JP2000080290A - Liquid crystalline resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystalline resin composition improved in heat resistance, residence stability and long-term heat stability by including a mixture of a liquid crystalline resin with another liquid crystalline resin and red phosphorous in a specific content ratio. SOLUTION: This liquid crystalline resin composition is obtained by including 100 pts.wt. mixture of (A) 99.5-0.5 wt.% liquid crystalline resin with (B) 0.5-99.5 wt.% liquid crystalline resin (pref. a wholly aromatized polyester resin or the like) different in copolymerization ratio, any structural unit forming the liquid crystalline resin, or the like and (C) 0.01-30 pts.wt. red phosphorous having pref. 0.1-1,000 μS/cm electric conductivity (measured value of extract water prepared by adding 100 mL deionized water to 5 g red phosphorous, by subjecting the mixture to extraction at 121 deg.C for 100 h., by filtering out red phosphorous in it and by diluting the filtrate up to 250 mL). The ingredient A is a polymer capable of manifesting anisotropy in a molten state and is e.g. a liquid crystalline polyester, a liquid crystalline polyesteramide, or the like.

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 composition having improved fluidity, impact resistance, thin-walled flame retardancy and heat resistance (solder resistance, retention stability, long-term heat resistance) and molding thereof. It is about goods.

[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, optics characterized by a parallel arrangement of molecular chains. Attention is paid to the fact that anisotropic liquid crystalline polymers have excellent fluidity and mechanical properties,
Especially because of its high rigidity, flame retardancy and heat resistance,
The demand for small molded products such as connectors, coil bobbins, relays and switches has been increasing in the fields of electronics and office equipment.

Examples of the polymer forming the anisotropic molten phase include a liquid crystalline polymer obtained by copolymerizing p-hydroxybenzoic acid with polyethylene terephthalate (Japanese Patent Laid-Open No.
No. 9-72393), p-hydroxybenzoic acid and 6
-Hydroxy-2-naphthoic acid copolymerized liquid crystal polymer (JP-A-54-77691), p-hydroxybenzoic acid copolymerized with 4,4'-dihydroxybiphenyl, terephthalic acid and isophthalic acid Polymers (JP-B-57-24407) are known.

As a method for improving the mechanical properties, fluidity, and moldability of a liquid crystalline polymer, a method of blending two kinds of liquid crystalline polymers having different molecular structures by a specific method is disclosed in Japanese Patent Application Laid-Open No. Sho 57-40550. Gazette, JP-A-2-17
156, JP-A-3-952560, and JP-A-5-186671.

[0005]

It is true that by devising a kneading method, it is possible to suppress a decrease in mechanical properties and to improve the fluidity.
No. 56, Japanese Unexamined Patent Publication No. 3-95560, etc., the flame retardancy at the time of thinning is reduced, or the generation of gas at the time of molding retention increases, and the obtained molded product has gas, debris, blister, etc. It has been found that when the surface appearance is poor, or when a liquid crystal polymer having high heat resistance is used and the liquid crystal polymer is immersed in a solder bath or the like, the gas trapped in the molded product causes blisters. In addition, it has been found that the method disclosed in Japanese Patent Application Laid-Open No. Hei 5-186671 is insufficient in flame retardancy especially in a thin wall.

The present invention solves the above-mentioned problems and provides a liquid crystal resin composition having improved fluidity, impact resistance, thin-walled flame retardancy and heat resistance, especially heat resistance, residence stability and long-term heat resistance, and a liquid crystal resin composition thereof. It is an object to obtain a molded product.

[0007]

