TW201107103A - Manufacturing method of liquid crystal resin composition, liquid crystal resin composition and apparatus for manufacturing liquid crystal resin - Google Patents

Abstract

The present invention provides a manufacturing method of liquid crystal resin composition for reducing the generation of black spots, liquid crystal resin composition with less content of black spots, and the apparatus for manufacturing liquid crystal resin composition with less content of black spots. During the melt compounding of liquid crystal resin with filler to manufacture liquid crystal resin composition, a biaxial extruder is used that has a liquid crystal resin supply port disposed at the upstream end part of the extrusion direction, and an ejection mold disposed at the downstream end part of the extrusion direction. Between the liquid crystal resin supply port and the ejection mold is disposed a filler supply port, at farther downstream side than the filler supply port is provided a first opening part. Meanwhile, within the steel tube of the biaxial extruder, a plasticizing part is disposed at the upstream side of the filler supply port, and a first compounding zone with feeding compounding elements is downstream disposed with the upstream end part of the filler supply port as the starting point. The compounding part of the biaxial extruder is disposed at the interval from the downstream end part of the first compounding zone to the upstream end part of the first opening part.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a liquid crystalline resin composition using a two-axis-stacking machine/valer melt-mixing liquid crystal tree and a filler. Du Shuyue [Prior Art] The mechanical strength, heat resistance, and resistance of the liquid crystalline polyester resin are known as the "Thundering, and the balance of the mouth and the electrical properties." As a high-performance work, part is used for injection molding. Plastic wins, special liquid crystal resin, large liquid crystal resin is usually used for 诂 _ &< ... read (four) I-dimensional and money-like fibrous true fillers' and A powdery granular filler and a plate-shaped filler filled with a oxidized stone, a mica, a mother clay, a glass bead, etc., are filled with a liquid crystal resin composition, and a liquid crystal resin composition filled with various fillers is flowed. Good balance between mechanical and mechanical strength 'suitable as a motor component such as a relay component, a bobbin (10) 丨bin) connector, a cymbal, a rectifier, a splitter, or the like, or a coil, a crystal vibrator, or an IC chip. A sealing material such as a component or the like has a thin and complex shape of an electrical or electronic component. The method for producing the liquid crystalline resin composition is known to have a main flow in the upper direction. In the lower part of the extrusion direction, the side part feeder is provided with a side-feeder 'in the steel cylinder part', and a screw such as a kneading disc is disposed at a position on the downstream side of the side feeder at a specific distance. A method of supplying liquid crystallinity from a main feeder, and supplying a filler from a side feeder to melt and knead the liquid crystalline resin and the filler, 201107103 (Patent Document 1). Patent Literature 1 JP-A-2006-035677 [Claim of the Invention] The method of Patent Document 1 is easy to carry out, such as a king screw thread (ful丨f丨丨screw screw) between the side feeder and the kneading 4 The attached resin is attached to the resin and the filler of the spirulina. At the same time, it is oxidized by the stagnation of the air in the extruder. Black foreign matter (hereinafter also referred to as BS) is generated, and black spots are mixed with the liquid crystalline resin. When the liquid crystalline resin composition contains black spots, there is a problem that the appearance of the molded article is impaired. Further, the liquid crystal resin composition is often used for a complicated shape having a thin wall thickness because of excellent fluidity. Electrical. The formation of electronic parts In the case where the size of the black spot is large, there is a problem that the black spot is crowded in the mold and short shots are formed when the thin-walled part is formed. In order to solve the above problem, the present invention aims to provide a reduction. A method for producing a liquid crystalline resin composition produced by black spots, a liquid crystal resin composition having a small black spot content, and a liquid crystal resin composition producing device having a small content of black spots. In the melt-kneading liquid crystal resin and the filler, a liquid crystal resin composition is produced, and the liquid crystal resin supply port is provided at the upstream end portion in the extrusion direction, and the downstream side of the pressurization/hardening direction is provided. The end portion is provided with a discharge mold ′, and the liquid crystal resin is provided with a filler supply port in the middle of the mouth and the discharge mold, and the first opening is provided on the downstream side of the filler supply port. 201107103 The mouth portion is provided with a plasticizing portion in the steel cylinder at the upstream side of the filler supply port, and a distribution mixture is provided with the upstream end portion of the filler supply port as a starting point. In the i-th kneading zone of the training element, the two-axis extruder in which the kneading section is provided is used in the section from the downstream side end portion of the second Kunming area to the upstream side end portion of the first opening portion, thereby reducing the generation of dark spots. Thus, the present invention has been completed. (1) 'The method for producing an inert resin composition, which uses a two-axis extruder to knead the liquid crystal resin to the right side, and the above-mentioned 2 2 is in the upstream side of the extrusion direction. The liquid crystal resin supply port is provided, and the second side is provided at the lower end side, the second side is provided on the liquid crystal resin supply port, and the second side is provided on the liquid crystal resin supply port, and the two-axis extruder is further plasticized at the filler supply port. In the steel cylinder, the upstream side of the filler supply port is provided, and the filler is supplied to the lower first mixing zone of the first kneading zone, and the upper side of the kneading 4 is provided at the lower end side to the first opening. The composition of the end portion is composed of the liquid crystal resin composition described in (1). The length of the first kneading zone is 5 to 15. The method of the material is described. (3) The liquid sw 4 ± method described in (2), the two sides are repeatedly issued, and the filling material supply 1 upstream side is also prepared in the manufacture of the composition. 