JPH0673239A - Liquid crystalline polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. excellent in mechanical properties. CONSTITUTION:100 pts.wt. compsn. comprising 1-99wt.% liq. crystalline polyester resin which forms an anisotropic melt phase and 99-1wt.% olefin polymer having a number-average mol.wt. of 20,000 or higher is compounded with 0.01-60 pts.wt. olefin oligomer having a number-average mol.wt. of lower than 20,000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel composition comprising a liquid crystal polyester, a polyolefin polymer and an olefin oligomer, which are useful as electric / electronic device parts, automobile parts, mechanical parts and the like and which have excellent mechanical properties and moldability. It is a thing.

[0002]

2. Description of the Related Art In recent years, the demand for higher performance of plastics has been increasing, and many polymers having various new properties have been developed. Among them, an optically anisotropic liquid crystal characterized by parallel arrangement of molecular chains. Attention has been paid to the fact that polyester has excellent fluidity and mechanical properties. However, in the present situation, the applications are limited because the molding shrinkage ratio and mechanical properties are different in the direction perpendicular to the molecular chain orientation direction and the cost is high.

On the other hand, it is known that a polyolefin-based polymer is significantly inferior in mechanical properties, fluidity at the time of molding and heat resistance as compared with a liquid crystal polyester. Therefore, in order to solve the drawbacks of both, attention has been paid to a blend of a liquid crystal polyester and a polyolefin-based polymer (for example, JP-A-1-121357).

[0004]

However, even if the two polymers are simply blended, the compatibility is not sufficient, so that no major improvement in physical properties is observed. An object of the present invention is to solve the above problems and obtain a liquid crystal polyester resin composition having excellent mechanical properties.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that when an unsaturated carboxylic acid-modified olefin oligomer is added to a liquid crystal polyester and a polyolefin-based polymer, the liquid crystal polyester and the polyolefin-based polymer are added. It was found that the compatibility of the coalesced product was improved and the desired mechanical properties were improved, and the present invention was reached.

That is, the present invention is a resin comprising (A) 1 to 99% by weight of a liquid crystal polyester resin forming an anisotropic molten phase and (B) 99 to 1% by weight of a polyolefin polymer having a number average molecular weight of 20,000 or more. It is intended to provide a resin composition comprising (C) 0.01 to 60% by weight of an olefin oligomer having a number average molecular weight of less than 20,000, relative to 100 parts by weight of the composition.

The compounds specifically used in the present invention will be described in detail below.

The liquid crystal polyester resin (A) used in the present invention is a polyester which forms an anisotropic melt phase, and includes p-hydroxybenzoic acid / polyethylene terephthalate type liquid crystal polyester and p-hydroxybenzoic acid / 6.
-Hydroxy-2-naphthoic acid type liquid crystal polyester, p
-Hydroxybenzoic acid / 4,4'-dihydroxybiphenyl / terephthalic acid / isophthalic acid type liquid crystal polyester and the like can be mentioned. Among them, the following structural units (I) and (I
I), (IV) or (I), (II), (III)
, (IV) are preferred.

[0009]

[Chemical 4] (However, R ₁ is

[0010]

[Chemical 5] R ₁ represents one or more groups selected from

[0011]

[Chemical 6] Represents one or more groups selected from Further, in the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)
] And the structural unit (IV) are substantially equimolar. )

The structural unit (I) is a structural unit of polyester produced from p-hydroxybenzoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl, 3,
3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2
-Bis (4-hydroxyphenyl) propane and 4,
A structural unit produced from an aromatic dihydroxy compound selected from 4'-dihydroxydiphenyl ether, a structural unit (III) is a structural unit produced from ethylene glycol, and a structural unit (IV) is terephthalic acid, isophthalic acid,
4,4'-diphenylcarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,
Each of the structural units formed from an aromatic dicarboxylic acid selected from 4'-diphenyl ether dicarboxylic acid is shown. Of these, particularly when the structural unit (III) is included, R ₁ is

[0013]

[Chemical 7] Is 70% by mole or more of the structural unit (II), R ₂
But

[0014]

[Chemical 8] Particularly preferably those which account for 70 mol% or more of the structural unit (IV).

