JPH03290460A - Molding liquid crystalline polyester carbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a molding resin composition having excellent mechanical properties and heat resistance and good surface state by blending a liquid crystalline polyester carbonate resin with mineral fibers as an essential component and inorganic fibers arbitrarily containing glass fibers. CONSTITUTION:A molding resin composition especially suitable for injection molding, comprising (A) 95-20wt.% liquid crystalline polyester carbonate resin, preferably resin composed of a: aromatic hydroxycarboxylic acid residue, b: aromatic diol residue, c: carbonate residue, d: aromatic dicarboxylic acid residue, having a molar ratio satisfying formula I to formula III, (B) 5-80wt.% inorganic fibers consisting essentially of B1: 5-100wt.% mineral fibers (e.g. rock wool or ceramic fibers), preferably ground fibers having 20-500mum average fiber length, 2-10mum average fiber diameter and 5-100 aspect ratio and B2: 95-0wt.% glass fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a moldable liquid crystalline polyester carbonate resin composition containing inorganic fibers as a reinforcing material. More specifically, the present invention relates to an inorganic fiber-reinforced liquid crystalline polyester carbonate resin composition for molding, which has excellent mechanical properties and heat resistance and has a good surface condition when used for bottom shapes.

Conventional technology In recent years, a large number of thermoplastic polymers with various new properties have been developed and put on the market. Among them, thermotropic liquid crystalline polyester has a high degree of molecular orientation that occurs during molding in the flow direction. It has attracted much attention because it provides excellent mechanical properties. Many of these liquid crystalline polyesters are made of glass fiber or carbon fiber in order to alleviate the anisotropy of mechanical properties caused by molecular orientation and obtain structural materials with a good balance between mechanical properties and anisotropy. Fillers such as talc and calcium carbonate in the form of fine powder blocks or scales are commercially available singly or in combinations of two or three.

However, although it has been recognized that adding various fillers to liquid crystalline polyester has the effect of achieving a balance between mechanical properties and its anisotropy, many mechanical properties are not affected by the anisotropy. Since the deterioration due to the relaxation effect is offset by the improvement due to the reinforcing effect of the filler, only an insufficient improvement effect is obtained.

In particular, tensile strength usually does not improve with the addition of fillers, and in some cases it actually decreases (Naoyuki Koide, ed., "Liquid Crystal Polymers - Synthesis, Molding, Applications", CMC (1987)) ) Furthermore, when a large amount of the above-mentioned filler is blended into liquid crystalline polyester, there arises the problem that the surface condition of the molded product deteriorates, resulting in poor appearance.

On the other hand, thermotropic liquid crystalline polyester carbonates are also being researched because they are expected to have specificity due to their high degree of molecular orientation (Japanese Patent Laid-Open Nos. 55-118923, 1999-153720, etc.). However, no prior art has been able to find a liquid crystalline polyester carbonate compounded with a filler as described above.

Problems to be Solved by the Invention The present invention is directed to an inorganic material having excellent mechanical properties and heat resistance as well as a good surface condition when made into an injection molded product.
! 1#I Reinforced Resin This is a reinforced resin composition.

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors found that if the basic resin is liquid crystalline polyester carbonate, it is possible to fill it with inorganic fibers when it is made into an injection molded product. We have arrived at the present invention by discovering that an inorganic male-reinforced composition can be obtained which has superior mechanical properties and heat resistance as well as a good surface condition.

That is, the present invention provides liquid crystalline polyester carbonate resin 9
The composition is mainly composed of 5 to 20% by weight and 5 to 80% by weight of inorganic fibers, and 5 to 100% by weight of the inorganic fibers are minerals ml! i, and the remaining 95 to 0% by weight is glass fiber.

The present invention will be explained in detail below.

The liquid crystal polyester carbonate resin in the present invention is a moldable thermotropic liquid crystal polyester carbonate that exhibits optical anisotropy when melted.

The nature of the anisotropic melt phase can be confirmed by conventional polarization testing using crossed polarizers.

More specifically, the anisotropic melt phase can be confirmed by observing a sample placed on a hot stage using a polarizing microscope.

The liquid crystalline polyester carbonate resin in the present invention is ■Aromatic oxycarboxylic acid residue ■Aromatic diol residue ■Carbonic acid residue ■Aromatic dicarboxylic acid residue The molar ratio is 0≦a/(a+b)≦0.99 0, O1≦c/(c+d)≦1.0 a+d>0 It is preferable that

In the present invention, component (1) consists of an aromatic oxycarboxylic acid residue.

The aromatic oxycarboxylic acid used as a raw material is, for example, p-oxybenzoic acid or its nuclear M-converted derivative (for example, a halogen atom such as a chlorine atom or a bromine atom, a lower alkyl group such as a methyl group or an ethyl group, or a methoxy group). , p-oxybenzoic acid derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or group such as an alkoxy group such as an ethoxy group), or p-oxybenzoic acid derivatives in which part or all of p-oxybenzoic acid is substituted with other aromatic Oxycarvone! (For example, m-oxybenzoic acid, oxynaphthoic acid, oxydiphenylcarboxylic acid, and their nuclear substituted derivatives, etc.).

