JPH05170903A - Copolyester amide and its production - Google Patents

Abstract

PURPOSE:To obtain a copolester amide capable of arbitrarily controlling a softening temperature, having excellent high fluidity, heat resistance, moldability and processability by copolymerizing raw materials with a hydroxyphenylalkyl alcohol-based compound as an essential raw material component. CONSTITUTION:Raw materials comprising compounds of formula I to formula V [R1 to R3 are organic group (derivative) of formula VI to formula VIII (X is O, CO, COO, SO2, S or alkylene group; (m) and (n) are 0 or 1); R4 and R5 are aromatic ring; Y is OH or NH2; (1) is 1-4 integer] are acylated with an acid anhydride of 1-4C aliphatic carboxylic acid, then subjected to condensation polymerization through deacidification to give a polyester amide comprising structural units of formula IX to formula XIII (Y is O or NH) wherein the amount of the unit of formula IX is 20-90mol% unit of formula IX + formula X, the amount of the unit of formula XII is 0.1-60mol% unit of formula XI + formula XII + formula XIII, the amount of the unit of formula XIII is 1-50mol% unit of formula IX + formula XII + formula XIII, the molar ratio of formula X/(formula IX + formula XII + formula XIII) is 10/9 to 9/10, the softening point is 150-400 deg.C and melt viscosity (melting point + 30 deg.C, 10<3>/second shear rate) is <=10<4> poise.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful copolymerized polyester and a method for producing the copolymerized polyester. More specifically, it is excellent in heat resistance and moldability obtained by using hydroxyphenylalkyl alcohols (D ′) as an essential raw material component.
The present invention relates to thermotropic liquid crystal polyesteramides and a method for producing the same.

Therefore, the copolyesters in the present invention are naturally atomic groups (groups) based on the hydroxyphenylalkyl alcohols (D ').

[0003]

[Chemical 21]

The following groups are contained in the molecule.

[0005]

2. Description of the Related Art In recent years, there has been an increasing demand from the industrial world for high performance of organic polymer materials, and injection molded products excellent in mechanical properties such as strength and elastic modulus and thermal properties such as heat resistance have been developed. Initially, the advent or emergence of various products such as films and fibers is strongly desired.

In particular, so-called thermotropic liquid crystal polyesters exhibiting an optically anisotropic molten phase have attracted attention as polymer materials satisfying the above requirements, and many copolyesters having different chemical structures have been noted. Kinds have been proposed. Some of them have already been manufactured industrially.

When such a copolyester is melted and molded, the molecular chains are easily aligned in one direction to form a highly oriented structure, and a molded product having excellent mechanical properties is provided.

Further, it is known that various molded products obtained from wholly aromatic polyester containing an aromatic chain at a high density have extremely high mechanical strength and heat resistance.

Thus, the wholly aromatic polyesters are
Excellent as a high-performance material, especially Japanese Patent Publication No. 47-47
870, JP-A-50-43223, JP-A-54-46291, JP-A-55-94930, JP-A-55-149321, and JP-A-56-4.
According to the procedures described in Japanese Patent No. 3319 and Japanese Patent Application Laid-Open No. 57-135830, a wholly aromatic polyester obtained from 4-hydroxybenzoic acid, terephthalic acid, and 4,4′-dihydroxybiphenyl is It is said that some of them have high strength and high elastic modulus and have practical heat resistance up to 350 ° C.

However, since the melting point is remarkably high at 400 ° C. or higher, the molding temperature also needs to be high at 380 to 420 ° C. or higher, and a special molding device or the like must be used. There is.

A method of co-condensing 2,6-hydroxynaphthoic acid in order to lower this melting point and thereby improve moldability (Japanese Patent Laid-Open Nos. 54-577691 and 55-144024). Japanese Laid-Open Patent Publication No. 56-1
0526, JP-A-57-87422, JP-A-57-177019, and JP-A-57-17702.
No. 0 and JP-A No. 57-172921) and a method of co-condensing a naphthalene derivative (JP-A No.
4-50594, JP-A-56-43319, JP-A-57-177021, JP-A-58-1.
No. 722 and JP-A No. 62-207327) have been proposed.

On the other hand, thermotropic liquid crystalline copolymerized polyesteramides in which amide groups are introduced into these copolymerized polyesters have been studied for the purpose of imparting further mechanical properties. Polyester amides are disclosed in JP-A-55-27391 and JP-A-5-27391.
7-172921, JP-A-57-177019, JP-A-57-177020, JP-A-57-
177021, JP-A-58-89618,
JP-A-59-47229, JP-A-60-4021
No. 7, JP-A-60-245631, JP-A-62-132927, and the like.

However, like the above-mentioned copolyesters, such a thermotropic liquid crystalline copolyester amide in which amide groups are introduced into the copolyesters has a property in which heat resistance and moldability are contradictory to each other. It is difficult to satisfy both requirements, and therefore it is not yet fully satisfactory.

[0014]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned disadvantages in the prior art and further impairs the balance between the excellent mechanical properties and the heat resistance of the thermotropic liquid crystal polyester amides. Without
By reducing the melt viscosity of the thermotropic liquid crystal polyester amides and allowing the melt phase to exhibit optical anisotropy (liquid crystallinity), the moldability is further improved, and the mechanical performance and thermal performance are improved. Various balanced thermotropic liquid crystal polyester amides,
That is, it is an object of the present invention to obtain thermotropic liquid crystal polyester amides having extremely high practicability which simultaneously satisfy the contradictory properties of heat resistance and easy moldability.

Therefore, the problem to be solved by the present invention is in accord with the above-mentioned object.
It is to provide high-performance, extremely practical thermotropic liquid crystal polyester amides.

[0016]

The present inventors have focused on the problems to be solved by the invention as described above,
As a result of earnest studies, the present invention has been completed by finding out that the above-mentioned object can be achieved by copolymerizing a compound having a specific structure.

That is, the present invention basically comprises the following structural units (A), (B), (C), (D) and (E), and has a softening temperature of 150. ~ 4
An object of the present invention is to provide a copolyesteramide having a melting point of 00 ° C., a melting point of + 30 ° C., and a melt viscosity at a shear rate of 10 ³ Sec ⁻¹ of 10 ⁴ poise or less. Specifically, the above structural unit (A) is the above structural unit (A).
And (B) total amount {below, structural unit [(A) +
(B)]. } As a reference, 20-9
It is within the range of 0 mol% and the above structural unit (D)
Is a structural unit [(C) + (D) + (E)] 0.1 to 60
Mol%, structural unit (E) is structural unit [(C) + (D) +
(E)], that is, based on the total amount of the structural units (C), (D), and (E) described above, 1 to
Within the range of 50 mol%, and the structural unit (B)
/ [(C) + (D) + (E)], that is, the above-mentioned structural unit with respect to the total number of moles of the structural units (C), (D) and (E). It is intended to provide a copolyesteramide having a ratio of (B) to the number of moles of 10/9 to 9/10.

[0018]

Embedded image (—O—R ₁ —C0—) (A)

[0019]

Embedded image (—OC—R ₂ —CO—) (B)

[0020]

Embedded image (—O—R ₃ —O—) (C)

[0021]

Embedded image [—O—R ₄ — (CH ₂ ) ₁ —O—] (D)

[0022]

Embedded image (−Y—R ₅ —NH—) (E)

[However, in the formula, R ₁ , R ₂ and R ₃
Respectively represent an organic group represented by the following formula (1), formula (2) or formula (3) or a derivative thereof, and R ₄ and R ₅ represent an aromatic ring, and Y Represents a group of —O— or —NH—, and l represents an integer of 1 to 4. ]

[0024]

[Chemical 27]

[0025]

[Chemical 28]

[0026]

[Chemical 29]

(However, X is -O-, -CO-, -CO
_{O -, - SO 2 -,} - shall represent S- or alkylene group, also, m or n are each 0 or 1
Shall be )

In addition, the present invention basically comprises the following compounds (A '), (B'), (C ') and (D').
An acid anhydride of an aliphatic carboxylic acid having 1 to 4 carbon atoms is added to a raw material containing (E ′) and acylated,
Subsequently, it is intended to provide a method for producing a copolymerized polyesteramide, which comprises deoxidizing and polycondensing.

[0029]

Embedded image HO—R ₁ —C0OH (A ′)

[0030]

Embedded image HOOC-R ₂ —COOH (B ′)

[0031]

Embedded image HO—R ₃ —OH (C ′)

[0032]

Embedded image HO—R ₄ — (CH ₂ ) ₁ —OH (D ′)

[0033]

Embedded image Y—R ₅ —NH ₂ (E ′)

[However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And Y are as described above, and l
Is as described above. ] In other words, the above compound (A ') is a compound [(A') + (B ')],
That is, it is within a range of 20 to 90 mol% based on the total amount of the compound (A ′) and the compound (B ′), and the compound (D ′) is the compound [(C ') + (D') + (E ')], that is, 0.1 to 0.1 based on the total amount of the compound (C'), the compound (D '), and the compound (E'). Within the range of 60 mol%, the above compound (E ′) is
[(C ′) + (D ′) + (E ′)], that is, 1 to 50 mol based on the total amount of the compound (C ′), the compound (D ′), and the compound (E ′) described above. Within the range, and in addition, the compound (B ′) / [(C ′) + (D ′) +
(E ′)] has a molar ratio of,
Production of copolymerized polyesteramide having a ratio of the number of moles of the above structural unit (B) to the total number of moles of the compound (C ′), the compound (D ′) and the compound (E) is 10/9 to 9/10. It is an attempt to provide the law.

[0035]

[Chemical 35]

[0036]

[Chemical 36]

[0037]

[Chemical 37]

(However, X is as described above, and
Both m and n are as described above. )

The above-mentioned copolymerized polyesteramide referred to in the present invention is, for example, a copolymerized polyester obtained from 4-hydroxybenzoic acid, terephthalic acid and 4,4'-dihydroxybiphenyl, 4-hydroxybenzoic acid or terephthalic acid. , 4,4'-dihydroxybiphenyl and a copolymerized polyesteramide obtained from aminophenol, the transition temperature to the liquid crystal phase can be designed to be low, and moreover, since the flow characteristics are good, It can be molded at low temperature.

The copolymerized polyesteramide of the present invention is characterized by using the hydroxyphenylalkyl alcohol compound represented by the above-mentioned general formula (D ') as an essential raw material component, and usually the above-mentioned general formula (A' ), An aromatic dicarboxylic acid represented by the above general formula (B ′), an aromatic dioxy compound represented by the above general formula (C ′), and the above general formula (D ′) ), An aromatic aminophenol or an aromatic diamine capable of forming an amide bond represented by the above-mentioned general formula (E ′) is added to the compound (A ′)
Is 20 to 90 mol% of the compound [(A ′) + (B ′)]
And the compound (D ′) is in the range of 0.1 to 60 mol% of the compound [(C ′) + (D ′) + (E ′)]. ) Is in the range of 1 to 50 mol% of the compound [(C ′) + (D ′) + (E ′)], and the compound (B ′) / [(C ′)
+ (D ′) + (E ′)] in a molar ratio of 10/9 to 9/1
It is obtained by using various raw materials in the range of 0 in the above-mentioned specific use ratio and further adding an acid anhydride of an aliphatic carboxylic acid having 1 to 4 carbon atoms to cause a reaction. is there.

The copolymerized polyesteramide obtained in the above-mentioned proportion of the repeating structural units represented by the structural units (A) to (E) is crystalline, and Excellent balance with softening temperature (heat resistance) and melt viscosity (molding processability).

The structural unit (A) is a structural unit [(A) +
When it exceeds 90 mol% of (B)],
The melt viscosity of the obtained copolymerized polyesteramide is remarkably high, and when it is less than 20 mol%, the melt moldability and heat stability are inevitably deteriorated. Absent.

