CN101479346A - Liquid crystalline resin composition - Google Patents
Liquid crystalline resin composition Download PDFInfo
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- CN101479346A CN101479346A CNA2007800235109A CN200780023510A CN101479346A CN 101479346 A CN101479346 A CN 101479346A CN A2007800235109 A CNA2007800235109 A CN A2007800235109A CN 200780023510 A CN200780023510 A CN 200780023510A CN 101479346 A CN101479346 A CN 101479346A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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Abstract
A liquid-crystalline resin composition which is reduced in conductivity unevenness in regions ranging from a semiconductive region to a highly conductive region, has high flowability, and gives a molded article having an excellent appearance; a liquid-crystalline resin masterbatch; and a molded liquid-crystalline resin formed from the composition. The liquid-crystalline resin composition comprises: 100 parts by weight of a liquid-crystalline resin (A) having (a1) a melting point of 250-350 DEG C and (a2) a melt viscosity, as measured at a temperature higher by 20 DEG C than the melting point and at a shear rate of 1,000 sec<-1>, of 1-80 Pa s; and 0.5-40 parts by weight of vapor-grown carbon fibers (B) having an outer fiber diameter of 10-500 nm and an aspect ratio of 5-1,000. This liquid-crystalline resin composition can be formulated into, e.g., a masterbatch and mixed with other thermoplastic resin (C) according to need to obtain a molded article therefrom. In this case, by selecting the resin (C) so that the melt viscosities of the two resins are close to each other, a molded article excellent in dispersion and conductivity is obtained.
Description
Technical field
The liquid crystal liquid crystal property resin forming product that the present invention relates to liquid crystalline resin composition, liquid crystal liquid crystal property resin concentrates and use their electroconductibility.In more detail, the present invention relates to for the useful electroconductive resin molding that contains matrix resin and conductive material of high conductionization.
Background technology
Along with the purposes variation of the conductive material in fields such as in recent years electricity, electrochemistry, the energy, Transport Machinery, develop a kind of electroconductive resin molding as conductive material.Therefore in general, because that synthetic resins is easy to is charged, be easy to adsorb dust or dust.As its countermeasure, dispersed electro-conductive material in resin is given electroconductibility or static resistance.
As the used representative conductive material of the resin combination of electroconductibility, can enumerate charcoal fiber or steel fiber, conductive carbon black, the resin that is combined with them is extensive use of in the industrial circle that requires electroconductibility or static resistance headed by the electrical and electronic parts.But, to original when giving electroconductibility for the resin of insulativity, be necessary to cooperate the conductive material of volume, therefore, have the basic problem that resin physical strength, thermotolerance, dimensional stability and plasticity (flowability) originally reduces, diminishes the molding outward appearance.
And then if dispersed electro-conductive material equably not, then the electroconductibility of gained molding takes place significantly uneven.In addition, the thin-walled property of parts, lightweight in recent years develops, and demand can show electroconductibility and suppress flowability and the resin of the reduction of physical strength with amount still less.So, for the electroconductive resin molding, promptly obtaining uniform conductive with the interpolation of less amount becomes important problem.
As the method that addresses these problems, as the research of setting out by the conductive material aspect, in following patent documentation 1, replace existing carbon black etc. by adding the charcoal fibril materials, thus the appearance of improvement molding.In addition, improve mechanical characteristics by vapor phase process charcoal fiber and anti-electrostatic polymer in the following patent documentation 2.And then, in following patent documentation 3 by and improve mechanical characteristics with charcoal fiber and vapor phase process charcoal fiber.But therefore these carbonaceous materials have the problem in the manufacturing because volume density is very little: produce feed bottleneck (feed neck), be difficult to cooperate required addition in resin.
On the other hand, if observe from the matrix resin aspect, then therefore the liquid crystal liquid crystal property resin of liquid crystalline polyester resin representative is that the center is just utilized widely as high function engineering plastics with the electrical/electronic field because balance has excellent physical strength, thermotolerance, chemical proofing, plasticity (flowability) etc. well.But, because the wettability of conductive materials such as liquid crystal liquid crystal property resin and carbon black, carbon nanotube is very poor, therefore not only be difficult to high density and add these fine fillers, and have and disperse the bad problem of damaging originally physical strength of liquid crystal liquid crystal property resin, thermotolerance, dimensional stability, plasticity (flowability) obviously, greatly.And then, because therefore the technological temperature height is difficult to add anti-electrostatic polymer.
Patent documentation 1: Japanese kokai publication hei 07-102112 communique
Patent documentation 2: TOHKEMY 2000-248186 communique
Patent documentation 3: TOHKEMY 2003-12939 communique
Summary of the invention
The problem to be solved in the present invention
So, though attempted in the performance rerum natura of liquid crystal liquid crystal property resin, give its uniform conductive in the past, can't realize both are taken into account as engineering plastics.
Specifically, contained in the liquid crystalline resin composition and molding thereof of conductive material in the past,, be necessary significantly to increase the loading level of conductive material in order to show the high conductivity after the shaping.But, have the mobile significantly variation of resin combination, the problem that plasticity is significantly worsened thus.And then, have the significantly uneven problem of electroconductibility.In addition, the result of highly-filled conductive material also has the problem that the molding outward appearance worsens.
Therefore, the object of the present invention is to provide from the semi-conductivity district to the high conductivity district the electroconductibility inequality less and have the also excellent resin combination of high workability and molding outward appearance and product of formation thereof.
The method that is used to deal with problems
The inventor etc. further investigate in order to solve above-mentioned problem, found that by the vapor phase process charcoal fiber specific liquid crystal liquid crystal property resin compoundedization with specific viscosity, the inequality of molding outward appearance excellence, electroconductibility less and can show high conductivity and flowability and then is finished the present invention.Specifically the invention provides following content.
(1) a kind of liquid crystalline resin composition, its following with respect to satisfying (a1) and liquid crystal liquid crystal property resin (A) 100 weight parts (a2), containing the fiber external diameter is that 10～500nm, length-to-diameter ratio are 5～1000 vapor phase process charcoal fiber (B) 0.5～40 weight part, wherein,
(a1) fusing point is 250 ℃～350 ℃,
(a2) be 1000sec in the temperature higher 20 ℃, shearing rate than above-mentioned fusing point
-1The time melt viscosity be 1～80Pas.