Examples of p-oxybenzoic acid and its nuclear substituted derivatives include p-oxybenzoic acid, 3-chloro-4-oxybenzoic acid, 3-bromo-4-oxybenzoic acid, 3-bromo-4-oxybenzoic acid,
Methyl-4-oxybenzoic acid, 3-methoxy-4-oxybenzoic acid, 3,5-dichloro-4-oxybenzoic acid,
Includes 3,5-dibromo-4-oxybenzoic acid and the like.

Component (2) consists of aromatic diol residues.

The aromatic diol that is the raw material for component (1) is, for example, dioxydiphenyl or its nuclear-substituted derivatives (such as chlorine atom, bromine atom, etc./\rogen atom, methyl group,
dioxydiphenyl derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or functional group such as a lower alkyl group such as an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a phenyl group), and hasyoxy Part or all of the diphenyl can be replaced with other aromatic diols (
For example, hydroquinone, resorcinol, dioxynaphthalene, bis(hydroxyphenyl) sulfide, bis(hydroxyphenyl) ether, bis(hydroxyphenyl) ketone, bis(hydroxyphenyl) sulfoxide, bis(hydroxyphenyl) sulfone, 4,4'- Bis(hydroxyphenyl)diisopropylbenzene, 2
．． 2-bis(4-hydroxyphenyl)propane, l.

1-bis(4-hydroxyphenyl)cyclohexane and their nuclear substituted derivatives, etc.), or aliphatic diols (e.g. ethylene glycol, neopentyl glycol, etc.) and alicyclic diols (e.g. cyclohexane dimethylol) within a range that does not impair liquid crystallinity. , cyclohexane diol, etc.).

Examples of dioxydiphenyl and its nuclear-substituted derivatives include dioxydiphenyl, dioxydiphenyl chloride, and dioxydiphenyl bromide.

Includes methyldioxydiphenyl, methoxydioxydiphenyl, phenyldioxydiphenyl, and the like.

■Component consists of carbonic acid residues.

Compounds providing this carbonic acid residue include, for example, diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, phenyltolyl carbonate and dinaphthyl carbonate, and/or compounds such as diethyl carbonate, dimethyl carbonate, dimethyl dicarbonate and diethyl dicarbonate. These include dialkyl carbonates, glycol carbonates, and the like.

Component (2) consists of aromatic dicarboxylic acid residues.

The aromatic dicarboxylic acid residue has 8 to 24 carbon atoms, and up to 4 01 to C4 per aromatic ring.
It may be substituted with an alkyl group, a 01-C4 alkoxy group or a halogen atom, such as naphthalene-1,5-dicarboxylic acid, diphenyl-2,2°-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenylmethane -4,4'-dicarboxylic acid, diphenyl ether-4,4''-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid and their nuclear substituted derivatives etc. are included.

In addition, a part of component (2) may be replaced with a residue of an aliphatic dicarboxylic acid such as succinic acid, adipic acid, etc., or an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, within a range that does not impair liquid crystallinity.

The molar ratio of the respective powers of the liquid crystalline polyester carbonate resin consisting of the above components (■, ■, ■, and ■) used in the present invention is 0≦a/(a+b)≦0.93 0, O1≦c/(c+d)≦ 1. It is preferable that O a+d>0, but more preferably 0.01≦a
/(a+b) ≦0.390.01≦c/(c+d)
It is preferable to satisfy ≦1.0.

The liquid crystalline polyester carbonate resin in the present invention can be obtained by a conventional polyester polycondensation method.

Mineral fibers used in the present invention include rock wool,
Examples include ceramic fibers.

Among these, rock wool usually has a Ca020-45
% by weight, 5i0230-50% by weight, and A1120
The main component is 35 to 20% by weight, and other components such as MgO are also contained in the skin. Rockwool is usually made of basalt, andesite,
It is made into fibers by melting naturally occurring rocks such as diabase and blast furnace slag, which is a by-product during iron manufacturing, and usually has a fiber length of several cm to several centimeters and a particle content of 30 to 40 cm. It is about % by weight.

Further, ceramic fiber is a general term for silica fiber, alumina fiber, silica alumina fiber, etc.

Such mineral fibers are crushed to have an average fiber length (L) of 2.
0 to 500 μm, preferably 70% by weight or more of 50 μm
~200 pm, average fiber diameter (D) of 2 to 10 gm, preferably 70% by weight or more of it is 3 to 5 gm, and average aspect ratio (L/D) of 5 to 100, preferably 10 to 60. It is best to prepare it as follows.

