TW397859B - Liquid crystal polyester resin mixture, and molding method using such mixture - Google Patents

Abstract

This liquid crystal polyester resin mixture is prepared by mixing 100 pts.wt. Liquid polyester composition mainly consisting of 100 pts.wt. Liquid crystal polyester and 0-150 pts.wt. Filler with 0.001-5 pts.wt. Higher fatty acid ester at below the flow temperature at which the melt viscosity is 48,000P when the resin heated at a rising rate of temperature of 4 DEG C/min is extruded through a nozzle of an inside diameter of 1mm and a length of 10mm under a load of 100kgf/cm<2> . This invention is to provide a liquid crystal polyester resin mixture which itself can be stably plasticized during molding and can be stably molded to give a molding excellent in mechanical properties and heat stability and to provide a method for molding the same.

Description

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (3) Invention of the invention The invention relates to making the liquid crystal polyester with stable plasticity during forming processing, stable forming processing, and A liquid crystal polyester resin mixture capable of providing a molded body excellent in mechanical properties and thermal stability, and a method for forming a liquid crystal polyester using the liquid crystal polyester resin mixture.琎 Mingxi Liquid Crystal Polyester Because the molecules are rigid and straight, even in the molten state, they do not cause complexation to form a polydomain with a liquid crystal state. By lowering the shear rate, the molecules can make the molecules The bond shows a significant directional behavior in the direction of flow, and is commonly referred to as a thermofropic liquid crystal polymer. Due to this specific behavior, liquid crystal polyacetate has superior melt flowability. Depending on the structure, it has a heat resistance of 30 〇 Μ. Therefore, it is widely used in electronic components, such as OA, AV components, and heat-resistant tableware. Body use. The forming method for producing these shaped bodies is generally a method using a screw extruder such as injection molding or extrusion molding. At this time, the liquid crystal polyester often suffers from instability problems during its plasticizing operation step. That is, the plasticizing time is not fixed and unstable, which occurs during injection molding. The plasticizing cannot be completed in the cooling time, and the molding cannot be performed within a fixed period. Therefore, the productivity is reduced, and the quality of the molding is also reduced. Has adverse effects. Although the reason why the plasticizing time of the liquid crystal polyester is unstable is not clear, one of the reasons is that the melt viscosity of the liquid crystal polyester itself has a large dependence on the shear rate and temperature. The surface of the particles is selectively plasticized to produce a fusion phenomenon. (Please read the precautions on the reverse side before filling out this page) 'Package. The size of the bound paper is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) 3 A7 B7 Printed by the Employees' Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs Description of the Invention (4) 1 I is a method for suppressing this phenomenon &gt; Japanese Patent Publication No. 5-1 2 5 2 59 No. 1 I reported that the molten liquid crystal type liquid crystal polymer is compounded with a higher fatty acid gold 1 1 I Method of composition containing fluorene and higher fatty acids 0 Another 1 Japanese Patent Application Laid-Open No. 5-/ · -—V 1 1 I Please refer to Japanese Patent Publication No. 125258 to disclose the use of molten liquid crystal type liquid crystal polymer particles and high-level preliminaries (1%) 鈒A mixture of particles made of fatty acid metal Μ is a method for making plasticization stable on the back I 1 1 0 Note 1 but 9 Any one of the above conditions has a high thermal conductivity of the liquid crystal The polymer will decompose at 1 t at high temperature * and because of the use of higher fatty acids or its writing on this page '— ^ | Jin Ye will produce the liquid crystal polymer molded article f within 1 1 | A large amount of gas is produced which is difficult to stabilize. 9 At the same time, there are still doubts about reducing the thermal stability of the resulting 1 1 product. 9 Therefore, it is still not very satisfactory for the highly practical 1 1 0 Order 1 IL Obviously 1 The 100th aspect of the present invention is to solve the above-mentioned problem point 9 and provide 1 + 1 I man-hours. The resin mixture itself has stable plasticity. * Stable 1 1 wire forming processing »and Liquid crystal polyester resin mixture K capable of forming a molded body having excellent Russian physical properties and thermal stability, and liquid 1 using the liquid crystal polyester resin mixture Forming method of crystalline polyester 0 1 1 The present inventors, etc. in order to solve the above-mentioned problems &gt; 9 results after an intensive review 1 I found &gt; In the liquid crystal polyester or M liquid crystal polyester and the filler as the main component of the liquid crystal 1 polymer In the ester resin composition, 9 can be obtained when a compound of at least 1 1 1 M in a group composed of a phosphorus compound gas 1 1 carbon-based surfactant and a higher fatty acid ester is blended with a specific amount of white. Liquid Crystal Polyester Resin Mix 1 1 by using this mixture for stable liquid crystal polymerization during the molding process 1 1 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 4 Central Bureau of Standards, Ministry of Economic Affairs A7 B7 printed by employee consumer cooperative V. Invention description (5) Plasticization of ester. Accordingly, the present invention has been completed. That is, the present invention is an invention as shown below. (1): 100 parts by weight of the liquid crystal polyester resin composition containing 100 to 150 parts by weight of the M liquid crystal polyfluorene and the filler as the main component will be selected from the group consisting of a phosphorus compound, an aerocarbon surfactant, and a higher fat The liquid crystal polyfluorene resin mixture, which is characterized by mixing K at a flow temperature below the liquid crystal polyester resin composition below 0.001 to 5 parts by weight of at least one compound of K in the group formed by the acid ester, is characterized by being mixed. Flow temperature: When the resin is under a load pressure of 100 kgf / cm2, the heating and heating speed of M4 / min makes the resin extrude from a nozzle with an inner diameter of linm and a length of 10mm to K, and shows a melt viscosity of 48000poise (poise ) Temperature. (2): A liquid crystal polyester resin mixture, which is a liquid crystal polyester resin mixture according to item (1), which is characterized by mixing 0.001 to 5 parts by weight of a phosphorus compound with 100 parts by weight of a liquid crystal polyester resin composition. (3): The liquid crystal polyester resin mixture described in the item (2) further contains 0.001 parts by weight of higher fatty acid M, and the total amount of the phosphorus compound and the higher fatty acid is 0.002 to 5 parts by weight. . (4): The liquid crystalline polyester resin mixture described in the item (3) further contains at least one selected from the group consisting of oxides, peroxides, multiple oxides, and carbonates of the 鼷 -free 1A or 2A group of gold tinctures. 0.001 parts by weight or more of the compound on M, and a phosphorus compound, a higher fatty acid, and at least one compound selected from the group consisting of oxides, peroxides, multiple oxides, and carbonates of gold sulfonium belonging to the 1A or 2A group The total amount is 0.003 ~ 5 parts by weight is 1—n Ji I-I n-ίί-I J- (please read the precautions on the back before filling this page). The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 5 7 Β It is stated that the 'five highs have a step 1 in the middle of the blend tree. Ester polymer crystal mixed with liquid resin, ester-containing polymer term crystal, liquid shock 2 / IV, high in lipids and compound phosphorus, and M1 parts 02. 0 s ο s. Tj 1 is ooft ο count The properties of the combined polygalacic acid is a fatty stearic acid-grade fatty ester polycrystalline liquid, which is characterized by the amount of S 3 5 groups of fatty resin polycrystalline liquid. Mixed fat): ί 6 trees &lt; special properties of the material ο combination of synthetic active fat surface dendritic ester polycarbon crystal fluorine liquid to be mixed together to record the number of parts 1) 6B 0 for the amount of 1 3 5 The composition of the special group of fatty resin esters of poly-gl-liquid 00 is 0., esters, fatty acids, mixed fatty resins, esters of M, polymer crystals, mixed liquid, 1 3 il, S 5 compounds, mixed resins Polycrystalline Poly-Yo-Yan's entry item in liquid formula containing M esters

