JP3111662B2 - Liquid crystal polyester resin composition - Google Patents

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 thermoplastic resin, and glycidylamine having excellent mechanical properties and moldability, useful as electric / electronic equipment parts, automobile parts, machine parts, and the like. It is.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed. Among them, optically anisotropic liquid crystals characterized by parallel alignment of molecular chains. Attention has been paid to polymers having excellent fluidity and mechanical properties. However, the molding shrinkage ratio and mechanical properties are different in the direction perpendicular to the molecular chain orientation direction, and the application is currently limited due to the high price and the like.

[0003] On the other hand, it is known that many thermoplastic polymers are inferior to liquid crystal polymers in mechanical properties and fluidity during molding and do not always have sufficient heat resistance.

[0004] In order to solve the drawbacks of both, a blend of a liquid crystal polyester and a thermoplastic resin has attracted attention (for example, Japanese Patent Laid-Open No. 57-25354).

[0005]

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

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when a glycidylamine compound having two or more glycidyl groups is added, the phase of a liquid crystal polymer and another thermoplastic polymer is reduced. It was found that the solubility was improved and the desired mechanical properties were improved, and the present invention was reached.

That is, the present invention relates to (A) 1 to 99% by weight of a liquid crystal polyester resin forming an anisotropic molten phase, and (B) polyester, polyamide, polycarbonate, polyarylene oxide, polyarylene not forming an anisotropic molten phase. (C) Glycidylamine compound 0 represented by the following general formula (I) or (II) per 100 parts by weight of a resin composition comprising 99 to 1% by weight of at least one thermoplastic resin selected from sulfides. The present invention provides a liquid crystal polyester resin composition to which 0.01 to 20 parts by weight is added.

[0008]

Embedded image (However, R represents a divalent organic group, G represents a glycidyl group, and R1 to R4 represent an alkyl group or a glycidyl group, but at least two are glycidyl groups.)

Hereinafter, the compounds used in the present invention will be described in detail.

The liquid crystal polyester resin (A) used in the present invention is a polyester forming an anisotropic molten phase, and is a p-hydroxybenzoic acid / polyethylene terephthalate type liquid crystal polyester, p-hydroxybenzoic acid / 6
-Hydroxy-2-naphthoic acid liquid crystal polyester, p
-Hydroxybenzoic acid / 4,4'-dihydroxybiphenyl / terephthalic acid / isophthalic acid-based liquid crystal polyesters, among others, the following structural units (III) and (I)
V), (VI) or (III), (IV),
Liquid crystal polyesters composed of (V) and (VI) are preferred.

[0011]

Embedded image (Where R1 is

[0012]

Embedded image R2 represents one or more groups selected from

[0013]

Embedded image Represents one or more groups selected from

In the formula, X represents a hydrogen atom or a chlorine atom, and the total of the structural units (IV) and (V) and the structural unit (VI) are substantially equimolar. )

The structural unit (III) is a structural unit of a polyester formed from p-hydroxybenzoic acid, and the structural unit (IV) is 4,4′-dihydroxybiphenyl,
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 generated from an aromatic dihydroxy compound selected from 4′-dihydroxydiphenyl ether, a structural unit (V) is a structural unit generated from ethylene glycol, a structural unit (VI) 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,
The structural units generated from aromatic dicarboxylic acids selected from 4'-diphenyl ether dicarboxylic acids are shown below.

In particular, when the structural unit (V) is contained, R1 is

Embedded image Is at least 70 mol% of the structural unit (IV)
But

[0017]

Embedded image In particular, those which occupy 70 mol% or more of the structural unit (VI) are particularly preferable.

The copolymerization amount of the above structural units (III), (IV), (V) and (VI) is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity. That is, when the above-mentioned structural unit (V) is contained, the total of the above-mentioned structural units (III) and (IV) is determined by
60 to the sum of the units (III), (IV) and (V)
95 mol% is preferable, and 75 to 92 mol% is more preferable. Structural units (V) are structural units (III), (IV) and
And preferably 40 to 5 mol% with respect to the total of (V) ,
25 to 8 mol% is more preferred. Also, the structural unit (III)
The molar ratio [(III) / (IV)] is preferably from the viewpoint of the balance between fluidity and mechanical properties 75 / 25-95 / 5 (IV)
And more preferably 78/22 to 93/7.
Structural unit (VI) is the same as structural units (IV) and (V).
Substantially equimolar to the sum .

On the other hand, when the structural unit (V) is not contained, the structural unit (III) is replaced with the structural unit (II ) from the viewpoint of fluidity.
It is preferably from 40 to 90 mol%, particularly preferably from 60 to 88 mol%, based on the sum of (I) and (IV) , and the structural unit (VI) is substantially equal to the structural unit (IV). Is a mole.