4) (3) 疋, the second opening of the museum. In the method of manufacturing a crystalline resin composition, the upstream side of the Ρ 充 供给 supply port is provided with a second opening 5 201107103 ′′, and the inside of the steel cylinder is at the portion to the filler supply port. 2 The mixing area is composed of the aforementioned £. A method of manufacturing a liquid crystalline resin composition as described in the second aspect of the kneading element having the kneading property in the section below the upstream end of the upstream side of the second mouth portion The length of the I training zone is greater than or equal to m from the lower portion of the second fascinating portion to the length of the filler side of the filler. In the method of the liquid crystal resin composition described in the above paragraphs (1) to (5), the kneading element having the transportability is a kneading process that is large and smaller than 9 〇t and overlaps. The method for producing a liquid crystalline resin composition according to any one of the above aspects, wherein the filler has a bulk specific gravity of Q6g/em3 or less. (8) The method for producing a liquid crystalline resin composition according to (7), wherein the filler has a volume specific gravity of 〇35 g/cm3 or less. (9) The method for producing a liquid crystalline resin composition according to any one of (1), wherein the filler comprises at least one selected from the group consisting of talc, mica, cerium oxide, and glass frit. Group. (10) A liquid crystalline resin composition produced by the method according to any one of (1) to (9). (11) The apparatus for producing a liquid crystal resin composition, which is provided with a liquid crystal resin supply port at the upstream end portion in the extrusion direction, and a 2-axis extruder having a discharge die at the end portion on the side of the flow in the extrusion direction, wherein The two-axis extruder includes a filler supply 201107103 port ' between the liquid crystal resin supply port and the discharge die, and a filler supply σ is provided on the filler σ flow side, and a plasticizable portion is provided in the steel cylinder as described above: In the case of the supply side: the upper end portion of the filler supply port is the area of the upstream side of the first-stage kneading zone to the upstream end of the first-stage kneading zone. The kneading section is provided, and the kneading zone is composed of a kneading element having a conveyance property. (12) The apparatus for producing a liquid crystalline resin composition according to (11), wherein the y (four) line ′ further includes a second opening at the same position as the filler supply port or the upstream side of the filler supply port. (2) The apparatus for producing a liquid crystalline resin composition according to (13), wherein the two-axis extruder is in the steel cylinder, and the lower portion of the upstream end of the second opening is provided to the filler supply port. The second kneading zone is provided in the section below the upstream side end portion, and the second kneading zone is constituted by a kneading element having transportability. According to the present invention, when the liquid crystal resin composition is produced by melt-kneading the liquid crystal resin and the filler, the end portion on the downstream side in the extrusion direction is provided by the end portion on the upstream side in the extrusion direction. a discharge opening is provided, and a true charge supply port is provided in the middle of the liquid crystal resin supply σ and the discharge die, and a second opening is provided on the downstream side of the filler supply port, and a plasticizable portion is provided in the steel cylinder. The L side of the filler supply port is an i-th training zone in which the upstream side end portion of the filler supply port is provided as a starting point and has a delivery kneading element, and the downstream side end of the i-th kneading zone is provided. The two-axis extruder of the kneading section is provided in the section of the upstream end of the opening, and the occurrence of dark spots can be reduced. [Embodiment] Hereinafter, an embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be appropriately modified and implemented within the scope of the object of the present invention. When the liquid crystal resin composition is produced by melt-kneading the liquid crystal resin and the filler, the liquid crystal resin supply port is provided at the downstream end portion in the extrusion direction, and the discharge is provided at the downstream end portion in the extrusion direction. In the mold, the filler supply port is provided in the middle of the liquid crystal resin supply port and the discharge mold, and the first opening is provided on the downstream side of the filler supply port, and the plasticizer is provided in the steel cylinder to supply the filler. On the upstream side of the port, the i-th training zone is provided with a flow-through component that is downwardly flowed and has a delivery kneading element at the upstream end of the filler supply port, and is at the downstream end of the second training zone to the first Pa „ ^ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Therefore, it is conventionally known that the thermoplastic resin (four) filler is placed in the true charge supply port when the two-axis extruder is used for the two-axis & Upstream P-β to the gap between the filling port of the filler, and from the