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 provides (1) a liquid crystalline resin (A) of 99.5 to 0.5.
5% by weight of a liquid crystal resin (B) having a structure different from that of (A).
5 to 99.5% by weight of a liquid crystalline resin composition (C)
A liquid crystalline resin composition containing 100 parts by weight and 0.01 to 30 parts by weight of red phosphorus; (2) a red phosphorus having a conductivity of 0.1;
(1) 100 parts by weight of the liquid crystalline resin (C), further containing 0.5 to 300 parts by weight of a filler. (4) The liquid crystalline resin according to any one of (1) to (3), wherein the liquid crystalline resin (A) contains an ethylenedioxy unit. (5) The liquid crystal resin composition according to any one of the above (1) to (4), wherein the liquid crystal resin (B) is a wholly aromatic liquid crystal polyester resin.
(6) The liquid crystal resin composition according to (1) to (5), which has a flame retardancy of V-0 when measured at a thickness of 1/64 inch in the UL-94 standard; ), Or part or all of the liquid crystalline resin (B), or part of (A) and (B) to be finally contained. (8) The method for producing a liquid crystalline resin composition according to any one of the above (1) to (6), by preparing a resin composition having a red phosphorus concentration higher than the amount of red phosphorus to be blended in the resin composition. A molded article comprising the flame-retardant resin composition according to any one of the above (1) to (6), wherein the molded article is a mechanical mechanism part,
Molded articles that are electric or electronic parts or automobile parts, (9)
A molded article according to the above (8), characterized in that the molded article has a thin portion of 0.8 mm or less and 10% or more of the total surface area of the molded article.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline resin (A) of the present invention is:
A polymer capable of forming anisotropy when melted, such as a liquid crystalline polyester, a liquid crystalline polyester amide, a liquid crystalline polycarbonate, a liquid crystalline polyester elastomer, and among others, those having an ester bond in the molecular chain are preferable, and in particular, Liquid crystalline polyester, liquid crystalline polyesteramide and the like are preferably used.

The liquid crystalline resin (A) which can be preferably used in the present invention is a liquid crystalline polyester containing a structural unit consisting of p-hydroxybenzoic acid as an aromatic oxycarbonyl unit, and an ethylenedioxy unit as an essential component. Liquid crystalline polyester can also be preferably used. More preferred are polyesters consisting of the following structural units (I), (III) and (IV) or polyesters consisting of the structural units of (I), (II), (III) and (IV), the most preferred being ( I),
It is a polyester comprising the structural units of (II), (III) and (IV).

[0010]

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(Where R ₁ in the formula is

[0012]

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R ₁ represents one or more groups selected from

[0014]

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R ₃ represents one or more groups selected from

[0016]

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And represents one or more groups selected from Also,
In the formula, X represents a hydrogen atom or a chlorine atom. Note that the sum of structural units (II) and (III) and structural unit (IV)
Are desirably substantially equimolar.

The structural unit (I) is a structural unit formed from at least one aromatic hydroxycarboxylic acid selected from p-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'
-Dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,
A structural unit formed from at least one aromatic dihydroxy compound selected from 7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether is converted into a structural unit (I
II) is a structural unit formed from ethylene glycol, and structural unit (IV) is terephthalic acid, isophthalic acid, 4,4'-
Diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-
Dicarboxylic acid, 1,2-bis (2-chlorophenoxy)
The structural units formed from one or more aromatic dicarboxylic acids selected from ethane-4,4'-dicarboxylic acid and 4,4'-diphenyletherdicarboxylic acid are shown below. Of these, R ₂ is

[0019]

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And R ₃ is

[0021]

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Are particularly preferred.

The above structural units (I), (II), (III) and (IV)
Is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (II) and (II)
I), in the case of a copolymer consisting of (IV), the structural unit (I)
The total of (II) and (II) is preferably from 30 to 95 mol%, more preferably from 40 to 93 mol%, based on the total of the structural units (I), (II) and (III). The structural unit (III) is the structural unit
It is preferably from 70 to 5 mol%, more preferably from 60 to 7 mol%, based on the total of (I), (II) and (III). The molar ratio [(I) / (II)] between the structural units (I) and (II) is preferably 75.
/ 25 to 95/5, more preferably 78/22 to
93/7. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

On the other hand, when the above-mentioned structural unit (II) is not contained, the structural unit (I) should be 40 to 90 mol% with respect to the total of the structural units (I) and (III) from the viewpoint of fluidity. Is preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

Further, as the liquid crystalline polyesteramide,
Polyesteramides that form an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferred.

The liquid crystalline polyesters and liquid crystalline polyesteramides which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2 ' -Aromatic dicarboxylic acids 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, 3,4'- Dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, 3,4 '
-Aromatic diols such as dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and aliphatic and fats such as 1,4-cyclohexanedimethanol Aromatic carboxylic acids such as cyclic diols and m-hydroxybenzoic acid and p
-Aminobenzoic acid and the like can be further copolymerized within a range that does not impair the liquid crystallinity.

The logarithmic viscosity of the liquid crystalline resin (A) used in the present invention can be measured in pentafluorophenol. At this time, 0.5 to 15.0 dl / g is preferable as a value measured at 60 ° C. at a concentration of 0.1 g / dl,
1.0 to 3.0 dl / g is particularly preferred.