When the preferred liquid crystal polyester is polycondensed, 3,3'-diphenyldicarboxylic acid, 2,3
Aromatic dicarboxylic acids such as 2'-diphenyldicarboxylic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecandioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, Aromatic diols such as 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, 1,4
Aliphatic, 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 and the like may be copolymerized in an amount that does not impair the purpose of the present invention.

The method for producing the liquid crystalline 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 production methods (1) to (4) when the structural unit (V) is not included, and the production method (5) when the structural unit (V) is included are preferable.

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

(2) p-hydroxybenzoic acid and 4,
A method of reacting an aromatic dihydroxy compound such as 4'-dihydroxybiphenyl or hydroquinone, or an aromatic dicarboxylic acid such as terephthalic acid with acetic anhydride to acylate a phenolic hydroxyl group, followed by a deacetic acid polycondensation reaction.

(3) Preparation from a phenyl ester of p-hydroxybenzoic acid or an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone and a diphenyl ester of an aromatic dicarboxylic acid such as terephthalic acid by a dephenol polycondensation reaction. how to.

(4) A predetermined amount of diphenyl carbonate is reacted with an aromatic dicarboxylic acid such as p-hydroxybenzoic acid and terephthalic acid to form a diphenyl ester, and then an aromatic compound such as 4,4′-dihydroxybiphenyl or hydroquinone is used. Group dihydroxy compound,
A method of producing by a dephenol polycondensation reaction.

(5) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β-
(Hydroxyethyl) terephthalate and the like, and a method of producing the bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid by the method of (1) or (2).

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

The liquid crystal polyester resin (A) used in the present invention is a resin whose logarithmic viscosity can be measured in pentafluorophenol, in which case 0.1 g / d
It is preferable that the value measured at 60 ° C. at a concentration of 1 is 0.5 or more, and particularly when the above structural unit (V) is contained,
1.0 to 3.0 dl / g is preferred.

The melt viscosity of the liquid crystal polyester resin (A) used in the present invention is preferably from 10 to 20,000 poise, more preferably from 20 to 10,000 poise. The melt viscosity is the melting point (Tm) + 10 ° C. when the structural unit (V) is included, and the liquid crystal onset temperature + 40 ° C. when the structural unit (V) is not included. It is a value measured by a high-pressure capillary viscometer under the condition of 1,000 / sec.

Here, the melting point (Tm) refers to the endothermic peak temperature (Tm1) observed when the polymer having undergone polymerization is measured from room temperature under a heating condition of 20 ° C./min in differential calorimetry. After holding at a temperature of Tm1 + 20 ° C. for 5 minutes, once cooling to room temperature under a temperature lowering condition of 20 ° C./min, and then measuring again at a temperature rising condition of 20 ° C./min, an endothermic peak temperature (Tm2) observed Point to. The liquid crystal onset temperature is a temperature at which the sample is placed on a sample stage of a polarizing microscope, heated and heated to emit opalescent light under shear stress.

The thermoplastic resin (B) which does not form an anisotropic molten phase used in the present invention includes polyester, polyamide,
One or more selected from polycarbonate, polyarylene oxide and polyarylene sulfide are shown. Among them, semi-aromatic polyesters are particularly preferred. Specific preferred examples are shown below.

The thermoplastic polyester is a polyester which is thermoplastic and has an aromatic ring in a chain unit of a polymer, and is composed of an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). Is a polymer or copolymer obtained by a condensation reaction containing as a main component. As the dicarboxylic acid here, terephthalic acid, isophthalic acid, phthalic acid, 2,2
6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p
-Carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 1,2-bis (p-carboxyphenoxy) ethane, or an ester-forming derivative thereof. Can be In addition, if it is 30 mol% or less, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, and dimer acid;
It may be substituted with an alicyclic carboxylic acid such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid. The diol component has 2 to 10 carbon atoms.
Aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, 1,5-pentane glycol, decamethylene glycol, 3-methyl-1,3-propenediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, and the like. But not limited to these. Specific examples of preferred polyesters include polyethylene terephthalate, polybutylene terephthalate,
Polyethylene-1,2-bis (phenoxy) ethane-
4,4'-dicarboxylate, polyethylene-2,6
-Naphthalate, poly-1,4-cyclohexane dimethylene terephthalate, etc. and polyethylene terephthalate / isophthalate, polybutylene terephthalate /
Examples include copolymerized polyesters such as isophthalate, polybutylene terephthalate / sebacate, polybutylene terephthalate / decanedicarboxylate, and poly-1,4-cyclohexane dimethylene terephthalate / isophthalate. Among these, particularly preferred polyesters include polybutylene terephthalate, polyethylene terephthalate, and poly-1,4-cyclohexane dimethylene terephthalate. Among them, polybutylene terephthalate is most preferable.

