JPH01182360A - Polyester composition with liquid crystal nature - Google Patents

Abstract

PURPOSE:To obtain the title composition afforded with flexibility, impact resistance, etc., while retaining high strength and high modulus, also improved in processability, by blending each specified amount of a polyester with liquid crystal nature and a specific hydrogenated block copolymer and/or modified one therefrom. CONSTITUTION:The objective composition can be obtained by blending (A) 70-99 pts.wt. of a polyester with liquid crystal nature capable of forming anisotropic melt, constituted of (i) 20-80mol% of a unit of formula I (R1 is 6-15C-divalent aromatic derivative residue), (ii) 40-10mol% of a second unit of formula II (R2 is 6-15C-divalent aromatic derivative residue, etc.) and (iii) 40-10mol% of a third unit of formula III (R3 is 6-15C-divalent aromatic derivative residue, etc.) with the molar ratio: (ii)/(iii)=1 and (B) 30-1 pts.wt. of a hydrogenated block copolymer produced by hydrogenation of a block copolymer constituted of (iv) at least one polymer block consisting mainly of vinyl aromatic compound and (v) at least one polymer block consisting mainly of conjugated diene compound and/or a modified one with carboxylic acid (derivative) group- contg. molecule bonded to said block copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a composition in which elongation, flexibility and impact resistance are imparted to liquid crystalline polyester.

More specifically, it can be plasticized to the extent that it maintains the advantages of liquid crystalline polyester that can form an anisotropic melt, such as liquid crystallinity, high strength, high flexural modulus, and low coefficient of linear expansion. The present invention relates to a composition of a liquid crystalline polyester and a hydrogenated block copolymer and/or a modified hydrogenated block copolymer for the purpose of imparting impact resistance.

[Conventional technology]

In recent years, basic and applied research on various liquid crystal compounds has become active in anticipation of their application to optical materials. Especially regarding polymer liquid crystals, Eastman Kodak's W,
J. Jackson et al. announced 9-motropic liquid crystalline polyester (J. Polym, Sc 1,
Polym, Chem, Ed.

Since 2043 (1976) L, the possibility of liquid crystal properties and high-strength, high-elastic polymer materials has attracted attention and many studies have been conducted. The liquid crystalline polyester reported by W., J., Jackson, et al. is a copolymer of polyethylene terephthalate and p-hydroxybenzoic acid, and is known to form an anisotropic melt within a specific composition range. This polynisder can be oriented in the melt, under shear, indexed and extruded. The molded product was highly oriented without being stretched, and had the advantage of having high strength and high flexural modulus.

Subsequently, liquid crystalline polyesters have been announced and their practical application is being considered, but despite the high expectations for high-strength and optical materials, there are still few examples of them being realized as industrial products. This is the current situation.

[Problem to be solved by the invention]

One of the reasons why such liquid crystalline polyester is difficult to put into practical use is that while its molded products have high strength and high elasticity,
It has the drawbacks of being inflexible, hard, and brittle, and easily breaking even when placed on a surface. Although it has been proposed to add a plasticizer to improve this drawback, it has not been possible to obtain a material that can withstand practical use, such as impairing liquid crystallinity.

It is also possible to copolymerize a component that imparts flexibility when compounding liquid crystalline polyester, but this generally leads to deterioration of compatibility, making it impossible to obtain a uniform molded product, and even worsening liquid crystallinity. The reality is that it is put away. Japanese Patent Publication No. 61-737
No. 30 proposes a liquid crystalline polyester containing p-hydroxybenzoic acid and polyethylene terephthalate as main components and modified with a specific amount of a specific copolymer component. Although such liquid crystalline polyester maintains high strength and a low coefficient of linear expansion and has improved flexibility to some extent, it has not yet reached a level where it can be put to practical use as an industrial product.