If the average fiber length is less than 20 gm or the average fiber diameter is less than 2 μm, the effect as a reinforcing material is small.

Furthermore, if the average fiber length exceeds 500 μm or the average fiber diameter exceeds logm, the surface condition when the composition is made into an injection molded product etc. tends to be poor.

Crushing of mineral fibers means cutting or crushing mineral fibers, and can be crushed using a rotating disc type crusher, a compression crusher, an opposed roll type crusher, or the like. As the crushing method, a grinding method is preferable.

As the crushed mineral fibers used in the present invention, it is particularly preferable to use crushed mineral fibers that have been crushed with a crusher as described above and then classified into fibers and particles using an air classifier. It is also possible to use surfaces treated with a coupling agent such as a silane type or titanate type, or a coating agent made of a low-molecular organic compound or a high-molecular compound.

The glass am blended into the liquid crystal polyester carbonate resin together with the above mineral fibers are Can, 5i02 and A
Main component is 12O3, usually CaO10-20
1i amount%, 5i0250-70% by weight, and M2O32
Although it is preferable that the content is 15% by weight, there is no restriction on the composition as long as it can be used as a reinforcing material for resins.

In addition, the fiber surface may be treated with a coupling agent such as a silane type or titanate type, a coating agent made of a low-molecular organic compound or a high-molecular compound, or an acid, or may not be surface-treated. Glass fibers coated with metals such as nickel and copper can also be used.

The shape may be am-shaped (either roving or chopped strands may be used, and hollow glass fibers may also be used. The size is usually an average mIl length (L) for ease of kneading. 1-10+am, average fiber diameter (
D) is preferably 5 to 20 gm, preferably 10 to 15 μm, and has an average aspect ratio (L/D) of 50 or more.

In the present invention, the blending ratio of fi weaving fibers to be blended into the liquid crystalline polyester carbonate resin varies depending on the type of liquid crystalline polyester carbonate resin used. %, but preferably 80 to 40% by weight of liquid crystalline polyester carbonate resin
It is preferable to mix inorganic m-fibers at a ratio of 20 to 60% by weight.

If the content of inorganic fibers in the composition is less than 5% by weight, the strength and heat resistance of the molded product obtained by molding the composition will hardly be improved; %, the melt viscosity of the composition in a molten state becomes extremely high, making it difficult to mold by injection molding or the like, and thus impractical.

The above-mentioned inorganic fibers may be used alone or in combination with mineral fibers and glass fibers.

Glass fiber alone can achieve the purpose of high strength, but the surface condition of the molded product is poor.The ratio between mineral fiber and glass fiber is 5 to 100% by weight, preferably 30 to 100% by weight, glass fiber! 85
-1% by weight of O, preferably 70-0% by weight. If the mineral fiber content is less than 5% by weight, the surface condition of the molded product will not be good.

The composition of the present invention includes: (1) thermotropic or liquid crystalline polymers other than liquid crystalline polyester carbonate resins, (2) thermoplastic resins that do not exhibit liquid crystallinity when melted, (2) thermosetting resins, (2) low-molecular organic compounds, and (2) inorganic substances. , (2) It may contain one or more types of m-fibers other than mineral m-fibers and glass fibers.

When the composition of the present invention contains at least one of ■, ■, or ■, the composition of ■, ■, or It is necessary to limit the blending ratio of at least one of these: If the liquid crystalline polyester carbonate resin does not form a continuous phase in the composition, molded products that have excellent mechanical properties, heat resistance, and a good surface condition. is not obtained.

When the composition of the present invention contains at least one of (1) or (2), mineral fibers, glass fibers, (1) and (2)
The blending temperature is such that mineral fiber is 5% by weight or more based on the total amount of (mineral fiber + glass m#l +
It is necessary to limit the sum of (i) + (i) to 85% by weight or less. If the mineral fiber content is less than 5% by weight, the surface condition of the molded product will not be good.

Examples of the above thermotropic liquid crystalline polymers include fully and non-fully aromatic polyesters, aromatic-aliphatic polyesters, aromatic polyazomethines, fully and non-fully aromatic polyester-amides, and the like.

Examples of the thermoplastic resin described in (■) above include polystyrene,
High impact polystyrene, AS resin, ABS resin, polydethylene, polypropylene, polyvinyl acetate, polyvinyl chloride, polyurethane, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyetherimide, polyamide imide, polyether ether Examples include ketone, polysulfone, polyphenylene sulfide, polyphenylene oxide, and the like.

Examples of the thermosetting resin (2) above include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, and the like.

The low-molecular organic compounds mentioned in (2) above include low-molecular organic compounds commonly used in plasticizers, stabilizers such as antioxidants and ultraviolet absorbers, flame retardants, colorants such as dyes and pigments, and lubricants.

