TW201022345A - Liquid crystalline resin composition for injection molding, forming body formed from the composition, and camera module formed from the forming body - Google Patents

Abstract

It is known that the ultrasonic cleaning for cleaning the forming bodies will cause fibrillation on the surface of the liquid crystalline resin formed products , and it is an important cause that forms new falling substances (impurities), and it is also known that small impurities, dusts and so on once attach to the forming bodies will reduce the forming body performance such as optical features. The invention is to prevent the reduction of the optical features of the forming bodies and provide a technology that even if cleaning the crystalline resin-containing forming body by ultrasound, it still inhibit fibrillation on the surface of the forming bodies. The difference of the surface roughness Ra of the forming body and the mold is adjusted to below 0.1mm, in which the forming body is formed by injection molding a crystalline resin composition that includes silica having an average primary particle diameter below 5 μm. The silica preferably has an average primary particle diameter below 0.7 μm.

Description

[Technical Field] The present invention relates to a liquid crystalline resin composition for injection molding and a molded article formed from the composition. [Prior Art] This type of plastic material, called engineering plastic, has a high strength and gradually replaces metal parts. Among them, a plastic called a liquid crystal resin retains a crystal structure during melting, and has a high strength due to a crystal structure, a large change in crystal structure at the time of solidification, and a change in volume during melting and solidification. The advantage is that the molding shrinkage is small and the dimensional accuracy of the molded article is excellent. The liquid crystal resin is excellent in dimensional accuracy and is used for precision machine parts. In the case of precision machines, especially optical machines such as lenses, slight impurities, dust, etc. can affect the machine function. For example, for parts of an optical machine such as a camera module, small impurities, oil, and dust adhere to the lens, and the optical characteristics are remarkably lowered, and a satisfactory function cannot be obtained, so that water or the like is usually used. The s wave cleans the parts to remove small impurities, oil, dust, etc. attached to the surface. 'Liquid However, the liquid crystalline resin is a resin which is relatively easy to fibrillate because its molecular alignment is particularly specific at the surface portion. In the case of the liquid crystal tree, the ultrasonic cleaning itself for cleaning the molded body itself fibrillates the surface of the crystalline resin molded article, and becomes an important cause of the new exfoliated material (the product of the product 201022345). Therefore, it is necessary to produce a fibrillated liquid crystalline resin under general ultrasonic cleaning. A resin molded body comprising a liquid crystalline polymer and a fiber-like filler as a resin molded body for improving surface characteristics is disclosed, which is characterized in that the flat portion is formed by a specific surface tape peeling test. The obtained surface roughness ^ value increases by 〇 4 " below. The method of preventing the surface particles (foreign matter) 1 from being exposed to an electric/electronic device can be improved if it is effective as disclosed in Patent Document 1 or a part of an optical machine. Therefore, if the surface property of the patent document is used, as disclosed in the embodiment of Patent Document 1, the patent document is available! The foreign matter produced is gently mixed in pure water for 1 minute to clean the surface = raw foreign matter. Therefore, the improvement of the surface characteristics brought about by the method disclosed in Patent Document 1 cannot achieve the results of the suppression of the superfibrillation of the object of the present invention. That is, according to the method disclosed above, if the resin molded body is exposed to such severe conditions as ultrasonic cleaning or the like, a large amount of foreign matter is generated. Further, the injection molded body is superior to the ±, and the molecular alignment in the surface portion is large, and it is easy to cause the surface of the original door to easily generate hair. Therefore, there is a need for ultrasonic cleaning, which is a technique for improving capacitance. 'The surface of the injection molded body is applied. [Patent Document] No. 50 of the Patent Publication No. 50, Patent Document No. 50, JP-A-2008 The above-mentioned method of ultrasonic cleaning of the fibrillation liquid crystal-containing resin is solved. And finished, the purpose is to provide a shape that still inhibits the surface of the shaped body

