WO2014021300A1 - Liquid crystal resin composition - Google Patents
Liquid crystal resin composition Download PDFInfo
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- WO2014021300A1 WO2014021300A1 PCT/JP2013/070566 JP2013070566W WO2014021300A1 WO 2014021300 A1 WO2014021300 A1 WO 2014021300A1 JP 2013070566 W JP2013070566 W JP 2013070566W WO 2014021300 A1 WO2014021300 A1 WO 2014021300A1
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- liquid crystalline
- resin composition
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- talc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/53—Physical properties liquid-crystalline
Definitions
- the present invention relates to a liquid crystalline resin composition containing talc.
- a resin characterized by high heat resistance and high dimensional accuracy such as a liquid crystalline resin
- a resin characterized by high heat resistance and high dimensional accuracy such as a liquid crystalline resin
- a resin characterized by high heat resistance and high dimensional accuracy such as a liquid crystalline resin
- the liquid crystalline resin is molded by heating and melting, but the melting temperature of the liquid crystalline resin is much higher than that of other resins. It becomes very hot.
- a peculiar phenomenon expresses due to such high temperature. For example, a reaction such as thermal decomposition or hydrolysis of a liquid crystalline resin by a catalytic action of an impurity metal in talc or, in some cases, talc itself. Due to this, a liquid crystalline resin composition containing talc has not been sufficient in mechanical properties and heat resistance in the past.
- Patent Document 1 discloses that talc having a total content of Fe 2 O 3 and Al 2 O 3 of less than 1% by weight and an average particle size of 2.5 to 3.5 ⁇ m with respect to 100 parts by weight of a predetermined copolymerized polyester.
- a heat resistant resin composition containing 5 to 200 parts by weight is described.
- Patent Document 2 discloses a composition containing talc containing only 35% to 65% aromatic polyester and 1% to 60% of a material that can be decomposed at an elevated temperature with a minimum content. Things are listed. However, in either case, the moldability and heat resistance have not reached sufficient levels, and a liquid crystalline resin composition with even better moldability and heat resistance is desired.
- the present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a liquid crystalline resin composition excellent in molding processability and heat resistance.
- a liquid crystalline resin composition comprising 5 to 200 parts by mass of talc with respect to 100 parts by mass of a liquid crystalline resin,
- the total content of Fe 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less with respect to the total solid content of the talc, and the total content of Fe 2 O 3 and Al 2 O 3 is 1 More than 0.0 mass% and 2.0 mass% or less, and the CaO content is less than 0.5 mass%.
- the liquid crystal resin is an aromatic polyester or an aromatic polyester amide having at least one compound selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines as a constituent component
- the total content of the Fe 2 O 3 , Al 2 O 3 and CaO is 1.0 mass% or more and 2.0 mass% or less, and the total content of Fe 2 O 3 and Al 2 O 3 is 1
- liquid crystalline resin composition having excellent molding processability and heat resistance can be provided.
- the liquid crystalline resin composition of the present invention is a liquid crystalline resin composition comprising 5 to 200 parts by mass of talc with respect to 100 parts by mass of the liquid crystalline resin, and Fe based on the total solid content of the talc.
- the total content of 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less, and the total content of Fe 2 O 3 and Al 2 O 3 is more than 1.0% by mass and 2.0% by mass or less.
- the CaO content is less than 0.5% by mass.
- the liquid crystalline resin used in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase.
- the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
- the liquid crystalline resin applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in a molten stationary state, and optically anisotropic.
- the type of liquid crystalline resin as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide.
- the polyester which partially contains aromatic polyester or aromatic polyester amide in the same molecular chain is also in that range.
- These have a logarithmic viscosity (IV) of preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by mass. .) are preferably used.
- the aromatic polyester or aromatic polyester amide as the liquid crystalline resin applicable to the present invention is particularly preferably constituted of at least one compound selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines and aromatic diamines. Aromatic polyesters and aromatic polyester amides as components.
- a polyesteramide comprising one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof; (4) mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof; (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof; and (c). One or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof; and (d) at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof, and And polyester amides composed of Furthermore, you may use a molecular weight modifier together with said structural component as needed.
