JP3355782B2 - Liquid crystalline polyesteramide and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystalline polymer, and more particularly, to a liquid crystalline polyester amide having a high elastic modulus, a small anisotropy of elastic modulus, and excellent impact resistance, and its production. About the method. The present invention also relates to an injection-molded article comprising such a liquid crystalline polyesteramide.

According to the present invention, materials for machine parts, materials for electric and electronic parts such as connectors, relays, bobbins, etc., sealing materials such as ICs, and automobile level by melt molding such as injection molding, extrusion molding and compression molding. Further, a liquid crystalline polyesteramide suitable for a material for a vertical outer panel, a material for various automobile parts, a material for a container such as a trunk and a case, a film, a sheet, a fiber, and the like can be provided.

[0003]

2. Description of the Related Art Liquid crystal polymers are increasing their sales volume in the market by taking advantage of their features such as high fluidity, high elastic modulus, high strength and good dimensional accuracy. However, the liquid crystalline polymer gives a high elastic modulus to the fiber, but in a three-dimensional molded article, for example, an injection molded article, the molecular chain is highly oriented in the flowing direction of the polymer. Is higher, but the elastic modulus in the direction perpendicular to the flow direction (TD direction) is as low as that of other polymers that do not exhibit liquid crystallinity. Therefore, fillers such as glass fiber and carbon fiber are used. Had to be reinforced by the addition of

However, when fillers are added, impact strength is reduced, surface roughness is deteriorated, and there are problems such as sorting during recycling due to addition of inorganic substances.
Further, when the anisotropy of the liquid crystalline polymer is reduced, there is a problem that liquid crystallinity is lost and impact resistance is reduced. Therefore, the liquid crystal polymer alone has been used in the MD direction,
Attempts have been made to develop a material having a high elastic modulus in any of the TD directions.

For example, JP-A-59-124925, JP-A-61-19627, JP-A-1-261418, JP-A-2-64123, and JP-A-2-64123 disclose wholly aromatic polyesters. No. 3-188124. Further, attempts to improve physical properties in both the MD and TD directions by copolymerizing a polyfunctional component with a wholly aromatic polyester have been disclosed in JP-A-2-227428 and JP-A-2-2380.
No. 52, JP-A-3-152123, JP-A-3-152
No. 124, JP-A-3-168213 and the like. Further, Japanese Patent Application Laid-Open Nos. 2-53819 and 3-4
JP 7829 discloses an attempt to reduce anisotropy by introducing an optically active group.

[0006]

However, these have low strength in both MD and TD directions, low impact strength,
If a conventional vertical polymerization device for polyester production is used, solidification occurs during polymerization or the material is pulled out of the lower part of the reactor in a molten state. There was a problem that it could not be delivered. The conventional vertical polymerization apparatus for producing polyester mentioned here includes, for example, those described in Textile Handbook (Material Edition), page 808, and FIG. 7.11.

On the other hand, an attempt to improve the elastic modulus and strength by using polyesteramide has been made in Japanese Patent Application Laid-Open No. 57-177021.
In this case, the elastic modulus in the TD direction decreases, the fluidity decreases, the molding temperature increases, the solidification in a conventional vertical polymerization apparatus, etc. There was a problem. In addition, since the wholly aromatic polyester has heat resistance, the SMT-compatible electric and electronic field,
It is used in the semiconductor field such as ICs, but when used in relay parts etc., there is a problem that a lot of gas is generated, causing abnormalities in the electrical system, corrosion, etc. When used, there are problems such as a decrease in hydrolysis resistance and a deterioration in adhesion to a metal. Furthermore, when used as a bobbin, the required high withstand voltage cannot be sufficiently obtained.

An object of the present invention is to have a high modulus of elasticity, low anisotropy of modulus of elasticity, high strength and excellent impact resistance, and excellent fluidity and heat resistance as well as hydrolysis resistance. It is an object of the present invention to provide a liquid crystalline polyesteramide excellent in gas properties and an injection molded product comprising the liquid crystalline polyamide. Further, the object of the present invention is high elasticity, anisotropy of elastic modulus is small, high strength and excellent impact resistance, and also excellent fluidity and heat resistance,
Another object of the present invention is to provide a method capable of industrially easily producing a liquid crystalline polyesteramide excellent in hydrolysis resistance and low gas property and stably with good productivity.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its gist is to provide a p-aminophenol unit represented by the following formula (1):

[0010]

Embedded image An aromatic diol unit represented by the following formula (2):

[0011]

Embedded image —O—Ar ₁ —O— (2) (wherein, in the formula (2), Ar ₁ is

[0012]

Embedded image

Wherein R is a C ₁ -C ₆ alkyl group;
_{It represents} an alkoxy group of ₁ to ₆ carbon atoms, a halogen group or an aromatic group of ₆ to ₁₀ carbon atoms, m is 1 or 2, n is the number of substituents, and represents an integer of 1 to 3. ) An aromatic diol unit represented by the following formula (3):

[0014]

Embedded image (Where, r represents an integer of 1 to 4) 2,6-naphthalenedicarboxylic acid unit represented by the following formula (4):

[0015]

Embedded image A p-hydroxybenzoic acid unit represented by the following formula (5),

[0016]

Embedded image

Equations (1), (2), (3),
When the number of moles of the structural unit represented by (4) and (5) is represented by [1], [2], [3], [4] and [5], respectively, the following formulas (6) to (9) )The filling,

[0018]

## EQU4 ## 0.30≤ [5] / ([1] + [2] + [3] + [4] + [5]) ≤0.65 (6) 0.02≤ [3] / ([2] + [3] ) ≦ 0.90 (7) 0.37 ≦ [1] / ([1] + [2] + [3]) ≦ 0.80 (8) 0.80 ≦ ｛2 × ([1] + [2] + [3]) + [ 5]｝ / {2 × [4] + [5]} ≦ 1.2 (9)

