JP3365104B2 - Tubular molded article, method for producing the same, and molded article formed by molding pellets - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention is an electric and electronic equipment parts BACKGROUND OF THE, automobile parts, tubular shaped body made of excellent liquid crystal polymer and a thermoplastic resin into useful mechanical properties and toughness as machine parts, methods and from its manufacturing Become pellets
The present invention relates to a molded product obtained by molding.

[0002]

2. Description of the Related Art In recent years, demands for higher performance of plastics have been increasing, and many polymers having various new properties have been developed. Among them, an optically anisotropic liquid crystal characterized by parallel arrangement of molecular chains. Resin has attracted attention because it has excellent fluidity and mechanical properties. However,
At present, the applications are limited because the molding shrinkage and mechanical properties are different in the direction perpendicular to the molecular chain orientation direction and the cost is high. On the other hand, it is known that many thermoplastic resins are not necessarily sufficient in mechanical properties and heat resistance as compared with liquid crystal resins.

In order to solve the drawbacks of both, attention has been paid to a blend of a liquid crystalline resin and a thermoplastic resin (for example, JP-A-57-25354). However, the present situation is that even if both are blended, satisfactory physical properties have not been obtained. It is considered that this is because the liquid crystal resin used does not have sufficient physical properties as a reinforcing material.

[0004]

As a method for improving the physical properties of a thermoplastic resin with a liquid crystalline resin, the liquid crystalline resin and the thermoplastic resin are melt-kneaded and stretched and oriented, and the resulting composition is used as a liquid crystal of the liquid crystalline resin. It is known that molding is performed at a temperature below the starting temperature (Japanese Patent Laid-Open Nos. 3-24911 and 5-
70700, JP-A-5-185431, etc.). However, the elongation ratio was not sufficient because the method of stretching the strand or the film cannot stably stretch. Further, there is a problem that it is difficult to cut a film into chips. Further, if the amount of the liquid crystalline resin added is increased to improve the physical properties of the composition, there arise problems that the toughness of the composition is lowered and the price is increased. An object of the present invention is to solve the above problems and obtain a liquid crystalline resin composition having excellent mechanical properties and toughness.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a mixture prepared by melt-kneading a liquid crystalline resin (A) and a liquid crystalline resin (B) having a specific structure is formed into a tube. It was found that the liquid crystalline resin in the composition can be stably highly oriented by stretching and aligning in a uniform shape, and the toughness is further improved, and the present invention has been reached.

That is, in the present invention, (A) 1 to 50% by weight of a liquid crystalline resin forming an anisotropic molten phase and (B) a melt molding process at a temperature lower than the liquid crystal starting temperature of the liquid crystalline resin (A). A mixture of 99 to 50% by weight of one or more thermoplastic resins capable of being produced is extruded into a tube shape, and the liquid crystalline resin (A) has an average aspect ratio of 10 to 10
A tubular molding characterized in that it becomes dispersed particles of 61 and is dispersed in the matrix phase of the thermoplastic resin (B).
It provides the body .

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

The liquid crystalline resin (A) used in the present invention is a resin which forms an anisotropic melt phase, and examples thereof include liquid crystalline polyester and liquid crystalline polyesteramide. The liquid crystalline polyester includes p-hydroxyl. Benzoic acid / polyethylene terephthalate liquid crystal polyester, p-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid liquid crystal polyester, p-hydroxybenzoic acid / 4,4′-
Examples thereof include dihydroxybiphenyl / terephthalic acid / isophthalic acid type liquid crystal polyesters. Among them, the following structural units (I), (II), (IV) or (I), (II), (III), (IV)
Liquid crystal polyesters consisting of are preferred.