The construction of the complex display table of the least-to-single order \ n / 1ί The sign of the A is the body of the 3 (7 all or 6) of the mixed polyester polycrystalline liquid

c = o

(A ---- * --- ^ --- ί installed ------ order-^ ---- line (please read the precautions on the back before filling out this page) Central Sample Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperatives (9): K Uses the liquid crystal polyester resin mixture described in (1), (2), (3), (4), (5), (6) or (7) A method for forming a liquid crystal polyester. A detailed description of the liquid crystal polyester used in the present invention is a polyester called a molten liquid crystal polymer, which can be listed as follows: (1) Aromatic dicarboxylic acid and aromatic diol Combination with aromatic hydroxycarboxylic acid This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm). 6 Consumption cooperation with employees of the Central Bureau of Standards of the Ministry of Economic Affairs. Printed A7 B7 5. Invention Description (7) · I (2) A combination of different types of aromatic hydroxycarboxylic acids, 1 (3) A combination of aromatic dicarboxylic acids and aromatic diols, (4) Poly (p-paraben) Reaction products such as polyesters and aromatic hydroxycarboxylic acids will form anisotropic melts at a temperature of 400ΌM. In addition, these aromatic dicarboxylic acids, aromatic diols, and aromatics The carboxylic acid can also be replaced by a reactive derivative that can form such an ester compound. As for the repeating structural unit of the liquid crystal polyester, the following can be exemplified, but not limited thereto. 1 Derived from aromatic hydroxycarboxylic acid Repeating construction unit:

(Xl: halogen, alkane.) Ο

, ------- I installed ------ order ------ line * 1 J (Please read the precautions on the back before filling in this page) (A2) ο This paper size applies to China Standard (CNS) A4 specification (210X297 mm) 7 Consumption cooperation by employees of the Central Bureau of Standards of the Ministry of Economic Affairs Du A7 B7 5. Description of the invention (8) Repeated structural units derived from aromatic dicarboxylic acids

Ji Xiangfang (please read the precautions on the reverse side before filling out this page). The size of the paper and thread is applicable to the Chinese National Standard (CNS) A4 (2 丨 0X297 mm) 8 Α7 Β7 V. Description of the invention (9) The repeating structural unit of the self-aromatic second yeast: 0 (Cl) 〇 quao ο 0 taste ο (C2) (C3) (Please read the precautions on the back before filling this page) -5 ο ο (¾: halogen, courtyard , Aromatic group) χ2 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

I The paper size applies to the Chinese National Standard (CNS) Λ4 is present (210X297 mm) V. Description of the invention (10) A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