The liquid crystalline resin (B) used in the present invention has a different structure from that of the liquid crystalline resin (A) and is a polymer capable of forming anisotropy when melted. Examples include polyester amide, liquid crystalline polycarbonate, and liquid crystalline polyester elastomer. Among them, a polymer having an ester bond is preferable, and examples thereof include a liquid crystalline polyester and a liquid crystalline polyesteramide.

The liquid crystalline resin (B) used in the present invention is a liquid crystalline resin having a structure different from that of the above liquid crystalline resin (A). And those having different structural units. When the structural units forming the liquid crystalline resin are the same as the liquid crystalline resin (A) and the copolymerization ratios are different, the melting point of the liquid crystalline resin (A) and the melting point of the liquid crystalline resin (B) are usually 10
It is effective when the copolymerization ratio is different to a degree different by not less than 15 ° C., preferably not less than 15 ° C. If the difference in melting points is too small, it will be close to a single system, and the effect (particularly fluidity) of the present invention will not be sufficiently exhibited. When the structural units forming the liquid crystalline resin are different, either a semi-aromatic type or a wholly aromatic type may be used, but from the viewpoint of heat resistance, impact resistance, etc., it is preferable to use a wholly aromatic liquid crystalline resin. A polyester resin is used.

More preferred structural units include wholly aromatic liquid crystalline polyesters comprising the structural unit (I) or
A wholly aromatic liquid crystalline polyester comprising the structural units (I), (II) and (IV) is preferably used. Specifically, a structural unit generated from p-hydroxybenzoic acid, a liquid crystalline polyester including a structural unit generated from 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, 4,4 ′ Liquid crystalline polyester comprising a structural unit formed from dihydroxybiphenyl, a structural unit formed from terephthalic acid and / or isophthalic acid,
Structural unit generated from p-hydroxybenzoic acid, structural unit represented by (II), liquid crystalline polyester generated from terephthalic acid, structural unit generated from p-hydroxybenzoic acid, represented by (II) Structural units, structural units formed from terephthalic acid and isophthalic acid, 2,
Examples of the liquid crystalline polyester include structural units generated from one or more aromatic dicarboxylic acids selected from 6-naphthalenedicarboxylic acid and the like.

When having the structures of (I), (II) and (IV), the structural unit (I) is 40 to 90% of the total of the structural units (I) and (II) from the viewpoint of fluidity. It is preferably mol%, and the structural unit (IV) is substantially equimolar to the structural unit (II).

The liquid crystalline polyester and the liquid crystalline polyester amide which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2 ' Aromatic dicarboxylic acids such as diphenyldicarboxylic acid, chlorohydroquinone, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfide, 4,4′-dihydroxybenzophenone, 3, Aromatic diols such as 4'-dihydroxybiphenyl, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid, p-aminobenzoic acid, and the like can be further copolymerized to the extent that liquid crystallinity is not impaired.

The logarithmic viscosity of the liquid crystalline resin (B) used in the present invention can be measured in pentafluorophenol. At this time, a value measured at 60 ° C. at a concentration of 0.1 g / dl is preferably 1.0 to 15.0 dl / g,
2.5 to 10.0 dl / g is particularly preferred.

Although not particularly limited, the melting point of the liquid crystalline resin (B) is preferably 280 ° C. or more, more preferably 300 ° C. or more, in order to obtain excellent heat resistance.

The mixing ratio of the liquid crystalline resin (A) and the liquid crystalline resin (B) used in the present invention is based on the sum of (A) and (B).
(A) 99.5 to 0.5% by weight, (B) 0.5 to 99.
5% by weight, preferably (A) 95 to 5% by weight, (B) 5
To 95% by weight, more preferably (A) 90 to 10% by weight, and (B) 10 to 90% by weight.

For example, as the liquid crystalline resin (A), a polyester composed of the structural units (I), (III) and (IV) or a structural unit of (I), (II), (III) and (IV) When a liquid crystalline resin (B) is selected and a wholly aromatic polyester or a liquid crystalline resin having a melting point higher than that used as the liquid crystalline resin (A) by 10 ° C. or more is used, (A) is set to 60. ~ 99.5% by weight, (B) 40 ~
By adjusting the content to 0.5% by weight, it is possible to particularly improve the heat stability while maintaining good fluidity,
By setting (A) to 40 to 0.5% by weight and (B) to 60 to 99.5% by weight, fluidity and impact resistance can be further maintained while maintaining thermal characteristics such as retention stability and long-term heat resistance. Can be improved. (A) is more than 40% by weight to less than 60% by weight, and (B) is less than 60% by weight to 40% by weight.
When the content is more than the weight percentage, a composition having an excellent balance between thermal characteristics such as retention stability and long-term heat resistance and fluidity can be obtained.