[0009]

[Chemical 4] (However, in the formula, R ₁ is

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

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

The above-mentioned structural unit (I) of the liquid crystalline resin (A) preferably used in the present invention is a structural unit of polyester produced from p-hydroxybenzoic acid.
(II) is 4,4'-dihydroxybiphenyl, 3,3 ',
5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone,
Phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-
Structural units formed from aromatic dihydroxy compounds selected from dihydroxydiphenyl ether are
II) is a structural unit formed from ethylene glycol, and structural unit (IV) is terephthalic acid, isophthalic acid, 4,4'-
Diphenylcarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid And structural units formed from an aromatic dicarboxylic acid selected from diphenyl ether dicarboxylic acid. Of these, especially structural units
When (III) is included, R ₁ is

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

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

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

On the other hand, when the structural unit (III) is not contained, the structural unit (I) is [(I) + (II)] from the viewpoint of fluidity.
Is preferably 40 to 90 mol%, and 60 to 88
It is particularly preferable that the amount is mol%, and the structural unit (IV) is substantially equimolar to the structural unit (II).

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

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

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

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

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

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

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

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

Liquid crystalline resin (B-1) used in the present invention
Is capable of measuring logarithmic viscosity in pentafluorophenol, and in that case, the value measured at 60 ° C. at a concentration of 0.1 g / dl is preferably 0.5 or more, 1 It is more preferably from 0.0 to 3.0 dl / g.

The melt viscosity is preferably 10 to 20,000 poise, and more preferably 20 to 10,000 poise. The melt viscosity is 1 m in diameter under the condition of melting point (Tm) + 10 ° C and shear rate of 1,000 / sec.
It is a value measured by a high-pressure capillary viscometer using a capillary with m and a length l ≧ 5 mm. Here, the melting point (Tm) is the difference between room temperature and 2
After observing the endothermic peak temperature (Tm1) observed when measured under a temperature rising condition of 0 ° C./min, the temperature was 5 at a temperature of Tm1 + 20 ° C.
After being held for a minute, the temperature is once cooled to room temperature under a temperature lowering condition of 20 ° C./min, and then the endothermic peak temperature (Tm2) observed when measured again under a temperature rising condition of 20 ° C./min. The liquid crystal starting temperature (TN) is the temperature at which opalescence is emitted under shear stress by heating the sample on a sample stage of a polarizing microscope.

The thermoplastic resin (B) used in the present invention is a non-liquid crystalline thermoplastic resin, and preferred specific examples thereof include polyesters, polyamides, polyarylene sulfides, polyoxymethylenes and polyolefin polymers.
Examples thereof include crystalline resins such as polystyrene, and amorphous resins such as polycarbonate, polyarylate, polyarylene oxide, and polyetherimide. Among these, polyester, polyarylene sulfide, polypropylene, polyethylene and polycarbonate are preferable, and polyester is most preferable. Further, two or more kinds of this thermoplastic resin may be used. The temperature at which the thermoplastic resin (B) can be processed (melting point in the case of a crystalline resin) needs to be lower than the liquid crystal starting temperature of the liquid crystalline resin (A) to be used, but may be 10 ° C. or more lower. It is more preferable that the temperature is 20 to 250 ° C. or more,
Most preferably, it is 30 to 200 ° C. or lower.

The polyester is a polyester having an aromatic ring as a chain unit of the polymer, and is a condensation reaction containing an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative) as main components. It is a polymer or copolymer obtained by. As the dicarboxylic acid here, terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl)
Examples thereof include methane, anthracene dicarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-diphenylethercarboxylic acid, 1,2-bis (p-carboxyphenoxy) ethane, and ester-forming derivatives thereof. In addition, if it is 30 mol% or less, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, and dimer acid, alicyclic rings such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid It may be substituted with a group carboxylic acid. The diol component is an aliphatic diol having 2 to 10 carbon atoms, that is, ethylene glycol, propylene glycol, butylene glycol, 1,5-pentane glycol, decamethylene glycol, 3-methyl-1,3-propene diol, neopentyl. Examples include, but are not limited to, glycol, cyclohexanedimethanol, cyclohexanediol, and the like. Specific examples of preferred polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene-2,6-naphthalate, poly-1,
4-Cyclohexane dimethylene terephthalate etc. and polyethylene terephthalate / isophthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / sebacate, polybutylene terephthalate / decane dicarboxylate, poly-1,4-cyclohexane dimethylene terephthalate / isophthalate etc. The copolymerized polyester of Among these, preferred polyesters include polybutylene terephthalate, polyethylene terephthalate, and poly-
1,4-cyclohexane dimethylene terephthalate is mentioned. Furthermore, polybutylene terephthalate is more preferable. The logarithmic viscosity of polybutylene terephthalate is preferably 0.9 to 1.3, more preferably 0.92 to 1.25. The logarithmic viscosity of polybutylene terephthalate was obtained by dividing the logarithm of the relative viscosity obtained by using a 0.5% orthochlorophenol solution at 25 ° C. by the concentration.