According to the technical scheme of (1), use to have the so-called vapor phase process charcoal fiber (VGCF) of regulation fiber external diameter and length-to-diameter ratio as conductive material.This VGCF compares with common charcoal fiber (CF), and fiber external diameter, staple length are all little.In addition, the structure between the fiber is compared for the linearity person with CF, and VGCF has the feature with non-linear shape structures such as arciform, bendings.Therefore, when being scattered in the resin when not fractureing VGCF, because the nonlinearity of VGCF, the contact probability between VGCF improves, and therefore can expect uniform conductive with the addition that is less than in the past.But,, therefore can destroy its non-linear shape structure owing to the melting mixing in resin on the contrary because VGCF has this non-linear shape structure.Thereby, can't be scattered in the resin all the time equably and can't bring into play uniform conductive.
Here, the inventor etc. are conceived to the low melt viscosity that the liquid crystal liquid crystal property resin is had, by in the liquid crystal liquid crystal property resin of regulation low viscosity scope, adding VGCF with specific fibre external diameter and length-to-diameter ratio, thereby can be scattered in the resin under the situation of the non-linear shape structure of not serious destruction VGCF, the result can be successfully to finish uniform dispersion on a small quantity.
(2) above-mentioned (1) described liquid crystalline resin composition, wherein, described liquid crystal liquid crystal property resin (A) contains 4-hydroxy-benzoic acid and 6-hydroxyl-2-naphthoic acid at least as constituting monomeric unit.
According to the technical scheme of (2), contain 4-hydroxy-benzoic acid and 6-hydroxyl-2-naphthoic acid at least and preferably use as the liquid crystal liquid crystal property resin of the low viscosity scope of afore mentioned rules as the liquid crystal liquid crystal property resin (A) that constitutes monomeric unit.Here, " containing at least " is meant the formation monomeric unit that also can contain other, can adjust the scope of melt viscosity thus.As this liquid crystal liquid crystal property resin, for example can enumerate " ベ Network ト ラ " (trade(brand)name: Polyplastics Co., Ltd. makes), as long as but the liquid crystal liquid crystal property resin that uses among the present invention has above-mentioned fusing point and the melt viscosity scope then is not particularly limited.Illustrated, the definition of liquid crystal liquid crystal property resin of the present invention and concrete example after be described in detail.
(3) above-mentioned (1) or (2) described liquid crystalline resin composition, wherein, it is that 300 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (A1) of 1～30Pas that described liquid crystal liquid crystal property resin (A) contains fusing point.
According to the technical scheme of (3), in liquid crystal liquid crystal property resin (A), liquid crystal liquid crystal property resin (A1) further is a low melting viscosity.Therefore, can under the situation of the non-linear shape structure of not destroying VGCF, be dispersed in the resin.
(4) each described liquid crystalline resin composition in above-mentioned (1)～(3), wherein, the fiber external diameter of described vapor phase process charcoal fiber (B) is that 30～200nm, length-to-diameter ratio are 20～500.Each described liquid crystalline resin composition in more preferably above-mentioned (1)～(3), wherein, the fiber external diameter of described vapor phase process charcoal fiber (B) is 70～180nm.
According to the technical scheme of (4), fiber external diameter by making VGCF and length-to-diameter ratio can further improve the dispersiveness of VGCF in above-mentioned scope.
(5) each described liquid crystalline resin composition in above-mentioned (1)～(4), wherein, described vapor phase process charcoal fiber (B) has hollow structure, the BET specific surface area is 2～250m
21341～1349cm of/g, raman scattering spectrum
-1The peak height of bands of a spectrum (Id) and 1570～1578cm
-1The ratio (Id/Ig) of the peak height of bands of a spectrum (Ig) is 0.1～2.0.
According to the technical scheme of (5), can further improve the dispersiveness of VGCF in resin.In addition, more clear and definite with the difference of common carbon nanotube.
(6) a kind of liquid crystal liquid crystal property resin forming product, it is the molding that is formed by each described liquid crystalline resin composition in above-mentioned (1)～(5), wherein, the surface resistivity of described molding is less than 10
12The logarithmic difference of Ω/ and its maximum value and minimum value is less than 3.
According to the technical scheme of (6), therefore liquid crystal liquid crystal property resin forming product of the present invention has excellent performance as the electroconductive resin molding owing to obtain extremely low and uniform surface resistance rate.
(7) a kind of liquid crystal liquid crystal property resin concentrates, it forms by each described liquid crystalline resin composition in the melting mixing above-mentioned (1)～(5).
Technical scheme according to (7), make masterbatch (MB) by in the liquid crystal liquid crystal property resin, suitably mixing VGCF, can under the state of the non-linear shape structure of keeping VGCF, handle, for the dilution adjustment of the VGCF concentration of final molding, also favourable with compoundization of other thermoplastic resin of aftermentioned (C) blended.Illustrated that especially the VGCF concentration among the MB can suitably be set, be preferably 5～40 quality %.
(8) above-mentioned (7) described liquid crystal liquid crystal property resin concentrates, it contains fusing point is that 300 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (A1) of 1～30Pas.
According to the technical scheme of (8), in liquid crystal liquid crystal property resin (A), liquid crystal liquid crystal property resin (A1) further is a low melting viscosity.Therefore, can under the situation of the non-linear shape structure of not destroying VGCF, carry out MBization.
(9) above-mentioned (8) described liquid crystal liquid crystal property resin concentrates, the fracture ratio of the vapor phase process charcoal fiber (B) during its melting mixing is below 50%.
According to the technical scheme of (9), because the fracture ratio of vapor phase process charcoal fiber (B) is below 50%, so the interfibrous contact of gas phase charcoal becomes easily, and the interpolation by a small amount of gas phase charcoal fiber can improve electroconductibility.
(10) a kind of liquid crystal liquid crystal property resin forming product, it is by melting mixing (7) or (8) described liquid crystal liquid crystal property resin concentrates and thermoplastic resin (C) and be shaped and form.