- Specific examples of the specific compound constituting the liquid crystalline resin applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6-dihydroxynaphthalene, 1 , 4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, aromatic diols such as compounds represented by the following general formula (I) and the following general formula (II); terephthalic acid, isophthalic acid, 4, Aromatic dicarboxylic acids such as 4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol and p-phenylenediamine It is done.
- aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid
- X a group selected from alkylene (C1 to C4), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—)
- the liquid crystalline resin used in the present invention can be synthesized by a known method using a direct polymerization method or a transesterification method from the above monomer compound (or a mixture of monomers), but usually a melt polymerization method or a slurry.
- a polymerization method or the like is used.
- the above compounds having ester-forming ability may be used for polymerization as they are, or may be modified from a precursor to a derivative having ester-forming ability in the previous stage of polymerization.
- various catalysts can be used.
- Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, carboxylic acid alkalis and Examples include alkaline earth metal salts and Lewis acid salts such as BF 3 .
- the amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.01 to 0.2% by weight, based on the total weight of the monomers. If the polymers produced by these polymerization methods are further necessary, the molecular weight can be increased by solid-phase polymerization by heating in a reduced pressure or an inert gas.
- the melt viscosity of the liquid crystalline resin obtained by the above method is not particularly limited. In general, those having a melt viscosity at a molding temperature of 10 Pa ⁇ s to 600 Pa ⁇ s at a shear rate of 1000 sec ⁇ 1 can be used. However, those having a very high viscosity are not preferable because the fluidity is extremely deteriorated.
- the liquid crystalline resin may be a mixture of two or more liquid crystalline resins.
- the total content of Fe 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less based on the total solid content of the talc, Fe 2 O 3 and Al
- the total content of 2 O 3 is more than 1.0% by mass and 2.0% by mass or less
- the content of CaO is less than 0.5% by mass. That is, the talc used in the present invention contains at least one of Fe 2 O 3 , Al 2 O 3 and CaO in addition to the main components SiO 2 and MgO, and each component has the above content range. It contains.
- the total content of Fe 2 O 3 , Al 2 O 3 and CaO is preferably 1.0% by mass or more and 2.0% by mass or less. Further, in the talc, the total content of 1.0 mass% of talc Fe 2 O 3 and Al 2 O 3 is difficult to obtain, exceeds 2.0 mass%, moldability and heat resistance Gets worse.
- the total content of Fe 2 O 3 and Al 2 O 3 is preferably more than 1.0 mass% and not more than 1.7 mass%. Furthermore, in the talc, when the content of CaO is 0.5% by mass or more, moldability and heat resistance deteriorate.
- the content of CaO is preferably 0.01% by mass or more and 0.4% by mass or less.
- the particle size (D50%) of the talc measured by a laser diffraction method is preferably 4.0 to 20.0 ⁇ m from the viewpoint of preventing warpage deformation and maintaining fluidity. More preferably, it is 18 ⁇ m.
- the talc is contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the liquid crystalline resin.
- the content is less than 5 parts by mass, the effect of preventing warping deformation is small, and when it exceeds 200 parts by mass, the fluidity is deteriorated.
- the content is preferably 5 to 100 parts by mass, and more preferably 10 to 40 parts by mass.
- talc commercially available products such as Crown Talc PP made by Matsumura Sangyo and MS-K made by Nippon Talc can be used.
- an inorganic filler other than talc may be blended.
- glass fiber asbestos fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, boron fiber, silicon carbide fiber, carbon fiber, light calcium carbonate, heavy or finely powdered calcium carbonate, special calcium filler, etc.