The structural unit (B) / [(C) + (D)
If the molar ratio of + (E)] deviates from the above range, mechanical properties are inevitably deteriorated, which is not preferable.

For example, when the structural unit (B) is a combination of structural units other than a terephthalic acid residue, or when the structural unit (C) is a combination of structural units other than a biphenyl residue or a hydroquinone residue. If, for example,
Since the softening temperature and the crystallinity can be adjusted to be low, it is possible to produce the copolymerized polyesteramide having various adjusted properties such as heat resistance.

As the aromatic oxycarboxylic acid represented by the general formula (A '), only typical ones are exemplified, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and 4-hydroxy-4. Various hydroxynaphthoic acids such as'-carboxydiphenyl ether, 4-hydroxy 4'-carboxydiphenyl or 2,6-hydroxynaphthoic acid, or halogen-substituted products thereof, such as methyl group and phenyl group. Examples thereof include alkyl-substituted compounds and aryl-substituted compounds, but are not necessarily limited to these. Further, it goes without saying that these may be used alone or in combination of two or more kinds.

As the aromatic dicarboxylic acid represented by the general formula (B '), only typical ones are exemplified, and terephthalic acid, isophthalic acid, methylisophthalic acid, 5-t-butylisophthalic acid are exemplified. , Various kinds of naphthalene dicarboxylic acids such as phenyl terephthalic acid or 2,6-naphthalenedicarboxylic acid; diphenyl dicarboxylic acids; diphenyl ether dicarboxylic acids; or diphenyl ketone dicarboxylic acid or diphenyl propane dicarboxylic acid, but not necessarily these It is not limited only. Further, it goes without saying that these may be used alone or in combination of two or more kinds.

Specific examples of the aromatic dioxy compound represented by the above general formula (C ') include only hydroquinone, resorcin, methylhydroquinone, t-butylhydroquinone and dit-butylhydroquinone. Trimethylhydroquinones; trimethylresorcins; phenylhydroquinones; various dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene; various dihydroxybiphenyls such as 4,4′-dihydroxybiphenyl;
Various methyldihydroxybiphenyls such as 3'-dimethyl-4,4'-dihydroxybiphenyl;bisphenols;

Bis (hydroxyphenyl) ketones; Bis (hydroxyphenyl) ethers; Bis (hydroxyphenyl) sulfones; Bis (hydroxyphenyl)
Sulfides; or (4-hydroxyphenyl)-
4-hydroxybenzoate, dihydroxybenzophenones, and the like, but not limited to these. Moreover, it goes without saying that these may be used alone or in combination of two or more kinds.

As the hydroxyphenylalkyl alcohol compound represented by the general formula (D '), only typical ones are exemplified. Parahydroxyphenethyl alcohol, parahydroxyphenylpropanol, parahydroxyphenylbutanol or parahydroxyphenylbutanol. Hydroxybenzyl alcohol and the like are not necessarily limited to these. Further, it goes without saying that these may be used alone or in combination of two or more kinds, and the meta isomers may be used in a mixed form in a small amount.

Further, those having various substituents such as a methyl group on the aromatic ring within a range not departing from the object of the present invention or within a range not impairing the effects of the present invention. Can also be used together.

As the compounds which can form an amide bond represented by the above general formula (E '), only typical ones are exemplified, such as p-aminophenol and m-aminophenol. , Various aminophenols; various phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 4-amino-1-naphthol, 4-amino-4′-hydroxydiphenyl, 4-amino-4′- Hydroxydiphenylmethane, 4-amino-4′-hydroxydiphenylethane,
4-amino-4'-hydroxydiphenyl sulfone, 4
-Amino-4'-hydroxydiphenyl sulfide,
4,4'-diaminophenyl sulfide or 4,4 '
-Diaminophenyl sulfone, or these halogen-substituted compounds, such as a methyl group and a phenyl group,
Examples thereof include alkyl-substituted products and aryl-substituted products, but are not necessarily limited to these. Further, it goes without saying that these may be used alone or in combination of two or more kinds. .

It should be noted that aromatic aminocarboxylic acids, aliphatic dicarboxylic acids, and aliphatic or alicyclic diols are used within the range not departing from the object of the present invention or within the range not impairing the effects of the present invention. The compounds or aliphatic diamines can be copolymerized in a small amount, and can be used in the same manner.

As the above-mentioned acylating agent used in the production of the copolyesteramide of the present invention, an acid anhydride of an aliphatic carboxylic acid having 1 to 4 carbon atoms is used. Of these, acetic anhydride, propionic anhydride, chloroacetic anhydride, and the like can be mentioned as only typical ones, but the present invention is not limited to these.

Above all, it is particularly preferable to use acetic anhydride as the acylating agent. In addition, the amount of the acylating agent used is usually 0.8 to 1. The amount of the acid anhydride group is 1 to 1 equivalent of the OH group and the NH ₂ group present in the reaction raw material.
It is within a range of 2 equivalents.

The copolymerized polyesteramide of the present invention can be produced by various methods. Usually, the compounds of the general formulas (A '), (C'), and
OH group and NH ₂ group in (D ') and (E')
It is a good idea to carry out melt polymerization by a so-called acidolysis method in which a lower alkyl ester is transformed into a lower alkyl ester by an acylating agent and then deoxidation polycondensation is carried out. Further, it goes without saying that solid phase polymerization may be carried out after melt polymerization.

The copolymerized polyesteramide of the present invention is industrially advantageous because it is produced on the basis of the melt polymerization method as described above, since post-treatment after polymerization is unnecessary.
Of course, other polymerization methods such as a solution polymerization method and an interfacial polymerization method can also be used.

Such melt polymerization is usually carried out in a temperature range of 150 ° C. or higher and 400 ° C. or lower, preferably 20.
Within the range of 0 to 400 ° C. in the presence of an inert gas,
It is carried out at normal pressure or under reduced pressure.

With the progress of polymerization, for example, when acetic anhydride is used as the acylating agent, acetic acid distills out. Therefore, the reaction temperature should be adjusted depending on the amount of distillate and the viscosity of the reaction system. The degree of polymerization is increased by increasing it stepwise or by adjusting the degree of vacuum. It should be noted that the polymerization time is usually appropriate within a range of 1 to 10 hours.

Further, the melt polymerization is used as the first step, the polymer is granulated if necessary, and solid phase polymerization (second step) is carried out at a temperature below its melting point to increase the degree of polymerization. The method of making it is also an excellent method. Of course, it is possible to react only to the first step to a degree of polymerization close to the theoretical deacetic acid amount.

A catalyst may be used to promote the above reactions. This type of catalyst is known, and examples thereof include alkali metal salts, Mn, Mg and Z.
A typical example is an n, Cd, Sb or Ti compound. The amount of the catalyst used is 0.001 to 1% by weight, preferably 0.01 to 0%, based on the total amount of the monomers. It is within the range of 0.2% by weight.

Hydroxyphenylalkyl alcohol residue (D) in the copolymerized polyesteramide of the present invention
Is based on [(C) + (D) + (E)), that is, the total amount of the structural unit (C), the structural unit (D), and the structural unit (E) described above, respectively. As a standard, it is used within a range of 0.1 to 60 mol%, preferably 0.5 to 30 mol%.

Compared with the case where the use of the hydroxyphenylalkyl alcohols was totally absent, not only the softening temperature of the obtained polymer and the melt phase showing the liquid crystal phase were adjusted to a wide range, but also the flow characteristics were It will also be a place to improve. When the amount of the hydroxyphenylalkyl alcohol used is less than the above value, the flow properties of the obtained polyester are not significantly improved as compared with the case where the component is not present, and the melt viscosity This is a process in which a copolymerized polyesteramide having poor practicality, which is not sufficiently lowered and has to be molded at a temperature much higher than the melting point or the softening temperature, is obtained.

On the other hand, when the hydroxyphenylalkyl alcohol component is present in a larger amount than the above value, even if a polyesteramide having optical anisotropy is obtained, such a polyesteramide is obtained. The molded article obtained from No. 1 does not exhibit preferable properties such as low strength.

By using a small amount of the component, it becomes a process showing high fluidity at a temperature not much higher than the melting point or softening temperature peculiar to the obtained polymer, and molding at such temperature is possible. That is, it is an unexpected matter that molding processability is improved while maintaining heat resistance.

As an index of the molding processability of the copolymerized polyesteramide of the present invention, liquid crystallinity and melt viscosity exhibiting optical anisotropy at the time of melting may be mentioned. Whether or not it exhibits liquid crystallinity is closely related to the fluidity during melting,
It is important that the copolymerized polyesteramide of the present invention exhibits liquid crystallinity in the molten state.

The optical anisotropy is measured by using a polarizing microscope, heating a sample placed on a hot stage equipped with a temperature raising device, heating it, and observing it at a magnification of about 40 times.

The preferred copolymerized polyesteramide in the present invention has, as its constituent component, a residue of hydroxyphenylalkyl alcohols represented by the above-mentioned general formula (D), and further, as its constituent component, for example, A 4-hydroxybenzoic acid residue represented by the above general formula (A), a phthalic acid residue represented by the above general formula (B), a compound represented by the above general formula (C) 4,
4'-dihydroxybiphenyl residue, aromatic aminophenol residue represented by the general formula (E) above and /
Alternatively, it is obtained by using various raw materials having a phenylenediamine residue.

The polyester amide exhibits liquid crystallinity when melted, and the softening temperature and melt viscosity are lower than expected as compared with the case where no hydroxyphenylalkyl alcohols are used.

Incidentally, as a component which gives characteristics to the polyester obtained by combining it with hydroxyphenylalkyl alcohols, among the above-mentioned compounds, as a component of the structural unit (A ′), 4-hydroxybenzoic An acid and its derivatives, or 2,6-hydroxynaphthoic acid and its derivatives are used as components of the structural unit (B ′), terephthalic acid, isophthalic acid,
Naphthalenedicarboxylic acids are 4,4′-dihydroxybiphenyls, hydroquinones and their alkyl or phenyl derivatives as structural unit (C ′) components,
Bis (hydroxyphenyl) ether, dihydroxynaphthalene and their derivatives are particularly excellent as 3- or 4-amiphenol or 3- or 4-phenylenediamine as the component of the structural unit (E '). There is.

The copolyester of the present invention has a softening temperature of 150 to 400 ° C., a melting point of + 30 ° C. and a melt viscosity of 10 ^{4 at} a shear rate of 10 ³ Sec ^-1 .
Poise or less.

The melt viscosity used in the present invention is a viscosity measured using a capillary rheometer (capillary rheometer) at a temperature 30 ° C. higher than the melting point and a shear rate of 10 ³ Sec ^-1. Is meant. A copolymerized polyester having a melt viscosity of more than 10 ⁴ poise can be extruded in a strand shape with a capillary rheometer (capillary rheometer) to measure the melt viscosity, ,
Even if it is possible to extrude into a strand shape at a temperature that greatly exceeds the melting point, it is impossible to obtain a satisfactory molded product with a clean surface using an ordinary injection molding machine or extrusion molding machine. is there.

The softening temperature referred to in the present invention refers to a temperature measured by using a thermomechanical analyzer (TMA apparatus), as will be shown later. The basic thermal properties of the copolyesters are usually indicated by using the melting point measured by a differential scanning calorimeter, but the thermotropic liquid crystal polymer according to the present invention is measured by the differential scanning calorific value. It is necessary to pay particular attention to the fact that when the polymer is measured, the change in the amount of heat when the polymer melts is too small, and it is often the case that it is difficult to grasp the melting point clearly.

Further, when a hot stage with a temperature raising device was placed on the sample stage of the polarizing microscope, and a thin piece of the polymer sample was set therein, and when it was heated and heated, it showed optical anisotropy. The temperature can be displayed as a liquid crystal starting temperature and a temporary melting point, but as a value with good reproducibility,
It is difficult to grasp clearly, and it usually does not match the above melting point.