filling port of the filler to the lower part of the interval between the two parts of the mixing section The pressure is on the η port, so the field-forming molten resin flows back to the filler material supply, so the kneading element is not used. However, after the inventor's inspection, the inventor found that even from the supply port of the filling material 201107103 The section of the kneading section that flows downward is matched with the % α of the kneading element in the section between the opening of the filler supply port in the two-axis extruder and the filler supply port, and can be manufactured when the liquid crystal resin is used. From the opening, the 卩 and the filler supply port do not cause the reverse flow of the molten resin, and do not significantly affect the discharge amount of the liquid crystalline resin composition, and the effect of the black spot is reduced, which is not possible. It is presumed that the liquid crystal resin generally has a low melt viscosity, and the pressure at the position where the kneading element is placed in the two-axis extruder is not significantly increased. [Liquid Crystal Resin] The liquid crystal used in the present invention The term "resin" refers to a melt-processable polymer having the property of forming an optically anisotropic molten phase. The nature of the anisotropic molten phase can be confirmed by a conventional polarized light inspection method using orthogonal photoconductors. More specifically, different The confirmation of the chiral melt phase can be carried out by using a Leitz polarizing microscope, and the molten sample of the heated Leiz is observed under a nitrogen atmosphere at a magnification of 4 。. The liquid crystal resin to which the present invention is applicable, 卩 orthogonal photon In the case of inspection, even when it is in a state of being in a static state, the polarized light is usually permeable, and it exhibits optical anisotropy. The liquid crystalline resin as described above is not particularly limited, but is preferably an aromatic poly-aromatic poly(tetra)amine 'aromatic (tetra) poly The vinegar or the family of polyacetamide has a polyester partially contained in the same molecular chain. The above range can also be used when it is dissolved in pentafluorophenol (Pentafiuor〇phen〇1) at a concentration of C.丨 at 60 C. Preferably, it is at least about 2 〇 di / g, more preferably from 2.0 to 10 Å. Odl / g logarithmic viscosity (IV). It is applicable to the liquid crystalline resin of the present invention. It is a polyacetal or aromatic 201107103 polyacetamide, particularly preferably having at least an acid, an aromatic hydroxylamine, and an aromatic hydroxy carbon group. The aromatic polyester, a compound of the aromatic group, constitutes a valence polyester amide. More specifically, (1) Polyester consisting mainly of aromatic enamel and anaerobic and sorghum; /, D conductor or 1 (2) mainly by (a) apricot sulphate and its induction One or two or more kinds of the body and (b) one of the ring-shaped dicarbonic acids of the aromatic scorpion scorpion and one or more of the inducers thereof ((〇^ „ β # ^ 0 rank- know, 舳 grade a polyester having at least one or more of a group diol, an aliphatic diol, and an inducer thereof; (3) a work species or two or more types of (4) aromatic transbasic carbonic acid and an inducer thereof, and (8) aromatic One or more of the group of the amine, the alicyclic bisamine and the inducer thereof, or the at least one or more of the alicyclic dicarbonic acid, the alicyclic dicarbonic acid, and the inducer thereof Polyester decylamine; (4) mainly composed of (a) aromatic hydroxycarbonic acid and one or more of its inducers and (b) an aromatic hydroxylamine, an alicyclic bisamine, and an inducer thereof or Two or more kinds of (c) aromatic dicarbonic acid, alicyclic dicarbonic acid, and at least one or more of the inducers thereof, and (d) an aromatic diol, an alicyclic diol A polyester-terminated amine having at least one or two or more kinds of aliphatic diols and an inducer thereof. The above-mentioned components may be used in combination with a molecular weight modifier, and may be applied to a specific compound constituting the liquid crystalline resin of the present invention. Preferred examples include aromatic hydroxycarbonic acid such as P-hydroxybenzoic acid, 6-hydroxy-2-naphthalene dicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 4,4-dihydroxyl linkage. Benzene (4,4'-dihydroxybipheny I ), p-benzoquinone 10 201107103 indole streptophenol, an aromatic diol such as the following general formula (1) and a compound represented by the following general formula (II); Aromatic phthalic acid, isophthalic acid, 4'4-diphenyldicarbonate 2,6-naphthalenedicarbonate, and aromatic dicarbonic acid of the following general formula (1丨J) jin; Hope, for aromatic amines such as stupid amines [Chemical Formula 1]

(I) (X: select -S0- > -S〇2- [Chemical Formula 2] Substituted groups (C1~C4), alkylidene, -〇--S-, -C0- )

[Chemical Formula 3] II)

H00C

C00H III) base) is selected from ~(CH2)n-(n = l~4), -0(CH2)n〇-(n=l~4). The purpose of the present invention is to reduce the use of 2-axis extrusion The black spot of the liquid crystal resin composition 睹_ @ π was produced. When a liquid crystal resin and a filler having a melting point 11 201107103 are melted by a two-axis extruder, the temperature difference between the temperature of the filler supplied to the second (four) outlet and the liquid crystalline resin in the molten state is large, and # is filled by a low temperature. The material is in contact with the liquid crystal resin in a molten state, and the temperature of the liquid crystal two resin in a molten state is lowered. 'The viscosity of the liquid crystalline resin will rise instantaneously. Therefore, the liquid crystalline resin portion is liable to adhere to the screw, and the resin adhering to the screw is stagnate in the two-axis and repeatedly exiting the machine, so that the BS is particularly unlikely to be generated. The method for producing a liquid crystalline resin composition of the present invention

It is easy to produce by using, for example, a melting point 33 (TC or more, more preferably ” L) and a horse d50 C or more.