According to the technical scheme of (10),, can under the situation of the non-linear shape structure of not destroying VGCF, carry out MBization by above-mentioned liquid crystal liquid crystal property resin concentrates.Therefore, when this MB of melting mixing and other thermoplastic resin (C), the destruction of the branched structure of VGCF also seldom.Thus, can be suppressed at the electroconductibility inequality very little.
(11) above-mentioned (10) described liquid crystal liquid crystal property resin forming product, wherein, it is that 300 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (A1) of 1～30Pas that described liquid crystal liquid crystal property resin concentrates contains fusing point, and it is that 250 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (C1) of 30～80Pas that described thermoplastic resin (C) contains fusing point.
According to the technical scheme of (11), the melt viscosity that becomes liquid crystal liquid crystal property resin (A1) is lower than the state of liquid crystal liquid crystal property resin (C1).But in the stage with liquid crystal liquid crystal property resin (A1) MBization, melt viscosity can rise, and approaches the melt viscosity (a little higher than thermoplastic resin of the melt viscosity of MB (C) at this moment) of liquid crystal liquid crystal property resin (C1).Thus, as mentioned above, when melting mixing MB and thermoplastic resin (C), the dispersiveness of VGCF also improves.
And liquid crystal liquid crystal property resin (A1) is the liquid crystal liquid crystal property resin with liquid crystal liquid crystal property resin (C1), but its composition has a little difference.Like this, by low liquid crystal liquid crystal property resin (A1) of combination melt viscosity and a little higher than its liquid crystal liquid crystal property resin (C1) of melt viscosity, become immiscible to a certain degree 2 phase systems between two liquid crystal liquid crystal property resins.And then, because the subtle difference (state of a little higher than thermoplastic resin of the melt viscosity of MB (C)) of both melt viscosities becomes the state that has liquid crystal liquid crystal property resin (A1) on the surface of liquid crystal liquid crystal property resin (C1).The result infers and can obtain uneven few electroconductibility.
(12) each described liquid crystal liquid crystal property resin forming product of above-mentioned (10) or (11), wherein, the surface resistivity of described liquid crystal liquid crystal property resin forming product is less than 10
12The logarithmic difference of Ω/ and its maximum value and minimum value is less than 3.
According to the technical scheme of (12), therefore liquid crystal liquid crystal property resin forming product of the present invention has the performance as electroconductive resin molding excellence owing to obtain extremely low and uniform surface resistance rate.
The invention effect
According to the present invention, the inequality that electroconductibility can be provided less and the resin combination with high conductivity and flowability and molding outward appearance excellence.Therefore, liquid crystal liquid crystal property resin forming product of the present invention is suitable for various electric components, electronic unit, optics etc.
Embodiment
＜liquid crystalline resin composition 〉
Below explain embodiments of the present invention.At first, liquid crystalline resin composition of the present invention following with respect to satisfying (a1) and liquid crystal liquid crystal property resin (A) 100 weight parts (a2), containing the fiber external diameter is that 10～500nm, length-to-diameter ratio are 5～1000 vapor phase process charcoal fiber (B) 0.5～40 weight part.
(a1) fusing point is 250 ℃～350 ℃,
(a2) at the temperature higher 20 ℃, shearing rate 1000sec than above-mentioned fusing point
-1The time melt viscosity be 1～80Pas.
Each formation below is described.
＜＜liquid crystal liquid crystal property resin (A)〉〉
Liquid crystal liquid crystal property resin of the present invention (A) is meant the melt processable polymkeric substance with the character that can form optical anisotropy fusion phase, has by be subjected to cutting off stress under molten state to make polymer molecular chain take the character that is arranged in parallel of rule.This polymer molecule is generally elongated, flat, and is considerably high along the major axis rigidity of molecule, is generally to have a plurality of chain lengthening bonded polymkeric substance that are in coaxial or parallel any relation.
The character of anisotropy fusion phase can be confirmed by the polarized light inspection method commonly used of utilizing the crossed nicols sheet.More particularly, the anisotropy fusion approve really mutually with by use the Leitz polarization microscope, multiplying power with 40 times under nitrogen environment observes the fusion sample that is placed on the Leitz warm table, thereby implements.When the spendable liquid crystal liquid crystal property resin of the present invention was checked between the crossed nicols sheet, even if the fusion stationary state, polarized light also saw through usually, the display optical anisotropy.
As this liquid crystal liquid crystal property resin, optimization aromatic polyester or aromatic polyester acid amides, the polyester that partly contains aromatic polyester or aromatic polyester acid amides in same molecular chain is also in its scope.
As the aromatic polyester or the aromatic polyester acid amides of liquid crystal liquid crystal property resin applicatory among the present invention, especially preferably have the compound more than at least a kind that is selected from the group that aromatic hydroxy-carboxylic, aromatic hydroxyl amine, aromatic diamine form aromatic polyester, aromatic polyester acid amides as constituent.
Can enumerate particularly:
(1) the main polyester that constitutes more than a kind or 2 kinds by aromatic hydroxy-carboxylic and derivative thereof;
(2) mainly by the polyester that constitutes more than at least a kind or 2 kinds of more than a kind or 2 kinds of (a) aromatic hydroxy-carboxylic and derivative thereof, (b) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and more than a kind or 2 kinds of derivative thereof, (c) aromatic diol, alicyclic diol, aliphatic diol and derivative thereof;
(3) mainly by the polyesteramide that constitutes more than a kind or 2 kinds of more than a kind or 2 kinds of (a) aromatic hydroxy-carboxylic and derivative thereof, (b) aromatic hydroxyl amine, aromatic diamine and more than a kind or 2 kinds of derivative, (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivative thereof;
(4) mainly by the polyesteramide that constitutes more than at least a kind or 2 kinds of more than a kind or 2 kinds of (a) aromatic hydroxy-carboxylic and derivative thereof, (b) aromatic hydroxyl amine, aromatic diamine and more than a kind or 2 kinds of derivative, (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and more than a kind or 2 kinds of derivative thereof, (d) aromatic diol, alicyclic diol, aliphatic diol and derivative thereof etc.Can also in above-mentioned constituent, adjust agent as required and with molecular weight.