- Clays such as silane modified clay (aluminum silicate powder), silica (silicon dioxide) powder such as fused silica, synthetic silica, crystalline silica, diatomaceous earth
- Silica-containing compounds such as silica sand, pulverized natural minerals such as pumice powder, pumice balloon, slate powder, and mica powder
- alumina-containing compounds such as alumina, alumina colloid (alumina sol), alumina white, aluminum sulfate, barium sulfate, Lithopone, calcium sulfate, molybdenum disulfide
- Minerals such as phyto (graphite), glass beads such as glass beads, glass hollow bodies, glass flakes, foamed glass beads, fly ash spheres, volcanic glass hollow bodies, synthetic inorganic hollow bodies, single crystal potassium titanate, carbon nanotubes, Carbon hollow sphere, carbon 64 fullerene, anth clay such as silane modified clay (aluminum silicate powder), silica (silicon dioxide
- the liquid crystalline resin composition of the present invention is put into an extruder, melted and kneaded into pellets, and the pellets are put into an injection molding machine equipped with a predetermined mold and injection molded to obtain a molded product.
- the melting temperature at the time of pelletization is preferably 250 to 400 ° C., more preferably 300 to 380 ° C.
- Examples 1 to 6 Comparative Examples 1 to 5
- LCP liquid crystalline resin
- E950i Vectra (registered trademark) LCP E950i
- ECS04T-790DE manufactured by Nippon Electric Glass Co., Ltd.
- Fe + Al + Ca and Fe + Al are the total content of Fe 2 O 3 , Al 2 O 3 and CaO with respect to the total solid content of talc, respectively, Fe 2 O 3 represents the total content of Al 2 O 3. Further, the content of each component in talc is a value obtained by analysis according to JIS M 8851, and the particle diameter is obtained by measurement by a laser diffraction method. Value.
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Abstract
Provided is a liquid crystal resin composition of excellent moldability and heat resistance. A liquid crystal resin composition containing 5 to 200 parts by mass of talc in relation to 100 parts by mass of liquid crystal resin, wherein the liquid crystal resin composition is characterized in that the total content of Fe2O3, Al2O3, and CaO is 2.5 mass% or less, the total content of Fe2O3 and Al2O3 is more than 1.0 mass% to 2.0 mass%, and the content of CaO is less than 0.5 mass%, in relation to the total solid content of the talc.
Description
本発明は、タルクを含有させてなる液晶性樹脂組成物に関する。
The present invention relates to a liquid crystalline resin composition containing talc.
タルクを液晶性樹脂に含有させて液晶性樹脂組成物を得ることについては、従来から種々の試みがなされている。しかし、液晶性樹脂のように、高耐熱性、高寸法精度を特徴とする樹脂においては、高温度下において種々の問題があった。すなわち、液晶性樹脂にタルクを含有させた液晶性樹脂組成物を成形する場合、当該液晶性樹脂を加熱溶融して成形することとなるが、液晶性樹脂の溶融温度は他の樹脂に比べ非常に高温となる。そして、そのような高温に起因して特異な現象が発現する。例えば、タルク中の不純物金属、あるいは場合によりタルクそれ自身による触媒的作用による液晶性樹脂の熱分解、加水分解などの反応である。これに起因し、タルクを含有させた液晶性樹脂組成物は、従来においては、機械的特性、および耐熱性が充分ではなかった。
Various attempts have been made to obtain a liquid crystalline resin composition by adding talc to a liquid crystalline resin. However, a resin characterized by high heat resistance and high dimensional accuracy, such as a liquid crystalline resin, has various problems at high temperatures. That is, when a liquid crystalline resin composition containing talc in a liquid crystalline resin is molded, the liquid crystalline resin is molded by heating and melting, but the melting temperature of the liquid crystalline resin is much higher than that of other resins. It becomes very hot. And a peculiar phenomenon expresses due to such high temperature. For example, a reaction such as thermal decomposition or hydrolysis of a liquid crystalline resin by a catalytic action of an impurity metal in talc or, in some cases, talc itself. Due to this, a liquid crystalline resin composition containing talc has not been sufficient in mechanical properties and heat resistance in the past.
