ether,
4/-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-diphenyl sulfide. 4t4'-dihydroxy-diphenyl sulfone, 4,4l-dihydroxy-diphenyl ketone, 4,
4'-dihydroxydiphenylmethane, 1,]-bis(4-hydroxyphenyl)monoethane, 2,2-bis(4-hydroxydiphenyl)propane, ],1-bis(4-hydroxyphenyl) )-n-butane, bis(4-
hydroxyphenyl) monocyclohexylmethane, 1,
1-bis(4-hydroxyphenyl)-2,2.2-}
Examples include lychloroethane, but the most commonly produced and representative one is 2,2-bis(4-hydroxyphenyl)-propane, which is called bisphenol A.

If necessary, two or more of the above bisphenols or bisphenols and small amounts of other divalent compounds such as glycols, aliphatic dicarboxylic acids, phosgene, etc. can be used.

The thermoplastic polyarylene polyether used in the present invention is a linear thermoplastic polymer having a basic structure composed of repeating units having the following formula (% Kosho 49-7799).

-0-E-E'- (1)(]
) In the formula, E is preferably a residue of a dinuclear phenol having the structure of formula (2) below, and B/ is preferably a residue of a penzenoid compound having a structure of formula (3) below,
Both residues E and E' are valently bonded to the etheric oxygen via an aromatic carbon atom.

The dinuclear phenol used here has the structure It can be characterized by having the following.

In the above formula, Ar is an aromatic group, preferably a phenylene group, Y and Y1 are an alkyl group having 1 to 4 carbon atoms,
a halogen atom, i.e. fluorine, chlorine, bromine or iodine, or 1
are the same or different inert substituents, such as alkoxy groups having ~4 carbon atoms, r and 2 are integers having a value of O ~ 4, and R is a substituent between aromatic carbon atoms, such as in dihydroxydiphenyl. or represents a bond of an inorganic group such as an alkylene group, an alkylidene group, a cycloaliphatic group or a halogen, alkyl, aryl or similar group substituted alkylene group, an alkylidene group, a cycloaliphatic group and an alkyl-substituted cycloaliphatic, alkyl group. Represents a divalent group such as a rylene group, an aromatic group, and a divalent organic hydrocarbon group such as a ring fused to a r group.

Examples of specific divalent dinuclear phenols include, among others, bis(hydroxyphenyl)alkanes such as 2,2-bis-(4-hydroxyphenyl)propane, bis(2-hydroxyphenyl)propane,
-hydroxyphenyl)methane, 1,]-bis-(4-
hydroxy-2-chlorophenyl)ethane, 2,2-bis(4-hydroxynaphthyl)propane, 2,2-bis-(4-hydroxyphenyl)hebutane, etc.; di(hydroxyphenyl)sulfone, fLL is bis( 4-hydroxyphenyl) sulfone, 5'-chloro-4,4/-
Hydroxydiphenyl sulfone, etc.; di(hydroxyphenyl) ether, examples include bis(4-hydroxyphenyl) ether, 4. 3'-dihydroxydiphenyl ether, 4,2'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 2,
3'-dihydroxydiphenyl ether, bis-(4-
hydroxy-3-promphenyl) ether and similar materials.

The present invention also contemplates the use of mixtures of two or more different dihydric phenols to achieve similar objectives as described above.

Thus, in the above discussion, when there is an E residue in the polymer structure, it may actually be the same or a different aromatic residue.

Preferred penzenoid compound residues E used herein
' can be obtained from any dihalopenzenoid compound or mixture of dihalopenzenoid compounds having the structure shown below.

Here, x and x'ci are halogens, and R is an electron withdrawing group, which can be used as an activating group.

As R, the following divalent groups can be mentioned.

where X is hydrogen or halogen] or difluorobenzoquinone, 1.4- or 1.5= or 1.
A divalent group capable of activating a halogen on the same ring as in 8-difluoranthraquinone.

If desired, mixtures of two or more dihalopenzenoid compounds each having this structure and having different electron withdrawing groups can be used to form the polymer.

Thus, the E groups of the penzenoid compounds in the polymer structure may be the same or different.

Also, the symbol E' defined as "residue of a penzenoid compound"
It will also be appreciated that when used herein it means the aromatic or penzenoid residue of the compound after removal of the halogen atom on the penzenoid nucleus.

From the above explanation, it is preferable that the linear thermoplastic polya IJ ++
It is clear that the rene polyether is one in which E is the residue of a dinuclear dihydric phenol and E' is the residue of a dinuclear benzenoid compound.

These preferred polymers therefore have the formula It is composed of repeating units with .

In the above formula, R is selected from the group consisting of bonds between aromatic carbon atoms and divalent bonding groups, and V is sulfone, carbonyl, vinyl, sulfoxide, azo, saturated fluorocarbon, organic phosphine oxide, is selected from the group consisting of ethylidene groups, and Y and Y1 each represent a halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and r and 2 is 0-4
is an integer with value .

Even more preferred are those in the above formula in which r and 2 are zero and R is selected from the group consisting of divalent bonding radicals lyl and halogen substituents thereof; and R" is a sulfonic group. It is a thermoplastic polyarylene polyether.