The melt viscosity measured at a temperature of 280 to 350 ° C. at a shear rate of 1000 sec ⁻¹ is 1
A liquid crystalline polyesteramide having a molecular weight of 0 to 50,000 poise; and p represented by the following formula (14):
-Aminophenol,

[0020]

Embedded image An aromatic diol represented by the following formula (15):

[0021]

Embedded image HO—Ar ₁ —OH (15) (wherein, in the formula (15), Ar ₁ is

[0022]

Embedded image

Wherein R is a C ₁ -C ₆ alkyl group;
_{It represents} an alkoxy group of ₁ to ₆ carbon atoms, a halogen group or an aromatic group of ₆ to ₁₀ carbon atoms, m is 1 or 2, n is the number of substituents, and represents an integer of 1 to 3. An aromatic diol represented by the following formula (16):

[0024]

Embedded image (Where r represents an integer of 1 to 4) 2,6-naphthalenedicarboxylic acid represented by the following formula (17):

[0025]

Embedded image P-hydroxybenzoic acid represented by the following formula (18),

[0026]

Embedded image

Using equations (14), (15), and (1)
6), (17) and (18), the number of moles of the starting monomer was [14], [15], [16],
When represented by [17] and [18], the following equation (19)
Raw materials are charged at a charging ratio satisfying (22),

[0028]

0.35 ≦ [18] / ([14] + [15] + [16] + [17] + [18]) ≦ 0.65 (19) 0.02 ≦ [16] / ([15] + [16] ) ≦ 0.90 (20) 0.37 ≦ [14] / ([14] + [15] + [16]) ≦ 0.80 (21) 0.80 ≦ ｛2 × ([14] + [15] + [16]) + [ 18]｝ / ｛2 × [17] + [18]｝ ≦ 1.2 (22)

Further, an acid anhydride is added and reacted. Then, at a temperature of 80 to 400 ° C., at least one of the acid anhydride, the acid, the excess of the raw materials of the above (14) to (18) and their derivatives The present invention is directed to a method for producing a liquid crystalline polyesteramide, wherein a polymerization reaction is carried out while distilling the above.

Hereinafter, the present invention will be described in detail. The liquid crystalline polyesteramide of the present invention has the above formula (1) to
It has a structural unit represented by (5). Examples of the diol unit represented by the formula (2) include methylhydroquinone, ethylhydroquinone, n-propylhydroquinone, t-butylhydroquinone, n-hexylhydroquinone, methoxyhydroquinone, chlorohydroquinone, 2,5-dimethylhydroquinone, and trimethylhydroquinone. Phenylhydroquinone, phenylethylhydroquinone, cumylhydroquinone, 3,3'-dimethyl-4,4'-biphenol, 3,3 ', 5,5'
-Tetramethyl-4,4'-biphenol, 1,4-naphthalenediol unit and the like, but are not limited thereto, and various units may be used.

Among these, methylhydroquinone,
t-butylhydroquinone, chlorohydroquinone, trimethylhydroquinone, phenylhydroquinone,
3,3 ', 5,5'-tetramethyl-4,4'-biphenol, 1,4-naphthalenediol unit is preferred,
Methylhydroquinone, t-butylhydroquinone, phenylhydroquinone, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol and 1,4-naphthalenediol unit are more preferable, and methylhydroquinone,
1,4-Naphthalene diol units are particularly preferred, and methylhydroquinone units are most preferred. In addition, two or more of these diol units may be used.

Examples of the diol unit represented by the formula (3) include hydroquinone, 4,4'-biphenol, p-tert-phenyl-4,4'-diol, and p-quarterphenyl-4,4 '. -Diol units;
All of them are used, but hydroquinone and 4,4'-biphenol units are preferable from the viewpoint of availability of raw materials and cost, and 4,4'-biphenol and p-terphenol are preferable from the viewpoint of impact resistance. Phenyl-4,4'-diol,
P-quarterphenyl-4,4'-diol units are preferred. Most preferred are 4,4'-biphenol units. Also, two or more of these may be used.

The content ratio of each unit is calculated by the formulas (1), (2),
When the number of moles of the structural unit represented by (3), (4) and (5) is represented by [1], [2], [3], [4] and [5], the following conditions are satisfied. Fulfill. [5] /
The ratio represented by ([1] + [2] + [3] + [4] + [5]) is usually 0.30 or more and 0.65 or less, preferably 0.30 or more and 0 or more. .60, more preferably 0.30 or more and 0.55 or less. When this ratio is less than 0.30, the hydrolysis resistance is reduced and the heat resistance is reduced, which is not preferable.
If it exceeds, the elastic modulus in the TD direction decreases, the strength in both the MD and TD directions decreases, and the fluidity decreases. In addition, when a conventional vertical polymerization apparatus for producing polyester is used, the resin is discharged from the lower part of the reactor in a molten state. It is not preferable because it becomes difficult to put out.

The ratio represented by [3] / ([2] + [3]) is usually 0.02 or more and 0.90 or less, preferably 0.02 or more and 0.80 or less. . If this ratio is less than 0.02, the impact strength of the molded article becomes weak, and if a conventional vertical polymerization apparatus for producing polyester is used, it becomes difficult to extract the molten product from the lower part of the reaction vessel. Is not preferred. If it exceeds 0.80,
The elastic modulus in the TD direction of the molded article decreases, or the anisotropy of the elastic modulus (the ratio of the elastic modulus in the MD direction to the elastic modulus in the TD direction)
Is undesirably increased.

The ratio represented by [1] / ([1] + [2] + [3]) is usually from 0.37 to 0.80, preferably from 0.45 to 0.8. 80 or less,
More preferably, it is 0.45 or more and 0.75 or less.
If this ratio is less than 0.37, the elastic modulus in the TD direction of the molded article decreases, and the anisotropy of the elastic modulus increases, which is not preferable. If it exceeds 0.80,
If the impact strength of the molded product is weakened, or if a conventional vertical polymerization apparatus for producing polyester is used, it is difficult to remove the molded product from the lower part of the reactor in a molten state, which is not preferable.

