JPH06172647A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition containing a polysulfone-based resin, a thermotropic liquid crystal polyester resin and a terminal alkaline metal- containing polyether sulfone, excellent in anisotropy, mechanical properties and processability and suitable for an electric and electronic component. CONSTITUTION:The objective resin composition is prepared by blending (A) 1 to 99 pts.wt. polysulfone-based resin composed of a thermoplastic aromatic polymer having a repeating unit derived from 4,4'-dichlorodiphenyl sulfone, etc., containing a sulfone skeleton structure in the molecule and excellent in heat resistance, (B) 99 to 1 pts.wt. thermotropic liquid crystal polyester resin composed of an aromatic dicarboxylic acid such as terephthalic acid, an aromatic diol such as 4,4'-dihydroxydiphenyl and others and (C) a polyether sulfone having a structure containing one or more terminal groups represented by formula R-OMe (R is a divalent hydrocarbon residue; Me is an alkaline metal) in an amount of 1 to 50 pts.wt. based on 100 pts.wt. total weight of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polysulfone resin,
The present invention relates to a resin composition comprising a thermotropic liquid crystal polyester resin and polyether sulfone having a specific structure.

[0002]

2. Description of the Related Art There are a great variety of engineering plastics on the market, and resins with excellent heat resistance and mechanical strength are widely used for electrical and electronic parts, automobile parts, precision machine parts, etc. according to their characteristics. There is. However, the demand for higher performance is increasing more and more, and in particular, polyesters composed of particularly rigid molecular chains and exhibiting optical anisotropy when melted (hereinafter sometimes referred to as LCP).
Is known to have low melt viscosity, good workability, excellent mechanical properties, and heat resistance.

However, these LCPs show a high degree of orientation in the molten state, resulting in anisotropy in mechanical properties, and in molded products, they are easily warped, their weld strength is weak, their surfaces are easily fibrillated, and they easily peel off. It also has practical drawbacks.

Various methods have been studied as a method for relaxing this anisotropy. For example, a method of filling glass fiber or an inorganic filler to alleviate the anisotropy has been devised, but in this method, the effect cannot be obtained unless it is filled by several +%, so
There is a problem in that the workability, which is a characteristic of CP, is sacrificed, and the fact that it cannot be used for a film or fiber due to the presence of a filler makes it practically insufficient.

Polysulfone-based resins also have characteristics such as high heat resistance, high rigidity at high temperatures, and good dimensional accuracy. In recent years, as a method of compensating for the drawbacks of LCP, it has been proposed to prepare a new material by mixing various polymers as a polymer alloy or a polymer blend. For example, in JP-A-56-115357, LCP and polyether ether sulfone ( PES) blending is being investigated.

However, in this simple blend, mechanical properties such as tensile strength and flexural modulus were not sufficient, and further improvement of anisotropy was not observed, which was not preferable. This is because the compatibility of the respective resins in the blend is poor, and even if the resins are thoroughly mixed, the respective resins are significantly separated.

[0007]

Although various methods have been studied and announced so far, there are few cases where LCP has been put into practical use, and products improved by filling fillers are products. Nothing more. This is because when the polymer is used alone, the polymer is highly oriented in the molten state, and as a result, the anisotropy becomes large.

Also in the case of blending with a polysulfone-based resin, LCP has poor compatibility, so that separation is large, and when formed into a molded product such as a film, the surface fibrillation is severe and cannot be practically used.

The present invention is to provide a composition which maintains excellent processability of LCP and has improved anisotropy and improved mechanical properties when blended with a polysulfone resin.

[0010]

Means for Solving the Problems The present invention is directed to a total of 1 to 99 parts by weight of a polysulfone resin (A) and 99 to 1 parts by weight of a thermotropic liquid crystal polyester resin (B) and components (A) and (B). At least one of the molecular terminals is 1 to 50 parts by weight of the polyether sulfone (C) having a structure of the following formula.

[0011]

[Chemical 2]

(Where R is a divalent hydrocarbon residue, Me
Is an alkali metal. )

The present invention will be further described below.