As the polyamide, polyamide obtained from ω-amino acid or ω-lactam, or dicarboxylic acid such as diamine or m-xylenediamine and adipic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid or isophthalic acid is used. And homopolymers or copolymers obtained from the above, mixed polymers and the like. Preferred polyamides are homopolyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, and adipic acid / terephthalic acid / hexamethylenediamine, adipic acid / 1,4-cyclohexanedicarboxylic acid / hexamethylenediamine, adipine. Examples thereof include copolyamides such as acid / 1,3-cyclohexanedicarboxylic acid / hexamethylenediamine, terephthalic acid / isophthalic acid / hexamethylenediamine / paraaminocyclohexylmethane.

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

Examples of polyoxymethylene include polyoxymethylene homopolymers and copolymers whose main chain is composed mainly of oxymethylene chains.

Examples of the polyolefin polymer include homopolymers or copolymers containing a repeating unit formed from α-olefins such as ethylene and propylene as a main component. For example, a homopolymer of propylene, a homopolymer of ethylene, and further A block or random copolymer obtained by copolymerizing ethylene with another α-olefin (for example, propylene and butene-1), specifically, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms (for example, ethylene / propylene copolymer). Polymer, ethylene / butene-
1 copolymer), a copolymer composed of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene (for example, an ethylene / propylene / 1,4-hexadiene copolymer,
Ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / ethylidene norbornene copolymer, etc.), and these may be used alone or in combination of two or more. Preferred polyolefin-based polymers are polypropylene homopolymer, polyethylene homopolymer, copolymers of ethylene having an ethylene content of 50 mol% or more and α-olefins having 3 or more carbon atoms (for example, ethylene / propylene copolymer, ethylene / butene-polymer). 1
Copolymer, etc.), a propylene / ethylene copolymer having an ethylene content of 30 mol% or less, an elastomeric copolymer composed of 50 wt% or less of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and polypropylene homo. Composition comprising a polymer, composition comprising an elastomeric copolymer comprising 50% by weight or less of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and polyethylene homopolymer and propylene having a propylene content of 30 mol% or less / Ethylene copolymer is mentioned.

Further, it is more preferable that the polyolefin copolymer is modified with an unsaturated carboxylic acid or its derivative. As the unsaturated carboxylic acid to be modified, acrylic acid, methacrylic acid, crotonic acid,
Maleic acid, fumaric acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid, tetrahydrophthalic acid, dimer acid and the like can be mentioned. Examples of the derivative include anhydrides, esters, amides, imides and salts of the above acids.

As polystyrene, in addition to polystyrene homopolymer, HIPS (high impact polystyrene), A
S (acrylonitrile / styrene copolymer), ABS
(Acrylonitrile / butadiene / styrene copolymer), MBS (methyl methacrylate / butadiene / styrene copolymer) and the like.

Examples of polycarbonate or polyarylate include bis (4-hydroxyphenyl), bis (3,
5-dialkyl-4-hydroxyphenyl) or hydrocarbon derivatives having bis (3,5-dihalo-4-hydroxyphenyl) substitution are preferred.
Polycarbonates or polyarylates based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) are particularly preferred. Moreover, these may contain a small amount of copolymerization components.