As the preferred example that constitutes the particular compound of spendable above-mentioned liquid crystal liquid crystal property resin among the present invention, can enumerate P-hydroxybenzoic acid, 6-hydroxyl-aromatic hydroxy-carboxylics, 2 such as 2-naphthoic acid, 6-dihydroxy naphthlene, 1,4-dihydroxy naphthlene, 4, aromatic diols such as compound shown in 4 '-dihydroxybiphenyl, quinhydrones, Resorcinol, following general formula [1] and the following general formula [2]; Terephthalic acid, m-phthalic acid, 4,4'-diphenyldicarboxylic acids, 2, aromatic dicarboxylic acids such as compound shown in 6-naphthalene dicarboxylic acids and the following general formula [3]; P-aminophenol, aromatic amines such as Ursol D.
[Chemical formula 1]
(wherein, in the formula, X be the alkylidene group (alkylene) that is selected from carbon number 1～4, alkylidene (alkylidene) ,-O-,-SO-,-SO
2-,-S-,-group of CO-, Y is for being selected from-(CH
2)
n-(n is 1～4 integer) ,-O (CH
2)
mThe group of O-(m is 1～4 integer).)
The melt viscosity of above-mentioned liquid crystal liquid crystal property resin (A) need be the low melting viscosity of the non-linear shape structure degree of not destroying VGCF.Its condition is following fusing point and melt viscosity.(a1) fusing point is 250 ℃～350 ℃ and (a2) at the temperature higher 20 ℃ than above-mentioned fusing point, shearing rate 1000sec
-1The time melt viscosity be 1～80Pas.More preferably fusing point is that 300 ℃～350 ℃, above-mentioned melt viscosity are the liquid crystal liquid crystal property resin (A1) of 1～30Pas.
When melt viscosity surpasses 80Pas, cause the non-linear shape of VGCF destructurized owing to shear, a spot of interpolation then can't obtain uniform conductive.In addition, mobile too high when less than 1Pas, can't carry out melting mixing.
＜＜vapor phase process charcoal fiber (B)〉〉
Vapor phase process charcoal fiber (B) is the vapor phase process charcoal fiber of fiber footpath 10～500nm, length-to-diameter ratio 5～1000, special optimum fiber footpath 30～200nm, length-to-diameter ratio 20～500.As this charcoal fiber, for example preferably use under hot environment the vapor-grown carbon fibers (for example with reference to No. 2778434 communique of Japanese Patent) that can make by the organic compound that is blown into aerification with iron that becomes catalyzer etc.
Fiber footpath is during less than 10nm, and volume density significantly reduces, and handles during with compoundization of liquid crystal liquid crystal property resin to become difficult, and is therefore not preferred; When surpassing 500nm, it is little that the electroconductibility of the molding of gained liquid crystalline resin composition improves effect, so not preferred.In addition, length-to-diameter ratio is less than 5, and it is also little that the electroconductibility of the molding of gained liquid crystalline resin composition improves effect, thus not preferred, surpassing at 1000 o'clock, the interfibrous winding grow of vapor phase process charcoal is even if also be difficult to equably with its dispersion by the aftermentioned manufacture method.
Vapor phase process charcoal fiber (B) for example can use former state charcoal fiber under the manufacturing state, under 800～1500 ℃ to the former state material under the manufacturing state heat-treat the charcoal fiber that obtains, the charcoal fiber that under 2000～3000 ℃, carries out graphitization processing any.Wherein, more preferably heat-treat about 1500 ℃ under the charcoal fiber that obtains or 2000～3000 ℃ and carry out the charcoal fiber that graphitization processing obtains.
And then vapor phase process charcoal fiber (B) has hollow structure, specific surface area (utilizing the BET method) is preferably 2～250m
2/ g, 10～200m more preferably
2/ g.In addition, utilize the centre plane spacing d002 of (002) face of X-ray diffraction method to be preferably following, the 0.336～0.340nm more preferably of 0.345nm.In addition, 1341～1349cm of raman scattering spectrum
-1The peak height of bands of a spectrum (Id) and 1570～1578cm
-1The ratio (Id/Ig) of the peak height of bands of a spectrum (Ig) is preferably 0.1～2.0.The BET specific surface area surpasses 250m
2During/g, the liquid crystal liquid crystal property resin (A) that becomes mother metal is covered fiber fully, when making this liquid crystalline resin composition, can cause the deterioration of electroconductibility, heat conductivity, physical strength, and is therefore not preferred.
Illustrated that it is more than the 0.03g/cc that vapor phase process charcoal fiber (B) preferably makes its volume density in advance.Thus, send into the mixing amount in the resin in the time of can increasing melting mixing in fact, so productivity improves.
＜＜thermoplastic resin (C)〉〉
Also can particularly when carrying out the MBization of liquid crystal liquid crystal property resin described later (A), add thermoplastic resin (C) as required in the liquid crystalline resin composition of the present invention, can carry out further compoundization thus.Thermoplastic resin (C) is not particularly limited, and can enumerate polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polymeric amide, polycarbonate, polyethersulfone, polyetherimide, polyarylester etc.In addition, also can add liquid crystal liquid crystal property resin with the identical or different kind of liquid crystal liquid crystal property resin (A).
＜＜other composition〉〉
In addition, can mix Ketjen black, acetylene black, the so non-fibrous carbon of graphite as other any composition in the liquid crystalline resin composition of the present invention is packing material.Therefore vapor phase process charcoal fiber when obtaining required electroconductibility, is packing material by add non-fibrous carbon in the scope that does not make characteristic degradations such as mechanical characteristics, flowability, thereby can obtains economical effectiveness owing to expensive.
And then, can also add whisker, glass fibre, spun fibers, silica fiber, silica alumina fiber, zirconia fiber, boron nitride fibre, silicon nitride fiber, boron fibre, potassium titanate fiber, and then can also to add non-carbon such as the tabular material of inanimate matter such as the inorganic fibre shape material such as fibrous material of metals such as stainless steel, aluminium, titanium, copper, brass and talcum, mica be strengthening material.Thus, can further improve mechanical characteristics.