When the liquid crystal resin of the high melting point of BS is made of a fine I w liquid resin, a remarkable effect of reducing BS production can be obtained. [Filling material] The filling material of the liquid crystal polyester of the present invention is not particularly limited, and a fibrous filler can be used to fill (4) various filler materials in a plate shape. Examples of the fibrous filler are, for example, glass fiber, asbestos fiber, dioxoid fiber, bismuth stone, sinite fiber, m soil fiber, oxidized fiber, nitriding, ray fiber, side fiber, chin The potassium acid fiber is an inorganic fibrous material such as a metal fiber or the like which does not have a steel, a metal, a titanium, a copper or a brass. The powdery granular filler may, for example, be a carbon block, .^α, a hole, a stone powder, a bead, a glass fiber, a glass ball, a flour, a moonstone, a clay, a stone, a limestone, a limestone. Acid salt; such as iron oxide, titanium oxide, oxidized yttrium® π „ 10 oxides of aluminum oxide, calcium carbonate, bismuth carbonate; sulphate of metal such as calcium sulphate or barium sulfate 1,1, /, he rolled magnets, bismuth telluride, tantalum nitride, boron nitride, various metal powders. Temple plate filler material example 12 201107103 Debris, various metal foils, etc. The Stupid temple filler can also be used in combination of two or more types. In the above-mentioned fillers, in the case of the use of the 5th grazing, the sputum is used, and the sputum is more than 0. 6g/cm3 or less, and the specific gravity is more than 0.35g/cm. Filling below cm3; y· pull + 0 soil, ^;,,,, material, the oxidation of the liquid crystalline resin in the 2-axis extruder is likely to cause BS generation. In the method for producing a Ba-based resin composition of the present invention, the use of the air-containing filler of the 詈 沾 π π π π π π π π π π π π π π π π π π甚 甚 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Manufacture of objects. In the present invention, for example, a filler having a large air content and a small specific gravity is included, for example, one or more groups selected from the group consisting of talc, mica, cerium oxide, and glass powder. The bulk specific gravity of the filler can be determined by the method of JIS K51〇1. The amount of the liquid crystalline resin to be added to the filler is not particularly limited as long as it does not impair the object of the present invention, and is usually 200 parts by mass or less, more preferably 15 parts by mass, per 1 part by mass of the liquid crystalline resin. In the following, it is preferable to match the ratio of the mass portion below 100. [Other components] In the case where the liquid crystalline resin composition is produced, the liquid crystal resin may be blended with other thermoplastic resin of a liquid crystalline resin in addition to the filler, insofar as the object of the present invention is not impaired. Additives such as nucleating agents, colorant oxidation inhibitors, stabilizers, plasticizers, slip agents, release agents, flame retardants, and the like. [2-axis extruder] 13 201107103 Μ Bu Very similar to the figure, the figure shows the structure of the 2-axis extruder used by the 6W Po. Figure 1 is a diagram showing the present invention. The two-axis extruder used in the present invention is a two-axis extruder 丨, in the rhyme M m rn a ω li, the upstream side end 4 in the direction of the soil is provided with a liquid daily resin supply port u, ^ , φ , 下 下 下 的 下 下 下 下 下 , , , , , , , , , , 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶The first opening portion 13 is provided on the side. Further, the two-axis extruder 1 used in the month of the month is provided with a plasticizing portion 15 on the side of the upper side of the filling material supply port 12 in the steel cylinder, and the upper end portion of the upper side of the filling supply port 12, „ 17 ^ , The kneading start point of the first kneading zone 17 'the lower flow end of the first kneading zone 17 to the upper end of the first opening 13 is provided with a kneading section 16 . In the case where the specification and the patent range are described in the "upstream" ^", respectively, it means "upward flow in the extrusion direction of the 2 (four) outlet" or "downward flow in the extrusion direction of the 2-axis extruder". The two-axis crimping wire used in the invention is not particularly limited as long as it does not hinder the present invention, and it is preferable to use only the two kings of the 70-king and the same-direction rotating type. The 9-amp;b w used by the present invention is a 2-axis extruder! , screw effective length (l) disk screw diameter (D) ratio L / D better county 9n 7n *, Dianjia 疋 20~70, more preferably 3 〇 ~ 6 〇. If the L/D is less than 20, the effective length of the screw diameter of the screw is 4, and the effective length is too short, so it is difficult to set it in the first kneading zone 17. If the L/D is greater than 7n, the denier is as high as 7β. Thermal deterioration of the liquid crystalline resin. [Plasticizing part and kneading part] ‘ 'The two-axis extruder i used in the present invention is provided with a moldable 15 and a kneading part in the steel cylinder! 6. Plastic servant Qiu type. &quot;5疋 in 2-axis extruder! Steel cylinder 14 201107103 The inner chamber is a section in which the liquid crystal resin is sufficiently melted by the shearing force of the liquid crystal resin. In addition, the kneading section 16 is a section in which the liquid crystalline resin in a molten state is sufficiently kneaded with the filler to uniformly disperse the filler in the liquid crystal resin. The length L/D of the plasticizing portion 15 is preferably $2〇~75, more preferably the length of the ^' kneading part ^ is preferably ^~丨^ more preferably 3. 5~7. 