As the polyarylene oxide, poly (2,6-dimethyl-1,4-phenylene) ether,
2,6-dimethylphenol / 2,4,6-trimethylphenol copolymer, 2,6-dimethylphenol /
2,3,6-triethylphenol copolymer and the like can be mentioned. These can be used by modifying with unsaturated carboxylic acid or its derivative by graft reaction. The unsaturated carboxylic acid to be modified is acrylic acid, methacrylic acid,
Crotonic acid, maleic acid, fumaric acid, itaconic acid, 5
-Norbornene-2,3-dicarboxylic acid, tetrahydrophthalic acid, dimer acid and the like. Examples of the derivative include anhydrides, esters, amides, imides and salts of the above acids.

The polyether imide is represented by the following formula (V)
And those represented by the following formula (VI) are preferably used.

[0034]

[Chemical 9] (However, R ₃ and R ₄ are divalent organic groups having at least one aromatic ring)

[Chemical 10] Two or more kinds of thermoplastic resins (B) may be used in combination,
Specific examples include a combination of styrene resin such as ABS and polyester, polyamide or polycarbonate, a combination of styrene resin such as polyarylene oxide and polystyrene, high impact polystyrene, polyester or polyamide, and the like.

The composition of the liquid crystalline resin (A) and the thermoplastic resin (B) is 99 to 50% by weight with respect to 1 to 50% by weight of (A), but 5 to 40% by weight of (A). Against (B) 95
It is preferably ˜60 wt%, and most preferably (B) 95-65 wt%, relative to (A) 5-35 wt%. If the addition amount of the liquid crystalline resin (A) exceeds 50%, the fluidity is extremely lowered and the moldability becomes extremely poor. On the contrary, if it is less than 1%, the effect of improving the physical properties is very small, which is not preferable.

The epoxy compound (C) used in the present invention is a compound having one or more epoxy groups and is not necessarily limited. It is rather more preferable number of epoxy groups of the epoxy compound is two or more, and most preferably two. Specific examples of this epoxy compound include the following compounds. Bisphenol A diglycidyl ether, orthophenylphenol glycidyl ether, glycidyl ethers synthesized from phenols and epichlorohydrin. Glycidyl ester ethers composed of epicarboxylic acid and hydroxycarboxylic acid such as p-hydroxybenzoic acid glycidyl ester ether. Diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, glycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, glycidyl methacrylate, diglycidyl dimer obtained by dimerizing dimer acid synthesized from stearic acid, 6-ethyl-1, Glycidyl esters such as 11-dodecanedicarboxylic acid diglycidyl. Epoxidized imide compounds such as N-glycidyl phthalimide. An epoxy group-containing copolymer comprising an unsaturated monomer having an epoxy group such as epoxidized polybutadiene and glycidyl methacrylate, and another unsaturated monomer such as ethylene. Epoxysilanes usually used as silane coupling agents such as γ-glycidoxypropyltrimethoxysilane. These epoxy compounds may be used alone or in combination of two or more.

Of the above epoxy compounds, glycidyl ester ethers and glycidyl esters are most preferable. Further, among these classes, epoxy compounds having no aromatic ring in the main chain are preferable. Specifically, it is diglycidyl dimer, 6-ethyl-1,11-dodecanedicarboxylic acid diglycidyl, or the like. The epoxy equivalent of the epoxy compound used is preferably 100 or more, more preferably 200 or more.

When the epoxy compound (C) is blended, the blending amount is 0.01 to 20 parts by weight based on 100 parts by weight of the blend of the liquid crystalline resin (A) and the thermoplastic resin (B). However, it is preferably in the range of 0.1 to 10 parts by weight.

