JPS60104155A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition composed of a specific polyarylate and a polyphenylene oxide, having excellent compatibitily, improved moldability and high mechanical properties and thermal resistance, and formable by stretch forming. CONSTITUTION:The objective resin composition contains (A) a polyarylate wherein <=95(mol)%, preferably <=80% of the whole acid component is terephthalic acid residue and >=25%, preferably >=40% of the whole glycol component is a bisphenol residue of formula I (X is O, S, SO2, etc.; R1-3 are H, halogen, alkyl, etc.) and (B) a polyphenylene oxide of formula II (A is substituted or unsubstituted aromatic group) or a polymer containing said polyphenylene oxide in an amount of preferably >=50wt%. The weight ratio of A:B is 10:90-90:10, preferably 20:80-80:20.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition, and more particularly to a resin composition comprising a specific polyarylate and polyphenylene oxide and exhibiting excellent compatibility. The purpose is to improve the moldability of polyphenylene oxide while maintaining high heat resistance and mechanical properties.
The present invention also provides a resin composition that can be stretched.

Polyphenylene oxide in a wide range.

Although it has attracted attention as a resin with excellent chemical, physical and electrical properties, it has the disadvantage that it is extremely difficult to mold it alone due to its low melt fluidity due to its monomolecular structure. In addition, since this polymer has a high melting point or softening point, it is necessary to raise the temperature during molding processing to a considerably high temperature, and many of the additives, including polyphenylene oxide itself, deteriorate or decompose during melt molding, resulting in molded products. It tends to significantly reduce physical properties and impair the appearance.

Therefore, in the molding process of polyphenylene oxide, lowering the molding temperature as much as possible and improving the flow characteristics is not only to improve moldability but also to control the decline in physical properties due to thermal deterioration.

It is extremely important in the development of its applications.

Conventionally, in order to improve the molding processability of such polyphenylene oxide, many compositions have been known that are made by combining low molecular weight plasticizers, low melt viscosity resins, etc. However, although most of these compositions improve fluidity, On the other hand, no material has been obtained that is satisfactory due to a significant decrease in physical properties. For example, polystyrene blends are important as they are one of the most important contributors to the practical application of polyphenylene oxide.

In this case, the mixed composition of the two has extremely good compatibility, so that a transparent molded article is obtained, and the glass transition point (hereinafter referred to as Tt) is the same. Hence, strength, elongation.

Although it has excellent mechanical properties such as elastic modulus, and greatly improves flow customization and processability, the T2 of the added polystyrene
Since the temperature is low ((105°C)), the temperature customization of the mechanical properties of the composition is significantly reduced because it is an amorphous polymer.

Since this composition is a combination of amorphous polymers, it cannot be formed into a film or fiber by ordinary stretching processing, and its uses are greatly limited.

On the other hand, the polymers to be added include crystalline and highly processable polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6 and nylon 6.6, and polyethylene terephthalate.

Compositions containing polyesters such as polybutylene terephthalate have poor compatibility, so it is impossible to obtain a composition that does not exhibit a single TV and provides a transparent molded product. For this reason, the higher the mixing ratio of crystalline polymer to polyphenylene oxide, the more the mechanical properties such as strength, elongation and elastic modulus decrease significantly, and the appearance is also poor, with the color being milky white to white, resulting in a transparent molded product. I can't. Furthermore, molded articles made of such compositions have the fatal drawback of not being able to be stretched, which greatly limits their use.

In view of the above circumstances, the present inventors have significantly improved the melt fluidity of polyphenylene oxide, which has good compatibility with polyphenylene oxide, has excellent transparency, provides a single T2, and has an amorphous polymer. The present invention was achieved as a result of intensive research in order to obtain a resin composition that has good mechanical and thermal properties and is stretchable by combining coalescent/crystalline polymers. That is, in the present invention, 95 molti or less of the total acid component is a terephthalic acid residue, and 25 molti or more of the total glycol component is a general formula CI) (However, in the formula, -X- is -0-t -5-t -802-
1-CO+.

R1-R8 are selected from the group consisting of alkylene groups, alkylidene groups, and substituents thereof, and R1-R8 are selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, substituted alkyl groups, cyano groups, alkoxy groups, phenoxy groups, and nitro groups. It will be done. ) Polyarylate consisting of bisphenol residues represented by The terephthalic acid residue is 95 molti or less, preferably 80 molti or less, and the terephthalic acid residue is 95 molti
If the melt viscosity of the polyarylate exceeds the molar mass, the melt viscosity of the polyarylate is too high.
This has the disadvantage that it is difficult to mold the composition with polyphenylene oxide. However, at the same time, the compatibility with polyphenylene oxide decreases, and furthermore, the crystallinity of the polyarylate itself is too high, making it difficult to form a composition! 11: This results in disadvantages such as a decrease in thermal properties, transparency, stretchability, etc.

