JP3241482B2 - Composite resin composition for molding and molding method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite resin composition for molding for enhancing the compounding effect of a fibrous liquid crystal resin in a matrix resin and a molding method using the same.

[0002]

2. Description of the Related Art A thermoplastic resin is used as a matrix resin,
A certain amount of liquid crystal resin having a liquid crystal transition point higher than the minimum melting temperature of the matrix resin is blended into the mixture, and the mixture is melt-extruded to make the liquid crystal resin into fibers in the matrix resin, thereby resulting in physical properties such as tensile strength of the matrix resin. (See, for example, JP-A-64-90255). Since this composite resin has an advantage of being recyclable, it is attracting attention as a substitute for a fiber reinforced plastic (FRP) in which a matrix resin is reinforced with glass fibers or the like. It has been found that the physical properties of this liquid crystal resin composite change depending on the degree of fiberization of the liquid crystal resin, and improve as fiberization proceeds.
It is recommended to perform melt extrusion so that the liquid crystal resin has an aspect ratio of 3 or more in the matrix resin, and to stretch this (see FIG. 2).

[0003]

However, there is a limit in improving the physical properties of the composite resin by fibrillating the liquid crystal resin by stretching, and since the composite resin material becomes a thin fiber shape by stretching, these are formed into a bundle. It is necessary to provide a method for securing a constant and constant strand diameter as a material (Japanese Patent Application No. 4-7634). Therefore, the present invention aims to improve the physical properties of the liquid crystal resin composite by a method other than the above-described method of stretching, and thus a composite resin composition capable of improving the physical properties of a molded composite by adding a third component. The main purpose is to provide

[0004]

SUMMARY OF THE INVENTION The present invention has been accomplished by finding that the addition of a compatibilizer compatible with both a matrix resin and a liquid crystal resin improves the composite effect of the two. A composite resin composition comprising a matrix resin made of a resin and a liquid crystal resin having a liquid crystal transition temperature higher than the minimum melting temperature of the resin in a region where the liquid crystal resin can be made into a fiber, and further comprising the matrix resin and the liquid crystal. The composite resin composition for molding comprises a compatibilizer having compatibility with both resins in an amount such that the liquid crystal resin has an aspect ratio of 3 or more when the composite resin composition is melt-extruded.

The thermoplastic resins used in the present invention include ABS resin, polystyrene resin, polycarbonate resin, polyphenylene oxide resin, polyester resin,
Examples include polyarylate resin, polyamide resin, and mixtures thereof.

[0006] On the other hand, the liquid crystal resin is not particularly limited as long as it has a minimum melting temperature higher than that of the matrix resin, preferably higher than 20 ° C. Preferably, specifically, liquid crystal resins such as Vectra, Econol, Zyder and the like are commercially available.

[0007] The compounding of the liquid crystal resin with the matrix resin must be adjusted and compounded so that the entire composition has a region where the fiber can be converted into a phase inversion or less (see FIG. 1). For example, when the matrix resin is a polyamide resin, 40
80 to 80% by weight, 30 to 75% by weight for ABS (acrylonitrile butadiene-styrene copolymer) resin, and 3 to 70% for polycarbonate (PC) / ABS resin
% By weight, 2 to 60% by weight for PC / PBT resin, polyphenylene oxide (PP0) / nylon (PA6)
3 to 65% by weight for modified PPO resin and 3 to 65% for modified PPO resin.
60% by weight, 2-70% by weight for polypropylene,
The appropriate range is 3 to 70% by weight for polycarbonate and 10 to 70% by weight for PBT resin.

On the other hand, as a compatibilizer, when the matrix resin is an ABS resin, a polystyrene resin, a polycarbonate resin, or a polyphenylene oxide resin, the resin is modified with a compound having an epoxy group and / or an acid anhydride. For example, EGMA-g-PS, EGMA-g-AS,
It is preferable to use an acid anhydride-modified polystyrene or an N-substituted maleimide copolymer. In the case of a polyolefin resin, the polyolefin resin is also modified with a compound having an epoxy group and / or an acid anhydride as described above, for example, EGMA,
Preference is given to using EGMA-g-olefins. On the other hand, in the case of polyester resins and polyarylate resins, compounds having two or more epoxy groups, carboxyl groups, oxazolinyl groups, hydroxyl groups, etc., for example, acid anhydride-modified polyolefins, EGMA, epoxy resins, acid anhydride-modified polyesters, phenoxy Resins and the like are preferable, and in the case of polyamide resins, compounds having two or more epoxy groups, carboxyl groups, oxazolinyl groups, amino groups and the like, for example, EGMA, epoxy resins, acid anhydride-modified polyesters and the like are preferable. Preferred examples of the combination are as follows.