As a method for mixing the liquid crystal resin (A) and the thermoplastic resin (B), various methods can be applied.
Examples of the apparatus for melt-mixing include a mixing roll, a Banbury mixer, a kneader, an extruder, and the like. Among them, an extruder is preferable. As this extruder, either a single-screw extruder or a twin-screw extruder can be used, but it is particularly preferable to use a twin-screw extruder. The kneading temperature is preferably not lower than the liquid crystal starting temperature of the liquid crystalline resin (A) and not lower than the melting point of the thermoplastic resin (B), and more preferably not lower than the melting point of the liquid crystalline resin (A).

The tubular extrusion molding used in the present invention is not particularly limited, and a conventionally known method can be used. For example, a tube die is installed in the embossing machine to form a cylindrical shape, which is subsequently formed and cooled to a predetermined size and a circular shape by a homing device, and this is elongated by a take-up machine or a strand cutter. The outer diameter of the discharge port of the tube die used is preferably 20 mm or less, more preferably 15 mm or less, from the viewpoint of uniformly aligning the liquid crystalline resin. The ratio of the outer diameter to the inner diameter of the discharge port of the tube die used is preferably 3 or less, more preferably 2 or less, and 1.5 or less in order to stably and highly extend the extruded tube. Is more preferable. The molten tube extruded from the die is
In order to maintain the circular shape and size, the homing portion can be processed by an internal pressure method, a vacuum homing method, or the like. When the ratio of the cross-sectional area of the stretched tube to the cross-sectional area of the extruded tube is defined as the stretch ratio, this ratio is preferably 8 or more, and more preferably in order to sufficiently align the liquid crystalline resin. It is 10 or more, more preferably 12 or more. The pellet (chip) obtained by shredding the tube thus extended is a hollow chip, and the hollow ratio of this chip is preferably 20 to 98%, and preferably 25 to 95%. Is more preferred and 3
Most preferably, it is 0 to 92%.

The tubular extrusion-obtained tubular shaped body can be pelleted by shredding a cutter after wound as such a cutter or winder. A normal pelletizing cutter can be preferably used for this shredding. Generally, in a thin gut, the orientation distribution of the liquid crystalline resin becomes more uniform, and therefore it is considered that a smaller thickness is preferable. However, in the case of a fiber-like form, it becomes extremely thin, so that it has a defect that the gut is not sufficiently caught during injection molding. A tubular molded body having a hollow shape does not have such a problem and is considered to have an optimum shape.

When a molded product is obtained from the tubular molding of the present invention, usual methods such as injection molding, extrusion molding, blow molding and press molding can be applied, but injection molding is particularly preferable. The molding temperature is preferably a temperature at which the thermoplastic resin (B) can be melt-molded and is lower than the liquid crystal starting temperature (TN) of the liquid crystalline resin (A). More preferably (TN −5) ° C. or lower, and even more preferably (TN
-10) below ℃. When molded in this temperature range, the dispersed state after stretching is preferably maintained, the dispersed state hardly changes inside the molded product and the surface layer portion, and a large effect of improving the physical properties is exhibited. Then, if the molding is performed at TN or more, the fibrous orientation of the liquid crystalline resin tends to be relaxed. The liquid crystal onset temperature (TN) is a temperature at which opalescence is emitted under shear stress by placing the sample on a sample stage of a polarization microscope and heating it. In the preferred liquid crystalline resin of the present invention, the melting point is higher than the melting point. Two
The temperature is often as low as 0 ° C.

In the present invention, the dispersion state of the liquid crystalline resin in the tubular molded body or molded piece can be observed by a scanning electron microscope. For example, a method in which a stretched gut or a molded piece is cut in parallel with the stretched direction of the resin and observed with a scanning electron microscope, or a liquid crystal resin used is not soluble but a thermoplastic resin used is a solvent that is soluble. The ratio of the major axis (L) to the minor axis (D) of the particles of the liquid crystalline resin (A) that are fibrous aligned by the method of observing the dispersed particles of the liquid crystalline resin that have been dissolved in
D), that is, the aspect ratio can be obtained. The average aspect ratio of the liquid crystalline dispersed particles in the blend observed by this method needs to be 10 or more in terms of weight average aspect ratio, more preferably 20 or more, and further preferably 30 or more. If this value is less than 10, a large effect of improving physical properties is not observed. The aspect ratio in the molded product is preferably 10 or more,
It is more preferably 20 or more. When molded at the preferred temperature of the present invention, the aspect ratio of the liquid crystalline resin in the tubular molded body and the aspect ratio of the molded product become substantially equal, and a molded product with excellent physical properties can be obtained. However,
When molded at a temperature higher than the preferred molding temperature of the present invention, the aspect ratio of the liquid crystalline resin tends to be small.