Regarding the composition ratio of the polyarylate copolymer and polyarylene polyether, 100 parts by weight or less of the polyarylene polyether is used per 100 parts by weight of the polyarylate copolymer.

When the amount of polyarylene polyether exceeds 100 parts by weight, the composition has improved properties in terms of moldability and resistance to environmental stress cracking, but transparency is undesirably reduced.

In the present invention, the polyarylate copolymer and polyarylene polyether may be mixed by any known method.

For example, the granules or powders of both are mixed in a type blender, Henschel mixer, super mixer, seconder, etc., and then molded directly, or mixed in a molten state using an extruder, co-kneader, intensive mixer, etc. It may also be made into chips and molded.

There is also a method of mixing solutions of both polymers and then removing the solvent. In either case, it is preferable to adopt an appropriate method depending on the composition ratio of the composition and the desired shape and properties of the product.

In order to improve the heat resistance, light resistance and oxidation resistance of the composition of the present invention, a thermal decomposition inhibitor, an antioxidant or an ultraviolet absorber may be present in the composition.

These may be present in each polymer before mixing, may be present in both polymers, or may be added when both polymers are mixed.

Other plasticizers, pigments, lubricants, etc. can also be used in the present composition, and glass fibers can also be added to strengthen the composition.

The composition obtained according to the present invention can be used in the form of powder, chips, or other forms to make various useful products by commonly known plastic molding methods such as press molding, injection molding, and extrusion molding.

Examples of such products include gears, bearings, electrical products,
It is widely used in containers and other products, and is used in a wide range of applications as an engineering plastic product that requires high performance.

Furthermore, the properties of the molded article can be further improved by heat treatment.

In order to further understand the present invention, examples will be described using a typical combination of a polyarylate copolymer of terephthalic acid/isophthalic acid and bisphenol A and a polyarylene polyether.

Example 1 A polyarylate copolymer is produced by an interfacial polymerization method using a methylene chloride solution of a mixed acid chloride having a ratio of terephthalic acid dichloride/isophthalic acid dichloride of 1:1 and an alkaline aqueous solution of bisphenol A.

The logarithmic viscosity of this in phenol/tetrachloroethane (6:4, weight ratio) was 0.65.

To 70 parts by weight of this polyarylate copolymer powder, 30 parts by weight of a powdered polyarylene polyether synthesized from 2-2-bis(4-hydroxyphenyl)propane and dichlorodiphenyl sulfone was added in a ■-type blender for 2 hours. Mixed.

This was extruded and cut using an extruder of 40 m71 Lφ and L/D=18 to obtain chips.

The melt viscosity of this chip was measured using a Koka type float tester.

The results are shown in the following table, and the melt viscosity of the composition of the present invention is lower than that of the polyarylate copolymer alone, which indicates that the composition of the present invention has good carpability.

Example 2 A polyarylate copolymer was produced in the same manner as in Example 1. 100 parts by weight of the polyarylate copolymer was mixed with 100 parts by weight of the polyarylene polyether produced in the same manner as in Example 1, and chloroform was added. A transparent and sticky film was obtained by casting the solution and evaporating the solvent.

Environmental (solvent) stress cracking tests were conducted by cutting the film into strips, creasing them, and then immersing them in acetone.

The creased film was then removed from the solvent, dried, and then repeatedly folded and stretched at the crease.

The samples did not crack during these tests. When similar tests were conducted on films made of polyarylate copolymer alone and polyarylene polyether alone, cracks occurred during immersion in acetone.

Example 3 The polyarylate copolymer of Example 1 and the polyarylene polyether used in Example 1 were mixed in the proportions shown in the table below, and after drying, the mixture was heated to 320 0C using an extruder.
pelletized.

Using this pellet, an injection molding machine is used to mold the product to a thickness of 1/8 inch.
A test piece with a width of 2 inches and a length of 5 inches was molded.

The obtained test piece was placed horizontally between two supports so that the span interval was I00rft711, and a load was applied to the center of the specimen, and the specimen was lifted from the horizontal plane by 3. 20°C when pressed down 2 mm
The sample was immersed in carbon tetrachloride for 1 minute.

The presence or absence of cracks in the treated test piece was visually observed.

The results are shown in the table below, and it was found that the composition of the present invention had better resistance to environmental stress cracking than the polyarylate copolymer* alone.

Example 4 The polyarylate copolymer of Example and the polyarylene polyether used in Example were mixed in the proportions shown in the table below, dried, and pelletized at 320°C using an extruder.

This pellet was injection molded at 300° C. to form a test piece with a thickness of 1 to 100 ml, and the transparency of this test piece was observed with the naked eye.

The results are shown in the table below, and it was found that the composition of the present invention had better transparency than that of the comparative example.

Claims (1)

[Claims] 1. A mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is 9: ] to ]:9) and bisphenols represented by the general formula ( However, -X- is -o-
, -s-, -so2-, -co or alkylene group,
selected from the group consisting of alkylidene groups, R1j R2
J R3J R49 R1t R29 R3 P and R4 are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group) and an aromatic polyester nonpolymer obtained from the formula group, E' is a residue of a penzesoid compound, and both of the above residues are valently bonded to etheric oxygen via an aromatic carbon atom]
A linear thermoplastic polyarylene polyether composed of repeating units having Resin composition.