[Table 1]

The amount of the compound varies depending on the type of the matrix resin and the liquid crystal resin to be used. As shown in FIG. 3, however, as shown in FIG. Is improved, and the tensile strength due to the composite effect increases,
On the other hand, the surface tension at the interface between the matrix resin and the liquid crystal resin is reduced, and the liquid crystal resin is dispersed and stabilized in the matrix resin. Therefore, a compatibilizing agent is used in an amount such that the aspect ratio of the liquid crystal resin becomes 3 or more during melt extrusion.
Is preferably limited to a range in which the synergistic effect of the effect of improving the compatibility and the reinforcing effect of fiberization is exhibited.

A composition comprising the thermoplastic matrix resin, a liquid crystal resin having a liquid crystal transition temperature higher than the minimum melting temperature of the resin, and a compatibilizer has a temperature not lower than the liquid crystal transition point of the liquid crystal resin and the liquid crystal resin is a matrix resin. Extrusion is performed at a resin shear rate at which the liquid crystal resin has a fibrous shape with an aspect ratio of 3 or more, and the resin shear rate at the time of extrusion is 3
× 10 ² to 10 ⁵ sec ⁻¹ or more is preferable.
In addition, in order for the compatibilizer to be present at the interface between the liquid crystal resin and the matrix resin, a predetermined preliminary material is once formed with the liquid crystal resin and the compatibilizer, and this is formed into a matrix resin or a composite material of the matrix resin and the liquid crystal resin. This may be added to a liquid crystal resin or a composite material of a matrix resin and a liquid crystal resin.

Therefore, the present invention relates to a matrix resin composed of a thermoplastic resin or a mixture of the matrix resin and a liquid crystal resin having a liquid crystal transition temperature higher than the minimum melting temperature of the resin. The compatibilizer having solubility may be added alone, or a composite resin composition obtained by previously mixing the compatibilizer and the liquid crystal resin is added or mixed, or the compatibilizer and the matrix resin are mixed. And a composite resin composition obtained by pre-mixing the above components and mixing them. At a melting temperature not lower than the liquid crystal transition point, an apparent resin shear rate of 3 × 10 ² to 10 ⁵ sec ^−1.
And may be molded so that the aspect ratio of the liquid crystal resin is 3 or more. The extruded strand or the like may be cooled once or may be continuously subjected to a stretching treatment without cooling. In this case, the stretching ratio (cross-sectional area of extruded product / cross-sectional area after stretching) is preferably 11 or more and 120 or less. The stretched strand is cut into a predetermined size and used as a material for molding.

[0011]

According to the present invention, the compatibilizing agent is present at the interface between the matrix resin and the liquid crystal resin to increase the bonding strength between the two and to improve the compounding effect while reducing the aspect ratio of the liquid crystal resin to 3 when extruded. Because of the above holding, a sufficient fiber reinforcing effect can be obtained only by extrusion molding. In the composite of matrix resin and liquid crystal resin alone, the liquid crystal resin fibers are usually cut off during molding using the above-mentioned material, and the tensile strength after molding is reduced, but when the material of the present invention is used, the tensile strength is reduced even in the above-mentioned molding. Not only can provide a molding material excellent in moldability that does not show, but also a molded article excellent in physical properties can be molded.

[0012]

(Example 1) PA6 (trade name: Ube Nylon 1030B, manufactured by Ube Industries, Ltd.) as a matrix resin 40 parts by weight of an aromatic polyester (trade name: Vectra.A) as a liquid crystal resin
950, manufactured by Polyplastics Co., Ltd.) 60 parts by weight, epoxy resin as a third component (trade name: Epicron 7050,
(Manufactured by Dainippon Ink and Chemicals, Inc.) at the mixing ratio shown in Table 1 below, and using a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.) with a screw diameter of 30 mm and a resin temperature of 29.
Extrusion molding was performed while elongating at 0 ° C., a screw rotation speed of 75 rpm, a die diameter of 2 mm, and a shear rate of 1700 sec −1. The obtained strand-shaped composite (diameter 1.4 mm)
Is cut into a length of 3 mm to obtain a pellet material. Next, the pellet material was subjected to a resin temperature of 25 using an injection molding machine (220 tons, manufactured by Toshiba Machine Co., Ltd.) and a test piece mold.
At 0 ° C. and an injection pressure of 1000 kg / cm 2, a molded product was obtained. The tensile strength of the injection molded product was measured and is shown in Table 1. This was compared with the tensile strength at the time of the strand, but no decrease was observed.