In producing the tubular molded article of the present invention, a conventionally known polyester polymerization catalyst,
Additives such as heat-resistant agents, weather-resistant agents, antistatic agents, dyes, colorants, crystal nucleating agents, flame retardants, talc, clay, mica, calcium metasilicate, silica sand, glass beads, glass flakes, graphite, titanic acid It is also possible to add inorganic fillers such as potassium whisker, aluminum borate fibers, and gypsum fibers, reinforcing agents such as glass fibers, asbestos fibers, carbon fibers, etc. as compatibilizers.

The tubular shape of the present invention thus obtainedMolded body
Has excellent mechanical properties and toughness, and is a three-dimensional molded product,
It can be processed into sheets, container pipes, etc.,
For example, various gears, various cases, sensors, LED lights
Pump, connector, socket, resistor, relay case,
Switch, coil bobbin, condenser, variable condenser
Devices, optical pickups, oscillators, various terminal boards, transformers,
Rug, printed wiring board, tuner, speaker, my
Crophons, headphones, small motors, magnetic heads
Base, power module, housing, semiconductor, liquid crystal
Display parts, FDD carriage, FDD shear
HDD, HDD parts, motor brush holder, parabola
Represented by antennas and computer-related parts
Electric / electronic parts; VTR parts, TV parts, irons,
Hair dryer, rice cooker parts, microwave oven parts, sound
Parts, audio / laser disk / compact disc
Audio equipment parts such as disk, lighting parts, refrigerator parts, air
Computer parts, typewriter parts, word processor
Household products represented by products, office electrical product parts, office
Computer related parts, telephone related parts, fax
Re-related parts, copier-related parts, cleaning jigs, oilless
Various bearings such as bearings, stern bearings, underwater bearings, motors
Machines represented by parts, lighters, typewriters, etc.
Represented by related parts, microscopes, binoculars, cameras, watches, etc.
Optical equipment, precision machinery related parts; alternator
Minal, alternator connector, IC regulator
ー 、 Light deer potentiometer base, exhaust
Various valves such as gas valves, fuel-related, exhaust system, intake
Various pipes, air intake nozzle snorkel, a
Intake manifold, fuel pump, engine coolant
Joint, carburetor main body, carburetor
Spacer, exhaust gas sensor, cooling water sensor, oil temperature
Sensor, brake pad wear sensor, slot
Position sensor, crankshaft position sensor
Sensor, air flow meter, brake butt wear sensor
Sensor, air conditioner thermostat base, heating hot air blower
Low control valve, bra for radiator motor
Fish holder, water pump impeller, turbi
Parts, wiper motor-related parts, dust review
Starter, Starter Switch, Starter Relay, Tran
Wire harness for transmission, window washer
ー Nozzle, air conditioner panel switch substrate, fuel related electromagnetic
Air valve coil, fuse connector, horn terminator
Insulation board for electrical components, step motor rotor, run
Socket, lamp reflector, lamp housing,
Brake piston, solenoid bobbin, engine oil
Automobile / vehicle related parts such as filters and ignition device cases
It is useful for products and various other purposes.

[0046]

EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples do not limit the scope of application of the present invention. In the examples, parts represent parts by weight, and PBT represents polybutylene terephthalate.