[Means for Solving the Problem] The inventors of this case have continuously made meticulous research in order to solve the above-mentioned problem. As a result, it has been studied to use the liquid crystal resin composition containing a monoclinic π λα _J _ human particle diameter m or less, &quot;the surface roughness Ra of the injection molding die and the finished molding The difference in the surface roughness of the body is controlled within a specific range to solve the above problems, and the present invention has been completed. More specifically, the present invention provides the following. (1) A liquid crystalline resin composition for injection molding, comprising silica having an average primary particle diameter of 5/zrn or less. (2) The average primary particle diameter of the oxidized cullet in the liquid crystal resin composition for injection molding described in the above (1) is not less than the following. (3) The molded article obtained by injection molding the liquid crystal resin composition for injection molding described in (1) or (2), wherein the surface roughness Ra of the mold and the surface roughness Ra of the molded body are rough. The difference in degrees is 0.1 mm or less. (4) The difference in surface roughness in the molded article according to (3) above is 〇_03 mm or less. (5) A camera module formed of the molded body described in the above (3) or (4). [Effect of the Invention] 201022345 According to the present invention, the surface roughness Ra# of a molded body obtained by injection-molding a liquid crystal resin composition containing a specific average-order particle diameter is used for injection molding. The difference in roughness of the surface of the mold is adjusted to 0.1 or less, and the surface characteristics of the formed body can be improved. As a result, fibrillation does not occur on the surface of the formed body which has been cleaned by ultra-wave cleaning, and the adverse effect on the electronic device or the like due to the fibrillation can be suppressed. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, an embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiments as long as it is within the scope of the object of the present invention. It can be implemented by appropriately changing it. The present invention is characterized in that the surface roughness Ra of a molded body obtained by injection molding a liquid crystalline resin composition containing a cerium oxide having an average primary particle diameter or less (hereinafter referred to as a "liquid crystalline resin composition") The difference from the surface roughness of the injection molding die is adjusted to 〇lmm or less. In other words, by using a liquid crystal resin composition for injection molding containing an average primary particle diameter of 5/zm or less as a molding material, the completed molded body is cleaned by 9 waves, and the surface does not occur. Fibrillation achieves the effects of the present invention. The surface roughness of the molded body means the surface roughness Ra of the molded body before ultrasonic cleaning; the average primary particle diameter ' of the cerium oxide can be measured by a laser diffraction type particle size distribution measurement. <Liquid Crystal Resin Composition> 201022345 • The liquid resin composition is a liquid crystal polymer containing cerium oxide having an average particle size of 5 or less. Hereinafter, these materials will be described in the order of a liquid crystalline polymer and cerium oxide. [Liquid Crystal Polymer] The liquid crystalline polymer 'as used in the present invention' means a melt-processable polymer having a property of forming an optically anisotropic molten phase. The nature of the anisotropic molten phase can be confirmed by a conventional polarizing inspection method using an orthogonal polarizing plate. More specifically, the confirmation of the anisotropic melt phase can be carried out by using a Leitz polarizing microscope under a nitrogen atmosphere at a magnification of 4 times to be placed on a hot stage. The molten sample is applied. The liquid crystalline polymer which can be suitably used in the present invention is when examined between orthogonal polarizing plates. 'Polarizing light generally penetrates in a molten stationary state, and exhibits optical anisotropy. The liquid crystal polymer as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic poly esteramide, which is partially encapsulated in the same molecular chain. Polyesters of aromatic polyester or aromatic polyurethane are also within the scope thereof. It is better to use the above substances at 60. (: at a concentration of 0.1% by weight. / / dissolved in pentafluorophenol (pentaf luorophenol), having a logarithmic viscosity of at least about 2. Odl / g, more preferably having a logarithmic viscosity of .2.0 ~ 10.0 dl / g. Particularly preferred is an aromatic polyester or an aromatic polyamidamide which is suitable for use in the liquid crystalline polymer of the present invention, and particularly preferably has an aromatic hydroxy carboxyl ic acid and an aromatic carboxylic acid group. More specifically, at least one or more compounds of the aromatic hydroxyamine and the aromatic bisamine (ar〇ma1: ic 201022345 ha^nne) are aromatic polyacetates and aromatic polyamines as constituent components. More specifically, Examples thereof include: (1) a polyester mainly composed of one or more of an aromatic hydroxycarboxylic acid and a derivative thereof; (2) mainly composed of (a) an aromatic hydroxycarboxylic acid and a derivative thereof Or two or more kinds, (b) one or more of an aromatic dicarboxylic acid (ar〇matic dicarb〇xyHc aCld), an alicyclic dicarboxylic acid and a derivative thereof, (c) aromatic Alkene (ar〇[natic diol), alicyclic diol Alicyclic di〇1), an aliphatic diol (al lphatic diol) and a derivative thereof, or a mixture of two or more; (3) mainly composed of (a) an aromatic hydroxycarboxylic acid and a derivative thereof One or more of (b) one or more of the aromatic hydroxylamine, the aromatic bisamine, and the derivative thereof, and one of the '(c) aromatic dicarboxylic acid, the alicyclic dicarboxylic acid, and a derivative thereof Or a polyamine which is composed of two or more kinds; (4) one or more of (a) an aromatic hydroxycarboxylic acid and a derivative thereof, and (b) an aromatic hydroxylamine, an aromatic bisamine, and One or more of the derivatives, (c) one or more of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof, (d) an aromatic diol, an alicyclic diol, A polyammonium ester composed of one or more of an aliphatic binary fermentation product and a derivative thereof, and a molecular weight modifier may be used together with the above-mentioned constituent components.