0 〇 constitutes a plasticizing part 15 and the screw element of the kneading unit 16 can sufficiently plasticize the liquid crystalline resin in the plasticizing portion 15. The kneading portion is preferably not sufficiently limited in the kneading portion, and various screw elements can be used. The general screw element used in the plasticizing unit 15 and the kneading unit 16 is, for example, a kneading element (a kneading element having a transporting property to be described later), and an anti-kneading element (having a product in which the contents of the two-axis extruder 1 are sent downward). Hybrid components), neutral kneading components (the position of the kneading discs, the moving and overlapping components), and the mixing components. [First kneading zone] The two-axis extruder used in the present invention is in the steel cylinder, and the lower portion of the lower end portion of the filling material supply port 12 is downwardly flowed from the starting point to have a P-mixing zone 17°. The second kneading zone of the shaft presser is constituted by a kneading element having transportability. Here, the conveyance-type kneading element has the ability to convey the liquid crystalline resin composition in a molten state downward in the extrusion direction, and can impart a gap portion between the inner wall of the steel cylinder and the screw top of the kneading element. The liquid crystal resin composition is not particularly limited in that it shears the force and disperses the filler in the composition of the liquid crystal number. The inner wall of the steel cylinder and the 15 201107103 screw-top, a, # a, 1 B scoop with transporting components are preferably less than 3 mm, more preferably less than 1 turn. If the gap is too large, the effect of mixing η搐古搐)琢5, will not be able to get a full color mixing effect and the filler can not be evenly dispersed. [Conveying element with transportability] A specific example of a kneading element having transportability is larger. Less than 9. . Between the movement and the meaning of the weight, practice (four) phase angle (Θ) part of the continuous spiral (four) components 'and the screw top with the rotor of the outer circumference of the rotor type mixing elements, etc.. Octasheng's mixing elements, so that liquid crystal The effect is hurting, the taste of the scent is more sturdy, and the filler is evenly dispersed, and the space between the shovel and the shovel is n. The kneading is used, for example, a kneading element which is formed by moving and overlapping with a phase angle of 0 小于 disc less than 0 and less than 9 n. The first kneading zone 17 7 does not hinder the present invention 17 麫 Xw .. purpose 1st kneading zone The transportability is limited, and it is also possible to combine the encountering elements such as the I white disc with the other screw elements. ^ Niuju, for example, the back-mixing screw, is an example of a kneading element suitable for the present invention. The pattern diagram of the training component 2 and the vertical direction of the rotary axis. The mixed phase and the angle of the phase of the white plate 21 are more than 0 and less than 9. The movement of the first guard Dong is formed. Explain that the phase angle of the mixed white disc is greater than that of less than 9〇4. Mixing components. Moving and overlapping, ^The transporting kneading component is composed of the overlapping of the kneading discs. The field is preferably 5 to: n. The phase angle between the white discs can be the same or different. The phase angle main 80' is better. It is 10 to 70°, preferably 15, 3〇'45 16 201107103, or 60. The kneading element in this range of phase angle kneading (4) moving and overlapping constitutes a good transportability. The thickness of each of the components of the mixed white discs may be the same or different, but usually a number of kneaded white discs of the same thickness are used to form a kneading. The thickness of the kneaded white disc is not particularly limited insofar as it does not hinder the object of the present invention, and usually In the present invention, the first kneading zone 17 is disposed downward from the lower portion of the flow-side end portion of the filler supply port 12 in the steel cylinder of the two-axis press. In the following:: The liquid crystal resin composition of the screw top of the X piece is subjected to the shearing force and generates heat. Therefore, the low temperature filler and the high temperature dissolved J eucalyptus are mixed to suppress the decrease in the temperature of the resin, and the body of the element is kneaded. Self-cleaning The adhesion of the liquid crystal resin composition to the inside of the 2-axis extruder is suppressed, that is, the reason for forming the BS. Further, by the kneading effect of the kneading element: the kneading action of the 3⁄4 wire meter, at the same time as the filler The liquid crystal resin composition in the inside of the 2-axis machine 1 is degassed. Therefore, the right side of the disk is filled with the air inside the 2-axis extruder 1 At least a part of the can be discharged from the outside of the conventional 2-axis extruder 1 from the filling material*, the brother supply, and the σ port. Thus, in the case of the 2-axis extruder, the inside of the machine 1 is * In the case of the first kneading zone 17, the smelting of the liquid crystal resin is suppressed, and the 混 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ When inside, "the lower 2-axis extruder of the supply port 12! The internal pressure does not rise rapidly, and it is difficult for the liquid crystalline resin composition to be supplied from the filler. 17 201107103 The length L/D of the first mixing zone 17 with r 5 is preferably from 2 to 15, more 5 to U, and even more preferably 5 to 1 (1 Shi Jia is the speaking sound * 10. By setting The first kneading zone 17 is the upper liquid crystal resin composition, and the shearing force of the liquid crystal resin composition causes heat generation, and the low-temperature filling of the 盥 盥 古 古 泽 、 、 、 、 〉 〉 〉 〉 的 的 的 的 的 容 容 容 容 容 容 容 廉 抑制 抑制The decrease in the degree of the dish and the self-cleaning property of the 70-piece body of the sputum, and the cause of the BS cause the adhesion of the inside of the 2-axis glaze extruder 1 of the liquid-day resin composition, which can reduce the generation of the BS. The starting point of the upper mixing zone 17 is not particularly limited as long as it is at the upstream end of the filler supply port 12. The first kneading zone π is supplied from the filler in a range that does not impair the object of the present invention. The lower portion of the flow-side end portion of the flow port 12 has a lower flow L/D of 2 or less, and may be at a position of 1 or less. Further, the first kneading zone 17 may be continuously provided with the kneading unit i 6 . In such a case The first length of the first mixing zone 17 and the kneading section 16 is preferably from 5. 5 to 25. 0' is preferably from 8.5 to 22. 