JPH05305643A - Molding method of sheet-like liquid crystal resin composite and device thereof - Google Patents

Abstract

PURPOSE:To make it possible to mold resin composite without removing the effective fiberized state of liquid crystal by a method wherein sheet-like stocks extruded from a plurality of dies are joined together at the temperature, which is higher than the lowest moldable temperature of matrix resin and lower than the liquid crystal transition temperature of liquid crystal resin. CONSTITUTION:Composite resin composition, which is prepared by blending thermoplastic liquid crystal resin, the liquid crystal transition temperature of which is higher than the lowest moldable temperature of the thermoplastic resin, in the region, in which the condition that the fiberization of the liquid crystal resin is possible is contained, is extruded from a plurality of nozzle dies 12 of an extruder 1. The extrusion is performed at the temperature, which is higher than the liquid crystal transition temperature, and at the resin shear rate, by which the aspect ratio of liquid crystal resin of 3 or more results. The extruded sheet-like stocks F are lead to a joining device so as to be pinched under piled up state between a pair of pressure rolls 22 at the junction temperature, which is higher than the lowest moldable temperature and lower than the liquid crystal transition temperature, in order to be welded into an integral body while discharging the air trapped between the respective sheet-like stocks for obtaining the aimed sheet-like liquid crystal resin composite.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for molding a sheet-shaped composite having a high composite effect with a liquid crystal resin.

[0002]

2. Description of the Related Art A thermoplastic resin is used as a matrix resin,
A predetermined amount of a liquid crystal resin having a liquid crystal transition point higher than the minimum moldable temperature of the matrix resin is mixed therein, and these are melt-extruded to fiberize the liquid crystal resin in the matrix resin, thereby increasing the tensile strength of the matrix resin. A composite resin that improves physical properties has been proposed (see, for example, JP-A-64-90255). Since this composite resin has the advantage of being recyclable, it is attracting attention as a substitute for fiber reinforced plastic (FRP) in which the matrix resin is reinforced with glass fibers or the like. By the way, it is generally known that the physical properties of the liquid crystal resin composite change depending on the degree of fiberization of the liquid crystal resin and improve as the fiberization progresses. However, when the liquid crystal resin composite is used as a plate material, When extruding with a thickness equivalent to that of the plate material, the liquid crystal resin is not sufficiently fiberized in the matrix resin, and it may be difficult to obtain desired physical properties.

[0003]

Therefore, as a result of earnest research, the present inventors have found that in order to effectively carry out such fiber formation, the liquid crystal resin in the matrix resin should have a certain aspect ratio of 3 or more. It has been found that it is necessary to carry out melt extrusion at a resin shear rate, and it is important to stretch this (see FIG. 1). However, in order to secure a resin shearing rate higher than a predetermined value, it is necessary to extrude it into a thin sheet shape, and if it is further stretched to improve the physical properties of the composite resin by fiberizing the liquid crystal resin, the obtained composite resin material Has a thin sheet shape and cannot be used as a molding plate as it is. Therefore, an object of the present invention is to provide a method and an apparatus for forming a sheet-shaped composite body having a high composite effect of liquid crystal resin.

[0004]

According to the present invention, a thin sheet material having a high fibrosis state of a liquid crystal resin is laminated and joined under a condition that does not extinguish the fibrosis. The present invention was completed by discovering that a matrix-like composite can be produced in a state of having a high compounding effect, and a matrix resin composed of a thermoplastic resin and a liquid crystal resin having a liquid crystal transition temperature higher than the minimum moldable temperature of the resin are Extruding a sheet-shaped material from a plurality of dies at a resin shear rate at which the composite resin composition blended in the fiberizable content region of the liquid crystal resin has a liquid crystal transition temperature of the liquid crystal resin or higher and the aspect ratio of the liquid crystal resin is 3 or higher, These sheet materials are superposed between a pair of pressure rolls at a joining temperature lower than the minimum moldable temperature of the matrix resin and lower than the liquid crystal transition temperature of the liquid crystal resin. In forming method of the sheet-like liquid crystal polymer composite material for molding into a sheet-like composite of integrally welded to one product while discharging air between the sheet material by the roll with sandwiched state.

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

On the other hand, the liquid crystal resin has a higher minimum moldable temperature than the above matrix resin, preferably 20
Although not particularly limited as long as it is higher than 0 ° C, thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides are preferable, and liquid crystal resins such as trade names Vectra, Econol, and Zider are commercially available.