The above inorganic substances include known inorganic fillers such as talc, calcium carbonate, calcium sulfate, mica, silicate, barium sulfate, kaolin, calcined ray, zeolite, bentonite, magnesium carbonate, iron oxide, zinc oxide, titanium. acid potassium, wollastonite, glass peas,
Contains glass powder, graphite, graphite, etc.

Fibers other than mineral fibers and glass fibers mentioned in (1) above include carbon fibers, various metal fibers, and various f#4 fibers.
! These include JI fibers, various whiskers such as silicon nitride whiskers and Poron whiskers.

The composition in the present invention is manufactured by a known method that is generally used as a method for manufacturing conventional thermoplastic resin compositions. For example, after tri-blending liquid crystalline polyester carbonate resin and inorganic fibers, the liquid crystalline polyester carbonate resin is charged into a mixing machine and melted and kneaded. A method in which glass fibers are successively introduced and kneaded can be used.

The kneading machine is not particularly limited, and any commonly used screw extruder, 20-hole mixer, etc. may be used.

The liquid crystalline polyester carbonate resin composition for molding thus prepared can be molded into a desired product by ordinary extrusion molding, injection molding, etc., but it is more preferable to use injection molding, for this reason: This will be explained below.

The reason why molded products obtained from the composition of the present invention exhibit better mechanical properties and heat resistance than those not filled with inorganic fibers has not yet been elucidated. This is thought to be due to the specificity of the crystal structure. When liquid crystalline polyester carbonate resin is molded, a high degree of molecular orientation similar to that of liquid crystalline polyester resin occurs along the flow direction, but in the former case, the molecules are packed slightly more sparsely than in the latter case, resulting in less alignment. Structural analysis has confirmed that the order is poor.

When the composition of the present invention is molded into a desired product, the inorganic fibers are successfully combined with the slightly disordered crystal structure of the liquid crystalline polyester carbonate resin, resulting in a synergistic reinforcing effect due to the complex orientation of one molecule and the inorganic fibers. appears, and it is thought that improvements in physical properties can be achieved.

The injection molding method is desirable because molecules and inorganic fibers tend to be oriented as described above due to large shear flow and elongation flow during molding.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Example 1 70.1 parts by weight of P-hydroxybenzoic acid, 63 parts by weight of 4,4"-dihydroxydiphenyl, 21 parts by weight of diphenyl carbonate
7 parts by weight, and 2 n-butylstanoic acid as a reaction catalyst.
．． 45×10 −5 parts by weight were charged into a polymerization reactor equipped with a stirrer and a vacuum distillation apparatus, the pressure was set at 650 mmHg, and the mixture was heated to 200° C. in a nitrogen stream. The reaction temperature was gradually raised to 320° C. over 2 hours and 30 minutes, and phenol was further distilled off. Then, gradually increase the pressure to 0.8 m
The reaction was reduced to mHH and carried out for 1 hour.

After the reaction is complete, light brown polyester carbonate resin (
Resin ■) was obtained. The transition temperature from the crystalline phase to the liquid crystalline phase of the obtained resin (1) was determined by differential scanning calorimetry (DSC) at 2.
The temperature was 66°C, and an optically anisotropic phase was observed at 260°C or higher under a polarizing microscope. After drying the resin (1) at 140° C. for 8 hours, it was used as a cross-wire material.

The inorganic fibers used for R kneading with resin ■ and their blending ratio,
This is shown in the following (A) and (B).

(A) 70 parts by weight of resin, 30 parts by weight of ground rock wool (average awi length 120 μm, average Iara diameter 4 μm, aspect ratio 20-40, particle content of 106 gm or more in diameter 1% by weight or less), and antioxidant (IRGANOX-8215 manufactured by Ciba Geigy) 0.07 parts by weight.

(B) If resin ■70ji (Okibe, 15 parts by weight and 0.07 parts by weight of the same ground rock wool and antioxidant as in (A), respectively, and glass fiber!i (chopped by Asahi Fiberglass Co., Ltd.) Dostrand C5-03-HA-429A
, average diameter 13 JLm, average length 3 mm) 15 parts by weight.

The tri-blends having the blending ratios of (A) and (B) above were respectively charged into a delta type two-blade mixer,
After mixing at 280° C. for 5 minutes, it was extruded into strands and cut into pellets.

The pellets of the obtained composition were dried at 140°C for 8 hours,
Using an injection molding machine with a mold clamping force of 12 tons, the barrel temperature was 28
A No. 1 (1/2) type small tensile test piece conforming to JIS-7113 was molded at 0° C. and a mold temperature of 100° C., and the tensile strength was measured. Also, under the same molding conditions, 12711! lX1
2.? +sm, thickness 3゜2II11 flat plate is formed, A
Bending strength and heat distortion temperature (bending stress 18.5kHz/cm2) in accordance with STM-0790 and ASTM-0648
were measured respectively.

Furthermore, the surface condition of these test pieces was visually observed as ■=
Evaluation was made using a four-level evaluation system: excellent, O: good, Δ: average, and ×: bad. The results are shown in Table 1.