On the other hand, liquid crystalline polyesters copolymerized with hydroxyaromatic carboxylic acids also have problems in processing, such as decomposition during melting, coloring, and decreased viscosity. As a method to improve such problems and improve flexibility at the same time, JP-A-61-73731Q and JP-A-61-97326@ disclose a method of reacting liquid crystalline polyester with a specific amount of phenylene bis oxyquilizoline. A method for imparting flexibility without decomposition or coloring is disclosed. however,
These methods use expensive and sublimable components and have the drawback of thickening during the reaction, so they require special reaction equipment, are complicated to operate, and have industrial problems such as increased costs. a. Therefore, it has become a problem to easily impart flexibility to liquid crystalline polyester without impairing its properties in practice.

[Means to solve problems]

The inventors of the present invention have improved elongation, flexibility, and durability within a range that practically maintains the advantages of liquid crystalline polyester obtained by copolymerizing hydroxyaromatic carboxylic acids, such as liquid crystallinity, high strength, and bullet ↑4. As a result of intensive research into methods for imparting impact resistance and eliminating defects such as brittleness to bending, weakness, and ease of cracking of molded products, we found that liquid crystalline polyester can be made using specific hydrogenated block copolymers or modified hydrogenated blocks. By blending a specific amount of copolymer, the advantages of liquid crystalline polyester are not lost.
The present invention was completed after discovering that flexibility can be imparted and processability is also improved.

That is, the present invention provides (a) 70 to 99 parts by weight (1) of a liquid crystalline polyester composed of repeating units of the following general formulas (I>, (II) and (1) and capable of forming an anisotropic melt)
-C-R1-0-20~80% (1) -C-R
3-0-40 to 10 mol% (however, (n) and (III)
In the formula, R1 is a residue of a divalent aromatic derivative having 6 to 15 carbon atoms, R2 is a residue of a divalent aromatic derivative having 6 to 15 carbon atoms, and 4 to 20 carbon atoms. is a divalent alicyclic derivative residue or a divalent aliphatic derivative residue having 1 to 20 carbon atoms, R3 is a divalent aromatic derivative residue having 6 to 15 carbon atoms,
Divalent alicyclic derivative residue having 4 to 20 carbon atoms or having 2 to 20 carbon atoms
20 divalent aliphatic derivative residues. ] (b) A block copolymer consisting of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound is hydrogenated to produce 1q A flexible hydrogenated block copolymer comprising 30 to 1 part by weight of a hydrogenated block copolymer and/or a modified hydrogenated block copolymer in which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to the hydrogenated block copolymer. This is a liquid crystalline polynisder composition.

The present invention will be explained in detail below.

The liquid crystalline polyester used as component (a) in the present invention has 20 to 8 hydroxy aromatic carboxylic acid residues.
0 mol%, dicarboxylic acid residues are 40 to 10-tl%, diol residues are 40 to 10 mol%, and the ratio of dicarboxylic acid residues to diol residues is 1. It is.

The residual group of the hydroxy aromatic carboxylic acid represented by the general formula (I>) in the liquid crystalline polyester of the present invention must be within the range of 20 to 80 mol% in order to exhibit liquid crystallinity.Liquid crystallinity 35 to 50 mol% is more preferable in terms of the balance between
15 divalent aromatic derivative residues, specifically p-hydroxybenzoic acid, m-hydroxybenzoic acid, 3,5-
Dimethyl-4-hydroxybenzoic acid, 2-hydroxy-
Examples include 6-naphthalenecarboxylic acid, 2-hydroxy-5-naphthalenecarboxylic acid, 1-hydroxy-5-naphthalenecarboxylic acid, p-hydroxycinnamic acid, and derivatives such as aromatic alkylated products and halides thereof.

These may be used alone or as a mixture of two or more. Among these, p-hydroxybenzoic acid and 2-hydroxy-6-naphthalenecarboxylic acid are preferred because they provide suitable rigid linear chains and good liquid crystallinity.