｛2 × ([1] + [2] + [3])
+ [5] ＋ / {2 × [4] + [5]} is usually 0.80 or more and 1.20 or less, preferably 0.85 or more and 1.15 or less. More preferably, it is 0.85 or more and 1.05 or less. This percentage is
If the ratio is less than 0.80 or exceeds 1.20, the degree of polymerization is not improved, so that the strength and elongation of the molded product are reduced, and the impact resistance is also reduced. Also,
When this ratio exceeds 1.20, when a molded product is used at a high temperature, a gas is generated from the molded product, which causes a problem such as abnormality of an electric system near the molded product, corrosion, and the like, which is preferable. Absent.

Further, the above [3] / ([2] + [3])
(Expressed as S) and [1] / ([1]
+ [2] + [3]), there is no particular limitation on the relationship with the ratio (expressed as T),

[0038]

It is preferable that the relationship T ≧ 0.35S + 0.4 is satisfied,

[0039]

[Formula 7] 0.35S + 0.65 ≧ T ≧ 0.35S + 0.45

It is more preferable that the above relationship is satisfied. The liquid crystalline polyesteramide of the present invention may contain, in addition to the above structural units, resorcinol, dihydroxy compound units such as 4,4'-dihydroxydiphenyl ether, terephthalic acid, isophthalic acid, 1,2-bis (2-
Chlorophenoxy) ethane-4,4'-dicarboxylic acid,
4,4'-dicarboxydiphenyl ether, 2,2 '
Dicarboxylic acid units such as -biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 6-hydroxy-2-naphthoic acid, 3-
Oxycarboxylic acid units such as chloro-4-hydroxybenzoic acid and m-hydroxybenzoic acid, p-aminobenzoic acid,
Even if a small amount of a structural unit such as an amino compound unit such as m-aminobenzoic acid, m-aminophenol, p-phenylenediamine and m-phenylenediamine is contained as a copolymer component within a range not to impair the effects of the present invention, Good.

The melt viscosity of the liquid crystalline polyesteramide of the present invention is 10 to 500 at a temperature of 280 to 350 ° C. and a shear rate of 1000 sec ^−1.
00 poise, preferably 50 to 10,000 poise, more preferably 70 to 5000 poise, and particularly preferably 100 to 3000 poise. The liquid crystalline polyesteramide of the present invention having a melt viscosity in such a range can be easily molded by heating and melting at 280 to 350 ° C. In addition, since molding can be performed at a low molding temperature of 350 ° C. or less, molding can be performed using a molding apparatus such as a conventional extrusion molding apparatus or injection molding apparatus. When the melt viscosity of the polyesteramide is less than 10 poise, the resin is sagged from a die and a nozzle at the time of molding due to low viscosity, and molding is difficult, or the strength or elongation of the molded product is preferably reduced. On the other hand, if it exceeds 50,000 poise, it is not preferable because high viscosity and high pressure and high speed molding are required at the time of molding and moldability deteriorates.

Next, the manufacturing method will be described. The polyesteramide of the present invention can be produced according to a conventional polyester production method. For example, it can be produced using a solution polycondensation method, an interfacial polycondensation method, a melt polycondensation method, or the like. Among these, the degree of polymerization is easily improved,
In addition, the melt polycondensation method is preferred in that no post-treatment such as solvent removal after polymerization is required.

The melt polycondensation method includes: 1) a method in which at least one or more of a phenolic compound, an amino compound and an acid compound is reacted with an acid anhydride and then produced by a deacidification polycondensation reaction; An acidic compound and / or an amino compound;
A method of reacting an acid anhydride and then adding an acid compound to produce the compound by a deacidification polycondensation reaction; 3) a phenolic compound and / or an amino compound;
From ester compounds such as phenyl esters of acid compounds,
A method in which a hydroxy compound such as phenol is produced while being desorbed. As the method for producing the polyesteramide of the present invention, any of the above methods can be used, and among them, the above methods 1) and 2) are preferable, and the method 1) is more preferable. Acid anhydrides used in the above methods 1) and 2) include acetic anhydride, propionic anhydride,
Any of benzoic anhydride and the like can be used,
Of these, acetic anhydride is preferred. These acid anhydrides may be used alone or as a mixture of two or more.

In the production method of the present invention, the above formula (1)
4) Use the raw material monomers shown in (18). Examples of the diol represented by the formula (15) include methylhydroquinone, ethylhydroquinone, n-propylhydroquinone, t-butylhydroquinone, n-hexylhydroquinone, methoxyhydroquinone, chlorohydroquinone, 2,5-dimethylhydroquinone, trimethylhydroquinone, Phenylhydroquinone, phenylethylhydroquinone, cumylhydroquinone, 3,
3'-dimethyl-4,4'-biphenol, 3,3 ',
5,5'-tetramethyl-4,4'-biphenol,
Examples thereof include 1,4-naphthalene diol and the like, but are not limited thereto, and various types may be used.

Among these, methylhydroquinone,
t-butylhydroquinone, chlorohydroquinone, trimethylhydroquinone, phenylhydroquinone,
3,3 ', 5,5'-Tetramethyl-4,4'-biphenol and 1,4-naphthalenediol are preferred, and methylhydroquinone, t-butylhydroquinone, phenylhydroquinone, 3,3', 5,5'- Tetramethyl-4,4'-biphenol and 1,4-naphthalenediol are more preferred, and methylhydroquinone, 1,4-
Naphthalenediol is particularly preferred, and methylhydroquinone is most preferred. These diols may be used as a mixture of two or more.