Reference Example 1 907 parts by weight of p-hydroxybenzoic acid, 168 parts by weight of 4,4'-dihydroxybiphenyl, 914 parts by weight of acetic anhydride, 150 parts by weight of terephthalic acid and an intrinsic viscosity of about 0.
295 parts by weight of 6 dl / g polyethylene terephthalate was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and deacetic acid polycondensation was carried out under the following reaction conditions.

After reacting in a nitrogen gas atmosphere at 100 to 250 ° C. for 1.5 hours, 290 ° C. and 0.5 m in 2 hours
When the pressure was reduced to mHg and the reaction was further continued for 1.0 hour to complete the polycondensation, almost the theoretical amount of acetic acid was distilled off, and a liquid crystal polyester (A) having the following theoretical structural formula was obtained.

[0049]

[Chemical 11] k / l / m / n = 77.5 / 7.5 / 15 / 22.5 The obtained polyester had a liquid crystal starting temperature of 275 ° C. and a melting point of 295 ° C.

Examples 1 to 5 and Comparative Examples 1 to 4 Liquid crystal resin (A) polymerized in Reference Example 1 and polybutylene terephthalate (PBT, intrinsic viscosity 1.20 dl / g) were weighed in predetermined amounts and dried. Blended. The mixture was put into a 30 mmφ extruder equipped with an internal pressure tube molding die (resin temperature 295 ° C.). The extruded tube was cooled in water through a sizing plate and then stretched by a take-up machine. The ratio of the cross-sectional area of the expanded tube to the cross-sectional area of the tube immediately after extrusion was calculated as the expansion ratio.

This tube was cut with a strand cutter, dried with hot air, the mold temperature was set to 80 ° C., and at the molding temperature (resin temperature) shown in Table 1, 1/8 "thickness x 1/2" width x 5 "long test piece and 1/8" thick ASTM
No. 1 dumbbell was molded. The flexural modulus was measured using a test piece of 1/8 "thickness x 1/2" width x 5 "length using a Toyo Baldwin Tensilon UTM-200 under the conditions of a strain rate of 1 mm / min and a span distance of 50 mm. In addition, according to ASTM D638, ASTM
No. The tensile strength of one dumbbell was measured. Table 1 shows the results of these tests.

Further, the stretched gut and a part of the injection molded test piece were dissolved in orthochlorophenol, and the remaining undissolved dispersed phase of the liquid crystalline resin (A) was observed by a scanning electron microscope to disperse the liquid crystalline resin. The aspect ratio of the particles was determined. Table 1 shows the elongation ratio and the aspect ratio.

As Comparative Example 1, a case where a die for discharging four strands having a radius of 2.5 mm was installed in place of the tube die was examined, but in order to stably stretch the strand, the stretching ratio was set to about 5. Only a tube having an aspect ratio of 4 could be obtained. Further, as Comparative Example 4, a tube having an outer diameter / inner diameter ratio of 4 was examined, but in this case, only a tube having an aspect ratio of 4 could be obtained because it could be stretched to the same extent as a strand die.

[0054]

[Table 1]

From the results shown in Table 1 above, it can be seen that the aspect ratio of the liquid crystalline resin (A) is 20 or more and the bending elastic modulus is greatly improved when the material is expanded into a tubular shape by 8 times or more. Further, it can be seen that the elongation at break becomes large and the toughness is improved.

Examples 6 to 10, Comparative Examples 5 to 8 Liquid crystalline resin (A) polymerized in Reference Example 1, polybutylene terephthalate (PBT, intrinsic viscosity 1.20 dl / g) and diglycidyl dimer acid (oiled shell epoxy) A predetermined amount of Epicoat EP-871 (C) manufactured by Co., Ltd. was weighed and dry-blended. Tube extrusion molding was performed in the same manner as in Examples 1 to 5.

This tube was cut with a strand cutter, dried with hot air, the mold temperature was set to 80 ° C., injection molding was carried out at the set temperature shown in Table 2 in the same manner as in Examples 1 to 5, and the mechanical properties were measured. . Further, the aspect ratio of the liquid crystalline resin dispersed particles was determined in the same manner as in Examples 1 to 5 using the stretched gut and the molding test piece. The results are shown in Table 2.