Comparative Example 1 Tri-blends having the following blending ratios (a), (b), and (c) were mixed and molded in the same manner as in the actual grave example.

(a) 100 parts by weight of the resin (1) synthesized in Example 1, and 0.1 parts by weight of the same antioxidant as in Example 1.

(b) 97 parts by weight of resin, 3 parts by weight each of the same ground rock wool and antioxidant as in Example 1, and 0.
087 parts by weight.

(c) 70 parts by weight of resin, 30 parts by weight each of the same glass fiber and antioxidant as in Example 1, 0.07
Weight part.

The tensile strength 1 bending strength and heat deformation temperature (bending stress 18.5 kg/cm2) of the obtained injection molded piece were measured by the same physical property measuring method as in Example 1, respectively. Further, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 1.

The results are shown in Table 1.

Table 1 Example 2 46.1 parts by weight of p-hydroxybenzoic acid, 82.2 parts by weight of 4,4'-dihydroxydiphenyl, 172 parts by weight of diphenyl carbonate, and 4.24 x 10-5 parts by weight of n-butylstanoic acid as a reaction catalyst. of the polymerization reactor equipped with a stirrer and a vacuum distillation device, and the pressure was increased to 850 mrsH.
g and heated to 200° C. in a nitrogen stream. The reaction temperature was gradually raised to 320°C over 2 hours and 40 minutes,
Further phenol was distilled off. Then gradually reduce the pressure to 0.
．． The reaction temperature was reduced to 8 mmHH and the reaction was carried out for 1 hour.

After the reaction was completed, a pale reddish-purple polyester carbonate resin (resin ■) was obtained. The transition temperature from the crystal phase to the liquid crystal phase of resin ① was determined by differential scanning calorimetry (DSC) to 286
℃, and an optically anisotropic phase was observed at 295°C or higher under a polarizing microscope.

After drying the resin (1) at 140° C. for 8 hours, it was used as a cross-wire material.

The P loom fiber used for cross-fertilization with resin■ and its blending ratio are as follows:
This is shown in the following (C:) and (D).

(C) 70 parts by weight of resin, 30 parts by weight of the same ground rock wool and antioxidant as in Example 1, and 0
．． 7 parts by weight.

(D) 70 parts by weight of resin (1), 15 parts by weight, 15 parts by weight, and 0.07 parts by weight of the same ground rock wool, glass #i fiber, and antioxidant as in Example 1, respectively.

The above triblends having the blending ratios of (C) and (D) were prepared in the same manner as in Example 1 to give 310%
The mixture was melt-kneaded at ℃ for 5 minutes.

The pellets of the obtained composition were dried at 140°C for 8 hours,
A small 1 (1/2) matrix tensile test piece was molded using the same method as in Example 1 at a barrel temperature of 310°C and a mold temperature of 100°C, and the tensile strength was measured. Also, under the same molding conditions, 12
A flat plate of 7+wm
g/c+w2) were measured. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 1.

The results are shown in Table 2.

Comparative Example 2 Triblends having the following blending ratios (d), (e), and (f) were kneaded and molded in the same manner as in Example 2.

(d) 100 parts by weight of the resin (1) synthesized in Example 2, and 0.1 parts by weight of the same antioxidant as in Example 2.

(e) Resin ■97 parts by weight, the same ground rock wool and antioxidant as in Example 2, 3 parts by weight each, and 0.
097 parts by weight.

(f) Resin ■70 parts by weight, the same glass fiber and antioxidant as in Example 2, 30 parts by weight each, 0.07
Weight part.

The tensile strength, bending strength, and thermal deformation temperature (bending stress 18.5 kg/ctm2) of the obtained injection molded piece were measured using the same physical property measuring method as in Example 2. Also,
The surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 2.

The results are shown in Table 2.

(Margin below) Table 2 (Note) Evaluation of surface condition O: Excellent, O: Good, Δ: Shinto, X: Bad Example 3 P-hydroxybenzoic acid 88.1 parts by weight, 4,4' - 38.2 parts by weight of dihydroxydiphenyl, 178 parts by weight of diphenyl carbonate, and 3.76 x 10-5 parts by weight of n-butylstanoic acid as a reaction catalyst were charged into a polymerization reactor equipped with a stirrer and a vacuum distillation device, and the pressure was adjusted to f150 msH.
g and heated to 200° C. in a nitrogen stream. The reaction temperature was gradually raised to 320°C over 2 hours and 40 minutes,
Further phenol was distilled off. Then gradually reduce the pressure to 0.
．． 7 mm) [H and the reaction was carried out for 1 hour.

After the reaction was completed, a pale reddish-purple polyester carbonate resin (resin ■) was obtained. The transition temperature from the crystalline phase to the liquid crystalline phase of the obtained resin (1) was determined by differential scanning calorimetry (DSC
) to 290°C, and an optically anisotropic phase was observed at 282°C or higher under a polarizing microscope.