The melt viscosity of the liquid crystalline resins (A) and (B) in the present invention is preferably 0.5 to 500 Pa · s, more preferably 1 to 250 Pa · s. When a composition having better fluidity is to be obtained, (A)
In (B), the melt viscosity of the component to be blended in a small amount is 30 Pa · s
It is preferable to set the following.

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).

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 was maintained at Tm1 + 20 ° C. for 5 minutes, and then cooled to room temperature once at a temperature lowering condition of 20 ° C./min.
It indicates the endothermic peak temperature (Tm2) observed when the temperature is measured again at a temperature rise condition of 20 ° C./min.

In the present invention, the effects of the present invention can be obtained by using the liquid crystal resin (A) and the liquid crystal resin (B) having a structure different from the liquid crystal resin (A). It does not mean that only one kind of polymer is used, and three or more kinds of resins may be used. In that case, each component is handled in consideration of the purpose of the present invention.

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 method.

For example, in the production of the liquid crystal polyester, the following production method is preferably mentioned. (1) p-acetoxybenzoic acid and diacylated aromatic dihydroxy compounds such as 4,4'-diacetoxybiphenyl and diacetoxybenzene and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction therefrom. (2) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and acetic anhydride. The phenolic hydroxyl group is acylated, and then a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction. (3) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid For producing liquid crystalline polyesters from polyphenols by a dephenol removal polycondensation reaction. (4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, respectively.
A method in which an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone is added, and a liquid crystalline polyester is produced by a phenol-elimination polycondensation reaction. (5) In the presence of a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as a polymer or oligomer of a polyester such as polyethylene terephthalate or an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, the liquid crystal is prepared by the method of (1) or (2). A method for producing a conductive polyester.

Although the polycondensation reaction of the liquid crystalline polyester proceeds without a catalyst, metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metal magnesium can also be used.

The red phosphorus used in the present invention is unstable as it is, and has a property of gradually dissolving in water or reacting gradually with water. Is preferably used. As such a method of treating red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and the red phosphorus is formed without forming a crushed surface having high reactivity with water or oxygen 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, Red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate a metal phosphorus compound on the red phosphorus surface and to stabilize it. That method, red phosphorus aluminum hydroxide, magnesium hydroxide, titanium hydroxide, a method of coating by such as zinc hydroxide, iron red phosphorus surface, cobalt, nickel, manganese,
Examples include a method of stabilizing by coating with electroless plating with tin and the like, and a method of combining them.Preferably, red phosphorus is formed without forming a crushed surface on the red phosphorus surface without crushing the red phosphorus. A method of forming fine particles, a method of stabilizing red phosphorus by coating it with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based or unsaturated polyester-based resin. Titanium, a method of stabilizing by coating with zinc hydroxide, etc., particularly preferably, a method of forming red phosphorus into fine particles without forming a crushed surface on the surface of red phosphorus, phenol-based red phosphorus, melamine-based, This is a method of stabilizing by coating with a thermosetting resin such as an epoxy-based or unsaturated polyester-based resin. Among these thermosetting resins, phenol-based thermosetting resin, red phosphorus coated with epoxy-based thermosetting resin can be preferably used from the viewpoint of moisture resistance, and phenol-based thermosetting resin is particularly preferable. Red phosphorus coated with resin.

The average particle size of red phosphorus before being blended 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 diameter of red phosphorus used in the present invention is as described above. However, red phosphorus having a large particle diameter contained in red phosphorus, that is, red phosphorus having a particle diameter 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 or more is preferably 10% by weight or less, more preferably 8% by weight or less, particularly preferably 5% by weight or less from the viewpoints of flame retardancy, mechanical properties, wet heat resistance and recyclability. It is. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the particle size contained in red phosphorus is 75 μm.
The above-mentioned red phosphorus content can be measured by classification using a 75 μm mesh. That is, red phosphorus 100
g when the g is classified with a mesh of 75 μm or more.
(G), the content of red phosphorus having a particle size of 75 μm or more is (A /
100) × 100 (%).