[0058]

[Table 2]

From the results shown in Table 2 above, it is understood that when the resin is stretched into a tubular shape by 8 times or more, the aspect ratio of the liquid crystalline resin (A) becomes 30 or more, and the flexural modulus is greatly improved. It is also found that when an epoxy compound is added and elongation is performed using a tube die, the elongation at break becomes larger than that of the strand die and the toughness is improved.

[0060]

INDUSTRIAL APPLICABILITY In the tubular molded article and pellets according to the present invention, the liquid crystalline resin in the blend is highly oriented and dispersed, and the molded article obtained from it has excellent mechanical properties and toughness. , Electrical and electronic parts,
It can be widely used in applications such as automobile parts.

Continuation of front page (51) Int.Cl. ⁷ identification code FI C08L 67/04 C08L 67/04 (56) Reference JP-A-5-186668 (JP, A) JP-A-5-200823 (JP, A) JP-A 5-112709 (JP, A) JP-A 5-70700 (JP, A) JP-A 1-259062 (JP, A) JP-A 3-95261 (JP, A) JP-A 62-288650 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08J 5/00 B29C 47/00 C08G 59/40 C08G 63/60

Claims (8)

(57) [Claims] 1. Melt molding can be performed at a temperature of (A) 1 to 50% by weight of a liquid crystalline resin forming an anisotropic molten phase and (B) a temperature lower than the liquid crystal starting temperature of the liquid crystalline resin (A). The thermoplastic resin is a liquid crystalline resin (A), which is obtained by extrusion-molding a mixture of 99 to 50 wt% of one or more thermoplastic resins into dispersed particles having an average aspect ratio of 10 to 61. A tubular shaped article, which is dispersed in the matrix phase of (B). 2. The tubular product according to claim 1, which is obtained by extrusion molding into a tubular product at an elongation ratio of 8 or more.
Molded body . 3. The tubular shaped article according to claim 1, which is extruded using a tube extrusion die having an outer diameter to inner diameter ratio of 3 or less. 4. A liquid crystalline resin (A) which forms an anisotropic molten phase.
Are the following structural units (I), (II), (IV) or (I), (II), (II
The tubular shaped article according to claim 1, which is a liquid crystalline polyester resin comprising I) and (IV). [Chemical 1] (However, R ₁ in the formula is R ₁ represents one or more groups selected from Represents one or more groups selected from Further, in the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)]
And structural unit (IV) are substantially equimolar. ) 5. Melt molding can be performed at (A) 1 to 50% by weight of a liquid crystalline resin forming an anisotropic molten phase and (B) at a temperature lower than the liquid crystal starting temperature of the liquid crystalline resin (A). Formulation 1 consisting of 99-50% by weight of one or more thermoplastic resins
(C) Epoxy compound 0.01-2 with respect to 00 parts by weight
The tube-shaped molded product according to any one of claims 1 to 4, characterized in that a composition further containing 0 part by weight is used. 6. The tubular shape according to claim 1.
Molded article obtained by molding the ing from molded pellets by the following LC transition temperature of the liquid crystal resin (A). 7. A liquid crystal resin (A) as dispersed particles having an average aspect ratio of 10 to 52 in a molded product, which is dispersed in the matrix phase of the thermoplastic resin (B). Item 7. A molded article according to item 6. 8. (A) A liquid crystalline resin which forms an anisotropic molten phase
1 to 50% by weight and (B) liquid crystal initiation of the liquid crystalline resin (A)
One that can be melt-formed at a temperature lower than the temperature
Compounds consisting of 99-50% by weight of the above thermoplastic resins
Is extruded into a tube with an extension ratio of 8 or more.
Therefore, the liquid crystal resin (A) has an average aspect ratio of 10 to 61.
Matrix particles of thermoplastic resin (B)
To produce a tubular molding that is dispersed in
Characteristic manufacturing method.