ο —Ί ----- /; 丨 install ------ order ------ line'-] (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards ( CNS) A4 (210X297 mm) is printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __B7 V. Description of the invention (11) From the balance of maturity resistance, mechanical characteristics, and processability, especially suitable is Those having a repeating structural unit represented by the aforementioned formula Aι of at least 30 moles. Specifically, a combination of repeating structural units M is preferably one of the following (3) to (f). (a): (/ U), (Βι) or (mixture of Bd and (B2), (Ci). (b): (Ai), (A2)) (c): Combination of structural units in (a) In part, Ai was replaced by A2. (D): In the structural unit combination of (a), B1 was replaced by B3. (E): In the structural unit combination of (a), Ci Partially replaced by Cs. (F): In the combination of structural units of (b), the structural units of Bi and Ci are added. The liquid crystal polyesters of (a) and (b) as the basic structure are each respectively It is described in, for example, Japanese Unexamined Patent Publication No. 47-47870 and Japanese Unexamined Patent Publication No. 63-38 88. In the present invention, a filler is added to the liquid crystal polyester as needed, and the amount of filler is added. For 100 parts by weight of liquid crystal polyester, the filler is added at 150 parts by weight, preferably 20 to 100 parts by weight is added to 100 parts by weight of liquid crystal polyester. When the amount of filler exceeds 150 parts by weight, the composition The melt viscosity of the material becomes higher, and the granulation and moldability will be reduced. As far as the liquid crystal polyester resin mixture of the present invention is concerned, its plasticity during the molding process ^ --.---- I Loading -------- Order ------ 0 (Please read the notes on the back before filling this page) This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) A7 B7 5 2. The stability effect of the invention description (l2) will be worse. The average particle size is the shape of the ingot, which is usually more common. Groups of groups jm § HHM ff-B tree resin polycrystalline liquid Liquid 〇 Use the shape to make a piece of crystal hair or the shape ο 1 × on the M em 1X diameter particles on the small diameter particles are flat at the moment of the addition of the stalk-like spiral ball to make or shape like a column, round -B in m and B in the state of difference between morphology and surface shape, which is obtained in the production process, 10 mm, 10 is easy to flatten in the body and in the air The diameter of the screw He can be injected into the stalk tree with a moment of time and the mixture is turned into a mixture of 'e group ns. The resin is made of resin, which can be difficult to crystallize, and the trapped liquid is limited to a specific system. The method should not be adopted and the film should not be merged, and the crystal height or the extract and the crystal liquid mixture should be mixed and rolled. The hot hole of the agent hole is fixed, the mold agent is good, the modified type is mixed and melted and added. When the line is OK, it must be squeezed, the material is filled, and the filler is colored with a die-cut blade or knife. After the shape of the spinner is used, the fat-fixed tree is melted and melted, and the IJ-reamer is used to turn the fat-rotate tree, and the melting point of the melted hole of the fat-hole tree is to be reversed. Ester-polycrystalline is more common than raw materials, and the shape is broken (please read the precautions on the back before filling out this page). Packing. Order staff of the China Standards Bureau of the Ministry of Economic Affairs Consumption cooperative printed fission alumina, aluminum oxide, sand crystals, crystallites or cellulose particles can be filled into crystal liquid materials, which can also be used for filling and filling. Titanium oxide in the slippery oxygen, use, stone, so that the cloud can be white. Aluminum and other calcium acid materials are filled with strong carbon, carbon filling, organic crystal materials without potassium, strong acid supplements such as titanium beads, glass-like glass fiber needles, carbon-like soil, viscose fiber, gray mother silicon There is no such thing as isocyanate and phosphorus. It is recommended to use the price 5 or 3M for the two species of phosphorous species, but the price 3 for the phosphorous compound. For example, if you list it, you can use a moderate rule of paper I. I Printed by A7 __B7, Employee Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China. V. Description of the invention (13) Distearate isopentaerythritol diphosphite, bis (2,6-di-third-butyl-4 -Methylphenyl) isopentaerythritol diphosphite, # (2,4-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-tert-butyl) (Phenyl) octyl sulfinate, (2,4-di-tert-butylphenol) 4,4'-diphenylphenyl diphosphonate, and the like. In the present invention, fatty acids having a higher fatty acid number of more than 10 are used. As examples of higher fatty acids, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, arsenic acid, arsenic tetrasulfonic acid, arsenic sulfonic acid, etc. can be listed, among which stearin Acid is preferred. The metal oxide supergases used in the present invention in the 1A or 2A group are represented by the general formula M20, M · 0, or M · 02 (where M is a group 1A and M ′ is a gold group 2A羼 element.) In particular, M is preferably selected from Ha, K, and M 'is preferably selected from Mg, Ca, and Ba. Specific examples include calcium oxide (99.9〆), magnesia (heavy-weight, reagent special grade), barium gasification (for chemical use), barium gasification (wako one), and Wako Pure Chemical Industries, Ltd., Micromag 3-30 of Kyowa Chemical Industry Co., Ltd. is not limited by these. The complex gas containing a metal belonging to the group 1A or 2A used in the present invention is pseudo-general formula M20. MM "〇2 · χΗ2〇, M'0 · mM" 〇2 · χΗ2〇, Μ2〇 · p Μ &quot; '2 0 3 ♦ m Μ &quot; 0 2 ♦ xH2〇 or M2〇 * ρΜ'ΟπιΜ &quot;, 2〇3 * η Μ &quot;' 0 2 ♦ χΗ2〇 (where M is a metal element belonging to group IA, M ′ is a metal element belonging to group 2A, M ″ is a metal element with a valence of four, M ″ ′ is a metal element with a valence of 3, ρ, m, and η are positive numbers of 1 or more, and x is a positive number of 0 or more). In particular, M is preferably K, and M 'is preferably selected from Mg, Ca, and Ba. As for specific examples, such as wollastonite, chain limestone, mica, potassium titanate, gadolinium titanate, etc., 13 paper sizes are applicable to China National Standard (CNS) A4 specification (210X297 mm) ----- -------- ^ ------, 1T ------- ^-* '-(Please read the precautions on the back before filling out this page) Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printing A7 B7 V. Description of Invention (14) is not limited by these. The rubidium acid containing a metal belonging to Group 1A or 2A used in the present invention is represented by the general formula M2CO3, M'C03 or M '* M "(C03) 2 (where M is Group 1A, M' And "M" is a golden hurricane element belonging to group 2A). In particular, M is preferably K, and 'M' is preferably selected from Mg, Ca, and Ba. Specific examples include, but are not limited to, potassium sulfonate, calcium sulphate, dolomite, and the like. The higher fatty acid metal hafnium used in the present invention means a metal hafnium of a fatty acid having a sulfonate number of 10 or more. As examples of the higher fatty acid metal rhenium, metal rheniums such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, osmanthus trisolic acid, ostetrasolic acid, and octasulfonic acid can be listed. The metals in these higher fatty acid metals are generally metals of Groups 1A, 1B, 2A, and 2B. As for the preferable metal, lithium, sodium, potassium, magnesium, calcium, barium and the like can be listed. Preferred higher fatty acid metal rhenium includes, for example, calcium stearate and barium stearate. The phosphorus compound, the higher fatty acid, and the higher fatty acid gold compound used in the present invention are preferably powdery or granular in order to easily mix with the liquid crystal polyester resin composition. In addition, the particle size of at least one or more compounds selected from the group consisting of phosphorus compounds, higher fatty acids, vapors, overgases, regasifications, and sulfonates of metals belonging to Groups 1A or 2A, and higher fatty acids, The average particle size is preferably less than 100wm, and the average particle size is less than 50wn. When the particle size is 100 wm or more, the plasticizing stability effect is insufficient during the forming process, so it is not good. In the liquid crystal polyester resin mixture of the present invention, the phosphorus compound is compounded. Ί batch clothing ------ ΐτ ------. Line-* V-(Please read the precautions on the back before filling this page ) This paper scale is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm). 1 Consumption cooperation by the Central Bureau of Standards of the Ministry of Economic Affairs. Printed B7. 5. Description of the invention. (15) Proportion to 100 parts by weight of liquid crystal polyester. Or the total weight of the liquid crystal polyester and the filler is 0.001 to 5 parts by weight, and the preferred compounding ratio is 0.003 to 1 part by weight. When the compounding ratio of the phosphorus compound is more than 5 parts by weight, gas will be generated due to the decomposition of the phosphorus compound during the molding process, and expansion artifacts are likely to be formed on the molded product. Therefore, the generated gas of the molded product will increase, which will not affect the product. good. In addition, when the compounding ratio of the phosphorus compound is less than 0.001 parts by weight, the plasticizing and stabilizing effect during the final molding process is insufficient, which is not good. In the liquid crystal polyester resin mixture of the present invention, the total proportion of the phosphorus compound and the higher fatty acid or the total amount of the phosphorus compound and the higher fatty acid metal is 100 parts by weight of the liquid crystal polyester, or the liquid crystal polyester and the filler. The total 100 parts by weight is 0.002 to 5 parts by weight, and the particularly preferred blending ratio is 0.003 to 1 part by weight. When the total amount of the phosphorus compound and the higher fatty acid, or the total proportion of the total amount of the phosphorus compound and the higher fatty acid gold tincture is more than 5 parts by weight, gas will be generated due to the decomposition of the phosphorus compound and the higher fatty acid during the molding process, and the molding It is easy to produce swelling on the product, and more gas is generated from the molded product, so it is not good. In addition, if the total amount of the phosphorus compound and the higher fatty acid, or the total ratio of the total amount of the phosphorus compound and the higher fatty acid gold tincture is less than 0.002 parts by weight, the plasticizing stabilization effect during the final forming process may be insufficient. good. In the liquid crystal polyester resin mixture of the present invention, a total of at least one compound selected from phosphorus compounds, higher fatty acids, and oxides, peroxides, multiple oxides, and carbonates of metals of Group 1A or 2A is compounded. The proportion is: for the 100 parts by weight of the liquid crystal polyester or the paper size of the liquid crystal polyester and the filler, the Chinese National Standard (CNS) A4 specification (21 ×: 297 mm> 1 to 5 ----- -^ ------, order ------ line «(Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (16 ) For a total of 100 parts by weight, it is 0.003 to 5 parts by weight, and a particularly preferred compounding ratio is 0.005 to 1 part by weight. When it is composed of phosphorus compounds, higher fatty acids, and gold oxides of 1A or 2A group, When the total compounding ratio of at least one compound selected from gaseous compounds, double oxides, and sulfonates is more than 5 parts by weight, gas is generated due to the decomposition of phosphorus compounds and higher fatty acids during the molding process, and it is easy to generate on the molded product. Swelling phenomenon, due to There is more gas in the molded product, so it is not good. In addition, when the total ratio of the phosphorus compound and the higher fatty acid, or the total ratio of the phosphorus compound and the higher fatty acid metal is less than 0.003 weight, the plasticity during the final molding process The stabilization effect of chemical conversion will be inadequate, so it is not good. 1 · The fluorosulfonate 糸 surfactant used in the present invention is based on fluorosulfonyl as the backbone, and it is more common to impart a hydrophilic group to it. Generally speaking, the use of The linear or side fluorinated perfluoroalkyl group (CnF2n + i) with a number of 6 to 10 is a hydrophobic backbone, and the hydrophilic group is sulfonium sulfonate, carboxylic acid sulfonium, ammonium sulfonium, ammonium sulfonate, etc. It is suitable that the fluorosulfonium surfactant has a particle size of 80 mesh. As examples of commercially available products, potassium persulfonium such as perfluoroalkylsulfonic acid can be cited, such as the trade names Florad FC-95 and FC-93. (Manufactured by 3M), Megafak F-110 [manufactured by Dainippon Ink Chemical Industry Co., Ltd.], lithium trifluoromethanesulfonic acid such as Florad FC-124 (manufactured by 3M), and highly side-bonded perfluorocarbon Compiled acid products such as commercial Futajent 100, 110 (manufactured by Neos), etc. In the Mingzhi liquid crystal polyester resin mixture, the blending ratio of the fluorescein surfactant is 0.001 to 5 parts by weight based on 100 parts by weight of the liquid crystal polyester or 100 parts by weight of the total of the liquid crystal polyester and the ballast. , Especially applicable to Chinese paper standard (CNS) A4 specification (210X297 mm) than this paper size 1 6 -------- fi installation ------ order ------., Line * / (Please read the notes on the back before filling out this page) A7 B7 V. Description of the invention (1?) The best blending ratio is 0.003 ~ 3 parts by weight. Fluorosulfur surfactants are usually formulated with a weight of 0. In the interim time, the plasticity can be changed. In addition, the time between plasticity and plasticity can be reduced by 5S. The formation of raw products will decrease at the same time. The strong machine is not good, and its color is added to increase the quantity of the body. 1 * foot 00 is not 0. It will be full of fruit and will not be instantiated. After adding the sulfonated fluorine, the outermost, at this time, the amount of fatty acid decanoate is as high as possible, and the atomic example of fatty acid fatty acid is higher than that used. The Ming wrote this. It is one of the best works, so it is a sulfonate based on diacid, sulfonated hard acid, saccharic acid, laconic acid, fat, and stearic acid ester. Vinegar and so on are made from palmitic acid, sulphuric acid and octave cardamom, beans, and exocarnitic acid. Sour good cassia is better than glutamate, sour, sour, succinyl, pentamyl, acetol, glucosamine, glucosamine, glucosamine, saccharine, etc. Phenyl sulfadiene, ethyl alcohol, and oxyalcohol are polymerized with fat and fat, the highest should be υ 30 to full P and 3 points to be used for melting, so that if the melting point of the good alpha ester is more acidic, it is fat. The upper level is melted with 50 points of high V (Please read the precautions on the back before filling this page)