It is necessary to mix the liquid crystal resin with the matrix resin so that the composition as a whole has a fiberizing region on the smaller side of the phase inversion amount (see FIG. 2). For example, the matrix resin is a polyamide resin. 40 to 80% by weight in the case of, and 30 to 75 in the case of ABS (acrylonitry butadiene-styrene copolymer) resin
% By weight, 3 to 70% by weight for polycarbonate (PC) / ABS resin, 2 to 60 for PC / PBT resin
% By weight, 3 to 65% by weight in the case of polyphenylene oxide (PP0) / nylon (PA6), 3 to 60% by weight in the case of modified PPO resin, 2 to 7 in the case of polypropylene.
0% by weight, in the case of polycarbonate 3 to 70% by weight,
In the case of PBT resin, the range of 10 to 70% by weight is suitable.

[0008]

According to the present invention, since the sheet material is extruded from a plurality of dies, the shear rate can be increased so that the aspect ratio of the liquid crystal resin is 3 or more, and the fiber can be effectively formed. Since the sheet-shaped materials are bonded at a bonding temperature lower than the minimum moldable temperature of the matrix resin and lower than the liquid crystal transition temperature of the liquid crystal resin, the sheet-shaped composite can be formed in a predetermined shape without extinguishing the effective fibrous state of the liquid crystal resin. The thickness of can be secured. Aspect ratio of liquid crystal resin is 3
In order to carry out extrusion at the above resin shear rate which becomes fibrous, the resin shear rate at the time of extrusion is 3 × 10 ² to 10 ⁵
It is preferably sec ^-1 . The extruded sheet may be once cooled, or may be continuously subjected to a stretching treatment before joining without cooling. The stretching ratio (cross-sectional area of extruded product / cross-sectional area after stretching) is preferably 11 or more and 120 or less.

In the present invention, it is preferable that the lamination joining of the sheet-shaped materials is carried out continuously after the extrusion, but in order to surely maintain the fibrous state of the liquid crystal resin at that time,
It is preferable that the sheet-shaped material extruded from the die is once cooled to a temperature equal to or lower than the minimum moldable temperature of the matrix resin, and each sheet-shaped material is heated to the bonding temperature by at least one of the pressing rolls. In the present invention, since the sheet-shaped materials are joined by the pressing roll, it is possible to perform the stretching at the same time when the sheet-shaped materials are joined by taking a large compression deformation rate. In addition, since the sheet-shaped material allows the liquid crystal resin to be formed into fibers in the extrusion direction, the sheet-shaped composite body to be formed has the unidirectionality of the liquid crystal resin. Therefore, a sheet-shaped composite having a pseudo isotropic property can be obtained by making the sheet-shaped composite having the directional property different from each other in the liquid crystal resin alignment direction and bonded.

In order to carry out the method of the present invention, a single sheet-shaped extrusion die or a plurality of sheet-shaped extrusion dies having the same extrusion direction and stacked sheet-shaped extrusion dies are used. As described above, an extruder that extrudes at a resin shearing rate such that the aspect ratio of the liquid crystal resin is 3 or more, and a minimum molding temperature of the matrix resin of a plurality of laminated sheet-shaped materials located downstream of the die. Above, and at least one pair of pressing rolls arranged above and below so as to be sandwiched at a bonding temperature lower than the liquid crystal transition temperature of the liquid crystal resin, and adjusted to a predetermined roll gap for pressure bonding, and located at the downstream of the rolls. It is preferable to use a sheet-shaped liquid crystal resin composite molding apparatus equipped with a cutting means for cutting the laminated and welded sheet-shaped composite into a predetermined length.

Further, a cooling means is provided downstream of the die for cooling the sheet-shaped material to a temperature lower than the minimum moldable temperature of the matrix resin, and the cooling means is provided downstream of the cooling means and upstream of the pressing roll. In, it is easy to set the sheet material to a predetermined joining temperature range by providing a heating means for heating the sheet material at a temperature equal to or higher than the minimum moldable temperature of the matrix resin and lower than the liquid crystal transition temperature of the liquid crystal resin. Becomes

Further, the pressing roll can be adjusted to a roll interval capable of stretching at the same time when the sheet-shaped material is joined, so that the sheet-shaped material can be stretched while being joined.

Further, in order to form a sheet-shaped composite having an isotropic property by bonding the sheet-shaped composite having a directional property by making the liquid crystal resin orientation directions different from each other and bonding.
The feeding direction of the laminate-bonded sheet-shaped composite body of the above molding apparatus is 9
It is preferable to provide a hot pressing unit which is arranged so as to intersect at an angle of 0 degrees or less and is laminated and bonded to a plurality of sheet-like composites downstream of the intersecting position.