[Table 2] Example 2 80 parts by weight of an aromatic polyester (trade name: Vectra A950, manufactured by Polyplastics Co., Ltd.) as a liquid crystal resin and ethylene-glycidyl styrene methacrylate copolymer as a third component (trade name: Modiper) A4100,
20 parts by weight of Nippon Oils & Fats Co., Ltd.) were mixed, and using a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.), the screw diameter was 30 mm, the resin temperature was 290 ° C., the screw rotation number was 75 rpm, and the die diameter was 2 mm. At a shear rate of 1700 sec-1, extrusion molding is performed while stretching, and the obtained composite in the form of a strand for molding (1 mm in diameter) is cut into a length of 3 mm to obtain a pellet material. Modified PPE as matrix resin
(Trade name: Noryl SE90, manufactured by Nippon GE Plastics Co., Ltd.) 60 parts by weight of an aromatic polyester as a liquid crystal resin (trade name: Vectra A950, manufactured by Polyplastics) 40 parts by weight, and the above-mentioned pellet material as a third component Were mixed at the compounding ratio shown in Table 2 below, and the screw diameter was adjusted to 3 using a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.).
The resin was extruded while being stretched at 0 mm, a resin temperature of 290 ° C., a screw rotation speed of 75 rpm, a die diameter of 2 mm, and a shearing speed of 1700 sec −1. The obtained strand-shaped composite (1.4 mm in diameter) was 3 mm in length. To obtain a pellet material. Next, the pellet material was injected into an injection molding machine (220 tons,
Using a Toshiba Machine Co., Ltd.) and a test piece mold, the resin temperature was set to 240 ° C. and the injection pressure was set to 1000 kg / cm 2 to obtain a molded product. Measure the tensile strength of the injection molded product,
It is shown in Table 1. This was compared with the tensile strength at the time of the strand, but no decrease was observed.

[Table 3] (Example 3) PC / ABS (trade name: Techniace T105, manufactured by Sumitomo Dow Co.) as a matrix resin 60 parts by weight of an aromatic polyester as a liquid crystal resin (trade name: Vectra. A950, manufactured by Polyplastics) 40 parts by weight,
As a third component, ethylene-glycidyl methacrylic acid acrylonitrile styrene copolymer (trade name: Modiper A4400, manufactured by NOF CORPORATION) is mixed at a mixing ratio shown in Table 3 below, and a twin-screw extruder is manufactured. Screw diameter 30 mm, resin temperature 29 using plastic engineering laboratory
Extrusion molding was performed while stretching at 0 ° C., a screw rotation speed of 100 rpm, a die diameter of 2 mm, and a shear rate of 1700 sec −1. The obtained strand-shaped composite (1.4 m in diameter)
m) is cut into a length of 3 mm to obtain a pellet material. Next, the above-mentioned pellet material was injected into an injection molding machine (220 tons, Toshiba Machine Co., Ltd.)
Resin) and a test piece mold.
At 50 ° C. and an injection pressure of 1000 kg / cm 2, a molded product was obtained. The tensile strength of the injection molded product was measured and is shown in Table 3.
This was compared with the tensile strength at the time of the strand, but no decrease was observed.

[Table 4] Example 4 70 parts by weight of PP (trade name: Sumitomo Noblen D501, manufactured by Sumitomo Chemical Co., Ltd.) as a matrix resin and aromatic polyester as a liquid crystal resin (trade name: Vectra.
A950, manufactured by Polyplastics) 30 parts by weight, 3rd
As an ingredient, an epoxy group-containing vinyl copolymer (trade name: Blemmer CP-30, manufactured by NOF Corporation) was mixed at the compounding ratio shown in Table 4 below, and a twin-screw extruder (Plastic Engineering Laboratory Co., Ltd.) Screw diameter 30 mm, resin temperature 290 ° C, screw rotation speed 150 rpm, die diameter 2
mm, and the shear rate was set to 2500 sec-1, and extrusion was performed while stretching. The obtained strand-shaped composite (diameter: 1.4 mm) is cut into a length of 3 mm to obtain a pellet material. Next, using an injection molding machine (220 tons, manufactured by Toshiba Machine Co., Ltd.) and a test piece mold, the pellet material was set at a resin temperature of 240 ° C. and an injection pressure of 1000 kg / cm 2.
A molded product was obtained. The tensile strength of the injection molded product was measured and is shown in Table 4. This was compared with the tensile strength at the time of the strand, but no decrease was observed.