• 1 &gt;.. VH gutters Printing department of the Central Consumers Bureau of the Ministry of Economic Affairs, Consumers Cooperative Co., Ltd. The plastics are available at all times. After adding the mixed resin into the ester of the tree, the liquid will be dry and dry. The former will form an ester into an acid and a fat, and a high-ester resin polycrystalline liquid of a high-grade ester and an easily-acceptable fatty acid ester. The effect of low-grade and high-decreasing fruits is clear and stable, and the hair is safe and stable. The mW is o ffl 10U, over 00, and the diameter is 0. The particles are uniform and flat, with a particle size or granular end ester. 3 powder acid. 5 as fat. Man Yizhi Wei, grade diameter and high-grain mixed, in addition to the material, this group should be the fat person in the diameter of the grain ο should be more suitable for this paper size China National Standards (CNS) A4 specifications (210X 297 mm ) B7 Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China. 5. Printed on the invention description (18), the stability effect of plasticization is insufficient during the forming process, so it is not good. In the liquid crystal polyester resin mixture of the present invention, the blending ratio of the higher fatty acid ester is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal polyfluorene or 100 parts by weight of the total liquid crystal polyester and the filler. Parts, particularly a suitable blending ratio of 0.003 to 1 part by weight. When the blending ratio of the higher fatty acid ester is more than 5 parts by weight, gas will be generated due to the decomposition of the phosphorus compound during the molding process, and a swelling phenomenon is easily generated on the molded product. At the same time, more gas is generated from the molded product. Not good. In addition, when the compounding ratio of the higher fatty acid ester is less than 0.001 parts by weight, the stabilization effect of plasticizing at the time of the final molding process becomes insufficient, so it is not good. '' In the liquid crystal polyester resin mixture of the present invention, at least one compound selected from the group consisting of higher fatty acids, oxides, peroxides, double oxides, and carbonates of the group 1A or 2A gold sulfonium, high fluorinated fatty acids Those with external lubrication effects such as metal rhenium and fluororesin can also be mixed with fluorocarbon rhenium surfactant or higher fatty acid ester simultaneously with the liquid crystal polyester resin composition. To the liquid crystal polyester resin composition used in the present invention or the liquid crystal polyester resin mixture of the present invention, as long as the purpose of the present invention is not impaired, coloring agents such as dyes and pigments can be added; antioxidants, heat stabilizers, ultraviolet absorbers f .. Additives, antistatic agents, surfactants and other common additives. In addition, you can also add a small amount of thermoplastic resins, such as polyamines, polyesters, polysulfide benzene, polyetherketones, polycarbonates, polyphenylene ethers and their modifications, polymills, polyethers, and polyethers. Imine, etc., or adding a small amount of thermosetting resin, such as phenol resin, epoxy resin, polyimide resin, etc. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) Γδ- ---------. ~ Pack ------ Order ------ Brigade (Please read the notes on the back before filling out this page) Printed by A7, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs B7 V. Description of the invention (η) or two kinds of M. In the production of the liquid crystal polyester resin mixture of the present invention, the liquid crystal polyester resin composition is mainly composed of liquid crystal polyester or K liquid crystal polyester and a filler, and is composed of a phosphorus compound, a gas-carbon surfactant, and a higher fatty acid. The compounding method of at least one compound selected from M among the esters at a temperature lower than the flow temperature of the liquid crystal polyester is not particularly limited. The liquid crystal polyester resin mixture of the present invention is to maintain, for example, particles or particles of a liquid crystal polyester resin composition and powders or particles of at least one compound selected from phosphorus compounds, gas-carbon surfactants, and higher fatty acid esters. In the following, Λ is prepared at room temperature or in a heated environment by mixing with a Kensel mixer, a tumbler, and the like. Examples of the present invention The embodiments of the present invention are shown below, but the present invention is not limited by these embodiments. The measurement and test of various physical properties in the examples were performed by the following methods. (1) Measureability during injection molding: Calculate the average measurement time and its standard deviation for the 50 times of continuous forming in Lian-Myan. (2) Tensile physical properties: An ASTM No. 4 dumb antelope tensile test piece was formed and measured according to the ASTM D638 method. (3) Relative amount of low-boiling gas generated from the molded product: A JIS 1 (1/2) dumb shape (thickness 0.8 mm) was formed, and the obtained molded product was cut into a length of 5 mm, a width of 5 mm, and a thickness Small piece of 0.8mm. Weigh accurately 4g of this small piece, wash it with distilled water, and put it into 25ml of vacuum-dried paper. The scale of the paper is applicable to China National Standard (CNS) A4 specifications __ (2IOX297mm) 1 ~ 9 -------- Packing ------ ordering ------- line (please read the notes on the back before filling in this I) Consumption Cooperation by Staff of the Central Standards Bureau of the Ministry of Economic Affairs Du A7 _B7 V. Invention Description (2) The small glass bottle was sealed with a gasket made of polytetrafluoroethylene, and then heated in a hot air oven set at 120 ° C for 20 hours, so that the gas was emitted from the molded product. This vial was installed in Shimadzu's Head Space Gas Chromatograph (GC-15A / HSS-3A) and kept at 1201C. At the same time, a 15-meter length using DB-WAX (manufactured by JeW SCIENTIFIC) as the filling material was injected. In the pipe column, the temperature of the pipe string was raised from 80t: M 2t: / min at the same time as the injection, and the total amount of gas with a holding time of 25 minutes was detected by a detector. The detector uses the FID type and uses ammonia as a carrier gas. The relative amount of this gas is expressed by the total area of various gases of K. The relative value of the gas emitted from the molded product is compared with the value of #. When no sample is placed in the vial, that is, the measured value of the empty bottle is 3000, the larger the value, the more low-boiling gas emitted from the molded product. In addition, the gas detected during the retention time to 25 minutes can be confirmed by gas chromatography mass spectrometry, including aromatic hydrocarbons, aliphatic hydrocarbons, acetic acid, and phenols. Examples 1 to 4. In Comparative Example 1 to 3 above, the repeating structural unit is composed of the aforementioned Ai, Bh B2, Ci, and the molar ratio of Aι: Bi: B2: Ci is 60: 15: 5: 20, Μ The liquid crystal polyester and crushed and refined glass fiber (manufactured by Centra 1 Glass Co., Ltd., EFH75-01) having the defined flow temperature of 3 2 3 t, as shown in Table 1, were mixed in a Hensi mixer. Using a twin-screw extruder (PCM-30 type manufactured by Ikeki Iron Works Co., Ltd.) and a K extrusion barrel temperature of 3 40 ° C for granulation to obtain a liquid crystal polyester resin composition. Each of the obtained liquid crystal polyester resin compositions was a cylinder having an average particle diameter of 2 mm and a length of 2.5 ram. Put the obtained liquid crystal polyester resin composition and phosphorus compound (distearyl group _-- ^ --- ί pack -------- order -------- sister) (Please read the precautions on the back before filling (This page) This paper size applies to Chinese National Standards (CNS) A4 specifications (210 × 297 mm). 20 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2 1) Isopentyl alcohol diphosphite) such as The proportions shown in Table 1 were mixed at room temperature using a tumbling machine to prepare a liquid crystal polyester resin mixture. 0 The liquid crystal polyester resin mixture was dried at the temperature shown in Table 2 using an injection molding machine (referred to as fine resin industry ( Co., Ltd. m PS40E5ASE), extrusion temperature of 3 5 0 C, mold J IS1 (1/2) dumb test piece was formed at a mold temperature of 1 30. Measurement of the continuous measurement time of 50 times of molding f to evaluate its stability. Also » From the obtained matte-shaped test piece, the amount of stretched physical properties was measured. 0 The same method was applied to a liquid crystal polyester resin composition containing no phosphorated η compound (comparative example). The stability of the measurement time and the amount of gas generated by the stretched physical properties were measured. The results are shown in Table 2. Compared with a phosphorous compound-containing liquid crystal polyester resin composition (Examples 1 to 4), compared with a phosphorous compound-free composition (Comparative Example 1), it was found that the measurement time between each molding was less changed, and the measurement time itself Also shortened f Stable plasticization and excellent mechanical properties t Less gas generated from the molded product 0 In addition »Mixed phosphorus compound 0. 0 0 0 5 Liquid crystal polyester resin composition by weight (Comparative Example) 2), the stable plasticizing effect during molding is not sufficient. 0 On the other hand, mixed with a phosphorous compound 1 0 weight of a liquid crystal polyester resin composition (Comparative Example 3), the molded product was found to be discolored and pulled at the same time. The elongation of physical properties is greatly reduced. 9 The amount of gas generated from the molded product is significantly increased. 