And then, in the liquid crystalline resin composition of the present invention as requested the suitable interpolation of performance generally can be added in known material in the synthetic resins, be stablizers such as antioxidant, UV light absorber, tinting materials such as static inhibitor, fire retardant, dyestuff or pigment, lubricant, releasing agent and crystallization promotor, nucleating agent etc.
＜＜cooperation ratio〉〉
Among the present invention,, contain vapor phase process charcoal fiber (B) 0.5～40 weight part, preferably contain 1～30 weight part with respect to liquid crystal liquid crystal property resin (A) 100 weight parts.Illustrated that this ratio is the content in the final molding.Vapor phase process charcoal fiber (B) is during less than 0.5 weight part, and is because electroconductibility becomes insufficient, therefore not preferred.In addition,, do not see that significantly electroconductibility improves even if surpass 40 weight parts yet, the problem that opposite generation flowability reduces, physical strength descends, therefore not preferred.Illustrated that above-mentioned other compositions can suitably cooperate in the scope of not damaging effect of the present invention.
＜＜extrusion method〉〉
Liquid crystalline resin composition of the present invention can be by known extrusion method acquisition in the past.For example, can possess the continuous mixing device of screw rod by utilization, preferably after the fusion of liquid crystal liquid crystal property resin (A), mix vapor phase process charcoal fiber (B) and carry out melting mixing.The method of melting mixing is not particularly limited, and preferably utilizes the twin screw extruder of engagement type to adopt the screw rod of single thread shape to constitute, thereby the feeding amount when increasing melting mixing, further boosts productivity.Here, the screw rod formation portion of single thread shape is the screw rod of a screw thread of advancing every 1 week of rotation, because the screw rod ditch depth is dark, the stream volume is big, therefore is suitable for the conveyance of the many vapor phase process charcoal fibers in space, can improve feed significantly to forcing machine, therefore preferred.In addition, the relative shear speed from engaging piece improves the dispersing and mixing ability excellence of being brought, the dispersive aspect of promotion vapor phase process charcoal fiber considers that the sense of rotation of screw rod is preferred equidirectional rotary-type.
＜manufacturing process 〉
Manufacturing process is not particularly limited, and can carry out extrusion molding and also can carry out injection molded.In addition, molding also is not particularly limited, and is not limited to the solid forming product, can also carry out sheet or membranaceous shaping, and these are also included within the liquid crystalline resin molding of the present invention certainly.Illustrated, also nonessential among the present invention so via masterbatch (MB), liquid crystal liquid crystal property resin concentrates of the present invention below is described.
＜liquid crystal liquid crystal property resin concentrates 〉
Then, liquid crystal liquid crystal property resin concentrates of the present invention is described.Liquid crystalline resin composition of the present invention can also be made masterbatch and use.By carry out MBization earlier, handle and become more easy.Thus, for example can adopt the mixing method that forms behind the particle MB that is modulated into of extruding of liquid crystalline resin composition; Different particle MB is formed in modulation earlier, and this particle is mixed (dilution) for being shaped and obtaining the method etc. of the molding of regulation composition with specified amount.In addition, in the modulation of molding composition therefor, if with the powder body of particle MB and thermoplastic resin part or all, other composition (glass fibre etc.) mixes and carry out melting mixing, and is then favourable for the dispersion of other composition of raising.Illustrated, preferably use when obtaining this MB screw rod continuous mixing device structure since with above-mentioned＜＜extrusion method in explanation identical, therefore omit.
Illustrated that in order to keep the nonlinearity structure of the vapor phase process charcoal fiber (B) in the final molding as far as possible, the fracture ratio that need experience the vapor phase process charcoal fiber (B) in the liquid crystal liquid crystal property resin concentrates of mixing operation once more is preferably below 50%.More preferably below 40%, be preferably below 30% especially.
The fracture ratio is by relatively mixing and the length-to-diameter ratio of the charcoal fiber of mixing front and back is estimated.Here, fracture ratio defines with following formula:
1-(length-to-diameter ratio/mixing of the charcoal fiber of molding composition and mixing before the length-to-diameter ratio of charcoal fiber) * 100
Length-to-diameter ratio is preferably utilized electron microscope (SEM) to observe and is measured and calculate.In addition, during the mensuration of the length-to-diameter ratio of the vapor phase process charcoal fiber in the masterbatch, be necessary to utilize proper method to remove matrix resin.Specifically, among the present invention, can enumerate the caustic leaching process that uses sodium chloride solution etc., the thermal decomposition method under the proper temperature etc.
In addition, for the fracture ratio that makes vapor phase process charcoal fiber (B) is below 50%, except at the temperature higher 20 ℃, shearing rate 1000sec than liquid crystal liquid crystal property melting point resin
-1The time melt viscosity be outside 1～80Pas, the resin pressure at the VGCF point of addition place when extruding by reduction is reached.The resin temperature at discharge-amount in the time of specifically, can extruding by reduction or raising VGCF point of addition place etc. is reached.
＜liquid crystal liquid crystal property resin forming product 〉
＜＜electroconductibility〉〉
So the electroconductibility of the liquid crystal liquid crystal property resin forming product of the present invention that obtains is very excellent, and inequality is also little in addition.Specifically, the surface resistivity of molding less than the denary logarithm difference of maximum value during a plurality of position finding and minimum value in 1012 Ω/ and the same molding less than 3.Preferred shape, the size according to molding of this mensuration increases to measure counts, and from improving the viewpoint of data precision, more preferably measures 5 more than the position.The mensuration of surface resistivity of the present invention can be used Loresta trier or the Hiresta trier according to the four terminal four point probe modes of JIS K7194.Loresta trier and Hiresta trier are measured probe owing to changing according to the shape/size of working sample, so the convenience height.
＜＜purposes〉〉
As above explanation, according to the present invention, can be to compare the uneven little liquid crystal liquid crystal property resin forming product that low addition obtains high conductivity and electroconductibility with existing conductive resin composition.In addition, the melt viscosity of liquid crystalline resin composition of the present invention is low, shaping processability, molding outward appearance are also excellent.Therefore, needing can be preferred for the electrical/electronic components of the means of delivery, fuel cell separators etc. of the lens barrel of digital still camera etc. of electroconductibility, static resistance or lens bracket, semi-conductor etc.