In addition, R in the dicarboxylic acid residue represented by general formula (n)
2 is a derivative residue in a divalent aromatic having 6 to 15 carbon atoms, and 4 carbon atoms.
~20 divalent alicyclic rings or divalent aliphatic derivative residues having 1 to 20 carbon atoms. Specific examples include terephthalic acid, isophthalic acid, 2-methylterephthalic acid, diphenic acid,
, 6-naphthalenedicarboxylic acid, 2.5-naphthalenedicarboxylic acid, 1.5-naphthalenedicarboxylic acid, p,
p-Dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,
4'-Sulfonylbenzoic acid, p-oxy(p-carboxyphenyl)benzoic acid, ethylene-bis-low benzoic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclopentanedicarboxylic acid, malonic acid,] Examples include dicarboxylic acids such as uccinic acid, geltaric acid, adipic acid, pimelic acid, speric acid, abilaic acid, sebacic acid, diglycolic acid, and dipropionic acid, and derivatives such as alkylated products and halogenated products thereof. Any of these may be used alone or in a mixture of two or more.

Among these dicarboxylic acids, aromatic dicarboxylic acids are preferred because they yield good liquid crystalline polyesters, and terephthalic acid and 2,6-naphthalene dicarboxylic acid are particularly preferred. Furthermore, if terephthalic acid or/and 2-6-naphthalenedicarboxylic acid is used for 80 mol% or more of the dicarboxylic acid, and the remaining 20 mol% or more is mixed with other types of dicarboxylic acids, the physical property balance and transparency This is preferred because it provides a liquid crystalline polyester with excellent properties.

On the other hand, R3 in the diol remaining base represented by general formula (II)
is a 2filli aromatic diluent residue having 6 to 15 carbon atoms, a divalent alicyclic derivative residue having 4 to 20 carbon atoms, or a residue having 2 to 2 carbon atoms.
0 divalent aliphatic derivative residues. Specific examples providing such diol residues include hydroquinone, resorcinol, 4,4°-diphenol, 4°4°-methylene diphenol, 4,4′-isopropylidenediphenol, 4,4′-sulfonyldiphenol. , 4,4°-dihydroxydiphenyl ether, 3°4-dihydroxydiphenyl ether, 4,4°-dihydroxydiphenylketone, 2,5-naphthalenediol, 2,6-naphthalenediol, 1,4-cyclohexanediol, 1.
6-cyclohexanediol, ethylene glycol, diethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 2,4-dimethyl-2
-Edylenehexane-1,3-diol, 2,2.4-
Trimethyl-1,3-bentanediol, 2,2-lame blue 1,3-butanediol, 1.3-butanediol, 1,4-butanediol, 1.5-bentanediol, 1.6-hexanediol, etc. Examples include diols and derivatives thereof such as alkylated products and halogenated products.

These diols may be used alone or in a mixture of two or more. Among these, ethylene glycol, hydroquinone, 4,4°-isopropylidenediphenol, 4,4°-diphenol, and 4.4°-dihydroxydiphenyl ether are preferred diols. In particular, it is preferable to use ethylene glycol or/and hydroquinone in 80 mol% or more of the diol, and mix the remaining less than 20 mol% with other types of diols, since this provides a liquid crystalline polyester with well-balanced physical properties.

In addition, in order to exhibit liquid crystallinity, the liquid crystalline polyester used in the present invention generally needs to have polymer chains consisting of rigid and straight chains with high linearity, but non-linear parts may be added to the extent that the liquid crystallinity is not impaired. may be contained to some extent, or may be reacted with a chain extender such as a bifunctional poxy compound or phenylenebisoxazoline within a range that does not impair liquid crystallinity.

The liquid crystalline polyester used in the present invention can be produced by various methods similar to ordinary polyesters. For example, a melting procedure may be carried out using an acetylation top, or a polyester obtained from a dicarboxylic acid component and a diol component and a hydroxy aromatic carboxylic acid may be heated and melted, and then co-produced by an acidolysis reaction under a stream of dry nitrogen. A method may also be used in which polymerized polyester fragments are produced and then the viscosity is increased under reduced scale. Further, the liquid crystalline polyester used in the present invention preferably has an intrinsic viscosity 1i (measured at 30° C. using a solvent with a medium weight ratio of 1,1,2,2-tetrachloroethane/pentafluorophenol=50150) of 0.3 or more. If the intrinsic viscosity is less than 0.3, it will not exhibit sufficient performance as a polymer such as strength, and will become brittle, failing to achieve the object of the present invention.