0 Comparative Example 4 Except that the phosphorus compound is previously mixed with pulverized and refined glass fiber and liquid crystal polyester and granulated by a biaxial extruder. »Implementation Example 1 The experiment was performed in the same way. The paper size is in accordance with the Chinese National Standard (CNS) A4 (210X 297 mm). It is printed by employees of the Central Bureau of Standards of the Ministry of Economic Affairs and printed by Du. 5. Description of the invention (22) The results are shown in Table 1. In the state where the phosphorus compound is kneaded into the liquid crystal polyester resin in advance (Comparative Example 4), the absolute value of the measurement time is large between each molding 9 The plasticization during molding is less stable 0 Duplicate Example- 9 The experiment was performed in the same manner as in Example 1 except that a mixture of a phosphorus compound and a higher fatty acid or a mixture of a phosphorus compound and a higher fatty acid gold tincture was used instead of the mono-X »monophosphorus compound. The results are shown in Table 2. 0 mixed in a liquid crystal polyester resin composition &gt; 1 a mixture of a phosphorus compound and a higher fatty acid, or a mixture of a phosphorus compound and a higher fatty acid gold tin f There is less change between each molding time in the measuring time. 9 The measuring time itself becomes shorter. It can be stabilized and plasticized. 9 It is also known that it has excellent mechanical properties and less gas generated from the molded product. 0 Comparative Example 6 Except for phosphorus compounds Mixture with higher fatty acid J or a mixture of phosphorus compound with higher fatty acid metal rhenium is mixed with pulverized refined glass fiber and liquid crystal polyester at the same time in advance and granulated with a biaxial extruder. The rest of the experiment was carried out in the same manner as in Example 1. The results are shown in Tables 1 and 2. The phosphorus compound and the higher fatty acid were mixed in advance in the molten state. The absolute value of the measurement time is large when the mixture of a substance or a phosphorus compound and a higher fatty acid metal rhenium is kneaded into a liquid crystal polyester resin. The plasticization during molding is less stable. 0 Example 1 〇13 Except the use of various phosphorus compounds No. 2 ~ 5 shown in Table 2 instead of distearyl isopentaerythritol diphosphite as the phosphorus compound M &gt; The rest is the same as in Example 1 on the same paper scale as in China National Standard (CNS) A4 specification (210X 297 mm) 22 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (23) method was used for experiments. The results are shown in Tables 1 and 2. Mixing various phosphorous compounds No. 2 to 5 in the liquid crystal polyester resin composition is also the same as mixing the distearyl isoamyl tetraphosphate diphosphite phosphorous compound. Less change, shorter measurement time itself, stable plasticization, and it is known that it has superior mechanical properties and less gas emitted from the molded product. Example 1 4 ~ 1 β Except that the phosphorous compound alone was replaced by a mixture of a europium compound and a higher fatty acid M and calcium oxide (trade name: VESTA PP, manufactured by Inoue Lime Industry Co., Ltd., with an average particle diameter of 9.6 mb). Experiments were performed in the same manner as in the examples. The results are shown in Tables 1 and 2. The liquid crystal polyester resin composition is mixed with a mixture of M phosphorus compound i, high-fat fatty acid K and calcium oxide, and is the same as that of the M-phosphorus compound alone. The measurement time has less variation between each molding and the measurement time. It also becomes shorter and can be stabilized and plasticized. At the same time, it is known that it has excellent mechanical properties and less gas generated from the molded product. In addition, the effect of stabilizing the metering time when the liquid crystal polyester resin mixtures of Examples 14 to 16 were subjected to preliminary drying before forming at 150 C was hardly reduced. The hh-age examples 7 and 8 were each obtained by mixing 0.0005 parts by weight of a K phosphorus compound, a higher fatty acid, and calcium oxide (comparative example 7) to the liquid crystal polyester resin composition, and the effect of stable plasticization during the molding process was not sufficient. On the other hand, when a liquid crystal polyester was mixed with 10 parts by weight of a K phosphorus compound, a higher fatty acid, and calcium oxide (Comparative Example 8), it was found that the molded product had a discoloration phenomenon, and the stretched physical properties were also greatly reduced. The amount of gas generated increased significantly (Table 1, Table 2). 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S 0 0 5 7 Ο 0 0 500 0 0 34000 0 S 3 0 0 0 0 0 0 5 * 0 0 0 0 0 5 4 0 0 0 S «0 0 0 w7 0 0 0 6 10 0 0 6 0 0 0 0 5®0 0 0 S 3 0 0 0 5 &lt; 0 0 0 w0 0 0 ^ »000 5 5 0 0 〇T 7 0 0 0 BJ 0 0oi # This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 25 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (26) Table 3 No. in Table 1 Compound name N. 1 Distearyl isopentaerythritol Phosphate Phosphate 2 Bis (2,6-di-tert-butyl-4-methylphenyl) Isopentaerythritol diphosphite esterified '3 Tris (2,4-di-tert-butylphenyl) Phosphite 4 2, 2-Methylenebis (4,6-di-tert-butylbenzyl) octyl phosphite 5 Tetrakis (2,4-di-tert-butylphenyl) 4 , 4'-Diphenylphenyl bisphosphonate Advanced 6 Stearic acid fatty acid 7 Lauric acid Advanced 8 Calcium stearate fatty acid 9 Barium stearate metal 塩 10 Calcium laurate 啻 Life Examples 17-20, hh Comparative Example 9 ~ 11 The repeating structural unit is composed of the aforementioned Aι, Bι, B2, Ci, and Aι --1, -------- t ^ 衣 ---- r--Order- ------- Line · m (Please read the precautions on the back before filling out this page) The size of this paper is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 26 Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printing A 7 B7 V. Description of the invention (27): Bι: B2: Ci with a molar ratio of 60: 15: 5: 20 The liquid crystal polyester with a flow temperature of 323C obtained by the above method and crushed and refined glass fiber ( EFH75-01 (manufactured by Central Glass Co., Ltd.) has the composition shown in Table 4. After mixing with a Hensel mixer, a biaxial extruder (type PCM-30 manufactured by Ikeki Iron Works Co., Ltd.) is used. 340Ϊ: Granulated to obtain a liquid crystal polyester resin composition. Each of the obtained liquid crystal polyester resin compositions was a cylinder having an average particle diameter of 2 μm and a length of 2.5 mm. The obtained liquid crystal polyester resin composition was mixed with calcium perfluoroalkylsulfonate 塩 Florad FC-95 (manufactured by 3M Co.) at the same time as the ratio shown in Table 4 with a tumbler at room temperature to obtain a liquid crystal polyester resin. mixture. These liquid crystal polyester resin mixtures were dried at 120C for 3 hours using an injection molding machine (PS40E5ASE manufactured by Nissei Resin Industry Co., Ltd.) and an extruder temperature of 35 0 ¾ ^ JISl (l / 2) No. (was formed at a mold temperature of 130t. Shape test piece, measure the measurement time of 50 forming times of continuous ore, and evaluate its stability. In addition, tensile properties and the amount of generated gas were measured from the obtained dummy test pieces. The liquid crystal polyester resin composition (Comparative Example 9) containing no fluorocarbon rhenium surfactant was measured in the same manner, and the stability of the measurement time, the stretching physical properties, and the amount of generated gas were measured. The results are shown in Table 4. The liquid crystalline ester resin composition (Examples 19 to 20) mixed with a fluorocarbon-based surfactant was compared with a composition (Comparative Example 9) containing no fluorocarbon rhenium surfactant, and it was found that The measurement time is less changed, and the measurement time itself is shorter. It can be stabilized and plasticized. At the same time, it has excellent mechanical properties and less gas generated from the molded product. In addition, mixed with fluorocarbon rhenium surfactant 〇. 〇〇〇 05 parts by weight of the liquid crystal -------- ί installed -------- order -------- line · (Please read first Note on the back page, please fill in this page again) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 27 A7 B7 V. Description of the invention (28) Polyester resin composition (Comparative Example 2), which is used for forming processing The stability of the plasticizing effect is not enough. On the other hand, 25 cases of mixed gas-carbon surfactants will be more homogeneous than the low-decreasing species II # when the tree puller is polyisomorphic, the liquid content of the liquid image will change, and the hair product will appear. The shape of the product is formed by the changeable and significant amount of system, compared with fch solution and fine glass powder, and the active surface boundary fluorocarbon will be pre-divided, and Bu Yan 3 is made of inner and inner fat. The tree machine h ® presses 5 poly to extrude the surface crystal axis, such as liquid, double fruit into the combination and knead. The mixed method of the test agent is the same as that of 7 1X cases, and the carbon is used to remove the carbon.), The fluorine 12 compares the cases first, and then melts together. The formation time between dynamic changes is relatively low. The value of plastic is not countable when compared to the time of instability. ΘΓ is a fluorocarbon that is substituted by sodium sulfonate, alkyl thioalkyl, hexyl ethyl I 2 and removed. The resin esters, such as polyfruit crystallization solution, are mixed together and tested. The esters are mixed with the same acid, 17-thioalkyl, and hexanoyl. The other two agents will show the properties. Please read the precautions on the back before filling out this page.) • Installation. The staffing of the Central Standards Bureau of the Ministry of Economy and the Consumer Cooperatives are not enough when printed. The hair products of tIL are formed, and by comparison, this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 28 A7