The conductivity of the red phosphorus (B) 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, and adding, for example, Extraction at 100 ° C. for 100 hours, and diluting the filtrate after red phosphorus filtration to 250 mL, and measure the conductivity of the extracted water) is the moisture resistance, mechanical strength, tracking resistance, and recyclability of the obtained molded product. 0.1 ~
1000 μS / cm, preferably 0.1 to 800
μS / cm, more preferably 0.1 to 500 μS / c
m.

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

In the present invention, the amount of red phosphorus to be added is as follows: the resin composition (C) (ie, the sum of the components (A) and (B))
Usually 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.06 to 100 parts by weight with respect to 00 parts by weight.
It is 10 parts by weight, more preferably 0.08 to 5 parts by weight, particularly preferably 0.1 to 1 part 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 work as a combustion accelerator contrary to the flame retardant effect.

The liquid crystalline resin composition of the present invention further improves the stability and strength during extrusion and molding, heat resistance, terminal corrosion of molded articles, etc. by adding a metal oxide as a stabilizer for red phosphorus. Can be done. 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 amount of the metal oxide to be added depends on the properties of the resin composition (C) (ie, the component (A) and the component (B)) in view of mechanical properties and moldability.
The amount is preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the total components.

In the present invention, it is possible to use a filler to impart mechanical strength and other properties to the liquid crystalline resin composition. The filler is not particularly limited, but may be in the form of fibrous, plate-like, or powder-like resin. A non-fibrous filler such as a granular filler can be used. Specifically, for example, glass fiber, PA
N-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 fiber, alumina fiber, silica fiber, oxidation Titanium fiber, silicon carbide fiber, rock wool,
Fibrous such as potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flake, glass micro balloon, clay, Molybdenum disulfide, wollastenite, titanium oxide,
A powdery, granular or plate-like filler such as zinc oxide, calcium polyphosphate, graphite and the like can be used. 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 filler used in the present invention may be used after its surface is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treatment agent. .

The glass fibers 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 amount of the filler to be added depends on the resin composition (C)
(That is, the total of the components (A) and (B)) is 0.5 to 300 parts by weight, preferably 10 to 100 parts by weight.
To 250 parts by weight, more preferably 20 to 150 parts by weight.

Further, the liquid crystalline resin composition of the present invention includes:
Antioxidants and heat stabilizers (such as hindered phenols, hydroquinones, phosphites and their substitutes), ultraviolet absorbers (such as resorcinol,
Coloring agents, such as salicylates, benzotriazoles, benzophenones), phosphites, hypophosphites, etc., lubricants, dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, etc.), lubricants and the like. Release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, 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, Melamine and cyanuric acid or a salt thereof), flame retardant aid, slidability improver (graphite,
Ordinary additives such as a fluororesin) and an antistatic agent can be added to further impart predetermined characteristics.

Further, according to the necessity of further property improvement, an acid-modified olefin polymer such as maleic anhydride, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene may be used. Copolymer, ethylene / ethyl acrylate copolymer, ethylene /
Glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene /
A propylene-g-maleic anhydride copolymer, an olefinic copolymer such as ABS, a polyester polyether elastomer, a polyester polyester elastomer, and one or more mixtures selected from elastomers are added to obtain predetermined characteristics. It can be further provided.

The liquid crystalline resin composition of the present invention is produced by a generally known method. For example, in the liquid crystalline resins (A) and (B), 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. Although it is prepared, it is preferable that a part of the liquid crystalline resins (A) and (B) (for example, a part or all of the component (A), a part or the whole of the component (B)) is preferable in terms of handling properties and productivity. Or a resin having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the liquid crystal resin composition by temporarily kneading and kneading (A) and (B) to be finally contained. A composition (D) is produced, and a resin composition (D) having a high red phosphorus concentration and other optional additives and fillers are added to the remaining liquid crystal polyester (A) or (B) component. It is prepared by melt-kneading.

Alternatively, a part or all of the liquid crystalline polyester (A), a part or all of the component (B), or a part of the components (A) and (B) finally contained with red phosphorus and other components Is melt-kneaded once to produce a resin composition (D) having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the liquid crystal resin composition, and the remaining By melt-kneading additives and fillers other than optional additives added in the liquid crystalline polyester (A) or (B) component and in the stage of the resin composition (D) having a high red phosphorus concentration, Prepared.

As described above, at the stage of producing the resin composition (D) having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the liquid crystal resin composition, other optional additives can be used. When formulating an agent, 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, the titanium oxide produces a high-concentration product (D) of red phosphorus. When red phosphorus and titanium oxide are mixed in advance using a mechanical mixing device such as a Henschel mixer, the stability of red phosphorus, the dispersibility of red phosphorus, and the obtained resin The non-coloring property of the composition can be improved.