Next, the hydrogenated block copolymer and/or modified hydrogenated block copolymer used as component (b) in the composition of the present invention is blended with the liquid crystalline polyester, which is component (a), to mainly improve flexibility. It is an essential component for imparting impact resistance. By blending the component (1)), it is possible to plasticize within a range that practically maintains the inherent advantages of liquid crystalline polyester, such as liquid crystallinity, high strength, and high flexural modulus. It imparts flexibility and elongation impact resistance to polyester, improves its brittleness and breakability, which were disadvantages in practical use, and improves processability.

The hydrogenated block copolymer that can be used as one of the components (b) comprises a polymer block A mainly composed of at least one vinyl aromatic compound and at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer consisting of a polymer block B, such as A-B, A-B-A, B-A-B-A.

It is a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having the structure (A B+'TSi, (B A B Nago 3i, etc.)).

This hydrogenated block copolymer contains 5 vinyl aromatic compounds.
~95% by weight, preferably 10 to 85% by weight, and when the vinyl aromatic compound is less than about 60% by weight, preferably less than 55% by weight, such a hydrogenated block copolymer exhibits properties as a thermoplastic elastomer. , is particularly effective for plasticizing liquid crystalline polyester. To briefly describe the block structure, the polymer block A mainly composed of a vinyl aromatic compound is a vinyl aromatic compound polymer block or a vinyl polymer block containing more than 50% by weight and preferably 70% by weight or more of a vinyl aromatic compound. It has a structure of a copolymer block of an aromatic compound and a hydrogenated conjugated diene compound, and furthermore, a polymer block mainly composed of a hydrogenated conjugated diene compound [1 B is a hydrogenated conjugated diene compound]. or a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing more than 50% by weight and preferably 70% by weight or more of a hydrogenated conjugated diene compound. It has a structure.

In addition, the polymer block A mainly composed of these vinyl aromatic compounds and the polymer block B mainly composed of a hydrogenated conjugated diene compound are hydrogenated conjugated diene compounds in the molecular chains of each polymer block. Or the distribution of vinyl aromatic compounds, galundum, Cheebird (in which the heptamer component increases or decreases along the molecular chain)
, may be partially block-shaped, or may consist of any combination thereof, and each has two polymer blocks mainly composed of the vinyl aromatic compound and two polymer blocks mainly composed of the hydrogenated conjugated diene compound. If there are more than one, each polymer block may have the same structure or may have different structures.

Examples of the vinyl aromatic compounds constituting the hydrogenated block copolymer include styrene, α-methylstyrene, p-methylstyrene, vinyltol: One or more types can be selected from among them, and styrene is preferred among them. Further, as the conjugated diene compound before hydrogenation constituting the hydrogenated co-IQ diene compound, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. One or more types may be selected, and among them, butadiene, imprene, and a combination thereof are preferred. The microstructure of each block can be arbitrarily selected for the polymer block mainly composed of a conjugated diene compound before being hydrogenated.
For the effect of imparting softness to the liquid crystalline polyester, for example, in the polybutadiene block, the 1,2-vinyl bond mother content is 10 to 65%, preferably 20 to 55%.

Further, the number average molecular weight of the hydrogenated block copolymer used in the present invention having the above-described structure is 5,000 to 1, ooo
, ooo, good mashikuha 10. OOO~500. ooooo
However, in order to maintain a balance between the physical properties and processability of the composition of the present invention, it is 30,000 to 300,000. ()00 is a more preferable range, and the molecular weight distribution [weight average molecule! (
Mw) and number average molecular weight (Mn) (MW/Mn)
) is 10 or less. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

These block copolymers may be produced by any method as long as they have the structure described above. For example,
A vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst etc. according to the method described in Japanese Patent Publication No. 3798@, and then, for example, as described in Japanese Patent Publication No. 42-8704, Kosho 43-6636
@Described in the official bulletin. Method, particularly preferably JP-A-59
-133203@publication and JP-A-60-79005@
According to the method described in the publication, the hydrogenated block copolymer used in the present invention can be synthesized by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst. At that time, the number of aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least 8.
By hydrogenating 0%, a polymer block mainly composed of a conjugated diene compound can be morphologically converted into an olefinic compound polymer block. In addition, hydrogen of an aromatic double bond based on a vinyl aromatic compound copolymerized into a polymer block A mainly composed of a vinyl aromatic compound and, if necessary, a polymer block B mainly composed of a conjugated diene compound. Although there is no particular restriction on the addition rate, it is preferable that the hydrogenation rate is 20% or less.