After drying the resin (1) at 140° C. for 8 hours, it was used as a cross-wire material.

The inorganic fibers used for cross-wire with resin ■ and their blending ratio are
It is shown in the following (E), CF).

(E) 70 parts by weight of resin, 30 parts by weight of the same ground rock wool and antioxidant as in Example 1, and 0
．． 07 parts by weight.

(F) Resin ■70 parts by weight, the same ground rock wool and glass fiber as in Example 1! 15 parts by weight, 15 parts by weight, and 0.07 parts by weight of I5 antioxidant, respectively.

Tri-blends having the blending ratios of (E) and (F) above were prepared in the same manner as in Example 1.

The mixture was melt-kneaded at 305°C for 5 minutes.

The resulting pellet of composition was dried at 140°C for 8 hours,
By the same method as in Example 1, a small 1 (1/2) stationary type tensile test piece was molded at a barrel temperature of 305°C and a mold temperature of 100°C, and the tensile strength was measured. In addition, the same molding conditions Te12
7mmX 12.7+yw, thickness 3.2m+* (7)
A flat plate is formed, and the bending strength and heat deformation temperature (bending stress 18.
5 kg/c1) was measured for each. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 1.

The results are shown in Table 3.

Comparative Example 3 Triblends having the following blending ratios (g), (h), and (j) were mixed and molded in the same manner as in Example 3.

(g) 100 parts by weight of the resin synthesized in Example 3, and 0.1 parts by weight of the same antioxidant as in Example 3.

(h) 97 parts by weight of resin, 3 parts by weight of the same ground rock wool and antioxidant as in Example 3, and 0.
097 parts by weight.

(j) 70 parts by weight of resin, 30 parts by weight of the same glass m fiber as in Example 3, and 0.07 parts of antioxidant, respectively.
Weight part.

The tensile strength 1 bending strength and heat deformation temperature (bending stress 18.5 kg/c+a2) of the obtained injection molded piece were measured by the same physical property measuring method as in Example 3, respectively. Also,
The surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 3.

The results are shown in Table 83.

@: I'm arrogant. O: Good, Δ: Fair, ×: Bad Example 4 55.2 parts by weight of p-hydroxybenzoic acid, 49.7 parts by weight of 4.4'-dihydroxydiphenyl, 154 parts by weight of diphenyl carbonate, 11.1 parts by weight of terephthalic acid. and 1.94XlO-5 parts by weight of n-butylstanoic acid as a reaction catalyst were charged into a polymerization reactor equipped with a stirrer and a vacuum distillation apparatus, and the pressure was set at 150 mmHg and the temperature was raised to 200 °C in a nitrogen stream. Heated. The reaction temperature was gradually raised to 320° C. over 2 hours and 50 minutes, and phenol was further distilled off. Then, the pressure was gradually reduced to 0.6 su+Hg, and the reaction was carried out for 1 hour.

After the reaction is complete, light brown polyester carbonate resin (
Resin ■) was obtained. The transition temperature from the crystal phase to the liquid crystal phase of the obtained resin (1) was determined by differential scanning calorimetry (DSC).
The temperature was 15°C, and an optically anisotropic phase was observed at 315°C or higher even under a polarizing microscope. After drying the resin (1) at 140° C. for 8 hours, it was used as a cross-wire material.

The inorganic miscellaneous material used for kneading with resin ■ and its blending ratio are as follows:
This is shown in the following (G) and ()l).

(G) 70 parts by weight of resin, 30 parts by weight of the same ground rock wool and antioxidant as in Example 1, and 0
．． 07 parts by weight.

(H) 70 parts by weight of resin, 1 part each of the same ground rock wool, glass fiber, and antioxidant as in Example 1.
5 parts by weight, 15 parts by weight, 0.07 parts by weight.

Tri-blend products having the above blending ratios of (G) and (H) were prepared in the same manner as in Example 1 to give 330%
The mixture was melt-kneaded at ℃ for 5 minutes.

The resulting pellet of composition was dried at 140°C for 8 hours,
A size 1 (1/2) small tensile test piece was molded using the same method as in Example 1 at a barrel temperature of 330°C and a mold temperature of 100°C, and the tensile strength was measured. Also, under the same molding conditions, 1
A flat plate of 27 mm x 12.7 + sm and thickness 3.20 was formed, and the bending strength and heat deformation temperature (bending stress 18.5 kg/
C2) were measured respectively. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 1.

The results are shown in Table 4.

Comparative Example 4 Triblends having the following blending ratios (k), (1), and (m) were kneaded and molded in the same manner as in Example 4, respectively.

(k) 100 parts by weight of the resin (1) synthesized in Example 4, and 0.1 parts by weight of the same antioxidant as in Example 4.