The melting point and softening temperature used in the present invention are measured as follows. That is, using a differential scanning calorimeter, measurement was performed at a temperature rising rate of 20 ° C./min to first determine the melting point, and then compression molding was performed at a temperature 30 ° C. higher than the melting point thus obtained to obtain a thickness. A test piece having a size of 2 mm was prepared, and the test piece was heated at 5 ° C./using a thermomechanical analyzer (penetration method; load = 20 g).
The softening temperature was measured at a temperature rising rate.

By the way, a copolyester obtained by the constitution excluding the structural unit (D), that is, terephthalic acid, 4,4'-dihydroxybiphenyl and 4-
Copolyesters obtained by using hydroxybenzoic acid are referred to as "Modern Plastics (Mode
rn Plastics ", Jul. 62 (197)
5) and "The British Polymer Jour.
nal) ", Dec. 154 (1980) and the like, in which it is argued that the melting point is lowered by combining compounds such as isophthalic acid, phenylhydroquinone, 2,6-naphthalenedicarboxylic acid, bisphenol compound and resorcin. It is stated that they have the effect of lowering the melting point.

However, in these documents, the copolymerized polyester obtained by combining the above-mentioned hydroxyphenylalkyl alcohols represented by the general formula (D ′) not only has a low melting point but also has a liquid crystallinity when melted. However, there is no suggestion or teaching to effectively lower the melt viscosity.

In the present invention, the softening temperature and melt viscosity of the obtained polyester can be adjusted widely by appropriately changing the amount of hydroxyphenylalkyl alcohols used. From the above-mentioned documents, this is a place that cannot be understood at all.

The copolymerized polyester of the present invention may contain various kinds of fibrous, powdery or plate-like inorganic and organic solid fillers and so-called reinforcing agents depending on the purpose of use. .

As the fibrous filler, only typical ones are exemplified, and glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber,
Zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, etc., and also various metal fibers such as stainless steel, aluminum, titanium, copper, brass, and inorganic fibers , And various high-melting-point organic fibers such as polyamide resin, fluorine resin, polyester resin, and acrylic resin. Among them, glass fibers and polyamide fibers are typical, and the performance of the copolyester can be adjusted by appropriately selecting the aspect ratio of these fibers.

As the powdery fillers, only typical ones will be exemplified. Carbon black, zinc, silica, sulfur powder, glass beads, glass balloon, glass powder, calcium sulfate, aluminum silicate. , Various kinds of silicates such as kaolin, talc, clay, diatomaceous earth, wstonite; various metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony oxide, alumina; various kinds of calcium carbonate, magnesium carbonate, etc. In addition to various metal carbonates, calcium sulfate, barium sulfate, and various metal sulfates, various metal powders such as ferrite, silicon carbide, and boron nitride can be used.

Specific examples of the plate-like fillers include various metal foils such as mica and glass flakes. Of course, these fillers may be used alone or in combination of two or more kinds,
For example, the combined use of the fibrous filler and the powdery or plate-like filler is preferable from the viewpoint of combining mechanical properties with dimensional stability and / or electrical properties. The amount of these fillers is appropriately in the range of 1 to 60% by weight. Further, if necessary, these fillers are preferably used in combination with various surface treatment agents.

The copolymerized polyester of the present invention can be kneaded with various thermoplastic resins depending on the purpose of use to produce a so-called polymer alloy. in this way,
As a thermoplastic resin to be used in combination with the copolyester, only typical ones are exemplified, such as polysulfone and polyethersulfone,
Various polysulfone-based resins; Polyphenylene sulfide-based resins; Polyimide-based resins; Polyetherimide-based resins; Polyamideimide-based resins; Various polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, and polyarylate; Polycarbonate resins; various polyamide resins such as 6-nylon and 6,6-nylon;

Polyester amide-based resins; polyphenylene oxide or polymer alloy resins thereof; various polyketone-based resins such as polyether ether ketone and polyether ketone; polyacetal-based resins; fluorine-based resins; Various polyolefin resins such as polyethylene, polypropylene, ethylene propylene terpolymer; polystyrene, AS, ABS
In addition to various polystyrene-based resins and the like, liquid crystal polymers having different properties such as polyvinyl chloride, acrylic resins and silicon-based resins.

The melting point, softening temperature, melt viscosity and optical anisotropy of the copolymerized polyesteramide of the present invention are measured as follows.

(1) Melting point and softening temperature Using a "DSC-21" type 0 differential scanning calorimeter manufactured by Seiko Denshi Kogyo Co., Ltd., the melting point was determined by measuring at a heating rate of 20 ° C./min. Compression molding was carried out at a temperature 30 ° C. higher than the obtained melting point to prepare a test piece having a thickness of 2 mm,
The test piece is a thermo-mechanical analyzer "TM" manufactured by the same company.
A / SS 120 "(penetration method; load = 20 g) was used to measure the softening temperature at a heating rate of 5 ° C./min.

(2) Melt viscosity The viscosity was measured using a capillary rheometer at a temperature 30 ° C. higher than the melting point obtained in the above (1) at a shear rate of 10 ³ Sec ^-1 .

(3) Optical anisotropy The fine powder sample was placed on a hot stage equipped with a temperature raising device, heated at a rate of 20 ° C./min, and observed with a polarizing microscope.

[0088]

EXAMPLES Next, the present invention will be described more specifically by way of examples.

Example 1 In a reaction vessel equipped with a stirring blade and a nitrogen gas inlet, 4-
3.0 mol of hydroxybenzoic acid and 1. of terephthalic acid.
0 mol, 0.6 mol of 4,4′-dihydroxybiphenyl, 0.2 mol of para-aminophenol and 0.2 mol of para-hydroxyphenethyl alcohol were charged, and the atmosphere was replaced with nitrogen under reduced pressure and sealed with nitrogen. 5.5 mol of acetic anhydride was added.

Then, with stirring, the mixture was heated to 145 ° C. and 3
After reacting for a time, the temperature was raised to 290 ° C. over 3 hours to continue the reaction, and further, the reaction was continued under a reduced pressure of 1 mmHg. The crude polymer obtained is ground to 1
Under reduced pressure of mmHg, the temperature was raised to 290 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 329.
℃, the softening temperature is 310 ℃, and the melt viscosity is 5 × 1
It was 0 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

This polymer also contains 60 mol% of hydroxybenzoic acid, 20 mol% of terephthalic acid, 12 mol% of dihydroxybiphenyl, 4 mol% of aminophenol, and 4 mol of hydroxyphenethyl alcohol. The composition was mol%.

Example 2 A reaction vessel equipped with a stirring blade and a nitrogen gas inlet was added with 4-
3.0 mol of hydroxybenzoic acid and 1. of terephthalic acid.
Charge 0 mol, 0.4 mol of 4,4′-dihydroxybiphenyl, 0.3 mol of para-aminophenol and 0.3 mol of para-hydroxyphenethyl alcohol, and replace with nitrogen under reduced pressure, and then seal with nitrogen. And 5.5 mol of acetic anhydride were added.

Then, the mixture is heated to 145 ° C. with stirring.
After the reaction for 3 hours, the temperature was raised to 290 ° C. over 3 hours to continue the reaction, and further the reaction was continued under a reduced pressure of 1 mmHg. The obtained crude polymer was pulverized, and the pressure was reduced to 1 mmHg under a reduced pressure for 10 hours.
The temperature was raised to 60 ° C. and solid phase polymerization was performed. The polymer obtained had a melting point of 311 ° C., a softening temperature of 300 ° C., and a melt viscosity of 5 × 10 ² poises. This polymer exhibited optical anisotropy when melted.

No raw material monomer was detected in the distilled acetic acid. This polymer had a composition of 60 mol% of hydroxybenzoic acid, 20 mol% of terephthalic acid, 8 mol% of dihydroxybiphenyl, 6 mol% of aminophenol, and 6 mol% of hydroxyphenethyl alcohol. .

Example 3 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 0.7 mol of terephthalic acid were added.
0.3 mol of 2,6-naphthalenedicarboxylic acid, 0.3 mol of para-aminophenol, 0.4 mol of 4,4′-dihydroxybiphenyl and 0.3 mol of parahydroxyphenethyl alcohol were charged, and under reduced pressure, After purging with nitrogen, the atmosphere was sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Subsequently, the mixture was heated to 145 ° C. with stirring and reacted for 3 hours, then heated to 290 ° C. over 3 hours to continue the reaction, and further under reduced pressure of 1 mmHg. Let it react. The obtained crude polymer was pulverized and 260 mm was taken for 10 hours under a reduced pressure of 1 mmHg.
The temperature was raised to ° C and solid phase polymerization was performed.

The melting point of the polymer thus obtained is 290.
℃, the softening temperature is 280 ℃, the melt viscosity is 1 ×
It was 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 4 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid, 1.0 mol of terephthalic acid,
0.2 mol of para-aminophenol, 0.7 mol of 4,4′-dihydroxybiphenyl and 0.1 mol of para-hydroxyphenethyl alcohol were charged, and under reduced pressure,
After purging with nitrogen, the atmosphere was sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Then, the mixture was heated to 145 ° C. with stirring and reacted for 3 hours, then at 290 ° C. over 3 hours.
The temperature is raised to 1, and the reaction is allowed to continue.
The reaction was allowed to continue under a reduced pressure of Hg. The obtained crude polymer was pulverized and heated to 300 ° C. under reduced pressure of 1 mmHg for 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 370.
° C, softening temperature is 358 ° C, melt viscosity is 1 x
It was 10 ³ poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 5 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 0.8 mol of terephthalic acid were added.
Charge 0.2 mol of 2,6-naphthalenedicarboxylic acid, 0.1 mol of p-phenylenediamine, 0.7 mol of 4,4′-dihydroxybiphenyl and 0.2 mol of parahydroxyphenethyl alcohol and reduce the pressure. The atmosphere was purged with nitrogen, sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Then, the mixture was heated to 145 ° C. with stirring and reacted for 3 hours, then 290 over 3 hours.
The temperature was raised to 0 ° C. to continue the reaction, and the reaction was further continued under a reduced pressure of 1 mmHg. The obtained crude polymer was crushed, and the pressure was reduced to 28 mm under a reduced pressure of 1 mmHg for 10 hours.
The temperature was raised to 0 ° C. and solid phase polymerization was performed.

The melting point of the polymer thus obtained is 315.
℃, softening temperature is 300 ℃, melt viscosity is 7 ×
It was 10 ² poise. This polymer exhibited optical anisotropy when melted.

Example 6 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were added.
Charge 0.2 mol of p-phenylenediamine, 0.5 mol of 4,4′-dihydroxybiphenyl and 0.3 mol of parahydroxyphenethyl alcohol, replace with nitrogen under reduced pressure, seal with nitrogen, and remove acetic anhydride. Was added.

Subsequently, the mixture was heated to 145 ° C. with stirring, reacted for 3 hours, heated to 290 ° C. over 3 hours to continue the reaction, and further reacted under reduced pressure of 1 mmHg. . The crude polymer obtained is crushed to 1 mmH
Under reduced pressure of g, the temperature was raised to 260 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 335.
℃, the softening temperature is 330 ℃, the melt viscosity is 1 ×
It was 10 ³ poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

This polymer also contains 50 mol% of hydroxybenzoic acid, 25 mol% of terephthalic acid, 5 mol of phenylenediamine, 12.5 mol% of dihydroxybiphenyl and 7.5% of hydroxyphenethyl alcohol. The composition was such that it was mol%.