Examples of the diol represented by the formula (16) include hydroquinone, 4,4'-biphenol,
Examples thereof include p-tert-phenyl-4,4'-diol and p-quarterphenyl-4,4'-diol, all of which are used. However, from the viewpoint of easy availability of raw materials and cost, hydroquinone, 4,4'-biphenol is preferred, and from the viewpoint of impact resistance, 4,4'-biphenol and
P-tert-phenyl-4,4'-diol and p-quarterphenyl-4,4'-diol are preferred. Most preferred is 4,4'-biphenol. These may be used as a mixture.

The charging ratio of each raw material monomer is expressed by the formula (1)
4), (15), (16), (17) and (18), the number of moles of the raw material monomers are [14],
When represented by [15], [16], [17] and [18], the following conditions are satisfied. [18] / ([1
4] + [15] + [16] + [17] + [18]) is usually 0.30 or more and 0.65 or less, preferably 0.30 or more and 0.60 or less. Is the following,
More preferably, it is 0.30 or more and 0.55 or less.
When this ratio is less than 0.30, hydrolysis resistance is reduced, or heat resistance is reduced, which is not preferable.
If it exceeds 0.65, the elastic modulus decreases in the TD direction, MD,
If the strength and the fluidity in both directions of TD decrease, and if a conventional vertical polymerization apparatus for producing polyester is used, it is difficult to extract the molten state from the lower part of the reactor, which is not preferable.

The ratio represented by [16] / ([15] + [16]) is usually 0.02 or more and 0.90 or less.
Preferably, it is 0.02 or more and 0.80 or less. If this ratio is less than 0.02, the impact strength of the molded article becomes weak, and if a conventional vertical polymerization apparatus for producing polyester is used, it becomes difficult to extract the molten product from the lower part of the reaction vessel. Is not preferred. If it exceeds 0.80, the elasticity of the molded article in the TD direction decreases, or the anisotropy of the elasticity (the ratio of the elasticity in the MD direction to the elasticity in the TD direction) increases. Not preferred.

[14] / ([14] + [15] + [1
6]) is 0.37 or more and 0.80 or less, preferably 0.45 or more and 0.80 or less, and more preferably 0.45 or more and 0.75 or less. . If this ratio is less than 0.37, the elastic modulus in the TD direction of the molded article decreases, and the anisotropy of the elastic modulus increases, which is not preferable. If it exceeds 0.80, the impact strength of the molded article becomes weak, or if a conventional vertical polymerization apparatus for producing polyester is used, it becomes difficult to remove the molded product from the lower part of the reaction vessel in a molten state. Absent.

Also, ｛2 × ([14] + [15] + [1
6]) + [18]｝ / {2 × [17] + [18]} is usually 0.80 or more and 1.20 or less, preferably 0.85 or more and 1.15 or more. Or less, more preferably 0.85 or more and 1.05 or less. If this ratio is less than 0.80 or more than 1.20, the degree of polymerization does not improve, so that the strength and elongation of the molded product are reduced, and the impact resistance is also reduced. If the ratio exceeds 1.20, when the molded product is used at a high temperature, a gas is generated from the molded product, causing a problem such as an abnormality in an electric system near the molded product, corrosion, and the like. Is not preferred.

Further, the above [16] / ([15] + [1
6]) (expressed as x) and [14] /
([14] + [15] + [16])
It is expressed as ) Is not particularly limited,

[0052]

It is preferable that the relationship y ≧ 0.35x + 0.4 is satisfied.

[0053]

## EQU9 ## 0.35x + 0.65 ≧ y ≧ 0.35x + 0.45

More preferably, the following relationship is satisfied. In addition, the liquid crystalline polyesteramide according to the production method of the present invention, in addition to the raw material monomers, resorcinol,
Dihydroxy compounds such as 4,4'-dihydroxydiphenyl ether, terephthalic acid, isophthalic acid, 1,2
-Bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'- Dicarboxylic acids such as biphenyl dicarboxylic acid, oxycarboxylic acids such as 6-hydroxy-2-naphthoic acid, 3-chloro-4-hydroxybenzoic acid and m-hydroxybenzoic acid, p-aminobenzoic acid, and m-aminobenzoic acid; m-aminophenol, p-
Raw monomers such as amino compounds such as phenylenediamine and m-phenylenediamine may be contained in a small amount as a copolymer component as long as the effects of the present invention are not impaired.

In the production method of the present invention, the above (14) to (14)
The raw material monomer represented by (18) is charged into the polymerization reactor at the above ratio, and an acid anhydride is added in the system to cause a reaction.
Examples of the type of the acid anhydride include acetic anhydride, propionic anhydride, benzoic anhydride and the like, but are not limited thereto, and any of them is used, and among them, acetic anhydride is preferable. These may be used as a mixture. The amount of the acid anhydride to be added is as follows:
It is preferred to 0.8 to 5.0 times by mole the addition of the total amount of group and -NH ₂ group, more preferably a 0.9 to 3.0-fold mol, particularly preferably 1.0 to 2. It is 0 times mol. The reaction temperature between the starting monomer and the acid anhydride is usually 80
-200 ° C, preferably 100-180 ° C, particularly preferably 120-160 ° C. The reaction time is usually from 5 minutes to
It is 10 hours, preferably 10 minutes to 5 hours, particularly preferably 30 minutes to 2 hours.

Then, at a temperature of 80 to 400 ° C., a polymerization reaction is carried out in a molten state while distilling off at least one of the acid anhydrides, acids, and excess materials (14) to (18) and their derivatives. . The temperature is preferably increased gradually from the acetylation reaction temperature to the final polymerization temperature,
The final polymerization temperature is preferably not higher than 350 ° C. 3
When the temperature is 25 ° C. or lower, the polymerization reaction is carried out using a conventional vertical polymerization reaction apparatus for producing polyester, and it can be discharged in a molten state from the lower part of the reaction vessel, which is more preferable. The conventional vertical polymerization reactor for producing polyester mentioned here includes, for example, those described in Textile Handbook (Material Edition), page 808, and FIG. 7.11.

