TW572955B - Semiconductive resin composition and molded article - Google Patents

Abstract

To provide a semiconductive liquid crystalline polymer composition which is advantageously used particularly for electronic parts where a stable antistatic property is given without a significantly lowering of mechanical property. That is, a semiconductive resin composition having a volume resistivity of from 1x10<4> to 1x10<11> Omega.cm in which 100 parts by weight of a liquid crystalline polymer (A) are compounded with 1-50 part(s) by weight of graphite (B) having not less than 95% by weight of fixed carbon, 1-50 part(s) by weight of a fibrous electrically conductive filler (C) and 1-50 part(s) by weight of a fibrous non-conductive filler (D) in such a manner that the total compounding amount of the components (B), (C) and (D) to 100 parts by weight of (A) is 25-100 parts by weight and that the ratio ranges of (B):(C) is from 1:3 to 4:1 and of [(B)+(C)]:(D) is from 1:2 to 2:1 are satisfied.

Description

572955 month of amendment No. 1 90130313 V. Description of the invention (1) The present invention relates to a semi-conductive resin composition, especially a liquid crystalline polymer formulated with a fibrous conductive filling material and a fibrous conductive filling material formula. The composition, more specifically, 75 is about-a kind of semi-conductive composition = Its composition is used for the electric charge of the function of preventing the charging function. The liquid crystal polymer of the sexually soluble phase, even in the thermoplasticity k: It is also widely known for its dimensional accuracy, vibration damping, good fluidity, and the description points of wool and cymbals during forming. It is customary to take advantage of such characteristics, adopting :: strong crystalline polymer composition as the electronic part of the finger, produced the belt 2 ::: in the parts' because of the contact during assembly and the same production banquet. In order to prevent the problem of electrical interference, in order to prevent this carbon black II bott Kaizhao 62-1 3 1 067 from being reported, an attempt was made to improve the conductivity of the liquid crystal polymer by formulating its 'ac ^ i' by the method. Ω.cm with the right, can increase the volume resistivity of 1 X itself has conductivity :, and therefore more than: the effect of electricity, but because the molded product only stops the effect of electrification! It is difficult to control without conductivity. This rate is at 1 χ 丨. 4 ~ 1X㈣ · ⑽, non-Gazette No. 281 885, ': Heisei 207083 or Gazette and JP 2000-Improving conductivity, but' the purpose is to use black error as a conductive filler material formula surface resistance value is related to the use of black When it is used as a conductive filling material, the electrification is stopped. If it is: ', it is quite excellent.' However, the filling amount of A is increased to prevent °° too much 'will cause fluidity and mechanical objects. 572955 Amendment _ Case No. 90130313 V. Invention Explanation (2) = change; open: ~ 就 ^ e; .2619, ^ V ″; t; fiber? The formula is to improve its flexibility, but the flexibility is improved: Second, the control of ¥ becomes difficult, making the volume of the molded product larger, and there is no material that can solve all the above problems. Right, In the light of the above-mentioned problem points, after committing to exploring and reviewing materials with electrical characteristics of 14: 方 止 ▼, I will now use black lead and fibrous conductive filling materials and fibrous conductive filling materials to specify The formula is mixed with the liquid crystal polymer, which can increase the mechanical properties, does not deteriorate, and has stable antistatic charging properties, and even complete the present invention. That is, the present invention is to provide a semi-conductive resin composition having a volume resistivity of 1 X 104 to 1 X 1011 Ω · cm, which will fix carbon 95 in 100 parts by weight of the liquid crystal polymer (A). 50% by weight or more of black lead (B), fibrous conductive filler ([) 1 to 50 weight part and fibrous non-conductive filler (D) 1 to 50 weight part, Formulated in the range stated above: (B), (C), (D) The total amount of ingredients is 25 to 100 parts by weight relative to (A) 100 parts by weight, and (B): (c) &lt; 1 : 3 to 4: 1 and [(B) + (C)]: (d) = 1: 2 to 2: 1 ratio The liquid crystalline polymer (A) used in the present invention means that it has different formation properties. Melt-processable polymer with a square melt phase. The nature of the anisotropic molten phase can be recognized by the conventional polarization inspection method of orthogonal polarized photons. More specifically, for confirmation of the anisotropic molten phase, L e i t2 can be used.