The polysulfone resin used in the present invention is
It is a thermoplastic aromatic polymer having a sulfone skeleton structure in the molecule and excellent in heat resistance, and is one of those called engineering plastics. For example, 4,
Polymers having repeating units derived from 4'-dichlorodiphenyl sulfone, more specifically, for example 4,
4'-dichlorodiphenyl sulfone and polysulfone having a repeating unit derived from bisphenol A. Further, a polymer having repeating units derived from 4,4′-dichlorodiphenyl sulfone and 4,4′-biphenol, which are called polyarylsulfones, is also exemplified. Usually, it has an ether group in addition to a sulfone skeleton in the molecule. The polysulfone-based resin is disclosed in, for example, JP-A-60-23448.

Commercially available products include polysulfone such as Udel and Mindel (both are trade names) manufactured by Amoco. As the polyaryl sulfone, there is Radel (trade name) manufactured by Amoco, and as the polyether sulfone, Victorex (trade name) manufactured by ICI.

The polysulfone-based resin used in the present invention removes these metals by washing or the like even if the intermediate in the production process contains an alkali metal salt of alcoholate or phenolate. In addition, the resin as the final product is substantially free of these metals.

The polysulfone resin of the above item (A) is mixed with the thermotropic liquid crystal polyester of the following item (B) in an amount of 1 to 99 parts by weight of the polysulfone resin (A) and the thermotropic liquid crystal polyester resin ( B) 99 to 1 part by weight (total 100 parts by weight). Desirably, the blending ratio is such that when one is used as a matrix in a two-component system, the other does not show a continuous layer.

The thermotropic liquid crystal polyester (B) used in the present invention is a thermoplastic meltable polymer which exhibits optical anisotropy when melted. Such a polymer exhibiting optical anisotropy when melted has the property that the polymer molecular chains take a regular parallel arrangement in the melted state. The properties of the optically anisotropic molten phase can be confirmed by a usual polarization inspection method using a crossed polarizer. A polymer that does not exhibit general melt anisotropy becomes isotropic in the molten state, but when it exhibits anisotropy in the melting process, it changes from a solid phase to an isotropic phase through an anisotropic liquid crystal phase.

The liquid crystal polyester also has mechanical anisotropy, that is, when it is injection-molded, the surface of the molded product is remarkably peeled and fibrillated, and the difference in the physical properties between the resin flow direction and the direction perpendicular to the direction. It can be confirmed by being large.

The thermotropic liquid crystal polymers are generally elongated, flattened, and composed of monomers that have a plurality of chain extension bonds that are either rigid or co-axial or parallel along the long chain of the molecule and in either parallel or parallel relationship. Manufactured.

Examples of the thermotropic liquid crystal polyesters include liquid crystal polyesters and liquid crystal polyester imides, and specifically (all) aromatic polyesters, polyester amides, polyester carbonates and the like. That is, as long as a plurality of ester bonds are contained in the molecule, the polyester is included in the category of polyester. A preferred polyester is an aromatic polyester.

In the thermotropic liquid crystal polyester used in the present invention, a part of one polymer chain is composed of polymer segments forming an anisotropic melt phase, and the remaining part does not form an anisotropic melt phase. Also included are polymers composed of polymer segments. Further, it also includes a composite of a plurality of thermotropic liquid crystal polymers.

Typical examples of the monomer constituting the thermotropic liquid crystal polyester include (a) at least one aromatic dicarboxylic acid, (b) at least one aromatic hydroxycarboxylic acid compound, and (c) aromatic diol compound. At least one compound, (d) (d1) aromatic dithiol, (d2) aromatic thiophenol, (d3) at least one aromatic thiolcarboxylic acid compound, (e) aromatic hydroxyamine, aromatic diamine system At least one kind of compound can be used. Although these may be configured independently, in most cases, (a) and (c), (a) and (d), (a)
(B) and (c), (a), (b) and (e), or (a), (b), (c) and (e) and the like.

The above-mentioned (a) aromatic dicarboxylic acid type compounds include terephthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid and 2,6-
Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,
4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenyl ether-3,
3'-dicarboxylic acid, diphenoxyethane-3,3'-
Aromatic dicarboxylic acids such as dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, 1,6-naphthalenedicarboxylic acid or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid,
Examples thereof include alkyl, alkoxy or halogen substitution products of the above aromatic dicarboxylic acids such as dimethyl terephthalic acid, ethyl terephthalic acid, methoxy terephthalic acid and ethoxy terephthalic acid.