7 B V. Description of the invention (29) Comparative Example 9 printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Comparative Example ΐϋ Comparative Example 11 Comparative Example 12 Comparative Example 13 Example 17 Example 18 Example 19 Example 20 〇) 03 〇 ) 03 Ο Ο Ο Ο 〇0 &gt; Cft 〇ο 〇〇 〇 Liquid crystal polyester (parts by weight) Sm * 龉 m me m Ma Yan salt m αχ. CDF 筘 π &gt;. Then ▲ each private 〇 &lt; = &gt; 〇〇〇〇 〇 C: 〇 glass fiber (parts by weight) 〇1 〇I 1 1 1111 gas-carbon surfactant (parts by weight) 'Ρ 〇i 丨 一 ο 1 〇 〇C71 0. 0 0 5 0 · 0 1 0. 0 3 α. Ο 5 W part 薤 oil ms ms doped π &gt; 〇〇1 1 1 1 III! Sodium alkyl sulfate (parts by weight) 1 6. 9 1 5. 0 3 1, 0 1 5. 0 2 0. 5 pa 533 cn 〇 03 CO average measurement time in seconds) D D μ μ »·-· • μ 〇C〇CO ** • · · ♦ · co -s; ca cji CJ · 〇 · 〇.〇 · 〇PC ^ 00 Deviation of accuracy (seconds) Each cn O CJ1 CD (S3 CO CO CO 〇〇〇〇〇r ςη C7 * re co ro OOO o Intensity (kg / 6m2) + review 141000 140000 106000 139000 138 coffee 143000 142000 141000 142000 _] modulus of elasticity fkg / cm2) [53000 52000 95000 55000 BG000 54000 53000 54000 53000 Relative amount of gas generated ----------------------------- Order -Line- · «(Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 29 Printed by A7 _B7 of the Central Standards Bureau of the Ministry of Economic Affairs 2. Description of the invention (30) Examples of window lumens 21 to 24, hh age examples 14 to Ί6 The repeating structural unit is made of the aforementioned Aι, Bι, B2, Ci, Aι, Bι, B2, Ci, Aι: Βι: B2: Ci with a Molar ratio of 60: 15: 5: 20 and a liquid crystal polyester with a defined flow temperature of 323υ and crushed and refined glass fiber (EFH 75-01 manufactured by Central Glass Co., Ltd.) are shown in Table 5 The composition shown is mixed with a Hense 1 mixer, and then a biaxial extruder (PCM-30 type manufactured by Ikeki Iron Works Co., Ltd.) is used. The extrusion temperature is 340t: granulation to obtain a liquid crystal polyester resin composition. Thing. The obtained liquid crystal polyester resin composition was mixed with a higher fatty acid ester (glyceryl stearate) at a ratio shown in Table 5 at a room temperature using a roll-n roller to prepare a liquid crystal polyester resin mixture. After drying the liquid crystal polyester resin mixture such as Iti at the temperature shown in Table 5 for 3 hours, an injection molding machine (PS40E5ASE manufactured by Nissei Resin Industry Co., Ltd.) was used. 2) Dumb-shaped test piece, measuring the measurement time of 50 consecutive forming times, and evaluating its stability. In addition, tensile properties were measured from the dummy dumb-shaped test piece obtained, and the amount of gas generated was 0. The liquid crystal polyester resin composition (Comparative Example 14) containing no higher fatty acid ester was measured in the same manner. Measurement time stability and tensile properties were measured. The amount of gas generated. The results are shown in Table 5. Compared with a composition containing no higher fatty acid ester (Comparative Example 14), the liquid crystal polyester resin composition containing higher fatty acid esters (Examples 21 to 24) shows that the measurement time between each molding is less. The change and measurement time itself is also shortened, and stable plasticization is possible. At the same time, it has excellent mechanical properties, and the amount of gas generated from the molded product is also small. *-------.---- ί Loading ----.--- Order ------. Line (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 Specification (210X297 mm) 30 A7 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs B7 V. Invention Description (3 1) In addition, it is mixed with higher fatty acid esters 〇 ο 〇〇5 重量 份 的The liquid crystal polyester resin composition (Comparative 仃 15) does not have sufficient plasticizing effect during molding. On the other hand, if a liquid crystal polyester resin composition (Comparative Example 16) containing 10 parts by weight of a higher fatty acid ester is mixed, the molded product may have a discoloration phenomenon, and at the same time, the stretched physical properties are greatly reduced, and the gas generated from the molded product is greatly reduced. Significantly more. Comparative Example 17 An experiment was performed in the same manner as in Example 21 except that a higher fatty acid ester and pulverized and refined glass fibers were mixed with a liquid crystal polyester in advance and granulated with a biaxial extruder. The results are shown in Table 5. The absolute value of the measurement time, which is obtained by kneading the higher fatty acid ester into the liquid crystal polyester resin in the molten state in advance (Comparative Example 17), is large between each molding, and the plasticization during molding is less. stable. Example 25 to 27 The experiment was performed in the same manner as in Example 21 except that No. 2 to No. 4 shown in Table 6 were used as the higher fatty acid ester. The results are shown in Table 5. The blending of KNo2 ~ No.4 higher fatty acid esters in liquid crystal polyester resin composition (Examples 25 ~ 27) is the same as that of blending with stearic acid monoglyceride. There is less variation between moldings, and the measurement time itself is shortened, allowing stable plasticization. At the same time, it is known that it has excellent mechanical properties and less gas generated from molded products. Example 18: Except the use of stearic acid K, which is a higher fatty acid, in place of the higher fatty acid ester, the experiment was performed in the same manner as in Example 21. The results are shown in Table 5. Mixed loading ---- r--order ------ line ... (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ) 31 V. Description of the invention (32 A7 B7 cases compared