[0014]

EXAMPLE FIG. 1 shows an outline of a preferable molding apparatus for carrying out the method of the present invention. Reference numeral 1 denotes an extruder, which comprises a thermoplastic resin chip and a thermoplastic liquid crystal resin chip which are matrix resins at a predetermined compounding ratio. While having a material inlet 11 to be charged, the matrix resin is melted in the inside 13, and the liquid crystal resin is dispersed and mixed therein in a non-melted state. The extrusion port has a plurality of extrusion nozzle dies 1
2 are formed so as to be vertically stacked in parallel with each other at regular intervals, and the composite resin is extruded from the nozzle die 12 in a sheet shape at a resin shear rate of 3 × 10 ² to 10 ⁵ sec ^-1. It is supposed to be. Therefore,
The extruded sheet-shaped material has a liquid crystal resin fiberized in a matrix resin with an aspect ratio of 3 or more and oriented in the extruding direction. The above sheet material is usually 0.1 to 0.
Extruded to a thickness of 2 mm. Reference numeral 2 denotes a joining device that melts and bonds the sheet material F immediately after extrusion by adjusting the temperature after stretching, and a plurality of cases 20 are enclosed in a case 20 that surrounds a part of the traveling path of the sheet materials F. Small-diameter rollers 21 whose surface temperature can be adjusted are orthogonal to the traveling direction of the sheet-shaped material and are arranged in parallel in parallel to the traveling direction, and the roller groups are arranged in a plurality of upper and lower parts to form a temperature adjusting section,
Subsequent to that, a pair of vertical pressing rolls 22, 22 are arranged to face each other at a predetermined roll interval. Therefore, each of the extruded sheet materials F passes between the small-diameter rollers 21 of the temperature control unit and has a predetermined joining temperature (above the minimum moldable temperature of the matrix resin and below the liquid crystal transition temperature of the liquid crystal resin). After being adjusted and held at the temperature of 1, the sheets are assembled so as to be overlapped and sandwiched between the pair of vertical pressing rolls 22 and 22. Therefore, the sheet material F immediately after being extruded is stretched, and the matrix resin at the interface is melted and welded while discharging the air between the sheet material between the vertical pressing rolls 22 and 22. In the stretching step, cooling means may be provided so as to blow the cooling air between the sheet-shaped materials at right angles to the sheet-shaped material extrusion direction. Further, the sheet material F is set and held at a predetermined joining temperature by the temperature adjusting roller 21, but the surface temperature of the pressing roll 22 is also set to a predetermined joining temperature (a liquid crystal at a temperature equal to or higher than the minimum moldable temperature of the matrix resin). It is preferable that the temperature can be set to a temperature lower than the liquid crystal transition temperature of the resin), and in this case, it is better to set the temperature slightly higher than that of the temperature adjusting roller 21. Reference numeral 3 denotes a roller device that prevents slack between the sheet-shaped materials of the sheet-shaped composite S after welding, and the slack is released when the sheet-shaped composite S runs between the rollers 31 arranged in a staggered manner. It After that, the sheet-shaped composite S is cut into a predetermined length by the cutting device 4 described above. The cutting device 4 has a predetermined length in the traveling direction of the sheet-shaped composite body, and a cutter 42 arranged near a pair of pressing plates 41, 41 having an area covering the entire width thereof. The sheet-like composite S is pressed by the plates 41 and 41 and cut into a predetermined length by a cutter 42. FIG. 2 shows a state where the extruding directions of the above-mentioned molding apparatus are orthogonal to each other and the sheet-like composite bodies S in which the liquid crystal resin orientation directions are orthogonal to each other are further laminated and joined, and both sheet-like composite bodies S intersect and overlap each other. At the position, the hot press device 5 shown in FIG. 3 is arranged in place of the pair of holding plate devices shown in FIG. This device 5 is a cutter 42
A heating / pressing press table 52 whose temperature is adjusted below the melting temperature of the matrix resin of the sheet-shaped composite S is provided above the base 51 located in the vicinity of The blank material B in which the orientation directions of the liquid crystal resin are orthogonal to each other is bonded and formed by pressing and pressing S2. The crossing angle between the sheet composites S1 and S2 can be adjusted in the range of 0 to 90 °,
A pseudo-isotropic material can be manufactured by changing the orientation direction of the liquid crystal resin fiber to 0, 0, 45, or 90 degrees, and can be used as an isotropic material. Therefore, it is useful as a material for floor panels and outer panel. On the other hand, the unidirectional material of liquid crystal resin is useful as a bumper reinforcement and a leaf spring. (Example 1) PA6 as a matrix resin (trade name:
Ube Nylon 1030B, manufactured by Ube Industries Ltd.) 40
Aromatic polyester (Product name:
Vectra. A950, manufactured by Polyplastics Co., Ltd.) A composite composition prepared by mixing 60 parts by weight of a twin-screw extruder (Co., Ltd.)
Screw diameter 3 using the Plastic Engineering Laboratory Co., Ltd.
0 mm, a resin temperature of 290 ° C., a screw rotation speed of 75 rpm, a die diameter of 2 mm and a shear rate of 1700 sec ^−1, and extrusion molding was performed while stretching. The obtained sheet material (thickness: 0.
1 to 0.2 mm) with a pair of heating pressure rollers (surface temperature 26
A plurality of sheets are laminated and passed at 0 ° C. and a roll gap of 5 to 10 mm) to obtain a sheet composite having a thickness of 5 to 10 mm. The tensile strength of the above-mentioned sheet-shaped composite was measured, and it was confirmed that the composite had the physical properties required for the composite by forming the liquid crystal resin into fibers. (Example 2) When the sheet-shaped material produced in Example 1 is laminated to produce a sheet-shaped composite, a PA resin containing no liquid crystal resin between the sheet-shaped materials (trade name: Ube Nylon 10
30B, manufactured by Ube Industries, Ltd. or a maleic acid modified polypropylene (trade name: Admer, manufactured by Mitsui Petrochemical Co., Ltd.) sheet material (thickness 0.01 to 0.1).
mm) to obtain a sheet-like composite having a thickness of 5 to 10 mm in the same manner as in Example 1. The tensile strength of the sheet composite was measured and compared with the tensile strength of the sheet composite of Example 1. It was confirmed that both of them have the physical properties required as a composite material by making the liquid crystal resin into fibers, but PA6 resin has a low melt viscosity at the time of bonding. (Example 3) PA6 as a matrix resin (trade name:
Ube Nylon 1030B, manufactured by Ube Industries Ltd. 30
Aromatic polyester (Product name:
Vectra. A950, manufactured by Polyplastics Co., Ltd.) was mixed with 70 parts by weight of a composite composition to prepare a twin-screw extruder (Co., Ltd.).
Screw diameter 3 using the Plastic Engineering Laboratory Co., Ltd.
0 mm, a resin temperature of 290 ° C., a screw rotation speed of 75 rpm, a die diameter of 2 mm and a shear rate of 1700 sec ^−1, and extrusion molding was performed while stretching. The obtained sheet material (thickness: 0.
1 to 0.2 mm) with the liquid crystal resin oriented in the same direction, and a pair of heating pressure rollers (surface temperature 260 ° C., roll gap 5 to 10).
mm) and a plurality of sheets are passed through to obtain a unidirectional sheet-shaped composite body having a thickness of 5 to 10 mm. On the other hand, 20 parts by weight of PA6 (trade name: Ube Nylon 1030B, manufactured by Ube Industries, Ltd.) is mixed with 80 parts by weight of an aromatic polyester (trade name: Vectra.A950, manufactured by Polyplastics Co., Ltd.) as a liquid crystal resin. The composite composition was extruded while being stretched using a twin-screw extruder. The obtained sheet material is cut into a length of about 25 mm in the extruding direction and stacked to obtain a random material. The random material is inserted between the two unidirectional sheet-like composites and thermocompression-bonded at an appropriate temperature higher than the melting temperature of the matrix resin and lower than the liquid crystal transition temperature of the liquid crystal resin to produce a composite panel. .. (Example 4) PA6 as a matrix resin (trade name:
Ube Nylon 1030B, manufactured by Ube Industries Ltd. 30
Aromatic polyester (Product name:
Vectra. A950, manufactured by Polyplastics Co., Ltd.) was mixed with 70 parts by weight of a composite composition to form a twin-screw extruder (Co., Ltd.).
Screw diameter 3 using the Plastic Engineering Laboratory Co., Ltd.
0 mm, resin temperature 290 ° C., screw rotation speed 75 rpm, die diameter 2 mm, shear rate 1700 sec ^−1, and extrusion molding was performed while stretching. The obtained sheet material (thickness: 0.
1 to 0.2 mm) is changed to -45 °, 0 °, 45 °, 90 ° and the liquid crystal resin fiber orientation direction is changed, and a plurality of sheets are laminated on a pair of heat pressing rollers (surface temperature 260 ° C., roll gap 5 to 10 mm). To obtain an isotropic sheet-like composite having a thickness of 5 to 10 mm. On the other hand, PA6 (trade name: Ube nylon 103
0B, manufactured by Ube Industries, Ltd.) 20 parts by weight of an aromatic polyester (trade name: Vectra.A95) as a liquid crystal resin.
0, manufactured by Polyplastics Co., Ltd.) A composite composition containing 80 parts by weight was extruded while being stretched using a biaxial extruder. About 25 sheets in the extruding direction
Cut into lengths of mm and stack them to obtain a random material. The random material is inserted between the two isotropic sheet-shaped composite bodies and thermocompression bonded in the same manner as in Example 3 to manufacture a composite panel.