[Table 5] (Example 5) An aromatic polyester (trade name: Vectra. A95) as a liquid crystal resin was added to 60 parts by weight of ABS (trade name: Clastic MH, manufactured by Sumitomo Dow Co., Ltd.) as a matrix resin.
0, manufactured by Polyplastics Co., Ltd.) 40 parts by weight, and ethylene-glycidyl acrylonitrile styrene copolymer (trade name: Modiper A440) as a third component
0, manufactured by Nippon Yushi Co., Ltd.) at the compounding ratio shown in Table 5 below, and using a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.), a screw diameter of 30 mm, a resin temperature of 290 ° C.,
Screw rotation speed 150 rpm, die diameter 2 mm, shear rate 2
Extrusion was performed while elongating while setting to 500 sec-1.
The obtained strand-shaped composite (diameter: 1.4 mm) is cut into a length of 3 mm to obtain a pellet material. Next, the above-mentioned pellet material was injected into an injection molding machine (220 tons, manufactured by Toshiba Machine Co., Ltd.).
And a test piece mold with a resin temperature of 240
C. and an injection pressure of 1000 kg / cm 2 to obtain a molded product. The tensile strength of the injection molded product was measured and is shown in Table 5. This was compared with the tensile strength at the time of the strand, but no decrease was observed.

[Table 6]

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a change in the state of a composite caused by the content of a liquid crystal resin with respect to a matrix resin.

FIG. 2 is a graph showing the effect of the interaction between extrusion shear rate and draw ratio on tensile strength.

FIG. 3 is a graph showing the interaction between the effect of the addition of the compatibilizing agent due to the improvement in compatibility and the reinforcing effect due to fiberization.

FIG. 4 is a graph showing the relationship between the compounding ratio of the compatibilizer and the tensile strength in Example 1.

FIG. 5 is a graph showing the relationship between the compatibilizer compounding ratio and the tensile strength of Example 2.

Continuation of front page (56) References JP-A-4-202462 (JP, A) JP-A-5-86267 (JP, A) JP-A-5-86266 (JP, A) JP-A-4-348154 (JP) JP-A-5-186668 (JP, A) JP-A-5-171016 (JP, A) JP-A-5-156161 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08L 1/00-101/16 C08K 3/00-13/08 C08J 3/20

Claims (2)

(57) [Claims] 1. A composite resin composition comprising a matrix resin made of a thermoplastic resin and a liquid crystal resin having a liquid crystal transition temperature higher than a minimum melting temperature of the resin in a fiberizable content region of the liquid crystal resin. the amount of further compatibilizing agent having compatibility with both the matrix resin and the liquid crystal resin, the aspect ratio of the liquid crystal resin during melt extrusion of the composite resin composition is 3 or more
When the matrix resin is an ABS resin,
Compounds and / or acids wherein the compatibilizer has an epoxy group
Selected from anhydride-modified matrix resins, wherein the matrix resin is polystyrene, polycarbonate
Or a polyolefin resin, the above compatibilizer
Is a matrix resin modified with an acid anhydride, and the matrix resin is a polyester resin
Means that the compatibilizer is a carboxyl group, an oxazolinyl group
Or when selected from compounds having an amino group and the matrix resin is a polyarylate resin
Means that the above compatibilizer has two or more epoxy groups,
Group, oxazolinyl group or amino group-containing compound
When selected , when the matrix resin is a polyamide resin,
The compatibilizer is a carboxyl group, an oxazolinyl group or
A composite resin composition for molding selected from compounds having an amino group . 2. A composite resin composition comprising a matrix resin made of a thermoplastic resin and a liquid crystal resin having a liquid crystal transition temperature higher than the minimum melting temperature of the resin in a fiberizable content region of the liquid crystal resin. A molding method in which a compatibilizer having compatibility with both the matrix resin and the liquid crystal resin is contained in an amount such that the aspect ratio of the liquid crystal resin becomes 3 or more when the composite resin composition is melt-extruded. An apparent resin shear rate of 3 × 10 ² to 1 at a melting temperature higher than the liquid crystal transition temperature described above.
0 ⁵ sec ^-1 extrusion above, the molding method of the liquid crystal polymer composite material, characterized in that molded to the aspect ratio of the liquid crystal resin is 3 or more.