〇. [first opening] In the two-axis extruder 1 used in the invention, the first opening portion 3 is provided on the downstream side of the kneading portion 16. The first opening portion 13 is used to remove air generated during the kneading of the resin and the filler. Further, the first opening portion 13 is usually deaerated under reduced pressure by a vacuum pump. The degree of pressure reduction in the case where the first opening portion 3 is dust-reduced is preferably 380 Torr (0 to 50.7). More preferably, it is 1 to 2 Torr Torr (0.13 to 26.7 kPa), more preferably 10 to 100 Torr (1.3 to 13.3 kPa). [Second opening] The present invention is used. The two-axis extruder 1' preferably further includes a second opening 18 201107103 portion 18. The second opening portion 18 is provided at the same position as the filler supply 2 of the two extruders or at the filler supply port 12 Here, the 'filler supply port 12 and the second opening 18 are provided at the "same position" 'the filler supply port 12 and the second opening 18, and are placed on the two-axis extruder 1 and pressed. The direction of the vertical direction is arranged in parallel. In the case of the second-axis extruder 1 and the second opening portion 8 is provided, the plasticizable portion 5 is disposed on the upstream side of the second opening portion 18. In addition, the second opening is used to discharge the two-axis extruder. The internal air is usually an open vent. The second opening is further provided by the two-axis extruder 1. 18' From the filler supply port 12 and the filler, the air discharged from the two-axis extruder 1 and stored in the inside of the two-axis press machine 1 is discharged, and the lowering of the air in the i-th kneading zone is reduced. Effect. Again, the volume specific gravity is used. In the case of the following filler material containing a large amount of air, the effect of reducing the amount generated by the second opening portion 18 is significantly improved. The length of the section of the upper opening side of the second opening portion 18 of the second opening portion 18 to the lower portion of the upstream side of the filler supply port 12 is provided on the upstream side of the filler supply port 12, L/ D is more than .... 5 to 10 5, more preferably 2.5 to 7. The filler is supplied from the upstream end of the second opening core to the filler. When the length of the section on the lower side of the upper flow side is too long (the combination of the second opening 18 and the filler supply port is provided), the supply σ 12 from the filler and the filler are simultaneously discharged from 2 (four): π The air remaining inside the 2-axis extruder i becomes difficult to discharge. The reduction effect by the BS of the Kunming District 17 is difficult to increase. 19 201107103 [Second kneading area] 12 in the upper = press machine to set the second opening 18 in the second supply of the filler supply port 2, preferably in the steel cylinder of the 2) extruder From the upper part of the flow side of the upper second::18 to the other end of the filling material supply port 12. The second kneading zone 19 is provided in the lower section of ρ. In the case where the second kneading zone 19 is also provided with the second kneading zone 19, the training zone 19' is constituted by the first winding zone. In addition, the second Dongba; 9 ', the same as the conveyance of the mixed training, 帛 ι, "19, without hindering the purpose of the present invention, the kneading zone 19 as a whole without loss of transportability, can also be combined with transportability In the present invention, the liquid crystal resin composition in the molten state of the i-th kneading zone is removed by providing the second kneading zone 19. The air contained in the filler material can be quickly discharged from the second opening portion 18 through the second kneading zone 19. Therefore, the first kneading zone Π, the second opening portion 18, and the second kneading zone are provided in the two-axis extruder 1 In the case of 19, the second kneading machine ι is provided with the kneading zone Π, and the second opening 18 is capable of obtaining a higher bs reduction effect. Further, the volume specific gravity 〇6g/cm3 is contained. The % port of the air filler is significantly improved by the provision of the second kneading zone 129. The second kneading zone 19 is below the flow end side of the second opening portion 18. The length of the section of the lower portion of the flow-side end portion of the filler supply port 2 is preferably 70% or more of the length, more preferably 9% or more. With the second kneading zone 19 of such a length, the air inside the 2-axis extruder can be filled with the air flowing at the same time as the 201107103 filling material. The outside of the two-axis extruder 1 is discharged. The second kneading zone 19' can be continuously provided with the plasticizer 15 in a range that does not impair the object of the present invention. The 2-axis extruder used in the present invention is in the steel cylinder In the third mixing zone, the second mixing zone 179, the plasticizing section ,5, and the screwing section of the section other than the kneading section ,6, the target liquid crystal resin composition can be formed according to the type and amount of the filler. In the physical properties of the material, a full-thread element, a neutral kneading element, a smelting element, a reverse kneading element, a mixing element, etc. are used in combination. [Method for Producing Liquid Crystal Resin Composition] Method for Producing Liquid Crystal Resin Composition of the Present Invention In addition to the two-axis extruder including the first kneading zone and the second kneading zone, the liquid crystal resin and the filler may be melted and kneaded according to a conventional method. The liquid crystalline resin composition is produced according to the method of the present invention. When you can 2, the opening portion 18 and/or the filler supply port 2 introduces an inert gas into the two-axis extruder 1. When the inert gas is introduced into the two-axis extruder i, it is replaced by two-axis extrusion; The air is an inert gas, and the oxidation of the molten resin can be suppressed, and the generation of the BS can be suppressed. The introduction of the inert gas into the 2-axis extruder 1 is not particularly limited insofar as it does not impair the object of the present invention, and for example, Nitrogen, helium, argon, etc. The liquid crystalline resin composition is produced by the method of the present invention described above, and the dipstick can be greatly reduced in the two-axis extruder (4). The liquid crystalline resin produced by the method of the present invention can be produced. In the composition, since the content of the BS is extremely small, the molded article can be given an excellent appearance. At the same time, it is difficult to occur due to the short shot of the BS when the injection molding is performed. Therefore, the liquid crystalline resin composition manufactured by the present invention = 201107103 is particularly