The red phosphorus high concentration product (D) includes (1) a red phosphorus high concentration product consisting of only the liquid crystalline polyester (A),
Both (2) a high-concentration product of red phosphorus composed of the liquid crystalline polyester (B) and (3) a high-concentration product of red phosphorus composed of the liquid crystalline polyesters (A) and (B) exhibit the effect. Preferably, a product using a high-concentration product of red phosphorus composed of only the liquid crystalline polyester (A) has high dispersibility of red phosphorus in the liquid crystalline resin composition, and has improved thin-walled flame retardancy and heat resistance.

The compounding amounts of the liquid crystalline polyesters (A) and (B) of the high-red-phosphorus-concentration product (D) are determined based on the productivity and the dispersibility of the high-red-phosphorus-concentration product. , And flame retardancy, mechanical properties, moldability of the finally obtained resin composition,
From the viewpoint of heat resistance, the amount is preferably 0.5 to 200 parts by weight, more preferably 1 to 180 parts by weight, more preferably 1 to 150 parts by weight, based on 100 parts by weight of the liquid crystalline polyesters (A) and (B). It is.

The resin composition having a high red phosphorus concentration (D)
Is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. The liquid crystalline polyesters (A) and (B) to be blended with the component (D) are preferably in the form of pellets, but are not limited thereto, and may be in the form of chips, powders, or a mixture of chips and powders. There may be. Preferably in the form of liquid crystalline polyesters (A) and (B),
It is preferable that the sizes and shapes are substantially the same or similar to each other, since they can be uniformly mixed. In producing the resin composition, 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 can be used.

The liquid crystalline resin composition thus obtained is a composition excellent in fluidity, thin-walled flame retardancy, and heat resistance.
Even with a thickness of 4 inches, it is possible to achieve the flame retardancy of V-0 according to UL-94 standard.

The liquid crystalline resin composition of the present invention can be molded by a generally known method.
It can be a molded article of any shape, such as a molded article such as compression molding, a sheet, and a film. Among them, it is particularly suitable for use in injection molded products. In addition, molded products having complicated shapes such as molded products having welds and hinges and insert molded products, thin molded products, especially thin portions having a thickness of 0.8 mm or less are, for example, a box-shaped molded product inside a molded product. This shows the structure of a plate-like wall having a thickness of 0.8 mm or less, preferably 0.2 to 0.8 mm, which further separates the structure. Further, the molded article may have a portion having a thickness exceeding 0.8 mm. The occupation amount of the thin portion in the molded product is preferably 10% or more of the total surface area of the molded product, more preferably 15% or more.
%, And is suitable for molded articles with
Suitable for electric and electronic parts or automobile parts.

Further, the liquid crystalline resin composition of the present invention can reduce defects such as unfilled, deformed and cracked due to insufficient fluidity when obtaining a molded product requiring fluidity and thin flame retardancy. Since the obtained molded product has good flame retardancy and improved heat resistance (solder resistance, retention stability, long-term heat resistance), it can be molded stably and the quality variation of the molded product is small, A highly reliable molded product can be obtained.

The molded article thus obtained is composed of various gears,
Various cases, sensors, LED lamps, connectors, sockets, paper separating claws, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, optical pickup slide bases, oscillators, various terminal boards, transformers, Plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FD
D / carriage, FDD chassis, HDD parts, motor brush holders, parabolic antennas, electric / electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, sound parts Audio equipment parts such as audio, laser disk, compact disk,
Homes represented by lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc.
Office electrical product parts, office computer related parts,
Telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, various bearings such as oilless bearings, stern bearings, underwater bearings, etc., motor parts, machine parts such as lighters and typewriters, microscopes , Binoculars, cameras, clocks, and other optical equipment, precision machinery-related parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, various valves such as exhaust gas valves, fuel-related, exhaust systems, intake systems Various pipes, 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, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter Switch, starter 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,
It is useful for automotive and vehicle related parts such as step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, power seat gear housing, ignition coil parts, and other various uses. is there. 0.8m, especially 10% or more of the whole molded product
It is particularly useful for various cases, switches, bobbins, connectors, sockets, connectors, and housings for mobile phones and the like having a thin portion of m or less.