The copolymerization amount of the above structural units (I), (II), (III) and (IV) is arbitrary. However, from the viewpoint of fluidity, the following copolymerization amount is preferable. That is, when the structural unit (III) is included, the structural unit [(I) + (II)] is [(I) +
(II) + (III)] is preferably 60 to 95 mol%, and 70
˜92 mol% is more preferred. Further, the structural unit (III) is preferably 40 to 5 mol% of [(I) + (II) + (III)], and more preferably 30 to 8 mol%. The molar ratio of the structural unit (I) / (II) is preferably 75/25 to 95/5, more preferably 78/22 to 93/7 from the viewpoint of the balance between fluidity and mechanical properties. The structural unit (IV) is substantially equimolar to the structural unit [(II) + (III)].

On the other hand, when the structural unit (III) is not contained, the structural unit (I) is [(I) +
(II)] is preferably 40 to 90 mol%, and 6
It is particularly preferably from 0 to 88 mol%, and the structural unit (IV) is substantially equimolar to the structural unit (II).

In the condensation polymerization of the preferred liquid crystalline polyester, 3,3'-diphenyldicarboxylic acid, 2,3'-diphenyldicarboxylic acid, and 2, in addition to the components constituting the structural units (I) to (IV) are used.
Aromatic dicarboxylic acids such as 2'-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, Aromatic diols such as 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxybenzophenone, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, 1,4
Aliphatic and alicyclic diols such as cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminophenol, p-amino Benzoic acid or the like may be copolymerized in such an amount that the object of the present invention is not impaired.

The method for producing the liquid crystal polyester resin (A) in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method. For example, among the liquid crystal polyesters that can be preferably used, the structural unit (I
When (II) is not included, (1) to (4), structural unit (III)
When it contains, the production method of (5) is preferable.

(1) p-acetoxybenzoic acid and 4,
A method for producing a diacylated aromatic dihydroxy compound such as 4′-diacetoxybiphenyl and an aromatic dicarboxylic acid such as terephthalic acid by deacetic acid condensation polymerization reaction.

(2) p-hydroxybenzoic acid and 4,
A method in which an aromatic dihydroxy compound such as 4′-dihydroxybiphenyl or an aromatic dicarboxylic acid such as terephthalic acid is reacted with acetic anhydride to acylate a phenolic hydroxyl group, and then a deacetic acid polycondensation reaction is performed.

(3) A method of producing from a phenyl ester of p-hydroxybenzoic acid and an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl and a diphenyl ester of an aromatic dicarboxylic acid such as terephthalic acid by a dephenol polycondensation reaction. .

(4) Aromatic dicarboxylic acids such as p-hydroxybenzoic acid and terephthalic acid are reacted with a predetermined amount of diphenyl carbonate to form diphenyl esters, and then aromatic dihydroxy such as 4,4'-dihydroxybiphenyl. A method of producing a compound by adding a compound and performing a dephenol polycondensation reaction.

(5) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β-
A method for producing by the method of (1) or (2) in the presence of bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as hydroxyethyl) terephthalate.

Typical examples of the catalyst used in the polycondensation reaction include stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, metal compounds such as sodium acetate, magnesium and the like. It is effective when

The liquid crystal polyester resin (A) used in the present invention is capable of measuring logarithmic viscosity in pentafluorophenol, and in that case, 0.1 g / d.
The value measured at 60 ° C. at a concentration of 1 is preferably 0.5 or more. In particular, when the above structural unit (III) is included, 1.
It is preferably 0 to 3.0 dl / g, and 2.0 to 10.0 dl / g when the structural unit (III) is not contained.

The melt viscosity of the liquid crystal polyester resin (A) used in the present invention is preferably 10 to 20,000 poise, and more preferably 20 to 10,000 poise. The melt viscosity is a value measured by a high pressure capillary viscometer under the conditions of melting point (Tm) + 10 ° C. and shear rate of 1,000 / sec.