(1) 97 parts by weight of resin, 3 parts by weight of the same ground rock wool and antioxidant as in Example 4, and 0.
097 parts by weight.

(Seal) 70 parts by weight of resin, 30 parts by weight each of the same glass fiber and antioxidant as in Example 4, 0.07
Weight part.

The tensile strength, bending strength, and heat deformation temperature (bending stress 18.5 kg/cl) of the obtained injection molded piece were measured using the same physical property measuring method as in Example 4. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 4.

The results are shown in Table 4.

(Margin below) Table 4 Example 5 55.2 parts by weight of p-hydroxybenzoic acid, 49.7 parts by weight of 4.4'-dihydroxydiphenyl, 163 parts by weight of diphenyl carbonate, 5.54 parts by weight of isophthalic acid, and reaction An overlapping portion of n-butylstanone st and 5axto-s as a catalyst was placed in a polymerization reactor equipped with a stirrer and a vacuum distillation device, the pressure was set at Ei 50 mmHH, and the mixture was heated to 200° C. in a nitrogen stream. The reaction temperature was gradually raised to 320° C. over 2 hours and 30 minutes, and phenol was further distilled off. Then, the pressure was gradually reduced to 0.8 mmHg, and the reaction was carried out for 1 hour.

After the reaction is complete, light brown polyester carbonate resin (
Resin ■) was obtained. The transition temperature from the crystalline phase to the liquid crystalline phase of the obtained resin (1) was determined by differential scanning calorimetry (DSC) at 2.
The temperature was 20°C, and an optically anisotropic phase was observed at 218°C or higher under a polarizing microscope. After drying the resin (1) at 100° C. for 8 hours, it was used as a cross-wire material.

The sIa fibers used for intermixing with resin (2) and their blending ratios are shown in (J) and (K) below.

('') 701 parts by weight of resin ■, 30 parts by weight each of the same ground rock wool and antioxidant as in Example 1,
0.07 parts by weight.

(K) 70 parts by weight of resin (1), 30 parts by weight, 10 parts by weight, and 0.07 parts by weight of the same ground rock wool, glass mis, and anti-# formation agent as in Example 1, respectively.

The above triblends having the blending ratios of (J) and (K) were prepared in the same manner as in Example 1 to give 240%
The mixture was melt-kneaded at ℃ for 5 minutes.

The pellets of the obtained composition were dried at 120°C for 8 hours,
By the same method as in Example 1, a small 1 (1/2) stationary type tensile test piece was molded at a barrel temperature of 240°C and a mold temperature of 100°C, and the tensile strength was measured. Also, under the same molding conditions, 12
A flat plate of 7 mm x 12.7 mm and 3.2 cm thick was formed, and the bending strength and heat distortion temperature (bending stress 18.5 kg/C1
) were measured respectively. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 1.

The results are shown in table s5.

Comparative Example 5 Triblends having the following blending ratios (31), (p), and (q) were mixed and molded in the same manner as in Example 5, respectively.

(Xl) 100 parts by weight of the resin (1) synthesized in Example 5, and 0.1 parts by weight of the same antioxidant as in Example 5.

(p) Resin ■97 parts by weight, the same ground rock wool and antioxidant as in Example 5, 3 parts by weight each, and 0
．． 097 parts by weight.

(q) 70 parts by weight of resin, 30 parts by weight of the same glass mIIj1 as in Example 5 and antioxidant, 0
．． 07 parts by weight.

The tensile strength, bending strength, and heat deformation temperature (bending stress 18.5 kg/cm2) of the obtained injection molded piece were measured using the same physical property measuring method as in Example 5. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 5.

The results are shown in Table 5.

Table 5 ■: Excellent, O: Good, Δ: Fair, ×: Bad Example 6 Methylhydroquinone 48.6 parts by weight, diphenyl carbonate 2
23 parts by weight, 46.5 parts by weight of terephthalic acid, and n-butylstanone @ 1.1l18X 10 as a reaction catalyst.
-5 parts by weight were charged into a polymerization reactor equipped with a stirrer and a vacuum distillation apparatus, the pressure was set at 650 mmHH, and the mixture was heated to 200° C. in a nitrogen stream. The reaction temperature was gradually raised to 320° C. over 2 hours and 30 minutes, and phenol was further distilled off. Then, the pressure was gradually reduced to 0.6 m+*Hg and the reaction was carried out for 1 hour.

After the reaction is complete, light brown polyester carbonate resin (
Resin ■) was obtained. The transition temperature from the crystalline phase to the liquid crystalline phase of the obtained resin (1) was determined by differential scanning calorimetry (DSC) at 2.
80°C, and an optically anisotropic phase was observed at 280°C or higher under a polarizing microscope. After drying the resin (1) at 140° C. for 8 hours, it was used as a cross-wire material.

1 used for kneading with resin■! ! The mechanical w/i cone and its blending ratio are shown in the following (L) and (M).