(B) Aromatic hydroxycarboxylic acid compounds include aromatic hydroxy such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 6-hydroxy-1-naphthoic acid. Carboxylic acid or 3-methyl-4-hydroxybenzoic acid, 3,5
-Dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl -2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid,
2-chloro-4-hydroxybenzoic acid, 3-chloro-4
-Hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3
-Bromo-4-hydroxybenzoic acid, 6-hydroxy-
Alkyl, alkoxy or halogen substitution of aromatic hydroxycarboxylic acid such as 5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, 6-hydroxy-5,7-dichloro-2-naphthoic acid The body.

As the aromatic diol (c), 4,4 '
-Dihydroxydiphenyl, 3,3'-dihydroxydiphenyl, 4,4'-dihydroxytriphenyl, hydroquinone, resorcin, 2,6-naphthalenediol, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxyphenoxy) ethane, 3 Aromatic diols such as 3,3′-dihydroxydiphenyl ether, 1,6-naphthalene diol, 2,2-bis (4-hydroxyphenyl) propane and bis (4-hydroxyphenyl) methane, or chlorohydroquinone, methylhydroquinone, t-butyl Examples thereof include alkyl-, alkoxy- or halogen-substituted aromatic diols such as hydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcin, and 4-methylresorcin.

Examples of the aromatic dithiol (d1) include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol and 2,7-naphthalene-dithiol.

(D2) The aromatic thiophenol includes
4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol and the like can be mentioned.

Examples of the aromatic thiol carboxylic acid (d3) include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid and 7-mercapto-2-naphthoic acid.

(E) As aromatic hydroxyamine and aromatic diamine compounds, 4-aminophenol and N-
Methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine,
N, N, -dimethyl-1,4-phenylenediamine, 3
-Aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-
1-naphthol, 4-amino-4′-hydroxydiphenyl, 4-amino-4′-hydroxydiphenyl ether, 4-amino-4′-hydroxydiphenylmethane,
4-amino-4′-hydroxydiphenyl sulfide,
4,4'-diaminophenyl sulfide (thiodianiline), 4,4 'diaminodiphenyl sulfone, 2,5-
Diaminotoluene, 4,4'-ethylenedianiline,
4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), 4,
4'-diamino diphenyl ether (oxydianiline) etc. are mentioned.

The thermotropic liquid crystal polyester used in the present invention can be produced from the above-mentioned monomers by various ester forming methods such as a melt acidolysis method and a slurry polymerization method.

As for the molecular weight, that of the thermotropic liquid crystal polyester suitable for use in the present invention is about 200.
0-200000, preferably about 10,000-1000
00. The molecular weight can be measured, for example, by measuring the end groups of a compressed film by infrared spectroscopy. Alternatively, GPC, which is a general measurement method involving solution formation, can be used.

Among thermotropic liquid crystal polymers obtained from these monomers, aromatic polyesters which are (co) polymers containing the monomer unit represented by the general formula [I] as an essential component are preferable. It is preferable that the monomer unit contains about 5 mol% or more.

[0034]

[Chemical 3]

A particularly preferred aromatic polyester of the present invention is a polyester represented by the general formula [II] having repeating units each having a structure derived from three compounds of p-hydroxybenzoic acid, phthalic acid and biphenol. The repeating unit having a structure derived from the biphenol of the polyester represented by the general formula [II] may be a polyester in which a part or all of the repeating unit is substituted with a repeating unit derived from dihydroxybenzene), p -A polyester represented by the general formula [III] having repeating units each having a structure derived from two compounds of hydroxybenzoic acid and hydroxynaphthalenecarboxylic acid.

[0036]

[Chemical 4]

[0037]

[Chemical 5]

The component (C) used in the present invention is a polyether sulfone having a structure of the general formula [IV] at least one of its molecular terminals as described above.

[0039]

[Chemical 6]

In the general formula [IV], R is an aromatic, aliphatic or alicyclic divalent hydrocarbon residue having a carbon number of 1 to 20, preferably 6 to 20.

The above Me is an alkali metal, specifically Li, Na, K, Rb, Cs, Fr, etc., preferably Li, Na, K, particularly preferably Na.

The more specific polyether sulfone used in the present invention is a compound containing the substituent of the general formula [IV] and a repeating unit represented by the following general formula [IV].

