JPH11116664A - Liquid crystalline resin and thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystalline resin with such advantages as high mechanical strength, abrasion resistance and long-term heat resistance when added to a thermoplastic resin without impairing the characteristics inherent in the thermoplastic resin, by including p-hydroxybenzoic acid residue as the essential component. SOLUTION: This liquid crystalline resin contains p-hydroxybenzoic acid residue as the essential component and has >=140 deg.C but <200 deg.C melting point. Among these liquid crystalline resins, a liquid crystalline polyester resin is obtained, for example, by deacetylating polycondensation reaction of an aromatic dihydroxy compound's diacylated product such as p-acetoxybenzoic acid, 4,4'- diacetoxybiphenyl, or diacetoxybenzene with an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid or isophthalic acid. When this liquid crystalline resin is to be compounded in a thermoplastic resin, the amount of the liquid crystalline resin is pref. 0.01-15 pts.wt. based on 100 pts.wt. of the thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystalline resin having a low melting point and exhibiting liquid crystallinity at a low temperature, has good dispersibility in a thermoplastic resin, and has been modified by the liquid crystalline resin. The present invention relates to a resin composition, a molded product, a film, and a fiber.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, a polymer is characterized by a parallel arrangement of molecular chains. Optically anisotropic liquid crystalline polymers have attracted attention because of their excellent fluidity and mechanical properties, and especially small molded products in the fields of electric / electronics and office equipment due to their high rigidity and moderate wear resistance. Demand is growing. An example of an LCP having a low melting point is a copolymer of P-hydroxybenzoic acid and polyethylene terephthalate. Numerous alloys with thermoplastic resins have been studied, such as POLYMER ENGINEERING AN
D SCIENCE, 1991, Vol.31, No.6 and Journal of applied Pol
ymer Science, Vol.62, (1996).

[0003]

However, even in the case of the copolymer of P-hydroxybenzoic acid and polyethylene terephthalate, which are LCPs having a low melting point, the melting point of the copolymer is 2%.
If the copolymerization amount of polyethylene terephthalate is increased to lower the melting point without lowering the temperature to less than 00 ° C., it seems to be due to a block reaction, but foreign substances are generated, and a homogeneous polymer cannot be obtained. In addition, the melting point of the liquid crystal polyester used in the above document is as high as 280 ° C. or higher, and the processing temperature must be 280 ° C. or higher in order to disperse the liquid crystal polymer to some extent. It was found that there were problems such as deterioration of physical properties. In addition, it was found that the dispersed particle size in the thermoplastic resin was large, and it was liable to be a foreign material, and the impact strength of a molded product was reduced, and the film was frequently broken or the yarn was broken.
Therefore, the present invention solves the above-mentioned problems, can be processed at the processing temperature of the conventional thermoplastic resin, and without impairing the conventional properties of the thermoplastic resin, newly has high strength, abrasion resistance, and long-term heat resistance. It is an object of the present invention to obtain a liquid crystalline resin which adds properties to a thermoplastic resin.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention comprises (1) a p-hydroxybenzoic acid residue as an essential component and a melting point of 140 ° C.
A liquid crystalline resin having a temperature of not less than 200 ° C., (2) a liquid crystalline resin according to the above (1) containing a dioxybiphenyl unit,
(3) The liquid crystalline resin is a liquid crystalline polyester having the following structural units (I), (III) and (IV), or (I), (I)
I), (III), a liquid crystalline polyester having a structural unit of (IV),

Embedded image (However, R1 in the formula is

Embedded image R2 represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) And at least as structural unit (III) —OCH ₂ CH ₂ O— and / or as structural unit (IV)

Embedded image (4) The liquid crystalline resin according to the above (1) or (2), comprising (4) structural units (I), (II), (III) and (IV), unit
The sum of (I) and (II) is 35 of the sum of (I), (II) and (III).
~ 90 mol%, structural units (III) are (I), (II) and (III)
And the molar ratio of the structural unit (I) / (II) is 70/30 to 90/10, and the structural unit (IV)
Is a liquid crystalline resin according to the above (3), which is substantially equimolar to the sum of the structural units (II) and (III), and (5) R of the structural unit (IV)
2. The liquid crystalline resin according to any one of the above (1) to (4), wherein R2 comprises at least one member selected from the following structures R3:

Embedded image (6) The liquid crystalline resin according to the above (5), wherein the ratio of R3 is 1 to 90 mol% based on 100 mol% of the total of all dicarboxylic acid components constituting the liquid crystalline resin, (7) the above (1) to (1).
The liquid crystalline resin according to any one of (6) and
A thermoplastic resin composition blended in an amount of 0.01 to 15 parts by weight with respect to 0 parts by weight.