Embodiment
Below enumerate embodiment the present invention is described in further detail, but the present invention is defined in this.Illustrated that the physical property measurement method among the embodiment is as described below.
[fusing point]
Use differential scanning calorimetric analysis device (パ-キ Application エ Le マ-company makes DSC7) under 20 ℃/minute heating and cooling condition, to measure.
[melt viscosity: MV]
Shearing rate 1000sec under fusing point+20 of resin shown in the table 1 ℃
-1Condition under, use the nozzle (orifice) of internal diameter 1mm, long 20mm to utilize the キ ヤ ピ ロ グ ラ Off 1B of Japan's essence machine manufacturing to measure.
[actual addition mensuration]
Use specific gravity hydrometer SD-120L (grinding Seiko industry Co., Ltd.) measures the proportion of each thermoplastic resin composition's molding, is calculated the addition of vapor phase process charcoal fiber by following material proportion.But, therefore calculate by the addition of masterbatch owing to be difficult to calculate when using a plurality of raw material.
Liquid crystalline polyester＜1 〉,＜2〉1.4g/cm
3
PC 1.2g/cm
3
VGCF 2.2g/cm
3
KB 1.7g/cm
3
CF 1.7g/cm
3
[surface resistivity is measured: SR]
Use is according to device Loresta GP MCP-T400 (Mitsubishi's oiling (strain) manufacturing) ASP probe, Hiresta-UP M CP-HT450 (Mitsubishi Chemical's manufacturing) the URS probe of JIS K7194, measure the φ 100cm * grid side of 3mmt plectane, anti-grid side, central authorities and about 5 positions altogether, put down in writing its maximum value, minimum value.
[molding ocular estimate]
The appearance of visual observation φ 100cm * 3mmt plectane is estimated in order to following standard.
Zero: the surface has gloss, does not have ripple (flow mark), crazing (silvermark) etc.
*: the surface is lackluster, has ripple or crazing etc.
[extruding status evaluation]
Utilize following standard visual observations to extrude situation.
Zero: on the screw rod/compactor (compactor) of carbon filler addition portion, do not accumulate carbon filler, add swimmingly.
*: on the screw rod/compactor of carbon filler addition portion, accumulate carbon filler, can't obtain required carbon filler amount.
＜Production Example 1〉(liquid crystalline polyester＜1〉manufacturing)
In the aggregation container that possesses stirrer, reflux column, monomer input port, nitrogen inlet, decompression/outflow circuit, pack into following starting monomer, catalyzer, acylation agent, the beginning nitrogen replacement.Behind the charging feedstock, the temperature of reaction system is warming up to 140 ℃, 140 ℃ of reactions 1 hour down.Afterwards, continue to be warming up to 330 ℃ with 3.3 hours, then with being decompressed to 10Torr (being 1330Pa) in 20 minutes, distill and remove acetic acid, excessive acetic anhydride, other low boiling component on one side, melt polymerization carries out on one side.After stirring moment of torsion arrival prescribed value, import nitrogen, arrive pressurized state from decompression state through normal pressure, discharge liquid crystalline polyester＜1 from the bottom of aggregation container 〉.
(A): 4-hydroxy-benzoic acid 226.4g (73 moles of %)
(B): 6-hydroxyl-2-naphthoic acid 114.1g (27 moles of %)
Potassium ethanoate 22.5mg
Acetic anhydride 233.8g
＜Production Example 2〉(liquid crystalline polyester＜2〉manufacturing)
Use following material as starting monomer, catalyzer, acylation agent,, similarly obtain polyester＜2〉with Production Example 1 except being warming up to 335 ℃ with 230 minutes.
(A) 4-hydroxy-benzoic acid 250.74g (78.5 moles of %)
(B) 6-hydroxyl-2-naphthoic acid 80.51g (18.5 moles of %)
(C) terephthalic acid 11.53g (3.0 moles of %)
Potassium ethanoate 15mg
Acetic anhydride 235.87g
The affirmation of＜liquid crystal liquid crystal property 〉
For gained polyester＜1〉utilizing polarization microscope under crossed nicols, to observe under 300 ℃ the molten state, for polyester＜2〉utilizing polarization microscope under crossed nicols, to observe under 340 ℃ the molten state, show clear and definite optical anisotropy, confirm as the thermotropic liquid crystal resin.The characteristic of each liquid crystalline resin is shown in table 1.
Table 1
| Polymkeric substance | Liquid crystalline polyester＜1 〉 | Liquid crystalline polyester＜2 〉 |
| Fusing point/℃ | 280 | 335 |
| Melt viscosity/Pas (measure temperature: fusing point+20 ℃) | 47 | 2.5 |
＜embodiment 1～3, comparative example 1～5 〉
As table 2; (engagement unit is a weight part shown in 3; below all the table in all identical); (Japan's system steel (strain) is made to use twin screw extruder; TEX-α 30) with table 2; the melting mixing of ratio shown in 3 liquid crystalline polyester＜1 〉; liquid crystalline polyester＜2 〉; polycarbonate resin [Supreme Being people changes into the L1225L that (strain) make, and (melt viscosity: 267Pas is (when measure by the differential scanning calorimetric analysis device of polycarbonate resin in utilizing the present invention; can't observe fusing point; therefore the measurement result under having put down in writing 300 ℃)) (being recited as PC in the table 2)]; vapor phase process charcoal fiber [VGCF-S (the fiber external diameter 100nm that clear and electrician's (strain) makes; length-to-diameter ratio 100)]; Ketjen black [EC600JD (being recited as KB in the table 2) that ラ イ Application ケ ミ-(strain) made]; charcoal fiber [HTA-C6-X132 (being recited as CF in the table 2) that the eastern テ of nation Na Star Network ス (strain) makes]; glass fibre [ECS03T-786H (being recited as GF in the table 2) that NEG (strain) is made] carries out granulating.