[0071]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the gist of the present invention is not limited to the following Examples. Reference Example 1 LCP1: 10.70 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.88 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.39 kg was charged into a pressure vessel and polymerization was performed.
77.5 molar equivalents of aromatic oxycarbonyl unit, 7.5 molar equivalents of aromatic dioxy unit, 1 ethylenedioxy unit
5 mol equivalent, 22.5 mol equivalent of aromatic dicarboxylic acid unit, melting point: 297 ° C, 15 Pa · s (307 ° C, orifice 0.5φ x 10 mm, shear rate: 1,000 (1 / sec))
Was obtained. LCP2: 11.05 kg of p-hydroxybenzoic acid,
1.49 kg of 4,4′-dihydroxybiphenyl, 1.33 kg of terephthalic acid, 2.31 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.78 kg was charged into a pressure vessel and polymerization was performed.
Melting point consisting of 80 molar equivalents of an aromatic oxycarbonyl unit, 8 molar equivalents of an aromatic dioxy unit, 12 molar equivalents of an ethylenedioxy unit, and 20 molar equivalents of an aromatic dicarboxylic acid unit, 319 ° C., 13 Pa · s (329 ° C., orifice 0.5φ) ×
Pellets having a thickness of 10 mm and a shear rate of 1,000 (1 / second) were obtained. LCP3: 11.05 kg of p-hydroxybenzoic acid,
2.04 kg of 4,4'-dihydroxybiphenyl, 1.83 kg of terephthalic acid, 1.73 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
1.14 kg and 29 g of sodium hypophosphite were charged into a pressure vessel and polymerization was carried out. As a result, 80 mole equivalents of aromatic oxycarbonyl units, 11 mole equivalents of aromatic dioxy units, 9 mole equivalents of ethylenedioxy units, and 330 ° C., 25 Pa · s consisting of 20 molar equivalents of acid units
(340 ° C., orifice 0.5φ × 10 mm, shear rate 1,000 (1 / sec)) were obtained. LCP4: 7.46 kg of p-hydroxybenzoic acid, 4,
1.68 kg of 4'-dihydroxybiphenyl, 0.99 kg of hydroquinone, 1.17 kg of 2,6-naphthalenedicarboxylic acid, 2.09 kg of terephthalic acid and 1,01 kg of acetic anhydride were charged into a reaction vessel equipped with stirring blades and a distillation tube. As a result of polymerization, aromatic oxycarbonyl units 6
0 mol equivalent, 20 mol equivalent of aromatic dioxy unit, 20 mol equivalent of aromatic dicarboxylic acid unit, melting point 337 ° C.,
A liquid crystalline resin having a pressure of 53 Pa · s (324 ° C., orifice 0.5φ × 10 mm, shear rate 1,000 (1 / sec)) was obtained. LCP5: p-hydroxybenzoic acid 8.01 kg, 4,
4.10 kg of 4'-dihydroxybiphenyl, 2.82 kg of terephthalic acid, 0.83 kg of isophthalic acid and 11.45 kg of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube to obtain a low-polymerized product. As a result of treating the polymer in a rotary kiln under a nitrogen atmosphere, 58 mole equivalents of aromatic oxycarbonyl units and 2 aromatic dioxy units
A liquid crystalline resin having a melting point of 341 ° C., 47 Pa · s (351 ° C., orifice 0.5φ × 10 mm, shear rate of 1,000 (1 / sec)) comprising 2 molar equivalents and 22 molar equivalents of aromatic dicarboxylic acid units was obtained. .