It is also preferable to carry out the reaction at 270 to 325 ° C. for 10 minutes to 2 hours at a constant temperature during or after the temperature raising step and before decompression, in order to make the charge ratio and the constituent ratio of the produced polymer coincide. Thereafter, if necessary, the temperature is raised again to the final polymerization temperature. Further, in order to adjust the composition ratio of the final polymer to a desired composition ratio, (I) a method in which each raw material is adjusted in advance to a desired composition ratio of the final polymer, and then charged (the desired polymer ratio of the final polymer) (Method used when composition ratio satisfies formulas (19) to (22)) (II) Each raw material is charged so as to satisfy formulas (19) to (22) and differ from the desired composition ratio of the final polymer. , Starting monomers, particularly aminophenols and / or aromatic diols and / or some of their derivatives,
Alternatively, a method of intentionally distilling during the polymerization under reduced pressure and adjusting the final polymer so as to have a desired composition ratio (the case where the desired composition ratio of the final polymer satisfies Formulas (19) to (22) is not satisfied) The method used also in the case) is used. When the method (II) is used, the time of the heating step is reduced, the inert gas such as nitrogen or argon is circulated during the heating step, the decompression rate during the decompression polymerization is increased, The aminophenol and / or the aromatic diol and / or some of their derivatives can be positively distilled off by a method such as increasing the temperature.

In this case, when methylhydroquinone is used as the aromatic diol represented by the formula (15) and acetic anhydride is used as the acid anhydride, the melting point and boiling point of the diacetate of methylhydroquinone are relatively low. For,
It is preferable because it can be easily distilled in a liquid state during the temperature raising step and the polymerization under reduced pressure. After reaching the final polymerization temperature, the polymerization reaction system is evacuated to a reduced pressure, and the acid anhydride, acid and excess (14) to (1)
It is preferable to distill off at least one or more of the raw material 8) and its derivative. The final degree of pressure reduction may be determined in relation to the polymerization time, but the higher the pressure reduction (the lower the pressure), the shorter the polymerization time. The pressure reduction rate is preferably 30 minutes or more, more preferably 60 minutes or more, to reduce the pressure from normal pressure to the final pressure reduction degree. In particular, it is important to gradually reduce the pressure from 50 mmHg to the final degree of reduced pressure. The preferred polymerization time is 10 hours or less, more preferably 5 hours or less from the start of pressure reduction to the end of polymerization.

In the production method of the present invention, a compound containing a metal of Group (VIII) of the periodic table is preferably used as a catalyst in the polymerization reaction. Examples of the metal of the Periodic Table Group (VIII) include iron, cobalt, nickel, ruthenium, palladium, platinum and the like. Of these, iron, cobalt,
Nickel and palladium are preferred, iron, cobalt and nickel are more preferred, and iron and nickel are particularly preferred. Most preferred is iron.

As the compound, acetate of the above metal,
Examples include, but are not limited to, acetylacetonate, chloride, bromide, oxide, and the like. Of these, acetate, acetylacetonate and chloride are preferred. The polymerization catalyst may be one with water of crystallization or an anhydride excluding water of crystallization. Further, the above polymerization catalysts may be used as a mixture.

The amount of the polymerization catalyst to be added is not particularly limited.
Preferably from 10 to the weight of the raw material monomer charged
10,000 ppm, more preferably 20 to 2000 pp
m, particularly preferably from 30 to 1000 ppm. The timing of adding the polymerization catalyst is not particularly limited, but when polymerization is finally performed under reduced pressure, it is preferable to add the polymerization catalyst after the initial raw material charge and before the start of pressure reduction at the final polymerization temperature. The compound may be added as a compound itself (powder or liquid) or may be added after being dissolved or dispersed in a solvent.

This polymerization can be carried out at a relatively low temperature. At that time, since it is possible to withdraw from the lower part of the polymerization apparatus in a molten state, there is no trouble at the time of withdrawal, and the conventional vertical length for polyester production can be used. It can be manufactured using a mold polymerization apparatus. The liquid crystalline polyesteramide of the present invention can be performed only by melt polymerization using a conventional vertical polymerization apparatus for producing polyester, a horizontal kneader-type reaction apparatus may be used, or solid-state polymerization may be performed after melt polymerization. It is also possible to increase the degree of polymerization by carrying out.

By adopting the above-mentioned production method, a liquid crystalline polyesteramide having terminal groups mainly composed of CH ₃ COO— and / or —COOH groups,
A liquid crystalline polyesteramide having many OH groups and few terminal CH ₃ COO— groups can be produced. Specifically, terminal CH ₃ COO- group, the concentration of -COOH group, respectively [CH ₃ COO -], - when expressed by [COOH], the following equation (12), to satisfy the (13) preferably .

[0064]

[CH ₃ COO−] ≦ 30 (equivalent / ton) (12) [−COOH] ≧ 120 (equivalent / ton) (13) More preferably,

[0065]

[CH ₃ COO−] ≦ 20 (equivalent / ton), and particularly preferably

[0066]

[CH ₃ COO−] ≦ 10 (equivalent / ton)

Is as follows. Incidentally, in the conventionally known method, the terminal C
The concentrations of the H ₃ COO— group and the —COOH group are substantially the same, but even in such a case, in the liquid crystalline polyesteramide having a structural unit in the present invention, MD,
The respective elastic moduli in both TD directions are improved. However, according to the above manufacturing method, the above formulas (12) and (1)
By simultaneously satisfying 3), the hydrolysis resistance is further improved, and the gas generated during use of the liquid crystalline polyesteramide molded product can be significantly reduced.