At this moment, vapor phase process charcoal fiber, carbon filler class and glass fibre use the side feeding, and (with the resin point of addition as C0, the 7th cylinder) adds from the cylinder C6 position of partition type.In addition, use following forcing machine melting mixing liquid crystalline polyester＜1 in advance 〉, liquid crystalline polyester＜2 and VGCF-S and obtaining.In addition, the screw rod part of C6 position uses the single thread part.Utilize injection molding machine to make above-mentioned test film and evaluation under the following conditions by this particle.This result is shown in table 2,3 in the lump.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Liquid crystalline polyester＜1 〉 | 100 | ||
| Liquid crystalline polyester＜2 〉 | 100 | 100 | |
| PC | |||
| VGCF | 11 | 14 | 5 |
| KB | |||
| CF | |||
| GF | |||
| Actual addition/wt.% | 10.4 | 11.7 | 4.4 |
| S.R. uneven minimum value (Ω/) | 1.3E+00 | 1.6.E+00 | 2.6.E+01 |
| S.R. uneven maximum value (Ω/) | 6.1E+01 | 2.6.E+00 | 4.8.E+01 |
| S.R. uneven (log (maximum value)-log (minimum value)) | 1.7 | 0.2 | 0.3 |
| MV/Pa·s | 199 | 110 | 54 |
| The molding outward appearance | ○ | ○ | ○ |
| Extrude situation | ○ | ○ | ○ |
Table 3
| Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Liquid crystalline polyester＜1 〉 | 100 | 100 | 100 | |
| Liquid crystalline polyester＜2 〉 | ||||
| PC | 100 | |||
| VGCF | 5 | |||
| KB | 4 | 8 | ||
| CF | 18 | |||
| GF | ||||
| Actual addition/wt.% | 2.1 | 3.6 | 6.1 | 14.4 |
| S.R. uneven minimum value (Ω/) | 5.7E+05 | >1E+13 | 2.2E+01 | 2.3.E+01 |
| S.R. uneven maximum value (Ω/) | >1E+13 | >1E+13 | 7.8E+04 | 7.2.E+04 |
| S.R. uneven (log (maximum value)-log (minimum value)) | >7.0 | - | 3.5 | 3.5 |
| MV/Pa·s | 451 | 171 | 336 | 72 |
| The molding outward appearance | ○ | ○ | ○ | × |
| Extrude situation | * (feed is bad) | ○ | ○ | ○ |
＜embodiment 4,5, comparative example 6 〉
The particle made among embodiment 1 and the embodiment 2 as masterbatch, is mixed various fillers with the dry type of ratio shown in the table 6, use twin screw extruder (Japan's system steel (strain) is made, TEX-α 30) to carry out melting mixing, carry out granulating.The technological temperature of embodiment 4 be 340 ℃, this moment liquid crystalline polyester＜1 melt viscosity be 24Pas.The technological temperature of embodiment 5 be 300 ℃, this moment liquid crystalline polyester＜1 melt viscosity be 47Pas.The screw rod part of C6 position uses the single thread part.Utilize injection molding machine to make above-mentioned test film under the following conditions by this particle and estimate.Its result is shown in table 5 in the lump.
(injection molded condition)
Forming mill: JSWJ75S SII-A
Temperature cylinder: embodiment 1 and embodiment 5,1～6300 ℃ of comparative example, 2～4340 ℃ of embodiment
Die temperature: under 90 ℃ the condition, the plectane of shaping φ 100 * 3mmt.
Table 4
| Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Liquid crystalline polyester＜1 〉 | 100 | 100 | 100 |
| Liquid crystalline polyester＜2 〉 | |||
| PC | |||
| Masterbatch＜1〉(embodiment 1) | 47 | ||
| Masterbatch＜2〉(embodiment 2) | 47 | ||
| KB(EC600JD) | |||
| GB | 9 | 20 | |
| CF | 17 | ||
| GF | 40 | 86 | |
| VGCF addition/wt.% | 3.7 | 3.1 | - |
| S.R. uneven minimum value (Ω/) | 7.3.E+03 | 1.6.E+06 | 7.3E+06 |
| S.R. uneven maximum value (Ω/) | 4.6.E+05 | 5.8.E+07 | >1E+13 |
| S.R. uneven (log (maximum value)-log (minimum value)) | 1.8 | 1.6 | >6.0 |
| MV/Pa·s | 23 | 192 | 113 |
| The molding outward appearance | ○ | ○ | ○ |
| Extrude situation | ○ | ○ | ○ |
＜evaluation result 〉
By table 2,3 result as can be known, the molding outward appearance of liquid crystal liquid crystal property resin forming product of the present invention, extrude situation, surface resistivity and inequality thereof and all be better than comparative example.
And then, as shown in Table 4, utilize liquid crystalline polyester＜1〉when making masterbatch, the molding outward appearance, extrude situation, surface resistivity and uneven excellent evaluation arranged all.
Industrial applicability
According to the present invention, the uneven little of electric conductivity can be provided and have high conductivity and the resin combination of flowability and formed products outward appearance excellence. Therefore, liquid-crystalline resin formed products of the present invention is suitable for various electric components, electronic unit, optics etc.
Claims (12)
1. liquid crystalline resin composition, its following with respect to satisfying (a1) and liquid crystal liquid crystal property resin (A) 100 weight parts (a2), containing the fiber external diameter is that 10～500nm, length-to-diameter ratio are 5～1000 vapor phase process charcoal fiber (B) 0.5～40 weight part, wherein,
(a1) fusing point is 250 ℃～350 ℃,
(a2) be 1000sec in the temperature higher 20 ℃, shearing rate than above-mentioned fusing point
-1The time melt viscosity be 1～80Pas.
2. liquid crystalline resin composition according to claim 1, wherein, described liquid crystal liquid crystal property resin (A) contains 4-hydroxy-benzoic acid and 6-hydroxyl-2-naphthoic acid at least as constituting monomeric unit.
3. liquid crystalline resin composition according to claim 1 and 2, wherein, it is that 300 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (A1) of 1～30Pas that described liquid crystal liquid crystal property resin (A) contains fusing point.