Each evaluation was measured according to the method described below. (1) Fluidity Injection speed 99%, injection pressure 500 using the following molding machine
The flow length (rod flow length) of a test piece having a thickness of 0.4 mm and a width of 12.7 mm was measured under the condition of kgf / cm ² . (2) Retention stability Using the following molding machine, the cylinder temperature shown in Table 1 was 1 /
Obtain an 8-inch bending specimen and follow ASTM D790,
The flexural strength was measured (flexure without retention). Also, the flexural strength was measured in the same manner except that the flexure was retained in the cylinder for 30 minutes (30-minute retention flexural strength). Flexural strength retention =
(30-minute retention bending strength / non-retention bending strength) x 100
(%) Was determined. (3) Solder Resistance A test piece having a thickness of 12.7 mm × 50 mm × 2 mm was prepared by using the following molding machine, and the cylinder temperature of −25 obtained in the above (2) was used.
The product was immersed in a solder bath at 15 ° C. for 15 seconds, and the surface change of the molded product was observed. No change: O, rough surface / swelling: X (4) Long-term heat resistance A molded product of ASTM No. 1 (1/2) was prepared using the following molding machine, and the tensile strength was measured according to ASTM D638 (tensile strength before heat treatment). Further, the molded article similarly prepared was treated at 260 ° C. in the air for 1000 hours, and the tensile strength was measured in the same manner (tensile strength after heat treatment). Tensile strength retention is (tensile strength after heat treatment / tensile strength before heat treatment)
× 100 (%) was calculated. (5) Evaluation of Flame Retardancy In accordance with UL-94, a 1/64 inch test piece was evaluated for flame retardancy. (6) Impact resistance 1/4 at the cylinder temperature shown in Table 1 using the following molding machine
Inch Izod test pieces were molded and the impact strength was measured according to ASTM D256. Examples 1 to 9, Comparative Examples 1 to 7 Of the liquid crystalline polyesters of Reference Example 1, 5 parts by weight of red phosphorus (Nova Excel 140) was dry blended with 100 parts by weight of the liquid crystalline polyester (A) in Table 1. 30m
The mixture was melt-kneaded at a melting point of the liquid crystalline polyester (A) of + 15 ° C. using a twin-screw extruder having a diameter of mφ and the red phosphorus high concentration product (D1) and 100 parts by weight of the liquid crystalline polyester (B) in Table 1 were mixed with red. 5 parts by weight of phosphorus (Nova Excel 140) is dry-blended and melt-kneaded at a melting point of liquid crystalline polyester (B) + 15 ° C. using a twin screw extruder of 30 mmφ to obtain pellets of red phosphorus high concentration product (D2). Was. Next, the liquid crystalline polyesters (A), (B) and (D1) at the ratios shown in Table 1
Or (D2) and glass fiber (6 μm diameter, 3 mm length)
Was dry-blended and melt-kneaded at a cylinder temperature of Table 1 using a 30 mmφ twin screw extruder to obtain pellets.
This pellet is used for Sumitomo Nestal injection molding machine Promat 4
0/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and a test piece was molded at a cylinder temperature shown in Table 1 and a mold temperature of 90 ° C. by a method for each evaluation item.

As is clear from Table 1, the composition of the present invention is excellent in fluidity, impact resistance and thin-walled flame retardancy as compared with Comparative Examples, and has no physical property deterioration due to deformation and stagnation of molded articles. In addition, since the molded article has good long-term heat resistance, it can be seen that the molded article is extremely excellent in obtaining a molded article having a thin portion.

[0074]

[Table 1]

[0075]

The liquid crystalline resin composition of the present invention has fluidity,
It has excellent impact resistance and thin-walled flame retardancy, and especially has high heat stability, so it is suitable for various applications such as electrical and electronic related equipment, precision machinery related equipment, office equipment, automobile, etc. where these characteristics are required. Material.

Claims (9)

[Claims] (1) 99.5 to 0.5% by weight of a liquid crystalline resin (A)
And liquid crystalline resin (B) having a structure different from that of (A) 0.5 to 9
A liquid crystalline resin composition comprising 100 parts by weight of a resin composition (C) consisting of 9.5% by weight and 0.01 to 30 parts by weight of red phosphorus. 2. The red phosphorus has a conductivity of 0.1 to 1000 μS / c.
The liquid crystalline resin composition according to claim 1, wherein m is m. 3. The liquid crystalline resin composition according to claim 2, further comprising 0.5 to 300 parts by weight of a filler per 100 parts by weight of the resin composition (C). 4. The liquid crystalline resin composition according to claim 1, wherein the liquid crystalline resin (A) contains an ethylenedioxy unit. 5. The liquid crystalline resin composition according to claim 1, wherein the liquid crystalline resin (B) is a wholly aromatic liquid crystalline polyester resin. 6. The liquid crystalline resin composition according to claim 1, which has a flame retardancy of V-0 when measured at a thickness of 1/64 inch in the UL-94 standard. 7. A part or all of the liquid crystal resin (A), a part or all of the liquid crystal resin (B), or a part of (A) and (B) finally contained and red The liquid crystalline resin according to any one of claims 1 to 6, wherein the resin composition 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 liquid crystalline resin composition. A method for producing a liquid crystalline resin composition, which comprises producing a composition. 8. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 6, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. . 9. The molded article according to claim 8, wherein a thin portion having a thickness of 0.8 mm or less has at least 10% of the total surface area of the molded article.