(8) The thermoplastic resin composition according to (7), further comprising 0.01 to 30 parts by weight of red phosphorus based on 100 parts by weight of the total of the liquid crystalline resin and the thermoplastic resin. ) 100 total of liquid crystalline resin and thermoplastic resin
The thermoplastic resin composition according to the above (7) or (8), further comprising 5 to 300 parts by weight of an inorganic filler based on parts by weight, (10) any of the above (7) to (9) A molded article composed of the thermoplastic resin composition of (1), and (1)
1) An object of the present invention is to provide an additive for a thermoplastic resin comprising the liquid crystalline resin according to any one of the above (1) to (6).

[0007]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The liquid crystalline resin of the present invention is a resin capable of forming an anisotropic molten phase, for example, an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an aliphatic dicarbonyl unit, an ethylenedicarbonyl unit. Liquid crystalline polyester forming an anisotropic molten phase consisting of structural units selected from oxy units, or a structure selected from the above structural units and aromatic iminocarbonyl units, aromatic diimino units, aromatic iminooxy units, etc. A liquid crystalline polyesteramide or the like that forms an anisotropic molten phase composed of units and has a melting point of 140 ° C. or more and less than 200 ° C.

The aromatic oxycarbonyl unit is, for example, a structural unit formed from p-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid, and the aromatic dioxy unit is, for example, 4,4'-dihydroxy Biphenyl, hydroquinone, 3,3 ', 5,5'-
Tetramethyl-4,4'-dihydroxybiphenyl, t
-Butylhydroquinone, phenylhydroquinone,
Examples of the structural unit or aromatic dicarbonyl unit formed from 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl ether, etc. , Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2- Chlorophenoxy) ethane-4,4'-dicarboxylic acid or a structural unit formed from 4,4'-diphenyl ether dicarboxylic acid, and aliphatic dicarbonyl units include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane Structural units purified from diacid or dodecanedioic acid, etc. The Nookishi unit, for example, a structural unit derived from such as 4-aminophenol.

Specific examples of the liquid crystalline polyester include p
Liquid crystalline polyester comprising a structural unit formed from -hydroxybenzoic acid, a structural unit formed from 6-hydroxy-2-naphthoic acid, a structural unit formed from an aromatic dihydroxy compound and a structural unit formed from an aliphatic dicarboxylic acid, p A structural unit generated from -hydroxybenzoic acid, a structural unit generated from 4,4'-dihydroxybiphenyl, a liquid crystalline polyester including a structural unit generated from terephthalic acid and adipic acid, a structural unit generated from p-hydroxybenzoic acid, A liquid crystalline polyester comprising a structural unit formed from ethylene glycol, a structural unit formed from terephthalic acid and isophthalic acid, p-
Structural units generated from hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from 4,4'-dihydroxybiphenyl, sebacic acid or liquid crystalline polyester composed of structural units generated from sebacic acid and terephthalic acid, Structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, aromatic dicarboxylic acids selected from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like And liquid crystalline polyesters comprising a structural unit generated from an acid.

Examples of preferred liquid crystalline polyesters that form an anisotropic molten phase include (I), (II), (III),
(IV) or a structural unit of (I), (III), (IV),

Embedded image (However, R1 in the formula is

Embedded image R1 represents one or more groups selected from

Embedded image And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) And at least as structural unit (III) —OCH ₂ CH ₂ O— and / or as structural unit (IV)

Embedded image And a liquid crystalline polyester having the following formula:

The total of the structural units (II) and (III) and the structural unit (IV) are preferably substantially equimolar.

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, the structural unit (II) is a structural unit formed from 4,4′-dihydroxybiphenyl, and the structural unit (III) is ethylene glycol. , 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,
A structural unit formed from one or more dihydroxy compounds selected from 4′-dihydroxydiphenyl ether,
The structural unit (IV) is terephthalic acid, isophthalic acid,
4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,
4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4 '
The structural units generated from one or more dicarboxylic acids selected from diphenyl ether dicarboxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, and dodecandioic acid are shown.

Examples of the liquid crystalline polyesteramide include those obtained by further copolymerizing the above structural unit with a structural unit formed from p-aminobenzoic acid or a structural unit formed from 4-aminophenol.

The structural units (I), (III) and (I)
V) or a copolymer comprising (I), (II), (III) and (IV), wherein the structural units (I), (II),
The copolymerization amount of (III) and (IV) is optional. But,
From the viewpoint of lowering the melting point, the following copolymerization amount is preferred.

The copolymer has at least a structural unit (III)
As —OCH ₂ CH ₂ O— and / or the structural unit (IV)
As

Embedded image Wherein, of all the structural units, these structural units are
Structural units (I), (III), (IV) or structural units (I), (I
Usually, 10 mol% to 5 mol based on the sum of (I), (III) and (IV)
0 mol%, preferably 12 mol% to 45 mol%, more preferably 13 mol% to 40 mol%.