Page 7 572955

Γ ancient 0 rate was observed. In the liquid crystal polymer to which the present invention is applied, even if it is molten, the polarized light can be penetrated through the interlayer inspection, and the optical anisotropy is displayed. The liquid crystalline polymer (A) of # 2 is not particularly limited, but it is preferable to use fragrant vinegar (Polyester) or aromatic polyester amine (afflide). Polyesteramide (amide) part of the same, including the same polyester in the knife lock is also included in this range. These are at 60. 〇 When redissolved in pentafluorophenol (Pentaf luorophenol) at a concentration of 0.1, it is preferably used to have a logarithmic viscosity of about 2.0 · di / g, preferably 2.0 · 〇 ~; ι〇 · 〇dl / g I · V ·). : Aromatic polyester or aromatic polyester amidamine suitable for the liquid crystalline polymer (A) of the present invention, especially suitable for selecting at least from the group of aromatic hydroxy carboxylic acid, aromatic hydroxy amine, and aromatic diamine Aromatic polyester or aromatic polyester amidamine having j or more compounds as constituents. More specifically, there are: (1) a polyester composed mainly of one or more aromatic hydrOxy carboxylic acid and its inducer; (2) a polyester mainly composed of (a) aromatic hydrOxy carb 〇xylic acid, and one or two or more kinds of attractants, and (b) aromatic dicarboxylic acid, cycloaliphatic dicarboxylic acid and its inducers, one or two or more kinds, and (c) aromatic diol, lipids Polyesters composed of one or more cyclic di0i, aliphatic di01, and its inducers; (3) one or two or more of the aromatic hydroxy carboxylic acids and their inducers And (b) aromatic hydroxy amine

572955 __Case No. 90130313 Amended on the 5th, the description of the invention (4), one or more aromatic diamines and their inducers, and (c) aromatic dicarboxylic acid, cycloaliphatic dicarb0Xylic acid and its inducers Polyesteramide composed of 1 or more types; (4) Mainly (a) one or two types of aromatic hydroxy carboxylic acid and its inducer, and (b) aromatic hydroxya in ine, aromatic diamine and its inducer i or two or more, and (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and its inducer, one or two or more, and (d) aromatic diol, alicyclic diol, Polyesteramide and the like composed of one or more aliphatic diols and their inducers. In addition, in accordance with the above-mentioned constituent components, a molecular weight modifier may be used in combination as necessary. Examples of specific compounds constituting the liquid crystalline polymer (A) that can be suitably used in the present invention include aromatic hydroxy carboxylic acids such as P-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 2,6-dihydroxy naphthalene, 1 Aromatic diols such as 4-dihydroxy naphthalene, 4,4'-dihydroxy biphenyl, hydroquinone 'resorcin, compounds shown by the following general formula (I) and the following general formula (II); terephthalic acid, iso phthalic acid, 4, Aromatic dicarboxylic acids such as 4'-diphenyl dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, and compounds shown by the following general formula (ΠI); aromatic amines such as p-aminophenol and p-phelene diamine.

Page 9 572955 ^ £ 90130313 V. Description of the invention (5) Amendment „〇_0.χ ^ 〇Η CI) Guanidine OXCC〇〇X5 ~ 〇H (I &gt; ROOC-0-^ '-0-COOH (Π) , But 5 疋 selected from X.alkylene (C1 ~ C4), alkyiidene, -〇 一, 一 SO-,-S02-, — s-, — c〇-, the selected base, Y:-(CH2) n-(ηΗ ~ 4), -〇 (CH2) n〇_ (η = Bu 4) selected