The number of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using field spectroscopy, nuclear magnetic resonance, or the like.

On the other hand, another modified hydrogenated block copolymer that can be used as component (B) is a component that has improved compatibility with liquid crystalline polyester. It is a combination of molecular units containing derivative groups. Such a modified hydrogenated block copolymer can be obtained by adding an unsaturated carboxylic acid or a derivative thereof to the hydrogenated block copolymer described above in a solution state or a molten state, with or without the use of a radical initiator. It will be done. The hydrogenated block copolymer that can be used for such addition modification can be any of those specified above, and unsaturated carboxylic acids or derivatives thereof that are added to the hydrogenated block copolymer can be used. Examples include maleic acid, halogenated maleic acid,
Itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo(2,2,1)
-5-hebutene-2,3-dicarboxylic acid, anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, crotonic acid, etc., and esters of these monocarboxylic acids, such as methyl methacrylate, Examples include derivatives such as glycidyl methacrylate and amides. Among these, maleic anhydride and glycidyl methacrylate are particularly preferred.

The method for producing these modified hydrogenated block copolymers is not particularly limited in the present invention, but the modified hydrogenated block copolymers obtained may contain undesirable components such as gel or have a significantly high melt viscosity. A manufacturing method that increases the processing/[1] or deteriorates the quality is not preferable. A preferred method is, for example, in an extruder, in the presence of a radical initiator,
There is a method of reacting an unmodified hydrogenated block copolymer with an unsaturated carboxylic acid or a derivative thereof.

The amount of unsaturated carboxylic acid or its afifj form added to the hydrogenated block copolymer is 100% of the hydrogenated block copolymer.
The amount per quick part is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less. Even if the added amount exceeds 20 parts by volume, there is hardly any increase in the improvement effect compared to when it is less than that. The unsaturated carboxylic acids or derivatives thereof used in the present invention can be used not only alone but also as a mixture of two or more.

The composition of the present invention includes, as a modifying component that imparts flexibility and impact resistance to the liquid crystalline polyester of component (a), described above.
It is constructed by essentially using the hydrogenated block copolymer and/or modified hydrogenated block copolymer as the component (b) described above. The blending ratio of such a composition is 10 to 99 parts by weight of the liquid crystalline polyester used as component (a) per 100 parts of the composition, and 10 to 99 parts by weight of the liquid crystalline polyester used as component (b). copolymer is 3
It is 0 to 1 part by weight. If component (a) is less than 70 parts by weight, the composition containing 1q will not form an anisotropic melt and will not exhibit liquid crystallinity, and the characteristics of liquid crystalline polyester, such as high strength and high elastic modulus, will also be impaired. Undesirable. On the other hand, (b)
If the amount of the component is less than 1 part by weight, the plasticizing effect will be insufficient and a flexible composition will not be obtained, but only a brittle and easily cracked composition will be obtained. A more preferable blending ratio of component (b) is 20 to 3 parts by weight and 10 to 5 parts by weight per 100 parts by weight of the composition.
Parts by weight are particularly preferred.

As the component (b) used in the composition of the present invention, any of the above hydrogenated block copolymers or modified hydrogenated block copolymers may be suitably used, and a mixture of both may be used. . In general, modified hydrogenated block copolymers have better compatibility with component (a), the liquid crystalline polyester, and can produce a modifying effect even when used in small amounts than unmodified hydrogenated block copolymers. and the homogeneity of the resulting composition,
It tends to have excellent transparency, but on the other hand, it tends to easily cause reactions between the six colors and components (a) and (b) during processing, and the modifying effect of both components (b) is less than that of (a). ) It differs slightly depending on the type of liquid crystalline polyester used as the component. Therefore, the molecular structure of the liquid crystalline polyester used as component (a), It may be appropriately selected depending on the molecular weight and properties, and is not particularly limited. or,(
When a hydrogenated block copolymer and a modified hydrogenated block copolymer are mixed and used as component b), the mixing ratio can be arbitrarily selected.