Furthermore, when the above-mentioned structural unit (II) is contained, the total of the above-mentioned structural units (I) and (II) is the sum of the structural units (I) and (II) from the viewpoint of having a low melting point and exhibiting liquid crystallinity.
And 35 to 90 mol%, more preferably 40 to 88 mol%, based on the total of (III) and (III). Also, structural units
(III) is preferably 65 to 10 mol%, more preferably 60 to 12 mol%, based on the total of the structural units (I), (II) and (III).
Is more preferred. The molar ratio [(I) / (II)] of the structural units (I) and (II) is preferably 70/30 to 90/10, more preferably 75/90, from the viewpoint of homogeneity of the obtained polymer. 25 to 88/12. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III). In order to further exhibit a low melting point and exhibit liquid crystallinity, R2 of the structural unit (IV) has the following structure R3, and from the viewpoint of a low melting point and liquid crystallinity, the total of 100 dicarboxylic acid components constituting the liquid crystalline resin is: R3 below
Is preferably 1 to 90 mol%, more preferably 3 to 88 mol%, and still more preferably 5 to 85 mol%.

R3:

Embedded image On the other hand, when the structural unit (II) is not contained, the structural unit (I) is 20 to 80 mol% based on the total of the structural units (I) and (III) from the viewpoint of lowering the melting point and fluidity.
Is preferably 25 to 75 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

In the polycondensation of the liquid crystalline polyester which can be preferably used in the present invention, in addition to the components constituting the above structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid, 2,2 Aromatic dicarboxylic acids such as' -diphenyldicarboxylic acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, undecandioic acid, aliphatic dicarboxylic acids other than dodecandioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4,4′-dihydroxydiphenylsulfone, Aromatic diols such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4 -Liquid crystallinity of aliphatic, alicyclic diols such as cyclohexane dimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid and p-aminophenol and p-aminobenzoic acid. A small percentage that does not impair In can be allowed to further copolymerization.

The method for producing the liquid crystalline resin used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystal polyester, the following production method is preferably mentioned.

(1) p-acetoxybenzoic acid and 4,
Diacylated aromatic dihydroxy compounds such as 4'-diacetoxybiphenyl, diacetoxybenzene, and 2,
A method of producing from 6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and other aromatic dicarboxylic acids by deacetic acid condensation polymerization.

(2) p-hydroxybenzoic acid and 4,
4′-dihydroxybiphenyl, an aromatic dihydroxy compound such as hydroquinone and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acylate a phenolic hydroxyl group. A method of producing by a deacetic acid polycondensation reaction.

(3) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl, hydroquinone and 2,6
-A method of producing from a diphenyl ester of an aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, etc. by a phenol removal polycondensation reaction.

(4) p-hydroxybenzoic acid and 2,
A predetermined amount of diphenyl carbonate is reacted with an aromatic dicarboxylic acid such as 6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone And a production method by a dephenol polycondensation reaction.

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

Although these polycondensation reactions proceed without a catalyst, metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide and metallic magnesium can also be used.

The liquid crystalline resin used in the present invention has a melting point of 14
It is essential that the temperature is 0 ° C or higher and lower than 200 ° C, preferably 145 ° C or higher and 198 ° C or lower, more preferably 150 ° C or lower.
C. to 195 C. or less. If the melting point is too high, when used as a thermoplastic resin modifier, it cannot be mixed neatly,
In some cases, the surface appearance is deteriorated as foreign matter, and the properties inherent to the thermoplastic resin are impaired, such as a decrease in impact resistance.

Here, the melting point (Tm) refers to an endothermic peak temperature (Tm) observed when a polymer that has been polymerized is measured from room temperature under a heating condition of 20 ° C./min.
After observation at m1), the temperature is maintained at a temperature of Tm1 + 20 ° C. for 5 minutes, cooled once to room temperature at a temperature lowering condition of 20 ° C./min, and then measured again at a temperature rising condition of 20 ° C./min. Refers to the endothermic peak temperature (Tm2).

The thermoplastic resin used in the present invention is preferably one having homogeneity, that is, one having a high melting point in the polymer, that is, having a homogeneous structure substantially not including a portion which becomes a foreign substance when melted. .

The liquid crystalline resin used in the present invention is:
The number average molecular weight is not particularly limited, but is preferably 400 to 2
It is preferably 0000, particularly preferably 500 to 15,000. The molecular weight can be measured by a GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the liquid crystalline resin is soluble.

Some liquid crystal resins used in the present invention can measure the logarithmic viscosity in pentafluorophenol. In this case, the value measured at 60 ° C. at a concentration of 0.1 g / dl is 0%. 0.03 or more, preferably 0.05 to 1
0.0 dl / g is particularly preferred.

Further, the melt viscosity of the liquid crystalline resin in the present invention is preferably 0.05 to 200 Pa · s, especially 0.1 to 200 Pa · s.
-100 Pa · s is more preferable.

The melt viscosity is calculated as melting point (Tm) +10
It is a value measured by a Koka type flow tester under the condition of ° C and a shear rate of 1,000 (1 / second).