Here, the melting point (Tm) means the endothermic peak temperature (Tm1) observed in the differential calorimetry, which is observed when the polymerized polymer is measured at a temperature rising condition from room temperature to 20 ° C./min. , Tm1 + 20 ° C. for 5 minutes, then once cooled to room temperature under a temperature lowering condition of 20 ° C./min, and then measured again under a temperature rising condition of 20 ° C./min, the endothermic peak temperature (Tm2) observed Refers to.

The polyolefin-based polymer (B) used in the present invention is not particularly limited as long as it has a number average molecular weight of 20,000 or more, but includes polyethylene, polypropylene, polystyrene and ABS. These may be copolymers. Of these, polypropylene polymers are the most preferable.

The polypropylene-based polymer is a crystalline polypropylene, and in addition to a homopolymer of propylene, it also contains a block or random copolymer obtained by copolymerizing propylene with other α-olefins (eg ethylene, butene-1 etc.). In addition, a copolymer of ethylene with an ethylene content of 50 mol% or more and an α-olefin having a carbon number of 3 or more (for example, ethylene / propylene copolymer, ethylene / butene-1 copolymer, etc.), ethylene, carbon number Copolymers composed of 3 or more α-olefins and non-conjugated dienes (eg ethylene / propylene / 1,4-hexadiene copolymers, ethylene / propylene / dicyclopentadiene copolymers, ethylene / propylene / ethylidene norbornene copolymers) Etc.) may be contained. Preferred polypropylenes include polypropylene homopolymers, propylene / ethylene copolymers having an ethylene content of 30 mol% or less, or ethylene-α-olefin copolymers having an ethylene content of 50 mol% or more, or ethylene and carbon. 50% by weight of an elastomeric copolymer consisting of several α-olefins and non-conjugated dienes
The polypropylene copolymer and the propylene / ethylene copolymer having an ethylene content of 30 mol% or less are included below.

It is more preferable that these polypropylene polymers are modified with an unsaturated carboxylic acid or a derivative thereof. Examples of the unsaturated carboxylic acid to be modified include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid, tetrahydrophthalic acid and dimer acid. Examples of the derivative include anhydrides, esters, amides, imides and salts of the above acids. Specifically, maleic anhydride, itaconic anhydride, 5-norbornene 2,3-dicarboxylic acid anhydride, tetrahydrophthalic anhydride, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate. , Glycidylmethacrylate, ethylcrotonate, butylcrotonate, glycidylcrotonate, diethyl maleate, dibutyl maleate, diglycidyl maleate, diethyl fumarate, dibutyl fumarate, diglycidyl fumarate, dibutyl itaconate, diglycidyl itaconate, 5 -Diethyl norbornene 2,3-dicarboxylate, dibutyl 5-norbornene 2,3-dicarboxylate, diglycidyl 5-norbornene 2,3-dicarboxylate, diethyl tetrahydrophthalate, dibutyl tetrahydrophthalate , Diglycidyl tetrahydrophthalate, diethyl dimer, dibutyl dimer, diglycidyl dimer, acrylamide, methacrylamide, crotonamide, maleamide, fumaramide, itaconamide, 5-norbornene 2,3-dicarbonamide, tetrahydrophthalamide, dimer Amide, N,
N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-dimethyl crotonamide, N,
N, N ′, N′-tetramethylmaleinamide, N,
N, N ', N'-tetramethylfumaramide, N,
N, N ′, N′-tetramethylitaconamide, N,
N, N ', N'-tetramethyl-5-norbornene 2,
3-dicarbonamide, N, N, N ', N'-tetramethyltetrahydrophthalamide, N, N, N', N'-
Tetramethyl dimer amide, malein imide, fumar imide, itacon imide, 5-norbornene-2,3
-Dicarbonimide, tetrahydrophthalimide, N-
Phenylmaleimide, N-phenylfumarimide, N
-Phenylitaconimide, N-phenyl-5-norbornene-2,3-dicarbonimide, N-phenyltetrahydrophthalimide and the like can be mentioned. Among them, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, glycidyl acrylate, glycidyl methacrylate, diglycidyl maleate, diglycidyl tetrahydrophthalate, diglycidyl dimer, acrylamide, methacrylamide, maleimide , N-phenylmaleimide and the like are preferable.