[0043]

[Chemical 7]

Here, X is a sulfonyl group (-SO ₂
-) And the group of R ₁ and R ₂ has 1 to 20 carbon atoms,
It is preferably 6 to 20 identical or different divalent aliphatic or alicyclic hydrocarbon residues or divalent aromatic hydrocarbon residues. Specific examples of the group of R ₁ and R ₂ include:
It is a divalent aromatic hydrocarbon group such as phenylene, naphthylene and biphenylene. n represents an integer in the range of 3 to 50. If it is less than 3, the strength and surface performance of the obtained composition may not be improved, and if it exceeds 50, the fluidity may be deteriorated. Further, as long as the repeating unit represented by the general formula [V] is included, other repeating units such as a repeating unit derived from bisphenol-A or a repeating unit derived from 4,4-biphenol, etc. Can be included as appropriate.

It should be noted that the polysulfone-based resin (A) is clearly distinguished by having a metal bond at the terminal.
Further, commercially available polyether sulfone resins and the like usually have a large molecular weight, and the terminal metal portion is removed by washing or the like, so that the terminal thereof is a hydroxyl group. Therefore, even if an ordinary available polysulfone resin is blended as the polyether sulfone of the item (C) of the present invention, the effect of the present invention cannot be obtained.

For example, 4,4'-dichlorodiphenyl
A compound containing a repeating unit derived from sulfone, and more specifically, a compound containing a repeating unit derived from 4,4′-dichlorodiphenyl sulfone and bisphenol A, and the like. Further, compounds having repeating units derived from 4,4'-dichlorodiphenyl sulfone and 4,4'-biphenol are also exemplified. In addition to the sulfone skeleton, the molecule also contains an ether group.

The synthesis of the polyether sulfone of the item (C) is not particularly limited, but generally Williamson
It can be synthesized by a synthesis method. For example, the monomers can be polymerized by heating an alkaline salt of 4,4′-dichlorodiphenyl sulfone and 4,4′-dihydroxyldiphenylpropane at 200 ° C. in an alkaline solvent of sulfone.

Specific examples of the organic compound represented by the general formula [V] represented by a specific structural formula are as follows.

[0049]

[Chemical 8]

In the present invention, the total amount of the mixture of (A) and (B) is 100 parts by weight, and the polyether sulfone (C) is blended in a proportion of 1 to 50 parts by weight.
If it is less than 1 part by weight, the mechanical strength and surface performance will not be improved, while if it exceeds 50 parts by weight, the physical properties will not be improved and it will be economically disadvantageous.

In the present invention, in addition to (A), (B) and (C), other resins can be mixed if necessary. Examples thereof include thermoplastic resins and thermosetting resins, specifically thermoplastic engineering plastics such as polyamide resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyphenylene sulfide resins, and polyether ether ketone resins.

A reinforcing agent or a filler may be added to the resin composition obtained in the present invention in order to further improve heat resistance and mechanical properties. Specific examples of the reinforcing agent or the filler include fibrous materials, powdery materials, and a mixture of both. Examples of the fibrous reinforcing agent include glass fibers, shirasu glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, inorganic fibers such as metal fibers (for example, stainless fibers), and carbon fibers. Further, as the granular reinforcing agent, wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconia, titanium oxide and the like. Metal oxides, calcium carbonate, magnesium carbonate,
Carbonates such as dolomite, calcium sulfate, calcium pyrophosphate, sulfates such as barium sulfate, glass beads, boron nitride, silicon carbide, Saloyan and the like, these may be hollow (for example, hollow glass fiber, Glass micro balloons, shirasu balloons, carbon balloons, etc.). The above-mentioned reinforcing agent can be used after being pretreated with a silane-based or titanium-based coupling agent, if necessary.

In the resin composition of the present invention, antioxidants and heat stabilizers (for example, hindered phenols, hydroquinones, phosphites and substitution products thereof, etc.) are used as long as the object of the present invention is not impaired. , UV absorbers (eg resorcinol, salicylate, benzotriazole, benzophenone, etc.), bone and mold release agents, dyes (eg nitrosine), and pigments (eg cadmium sulfide, phthalocyanine, carbon black etc.) , A flame retardant, a plasticizer, an antistatic agent, and the like can be added to impart predetermined properties. Reinforcing agents and fillers can be added in an amount of 80% by weight or less, preferably 70% by weight or less, based on the entire composition.