suitable for a board-to-board (B t0 B) connector, a flexible printed circuit board (FPC), and a soft signal transmission line. A material having a thin-walled molded article. EXAMPLES Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples. In the examples and the comparative examples, the following liquid crystal resin and filler were used to produce a liquid crystalline resin composition using the following θ α ^ dry 』T. <Liquid Crystal Resin> The liquid crystal resin obtained in the production example of the liquid crystal resin described below was used. <Example of liquid crystal resin production> The following (IMIV) monomer '(V) metal catalyst is placed in a polymerization vessel equipped with a stirrer, a circulating reaction column, and a monomer inlet, but a quick introduction port and a pressure reduction/outflow line. And (VI) aminating agents. (I) 2-hydroxy-6-naphthoic acid (HNA) 166 g (48 mol%) (II) terephthalic acid (TA) 76 g (25 mol%) (III) 4,4'-dihydroxyl Biphenyl (Bp) 86g (25 mole %) (IV) 4 - benzoic acid (HBA) 5g (2 mole %) (V) calcium acetate (catalytic amount) (乂1) anhydrous acetic acid (for 1 ^,6卩, and 11^的基基11倍摩尔) Then 'under nitrogen gas flow' was stirred at 1401 for 1 hour, while the side was lifted and heated to 365 hours for 5.9 hours. (: Then, after 3 〇 minutes minus 22 201107103, the pressure is reduced to 5 Torr (667 Pa), and low-boiling components such as acetic acid are flowed out and melt-polymerized. After the stirring torque reaches a predetermined value, nitrogen is introduced into the polymerization vessel to make the polymerization vessel. The pressurized state was exhibited, the polymer was discharged from the lower portion of the polymerization vessel, and the polymer string was pelletized. The obtained pellet was heat-treated at 300 ° C for 8 hours under a nitrogen gas flow to obtain a liquid crystalline resin. The liquid crystal resin obtained by the instrument (DSC) was measured to have a melting point of 352 〇c. The melting point was also determined by the following method. [Melt melting method] A polymer was scanned using a scanning thermal differential (DSC7 manufactured by PerkinElmer). The sample amount is about 1〇mg, and the temperature is raised from 5〇°c to 2〇c/min to 45〇°C, then cooled to 5°C at 20°C/min, and then at 2 (TC/min speed). The temperature was raised to 450 C, and the endotherm was measured. The melting point (C) was obtained by the endothermic peak of 2 times. <Filling material> Using marble and glass fiber as a filler, liquid crystalline resin/mica The mass ratio of glass fiber is 6 8 / 2 2 /1 〇, melting The liquid crystal resin and the filler are used. The mica and the glass fiber are as follows: Marble: AB-25S (The average particle size of Yamaguchi Mica Co., Ltd. is 25 m' volume specific gravity . Glass fiber: PF70E001 (grinding Crushed glass fiber manufactured by Nitto Textile Co., Ltd., fiber diameter 10 V ro, weight average length 7 〇m, volume specific gravity 〇. 5g/cm3) (Examples 1 to 3 'Comparative Example 1 and Comparative Example 2) Liquid crystallinity The melt-kneading of the resin and the filler is performed using ΤΕχ44 α 23 201107103 11 (manufactured by Nippon Steel Co., Ltd., L/D = 45.5, the first „0 plus snail diameter 46.25 inm, above ^ * 〇P 3 upper side The length of the end filler 佴仏~side end is L/D = 3.5(161.9_)), and the condition of two ports is 12. 1 c planted 2, B: set in the 帛1 kneading area 17 and the second kneading area 19 i practice component two thickness u to u" off the mixed white disc 21 phase angle 45. And, and the mouth of the transportable kneading elements are combined. In each of the examples and comparative examples, the i-th kneading The area 17, the second kneading area 19, the plasticizing part 15, and the kneading part 16 are shown in Table 2. The position and the length are placed in the steel cylinder of the two-axis extruder. Further, the plasticizing unit b and the kneading unit 16 are provided with the screw elements described in Table 2. Further, in the second and comparative examples, Nitrogen was introduced into the 2-axis extruder from the filler supply port and the second opening at a flow rate of 75 m3/hr.

^_Cylinder temperature 370〇C 1 Output volume 75kg/hr Drift rotation number 350rpm Complex temperature 365〇C Table 2 - Example 1, 2 Example 3 Comparative example 1. 2 Length of the first mixing zone L/D=6.5 L/D=6. 5 L/D=〇(300mm) (300mm) The lower part of the filling material supply port at the beginning of the first kneading zone (the flow side end of the filler supply port L/D=l. 5 downflow) The lower part of the filler supply port (the upstream side of the filler supply port L/D=1.75 is downflow) j 2 The length of the kneading zone L/D=0 L/D-3. 5 L/D=〇24 201107103 (161. 9mm ) 2nd kneading zone starting position - upper end of the second opening 18 - plasticizing section length L / D = 5.5 L / D = 5.5 L / D = 5.5 (254mm) (254mm) (254mm) plasticizable Part of the screw is arranged according to the flow smoothing component / According to the flow smoothing component / Reverse mixing according to the flow smoothing component Reverse mixing element component / Reverse kneading component Mixing section length L / D = 4.5 L / D - 4.5 L / D - 4.5 (208mm ) (208mm) (208mm) The mixing part of the screw is made up of the flow-mixing element / the flow-mixing element / the back-mixing, the flow-mixing element, the inverse kneading element / the inverse kneading element are measured by the following method. The dark spot content of the liquid crystalline resin composition obtained in Examples 1 to 3, Comparative Example 1 and Comparative Example 2 was obtained. The results of the black spot content measurement are shown in Table 4. [Evaluation method of black spot] A film-forming machine (2. 5 g/mud, film thickness 150 #m) liquid crystalline resin was used under the conditions described in Table 3 using a film extruder (a kneading machine/Labo-plastmi 1 and manufactured by Toyo Seiki Seisakusho Co., Ltd.). Composition. The film was placed in a white backlight, and the number of dark spots on each size (0.2-0.3 mm, 0.3-0.4 mm, 0.4-0.5 mm, g〇.5 mm) was confirmed using a magnifying glass. The above-mentioned black spot content was confirmed for the 40-grain mold (100 g), and the black spot content per unit weight was determined. Table 3 Screw diameter 20mm Screw length L/D=29 (groove depth: supply part 4. 0mm, metering part 1 · 7mm) Compression ratio 2.1 1 die 150mm wide, hanger type laminating mold impregnation thickness 150 // m 25 201107103 Table 4 BS size (mm) Example 1 (pieces/g) Example 2 (pieces/g) Example 3 (pieces/g) Comparative Example 1 (pieces/g) Comparative Example 2 (pieces/g) 0.2 - 0.3 0.40 0. 