Preferable examples of the composition of the above-mentioned liquid crystalline polymer which can be applied to the present invention, +, AB &amp; A m β 201022345 are p-hydroxybenzoic acid (p-hydroxybenzoic acid). , an aromatic hydroxycarboxylic acid such as 6-hydroxy-2-naphthoic acid, 2,6-di-naphthalene (2,6-(11117(11'〇1丫11&amp;;?111:11&amp;16116), 1,4-di-naphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, the following Aromatic binary fermentation of a compound represented by the general formula (I) and the following general formula (II); terephthalic acid, isophthalic acid

Acid) '4,4 4,4 diphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and the compound represented by the following general formula (III) Aromatic ditaminic acid; aromatic amines such as p-aminophenol and p-phenylenediamine. 【化1】

❹ (X. is selected from the group consisting of acetylene (C1-C4), alky 1 idene, 0-, -SO-, -s〇2-, one-S-, one-CO- ) 【化2】

9 201022345 【化3】

HOOC

COOH (Y. selected from -(CH2)n-(n=l~4), functional group) -(CH2)n - (n=i~4) [-emulsified second] The present invention is characterized by containing an average The particles are pinched by one or less dioxins. By injecting and molding a liquid crystal resin composition containing the above-described particle diameter of the above-mentioned particle diameter, the difference between the surface roughness of the molded body and the surface roughness Ka of the mold can be made (Klmm or less. As a result, ultrasonic cleaning is performed. It is still possible to suppress fibrillation on the surface of the molded body. It is preferable to use cerium oxide having an average primary particle diameter of 7 Å or less. As long as it is a bismuth oxide having the above-described general average-order particle diameter, it is easy to form. The difference between the surface roughness Ra of the body and the surface roughness Ra of the mold is adjusted as follows. By using the liquid crystalline resin composition described above, the surface characteristics of the molded body are greatly improved, and the molded body is ultrasonically cleaned and formed. The surface of the body does not cause two fibers to be formed. As a result, it is possible to suppress the adverse effects on the surface of the molded body due to fibrillation of the molded body, and it is extremely difficult to form a liquid crystal resin composition. The surface roughness of the molded body is adjusted to be within 〇1 mm from the difference in the surface roughness Ka of the mold; however, it is easy to contain cerium oxide having the above average primary particle diameter. Decoupling from the molding conditions and adjusting the surface roughness of the molded body to not more than 1 mm. However, if the average primary particle size is larger than the above range, it may be difficult to differ the surface roughness Ra of the molded body from the surface roughness Ra of the mold. The tendency to adjust to within 01ππη. The knot 201022345 • If the molded body is washed with super-sonic waves compared with the case of using the above-mentioned preferred particle size of cerium oxide, the surface of the molded body is likely to be hairy. The average primary particle diameter of the cerium oxide is 0.77 m or less, and it is easy to suppress the difference between the surface roughness of the molded body Ra and the rough radiance Ra of the mold surface to be less than min 3 min. Thus by using the average primary particle二 〇 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 In general, in the case of precision machine parts, especially in the case of an optical machine having a lens, a slight 'impurity dust, etc.