The acid components other than terephthalic acid are aromatic.

A wide range of dicarboxylic acids and oxycarboxylic acids such as aliphatic acids can be used.

On the other hand, as a glycol component, bisphenols represented by the above general formula [1] are used at 25% of the total glycol component.
It is necessary to contain at least 40 molar units, preferably at least 40 molar units. If the amount of bisphenol M76X is less than 25 mol %, the compatibility with polyphenylene oxide will decrease, resulting in a disadvantage that various physical properties will be poor. Bisphenols that can be used include, for example, 4,4'-dihydroxydiphenyl ether, 4'4'-dihydroxydiphenylsulfine, 4,4'-dihydroxydiphenylsulfone (
Bisphenol S), 4.4'-dihydroxydiphenylketone, 4.4'-dihydroxydiphenylmethane, 4゜4'-dihydroxydiphenylpropane ([
Bisphenol A and bisphenol S are particularly preferred compounds, although a wide range of others can be used. Glycol components other than the above bisphenol may include hydroquinone, resorcinol, 2,6-hydroxytoluene,
2,6-hydroxynaphthalene, 2,2'-hydroxydiphenyl and other glycols can be used as the copolymerized glycol component.

Unlike polystyrene and the like, polyarylates having these compositions can be imparted with appropriate crystallinity, and therefore, the composition of the present invention is characterized in that it is custom-stretched. Therefore, the obtained stretched film has high transparency, and has excellent heat resistance and gas barrier properties.

The polyarylate used in the present invention can be obtained by various polymerization methods. For example, a melt polymerization method using an acetate ester of bisphenols and an acid component, a solution polymerization method in which dichlorophyte of a dicarboxylic acid and bisphenols are reacted in an organic melt in the presence of an amine as a deoxidizing agent, and a dichloride of a dicarboxylic acid and bisphenols. This method includes an interfacial polymerization method in which polycondensation is performed in the presence of an alkali after dissolving the two solvents in two mutually incompatible solvents. At that time, a catalyst, a stabilizer, a reformer, etc. can be used.

Furthermore, the polyphenylene oxide used in the present invention is represented by the general formula (■), more preferably the general formula [
■'] is indicated.

(-A-0-), 1 ...... Hit... (fl
, ) [wherein A is a substituted or unsubstituted aromatic group *
nrri positive integer] (wherein R9 to RI2 are the same or different hydrogen atoms,
A halogen atom, a hydrocarbon group, a substituted hydrocarbon group, a cyano group, an alkoxy group, a phenoxy group or a nitro method,
n is an integer indicating the degree of polymerization. ) Specific examples of R9-12 are hydrogen, chlorine, and bromine.

Iodine, methyl, ethyl, propyl, allyl, benzyl, methylbenzyl, chloromethyl, bromomethyl. Cyanoethyl, cyanide, methoxy, ethoxy, phenoxy,
Examples include nitro groups.

A specific example of polyphenylene oxide is:

For example, poly-2,6-dimethyl-1,4-phenylene oxide, poly-2,6-diethyl-1,4-phenylene oxide, poly-2,6-dipropyl-1,4-
Phenylene oxide, poly-2,6-simethoxy 1
, 4-7 dinylene oxide, poly-2゜6-cyclomethyl-1,4-phenylene oxide, poly-2,6
-dipromemethyl-1,4-phenylene oxide, poly-2,6-dichloro-1,4-phenylene oxide, and the like. Also.

A polymer containing polyphenylene oxide refers to polyphenylene oxide and 1 other than polyphenylene oxide.
Blends with one or more polymers or copolymers grafted with one or more polymers other than polyphenylene oxide are included. and t[polyphenylene oxide and styrene or styrene derivatives alone or co-polymerized, polycarbonate, polysulfone, polyamide, polyolefin, rubbery polymer, etc., or the following may be obtained by blending one or more of them, and It is also possible to polymerize the polymer on the other raw material in the presence of one polymer. Contains polyphenylene oxide fJttt
-t is preferably 50% by weight or more.

The blending ratio of polyarylate and polyphenylene oxide in the present invention is not particularly limited, and is appropriately determined depending on the purpose, use, etc., but from the viewpoint of stretch formability, heat resistance, etc. is preferable, and 20:80 to 80:20 is particularly preferable.

Various methods can be used for mixing polyarylate and polyphenylene oxide in the present invention. Examples include a method in which both powders or pellets are mixed and supplied, and then kneaded in an extruder, and a method in which both are dissolved in a solvent, wet-mixed, coprecipitated, and then the solvent is removed. The composition thus obtained can be formed into various maple molded parts, films, fibers, pipes, containers, etc. directly in the mixing process or once made into pellets.
It is also possible to perform a stretching process if necessary. Also,
It can also be used in coating agents, paints, impregnation agents, etc.