48 〇86 〇. 77 0.3 - 0.4 0.4 - 0.5 —-Μ〇0.15 0. 19 V/ · V/ V/ 1. 14 1.02 〇. 12 0.11 0. 11 0.77 0.58 0.56 0.47 ^0.5 0.09 0.11 From Table 4, from the results of Comparative Example 比较 and Comparative Example 2, the 2 axes were confirmed [within the exit. P, which only introduces the inert gas nitrogen, cannot sufficiently prevent the oxidation of the liquid crystalline resin and reduce the reduction effect of the BS. On the other hand, from the comparison of Example 1 and Example 2 with Comparative Example 1, the 纟2-axis extruder was confirmed! In the steel cylinder, the kneading element having the conveying force is used, and the generation of the first corpse 17' Bs is remarkably lowered. In the liquid crystal resin composition obtained in Example i, the production of the large-sized Bs of 3 mm or more was remarkably lowered, and it was applicable to a material having a thin-walled molded article of not less than 3 mm. From the results of the first embodiment and the second embodiment, it was confirmed that the introduction of nitrogen into the inside of the two-axis extruder 1 can improve the effect of reducing the occurrence of BS. Further, from the results of the first embodiment and the third embodiment, it was confirmed that the first kneading zone 17' was added to the two-axis extruder 并 and the second kneading zone 19 was provided, whereby the effect of lowering the production was improved. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a cross section of a 2-axis extruder used in the present invention. FIG. 26 201107103 ^ FIG. 2(a) and (b) are diagrams showing an example of a kneading element used in the present invention. 0 [Description of main component symbols] 1 to 2 axis extruder; 11 to liquid crystal resin supply port; 12 to filler supply port; 13 to first opening; 14 to discharge die; 1 5 to plasticizable section; 6 to the kneading department; 17 to the first kneading area; 18 to the second opening; 19 to the second kneading area; 2 to the kneading element; 27

Claims (1)

201107103 VII. Patent application scope: Manufacturing method, using a 2-axis extrusion to manufacture a liquid crystalline resin group 1. A liquid crystal resin composition is melted and mixed with a liquid crystal resin and a filler, wherein two axes are described. In the extruder, the upstream side liquid crystal resin supply port in the extrusion direction and the downstream side end portion in the extrusion direction are provided with a spout: ^ a liquid material supply port and a discharge mold W are provided with a filler supply port and a filler supply. The lower opening side has an i-th opening, and the two-axis extruder has a plasticized member supply port in the steel cylinder, and ι. * ^ ^ 向下 向下 且 且 且 且 且 且 且 且The upstream side end portion of the supply port is: / The first kneading zone ' is provided at the downstream side of the first kneading zone. = The section of the upper end portion of the first βρί mouth portion is provided with a kneading portion, and (1) the first kneading region is constituted by a kneading element having transportability. Manufacture: The liquid crystal resin composition described above, wherein the first kneading zone has a length L/D of 5 to 15. In the case of the liquid crystal resin composition described in the above paragraph, the two-axis extruder is provided with the second opening at the same position as the filler supply port or the upstream side of the filler supply port. unit. In the above-mentioned second opening, the second opening is provided in the filler supply port, and the second opening is provided in the second inlet of the liquid material resin composition of the above-mentioned liquid crystal resin composition. The lower section includes:::=: the upstream side end portion of the crucible, and the second kneading area is composed of a transporting kneading element. /, There are 28 201107103 Manufacture method::: The length of the 2nd I-zone of the liquid crystal resin composition described in the item "The circumference of the second aspect" is wide relative to the lower part of the first side end The length of the interval of the flow 曰 on the filler supply port is 70% or more. Manufacturer: The liquid crystal resin composition described in the scope of the patent application 帛1 &amp; method 'Yang Lai (4) Practicing phase angle 屮A 4·~η 丨卞疋 * * 练 练 练 练 练 练 练 练 练 练 练 练 练 练 练 练 练 练 练 制造 制造 制造 制造 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The volume specific gravity is 〇6g/cm3 or less. Each method of the liquid crystalline resin composition described in the above-mentioned patent scope 帛7, wherein the volume specific gravity of the filler is 〇.35 valence or less. 9: Patent application scope The liquid crystal resin composition according to the above aspect, wherein the filler contains at least one or more selected from the group consisting of talc, = mother, cerium oxide, and glass frit. 10. Liquid crystalline resin Form * to apply for the method described in the patent scope 帛i U. A device for producing a liquid crystal resin composition, which has a liquid crystal resin supply port at the t = side end portion in the extrusion direction, and a 2-axis extruder having a discharge mold at the downstream end portion in the extrusion direction In the above-described two-axis extruder, a filler supply port is provided in the middle of the liquid crystal resin supply port and the discharge die, and a first opening is provided on the downstream side of the filler supply port, and the two-axis extruder is in steel. The inside of the cylinder is provided with a plasticizing portion on the upstream side of the filler supply port, and the upstream end portion of the filler supply port is 29 201107103, and the second mixing portion is provided to the first opening portion. The section of the first end portion of the downstream side of the first kneading zone is provided with a kneading section, and is composed of a kneading component of the patent application scope and it: delivery. In the manufacturing apparatus, the liquid crystal resin composition of the above-mentioned liquid crystal resin composition is provided in the same position, and the second opening portion is further provided on the upstream side of the filling material supply port. In the above-mentioned two-axis extruder in the above-mentioned two-axis extruder in the above-mentioned steel cylinder, the lower portion of the upstream side end portion of the second opening is supplied to the filler. The second kneading zone is provided in a section below the upper side of the upstream side of the supply port, and the second kneading zone is constituted by a kneading element having a transport property. 30