Enter V times. Each time, the safety value is not the same as the extinction of the plastic room, the amount of timepieces, the addition of the timepieces, the shape of the mixture in the fat process, the tree passes through the same ester shape, after the large crystals are homogenized and the liquid is dry. Sour dried fat Bijian hard preform has been completed (please read the precautions on the back before filling out this page)-· Packing. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Employees' Cooperatives. This paper is printed in accordance with Chinese national standards (CNS ) A4 size (210X297 mm) 32 397859

7 7 AB V. Description of the invention (33) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs,-^ * ft * Comparative example / V is 夂.% V% Award. K * VN _J21 cn cn oo 〇ao C5 〇 05 〇 〇C5 o 0¾ o Oi o cn o Liquid crystal polyester parts by weight of liquid crystal polyacetate resin composition me • 233 me ΠΠ &gt; 豸 么 OO OO 〇 oo 〇 〇〇 厶 o 厶 oao glass fiber Mβ &gt; Να 1 (α 03) MW fat weight w n a No. 1 (0. 0005) No. 4 (a 03) 丨 No. 3 (0.03) Ho. 2 (0.03) | No. I (0.05) No 1 (0.03) Ha 1 (0.01) No. 1 (a 005) parts by weight of higher fatty acid esters; mixed with a wave converter 〇Ξ f stearic acid 1 parts by weight P〇17.6 cn cn cn Ρ »P &gt; cry P * C \ 3 OO pi OO si! 15 ^ UUI, _ cn S〇O CO P &gt; C = 1 c = drift error (seconds) P〇tsa u &gt; OO J ^ &gt; oo P * Ρ »c〇pi 〇Ί pn C * J Time for second job post (seconds) Move 5 〇 ° 4J c〇1 HI 9 | 5 »oe ¢ = 5 ra f = &gt; U9 P = Ξ .〇 Insect accuracy is also poor (seconds) s O i cn i cn cr * s 菪 ic n cn Ca9 cr &gt; CO strength k% cm ^ i Tensile properties 140000 139000 -1 78000 140000 '141000 136000 137000) 38000 141000 139000 137000 138000 Elasticity kg / cm? 57000 56000 243000 55000 53000 &amp; 80UO 57000 54000 56000 &amp; 6000 55000 1 Relative amount of gas 1 generated 11 Miscellaneous

Order I '(Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 (210 X297 mm) 33 397859 A7

7 B V. Description of the invention (34) Table 6 No. in Table 5 Melting point (C) of compound name No. 1 Monoglyceryl stearate 59 ~ 62 No. 2 Monoglyceryl stearate 63 ~ 68 Ν. 3 Twenty-eight Sodium Monoglycerides-No. 4 Glucitol Tristearate 54 Hair: &gt; Efficacy (Please read the precautions on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The liquid crystal polyester resin mixture of the present invention can stably plasticize the liquid crystal polyester during molding processing, can perform stable molding processing, and can provide a molded body with excellent physical properties and thermal stability. The method for forming a liquid crystal polyester using the liquid crystal polyester resin mixture is very useful for molding using a screw extruder using injection molding, extrusion molding, or the like. This paper size applies to China National Standard (CN ’S) A4 (210X297 mm) 34

Claims (1)