> sounds the function of the machine. A molded body which is ultrasonically cleaned and has no hairy surface at all on the surface of the molded body, and is particularly suitable as a component of a precision machine or the like. As described above, by using a liquid crystal containing a TiO2 having an average primary particle diameter of 7 μm or less. The resin composition remarkably improves the surface characteristics of the molded body, and is particularly suitable as a component such as a precision machine. 平均 The average primary particle diameter of the liquid crystalline resin composition is 5 #m or less. The content of cerium oxide is not In particular, it is preferably 5% by mass to 50% by mass, and the content is preferably 5% by mass in the case of 5% by mass, so that it can be stably formed, and if the content is 50% by mass or less, significant accuracy is improved. The content of the liquid crystalline polymer is preferably from 1% by mass to 40% by mass. [Other components] The liquid crystalline polymer can be blended with other thermoplastic resins in a range that does not impair the effects of the present invention ( P〇iy· Mend). The thermoplastic resin to be used in this case is not particularly limited, but examples of 11 201022345 include polyolefins such as polyethylene and polypropylene; and polyethylene terephthalate (PET). An aromatic polyester composed of an aromatic dicarboxylic acid such as polybutylene terephthalate (PBT) and a diol or ox year boxy 1 ic acid; Polyacetal (homopolymer or copolymer); polystyrene; polyvinyl chloride; polyamine, polycarbonate, ABS, polyoxyphenylene oxide; polyphenylene sulfide 〇 lyOXyphenyiene sul f ide); fluorocarbon resin. Further, the thermoplastic tree of the above _ may be used in combination of two or more kinds. Further, in the above-mentioned resin, various additives and reinforcing agents may be added as needed in order to improve various properties such as mechanical properties, electrical properties, chemical properties, and flame retardancy. In the liquid crystalline resin composition of the present invention, a pigment such as a nucleating agent, carbon black, or an inorganic sintered pigment, an antioxidant, a stabilizer, a plasticizer, and a lubricant are added to the extent that the effects of the present invention are not impaired. A composition which imparts desired characteristics to an additive such as a release agent or a flame retardant is also included in the liquid crystalline resin composition used in the present invention. <Production of a molded article> The molded article of the present invention is obtained by injection molding the above-mentioned liquid crystal polymer for injection molding. When the liquid crystalline resin composition is injection molded, the molecular alignment is particularly large on the surface of the molded body, and the surface of the molded body is easily fibrillated when the molded body is ultrasonically cleaned. However, the burial J field uses a specific liquid crystalline resin composition as in the present invention' due to the surface roughness of the formed body.

Ra and the surface roughness of the mold are close to each other, and the cleaning of the surface of the formed body can be suppressed by ultra-cleaning, and the cleaning of the surface of the molded body can reduce the adverse effects of the fibrillation. The molding conditions are not particularly limited, and can be appropriately changed to the optimum conditions depending on the type of the liquid crystalline resin composition. The molding conditions at the time of the injection molding are not particularly limited, and although the type of the liquid crystalline resin composition may be a small amount of a stone, it is preferably a mold temperature of 80 〇C to 250 〇C.屮, by * ' m ® fandom at 30mm / Sec ~ 300mm / sec. Although the above forming conditions are very wide