The logarithmic viscosity of the polybutylene terephthalate used in the composition of the present invention is preferably from 0.9 to 1.3, more preferably from 0.92 to 1.25.
The logarithmic viscosity of polybutylene terephthalate is 25
It was determined by dividing the logarithm of the relative viscosity determined using a 0.5% orthochlorophenol solution at ° C by the concentration.

As the polyamide, polyamide obtained from ω-amino acid or ω-lactam, or dicarboxylic acid such as diamine, m-xylenediamine and adipic acid, sebacic acid, dodecandionic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. And a homopolymer or a copolymer obtained from the above.
Preferred polyamides are nylon 6 and nylon 1.
1, homopolyamides such as nylon 12, nylon 46 and nylon 66, and adipic acid / terephthalic acid / hexamethylenediamine, adipic acid / 1,4-cyclohexanedicarboxylic acid / hexamethylenediamine, adipic acid / 1,3-cyclohexanedicarboxylic acid Copolymer polyamides such as acid / hexamethylenediamine and terephthalic acid / isophthalic acid / hexamethylenediamine / paraaminocyclohexylmethane. As the polycarbonate, a polycarbonate based on a hydrocarbon derivative having bis (4-hydroxyphenyl), bis (3,5-dialkyl-4-hydroxyphenyl) or bis (3,5-dihalo-4-hydroxyphenyl) substitution is used. And polycarbonates based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) are particularly preferred.

Examples of the polyarylene oxide include poly (2,6-dimethyl-1,4-phenylene) ether,
2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol /
2,3,6-triethylphenol copolymer and the like. Polyarylene oxide includes polystyrene,
A styrene resin such as high impact polystyrene can be added.

Polyarylene sulfide is a compound in which an aromatic ring and sulfur are bonded. Preferred polyarylene sulfides include polyparaphenylene sulfide, which may be partially branched.

The blend composition of (A) the liquid crystal polyester and (B) the thermoplastic resin is 1-99 / 99-1.
More preferably, it is 5-50 / 95-50. More preferably, it is 10-40 / 90-60.

The liquid crystalline polyester (A) and the thermoplastic resin (B) used in the present composition were prepared by melting the liquid crystalline polyester (A) and the thermoplastic resin (B) at the same temperature and at the same shear rate (1000 / sec). Desirably, the viscosity ratio is less than 3. It is more preferably 2 or less, further preferably 1 or less. When the ratio is 3 or more, the liquid crystal polyester is not dispersed well, so that a sufficient effect of improving mechanical properties is not observed.

The glycidylamine compound (C) used in the present invention is obtained by glycidylating a primary or secondary amine and is not necessarily limited, but includes the following compounds.

[0040]

Embedded image (In the formula, G represents a glycidyl group.)

The aromatic ring of these compounds may be substituted with another alkyl group. These diglycidylamine compounds may be used alone or in combination of two or more, or may be used in combination with a diepoxy compound having a structure other than the above.

The amount of the glycidylamine compound (C) added in the composition of the present invention is 0.01 to 20 parts by weight based on 100 parts by weight of the resin composition comprising (A) the liquid crystal polyester and (B) the thermoplastic resin. However, it is preferably in the range of 0.05 to 10 parts by weight. If the amount is less than 0.01 part by weight, the bonding strength at the interface between both polyesters is weak and the improvement in mechanical properties is extremely small. Conversely, if it exceeds 20 parts by weight, the mechanical properties and flow of the thermoplastic resin composition Properties are greatly reduced, and both are not preferred.

In producing the liquid crystal polyester resin composition of the present invention, conventionally known additives such as a polymerization catalyst for polyester, a heat-resistant agent, a weathering agent, an antistatic agent, a dye, a colorant, a crystal nucleating agent, a flame retardant and the like. And talc, clay, mica,
It is also possible to add inorganic fillers such as calcium metasilicate, silica sand, glass beads, glass flakes, potassium whisker, and gypsum fibers, and reinforcing agents such as glass fibers, asbestos fibers, and carbon fibers.

Various methods can be applied as a method for mixing the liquid crystal polyester, the thermoplastic resin and the glycidylamine compound. Examples of the apparatus for melt-mixing include a mixing roll, a Banbury mixer, a kneader, and an extruder. Among them, an extruder is preferable. As the extruder, any having 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 article is obtained from the resin composition of the present invention, ordinary methods such as injection molding, extrusion molding and blow molding can be applied, and the obtained molded article exhibits good performance.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but these examples do not limit the scope of the present invention. In addition, the part in an Example represents a weight part.