Example 7 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 0.8 mol of terephthalic acid were added.
0.2 mol of isophthalic acid, 0.2 mol of para-aminophenol, 0.7 of 4,4'dihydroxybiphenyl
Molar and para-hydroxyphenethyl alcohol of 0.
1 mol was charged, the atmosphere was replaced with nitrogen under reduced pressure, the atmosphere was sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Subsequently, with stirring, the mixture was heated to 145 ° C. and heated to 3
After reacting for a period of time, the temperature was raised to 290 ° C. over 3 hours to continue the reaction, and further the reaction was continued under a reduced pressure of 1 mmHg. The obtained crude polymer was crushed, and the pressure was reduced to 29 mm under reduced pressure of 1 mmHg for 10 hours.
The temperature was raised to 0 ° C. and solid phase polymerization was performed.

The melting point of the polymer thus obtained is 349.
℃, softening temperature is 342 ℃, melt viscosity is 2 ×
It was 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 8 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid, 1.0 mol of terephthalic acid,
Charge 0.15 mol of 2,6-dihydroxynaphthalene, 0.15 mol of para-aminophenol, 0.67 mol of 4,4'-dihydroxybiphenyl and 0.03 mol of para-hydroxyphenethyl alcohol, and add nitrogen under reduced pressure. After displacement, blanket with nitrogen and add 4.5 moles of acetic anhydride.

Subsequently, the mixture was heated to 145 ° C. under stirring, reacted for 3 hours, heated to 290 ° C. over 3 hours to continue the reaction, and further, under reduced pressure of 1 mmHg, The reaction was allowed to continue. The obtained crude polymer was crushed, and the pressure was reduced to 29 mm under reduced pressure of 1 mmHg for 10 hours.
The temperature was raised to 0 ° C. and solid phase polymerization was performed.

The melting point of the polymer thus obtained is 340.
℃, softening temperature is 327 ℃, melt viscosity is 3 ×
It was 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 9 In a reaction vessel equipped with a stirring blade and an inlet, 3.0 mol of 4-hydroxybenzoic acid and 0.8 mol of terephthalic acid were added.
0.2 mol of 2,6-naphthalenedicarboxylic acid, 0.2 mol of paraaminophenol, 0.2 mol of 2,6-dihydroxynaphthalene, 0.55 mol of 4,4′-dihydroxybiphenyl and parahydroxyphenethyl alcohol. 0.05 mol of the above was charged, the atmosphere was replaced with nitrogen under reduced pressure, the atmosphere was sealed with nitrogen and 5.5 mol of acetic anhydride was added.

Then, the mixture was heated to 145 ° C. under stirring, reacted for 3 hours, heated to 290 ° C. over 3 hours to continue the reaction, and further, under reduced pressure of 1 mmHg,
The reaction was allowed to continue. The crude polymer obtained is ground to 1
Under reduced pressure of mmHg, the temperature was raised to 260 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 306.
℃, the softening temperature is 288 ℃, the melt viscosity is 1 ×
It was 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 10 In a reaction vessel equipped with a stirring blade and an inlet, 2.8 mol of 4-hydroxybenzoic acid, 0.2 mol of 2,6-hydroxynaphthoic acid, 0.75 mol of terephthalic acid, 2,6
-Prepare 0.25 mol of naphthalenedicarboxylic acid, 0.3 mol of para-aminophenol, 0.67 mol of 4,4'-dihydroxybiphenyl and 0.03 mol of para-hydroxyphenethyl alcohol and replace with nitrogen under reduced pressure. From above, a nitrogen blanket was added, and 5.5 mol of acetic anhydride was added.

Then, the mixture was heated to 145 ° C. with stirring, reacted for 3 hours, heated to 290 ° C. over 3 hours to continue the reaction, and further reacted under reduced pressure of 1 mmHg. After that, the temperature was raised to 330 ° C. to continue the reaction.

The melting point of the polymer thus obtained is 275.
° C, softening temperature is 272 ° C, melt viscosity is 1 x
It was 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 11 In a reaction vessel equipped with a stirring blade and an inlet, 0.5 mol of 4-hydroxybenzoic acid and 0.7 mol of terephthalic acid were added.
0.3 mol of 2,6-naphthalenedicarboxylic acid, 0.2 mol of para-aminophenol, 0.1 mol of phenylhydroquinone, 0.65 mol of 4,4'-dihydroxybiphenyl and 0.05 of para-hydroxyphenethyl alcohol. Mol of the mixture was charged, the atmosphere was replaced with nitrogen under reduced pressure, the atmosphere was sealed with nitrogen, and 3.5 mole of acetic anhydride was added.

Then, the mixture was heated to 145 ° C. under stirring, reacted for 3 hours, heated to 290 ° C. over 3 hours to continue the reaction, and further reduced pressure of 1 mmHg. The reaction was continued, and then the temperature was raised to 330 ° C. to continue the reaction.

The melting point of the polymer thus obtained is 303.
℃, the softening temperature is 298 ℃, the melt viscosity is 6 ×
It was 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Comparative Example 1 3.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were placed in a reaction vessel equipped with a stirring blade and an inlet.
0.7 mol of 4,4′-dihydroxybiphenyl and 0.3 mol of para-aminophenol were charged, the atmosphere was replaced with nitrogen under reduced pressure, and the atmosphere was sealed with nitrogen.
Mole was added.

Subsequently, the mixture was heated to 145 ° C. with stirring, reacted for 3 hours, heated to 290 ° C. over 3 hours to continue the reaction, and further reacted under reduced pressure of 1 mmHg. Allowed me to continue.

After that, the crude polymer thus obtained was pulverized, and was crushed under a reduced pressure of 1 mmHg for 10 hours.
The temperature was raised to 300 ° C. and solid phase polymerization was performed. The polymer thus obtained then had a melting point of 420 ° C., a softening temperature of 390 ° C. and a melt viscosity of 2 × 10 ⁴ poises.

This polymer had a composition of 60 mol% of hydroxybenzoic acid, 20 mol% of terephthalic acid, 14 mol% of dihydroxybiphenyl and 6 mol% of aminophenol. It was

Comparative Example 2 In a reaction vessel equipped with a stirring blade and an inlet, 3.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were added.
0.3 mol of p-phenylenediamine and 4,4'-
The procedure of Comparative Example 1 was repeated, except that 0.7 mol of dihydroxybiphenyl was charged, and the polymer thus obtained had a melting point of 425 ° C. and a softening temperature of 420.
However, the melt viscosity could not be measured.

[0129]

The copolymerized polyesteramide of the present invention is
In particular, the softening temperature is controlled in a wide range, and furthermore, it gives a highly heat-resistant polymer material having excellent fluidity, which is extremely practical.

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[Procedure amendment]

[Submission date] July 2, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

Embedded image (—O—R ₁ —CO—) (A)

Embedded image (—OC—R ₂ —CO—) (B)

Embedded image (—O—R ₃ —O—) (C)

Embedded image [—O—R ₄ — (CH ₂ ) ₁ —O—] (D)

Embedded image (−Y—R ₅ —NH—) (E) [wherein R ₁ , R ₂ and R _{3 in the} formula are respectively:
An organic group represented by the following formula (1), formula (2) or formula (3) or a derivative thereof is represented, R ₄ and R ₅ are aromatic rings, and Y is-.
Represents a group O- or -NH-, and l
Is an integer of 1 to 4. ]

[Chemical 6]

[Chemical 7]

[Chemical 8] [However, X in the formula is -O-, -CO-, -COO-,
It represents —SO ₂ —, —S— or an alkylene group, and m or n is an integer of 0 or 1, respectively. ]

[Chemical 9] The copolymerized polyesteramide according to claim 1 or 2, which is represented by

[Chemical 10] The copolymerized polyesteramide according to claim 1 or 2, which is represented by

Embedded image HO—R ₁ —COOH (A ′)

Embedded image HOOC-R ₂ —COOH (B ′)

Embedded image HO—R ₃ —OH (C ′)

Embedded image HO—R ₄ — (CH ₂ ) ₁ —OH (D ′)

Embedded image Y—R ₅ —NH ₂ (E ′) [wherein R ₁ , R _{2 and} R _{3 in the} formula respectively represent
It represents an organic group represented by the formula (1), (2) or (3) or a derivative thereof, R ₄ or R ₅ represents an aromatic ring, and Y represents a group of —OH or —NH _2. And l is an integer from 1 to 4. ]

[Chemical 16]

[Chemical 17] [However, X in the formula is -O-, -CO-, -COO-,
It represents —SO ₂ —, —S— or an alkylene group, and m or n is an integer of 0 or 1, respectively. ]

[Chemical 18]

[Chemical 19] The method according to claim 5 or 6, which is represented by

[Chemical 20] The method according to claim 5 or 6, which is represented by

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

That is, the present invention basically comprises the following structural units (A), (B), (C), (D) and (E) and has a softening temperature of 150 to 400 ° C. There is a melting point of + 30 ° C and 10 ³ sec
The melt viscosity under the condition of a shear rate of ^-1 is 10 ⁴
An object of the present invention is to provide a copolymerized polyesteramide having a poise or less. Specifically, the above-mentioned structural unit (A) is composed of the above-mentioned structural unit (A) and structural unit (B). Total amount of {below, structural unit [(A) +
(B)]. } As a reference, 20-9
It is within the range of 0 mol% and the above structural unit (D)
Is based on the total amount of the structural unit [(C) + (D) + (E)], that is, the structural unit (C), the structural unit (D), and the structural unit (E). Within the range of mol%, the structural unit (E) is the structural unit [(C) +
(D) + (E)], that is, within the range of 1 to 50 mol% based on the total amount of the above structural units (C), structural units (D) and structural units (E). Yes, and structural unit (B) / structural unit [(C) + (D) +
(E)], that is, the number of moles of the structural unit (B) with respect to the total number of moles of the structural unit (C), the structural unit (D), and the structural unit (E). To provide a copolyesteramide having a ratio of 10/9 to 9/10.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And Y are as described above, and l
Is as described above. ] Specifically, the above compound (A ′) is a compound [(A ′) + (B ′)],
That is, it is within a range of 20 to 90 mol% based on the total amount of the compound (A ′) and the compound (B ′), and the compound (D ′) is the compound [(C ′) +
(D ') + (E')], that is, each of the above,
It is within a range of 0.1 to 60 mol% based on the total amount of the compound (C ′), the compound (D ′) and the compound (E ′), and the above compound (E ′) is [(C ') +
(D ') + (E')], that is, each of the above,
Within the range of 1 to 50 mol% based on the total amount of the compound (C ′), the compound (D ′) and the compound (E ′), the compound (B ′) / the following three compounds The molar ratio of the total amount [(C ′) + (D ′) + (E ′)] is, that is, the sum of the compound (C ′), the compound (D ′), and the compound (E ′) described above. The ratio of the number of moles of the structural unit (B) to the number of moles is 10/9 to 9 /
It is intended to provide a method for producing a copolyester amide No. 10.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction content]

The copolymerized polyesteramide of the present invention has a softening temperature in the range of 150 to 400 ° C., a melting point of + 30 ° C., and a melt viscosity under the conditions of a shear rate of 10 ³ sec ^-1. Is 10 ⁴ poise or less.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

The copolymerized polyesteramide of the present invention is kneaded with various thermoplastic resins according to the purpose of use,
It is also possible to produce so-called polymer alloys. As described above, if only representative examples of the thermoplastic resin that can be used in combination with the copolymerized polyesteramide are exemplified, various polysulfone-based resins such as polysulfone and polyethersulfone; polyphenylene Sulfide resins; Polyetherimide resins; Polyamideimide resins; Polyethylene terephthalate, Polybutylene terephthalate,
Various polyester resins such as polyarylate;
Polycarbonate resins; various polyamide resins such as 6-nylon and 6,6-nylon;

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0083

[Correction method] Change

[Correction content]

Polyester amide type resins; polyphenylene oxide or polymer alloy type resins thereof; various polyketone type resins such as polyether ketone and polyether ether ketone; polyacetal type resins; fluorine type resins; polyethylene , Polypropylene, Ethylene / Propylene / Terpolymer, Various Polyolefin Resins; Polystyrene, AS, AB
Including various polystyrene resins such as S,
Examples thereof include polyvinyl chloride, acrylic resins or silicone resins, and liquid crystal polymers having different properties.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