The method of graft-copolymerizing the unsaturated carboxylic acid or its derivative on the polypropylene polymer is not necessarily limited, but the polypropylene polymer is heated and dissolved in a solvent such as benzene or toluene. Unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative, and a method of adding and reacting a radical generator,
Examples thereof include a method in which a polypropylene polymer, an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative and a radical generator are melt-kneaded using an extruder, a kneader or the like.

The amount of unsaturated carboxylic acid or unsaturated carboxylic acid derivative to be graft-copolymerized is 0.01 to 20% by weight, preferably 0.1 to 20% by weight, in the modified polypropylene polymer.
It is 10% by weight. If the graft amount is less than 0.01% by weight, the effect of improving the mechanical properties is not sufficient, and if it exceeds 20% by weight, there is a problem that the molding fluidity decreases, which is not preferable.

Other monomers, such as styrene, acrylonitrile, butadiene, etc., may be simultaneously used as a graft component monomer as long as the amount is small.

The blend composition of the liquid crystal polyester (A) and the propylene polymer (B) is from 1 to 99/99 to 1, and more preferably from 5 to 40/95 to 60 and 60.
˜95 / 40-5. More preferably 10-35
/ 90-65 and 65-90 / 35-10. Four
In the case of 0-60 / 60-40, the compatibility of both is not sufficient,
The effect of improving mechanical properties is small.

The polyolefin oligomer (C) modified with an unsaturated carboxylic acid or a derivative thereof used in the present invention is a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof and is not necessarily limited, but may be polyethylene. Examples thereof include oligomers, polypropylene oligomers, polystyrene oligomers and the like. Among them, polyethylene oligomer and polypropylene oligomer are preferable. The number average molecular weight of the oligomer used here is 20,000 in terms of polystyrene by GPC measurement.
It is preferably less than 10000, more preferably 15,000
It is 0 or less.

As the preferred unsaturated carboxylic acid or its derivative for modifying the polyolefin oligomer, the same compound as the above-mentioned polypropylene polymer can be used. The modification method can be the same as in the case of the polypropylene polymer.

The amount of the (C) olefin oligomer added to the composition of the present invention is (A) liquid crystal polyester and (B)
The amount is 0.01 to 60 parts by weight, preferably 0.05 to 30 parts by weight, based on 100 parts by weight of the resin composition comprising the polyolefin polymer. If it is less than 0.01 parts by weight, the bonding force at the interface between the two polymers is weak and the effect of improving the mechanical properties is remarkably small. On the contrary, if it exceeds 60 parts by weight, the mechanical properties of the composition are significantly deteriorated. , Neither is preferable.

In producing the liquid crystal polyester resin composition of the present invention, conventionally known polymerization catalysts for polyolefins and polyesters, heat-resistant agents, weather-resistant agents, antistatic agents, dyes, colorants, crystal nucleating agents, flame retardants, etc. Reinforcement of additives, inorganic fillers such as talc, clay, mica, calcium metasilicate, silica sand, glass beads, glass flakes, graphite, potassium whisker titanate, gypsum fiber, glass fiber, asbestos fiber, carbon fiber, etc. It is also possible to add agents and the like.

Various methods can be applied as a method for mixing the liquid crystal polyester, the polyolefin polymer and / or the olefin oligomer. Examples of the apparatus for melt-mixing include a mixing roll, a Banbury mixer, a kneader, an extruder, and the like. Among them, an extruder is preferable. As the extruder, either a single screw or a screw having two or more screws can be used, but it is particularly preferable to use a twin screw extruder.

When a molded product is obtained from the resin composition of the present invention, usual methods such as injection molding, extrusion molding and blow molding can be applied, and the obtained molded product exhibits good performance.

[0041]

EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples do not limit the scope of application of the present invention. The parts in the examples are parts by weight, and the abbreviations are as follows.

C-1: Propylene oligomer (number average molecular weight 4,000) Sanyo Kasei MPX-1100 C-2: Propylene oligomer (number average molecular weight 12,0)
00) Sanyo Kasei MPX-1001 C-3: ethylene oligomer (number average molecular weight 2,000
0) Sanyo Kasei MPX-2000

Reference Example 1 p-Hydroxybenzoic acid 870 parts by weight, 4,4'-dihydroxybiphenyl 168 parts by weight, acetic anhydride 914 parts by weight, terephthalic acid 150 parts by weight and an intrinsic viscosity of about 0.
259 parts by weight of 6 dl / g polyethylene terephthalate was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and deacetic acid polycondensation was carried out under the following reaction conditions.