4. according to each described liquid crystalline resin composition in the claim 1～3, wherein, the fiber external diameter of described vapor phase process charcoal fiber (B) is that 30～200nm, length-to-diameter ratio are 20～500.
5. according to each described liquid crystalline resin composition in the claim 1～4, wherein, described vapor phase process charcoal fiber (B) has hollow structure, the BET specific surface area is 1341～1349cm of 2～250m2/g, raman scattering spectrum
-1The peak height of bands of a spectrum (Id) and 1570～1578cm
-1The ratio (Id/Ig) of the peak height of bands of a spectrum (Ig) is 0.1～2.0.
6. liquid crystal liquid crystal property resin forming product, it is the molding that is formed by each described liquid crystalline resin composition in the claim 1～5, wherein, the surface resistivity of described molding is less than 10
12The logarithmic difference of Ω/ and its maximum value and minimum value is less than 3.
7. liquid crystal liquid crystal property resin concentrates, it forms by each described liquid crystalline resin composition in the melting mixing claim 1～5, wherein, with respect to liquid crystal liquid crystal property resin (A) 100 weight parts, contain vapor phase process charcoal fiber (B) 5～40 weight parts in this liquid crystalline resin composition.
8. liquid crystal liquid crystal property resin concentrates according to claim 7, it contains fusing point is that 300 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (A1) of 1～30Pas.
9. liquid crystal liquid crystal property resin concentrates according to claim 8, the fracture ratio of the vapor phase process charcoal fiber (B) during its melting mixing is below 50%.
10. liquid crystal liquid crystal property resin forming product, it is by melting mixing claim 7 or 8 described liquid crystal liquid crystal property resin concentrates and thermoplastic resin (C) and be shaped and form.
11. liquid crystal liquid crystal property resin forming product according to claim 10, wherein, it is that 300 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (A1) of 1～30Pas that described liquid crystal liquid crystal property resin concentrates contains fusing point, and it is that 250 ℃～350 ℃, described melt viscosity are the liquid crystal liquid crystal property resin (C1) of 30～80Pas that described thermoplastic resin (C) contains fusing point.
12. according to claim 10 or 11 described liquid crystal liquid crystal property resin forming products, wherein, the surface resistivity of described liquid crystal liquid crystal property resin forming product is less than 10
12The logarithmic difference of Ω/ and its maximum value and minimum value is less than 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP174866/2006 | 2006-06-26 | ||
| JP2006174866A JP5132899B2 (en) | 2006-06-26 | 2006-06-26 | Liquid crystalline resin composition |
| PCT/JP2007/062668 WO2008001708A1 (en) | 2006-06-26 | 2007-06-25 | Liquid-crystalline resin composition |
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|---|---|
| CN101479346A true CN101479346A (en) | 2009-07-08 |
| CN101479346B CN101479346B (en) | 2012-01-04 |
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|---|---|
| JP (1) | JP5132899B2 (en) |
| CN (1) | CN101479346B (en) |
| TW (1) | TW200806779A (en) |
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| CN114854227A (en) * | 2022-03-15 | 2022-08-05 | 珠海万通特种工程塑料有限公司 | LCP composite material and preparation and application thereof |
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| JP5229462B2 (en) * | 2008-07-24 | 2013-07-03 | 三菱瓦斯化学株式会社 | Insulating high thermal conductivity resin composite material |
| JP2015061891A (en) * | 2012-01-27 | 2015-04-02 | 昭和電工株式会社 | Production method of conductive resin composition master batch and master batch |
| JP7096590B2 (en) | 2016-05-24 | 2022-07-06 | ユニチカ株式会社 | Resin compositions and molded products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4161470A (en) * | 1977-10-20 | 1979-07-17 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing |
| JP2942840B2 (en) * | 1989-05-24 | 1999-08-30 | ダイセル化学工業株式会社 | Laminated film |
| JPH03243632A (en) * | 1990-02-20 | 1991-10-30 | Unitika Ltd | Production of sliding parts made of liquid crystal polymer |
| JPH06312423A (en) * | 1993-04-28 | 1994-11-08 | Kobe Steel Ltd | Resin composite material, and pellet to form resin composite material |
| JP2000248186A (en) * | 1999-02-26 | 2000-09-12 | Teijin Ltd | Resin composition and jig for transporting electronic part made of it |
| JP2001089581A (en) * | 1999-09-22 | 2001-04-03 | Toray Ind Inc | Sheet and its production |
| JP2003268249A (en) * | 2002-03-20 | 2003-09-25 | Showa Denko Kk | Electroconductive curable resin composition, its cured product and its production method |
| JP2005264134A (en) * | 2003-09-02 | 2005-09-29 | Showa Denko Kk | Conductive polymer, its preparation process and its application |
| JP4504675B2 (en) * | 2003-12-25 | 2010-07-14 | ウィンテックポリマー株式会社 | Resin composition and jig for transportation in the electronics field |
| JP4302508B2 (en) * | 2003-12-26 | 2009-07-29 | ポリプラスチックス株式会社 | Conductive resin composition |
| JP2005310533A (en) * | 2004-04-21 | 2005-11-04 | Polyplastics Co | Fuel cell separator |
| JP2006097006A (en) * | 2004-08-31 | 2006-04-13 | Showa Denko Kk | Method for producing electrically conductive resin composition and application thereof |
| JP2006097005A (en) * | 2004-08-31 | 2006-04-13 | Showa Denko Kk | Electrically conductive resin composition and method for producing the same |
-
2006
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-
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- 2007-06-23 TW TW096122720A patent/TW200806779A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854227A (en) * | 2022-03-15 | 2022-08-05 | 珠海万通特种工程塑料有限公司 | LCP composite material and preparation and application thereof |
| CN114854227B (en) * | 2022-03-15 | 2023-09-05 | 珠海万通特种工程塑料有限公司 | LCP composite material and preparation and application thereof |
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| TW200806779A (en) | 2008-02-01 |
| JP5132899B2 (en) | 2013-01-30 |
| JP2008001848A (en) | 2008-01-10 |
| CN101479346B (en) | 2012-01-04 |
| WO2008001708A1 (en) | 2008-01-03 |
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