Supplementary data of Patent Application No. 85103456 No. 85103456 printed by the Shell and Welfare Commission of the Central Bureau of Standards of the Ministry of Economic Affairs-Ael H3 sa a). ^ Η Revision Ύ: (October 19, 88) Example 28, Comparison Example 19 The repeating structural unit is composed of the aforementioned A 丨, B2, and q, and the Molar ratio of A,: B,: B2: C! Is 60: 15: 5: 20, and the flow temperature obtained by the above method is 323. . (: The liquid crystal polyester uses two extruders (PCM-30, manufactured by Ikego Iron Works Co., Ltd.), and is granulated at a cylinder temperature of 340 ° C to obtain a liquid crystal polyester resin composition (excluding glass weaving) The liquid crystal polyester resin composition pellets obtained by β are cylindrical bodies having an average particle diameter of 2 mm and a length of 2-5 mm. The obtained liquid crystal polyester resin composition pellets are phosphorous compounds (distearyl isoprene) The ratio shown in the following table was mixed with a tumbler at room temperature to prepare a liquid crystal polyester resin mixture. The liquid crystal polyester resin mixture was dried at 120 t for 3 hours, and then injection molded. Machine (PS40E5ASE manufactured by Nissei Resin Industry Co., Ltd.), extruding temperature of 350eC, forming a JISl (l / 2) dumb-shaped test piece at a mold temperature of 130 ° C, measuring the measurement time of 50 consecutive molding cycles, and evaluating the "Stability" In addition, the stretched physical properties and the amount of generated gas were measured from the dumb-shaped test piece. The liquid crystal polyester resin composition (comparative example) containing no phosphorus compound was measured by the same method. Tensile physical properties and the amount of generated radon. The results are shown in the table below. Phosphate mixed Compared with the composition containing no phosphorus compound (Comparative Example 19), the liquid crystal poly-resin composition (Example 28) of the material was found to have less variation in the measurement time between each molding, and the measurement time itself became shorter. It can be stabilized and plasticized, and has excellent mechanical properties, and there is less air entrapment from the molded product. Table liquid crystal% m green green metering station% m employment new product to roll # ϋΐ 泥 合 120eC * IU * Convergence of stretched physical properties as (heavy side (heavy touch (heavy flat break * time (sec)) 楳 quasi supply difference (sec) strength (tefcm2) rate Example 28 100-0.02 83 1.8 1250 54900 42000 Peach Example 19 100 — — 16.3 32 1280 54200 41000 This paper size is in accordance with China B family standard (CNS) A4 size (210X 297 gigabytes) 38097 Printed by Annex I of 591B59 No. 85103456 patent application by the Shell and Welfare Commission of the Central Standards Bureau of the Ministry of Economic Affairs Supplementary data-Ael H3 sa a). ^ Η Correction: (October 19, 1988) Example 28, Comparative Example 19 The repeating structural unit is composed of the aforementioned A 丨, B2, q, A ,: B,: B2: C! Molar ratio of 60: 15: 5: 20 The flowing temperature is 323. (: The liquid crystal polyester uses two extruder (Ikego Iron Works Co., Ltd. PCM-30 type), and the liquid crystal polyester resin composition is obtained by granulating at an extrusion barrel temperature of 340 ° C. The liquid crystal polyester resin composition pellets (including fillers such as glass woven fabrics) β are cylindrical bodies having an average particle diameter of 2 mm and a length of 2-5 mm. The obtained liquid crystal polyester resin composition pellets of phosphorous compounds (distearyl isoamyltetraphosphate diphosphite) were mixed at room temperature with a tumbler to prepare a liquid crystal polyester blend. 》 After drying these liquid crystal polyester resin mixtures at 120 t for 3 hours, an injection molding machine (PS40E5ASE manufactured by Nissei Resin Industry Co., Ltd.) was used, the extrusion temperature was 350 eC, and JISl (l / 2) Dumb-shaped test piece, measuring the measurement time of 50 consecutive forming cycles, and evaluating its stability. In addition, the dumb-shaped test piece # was used to measure the tensile properties and gas generation. The liquid crystal polyester resin composition (comparative example) not containing a phosphorus compound was measured in the same method, and the stability of the measurement time, the physical properties of stretching, and the amount of generated radon were measured. The results are shown in the following table. Compared with a composition containing no phosphorus compound (Comparative Example 19), the liquid crystal poly-resin composition mixed with a phosphorus compound (Example 28) shows that the measurement time between each molding is less changed, and the measurement time itself is also smaller. Shortened, stable and plasticizable, with excellent mechanical properties, and less suffocation from molded products. Table liquid crystal% m green green metering station% m hires new product to roll # ϋΐ 泥 合 120eC * IU * stretched physical properties occur convergence (heavy side (heavy touch (heavy flat break * time (seconds)) accurate Supply difference (sec) Strength (tefcm2) Rate Example 28 100-0.02 83 1.8 1250 54900 42000 Peach example 19 100 — 16.3 32 1280 54200 41000 This paper size is in accordance with China B family standard (CNS) A4 size (210X 297 Public badge) 38097 397859 Application No. 85103456 for amendment of the scope of patent application. (October 8, 88) 1. A liquid crystal polymer resin mixture, which is characterized by 100 parts by weight of cylindrical or spherical ingot liquid crystal polymer with an average particle diameter of K above 1 mm and 10 fflmK and a filling material of 0 to Within 100 parts by weight of the liquid crystal polyester resin composition containing 150 parts by weight as a main component, an average particle diameter of at least one selected from the group consisting of a phosphorus compound, a fluorocarbon-based surfactant, and a higher fatty acid is less than 100 wm 0.001 to 5 parts by weight of the compound at a temperature lower than the flow temperature of the liquid crystal polymer resin composition ('refers to the heating and heating speed of M4Ό / Β 升温 ίη under a load pressure of 100kgf / cm2, so that the resin has an inner diameter of 1mm, When the nozzle with a length of 10 μπί is extruded, it shows a melt viscosity of 48000 PoiSe (poise) at the temperature) and M is mixed, and the liquid crystal polyester contains the following formula (Αι) c ΗΗ ο \ 1/4 ^-person. 〆Synthesizer's ear mix composition &gt; Mozhizhi and 3 tree branches of esters, esters, polycondensation, polycrystalline, full crystals ~ 5 is liquid and 1 ~ less than 00 to item system 0. 1 item The combination of the mixed structure of the lipid and phosphorus compound tree and the weight of the special ester is mixed. Please indicate the content of the crystals as shown in the liquid amount. The second range of the special interest is ¢ such as 3 fatty acids with high M content. Fatty Fat Fan Li specially asked Shen Ru Guozhong to use a suitable paper for its heavy weight, medium and high, mixed with the material and mixed with the ester of the phosphorus phosphate tree, the polycrystalline content of the liquid crystal weight 1 of the item 00 of which »» The material is mixed with special lipids and the amount of resin is 5 weights of polyesters ~ 2 of 0 items. 0 male 97 2 X 10 2 / IV standard 4 A Nly s N c standard 397859 Application No. 85103456 for amendment of the scope of patent application. (October 8, 88) 1. A liquid crystal polymer resin mixture, which is characterized by 100 parts by weight of cylindrical or spherical ingot liquid crystal polymer with an average particle diameter of K above 1 mm and 10 fflmK and a filling material of 0 to Within 100 parts by weight of the liquid crystal polyester resin composition containing 150 parts by weight as a main component, an average particle diameter of at least one selected from the group consisting of a phosphorus compound, a fluorocarbon-based surfactant, and a higher fatty acid is less than 100 wm 0.001 to 5 parts by weight of the compound at a temperature lower than the flow temperature of the liquid crystal polymer resin composition ('refers to the heating and heating speed of M4Ό / Β 升温 ίη under a load pressure of 100kgf / cm2, so that the resin has an inner diameter of 1mm, When the nozzle with a length of 10 μπί is extruded, it shows a melt viscosity of 48000 PoiSe (poise) at the temperature) and M is mixed, and the liquid crystal polyester contains the following formula (Αι) c ΗΗ ο \ 1/4 ^-person. 〆Synthesizer's ear mix composition &gt; Mozhizhi and 3 tree branches of esters, esters, polycondensation, polycrystalline, full crystals ~ 5 is liquid and 1 ~ less than 00 to item system 0. 1 item The combination of the mixed structure of the lipid and phosphorus compound tree and the weight of the special ester is mixed. Please indicate the content of the crystals as shown in the liquid amount. The second range of the special interest is ¢ such as 3 fatty acids with high M content. Fatty Fat Fan Li specially asked Shen Ru Guozhong to use a suitable paper for its heavy weight, medium and high, mixed with the material and mixed with the ester of the phosphorus phosphate tree, the polycrystalline content of the liquid crystal weight 1 of the item 00 of which »» The compound is a mixture of phyto-stimulant and its lipids. It is a resin ester amount of polyheavy 5 liquids ~ 2 of 00 items. 0 public 97 2 X 10 2 / IV standard 4 A Nly s N c Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Quasi-economics 397859 _H3_ 0.001 parts by weight of at least one compound of the group consisting of oxides, peroxides, double oxides, and carbonates of gold tincture containing 遘 free 1A or 2A group, and is selected from the group consisting of Phosphorus compounds, higher fatty acids, and oxygen from gold ions of Group 1 Α or 2 Α Thereof, peroxide, carbonate and complex oxide thereof consisting of at least one group in the total amount of the compound to its 0.003~5 parts by weight Laid by shake. 5. For example, the liquid crystal polyester resin mixture of the second patent application range, wherein the total amount of the phosphorus compound and the higher fatty acid gold tincture is 0.001 to 5 parts by weight containing 0.001 parts by weight of the upper fatty acid gold tincture. Special person. 6. For example, the liquid crystal polyester resin mixture in the first patent application range, wherein 0.001 to 5 parts by weight of the fluorocarbon-based surfactant is mixed with 100 parts by weight of the liquid crystal polyester resin composition. 7. The liquid crystal polyester wax mixture according to item 1 of the patent application, wherein 0.001 to 5 parts by weight of a higher fatty acid ester is mixed in 100 parts by weight of the liquid crystal polyester resin composition as a special exciter. This paper size is applicable to China National Standard (CNS) A4 (210X297)