The composition of the present invention may be prepared by adding the component (b) to a molten liquid crystalline polyester and mixing with heating, or by adding a component (b) to a molten liquid crystalline polyester, or by preparing a solid (
Components a) and (b) may be mixed in advance and then melt-mixed. Generally, the composition can be obtained by mixing components (a) and (b) in a Henschel mixer, blender, etc., and then kneading them with heated rolls or kneading with an extruder, etc. When melting and kneading, (a) and (b)
In order to avoid decomposition and gluing of the components, it is preferable to carry out the reaction at a temperature of 400°C or lower, particularly 320°C or lower.

In this way, the composition 17 can be easily obtained in the form of a sheet by hot pressing, and can also be molded into various molded products by extrusion molding, injection molding, etc.

(Effects of the Invention) The composition obtained by the present invention has liquid crystallinity, and maintains high strength and high modulus in practical use, while maintaining flexibility, elongation, and
It is endowed with bending strength, impact resistance, low-temperature properties, etc., and has improved processability, making it suitable for a wide range of industrial uses such as various molded resins, fibers, films, composite materials, adhesives, and paints. It can be used for.

〔Example〕

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.

Reference Example A Synthesis of liquid crystalline polyester (8-1) 11 autoclave unit equipped with a stirrer and a condenser, 4-1t toxyamne mJM 144. Og(0,
80 mol), 99.6 g (0.60 mol) of terephthalic acid
, 4.4°-diacetoxyisopropylidene diphenyl 187.2 g (0.60 mol) and thorium acetate 0
．． 49, and the inside of the system was replaced with nitrogen by vacuum operation.

Next, the temperature was maintained at 240°C for 20 minutes with stirring, and then the temperature was raised to 260°C, and distillation of acetic acid started. After holding at this temperature for 45 minutes, it was held at 290°C for 45 minutes and at 320°C for 35 minutes to further distill m-acid. The viscosity in the system increased as the reaction progressed. Next, the amount in the system was gradually reduced and held at 15 to 11 g for 15 minutes, and then the temperature was raised to 350°C and 0.5 mH.
(The pressure was reduced to below 1 liter and maintained for 20 minutes to perform a polycondensation reaction.

Then, after introducing dry nitrogen and returning the system to normal pressure, 5 kg
By applying pressure to about /7 and cooling the polymer while extruding it in a molten state from the lower part of the autoclave, residues of hydroxybenzoic acid/residues of terephthalic acid/lt,
A polyester having a molar ratio of 4°-isopropylidene diphenol residues of 40.0/30.0/30.0 was obtained. This product is 1,1,2.2-tetrachloroethane/pentafluorophenol = 50150 (weight ratio)
The intrinsic viscosity measured at 30°C at a concentration of 0.1 g/107 was 0.85. This polymer was observed under a polarizing microscope (L).
Approximately 300
It was confirmed that an optically anisotropic molten phase was formed at around ℃ and exhibited liquid crystallinity.

(A-2) The residues of parahydroxybenzoic acid Terephthalic acid residue/4.4°
- Molar ratio of diphenol residues = 64.0/18.0/
18.0, and a polyester having an intrinsic viscosity of 0.82 and liquid crystallinity was obtained.

(A-3) Same as (A-1) except that 4,4-diacetoxydiphenyl ether was used instead of 4,4°-diacetoxyisopropylidene diphenyl, and 6-acetoxy-2-naphthalenecarboxylic acid was further used. In a similar manner, residues of rose hydroxybenzoic acid/6-hydroxy-2
- Naphthalene dicarboxylic acid residue/terephthalic acid residue J
A polyester having a molar ratio of residues of l/4.4-dihydroxydiphenyl ether = 49.0/3.0/24.0/24.0 and exhibiting liquid crystallinity with an intrinsic viscosity of [0.7B] was obtained.