First, 100 to 250 is applied in a nitrogen gas atmosphere.
The reaction was carried out at ℃ for 1.5 hours. Thereafter, the pressure was reduced to 0.5 mmHg in 2 hours at 290 ° C., and polycondensation was performed for 1 hour. At the end of the polymerization, almost the theoretical amount of acetic acid was distilled off to obtain a liquid crystal polyester having the following theoretical structural formula.

[0045]

[Chemical 9] k / l / m / n = 70/10/20/30

The melting point of the obtained liquid crystal polyester is 267.
It became ℃. The melt viscosity at a shear rate of 1000 / sec at 277 ° C. was 610 poise.

Reference Example 2 Various unsaturated carboxylic acid derivatives and 1,3-bis (t-butylperoxy-isopropyl) benzene 0.1 to 0.
Dry blend 3 parts by weight with V-Bravender and
Using a mmφ twin-screw extruder, melt kneading at 200 to 250 ° C. and pelletization were performed to obtain a modified polypropylene copolymer.
The obtained pellets were subjected to Soxhlet extraction with acetone for 12 hours, and the graft component was quantified by IR spectrum. The results are shown in Table 1.

[0048]

[Table 1]

Examples 1 to 11, Comparative Examples 1 to 6 (A) Liquid crystal polyester, (B) polypropylene polymer and (C) olefin oligomer were weighed in predetermined amounts as shown in Table 1 and dry blended. . 270
It was melt-extruded with a 30 mmφ twin-screw extruder set at ℃, cooled with water and pelletized. Using the dried pellets, an injection molding machine in which the cylinder temperature was 270 ° C. and the mold temperature was 80 ° C., a test piece of ⅛ ″ thickness × 1/2 ″ width × 5 ″ length and a ⅛ ″ thickness were used. ASTM No. 1 dumbbell was molded. Bending strength was measured using a test piece of 1/8 "thickness x 1/2" width x 5 "length using a Toyo Baldwin Tensilon UTM-200 under the conditions of a strain rate of 1 mm / min and a span distance of 50 mm. In addition, ASTM
ASTM No. The tensile strength of one dumbbell was measured. The results of these tests are shown in Table 2.

[0050]

[Table 2]

From the results in Table 2 above, it is understood that addition of the olefin oligomer improves both tensile strength and bending strength as compared with the case of the composition comprising only (A) and (B).

[0052]

The molded product obtained from the liquid crystal polyester resin composition according to the present invention has excellent heat resistance, mechanical properties and moldability, and can be widely used in applications such as electric and electronic equipment parts and automobile parts. Is possible.

Claims (3)

[Claims] 1. A liquid crystal polyester resin which forms an anisotropic molten phase (A) 1 to 99% by weight and (B) a number average molecular weight 20,
Olefin oligomer 0.0 having a number average molecular weight of less than 20,000 (C) per 100 parts by weight of a resin composition consisting of 99 to 1% by weight of a polyolefin-based polymer of 000 or more.
A resin composition containing 1 to 60% by weight. 2. The (B) polyolefin having a number average molecular weight of 20,000 or more is a polypropylene-based polymer,
The liquid crystal polyester resin composition according to claim 1, wherein the olefin oligomer (C) having a number average molecular weight of less than 20,000 is a propylene or ethylene oligomer modified with an unsaturated carboxylic acid or a derivative thereof. 3. A liquid crystal polyester resin comprising the following structural units (I), (II), (IV), or (I),
The liquid crystal polyester resin composition according to claim 2, which is a liquid crystal polyester resin which forms an anisotropic molten phase consisting of (II), (III) and (IV). [Chemical 1] (However, in the formula, R ₁ is R ₁ represents one or more groups selected from Represents one or more groups selected from Further, in the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)
] And the structural unit (IV) are substantially equimolar. )