The composition of the present invention may contain various additives, such as light stabilizers and heat stabilizers, depending on the purpose, use, and other needs.

Dyes and pigments, mold release agents, crosslinking agents, reinforcing agents such as powdered reinforcing agents, fibrous reinforcing agents, sliding properties improvers, nucleating agents, flame retardants, flame retardant aids, conductive agents, antistatic agents, plasticizers, etc. Others.

Other resins and modifiers can also be blended as appropriate within a range that does not impair the gist of the present invention.

Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, in the examples, the term ``bu'' simply means ``Eizaibu''.

In addition, various physical properties were measured using the following method: Reduced viscosity of polyarylate (η81)/c) Polymer concentration Q, 4r/c) in a solvent of phenol/tetrachloroethane (6/4 double ffi ratio) dJ, measured at 30°C.

Flow rate i Using a chemical flow tester, the cylinder temperature was 95°C.
At a pressure of 250 kF/-, the amount of resin flowing out of a nozzle of 1 diameter x 8 rods (cQA/5ec) was measured.

Glass melting point (TVL bullet injection rate (E') die thickness 0
．． Discharge jd using a 5 Inn x width 50 mm nozzle
The composition was extruded for 4217 minutes at a cylinder and die temperature of 295°C to produce an unstretched film with a thickness of 300μ. E', E'', and tan δ were measured using a Toyo Baldwin Vigron L type in the range from room temperature to 250°C, and T1 and E' were determined. A comparative display of E' at

Tensile strength The above unstretched film was pulled at a speed of 20 m using an Instron.
/min.

Transparency The transparency of the unstretched film was visually observed and ranked as ◎〉○〉Δ〉△〉× in descending order of transparency.

Note: In the preparation of the above unstretched film, 90 to 1
Stretching was carried out by 5.2 times at a tensile rate of 24 nz for 7 minutes at 45°C. Ranking was performed in the same manner based on the ease of stretching and film properties.

Example work.

Acetate esters such as terephthalic acid, copolymerized acid, bisphenol, and copolymerized phenol were put into a reaction vessel together with a catalyst, and reacted for 60 minutes at 220 to 240°C under a nitrogen stream.Then, the temperature was raised to 285 to 315°C. , 0.1mHf
Nail condensation reaction was carried out for 90 minutes. The composition and reduced viscosity of the obtained polyarylate are shown in Table 1. 9~ in the table
121d is a comparative example.

Example 2゜2,6-dimethyl-1,4-phenylene oxide 75
5 m
It was dried at 120° C. for 12 hours under reduced pressure of Hf. Next, this was extruded at 305° C. using an extruder and kneaded. Using this sample, the flow rate was measured, and a film sample was prepared using a die, and the glass transition point (Tf), elastic modulus (E'), tensile strength, transparency, and stretchability were evaluated. In addition, as a comparative example, instead of polyarylate, polystyrene (molecular ff 180,000), polyethylene terephthalate (phenol/tetrachloroethane-6/4
Intrinsic viscosity measured at 30° C. 0.62) and t polyethylene (molecular jft 250,000.1) are also shown in the M amount ratio. These results are shown in Table 2.

Table 931 with blank spaces below TPA: Terephthalic acid I PA: Isophthalic acid AA: Adivic acid SA: Sebacic acid NDA: 2,6-naphthalenedicarboxylic acid DDA Nidodecanedionic acid FA: Fumaric acid OB: p-oxybenzoic acid BPA: Bisphenol A BPS: Bisphenol S HQ: Hydroquinone R8N Niresorcinol DBP: 4,4'-dihydroxybenzophenone DDE
: 4.4'-dihydroxydiphenyl ether DD
S: 4,4'-Dihydroxydiphenyl sulfide Table 2 Molded articles made from the composition of the present invention showed a single 12 and had excellent stretchability and transparency.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] 95 molti or less of the total acid component is terephthalic acid residue,
and 25 mol or more of the total glycol components are of the general formula [I] (wherein -X- is -0-* -5-1-802-*
-CO-i selected from the group consisting of alkylene groups, alkylidene groups and substituents thereof, R1-Rafi consisting of hydrogen atoms, halogen atoms, alkyl groups, substituted alkyl groups, cyano groups, alkoxy groups, phenoxy groups and nitro groups chosen from the group. ) Polyarylate fz from bisphenol residues represented by the general formula [...] MoA-0+n... Song... Song [■] (However, the middle person in formula 1 is a substituted or unsubstituted aromatic group. , n is a positive integer.) A resin composition characterized by being formed by combining polyphenylene oxide or a polymer containing polyphenylene oxide.