(A-4) Polyethylene terephthalate 21 with an intrinsic viscosity of 0.68 was placed in an 11-otoclave polymerization machine equipped with a stirrer.
5.4 g (1,12 mol) and p~hydroxybenzoic acid 2
59.49 (1.88 mol) was charged, the temperature was raised to 280° C. in a stream of dry nitrogen, and the acidolysis reaction was allowed to proceed according to the method described in Japanese Patent Publication No. 18016/1983.

Next, the reaction system was gradually weakened and heated to about 0.2 mHg for 5 seconds.
The liquid crystalline polyester was polymerized for 4 hours, and then cooled under a dry nitrogen pressure of 5/cm while extruding the polymer in a molten state from the lower part of the autoclave. The intrinsic viscosity of this product was measured in the same way as (^-1) and was 0.70, and the molar ratio of hydroxybenzoic acid residue/terephthalic acid residue/ethylene glycol residue = 45.6/27
．． It was 2/27.2, indicating liquid crystallinity.

(A-5) Terephthalic acid 0 in the same manner as (A-4)
．． A copolymerized polyester with an intrinsic viscosity of 0.71 composed of residues of 95 mol, inphthal 110.05 mol, ethylene glycol 0.09 mol, and 4,4°-isopropylidene diphenol 0.10 mol, and p-acetoxybenzoin. ! 11.03 moles, moles of p-hydroxybenzoic acid residues/terephthalic acid residues/isophthalic acid residues/ethylene glycol residues/4,4°-isopropylidene diphenol residues with an intrinsic viscosity of 0.74. Ratio = 34.0/31.4
A liquid crystalline polyester consisting of /1.6 /29.7/3.3 was obtained.

(A-6) Instead of p-acetoxybenzoic acid, p-
1.50 mol of acetoxybenzoic acid and 6-acetoxy-
In the same manner as (A-5) except that 15 mol of 2-naphthalenecarboxylic acid MO was used, p-hydroxybenzoic acid residue/6-hydroxy-2-naphthalenecarboxylic acid residue/ Molar ratio of terephthalic acid residue/isophthalic acid residue/ethylene glycol residue/4,4°-isopropylidene diphenol residue = 41.1/4.1/
A liquid crystalline polyester having a ratio of 26.0/1.4/24.7/2.7 was obtained.

Reference example day Synthesis of hydrogenated block copolymer (T1) Hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure was prepared by the method described in JP-A-59-133203. 20% bonded styrene, 1% of the polybutadiene portion before hydrogenation.
2-vinyl bond amount 40%, number average molecule ffl 5300
0, a molecular weight distribution of 1.04, and a hydrogenation rate of 99% in the polybutadiene portion.

(B-2) Similar to (B-1), it has a polystyrene-hydrogenated polybutadiene-polystyrene structure, with a bonded styrene content of 30% and 1 of the polybutadiene moiety before hydrogenation.
2-vinyl bond M33%, number average molecular weight 46,000.

A hydrogenated block copolymer with a molecular weight distribution of 1.03 and a hydrogenation rate of 100% in the polybutadiene portion was synthesized.

(B-3) Similar to (B-1), (polystyrene-
It has the structure of hydrogenated polybutajenna H3i,
Bonded styrene matrix 30%, 1,2-vinyl bond amount in polybutadiene part before hydrogenation 55%, number average molecular weight 9200
0, a molecular weight distribution of 1.42, and a hydrogenation rate of 98% in the polybutadiene portion.

Reference Example C Synthesis of modified hydrogenated block copolymer (C-1)
Per 100 polymerized parts of the hydrogenated block copolymer obtained in (B-1), 1 part by weight of maleic anhydride, 0.1 part by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane
Parts by weight were mixed and an addition modification reaction was carried out in a twin screw extruder with a diameter of 50 #φ and set at 250°C. The obtained modified hydrogenated block copolymer had 4 parts of 0.75t of maleic anhydride added thereto.