base). The liquid crystalline polymer (A) particularly suitable for the present invention is an aromatic polyglyceride which is composed mainly of ρ-hydroxydibenzoic acid and 6_hydroxy-2-naphthoic acid. The purpose of the present invention is to increase the mechanical properties, not to deteriorate, and to provide stable antistatic charging properties. Therefore, it is necessary to fix black lead of 95% by weight or more in the liquid crystal polymer (A) 100 weight portion. (B) 1 to 50 parts by weight, fibrous conductive filler (C) 1 to 50 parts by weight and fibrous non-conductive filler (D) 1 to 50 parts by weight, formulated to meet the following range · (B), (C), (D) The total amount of ingredients is 25 to 100 parts by weight based on (A) 100 parts by weight, (B): (c) = 1: 3 to 4: 1,

And [(B) + (C)]: (D) = 1: 2 to 2: 1 ratio. In the present invention, although (B) black lead, scaly black errors such as artificial black errors and natural black errors, scaly black errors, earthy black errors, and other types of black errors can be used. The electrified conductivity must be 95% by weight or more, and preferably 98% by weight of black carbon. Among them, from a functional point of view, artificial black lead having a high fixed carbon ratio, and scaly black lead or scaly / wrong structures easily formed in the molded product.

572955 Case No. 90130313 Amendment 5. The invention description (6) is better. Secondly, in the present invention, (C) a fibrous conductive filler, conductive fibers such as carbon fibers, metal fibers, and glass fibers, single crystal short fibers (wh i sker), inorganic fibers, ores can be used. Fibers and other materials are coated with metals such as nickel and copper to add conductivity. As the carbon fiber, a PAN-based fiber using polyacry ion trile as a raw material and a wood pitch-based fiber using wood pitch (pi t c h) as a raw material can be used. Metal fibers can be soft steel, stainless steel, steel and its alloys, copper, Shao and its alloys, and oblique fibers. If these metal fibers require more electrical conductivity, they can also be coated with other metals for ease of use. ° Single crystal short fibers (whisker) used for ore-coated metal can use nitridated single crystal short fibers, trinitrided single crystal short fibers, 5 = magnesium single crystal short fibers, carbide single crystal short fibers, fibers, etc. 'Inorganic fiber, you can use glass fiber _si! IcaN ,, ^., &Quot; (rconia), aluminum silicate (alumina ica), titanium i potassium, barium titanate, oxygen silicon dioxide, slag (sl) As for the soil, aluminum, and asbestos fibers (asbest) can be used, carbon fibers are preferred. Searching. Among them, from a functional point of view, in the present invention, (> sister, can use glass fiber, single fiber, touch-dimensional non-conductive filling material machine-based fiber, ore-based fiber, etc .: Fiber (whisker), none of them, from the functional side In addition: raw filler material, coated with mineral metal and the above ⑷ fiber shape, glass fiber is preferred. Use the same composition to form

Real materials (D Page 1) Page 572955 MM 9013031 ^ V. Description of the invention (7) _ :: The average fiber length of the weight is better than 6 • Long J super paste _ the previous day, the flame resistance is not: 2 ^ Attached An ld :; defense: ίϊΓ, good formability, mechanical and physical properties, and is the anti-charging properties of Wen Wen, so "(町 九 J :; ^ (c) ^ ^ ^ ^ ^ t ^^ # ^ f } Also ^ square Λ and denier must be within the range of characteristics: the formability will deteriorate, resulting in poor mechanical strength. In addition: when the extrusion and too little, the conductivity cannot be effectively achieved to prevent; U Formulation amount: If you want to increase the fibrous conductive filling material when the dagger is used; c electric efficiency = to achieve conductivity, the formula with poor conductivity () will prevent the charging effect. Therefore, black lead (B) The method is to reach 100 parts by weight of the nun (A), and it must be limited to the range of 10 to 30 parts by weight relative to the liquid. Lili 4, take the ancient θ 夕 Xi Shi Bu 'fibrous conductive filling material (C) The amount of the formula, when formula 1 is too much, 'although the shape can be improved in the machine, it will deteriorate', and even the conductivity is too good to cause conduction. On the other hand, when the amount of the formula is too small, 'the electrical conductivity cannot be effectively reached = electrical = the word' will be as described above, the extrusion and moldability will be reduced, resulting in poor strength. Therefore, the fibrous conductive filling Material i7C) formula f 'with respect to the liquid crystalline polymer 10., b) Bu 5. The weight part' is preferably in the range of 5 to 25 weight part .... In addition, 'black heat (B) and fiber State is more important than contact. 'Must (B): (0 = 1: 3M :! 0) (B) 572955