[Brief description of drawings]

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

FIG. 2 is an explanatory diagram showing a change in the state of the composite which is affected by the content of the liquid crystal resin with respect to the matrix resin.

FIG. 3 is a schematic view of a sheet-shaped composite body manufacturing apparatus according to the present invention.

FIG. 4 is a layout view showing a modified example of the manufacturing apparatus according to the present invention.

5 is an operation explanatory view of the hot press device shown in FIG. 4. FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Extruder 12 Nozzle die 2 Joining device 22 Pressing roll 4 Cutting device 5 Heat press device

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area B29L 7:00 4F

Claims (8)

[Claims] 1. A liquid crystal 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 moldable temperature of the resin in a fibrizable content region of the liquid crystal resin. Sheet-like material is extruded from a plurality of dies at a resin shearing rate such that the aspect ratio of the liquid crystal resin becomes 3 or more at the liquid crystal transition temperature of the resin or higher, and the temperature is higher than the minimum moldable temperature of the matrix resin and lower than the liquid crystal transition temperature of the liquid crystal resin. These sheet materials are sandwiched between a pair of pressing rolls at a joining temperature of 1 and the air between the sheet materials is discharged and integrated by the rolls to form a single sheet composite. A method for molding a sheet-shaped liquid crystal resin composite, which comprises molding. 2. The sheet-shaped material extruded from a plurality of dies is once cooled to a temperature lower than the minimum moldable temperature of the matrix resin, and then, on the upstream side of the pressure roll, each sheet-shaped material is bonded to the above-mentioned joining temperature by a heating means. The molding method according to claim 1, wherein the heating is carried out. 3. The method according to claim 1, wherein the sheet material is stretched at the same time as the sheet material is joined by the pressing roll. 4. The method according to any one of claims 1 to 3, wherein the sheet-shaped material is bonded by making the liquid crystal resin orientation directions different from each other. 5. A single sheet-shaped extrusion die or a plurality of sheet-shaped extrusion dies having the same extrusion direction and having stacked sheet-shaped extrusion dies, wherein the composite resin composition has an aspect ratio of the liquid crystal resin above the liquid crystal transition temperature of the liquid crystal resin. An extruder that extrudes at a resin shearing rate of 3 or more, and a plurality of sheet-like materials to be laminated, which are located on the downstream side of the die, at a temperature equal to or higher than the minimum moldable temperature of the matrix resin, and a liquid crystal of a liquid crystal resin. At least one pair of pressure rolls arranged above and below the transition temperature so as to be sandwiched at a bonding temperature lower than the transition temperature, and adjusted to a predetermined roll gap for pressure bonding, and a sheet-like composite that is positioned downstream of the rolls and laminated and welded. An apparatus for molding a sheet-shaped liquid crystal resin composite, comprising cutting means for cutting a body into a predetermined length. 6. A cooling means, which is located on the downstream side of the die and cools the sheet material to a temperature lower than the minimum moldable temperature of the matrix resin, downstream of the cooling means,
The molding apparatus according to claim 5, further comprising heating means for heating the sheet material at a temperature above the minimum moldable temperature of the matrix resin and below the liquid crystal transition temperature of the liquid crystal resin on the upstream side of the pressing roll. 7. The pressure roll can be adjusted to a roll interval that allows stretching at the same time when the sheet materials are joined.
The molding apparatus described. 8. The molding apparatus according to claim 5, wherein the laminate-bonded sheet-shaped composite bodies are arranged so that the feeding directions intersect at an angle of 90 degrees or less, and a plurality of sheet-shaped composite bodies are laminated and bonded at the intersecting positions. A molding apparatus provided with a hot pressing means.