(C-2) 0.5 parts by weight of maleic anhydride per 100 parts by weight of the hydrogenated block copolymer obtained in (B-3),
Mix 0.1 part by weight of dicumyl peroxide and 0.2 part by weight of magnesium hydroxide, and mix with a 40 mφ diameter single screw extruder.
Addition modification reaction was carried out under a temperature condition of 40°C.

The modified block copolymer obtained in 1q was one to which 0.15 parts of maleic anhydride was added.

(C-3) 2.0 parts of glycidyl methacrylate per 100 parts by weight of the hydrogenated block copolymer obtained in (B-3).
5 parts by weight of di-t-butyl peroxide and 0.5 parts by weight of di-t-butyl peroxide were mixed, and in a 45 #φ vented twin-screw extruder set at 190°C, forced venting was performed using a vacuum pump (degree of decompression:
The denaturation reaction was carried out under a pressure of 750 mHO gauge pressure). The obtained modified block copolymer had 1.5 parts by weight of glycidyl methacrylate added thereto.

Examples 1 to 6, Comparative Examples 1 to 6 90 parts by weight of various liquid crystalline polyesters obtained in Reference Example A and 10 parts by weight of the hydrogenated product copolymer obtained in Reference Example B-1
ffl! parts were blended at 300°C in a 30Mφ twin-screw extruder (L/D=28) to yield 1q of pelletized composition.

This composition was injection molded at 300°C and various physical properties were measured. The results are shown in Table 1. For comparison, the physical properties of each liquid crystalline polyester alone are shown, but it can be seen that the composition obtained by the present invention has improved impact resistance and elongation, and is imparted with flexibility while maintaining liquid crystallinity. I understand.

(Leaving space below) Examples 7 to 12 95 parts by weight of the liquid crystalline polyester obtained in Reference Example A-1 and 5 parts by weight of various hydrogenated block copolymers obtained by 1q in Reference Examples B and C were combined with Example 1. They were mixed and evaluated in the same manner. The results are shown in Table 2.

Table 2 shows that all of the compositions according to the present invention exhibit good strength, elongation, impact resistance, etc. while maintaining liquid crystallinity, but at the same blending ratio, the modified hydrogenated block copolymer is more flexible. It can be seen that the effect of the addition is large.

(Left below) Examples 13 to 16, Comparative Example 7 Liquid crystalline polyester obtained in Reference Example A-4 and Reference Example 8
The hydrogenated block copolymer obtained in Example 1 was mixed with the hydrogenated block copolymer obtained in Example 1 at various composition ratios and evaluated.

As shown in Table 3, good characteristics are shown within the composition range of the present invention, but in Comparative Example 7, which is outside the composition range of the present invention, although flexibility is imparted, liquid crystallinity may be lost. I understand.

(Margin below)

Claims (1)

[Scope of Claims] 1. (a) 70 to 99 parts by weight of a liquid crystalline polyester composed of repeating units of the following general formulas (I), (II) and (III) and capable of forming an anisotropic melt. (I) ▲ Formula,
There are chemical formulas, tables, etc. ▼ 20 to 80 mol% (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ 40 to 10 mol% (III) -O-R_3-O-40 to 10 mol% [However,
The molar ratio of (II) and (III) is 1, and in the formula, R_1
is a divalent aromatic derivative residue having 6 to 15 carbon atoms, and R_
2 is a divalent aromatic derivative residue having 6 to 15 carbon atoms, 4 carbon atoms
~20 divalent alicyclic derivative residues or 2 with 1 to 20 carbon atoms
R_3 is a divalent aromatic derivative residue having 6 to 15 carbon atoms, a divalent alicyclic derivative residue having 4 to 20 carbon atoms, or a divalent aliphatic derivative having 2 to 20 carbon atoms. It is a group derivative residue. ] (b) Obtained by hydrogenating a block copolymer consisting of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound. and/or a modified hydrogenated block copolymer in which a molecular unit containing a carboxylic acid group or its derivative group is bonded to the hydrogenated block copolymer. Applied liquid crystalline polyester composition.