The melting point, softening temperature, melt viscosity and optical anisotropy of the copolyesteramide of the present invention are measured as follows.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction content]

(1) Melting point and softening temperature Using a "DSC-210" type differential scanning calorimeter manufactured by Seiko Denshi Kogyo Co., Ltd., the melting point and the softening temperature were measured at a heating rate of 20 ° C./min. And then compression-molded at a temperature 30 ° C. higher than the obtained melting point to obtain a thickness of 2
mm test piece was prepared, and the test piece was heated using a thermomechanical analyzer “TMA / SS120” (penetration method; load = 20 g) manufactured by the same company at a heating rate of 5 ° C./min. The softening temperature was determined by measuring with.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0094

[Correction method] Change

[Correction content]

Then, while stirring, the mixture was heated to 145 ° C., the reaction was carried out for 3 hours, and then the reaction was conducted for 2 hours over 3 hours.
Raise the temperature to 90 ° C to allow the reaction to continue, and
The reaction was allowed to continue under reduced pressure of mmHg. Next, the crude polymer thus obtained was pulverized and heated to 260 ° C. over 10 hours under reduced pressure of 1 mmHg to carry out solid phase polymerization. The melting point of the polymer obtained here is 31.
1 ° C, softening temperature 300 ° C, melting temperature 5
It was × 10 ² poise. This polymer exhibited optical anisotropy when melted. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 16, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title: Copolymerized polyesteramide and method for producing the same

[Claims]

[Formula 1] _{(- O-R 1 -CO-)} (A)

## STR2 ## _{(- OC-R 2 -CO-)} (B)

Embedded image (—O—R ₃ —O—) (C)

Embedded image _{[- O-R 4 - (CH} 2) l -O- ] (D)

Embedded image (−Y—R ₅ —NH—) (E) [wherein R ₁ , R ₂ and R _{3 in the} formula are respectively:
It represents an organic group represented by the following formula (1) or formula (2) or a derivative thereof, R ₄ and R ₅ represent an aromatic ring, and Y represents —O— or —
NH represents a group, and l is an integer of 1 to 4. ]

[Chemical 6] (However, X in the formula is -O-, -CO-, -COO.
-, - SO ₂ -, - shall represent S- or alkylene group, also, m or n, respectively, assumed to be 0 or 1 becomes an integer. )

[Chemical 7]

[Chemical 8] The copolymerized polyesteramide according to claim 1 or 2, which is represented by

[Chemical 9] The copolymerized polyesteramide according to claim 1 or 2, which is represented by

Embedded image HO—R ₁ —COOH (A ′)

Embedded image HOOC-R ₂ —COOH (B ′)

Embedded image HO—R ₃ —OH (C ′)

Embedded image HO—R ₄ — (CH ₂ ) ₁ —OH (D ′)

Embedded image Y—R ₅ —NH ₂ (E ′) [wherein R ₁ , R ₂ and R _{3 in the} formula are respectively:
It represents an organic group represented by the following formula (1) or formula (2) or a derivative thereof, R ₄ or R ₅ represents an aromatic ring, and Y represents —OH or —
It represents a group of NH ₂ and l is an integer of 1 to 4. ]

[Chemical 15] (However, X in the formula is -O-, -CO-, -COO.
-, - SO ₂ -, - shall represent S- or alkylene group, also, m or n, respectively, assumed to be 0 or 1 becomes an integer. )

[Chemical 16]

[Chemical 17] The method according to claim 5 or 6, which is represented by

[Chemical 18] The method according to claim 5 or 6, which is represented by

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful copolymerized polyesteramide and a method for producing the copolymerized polyesteramide. More specifically, it relates to thermotropic liquid crystal polyester amides obtained by using hydroxyphenylalkyl alcohols (D ′) as an essential raw material component, which are excellent in heat resistance and moldability, and a production method thereof.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand from the industrial world for high performance of organic polymer materials, and injection molded products excellent in mechanical properties such as strength and elastic modulus and thermal properties such as heat resistance have been developed. Initially, the advent or emergence of various products such as films and fibers is strongly desired.

In particular, so-called thermotropic liquid crystal polyesters exhibiting an optically anisotropic molten phase have been attracting attention as polymer materials satisfying the above requirements, and many copolyesters having different chemical structures have been noted. Kinds have been proposed. Some of them have already been manufactured industrially.

When these copolymerized polyesters are melted and molded, the molecular chains are easily aligned in one direction to form a highly oriented structure, and a molded product having excellent mechanical properties is provided.

Further, it is known that various molded articles obtained from wholly aromatic polyesters containing aromatic chains at a high density have extremely high mechanical strength and heat resistance.

Thus, wholly aromatic polyesters are
Excellent as a high-performance material, especially Japanese Patent Publication No. 47-47
870, JP-A-50-43223, JP-A-54-46291, JP-A-55-94930, JP-A-55-149321, and JP-A-56-4.
According to the procedures described in Japanese Patent No. 3319 and Japanese Patent Application Laid-Open No. 57-135830, a wholly aromatic polyester obtained from 4-hydroxybenzoic acid, terephthalic acid, and 4,4′-dihydroxybiphenyl is It is said that some of them have high strength and high elastic modulus and have practical heat resistance up to 350 ° C.

However, since the melting point is remarkably high as 400 ° C. or higher, the molding temperature also needs to be high at 380-420 ° C. or higher, and a special molding device or the like must be used. There is.

A method of co-condensing 2,6-hydroxynaphthoic acid in order to lower the melting point and thereby improve moldability (Japanese Patent Laid-Open Nos. 54-577691 and 55-144024). Japanese Laid-Open Patent Publication No. 56-1
0526, JP-A-57-87422, JP-A-57-177019, and JP-A-57-17702.
No. 0 and JP-A No. 57-172921) and a method of co-condensing a naphthalene derivative (JP-A No.
4-50594, JP-A-56-43319, JP-A-57-177021, JP-A-58-1.
No. 722 and JP-A No. 62-207327) have been proposed.

On the other hand, these copolyesters are
Thermotropic liquid crystalline copolymerized polyesteramides having an amide group introduced therein have been studied for the purpose of imparting further mechanical properties. The copolymerized polyesteramides are disclosed in JP-A-55-27391. Japanese Laid-Open Patent Publication No. 57-172921, Japanese Laid-Open Patent Publication No. 57-17701.
No. 9, JP-A-57-177020, JP-A-Sho 5
7-177021, JP-A-58-89618, JP-A-59-47229, JP-A-60-40.
This is as proposed in Japanese Laid-Open Patent Publication No. 217, Japanese Patent Laid-Open No. 60-245631, Japanese Laid-Open Patent Publication No. 62-132927, and the like.

However, like the above-mentioned copolyesters, such a thermotropic liquid crystalline copolyesteramide in the form of introducing an amide group into the copolyester has a property in which heat resistance and moldability are contradictory to each other. It is difficult to satisfy both requirements, and therefore it is not yet fully satisfactory.

[0011]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned disadvantages in the prior art and further impairs the balance between the excellent mechanical properties and the heat resistance of the thermotropic liquid crystal polyester amides. Without
By reducing the melt viscosity of the thermotropic liquid crystal polyester amides and allowing the melt phase to exhibit optical anisotropy (liquid crystallinity), the moldability is further improved, and the mechanical performance and thermal performance are improved. Various balanced thermotropic liquid crystal polyester amides,
That is, it is an object of the present invention to obtain thermotropic liquid crystal polyester amides having extremely high practicability which simultaneously satisfy the contradictory properties of heat resistance and easy moldability.

[0012] Therefore, the problem to be solved by the present invention depends on one and meets the above-mentioned object.
It is to provide high-performance, extremely practical thermotropic liquid crystal polyester amides.

[0013]

Therefore, the present inventors have
Focusing on the problems to be solved by the invention as described above, as a result of intensive and intensive studies, by copolymerizing a compound having a specific structure, it was found that the above-mentioned object is achieved. Thus, the present invention has been completed here.

That is, the present invention basically comprises the following structural units (A), (B), (C), (D) and (E), and has a softening temperature of 150. ~ 4
At a temperature of 00 ° C. and 30 ° C. higher than the melting point, and
An object of the present invention is to provide a copolymerized polyesteramide having a melt viscosity of 10 ⁴ poise or less under a shear rate of 10 ³ sec ^-1 .

[0015]

Embedded image (—O—R ₁ —CO—) (A)

[0016]

Embedded image (—OC—R ₂ —CO—) (B)

[0017]

Embedded image (—O—R ₃ —O—) (C)

[0018]

Embedded image [—O—R ₄ — (CH ₂ ) ₁ —O—] (D)

[0019]

Embedded image (−Y—R ₅ —NH—) (E)

[However, in the formula, R ₁ , R ₂ and R ₃
Respectively represent an organic group represented by the following formula (1) or formula (2) or a derivative thereof, and R ₄ and R ₅ represent an aromatic ring,
Y represents a group of —O— or —NH—, and l is an integer of 1 to 4. ]

[0021]

[Chemical formula 24]

(However, X in the formula is -O-, -CO
-, --COO--, --SO _2- , --S-- or an alkylene group, and m or n are respectively
It shall be an integer of 0 or 1. )

[0023]

[Chemical 25]

Specifically, the above-mentioned structural unit (A) is
The total amount of the respective structural units (A) and (B) described above {abbreviated as structural unit [(A) + (B)] below. } In the range of 20 to 90 mol%, and the structural unit (D) is the structural unit [(C) +
(D) + (E)], that is, within the range of 0.1 to 60 mol% based on the total amount of the structural unit (C), the structural unit (D) and the structural unit (E). Yes,

The above-mentioned structural unit (E) is based on the structural unit [(C) + (D) + (E)], that is, the above-mentioned respective structural unit (C) and structural unit (D). Based on the total amount with the structural unit (E), it is within a range of 1 to 50 mol%, and the molar ratio of structural unit (B) / structural unit [(C) + (D) + (E)] That is, the ratio of the number of moles of the structural unit (B) to the total number of moles of the structural unit (C), the structural unit (D), and the structural unit (E) is 10/9. It is intended to provide a copolyester amide consisting of ˜9 / 10.

In addition, the present invention basically comprises the following compounds (A '), (B'), (C ') and (D').
An acid anhydride of an aliphatic carboxylic acid having 1 to 4 carbon atoms is added to a raw material containing (E ′) and acylated,
Subsequently, it is intended to provide a method for producing a copolymerized polyesteramide, which comprises deoxidizing and polycondensing.

[0027]

Embedded image HO—R ₁ —COOH (A ′)

[0028]

Embedded image HOOC-R ₂ —COOH (B ′)

[0029]

Embedded image HO—R ₃ —OH (C ′)

[0030]

Embedded image HO—R ₄ — (CH ₂ ) ₁ —OH (D ′)

[0031]

Embedded image Y—R ₅ —NH ₂ (E ′)

[However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And Y are as described above, and l
Is as described above. ]

Specifically, the above-mentioned compound (A ') is
Based on the compound [(A ′) + (B ′)], that is,
Compound (A ') and compound (B'), respectively, as described above.
It is within a range of 20 to 90 mol% based on the total amount of the compound (D ') and the compound [(C')
+ (D ′) + (E ′)] as a standard, that is, based on the total amount of the compound (C ′), the compound (D ′), and the compound (E ′) described above, respectively. Within the range of 60 mol%

Further, the above compound (E ') is
Based on [(C ′) + (D ′) + (E ′)], that is, based on the total amount of the compound (C ′), the compound (D ′), and the compound (E ′), 1 Within a range of up to 50 mol, and the compound (B ′) / [(C ′) +
The molar ratio of (D ′) + (E ′)] is, that is,
The ratio of the number of moles of the above structural unit (B) to the total number of moles of the compound (C ′), the compound (D ′) and the compound (E) is 10/9 to 9/10, respectively, and the polyester copolymer amide is It is intended to provide a manufacturing method of.