(L) 70 parts by weight of resin, 30 parts by weight of the same ground rock wool and antioxidant as in Example 1, and 0
．． 07 parts by weight.

(N) 1 part of resin ■70i, 3 parts each of the same ground rock wool, glass fiber, and antioxidant as in Example 1.
0 parts by weight, 10 parts by weight, 0.07! ! U quantity part.

Tri-blends having the above blending ratios of (L) and (M) were prepared in the same manner as in Example 1 to give 285%
The mixture was melt-kneaded at ℃ for 5 minutes.

The resulting pellet of composition was dried at 140°C for 8 hours,
A size 1 (1/2) type small tensile test piece was molded using the same method as in Example 1 at a barrel temperature of 295°C and a mold temperature of 100°C, and the tensile strength was measured. Also, under the same molding conditions, 12
? Sn
Seal 2) was measured respectively. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 1.

The results are shown in Table 6.

Comparative Example 6 Triblends having the following blending ratios of (r), (s), and (t) were mixed and molded in the same manner as in Example 6.

(r) 100 parts by weight of the resin (1) synthesized in Example 6, and 0.1 parts by weight of the same antioxidant as in Example 6.

(s) Resin ■97 parts by weight, the same ground rock wool and antioxidant as in Example 6, 3 parts by weight each, and 0.
097 parts by weight.

(1) 70 parts by weight of resin, 30 parts by weight of each of the same glass fiber and antioxidant as in Example 6, 0.07
Weight part.

The tensile strength, bending strength, and heat deformation temperature (bending stress 18.5 kg/cm2) of the obtained injection molded piece were measured using the same physical property measuring method as in Example 6. Furthermore, the surface condition of these test pieces was evaluated using the same four-level evaluation method as in Example 6.

The results are shown in Table 6.

(Margin below) Table 6 Comparative Example 7 A zero-order ( U), (Ma),
(The tri-blends having the compounding ratio of

(u) EPE-220 tree p! ! 70 parts by weight, 30 parts by weight of the same ground rock wool as in Example 1.

(Ma) 70 parts by weight of EPE-220 resin, 1 part of each of the same ground rock wool and glass fiber as in Example 1.
5 parts by weight.

(70 parts by weight of EPE-220 resin, Example 1 (7
) 30 parts by weight of glass fiber as in the case.

The tensile strength of the obtained injection molded pieces was measured by the same physical property measuring method as in Example 1.

Furthermore, the surface conditions of these test pieces were evaluated using the same four-level evaluation method as in Example 1.

The results are shown in Table 7.

Table 7 ■ = Excellent, 0: Good, Δ: Fair, ×: Bad From Tables 1 to 6, molded products obtained from the compositions of the present invention (A-M in Examples) , as well as having good surface condition? ! In the case where A texture loom is not blended at all (a, d, g, k, n, r in the comparative example) or when the content of inorganic fiber is extremely small (s, e, h, 1 in the comparative example). p,
It can be seen that the strength and heat distortion temperature are significantly improved compared to s).

In addition, the molded products obtained from the compositions of the present invention (A-M in the examples) were better than those in which only glass fiber was blended (c, f, j, m, q, t in the comparative examples). It can be seen that a much better surface condition can be obtained.

Table 7 shows comparative examples in which liquid crystalline polyester resin was used instead of liquid crystalline polyester carbonate resin.

It can be seen that even if inorganic fibers are blended into the liquid crystalline polyester resin at the blending ratio limited by claim (1) of the present invention, the strength is not improved.

Effects of the Invention As is clear from the above explanation, the composition of the present invention not only has a good surface condition when made into an injection molded product, but also has a significantly improved surface condition compared to the case where no inorganic fiber is blended. Since molded products with strength and heat resistance can be obtained, it is expected to have a wide range of industrial applications as an extremely superior structural material never seen before.

Claims (1)

[Claims] (1) Liquid crystalline polyester carbonate resin 95-20
% by weight and 5-80% by weight of inorganic fibers, 5-100% by weight of the inorganic fibers are mineral fibers, and the remaining 95-0% by weight is glass fibers. Characteristic liquid crystalline polyester carbonate resin composition for molding. (2) The liquid crystalline polyester carbonate resin is [a]
Consists of aromatic oxycarboxylic acid residue [b] aromatic diol residue [c] carbonic acid residue [d] aromatic dicarboxylic acid residue, the molar ratio of which is 0≦a/(a+b)≦0.99 0. The liquid crystal polyester carbonate resin composition for molding according to claim 1, wherein 01≦c/(c+d)≦1.0 a+d>0. (3) The resin composition according to claim 1 or 2, wherein the mineral fibers are crushed mineral fibers having an average fiber length of 20 to 500 μm, an average fiber diameter of 2 to 10 μm, and an average aspect ratio of 5 to 100. (4) The resin composition according to claim 1 or 3, wherein the mineral fiber is rock wool or ceramic fiber.