The liquid crystalline resin of the present invention is blended with a thermoplastic resin to give the thermoplastic resin properties such as strength, surface modifier, chemical resistance, impact resistance, long-term heat resistance and abrasion resistance. Since it can be improved, it can be used as an additive such as, for example, a strength improver, a surface appearance improver, a chemical resistance improver, and an impact resistance improver.

The thermoplastic resin in which the liquid crystalline resin of the present invention is blended is not particularly limited, but it is a synthetic resin which exhibits fluidity when heated and can be molded by utilizing this. As a specific example, for example, polyester, melting point 200
℃ or higher liquid crystal polyester, polycarbonate, polyamide, polyoxymethylene, wholly aromatic polyamide, wholly aromatic polyester, polyimide, polybenzimidazole, polyketone, polyetheretherketone, polyetherketone, polyethersulfone, polyphenylene oxide, phenoxy resin , Polyphenylene sulfide, phenol resin, phenol-formaldehyde resin, olefin polymers such as polypropylene, polyethylene, polystyrene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer , Ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / Propylene -g- maleic anhydride copolymers, olefin copolymers such as ABS, polyester polyether elastomers, include one or a mixture of two or more selected from elastomers and polyester polyester elastomer. Further, specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, and polyethylene-1,2-bis (phenoxy) ethane-4,4′-. In addition to dicarboxylate and the like, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decanedicarboxylate and polycyclohexane dimethylene terephthalate / isophthalate are exemplified. Specific examples of the polyamide include, for example, a ring-opening polymer of a cyclic lactam, a polycondensate of an aminocarboxylic acid, and a polycondensate of a dicarboxylic acid and a diamine. 6, Nylon 6.6, Nylon 6.6, Nylon 6.6, Nylon 11, Nylon 11, Aliphatic polyamide such as Nylon 12, Poly (meta-xylene adipamide), Poly (hexamethylene terephthalamide), Poly (hexamethylene isophthalate) Amide), poly (tetramethylene isophthalamide), polynonamethylene methylene terephthalamide (nylon 9T), etc., and polyhexamethylene adipamide / polyhexamethylene as copolymers or mixtures thereof. Terephthalamide copolymer (nylon 66/6
T), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polydodecamide / polyhexamethylene terephthalamide copolymer ( Nylon 12 / 6T), polyhexamethylene adipamide /
Polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T
/ 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide /
Poly (2-methylpentamethylene terephthalamide) copolymer (nylon 6T / M5T) and the like can be mentioned.

Among them, polyesters such as polybutylene terephthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate and polyethylene terephthalate, nylon 6, nylon 6.6, etc. Polyamide, polyoxymethylene, melting point 2
Liquid crystalline polyester of 00 ° C. or higher, liquid crystalline polyester amide having a melting point of 200 ° C. or higher, polycarbonate, polyphenylene sulfide, polyethylene, polypropylene,
One or a mixture of two or more selected from polystyrene, ABS, polyphenylene oxide, phenoxy resin, phenol resin, and phenol-formaldehyde resin is preferable, and polybutylene terephthalate, polyethylene terephthalate, nylon 6, nylon 6.6, and poly are more preferable. 1 selected from oxymethylene, a liquid crystalline polyester having a melting point of 200 ° C. or higher, a liquid crystalline polyester amide having a melting point of 200 ° C. or higher, polycarbonate, polyphenylene sulfide, ABS, and polyphenylene oxide
Species or a mixture of two or more.

The compounding amount of the liquid crystalline resin of the present invention to the thermoplastic resin does not impair the inherent properties of the thermoplastic resin and newly imparts various properties such as high strength, abrasion resistance and long-term heat resistance. From the viewpoint, it is usually 0.01 to 15 parts by weight, preferably 0.05 to 12 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
Parts by weight, more preferably 0.1 to 10 parts by weight.

The red phosphorus used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting gradually with water. Is preferably used. As a method for treating such red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and a red crushed surface having high reactivity with water and oxygen is not formed on the surface of red phosphorus. A method of finely dividing phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, a method of coating red phosphorus with paraffin or wax to suppress contact with moisture A method of stabilizing by mixing with ε-caprolactam or trioxane, a method of stabilizing by coating red phosphorus with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, unsaturated polyester-based, A method in which red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate and stabilize a metal phosphorus compound on the red phosphorus surface. Coating with luminium, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., stabilizing by coating the surface of red phosphorus with iron, cobalt, nickel, manganese, tin, etc. by electroless plating and combining them Examples of the method include, but are not limited to, a method of pulverizing red phosphorus without pulverizing the red phosphorus and forming a crushed surface on the surface of the red phosphorus; a method of converting the red phosphorus into a phenolic, melamine, epoxy, or unsaturated A method of stabilizing by coating with a thermosetting resin such as a polyester-based resin, converting red phosphorus to aluminum hydroxide,
It is a method of stabilizing by coating with magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., and particularly preferred is a method of forming red phosphorus into fine particles without forming a crushed surface on the surface of red phosphorus. This is a method of stabilizing by coating with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, and unsaturated polyester-based resin. Among these thermosetting resins, red phosphorus coated with a phenolic thermosetting resin or an epoxy thermosetting resin can be preferably used from the viewpoint of moisture resistance, and particularly preferably a phenolic thermosetting resin. Red phosphorus coated with resin.