The above-mentioned copolymerized polyesteramide referred to in the present invention is, for example, a copolymerized polyester obtained from 4-hydroxybenzoic acid, terephthalic acid and 4,4'-dihydroxybiphenyl, 4-hydroxybenzoic acid or terephthalic acid. , 4,4'-dihydroxybiphenyl and a copolymerized polyesteramide obtained from aminophenol, the transition temperature to the liquid crystal phase can be designed to be low, and moreover, since the flow characteristics are good, It can be molded at low temperature.

The copolymerized polyesteramide of the present invention is characterized by using the above-mentioned hydroxyphenylalkyl alcohol compound represented by the general formula (D ') as an essential raw material component, and usually, the above-mentioned general formula (D) is used. A ')
, The aromatic dicarboxylic acid represented by the above general formula (B ′), the aromatic dioxy compound represented by the above general formula (C ′), and the above general formula (D ′) A hydroxyphenylalkyl alcohol compound represented by the following, aromatic aminophenols and aromatic diamines capable of forming an amide bond represented by the above general formula (E ′),

This compound (A ') is a compound [(A')
+ (B ′)] in the range of 20 to 90 mol%, and the compound (D ′) is a compound [(C ′) + (D ′) +
(E ′)] in the range of 0.1 to 60 mol%, and the compound (E ′) is a compound [(C ′) + (D ′) +
1 to 50 mol% of (E ′)], and moreover, the compound (B ′) / [(C ′) + (D ′) +
(E ′)] various raw materials whose molar ratio is in the range of 10/9 to 9/10 are used at the above-mentioned specific use ratios, and further, an acid of an aliphatic carboxylic acid having 1 to 4 carbon atoms is used. It is obtained by adding an anhydride and reacting.

The repeating polyesters represented by the above structural units (A) to (E) in which the repeating units are obtained in the above proportions are crystalline and have a softening temperature. Excellent balance with (heat resistance) and melt viscosity (molding processability).

The structural unit (A) is the structural unit [(A) +
When it exceeds 90 mol% of (B)],
The melt viscosity of the obtained copolymerized polyesteramide is remarkably high, and when it is less than 20 mol%, the melt moldability and heat stability are inevitably deteriorated. Absent.

Structural unit (B) / structural unit [(C)
If the molar ratio of + (D) + (E)] deviates from the above-mentioned range, mechanical properties are inevitably deteriorated, which is not preferable.

For example, when the structural unit (B) is a combination of structural units other than a terephthalic acid residue, or when the structural unit (C) is a combination of structural units other than a biphenyl residue or a hydroquinone residue. If, for example,
Since the softening temperature and the crystallinity can be adjusted to be low, it is possible to produce the copolymerized polyesteramide having various adjusted properties such as heat resistance.

As the aromatic oxycarboxylic acid represented by the above general formula (A '), only representative ones are exemplified, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and 4-hydroxy-4. Various hydroxynaphthoic acids such as'-carboxydiphenyl ether, 4-hydroxy 4'-carboxydiphenyl or 2,6-hydroxynaphthoic acid, or halogen-substituted products thereof, such as methyl group and phenyl group. Examples thereof include alkyl-substituted compounds and aryl-substituted compounds, but are not necessarily limited to these. Further, it goes without saying that these may be used alone or in combination of two or more kinds.

As the aromatic dicarboxylic acid represented by the general formula (B '), only typical ones are exemplified, and terephthalic acid, isophthalic acid, methylisophthalic acid and 5-t-butylisophthalic acid are listed. , Various kinds of naphthalene dicarboxylic acids such as phenyl terephthalic acid or 2,6-naphthalenedicarboxylic acid; diphenyl dicarboxylic acids; diphenyl ether dicarboxylic acids; or diphenyl ketone dicarboxylic acid or diphenyl propane dicarboxylic acid, but not necessarily these It is not limited only. Further, it goes without saying that these may be used alone or in combination of two or more kinds.

Specific examples of the aromatic dioxy compound represented by the general formula (C ') are given below. Hydroquinone, resorcin, methylhydroquinone, t-butylhydroquinone, dit-butylhydroquinone. Trimethylhydroquinones; trimethylresorcins; phenylhydroquinones; various dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene; various dihydroxybiphenyls such as 4,4′-dihydroxybiphenyl;
Various methyldihydroxybiphenyls such as 3'-dimethyl-4,4'-dihydroxybiphenyl;bisphenols;

Bis (hydroxyphenyl) ketones; Bis (hydroxyphenyl) ethers; Bis (hydroxyphenyl) sulfones; Bis (hydroxyphenyl)
Sulfides; or (4-hydroxyphenyl)-
4-hydroxybenzoate, dihydroxybenzophenones, and the like, but not limited to these. Moreover, it goes without saying that these may be used alone or in combination of two or more kinds.

As the hydroxyphenylalkyl alcohol compound represented by the general formula (D '), only typical ones are exemplified. Parahydroxyphenethyl alcohol, parahydroxyphenylpropanol, parahydroxyphenylbutanol or parahydroxyphenylbutanol. Hydroxybenzyl alcohol and the like are not necessarily limited to these. Further, it goes without saying that these may be used alone or in combination of two or more kinds, and the meta isomers may be used in a mixed form in a small amount.

Further, those having various substituents such as a methyl group on the aromatic ring within a range not departing from the object of the present invention or within a range not impairing the effect of the present invention. Can also be used together.

As the compounds which can form an amide bond represented by the above general formula (E '), only typical ones are exemplified, and p-aminophenol and m-aminophenol are exemplified. , Various aminophenols; various phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 4-amino-1-naphthol, 4-amino-4′-hydroxydiphenyl, 4-amino-4′- Hydroxydiphenylmethane, 4-amino-4′-hydroxydiphenylethane,
4-amino-4'-hydroxydiphenyl sulfone, 4
-Amino-4'-hydroxydiphenyl sulfide,
4,4'-diaminophenyl sulfide or 4,4 '
-Diaminophenyl sulfone, or these halogen-substituted compounds, such as a methyl group and a phenyl group,
Examples thereof include alkyl-substituted products and aryl-substituted products, but are not necessarily limited to these. Further, it goes without saying that these may be used alone or in combination of two or more kinds.

It should be noted that aromatic aminocarboxylic acids, aliphatic dicarboxylic acids, and aliphatic or alicyclic diols are used within the range not departing from the object of the present invention or within the range not impairing the effects of the present invention. The compounds or aliphatic diamines can be copolymerized in a small amount, and can be used in the same manner.

As the above-mentioned acylating agent used in the production of the copolymerized polyesteramide of the present invention, acid anhydrides of aliphatic carboxylic acids having 1 to 4 carbon atoms are used. Of these, acetic anhydride, propionic anhydride, chloroacetic anhydride, and the like can be given to exemplify only typical ones, but the present invention is by no means limited to these.

Above all, it is particularly preferable to use acetic anhydride as the acylating agent. In addition, the amount of the acylating agent used is usually 0.8 to 1. The amount of the acid anhydride group is 1 to 1 equivalent of the OH group and the NH ₂ group present in the reaction raw material.
It is within a range of 2 equivalents.

The copolymerized polyesteramide of the present invention can be produced by various methods, but usually, as the starting materials for reaction, the general formulas (A '), (C'), and
OH group and NH ₂ group in (D ') and (E')
It is a good idea to carry out melt polymerization by a so-called acidolysis method in which a lower alkyl ester is transformed into a lower alkyl ester by an acylating agent and then deoxidation polycondensation is carried out. Further, it goes without saying that solid phase polymerization may be carried out after melt polymerization.

The copolymerized polyesteramide of the present invention is produced on the basis of the melt polymerization method as described above, which is industrially advantageous because post-treatment after polymerization is unnecessary.
Of course, other polymerization methods such as a solution polymerization method and an interfacial polymerization method can also be used.

Such melt polymerization is usually carried out in a temperature range of 150 ° C. or higher and 400 ° C. or lower, preferably 20.
Within the range of 0 to 400 ° C. in the presence of an inert gas,
It is carried out at normal pressure or under reduced pressure.

With the progress of polymerization, for example, when acetic anhydride is used as an acylating agent, acetic acid distills out. Therefore, the reaction temperature is adjusted depending on the amount of distillate and the viscosity of the reaction system. The degree of polymerization is increased by increasing it stepwise or by adjusting the degree of vacuum. It should be noted that the polymerization time is usually appropriate within a range of 1 to 10 hours.

Further, the melt polymerization is used as the first step, the polymer is granulated if necessary, and solid phase polymerization (second step) is carried out at a temperature below its melting point to increase the degree of polymerization. The method of making it is also an excellent method. Of course, it is possible to react only to the first step to a degree of polymerization close to the theoretical deacetic acid amount.

A catalyst may be used to promote the above reactions. This type of catalyst is known, and examples thereof include alkali metal salts, Mn, Mg and Z.
A typical example is an n, Cd, Sb or Ti compound. The amount of the catalyst used is 0.001 to 1% by weight, preferably 0.01 to 0%, based on the total amount of the monomers. It is within the range of 0.2% by weight.

Hydroxyphenylalkyl alcohol residue (D) in the copolymerized polyesteramide of the present invention
Is based on [(C) + (D) + (E)), that is, the total amount of the structural unit (C), the structural unit (D), and the structural unit (E) described above, respectively. As a standard, it is used within a range of 0.1 to 60 mol%, preferably 0.5 to 30 mol%.

As compared with the case where the use of the hydroxyphenylalkyl alcohols is completely absent, not only the softening temperature of the obtained polymer and the melt phase showing the liquid crystal phase are adjusted to a wide range, but also the flow characteristics are It will also be a place to improve. When the amount of the hydroxyphenylalkyl alcohol used is less than the above value, the flow properties of the obtained polyester are not significantly improved as compared with the case where the component is not present, and the melt viscosity This is a process in which a copolymerized polyesteramide having poor practicality, which is not sufficiently lowered and has to be molded at a temperature much higher than the melting point or the softening temperature, is obtained.

On the other hand, when the hydroxyphenylalkyl alcohol component is present in a larger amount than the above value, even if a polyesteramide having optical anisotropy is obtained, such a polyesteramide is obtained. The molded article obtained from No. 1 does not exhibit preferable properties such as low strength.

By using a small amount of the component, a high fluidity can be obtained at a temperature which is not much higher than the melting point or softening temperature peculiar to the obtained polymer, and molding can be performed at such a temperature. That is, it is an unexpected matter that molding processability is improved while maintaining heat resistance.

As an index of the moldability of the copolymerized polyesteramide of the present invention, there may be mentioned liquid crystallinity and melt viscosity which show optical anisotropy when melted. Whether or not it exhibits liquid crystallinity is closely related to the fluidity during melting,
It is important that the copolymerized polyesteramide of the present invention exhibits liquid crystallinity in the molten state.

The optical anisotropy is measured by using a polarizing microscope, heating a sample placed on a hot stage equipped with a temperature raising device, heating it, and observing it at a magnification of about 40 times.

The preferred copolymerized polyesteramide in the present invention has, as its constituent component, a residue of hydroxyphenylalkyl alcohols represented by the above-mentioned general formula (D), and as its constituent component, for example, A 4-hydroxybenzoic acid residue represented by the above general formula (A), a phthalic acid residue represented by the above general formula (B), a compound represented by the above general formula (C) 4,
4'-dihydroxybiphenyl residue, aromatic aminophenol residue represented by the general formula (E) above and /
Alternatively, it is obtained by using various raw materials having a phenylenediamine residue.

Such a polyesteramide exhibits liquid crystallinity when melted, and further, the softening temperature and the melt viscosity are lower than expected when hydroxyphenylalkyl alcohols are not used.