It is also one of the features a of the present invention to provide a technique in which the difference between the surface roughness Ra of the molded body and the surface roughness of the mold is adjusted to be less than or equal to o.iram. As described above, if the average primary particle diameter 〇7 is used, the range of the forming conditions of the sulphur dioxide can be wider, and the surface roughness Ra of the molded body and the surface roughness Ra of the mold can be almost decoupled from the molding conditions. The difference is adjusted to be less than 0.1 mm. &lt;Molded article&gt; φ The molded article of the present invention is a molded article obtained by molding the above-described liquid crystalline resin composition by the above-described method. The molded article of the present invention is characterized in that the difference between the surface roughness Ra of the molded body after molding and the surface roughness of the mold is adjusted to 0.1 mm or less. By adjusting the difference in the surface roughness to the above range, it is possible to suppress the fibrillation of the surface of the molded body which occurs when the molded body is ultrasonically cleaned, and it is possible to prevent the resin from being fluffed by the fibrillation. And it has an adverse effect on electronic machinery and the like. The difference between the surface roughness Ra of the more preferable molded body and the surface roughness Ra of the mold is 〇. 3 dragons or less. The difference in surface roughness is suppressed to 〇·03 min or less, because the reason is that, as described above, by washing the completed molded body by ultrasonic waves, it is possible to obtain an excellent molded body which is visually confirmed to have no hairiness at all. It is especially suitable as a part for precision machines and the like. The molded body of the present invention is suitable for use as a carriage or a carrier for, for example, a camera, a laser disc pickup, or a floppy disk player (fl〇ppy (registered trademark) disk player) The precision machine parts that are ultrasonically cleaned after forming, such as the lead SCrew or the read head of the optical disc player, are also particularly suitable for precision zeros that are subject to friction, impact, and the like. According to the present invention, the molded body is formed by suppressing the difference between the surface roughness Ra of the molded body and the surface roughness Ra of the mold, so that the surface of the molded body can be suppressed by ultrasonic cleaning of the molded body. . Therefore, it is possible to avoid the adverse effects of the resin powder caused by fibrillation. In particular, the molded body 'of the present invention' is suitable for use as a camera module in a camera part. As described above, in particular, if the average primary particle diameter of the dioxo prior is 0.7 or less, it is easy to suppress the surface roughness of the molded body to 0.30 nm or less. An excellent molded body in which no hairy matter is produced at all. In this way, if it is a molded body in which no hair is generated, it is particularly applicable to precision machine parts such as a camera module, a surface acoustic wave chopper (a filter), and a hermetic seal such as a _^ (4). use. [Examples] The following examples are given to illustrate the invention in more detail and are not limited by these examples.仁本本14 201022345 • <Materials> • Liquid crystal polymer: VECTRA E950 iSX (Bao Li plastic (polypIasi: ics) company) Glass fiber: ECS03T-786H (made by Nippon Electric Glass Co., Ltd.) fiber diameter 10. 5 &quot; m (The fiber length of the glass fiber is adjusted by the extrusion conditions (screw speed, cylinder temperature)) 真 True spherical cerium oxide: ADMAFINE S0-C2 (manufactured by Admatechs), average primary particles 〇5# m True spherical cerium oxide: DENKA molten cerium oxide (]) J: nKA FUSED SILICA) (manufactured by Electric Chemical Industry Co., Ltd.), average primary particle diameter 4.0# ^ <Example> Table 1 The ratio is formed using the materials shown in Table i under the molding conditions shown below. The mold temperature and the ejection speed were formed under the conditions shown in Table i. A molded body of 12. 