The average particle size of red phosphorus before being mixed with the resin is 35 from the viewpoints of flame retardancy, mechanical properties, wet heat resistance, and chemical and physical deterioration of red phosphorus due to pulverization during recycling. The thickness is preferably from 0.01 to 0.01 μm, and more preferably from 30 to 0.1 μm.

The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. There are two types of particle size distribution analyzers: wet method and dry method.
Either one may be used. In the case of the wet method, water can be used as a dispersion solvent for red phosphorus. At this time, red phosphorus surface treatment may be performed with an alcohol or a neutral detergent. It is also possible to use phosphates such as sodium hexametaphosphate and sodium pyrophosphate as the dispersant. It is also possible to use an ultrasonic bath as a dispersing device.

The average particle size of red phosphorus used in the present invention is as described above. However, red phosphorus having a large particle size contained in red phosphorus, that is, red phosphorus having a particle size of 75 μm or more is difficult. In order to significantly reduce the flammability, mechanical properties, wet heat resistance, and recyclability, red phosphorus having a particle size of 75 μm or more is preferably removed by classification or the like. The content of red phosphorus having a particle size of 75 μm is preferably 10% by weight or less, more preferably 8% by weight, in view of flame retardancy, mechanical properties, wet heat resistance and recyclability.
% By weight, particularly preferably 5% by weight or less. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the content of red phosphorus having a particle diameter of 75 μm contained in the red phosphorus can be measured by classification using a 75 μm mesh. That is, 100 g of red phosphorus
From the residual amount Z (g) when classified with a mesh of m, the content of red phosphorus having a particle size of 75 μm or more is Z / 100 × 100 (%).
Can be calculated.

The conductivity of the red phosphorus used in the present invention when it is extracted in hot water (the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, for example, in an autoclave to obtain a conductivity of 12 g).
Extraction treatment was performed at 1 ° C for 100 hours.
Measuring the conductivity of the extracted water diluted to 0 mL), the moisture resistance, mechanical strength, tracking resistance,
0.1 to 1000 μS from the viewpoint of recyclability
/ Cm, preferably 0.1-800 μS / cm,
More preferably, it is 0.1 to 500 μS / cm.

Examples of such preferred commercial products of red phosphorus include "NOVA EXCEL 140" and "NOVA EXCEL F5" manufactured by Rin Kagaku Kogyo KK.

The amount of red phosphorus added in the present invention is usually 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the total of the liquid crystalline resin and the thermoplastic resin of the present invention.
Parts by weight, more preferably 0.06 to 10 parts by weight, even more preferably 0.08 to 5 parts by weight. If the added amount of red phosphorus is too small, the effect of improving the flame retardancy is not exhibited, and if it is too large, the physical properties are reduced and the composition tends to act as a combustion accelerator contrary to the flame retardant effect.

The thermoplastic resin composition obtained by adding the liquid crystalline resin of the present invention further comprises a metal oxide as a stabilizer for red phosphorus, thereby obtaining stability, strength and heat resistance during extrusion and molding. Properties, terminal corrosion of molded products, etc. can be improved. Specific examples of such a metal oxide include cadmium oxide, zinc oxide, cuprous oxide, cupric oxide, ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and Titanium oxide and the like can be mentioned, among which cadmium oxide, cuprous oxide, cupric oxide, metal oxides other than Group I and / or II metals such as titanium oxide are preferable, and particularly cuprous oxide, Cupric oxide and titanium oxide are preferred, but may be Group I and / or II metal oxides. Titanium oxide is most preferable in order to further improve non-coloring properties in addition to stability and strength during extrusion and molding, heat resistance, and terminal corrosion of molded articles.

The addition amount of the metal oxide is 100 in total of the liquid crystalline resin and the thermoplastic resin of the present invention in view of mechanical properties and moldability.
The amount is preferably from 0.01 to 20 parts by weight, particularly preferably from 0.1 to 10 parts by weight, per part by weight.

In the present invention, a filler can be used for imparting mechanical strength and other properties to the thermoplastic resin composition. The filler is not particularly limited, but may be in the form of fibrous, plate-like, or powdery. , A granular filler or the like can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia Fibrous such as fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc, Powder, granular or plate-like fillers such as kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastenite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, etc. Is . Among the above fillers, glass fibers are preferably used. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used. Further, two or more of the above fillers can be used in combination. The surface of the filler used in the present invention is a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.),
It can be used after being treated with another surface treating agent.