In addition, as a component that imparts characteristics to the polyester obtained by combining it with hydroxyphenylalkyl alcohols, 4-hydroxybenzoic acid as a component of the structural unit (A ') in the above-mentioned compounds is used. Acids and their derivatives, or 2,6
-Hydroxynaphthoic acid and its derivatives as a component of the structural unit (B '), terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid as a component of the structural unit (C'),

4,4'-dihydroxybiphenyl, hydroquinones and their alkyl or phenyl derivatives, bis (hydroxyphenyl) ether, or dihydroxynaphthalene and their derivatives are used as a component of the structural unit (E '). 3- or 4-amiphenol, 3- or 4-phenylenediamine, etc. are particularly excellent.

The copolymerized polyesteramide of the present invention has a softening temperature of 150 to 400 ° C. and a temperature of 30 ° C. higher than the melting point.
It has a melt viscosity of 10 ⁴ poise or less at a high temperature and a shear rate of 10 ³ sec ^-1 .

The melt viscosity used in the present invention is a capillary rheometer (capillary rheometer).
Is used to indicate the viscosity measured at a temperature 30 ° C. higher than the melting point and a shear rate of 10 ³ sec ⁻¹ . This melt viscosity value is 10 ⁴
Copolyesters that exceed the poise are
With a capillary rheometer (capillary rheometer),
Even if it is possible to measure the melt viscosity by extruding in a strand shape, and even if it is possible to extrude in a strand shape at a temperature that greatly exceeds the melting point, a normal injection molding machine or extrusion machine is used. With a molding machine or the like, a satisfactory molded product with a clean surface cannot be obtained.

The softening temperature referred to in the present invention refers to a temperature measured by using a thermomechanical analyzer (TMA apparatus) as described later. The basic thermal properties of the copolyesters are usually indicated by using the melting point measured by a differential scanning calorimeter, but the thermotropic liquid crystal polymer according to the present invention is measured by the differential scanning calorific value. It is necessary to pay particular attention to the fact that when the polymer is measured, the change in the amount of heat when the polymer melts is too small, and it is often the case that it is difficult to clearly grasp the melting point of the polymer.

When a hot stage with a temperature raising device was placed on the sample stage of a polarizing microscope and a thin piece of a polymer sample was set therein and heated at elevated temperature, it showed optical anisotropy. The temperature can be displayed as a liquid crystal starting temperature and a temporary melting point, but as a value with good reproducibility,
It is difficult to grasp clearly, and it usually does not match the above melting point.

The above-mentioned melting point and softening temperature used in the present invention are measured as follows. That is, using a differential scanning calorimeter, measurement was performed at a temperature rising rate of 20 ° C./min to first determine the melting point, and then compression molding was performed at a temperature 30 ° C. higher than the melting point thus obtained to obtain a thickness. A test piece having a size of 2 mm was prepared, and the softening temperature of the test piece was measured with a thermomechanical analyzer (penetration method; load = 20 g) at a heating rate of 5 ° C./min. .

In the present invention, the softening temperature and melt viscosity of the obtained polyesteramide can be widely adjusted by appropriately changing the amount of hydroxyphenylalkyl alcohols used. However, it is completely unknown from the above-mentioned documents.

The copolymerized polyesteramide of the present invention may be blended with various inorganic fillers such as fibrous, powdery or plate-like fillers and organic solid fillers and so-called reinforcing agents depending on the purpose of use. I can.

As the fibrous filler, only typical ones are exemplified, and glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber,
Zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, etc., and also various metal fibers such as stainless steel, aluminum, titanium, copper, brass, and inorganic fibers , And various high-melting-point organic fibers such as polyamide resin, fluorine resin, polyester resin, and acrylic resin. Of these, glass fibers and polyamide fibers are typical, and the performance of the copolymerized polyesteramide can be adjusted by appropriately selecting the aspect ratio of these fibers.

As the powdery filler, only typical ones are exemplified, such as carbon black, zinc, silica, sulfur powder, glass beads, glass balm, glass powder, calcium sulfate, and aluminum silicate. , Various kinds of silicates such as kaolin, talc, clay, diatomaceous earth, wstonite; various metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony oxide, alumina; various kinds of calcium carbonate, magnesium carbonate, etc. In addition to various metal carbonates, calcium sulfate, barium sulfate, and various metal sulfates, various metal powders such as ferrite, silicon carbide, and boron nitride can be used.

Specific examples of the plate-like filler include mica, glass flakes and metal foils. Needless to say, these fillers may be used alone or in combination of two or more kinds. For example, the combined use of the fibrous filler and the powdery or plate-like filler results in mechanical properties and dimensional stability and / or Alternatively, it is preferable in terms of combining electrical characteristics and the like. The amount of these fillers is appropriately in the range of 1 to 60% by weight. Further, if necessary, these fillers are preferably used in combination with various surface treatment agents.

The copolymerized polyesteramide of the present invention is kneaded with various thermoplastic resins according to the purpose of use,
So-called polymer alloys can also be manufactured. As described above, if only representative examples of the thermoplastic resin that can be used in combination with the copolymerized polyesteramide are exemplified, various polysulfone-based resins such as polysulfone and polyethersulfone; polyphenylene Sulfide resins; Polyimide resins; Polyetherimide resins; Polyamideimide resins; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyarylate; Polycarbonate resins; 6-nylon , Various polyamide resins such as 6,6-nylon;

Polyesteramide-based resins; polyphenylene oxide or polymer alloy resins thereof; various polyketone-based resins such as polyetheretherketone and polyetherketone; polyacetal-based resins; fluorine-based resins; Various polyolefin resins such as polyethylene, polypropylene, ethylene propylene terpolymer; polystyrene, AS, ABS
In addition to various polystyrene resins, polyvinyl chloride, acrylic resins or silicone resins, and liquid crystal polymers having different properties.

The melting point, softening temperature, melt viscosity and optical anisotropy of the copolymerized polyesteramide of the present invention are measured as follows.

(1) Melting point and softening temperature Using a "DSC-210" type differential scanning calorimeter manufactured by Seiko Denshi Kogyo Co., Ltd., the melting point was determined by measuring at a heating rate of 20 ° C./min. Compression molding at a temperature 30 ° C. higher than the melting point to produce a test piece having a thickness of 2 mm,
The test piece is a thermo-mechanical analyzer "TM" manufactured by the same company.
A / SS 120 "(penetration method; load = 20 g) was used to measure the softening temperature at a heating rate of 5 ° C./min.

(2) Melt Viscosity Using a capillary rheometer at a temperature 30 ° C. higher than the melting point obtained in (1) above and 10 ³ sec ^−1.
It was measured by the following shear rate.

(3) Optical Anisotropy The fine powder sample was placed on a hot stage equipped with a temperature raising device, heated at a rate of 20 ° C./min, and observed with a polarizing microscope.

[0084]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples.

Example 1 In a reaction vessel equipped with a stirring blade and a nitrogen gas inlet, 4-
3.0 mol of hydroxybenzoic acid and 1. of terephthalic acid.
0 mol, 0.6 mol of 4,4′-dihydroxybiphenyl, 0.2 mol of para-aminophenol and 0.2 mol of para-hydroxyphenethyl alcohol were charged, and the atmosphere was replaced with nitrogen under reduced pressure and sealed with nitrogen. 5.5 mol of acetic anhydride was added.

Then, with stirring, the mixture was heated to 145 ° C. and 3
After reacting for a time, the temperature was raised to 290 ° C. over 3 hours to continue the reaction, and further, the reaction was continued under a reduced pressure of 1 mmHg. The crude polymer obtained is ground to 1
Under reduced pressure of mmHg, the temperature was raised to 290 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 329.
℃, the softening temperature is 310 ℃, and the melt viscosity is 5 × 1
It was 0 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

This polymer also contains 60 mol% of hydroxybenzoic acid, 20 mol% of terephthalic acid, 12 mol% of dihydroxybiphenyl, 4 mol% of aminophenol, and 4 mol of hydroxyphenethyl alcohol. The composition was mol%.

Example 2 A reaction vessel equipped with a stirring blade and a nitrogen gas inlet was added with 4-
3.0 mol of hydroxybenzoic acid and 1. of terephthalic acid.
Charge 0 mol, 0.4 mol of 4,4′-dihydroxybiphenyl, 0.3 mol of para-aminophenol and 0.3 mol of para-hydroxyphenethyl alcohol, and replace with nitrogen under reduced pressure, and then seal with nitrogen. And 5.5 mol of acetic anhydride were added.

Then, while stirring, the mixture was heated to 145 ° C., and the reaction was carried out for 3 hours.
Raise the temperature to 90 ° C to allow the reaction to continue, and
The reaction was allowed to continue under reduced pressure of mmHg. Next, the crude polymer thus obtained was pulverized and heated to 260 ° C. over 10 hours under reduced pressure of 1 mmHg to carry out solid phase polymerization.

The melting point of the polymer obtained here is 311 ° C.
The softening temperature was 300 ° C., and the melt viscosity was 5 × 10 ² poise. This polymer, when melted,
It showed optical anisotropy.

No raw material monomer was detected in the distilled acetic acid. In addition, this polymer has a composition of 60 mol% of hydroxybenzoic acid, 20 mol% of terephthalic acid, 8 mol% of dihydroxybiphenyl, 6 mol% of aminophenol, and 6 mol% of hydroxyphenethyl alcohol. there were.

Example 3 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 0.7 mol of terephthalic acid were added.
0.3 mol of 2,6-naphthalenedicarboxylic acid, 0.3 mol of para-aminophenol, 0.4 mol of 4,4′-dihydroxybiphenyl and 0.3 mol of parahydroxyphenethyl alcohol were charged, and under reduced pressure, After purging with nitrogen, the atmosphere was sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Subsequently, the mixture was heated to 145 ° C. with stirring and reacted for 3 hours, then heated to 290 ° C. over 3 hours to continue the reaction, and further 1 mmHg
The reaction was carried out under reduced pressure.

The crude polymer obtained here was pulverized to 1 m.
Under reduced pressure of mHg, the temperature was raised to 260 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 290.
A ° C., the softening temperature is 280 ° C., and a melt viscosity of 1 × 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 4 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were added.
0.2 mol of para-aminophenol, 0.7 mol of 4,4′-dihydroxybiphenyl and 0.1 mol of para-hydroxyphenethyl alcohol were charged, and under reduced pressure,
After purging with nitrogen, the atmosphere was sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Subsequently, with stirring, the mixture was heated to 145 ° C. and reacted for 3 hours, then 290 over 3 hours.
The temperature was raised to ℃, and the reaction was allowed to continue.
The reaction was allowed to continue under a reduced pressure of Hg.

The crude polymer obtained here was pulverized to 1 m.
Under reduced pressure of mHg, the temperature was raised to 300 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 370.
A ° C., the softening temperature is 358 ° C., and a melt viscosity of 1 × 10 ³ poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 5 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 0.8 mol of terephthalic acid were added.
Charge 0.2 mol of 2,6-naphthalenedicarboxylic acid, 0.1 mol of p-phenylenediamine, 0.7 mol of 4,4′-dihydroxybiphenyl and 0.2 mol of parahydroxyphenethyl alcohol and reduce the pressure. The atmosphere was purged with nitrogen, sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Subsequently, while stirring, the mixture was heated to 145 ° C. and reacted for 3 hours, then 290 over 3 hours.
The temperature was raised to ℃ to continue the reaction, and further 1mmHg
The reaction was allowed to continue under reduced pressure.

The crude polymer obtained here was pulverized to 1 m.
Under reduced pressure of mHg, the temperature was raised to 280 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 315.
A ° C., the softening temperature is 300 ° C., and a melt viscosity of 7 × 10 ² poise. This polymer exhibited optical anisotropy when melted.