5 mm x l 2 0 mm x 0 · 8 mm was completed. The cut into the form is cut into half for evaluation. [Molding conditions] Forming machine EC40 (manufactured by Toshiba Machine Co., Ltd.) &amp; body temperature 350 ° C Holding pressure 50 MPa x 5 seconds Cooling time 10 0 screw speed 100 r. p. m Screw back pressure IMPa 15 201022345 <Comparative example> Table 1 The materials shown in Table 1 were used in the proportions, and they were molded under the same molding conditions as in the examples. A molded body of the same size as the embodiment was completed. <Evaluation> The surface roughness of the completed molded body was measured. For the central portion of the formed body which was cut into half, the surface roughness Ra was measured using an ultra-deep color 3D shape measuring microscope VK-9500 (manufactured by KEYENCE). Further, the surface roughness Ra of the mold was also measured in the same manner as the molded body. The molded articles cut into half of the examples and the comparative examples were subjected to the action of the ultrasonic cleaner under the conditions of 1 minute of water at room temperature. Thereafter, the molded body before and after the action of the ultrasonic cleaner was compared, and the area (hair raising area) of the hairy portion on the surface of the molded body was evaluated. The measurement of the area of the hairy portion that has been produced is performed by visual inspection. Table 1 shows the average of the three-person assessment. Further, Fig. 1 shows the relationship between the surface roughness before the action by the ultrasonic cleaner and the raised area after being subjected to the ultrasonic cleaner. The evaluation area is 750mm2 (12.5mmx60mm). [Table 1] Liquid crystalline polymer mass % Glass weave quality! *6 Glass fiber length yin Ceria mass% Mold temperature V Injection speed mm/sec Fleece area mm2 Surface roughness of molded body Ra mm Mold surface roughness Ra Mm surface roughness of the dish η Example 1 (A) 90 10 (: * 1) 90 80 0.0 0. 227 0.25 0.023 Example 2 (B) 80 2〇mi) 90 80 0.0 0.232 0.25 0.018 Example 3 ( C) 70 30 not 1) 90 80 0.0 0.223 0,25 0.027 Example 4 (D) 60 40 not 1) 90 80 0.0 0.222 0.25 0.028 Example 5 (E) 70 30 (*2) 90 80 4.7 0.312 0.25 0.062 Comparative Example 1 (F) 70 30 500 90 80 101.3 0. 383 0.25 0.133 Comparative Example 2 (G) 70 30 390 90 80 66.2 0.374 0.25 0.124 Comparative Example 3 (H) 70 30 280 90 80 25.8 0.355 0.25 0.105 *l : ADMAFINE SO-C2 (manufactured by Admatech Co., Ltd.) ※: DENKA FUSED SILICA (manufactured by Electric Chemical Industry Co., Ltd.) 201022345 was used. Results from Example 5 and Comparative Example 4 of Fig. 1 and Table 1. Ming Media shows that by using the liquid crystal of the two gasification dreams containing the average-order particle diameter below Lipid composition, surface roughness of the formed body can be rib mold surface roughness Ra of the difference between the adjustment slit below to ultrasonic cleaning may still be suppressed to the molded article surface area of fuzz. The raised area after ultrasonic cleaning of the molded body is preferably below the heart, more preferably 0 or less. When the surface characteristics of the molded article can be improved to a considerable extent as to achieve the above-described preferred raised area, the adverse effect of the resin powder due to fibrillation can be sufficiently suppressed. When the average-human particle diameter 7·7 以下 or less is used, the raised area after ultrasonic cleaning can be suppressed to 〇龅2, and it is particularly suitable for parts such as precision machinery. [Simplified illustration] The figure shows the relationship between the difference between the surface roughness Ra of the molded body and the surface roughness φ Ra of the mold and the area of the raised surface after being subjected to the action of the ultrasonic cleaner. [Description of main components] No. 17

Claims (1)

201022345 VII. Patent application range: 1. A liquid crystal resin composition for injection molding, comprising cerium oxide having an average particle diameter of 5/zm or less. 2. Liquid crystal for injection molding as described in claim 1 of the patent application. A resin composition in which the average primary particle diameter of the cerium oxide is as follows. 3. The molded article of the present invention is obtained by injection molding a liquid crystalline resin composition for injection molding as described in the above-mentioned Patent Publication No. i, wherein the surface roughness Ra of the mold and the surface roughness Ra of the molded body are surface roughness. The difference is 0. lmm or less. 4. The molded body according to the third aspect of the invention, wherein the difference in the roughness of the surface is 0. 〇 3 mm or less. A camera module is formed by a forming body as described in claim 3 of the patent application. 18