The glass fiber may be covered or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

The above filler is added in an amount of 300 parts by weight per 100 parts by weight of the resin component (total of the liquid crystalline resin and the thermoplastic resin).
It is not more than 10 parts by weight, preferably 10 to 250 parts by weight, more preferably 20 to 150 parts by weight.

Further, the thermoplastic resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like) and an ultraviolet absorber (for example, resorcinol, salicylate). , Benzotriazole, benzophenone, etc.), phosphites, hypophosphites, etc., coloring agents and lubricants (montanic acid and its salts, esters, half esters thereof, stearyl alcohol, stearamide and polyethylene wax) Such),
Colorants including dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, etc.),
Carbon black as a conductive agent or a coloring agent, a crystal nucleating agent, a plasticizer, and red phosphorus as a flame retardant are preferably used, but other flame retardants (eg, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, Normal additives such as melamine and cyanuric acid or a salt thereof), a flame retardant aid, an antistatic agent, a slidability improver (graphite, fluororesin), and an ultraviolet absorber are added to further improve the predetermined properties. Can be granted.

The thermoplastic resin composition of the present invention is usually produced by a known method. For example, in the liquid crystalline resin and the thermoplastic resin component of the present invention, red phosphorus and other necessary additives and fillers are premixed or supplied to an extruder or the like without or with sufficient melting and kneading. Prepared,
Preferably, from the viewpoint of handling properties and productivity, the liquid crystal resin of the present invention, a part of the thermoplastic resin (for example, part or all of the liquid crystal resin, part or all of the thermoplastic resin component, or final Is melt-kneaded once to produce a resin composition having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the thermoplastic resin composition. It is prepared by melt-kneading a resin composition having a high red phosphorus concentration and other optional additives and fillers in the remaining liquid crystal resin or thermoplastic resin component.

Alternatively, part or all of the liquid crystal resin of the present invention, part or all of the thermoplastic resin component, or a part of the liquid crystal resin and the thermoplastic resin finally contained, and red phosphorus and other components The additive which can be optionally used is once melt-kneaded to produce a resin composition having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the thermoplastic resin composition, and the remaining liquid crystal resin Alternatively, it is prepared by melt-kneading additives and fillers other than the optionally used additives added in the thermoplastic resin component and at the stage of the resin composition having a high red phosphorus concentration.

At the stage of producing a resin composition having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the thermoplastic resin composition, other optional additives can be blended. In this case, it is preferable that these optional additives can be previously mixed with red phosphorus.

Among the additives that can be used arbitrarily, when a metal oxide used as a stabilizer for red phosphorus, particularly titanium oxide is added, titanium oxide is used in the step of producing a high-concentration product of red phosphorus. It is preferable to mix red phosphorus and titanium oxide in advance using a mechanical mixing device such as a Henschel mixer, so that the stability of red phosphorus, the dispersibility of red phosphorus and the obtained resin composition The non-coloring property can be improved.

The amount of red phosphorus compounded in the high-concentration red phosphorus product depends on the production of the high-concentration red phosphorus product, the dispersibility of red phosphorus, the flame retardancy of the thermoplastic resin composition finally obtained, and the mechanical properties. From the viewpoint of properties and moldability, with respect to 100 parts by weight of a thermoplastic resin composition comprising a thermoplastic resin to which the liquid crystalline resin of the present invention is added,
It is preferably from 5 to 300 parts by weight, particularly preferably from 15 to 2 parts by weight.
00 parts by weight.

The high-concentration products of red phosphorus include (1) a high-concentration product of red phosphorus composed only of the liquid crystalline resin of the present invention, (2) a high-concentration product of red phosphorus composed of only the thermoplastic resin, and (3) a high-concentration product of red phosphorus. Both of the high-concentration red phosphorus products composed of a liquid crystal resin and a thermoplastic resin exhibit this effect. Preferably, those using a high-concentration product of red phosphorus comprising only a thermoplastic resin have high dispersibility of red phosphorus in the thermoplastic resin composition, and have improved thin-walled flame retardancy and heat resistance.

The compounding amounts of the liquid crystalline resin and the thermoplastic resin of the high-red phosphorus-concentrated product are determined in terms of manufacturability in producing the high-red-phosphorus-concentrated product, dispersibility of red phosphorus, and finally, From the viewpoint of flame retardancy, mechanical properties, moldability and heat resistance of the resulting resin composition, the amount is preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the liquid crystalline resin and the thermoplastic resin. It is 180 parts by weight, more preferably 1 to 150 parts by weight.

The resin composition having a high red phosphorus concentration is preferably used in the form of a so-called master pellet.
The present invention is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. Further, the liquid crystalline resin and the thermoplastic resin to be mixed with the resin composition component having a high liquid phosphorus concentration are preferably in the form of pellets, but not limited thereto, so-called chip-like, powder-like, or chip-like and powder-like. A mixture may be used, but it is preferable that the liquid crystal resin and the thermoplastic resin have substantially the same form, size, and shape, or that they are similar to each other, since they can be uniformly mixed. In producing the resin composition, the composition is melt-kneaded at 180 to 350 ° C. using, for example, a single-screw extruder equipped with a “Unimelt” type screw, a twin-screw extruder, a tri-screw extruder, and a kneader-type kneader. Things.