The liquid crystalline polyester amide of the present invention
The bending elastic modulus in the TD direction of a molded plate having a square or circular projection surface, which is obtained by heating and melting at 80 to 350 ° C. and formed, is preferably 5 GPa or more, and more preferably 5.5 GPa or more. Further, the ratio of the bending elastic modulus FMMD in the MD direction to the bending elastic modulus FMTD in the TD direction (FMM
D / FMTD) is preferably 2 or less, and 1.5
It is more preferred that:

As a method of measuring the elastic modulus, it is preferable to use a molded flat plate having a square or circular projection surface.
For commonly used molded pieces such as dumbbell type and strip type,
Since the flow lengths in the MD direction and the TD direction are significantly different, it is difficult to accurately measure the original physical properties in both directions, and it is difficult to accurately measure the anisotropy between the two directions even in the measurement of the elastic modulus. is there. Therefore, when measuring the elastic modulus of a material having low anisotropy of elastic modulus, such as the polyesteramide of the present invention, it is preferable to use a molded plate having the same size in both the MD and TD directions. The size and thickness of the formed plate are not limited, but the length (d ₁ ) of a square or the diameter (d ₂ ) of a circle is preferably 1 to 500 cm. Plate thickness (t)
Is preferably 0.01 to 10 cm, and 0.05 to 10 cm.
10 cm is more preferred, but in any case,

[0070]

## EQU13 ## 10 ≦ (d ₁ or d ₂ ) / t ≦ 1000

It is preferable that In addition, ASTM
 Notched Izod impact measured according to D256
Strength is 10kg · cm / cm^TwoPreferably more than
15kg ・ cm / cm ^TwoMore preferably
Good. The liquid crystalline polyesteramide of the present invention is
Shows optical anisotropy. In particular, the melting start temperature
Then, raise the temperature a little,
Since most of them melt and show optical anisotropy,
It has better fluidity than steal. Therefore, moldability
Good for extrusion molding, injection molding, compression molding, etc.
Melt molding can be performed, thereby
It can be processed into products, films, fibers and the like.

Industrial applications of the liquid crystalline polyesteramide of the present invention include melt molding such as injection molding, extrusion molding, and compression molding, as well as materials for machine parts, connectors, relays, and the like.
It is used as a material for electric and electronic parts such as bobbins, a sealing material such as ICs, a material for horizontal and vertical outer panels of automobiles, a material for various automobile parts, a material for containers such as trunks and cases, films, sheets, fibers and the like. In particular, injection-molded products have excellent hydrolysis resistance, and when used at high temperatures, or when re-melted for recycling, etc., generate very little gas and generate little burrs during molding. Because of its excellent dimensional accuracy, it is suitable for thin molded products and precision molded products.

Further, since it has excellent adhesiveness, paintability, and heat resistance, it can be suitably used as a material for horizontal and vertical outer panels for automobiles and automobile parts having good paintability. Also, 2
Since it also has solder heat resistance of 60 ° C. or higher, it is suitable for electric and electronic component materials compatible with surface mounting technology (SMT), particularly for components such as relays, connectors, coil bobbins, and IC sealing materials.

Further, the liquid crystalline polyesteramide of the present invention may be mixed with fibers such as glass fibers and carbon fibers, fillers such as talc, mica and calcium carbonate, nucleating agents, pigments, antioxidants, lubricants, flame retardants, By adding a stabilizer or the like to impart desired properties to the molded article, or by blending it with another polymer, a composition having the features of both polymers can be obtained.

[0075]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. In addition, the measurement of the physical properties in the following Examples and Comparative Examples was performed as follows. (1) Melt viscosity Using a flow tester CFT500 manufactured by Shimadzu Corporation,
Using a nozzle having a length / diameter of 20 and a shear rate of 1000 s
It was measured at ec ^-1 .

(2) Preparation of Test Specimen A polymer was melted at 280 to 350 ° C. using a J5S type manufactured by Nippon Steel Works or an IS45 type manufactured by Toshiba Machine Co., Ltd. Was molded. As a test piece for measuring bending properties in both MD / TD directions,
A flat plate having a thickness of 80 mm x 80 mm x 2 mm was formed. One of these molded pieces has the major axis in the MD direction, and the other has T
With the major axis in the direction D, the sheet was cut out to a thickness of 40 mm × 6 mm × 2 mm, and the bending properties were measured. The molded piece for the impact strength test conformed to ASTM D256. A 1/8 inch thick non-notched molded piece was molded. In addition, a molded piece having a thickness of 60 mm × 3.2 mm × 1.0 mm was formed for a hydrolysis resistance test.

(3) Flexural Properties (Flexural Modulus (FM) and Flexural Strength (FS)) Using the above molded specimen for flexural properties test, it was measured using TENSILON / UTM (III) L manufactured by Toyo Baldwin. (4) Terminal group analysis n-propylamine was added to the pulverized polymer, and the mixture was treated at room temperature for 24 hours. The product was purified by HPLC (terminal-CO
OH measurement) and GC (terminal CH ₃ COO-group measurement) to separate and quantitate the product from the terminal.

(5) Measurement of Hydrolysis Resistance Using the above molded pieces, the retention of bending strength before and after treatment at 121 ° C., 2 atm, 100% RH and 100 hours was measured using a pressure cooker tester. (6) Heat generation gas amount analysis Pelletized polymer is put into a glass vial,
After sealing and heating at 200 ° C. for 1 hour, the gas in the vial was charged into the GC to quantify the components.

(7) Composition Ratio Analysis A methanol solution of tetramethylammonium hydroxide was added to the pulverized polymer, and the polymer was pyrolyzed using pyrolysis GC to quantify the components. (8) Optical Anisotropy (Liquid Crystallinity) Observation was performed using a polarizing microscope equipped with a hot stage. In the case of exhibiting liquid crystallinity, a schlieren pattern was observed.