No. 90130313 V. Description of the invention (8) When there are more components than proportions, there will be many examples of failure to effectively achieve the purpose, which will make the conductivity too good and cause conduction. Comparison of electricity generation. In addition, in the present invention, the formulation effect of the fibrous non-J electrical filling material D) is particularly important. That is, when adding fibrous (in the liquid crystalline polymer composition, the shape of the product is added by 4 inches. ^ The shape of the buckle will be rough, and the movement will be low, but, on the contrary, the mystery of the mine will appear. History ... ^ H Fanjin maintains the effect of son-in-law. However, when this formula is increased with a fibrous conductive filling material (c), the continuity problem mentioned above will occur. Therefore, there must be a specific The amount of the formula of the non-conductive filling material (D). That is, when the amount of the formula of the fibrous non-conductive filling material (D) is too large, although the human conductivity can be stabilized, On the other hand, when the amount of the formulation is too small, the conductivity becomes unstable and the mechanical strength is deteriorated. Therefore, the amount of the formulation of the fibrous non-conductive filler (D) is polymerized relative to the liquid crystal. The object (A) 100 weight part must be limited to 50 weight part, preferably 10 to 40 weight part, and is limited to [(B) + (c)]: (D) = 1: 2 ~ Within the ratio of 2: 1. In addition, the total formula of (B), (C), (D), When the amount is ^, the extrusion properties and moldability will be deteriorated. On the other hand, if the amount of the formula is too large, the conductivity will be unstable and the mechanical strength will be deteriorated. Therefore, for the liquid crystalline polymer (A) 100 The weight part must be limited to 25 to 100 weight parts, preferably 40 to 80 weight parts, and more preferably 50 to 70 weight parts.

In addition, the semi-conductive resin composition of the present invention can also use a plate-like or powder-like filling material as a formula, as long as the purpose of preventing the electrification function is not impaired by the present invention. Non-fibrous filling material, specifically 572955, Amendment No. 90130313 V. Description of the invention (9) is composed of the following materials: talc, mica, kaol in clay (ciay ), Graphite (graph j te), vermiculUe, potassium silicate, aluminum silicate, feldspar powder, acid white clay, loam ^ clay ^ sericite, 5 guilinite jizhirun soil, bent. n] te), glass flakes (gUss fiake), slate powder, sane, and other silicates, potassium carbonate, pulverized powder, acid locks, carbonic acid town, domitite, and other carbonates , Barite (dianc fixe), settling potassium sulfate ① moonstone, barium stone clawate and other sulfates, water and oxides, oxide records, locks, oxides, zinc oxide, two = two, stone Materials such as sulphur, yoke, etc., such as central carbon, white carbon, and ribeite, metal powder and granules, etc. Suotu 4 emulsified product, black lead used in the present invention, fiber shape = electricity Filling material, non-fibrous filling material to make J i, but it can also be used in combination with a general-purpose surface treatment agent. In addition, for liquid crystal polymer compositions, pigments such as organic firing pigments, additives such as anti-nuclear agents, carbon black, none, release agents, and flame retardants, including ===, plasticizers, and lubricants include The liquid crystalline composition of the present invention is also the liquid crystalline polymer composition of the present invention. Within the range. The conductive filler and i or more kinds of ^ are wrong due to the lack of two or more kinds. Get non-destructive two = filling material 'can supplement excellent materials' and uniformly disperse the molded body :: species 3 performance of preventing chargeability. In the dispersed state, play higher 572955