The thermoplastic resin composition thus obtained can be subjected to ordinary molding such as injection molding, extrusion molding, compression molding, etc., and is used as a film, a fiber, and various molded articles, such as electric / electronic parts, precision parts, and automobiles. Very useful for parts and the like.

The thermoplastic resin composition using the liquid crystalline resin of the present invention makes use of properties such as excellent high strength, abrasion resistance and long-term heat resistance, and can be used for various kinds of three-dimensional molded articles, sheets, container pipes and the like. It can be processed into molded products, for example, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various types Terminal board, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD chassis, HDD parts, motor brush holder , Parabolic antenna, computer Electrical and electronic parts typified by the relevant parts; VTR parts, TV parts, iron,
Hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio / laser disks / compact disks / mini disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Home, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, washing jigs, oilless bearings, stern bearings, underwater bearings, etc. various bearings, motor parts, lighters, types Machine-related parts such as lighters, optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machinery-related parts; alternator terminals, alternator connectors, I
C regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer , Exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water Pump impeller, turbine vane, parts related to wiper motor, dust distributor, starter switch, star Relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston It is useful for automotive and vehicle related parts such as solenoid bobbins, engine oil filters, and ignition device cases, and various other uses.

[0063]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention.

Example 1 (A-1) 808 parts by weight of p-hydroxybenzoic acid, 251 parts by weight of 4,4'-dihydroxybiphenyl, 273 parts by weight of sebacic acid, polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g Then, 346 parts by weight of acetic acid and 969 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polymerization was carried out. A melting point of 191 ° C. composed of 65 mol% of aromatic oxycarbonyl units, 15 mol% of aromatic dioxy units, 20 mol% of ethylenedioxy units, 15 mol% of aliphatic dicarbonyl units and 20 mol% of aromatic dicarbonyl units, number average A resin having a molecular weight of about 3200 was obtained.

Example 2 (A-2) 746 parts by weight of p-hydroxybenzoic acid, 168 parts by weight of 4,4'-dihydroxybiphenyl, 150 parts of isophthalic acid
Parts by weight, 519 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 816 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube for polymerization. Melting point 1 composed of 60 mol% of aromatic oxycarbonyl units, 10 mol% of aromatic dioxy units, 30 mol% of ethylenedioxy units and 40 mol% of aromatic dicarbonyl units
A resin having a number average molecular weight of about 2,600 at 93 ° C. was obtained.

Comparative Example 1 (A-3) A reaction vessel equipped with a distilling tube containing 1265 parts by weight of p-acetoxybenzoic acid and 456 parts by weight of 6-acetoxy-2-naphthoic acid according to JP-A-54-77691. And subjected to polycondensation. A resin having a melting point of 293 ° C. and a number average molecular weight of about 7000, comprising 100 mol% of aromatic oxycarbonyl units was obtained.

Comparative Example 2 (A-4) 746 parts by weight of p-hydroxybenzoic acid, 692 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 606 parts by weight of acetic anhydride were distilled with a stirring blade. It was charged into a reaction vessel equipped with a tube and polymerization was performed. Melting point 1 composed of 60 mol% of aromatic oxycarbonyl units, 40 mol% of ethylenedioxy units and 40 mol% of aromatic dicarboxylic acid units
A resin having a number average molecular weight of about 3,000 at 90.5, 206 ° C. was obtained.

(1) Polymer homogeneity The polymer was heated on a slide glass at 200 ° C. and a melting point of + 10 ° C., and either completely melted or observed using a melting point microscope.
At both temperatures, complete dissolution ◎, melting only at the melting point △, and insoluble matter remained x were evaluated. For those having a plurality of melting points, the lowest temperature value was measured as the melting point.

(2) Tensile Properties ASTM No. 1 tensile test piece was molded with Toshiba IS-55EPN at a cylinder temperature of 280 ° C. and a mold temperature of 130 ° C.
It was measured according to TM D638 to determine the tensile strength.

(3) Abrasion resistance Tabor abrasion test (ASTM D-1044-56)
Wear wheel CS-17, load 1kg, rotation speed 1000
The amount of wear was measured at times.

(4) Heat Aging Test An ASTM No. 1 tensile test piece was molded with a Toshiba IS-55EPN at a cylinder temperature of 280 ° C. and a mold temperature of 130 ° C., and the obtained test piece was treated in a hot air oven at 190 ° C. for 30 days. After that, the tensile strength was measured based on ASTM D638, and the tensile strength after treatment at 190 ° C. for 30 days / initial tensile strength × 100 was determined as the tensile strength retention.