Example 6 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were added.
Charge 0.2 mol of p-phenylenediamine, 0.5 mol of 4,4′-dihydroxybiphenyl and 0.3 mol of parahydroxyphenethyl alcohol, replace with nitrogen under reduced pressure, seal with nitrogen, and remove acetic anhydride. Was added.

Then, with stirring, the mixture was heated to 145 ° C., the reaction was carried out for 3 hours, and then, over 3 hours.
The temperature was raised to 290 ° C. to continue the reaction, and
The reaction was performed under a reduced pressure of 1 mmHg.

The crude polymer obtained here was pulverized to 1 m.
Under reduced pressure of mHg, the temperature was raised to 260 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 335.
A ° C., the softening temperature is 330 ° C., and a melt viscosity of 1 × 10 ³ poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

This polymer also contained 50 mol% of hydroxybenzoic acid, 25 mol% of terephthalic acid, 5 mol of phenylenediamine, 12.5 mol% of dihydroxybiphenyl, and 7 mol of hydroxyphenethyl alcohol. The composition was 0.5 mol%.

Example 7 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 0.8 mol of terephthalic acid were added.
0.2 mol of isophthalic acid, 0.2 mol of para-aminophenol, 0.7 of 4,4'dihydroxybiphenyl
Molar and para-hydroxyphenethyl alcohol of 0.
1 mol was charged, the atmosphere was replaced with nitrogen under reduced pressure, the atmosphere was sealed with nitrogen, and 4.5 mol of acetic anhydride was added.

Then, the mixture was heated to 145 ° C. with stirring and heated to 3
After reacting for a period of time, the temperature was raised to 290 ° C. over 3 hours to continue the reaction, and further the reaction was continued under a reduced pressure of 1 mmHg.

The crude polymer obtained here was pulverized to 1 m.
Under reduced pressure of mHg, the temperature was raised to 290 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 349.
A ° C., the softening temperature is 342 ° C., and a melt viscosity of 2 × 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 8 In a reaction vessel equipped with a stirring blade and an inlet, 2.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were added.
Charge 0.15 mol of 2,6-dihydroxynaphthalene, 0.15 mol of para-aminophenol, 0.67 mol of 4,4'-dihydroxybiphenyl and 0.03 mol of para-hydroxyphenethyl alcohol, and add nitrogen under reduced pressure. After displacement, blanket with nitrogen and add 4.5 moles of acetic anhydride.

Subsequently, while stirring, the mixture was heated to 145 ° C., reacted for 3 hours, and then heated to 290 ° C. over 3 hours.
The temperature is raised to 1, and the reaction is continued, and further 1 mmH
The reaction was allowed to continue under a vacuum of g.

The crude polymer obtained here was pulverized to 1 m.
Under reduced pressure of mHg, the temperature was raised to 290 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 340.
A ° C., the softening temperature is 327 ° C., and a melt viscosity of 3 × 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 9 In a reaction vessel equipped with a stirring blade and an inlet, 3.0 mol of 4-hydroxybenzoic acid and 0.8 mol of terephthalic acid were added.
0.2 mol of 2,6-naphthalenedicarboxylic acid, 0.2 mol of paraaminophenol, 0.2 mol of 2,6-dihydroxynaphthalene, 0.55 mol of 4,4′-dihydroxybiphenyl and parahydroxyphenethyl alcohol. 0.05 mol of the above was charged, the atmosphere was replaced with nitrogen under reduced pressure, the atmosphere was sealed with nitrogen and 5.5 mol of acetic anhydride was added.

Then, while stirring, the mixture was heated to 145 ° C., reacted for 3 hours, and then heated to 290 ° C. over 3 hours.
The temperature was raised to 1, the reaction was continued, and the reaction was further continued under a reduced pressure of 1 mmHg.

The crude polymer obtained here was pulverized to 1 m.
Under reduced pressure of mHg, the temperature was raised to 260 ° C. over 10 hours to carry out solid phase polymerization.

The melting point of the polymer thus obtained is 306.
A ° C., the softening temperature is 288 ° C., and a melt viscosity of 1 × 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 10 In a reaction vessel equipped with a stirring blade and an inlet, 2.8 mol of 4-hydroxybenzoic acid, 0.2 mol of 2,6-hydroxynaphthoic acid, 0.75 mol of terephthalic acid, 2,6
-Prepare 0.25 mol of naphthalenedicarboxylic acid, 0.3 mol of para-aminophenol, 0.67 mol of 4,4'-dihydroxybiphenyl and 0.03 mol of para-hydroxyphenethyl alcohol and replace with nitrogen under reduced pressure. From above, a nitrogen blanket was added, and 5.5 mol of acetic anhydride was added.

Subsequently, while stirring, the mixture was heated to 145 ° C., the reaction was carried out for 3 hours, and then the reaction was conducted for 2 hours over 3 hours.
The temperature was raised to 90 ° C to allow the reaction to continue, and further 1 mm.
The reaction was continued under a reduced pressure of Hg, and then the temperature was raised to 330 ° C. to continue the reaction.

The melting point of the polymer thus obtained is 275.
A ° C., the softening temperature is 272 ° C., and a melt viscosity of 1 × 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Example 11 In a reaction vessel equipped with a stirring blade and an inlet, 0.5 mol of 4-hydroxybenzoic acid and 0.7 mol of terephthalic acid were added.
0.3 mol of 2,6-naphthalenedicarboxylic acid, 0.2 mol of para-aminophenol, 0.1 mol of phenylhydroquinone, 0.65 mol of 4,4'-dihydroxybiphenyl and 0.05 of para-hydroxyphenethyl alcohol. Mol of the mixture was charged, the atmosphere was replaced with nitrogen under reduced pressure, the atmosphere was sealed with nitrogen, and 3.5 mole of acetic anhydride was added.

Then, with stirring, the mixture was heated to 145 ° C., reacted for 3 hours, and then over 3 hours.
The temperature was raised to 290 ° C. to continue the reaction, and
The reaction was continued under a reduced pressure of 1 mmHg and then 33
The temperature was raised to 0 ° C. and the reaction was allowed to continue.

The melting point of the polymer thus obtained is 303.
A ° C., the softening temperature is 298 ° C., and a melt viscosity of 6 × 10 ² poise. This polymer exhibited optical anisotropy when melted. No raw material monomer was detected in the distilled acetic acid.

Comparative Example 1 3.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were placed in a reaction vessel equipped with a stirring blade and an inlet.
0.7 mol of 4,4′-dihydroxybiphenyl and 0.3 mol of para-aminophenol were charged, the atmosphere was replaced with nitrogen under reduced pressure, and the atmosphere was sealed with nitrogen.
Mole was added.

Then, while stirring, the mixture was heated to 145 ° C., the reaction was carried out for 3 hours, and then 2 hours were taken over 3 hours.
The temperature was raised to 90 ° C to allow the reaction to continue, and further 1 mm.
The reaction was allowed to continue under a reduced pressure of Hg.

After that, the crude polymer thus obtained was pulverized, and the mixture was crushed under a reduced pressure of 1 mmHg for 10 hours.
The temperature was raised to 300 ° C. and solid phase polymerization was performed. The polymer thus obtained then had a melting point of 420 ° C., a softening temperature of 390 ° C. and a melt viscosity of 2 × 10 ⁴ poises.

This polymer has a composition of 60 mol% of hydroxybenzoic acid, 20 mol% of terephthalic acid, 14 mol% of dihydroxybiphenyl and 6 mol% of aminophenol. Met.

Comparative Example 2 3.0 mol of 4-hydroxybenzoic acid and 1.0 mol of terephthalic acid were placed in a reaction vessel equipped with a stirring blade and an inlet.
0.3 mol of p-phenylenediamine and 4,4'-
The procedure of Comparative Example 1 was repeated, except that 0.7 mol of dihydroxybiphenyl was charged, and the polymer thus obtained had a melting point of 425 ° C. and a softening temperature of 420.
However, the melt viscosity could not be measured.

[0133]

The copolymerized polyesteramide of the present invention is
In particular, the softening temperature is controlled in a wide range, and furthermore, it gives a highly heat-resistant polymer material having excellent fluidity, which is extremely practical.

Claims (8)

[Claims] 1. A structural unit (A) as described below,
Including (B), (C), (D) and (E), and
A softening temperature of 150 to 400 ° C., a melting point of + 30 ° C., and a melt viscosity at a shear rate of 10 ³ Sec ⁻¹ of 10 ⁴ poise or less.
Copolyester amide. ## STR1 ## _{(- O-R 1 -C0-)} (A) ## STR2 ## _{(- OC-R 2 -CO-)} (B) ## STR3 ## _{(- O-R 3 -O-)} (C ) embedded image _{[- O-R 4 - (CH} 2) l -O- ] (D) embedded image _{(- Y-R 5 -NH-)} (E) [provided that, R ₁ in the formula, R ₂ and R ₃ are respectively
An organic group represented by the following formula (1), formula (2) or formula (3) or a derivative thereof is represented, R ₄ and R ₅ are aromatic rings, and Y is-.
Represents a group O- or -NH-, and l
Is an integer of 1 to 4. ] [Chemical 6] [Chemical 7] [Chemical 8] (However, X in the formula is -O-, -CO-, -COO-,
It represents —SO ₂ —, —S— or an alkylene group, and m or n is an integer of 0 or 1, respectively. ) 2. The structural unit (A) is within a range of 20 to 90 mol% of the structural unit [(A) + (B)], and the structural unit (D) is structural unit [( C) +
(D) + (E)] in the range of 0.1 to 60 mol%, wherein the structural unit (E) is the structural unit [(C) +
(D) + (E)] in the range of 1 to 50 mol%,
Moreover, the structural unit (B) / [(C) + (D) + (E)]
The copolymerized polyesteramide according to claim 1, wherein the molar ratio of is 10/9 to 9/10. 3. R ₄ in the above structural unit (D)
Is an equation such as The copolymerized polyester according to claim 1 or 2, which is represented by 4. R ₅ in the above structural unit (E)
Is an equation such as The copolymerized polyester according to claim 1 or 2, which is represented by 5. A compound (A ′) as described below,
To a raw material containing (B '), (C'), (D ') and (E'), an acid anhydride of an aliphatic carboxylic acid having 1 to 4 carbon atoms is added for acylation, and then, A method for producing a copolymerized polyesteramide, which comprises deoxidizing and polycondensing. HO-R ₁ -C0OH (A ') HOOC-R ₂ -COOH (B') HO-R ₃ -OH (C ') HO-R ₄ — (CH ₂ ) ₁ —OH (D ′) embedded image Y—R ₅ —NH ₂ (E ′) [wherein R ₁ , R _{2 and} R _{3 in the} formula respectively represent
It represents an organic group represented by the formula (1), (2) or (3) or a derivative thereof, R ₄ or R ₅ represents an aromatic ring, and Y represents a group of —OH or —NH _2. And l is an integer from 1 to 4. ] [Chemical 16] [Chemical 17] (However, X in the formula is -O-, -CO-, -COO-,
It represents --SO _2- , --S-- or an alkylene group, and m or n is an integer of 0 or 1, respectively. ) [Chemical 18] 6. The compound (A ′) is in the range of 20 to 90 mol% of the compound [(A ′) + (B ′)], and the compound (D ′) is the compound [( C ')
+ (D ′) + (E ′)] in the range of 0.1 to 60 mol%, and the compound (E ′) is the compound [(C ′) + (D ′) + (E ′) ] In the range of 1 to 50 mol%, and the compound (B ′) /
The molar ratio of [(C ') + (D') + (E ')] is 10/9.
The manufacturing method according to claim 5, which is ˜9 / 10. 7. R ₄ in the above compound (D ′)
Is an equation such as The method according to claim 5 or 6, which is represented by 8. R ₅ in the above compound (E ′)
Is an equation such as The method according to claim 5 or 6, which is represented by