Reference Example 1 870 parts by weight of p-hydroxybenzoic acid, 168 parts by weight of 4,4'-dihydroxybiphenyl, 914 parts by weight of acetic anhydride, 150 parts by weight of terephthalic acid and an intrinsic viscosity of about 0.1 part by weight.
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 subjected to deacetic acid polycondensation under the following reaction conditions.

First, 100-250 in a nitrogen gas atmosphere.
The reaction was carried out at 1.5 ° C. for 1.5 hours. Thereafter, the pressure was reduced to 0.5 mmHg at 290 ° C. for 2 hours to complete the polycondensation. The polymerization was carried out for 1.0 and 3.0 hours. At the end of both polymerizations, almost the theoretical amount of acetic acid was distilled off, and a liquid crystal polyester having the following theoretical structural formula was obtained.

[0049]

Embedded image k / l / m / n = 70/10/20/30

The polyester (A-1) had a melting point of 267 ° C. when polymerized for 1.0 hour, and 263 ° C. when polymerized for 3.0 hours (A-2). The melt viscosity at 270 ° C. and a shear rate of 1000 / sec was 710 and 44, respectively.
It was 00 poise. The melt viscosities measured at the melting point + 10 ° C. were 600 and 3500 poise, respectively.

Examples 1 to 9, Comparative Examples 1 to 4 (A) Liquid crystal polyester A-1 or A-2, (B) polybutylene terephthalate (270 ° C., shear rate 10
Melt viscosity at 00 / sec: PBT1, 3650 poise; P
BT2, 1100 poise) and the following glycidylamine compound (C) were weighed in predetermined amounts, and were dry-blended. The mixture was melt-extruded with a 30 mmφ twin-screw extruder set at 270 ° C., cooled with water, and pelletized. Using the dried pellets, a test piece of １ ／ ″ thickness ×× ″ width × 5 ″ length and a ８ ″ thickness were measured on an injection molding machine set at a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. ASTM No. 1
Dumbbells were molded. Flexural strength is 1/8 "thickness x 1/2"
Using a test piece having a width of 5 "long and a strain rate of 1 mm / Tensilon UTM-200 manufactured by Toyo Baldwin Co., Ltd.
The measurement was carried out under the conditions of a distance of 50 mm between the spans. Further, according to ASTM D638, ASTM No. 1
The dumbbell tensile strength was measured. Table 1 shows the test results.

[0052]

Embedded image

[0053]

[Table 1]

From the results shown in Table 1, it can be seen that the addition of the glycidylamine compound improves both the tensile strength and the elongation at break as compared with the case of the composition comprising only (A) and (B).

Examples 10 to 14 and Comparative Examples 5 to 9 (A) 30 parts of liquid crystalline polyester A-1, 30 parts of (B) thermoplastic resin shown in Table 2 and 1 part of the above glycidylamine compound a were weighed in predetermined amounts. And dry blended. The mixture was melt-extruded with a 30 mmφ twin-screw extruder set at 270 to 320 ° C, cooled with water, and pelletized. The pellet was dried, and the tensile strength and the bending strength were measured using a test piece molded in the same manner as described above. In addition, all the resin used here used the thing whose melt viscosity is higher than liquid crystal polyester A-1.

[0056]

[Table 2]

From the results shown in Table 2, it can be seen that the addition of the glycidylamine compound improves both the tensile strength and the elongation at break as compared with the case of the composition comprising only (A) and (B).

[0058]

The molded article 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)

(57) [Claims] (1) 1 to 99% by weight of a liquid crystal polyester resin which forms an anisotropic molten phase and (B) polyester, polyamide, polycarbonate which does not form an anisotropic molten phase,
With respect to 100 parts by weight of a resin composition comprising 99 to 1% by weight of at least one thermoplastic resin selected from polyarylene oxide and polyarylene sulfide, (C) a compound represented by the following general formula (I) or (II): Liquid crystal polyester resin composition obtained by adding 0.01 to 20 parts by weight of a glycidylamine compound to be used. Embedded image (However, R represents a divalent organic group, G represents a glycidyl group, and R1 to R4 represent an alkyl group or a glycidyl group, but at least two are glycidyl groups.) 2. The liquid crystal polyester resin composition according to claim 1, wherein the thermoplastic resin is a polyester. 3. A liquid crystal polyester resin having the following structural unit (II)
I), (IV), (VI) or (III), (I
3. The liquid crystal polyester resin composition according to claim 2, which is a liquid crystal polyester resin forming an anisotropic molten phase comprising V), (V) and (VI). Embedded image (Where R1 is R2 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit (IV) and
The sum of (V) and the structural unit (VI) are substantially equimolar. )