(5) Surface Appearance The surface appearance of the molded article obtained in (2) was observed, and visually observed for swelling due to foreign matter. (6) Flame retardancy In accordance with UL-94, a 1/32 inch thick test piece was evaluated for flame retardancy.

Examples 3 and 4, Comparative Examples 3 to 5 The liquid crystalline polyester (LCP) shown in Examples 1 and 2 and Comparative Examples 1 and 2, PET (T900E manufactured by Toray Industries, Inc.) and a filler (fiber length 3 mm, After dry-blending glass fibers having a fiber diameter of 9 μm) in the proportions shown in Table 1, the mixture was melt-kneaded with a 30 mmφ twin-screw extruder to obtain pellets. Then, a test piece was obtained from the pellet by a method for each evaluation item.

Table 1 shows the evaluation results.

[0075]

[Table 1]

Examples 5 and 6 and Reference Example 1 In the composition of Reference Example 1 (Example 3), 30 parts by weight of red phosphorus (Nova Excel 140) was dry-blended with 70 parts by weight of PET, and a twin screw extruder of 30 mmφ was used. Using 28
The mixture was melt-kneaded at 0 ° C. to obtain pellets of a high concentration of red phosphorus. Next, liquid crystal resin, thermoplastic resin and red phosphorus high concentration product or red phosphorus and glass fiber (9 μm diameter, 3 μm diameter,
mm length) was dry-blended and melt-kneaded at 280 ° C. using a 30 mmφ twin-screw extruder to obtain pellets. This pellet is used for Toshiba IS-55EPN (manufactured by Toshiba Machine Co., Ltd.).
, Cylinder temperature 280 ° C, mold temperature 130 ° C
The test piece was molded by the method for each evaluation item under the conditions described above, and evaluated.

[0077]

[Table 2]

From the results shown in Table 1, the liquid crystalline resin of the present invention is excellent in homogeneity, and the thermoplastic resin to which the liquid crystalline resin is added has improved tensile strength, friction characteristics and heat aging resistance, and has a surface appearance with less foreign matter. Excellent materials can be obtained. Further, from the results in Table 2, it is possible to obtain a material having not only improved flame retardancy but also improved physical properties by adding red phosphorus.

[0079]

By using the liquid crystalline resin of the present invention as a thermoplastic resin, strength, abrasion resistance and heat aging characteristics are improved without impairing the original characteristics of the thermoplastic resin. It can further improve physical properties and add flame retardancy, and for films, fibers, molded products, electrical and electronic equipment, precision equipment, office equipment, automobile and vehicle parts, and other various applications. It is suitable.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 67:00)

Claims (11)

[Claims] 1. A liquid crystalline resin containing a p-hydroxybenzoic acid residue as an essential component and having a melting point of 140 ° C. or more and less than 200 ° C. 2. The liquid crystalline resin according to claim 1, which contains a dioxybiphenyl unit. 3. A liquid crystalline resin comprising the following structural units (I), (III) and (I)
Liquid crystalline polyester having the structural unit of V), or
A liquid crystalline polyester having structural units of (I), (II), (III) and (IV), (Where R1 in the formula is And R2 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) And at least as —OCH ₂ CH ₂ O— as structural unit (III) and / or as structural unit (IV) The liquid crystalline resin according to claim 1, comprising a liquid crystalline polyester having: 4. A composition comprising structural units (I), (II), (III) and (IV), wherein the total of structural units (I) and (II) is (I), (II) and (II)
35 to 90 mol% of the total of (I), the structural unit (III) is composed of (I) and (I)
65 to 10 mol% of the total of I) and (III), the molar ratio of the structural unit (I) / (II) is 70/30 to 90/10, and the structural unit (IV) is the structural unit (II) 4. The liquid crystalline resin according to claim 3, which is substantially equimolar to the total of (III) and (III). 5. The liquid crystalline resin according to claim 1, wherein R2 of the structural unit (IV) includes at least one selected from the following structures R3. R3: 6. The liquid crystalline resin according to claim 5, wherein the ratio of R3 is 1 to 90 mol% based on 100 mol% of all the dicarboxylic acid components constituting the liquid crystalline resin. 7. A thermoplastic resin composition comprising 0.01 to 15 parts by weight of the liquid crystalline resin according to claim 1 based on 100 parts by weight of the thermoplastic resin. 8. A total of 10 liquid crystal resins and thermoplastic resins.
The thermoplastic resin composition according to claim 7, further comprising 0.01 to 30 parts by weight of red phosphorus based on 0 part by weight. 9. A total of 10 of a liquid crystalline resin and a thermoplastic resin.
The thermoplastic resin composition according to claim 7 or 8, further comprising 5 to 300 parts by weight of an inorganic filler based on 0 part by weight. 10. A molded article comprising the thermoplastic resin composition according to any one of claims 7 to 9. 11. An additive for a thermoplastic resin comprising the liquid crystalline resin according to claim 1.