Example 1 A glass reactor equipped with a stirrer, a pressure reducing port, and a nitrogen inlet tube was used.

[0081]

TABLE 1 14.10 g of p-aminophenol
(0.129 mol) 15.24 g of methylhydroquinone
(0.123 mol) 4,4'-biphenol 1.20 g
(0.006 mol) 2,6-naphthalenedicarboxylic acid 55.89 g
(0.259 mol) p-hydroxybenzoic acid 53.56 g
(0.388 mol) 101.61 g of acetic anhydride
(0.996 mol) (1.1 of the total amount of -OH groups and -NH ₂ groups of the raw material monomers)
0.07 g of iron (III) acetylacetone (500 ppm based on the weight of the raw material monomer)

After the vacuum / nitrogen substitution was performed three times, the mixture was placed in a 150 ° C. oil bath. 1 with stirring
After reacting at 50 ° C. for 1 hour, the oil bath temperature was raised to 290 ° C. over 2 hours, and the reaction was carried out at that temperature for 30 minutes. Thereafter, the temperature was raised to 320 ° C. over 30 minutes, and then the pressure was reduced from normal pressure to 10 mmHg over 1 hour. The polymerization reaction was continued for 2 hours, and the polymerization reaction was terminated. This polymer dropped under its own weight in the molten state from the bottom of the reactor, had good pull-out properties, and was found to be able to be produced in a normal polyester polymerization apparatus. The composition ratio (molar ratio) of the structural units of this polymer was as follows, and was consistent with the charging ratio.

[0083]

[14] [5] / ([1] + [2] + [3] + [4]
+ [5]) = 0.43 [3] / ([2] + [3]) = 0.05 (= S) [1] / ([1] + [2] + [3]) = 0. 50 (=
T) T−0.35S = 0.48 ｛2 × ([1] + [2] + [3]) + [5]｝ / ｛2 ×
[4] + [5]｝ = 1.00 The physical properties of this polymer were as shown in Table-2.

Examples 2 to 19 Reaction was carried out in the same manner as in Example 1 except that the types of raw materials and the charging ratios were changed as shown in Table 1, to obtain polymers. The physical properties of each polymer were as shown in Table-2. Also,
The composition ratio (molar ratio) of the structural units of these polymers was consistent with the charge ratio. The injection molding was performed at the melt viscosity measurement temperature in each example.

Comparative Examples 1 to 8 Reactions were carried out in the same manner as in Example 1 except that the types of raw materials and the charging ratios were changed as shown in Table 1, to obtain polymers. The physical properties of each polymer were as shown in Table-2. Also,
The composition ratio (molar ratio) of the structural units of these polymers was consistent with the charge ratio. The injection molding was performed at the melt viscosity measurement temperature in each example.

Example 20 A glass reactor equipped with a stirrer, a pressure reducing port, and a nitrogen inlet tube was used.

[0087]

Table 2 16.01 g of p-aminophenol
(0.147 mol) 7.42 g of methylhydroquinone
(0.060 mol) 2.78 g of 4,4'-biphenol
(0.015 mol) 47,89 g of 2,6-naphthalenedicarboxylic acid
(0.222 mol) p-hydroxybenzoic acid 45.89 g
(0.333 mol) 87.07 g of acetic anhydride
(0.854 mol) (1.1 of the total amount of -OH groups and -NH ₂ groups of the raw material monomers)
0.06 g of iron (III) acetylacetone (500 ppm based on the weight of the raw material monomer)

After the vacuum / nitrogen substitution was performed three times, the mixture was placed in an oil bath at 150 ° C. 1 with stirring
After reacting at 50 ° C. for 1 hour, the oil bath temperature was raised to 290 ° C. over 2 hours, and the reaction was carried out at that temperature for 30 minutes. Thereafter, the temperature was raised to 320 ° C. over 30 minutes, and then the pressure was reduced from normal pressure to 10 mmHg over 1 hour. The polymerization reaction was continued for 2 hours, and the polymerization reaction was terminated. This polymer dropped under its own weight in the molten state from the bottom of the reactor, had good pull-out properties, and was found to be able to be produced in a normal polyester polymerization apparatus. The composition ratio (molar ratio) of the structural units of this polymer was as follows, and was consistent with the charging ratio.

[0089]

[Equation 15] [5] / ([1] + [2] + [3] + [4]
+ [5]) = 0.43 [3] / ([2] + [3]) = 0.20 (= S) [1] / ([1] + [2] + [3]) = 0. 66 (=
T) T−0.35S = 0.59 ｛2 × ([1] + [2] + [3]) + [5]｝ / ｛2 ×
[4] + [5]｝ = 1.00 The physical properties of this polymer are shown in Table-4.

Examples 21 to 33 The reaction was carried out in the same manner as in Example 21 except that the types of raw materials and the charging ratios were changed as shown in Table 3, to obtain polymers.
In each example, the total charged amount of the raw material monomers (14) to (18) is 120 g. The physical properties of each polymer are shown in Table-4. The composition ratio (molar ratio) of the structural units of these polymers was consistent with the charge ratio. The injection molding was performed at the melt viscosity measurement temperature in each example.

Comparative Examples 9 to 13 A reaction was carried out in the same manner as in Example 21 except that the kinds of raw materials and the charging ratios were changed as shown in Table 3, to obtain polymers.
The total charged amount of the raw material monomers (14) to (18) in each comparative example is 120 g. In Comparative Example 14, hydroquinone was used in place of the raw material monomer (15).
5). The physical properties of each polymer are shown in Table-4. Composition ratio (molar ratio) of structural units of these polymers
Was consistent with the charge ratio. The injection molding was performed at the melt viscosity measurement temperature of each comparative example.