Case No. 901303U; Description of the invention (10) In the production of the liquid crystalline polymer composition, the former and the former are proportionally formulated and kneaded. Generally, extruder kneading, f-peening (pe 1 1 e t), injection molding, etc. are used, but it is not limited to: machine kneading. Extrusion The following describes the present invention in detail with examples, but the present invention is not limited to these examples. The measurement and measurement of physical properties in the examples were performed by the following methods. ♦ &amp; I used (1) the volume resistivity to use a 0100 X 3t flat test piece, ASTM D257 as the standard, and measured the volume resistivity. The average value of 5 pieces was used as the volume resistivity. The average of the volume resistivity is calculated as pairs = sheets. In addition, the evaluation of the measurement variation between the five test pieces was also performed. Flat (2) Tensile test (tensile) adopts ASTM No. 1 、 shape, said, = as the standard, the tensile strength and tension :::: (3) Bending test uses a 130 X 13 X 0.8mm bend Erdingyi D790 is used as the standard, and the flexural strength and flexural elasticity are measured. (4) Pellets for measuring the fiber length of glass fiber (GF). The electrical furnace is used to enter and withdraw about 700 t 埶, 、, 踹 镳, and 踹 镳. Goo Yin, disperse M fat, black lead-alcohol t Γ Wang :, 'Disperse the ash-retained glass fibers in a 5% aqueous solution of polyethylene (giyco), and transfer an appropriate amount to 50. ] _ The weight of the fibers is flat. The average fiber length. . The image is inserted into the second piece. * Bending test with 130χΐ3χ〇 ._- 1J: 94 is 彳 if, and the flammability is measured. Example 5 and ratio 572955 _Case No. 90130313_ year month day __ five Description of the invention (11) Comparative examples 1 to 12 are based on liquid crystal polyester (LCP; PolyPlastic, Inc., Beetra A94 0) 1 0 0 by weight. After dry mixing in the proportions shown in Fig. 1 to Fig. 2, it is melt-kneaded with a two-axis extruder (manufactured by Ikegai Iron Works Co., Ltd., PC M-30 model) and pelletized. The pellets were formed into the above-mentioned test pieces by an injection molding machine, and the evaluation was performed. The results are shown in Figs. 1 to 2.

Page 16 572955 Case No. 90130313 A_η Revision diagram Brief description Figure 1 shows the composition and test results of Examples 1 to 5 used in the present invention. Figure 2 shows the comparative examples 1 to 12 used in the present invention. Composition and test results page 第 17 页

Claims (1)

572955,1. 4-1 W i _ Case No. 90130313_Year_Month__ VI. Patent application scope1. A semi-conductive resin composition which is an aromatic polyester and / or aromatic polyester amine In the liquid crystal polymer (A) 100 weight parts, black lead (B) with a fixed carbon content of 95% by weight or more and 50 weight parts are selected from carbonized fibers, metal fibers, and glass fibers covered with metal. One or two or more fibrous conductive fillers (C), which are made of crystal, inorganic fiber or ore fiber, and impart conductivity, 1 to 50 parts by weight and selected from glass fiber, whisker, inorganic fiber or ore One or two or more kinds of fibrous non-conductive filler materials (D) 1 to 50 parts by weight, formulated to meet the following ranges: (B), (C), (D) The total amount of ingredients is 25 to 100 parts by weight based on (A) 1 0 0 weight parts, (B): (C) = 1: 3 to 4: 1 and [(B) + (C )]: (D) = 1: 2 ~ 2: 1 ratio, and its volume resistivity is 1 X 1 0 4 ~ 1 X 10 11 Ω · cm. 2. The semi-conductive resin composition according to item 1 of the scope of the patent application, in which the weight-average fiber length of the fibrous non-conductive filler (D) is dispersed at 600 #m. 3. The semi-conductive resin composition according to item 1 or 2 of the scope of the patent application, wherein the fibrous conductive filler (C) is PAN-based carbon fiber. 4. The semi-conductive resin composition according to any one of claims 1 or 2 in which the fibrous non-conductive filler (D) is glass fiber. Page 18