The method of mixing the respective components of the present invention is not particularly limited, and a conventionally known method can be used. For example, there are a method of heating and melting using an extruder to react, a method of mixing a polysulfone resin and a polyether sulfone in the process of melting and synthesizing LCP, and a method of crushing the mixture and reacting in a solid state. . In addition, the ropolysulfone-based resin may be mixed with a mixture of LCP and polyether sulfone in advance. Further, polyether sulfone may be mixed after previously mixing the polysulfone-based resin with the LCP.

In the present invention, the method of melt-kneading with an extruder is the most preferable because it is simple and can be uniformly mixed. At this time, it is also possible to appropriately add a small amount of solvent. As a device for melting and kneading, a Banbury mixer,
A static mixer roller, a kneader or the like can be used continuously or batchwise, but it is effective to use a single screw extruder or a twin screw extruder continuously.

[0056]

The present invention will be described in detail below with reference to Examples.

The formulations used in the examples are as follows:

Polysulfone resin (A): Polysulfone resin (A-1): Udel P manufactured by Amoco
1700 (trade name) Tensile strength: 720 kg / cm ² , bending strength 1080 kg
/ Cm ² , HDT 174 ° C Polysulfone resin (A-2): Mindel S manufactured by Amoco
-1000 (trade name) Tensile strength: 670 kg / cm ² , bending strength 990 kg /
cm ² , HDT149 ° C. Polysulfone-based resin (A-3): Victorex 450G (trade name) manufactured by ICI Tensile strength: 8400 kg / cm ² , bending strength 1130 k
g / cm ² , HDT 204 ° C

As liquid crystalline polyester (B); LCP (B-1): LCP powder synthesized from phthalic acid, isophthalic acid, 4-hydroxybenzoic acid and 4,4-dihydroxydiphenyl. When the optical anisotropy was observed using a polarization microscope equipped with a hot stage, it showed the optical anisotropy in the molten state at 340 ° C. or higher.

LCP (B-2): LCP synthesized from polyethylene terephthalate and 4-acetoxybenzoic acid. This polyester was in a molten state in the temperature range of 210 ° C. to 370 ° C. and showed optical anisotropy when observed with a polarizing microscope.

As a polyether sulfone of the section C;

[0062]

[Chemical 9]

Metal phenolate (C-1): 4,4'-
A metal phenolate compound synthesized using dihihydroxyphenyl sulfone and 4,4′-dichlorophenyl sulfone as monomers in an excess of sodium hydroxide sulfolane solvent.

Metal phenolate (C-2): 4,4'-
A metal phenolate compound synthesized using dihihydroxyphenyl sulfone and 4,4-chlorosulfonylbiphenyl as monomers in an excess of sodium hydroxide in a sulfolane solvent.

Examples and Comparative Examples The raw materials shown in the table were melt-mixed at a kneading section temperature of 350 ° C. by a twin-screw extruder to form pellets by extrusion. Sample pieces for various measurements were prepared from this pellet by injection molding.

The evaluation items were tensile strength test (ASTM D638) for measuring the mechanical properties of the prepared test piece,
HDT (deflection temperature under load; ASTM D648) was measured.

The degree of fibrillation of the surface of the molded product was confirmed as an index for improving the anisotropy. For confirmation, a commercially available adhesive tape was wrapped around a steel rod having a diameter of 5 mm, the surface of the test piece was rubbed 10 times with a force of 5 kgf, and the trace was visually confirmed.

As an index of moldability, the quality of the appearance of the molded product was visually evaluated.

The results are shown in the table.

[0070]

The effect of the present invention is that the fibrils of LCP are suppressed and the mechanical strength is improved. INDUSTRIAL APPLICABILITY The present invention solves the problem of LCP and can broaden the range of application, and is industrially useful.

[0071]

[Table 1]

[0072]

[Table 2]

Claims (1)

[Claims] 1. A polysulfone resin (A) in an amount of 1 to 99 parts by weight and a thermotropic liquid crystal polyester resin (B).
1 to 50 parts by weight of polyether sulfone (C) in which at least one of the molecular ends has the structure of the following formula, relative to 99 to 1 parts by weight and 100 parts by weight as the total of the components (A) and (B). A resin composition comprising: [Chemical 1] (Here, R is a divalent hydrocarbon residue and Me is an alkali metal.)