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

[0095]

[Table 6]

[0096]

According to the present invention, the liquid crystalline polyesteramide is
It shows high elastic modulus and high strength not only in the flow direction (MD) of the resin but also in the direction (TD) perpendicular to the flow direction, and shows high impact strength despite low anisotropy. In addition, because of its excellent fluidity, heat resistance, hydrolysis resistance and low gas resistance, it can be used as a material for machine parts, connectors and relays by melt molding such as injection molding, extrusion molding and compression molding. , Materials for electric and electronic parts such as bobbins, sealing materials such as ICs, materials for horizontal and vertical outer panels of automobiles, materials for various automobile parts, materials for containers such as trunks and cases, films, sheets, fibers, etc. Can be.

Further, by producing a liquid crystalline polyamide according to the production method of the present invention, the liquid crystalline polyamide has a high modulus of elasticity, a small anisotropy of the modulus of elasticity, not only in the flow direction (MD) of the resin but also in the flow direction. Shows high elastic modulus in the vertical direction (TD), high strength, excellent impact resistance, excellent fluidity and heat resistance, and excellent hydrolysis resistance and low gas resistance. The advantage is that the liquid crystalline polyesteramide can be produced industrially simply and stably with good productivity.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-132925 (JP, A) JP-A-6-3455863 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 69/00-69/50

Claims (9)

(57) [Claims] 1. A p-aminophenol unit represented by the following formula (1): An aromatic diol unit represented by the following formula (2): —O—Ar ₁ —O— (2) (wherein, in the formula (2), Ar ₁ is R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a halogen group or a C ₆ -C ₁₀ aromatic group, m is 1 or 2, and n is the number of substituents. And 1 to 3
Represents an integer. ) An aromatic diol unit represented by the following formula (3): (Where r represents an integer of 1 to 4) 2,6-naphthalenedicarboxylic acid unit represented by the following formula (4): A p-hydroxybenzoic acid unit represented by the following formula (5): And the number of moles of the structural units represented by the formulas (1), (2), (3), (4) and (5) is
When represented by [1], [2], [3], [4], and [5], the following expressions (6) to (9) are satisfied, and: 0.30 ≦ [5] / ([1] + [2] + [3] + [4] + [5]) ≦ 0.65 (6) 0.02 ≦ [3] / ([2] + [3]) ≦ 0.90 (7) 0.37 ≦ [1] / ([ 1] + [2] + [3]) ≦ 0.80 (8) 0.80 ≦ {2 × ([1] + [2] + [3]) + [5]} / ｛2 × [4] + [5] ｝ ≦ 1.2 (9) The melt viscosity measured at a temperature of 280 to 350 ° C. and a shear rate of 1000 sec ⁻¹ is 10 to 5000.
A liquid crystalline polyesteramide having 0 poise. 2. The liquid crystalline polyesteramide according to claim 1, wherein the aromatic diol unit represented by the formula (2) is a methylhydroquinone unit represented by the following formula (10). Embedded image 3. The unit according to claim 1, wherein the aromatic diol unit represented by the formula (3) is a 4,4′-biphenol unit represented by the following formula (11). Liquid crystalline polyester amide. Embedded image 4. The terminal group mainly comprises a CH ₃ COO— group and / or a —COOH group, and a CH ₃ COO— group, a —C
The concentration of the OOH group was changed to [CH ₃ COO-], [-C
OOH], wherein the following formulas (12) and (13) are satisfied. [CH ₃ COO−] ≦ 30 (equivalent / ton) (12) [−COOH] ≧ 120 (equivalent / ton) (13) 5. A flexural modulus in the TD direction of a molded plate having a square or circular projection surface obtained by heating and melting at 280 to 350 ° C. and having a square or circular shape is 5 GPa or more, and a flexural modulus in the MD direction FMMD. And flexural modulus FMTD in TD direction
Ratio (FMMD / FMTD) is 2 or less, and ASTM
The liquid crystalline polyesteramide according to any one of claims 1 to 4, wherein a notch-free Izod impact strength measured according to D256 is 15 kg · cm / cm ² or more. 6. An injection molded article comprising a liquid crystalline polyamide obtained by injection molding the liquid crystalline polyesteramide according to any one of claims 1 to 5. 7. A p-aminophenol represented by the following formula (14): An aromatic diol represented by the following formula (15): HO—Ar ₁ —OH (15) (wherein, in the formula (15), Ar ₁ is R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a halogen group or a C ₆ -C ₁₀ aromatic group, m is 1 or 2, and n is the number of substituents. And 1 to 3
Represents an integer. ) An aromatic diol represented by the following formula (16): (Where r represents an integer of 1 to 4) 2,6-naphthalenedicarboxylic acid represented by the following formula (17): P-hydroxybenzoic acid represented by the following formula (18): And the molar numbers of the starting monomers represented by the formulas (14), (15), (16), (17) and (18) are respectively [14], [15], [16], [17] and When represented by [18], the raw materials are charged at a charging ratio that satisfies the following formulas (19) to (22), and 0.30 ≦ [18] / ([14] + [15] + [16] + [17] + [18]) ≦ 0.65 (19) 0.02 ≦ [16] / ([15] + [16]) ≦ 0.90 (20) 0.37 ≦ [14] / ([14] + [15] + [ 16]) ≦ 0.80 (21) 0.80 ≦ {2 × ([14] + [15] + [16]) + [18]} / {2 × [17] + [18]} ≦ 1.2 (22) Further acid The anhydride was added and reacted, and then 80-40
At a temperature of 0 ° C., acid anhydride, acid, excess (14) to
(18) A method for producing a liquid crystalline polyesteramide, wherein the polymerization reaction is carried out while distilling off at least one or more of the raw materials and their derivatives. 8. The process for producing a liquid crystalline polyesteramide according to claim 7, wherein a compound containing a metal of Group (VIII) of the periodic table is used as a catalyst in the polymerization reaction. 9. The method for producing a liquid crystalline polyesteramide according to claim 8, wherein the metal of Group (VIII) of the periodic table is Fe.