上記のような問題を解決する液晶性樹脂組成物として、種々提案されている（例えば、特許文献１及び２参照。）。特許文献１には、所定の共重合ポリエステル１００重量部に対し、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１重量％未満かつ平均粒子径が２．５～３．５μｍであるタルク５～２００重量部を含有する耐熱性樹脂組成物が記載されている。
また、特許文献２には、３５％乃至６５％の芳香族ポリエステル、１％乃至６０％の、高められた温度で分解し得る材料を最小の含有率でしか含有しないタルクを含有してなる組成物が記載されている。
しかしながら、いずれの場合も、成形加工性及び耐熱性は十分なレベルには達しておらず、成形加工性及び耐熱性がさらに良好な液晶性樹脂組成物が求められている。 Various liquid crystalline resin compositions that solve the above problems have been proposed (see, for example, Patent Documents 1 and 2). Patent Document 1 discloses that talc having a total content of Fe 2 O 3 and Al 2 O 3 of less than 1% by weight and an average particle size of 2.5 to 3.5 μm with respect to 100 parts by weight of a predetermined copolymerized polyester. A heat resistant resin composition containing 5 to 200 parts by weight is described.
Patent Document 2 discloses a composition containing talc containing only 35% to 65% aromatic polyester and 1% to 60% of a material that can be decomposed at an elevated temperature with a minimum content. Things are listed.
However, in either case, the moldability and heat resistance have not reached sufficient levels, and a liquid crystalline resin composition with even better moldability and heat resistance is desired.
また、特許文献２には、３５％乃至６５％の芳香族ポリエステル、１％乃至６０％の、高められた温度で分解し得る材料を最小の含有率でしか含有しないタルクを含有してなる組成物が記載されている。
しかしながら、いずれの場合も、成形加工性及び耐熱性は十分なレベルには達しておらず、成形加工性及び耐熱性がさらに良好な液晶性樹脂組成物が求められている。 Various liquid crystalline resin compositions that solve the above problems have been proposed (see, for example, Patent Documents 1 and 2). Patent Document 1 discloses that talc having a total content of Fe 2 O 3 and Al 2 O 3 of less than 1% by weight and an average particle size of 2.5 to 3.5 μm with respect to 100 parts by weight of a predetermined copolymerized polyester. A heat resistant resin composition containing 5 to 200 parts by weight is described.
Patent Document 2 discloses a composition containing talc containing only 35% to 65% aromatic polyester and 1% to 60% of a material that can be decomposed at an elevated temperature with a minimum content. Things are listed.
However, in either case, the moldability and heat resistance have not reached sufficient levels, and a liquid crystalline resin composition with even better moldability and heat resistance is desired.
[規則91に基づく訂正 15.11.2013]
特開平４－２０２５５７号公報 特開昭５９－３６１５４号公報
[Correction based on Rule 91 15.11.2013]
JP-A-4-202557 JP 59-36154 A
本発明は、上記従来の問題点に鑑みなされたものであり、成形加工性及び耐熱性に優れた液晶性樹脂組成物を提供することを目的とする。
The present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a liquid crystalline resin composition excellent in molding processability and heat resistance.
上記課題を解決する本発明は以下の通りである。
（１）液晶性樹脂１００質量部に対してタルクを５～２００質量部含有してなる液晶性樹脂組成物であって、
前記タルクの全固形分量に対して、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超２．０質量％以下であり、かつＣａＯの含有量が０．５質量％未満であることを特徴とする液晶性樹脂組成物である。 The present invention for solving the above problems is as follows.
(1) A liquid crystalline resin composition comprising 5 to 200 parts by mass of talc with respect to 100 parts by mass of a liquid crystalline resin,
The total content of Fe 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less with respect to the total solid content of the talc, and the total content of Fe 2 O 3 and Al 2 O 3 is 1 More than 0.0 mass% and 2.0 mass% or less, and the CaO content is less than 0.5 mass%.
（１）液晶性樹脂１００質量部に対してタルクを５～２００質量部含有してなる液晶性樹脂組成物であって、
前記タルクの全固形分量に対して、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超２．０質量％以下であり、かつＣａＯの含有量が０．５質量％未満であることを特徴とする液晶性樹脂組成物である。 The present invention for solving the above problems is as follows.
(1) A liquid crystalline resin composition comprising 5 to 200 parts by mass of talc with respect to 100 parts by mass of a liquid crystalline resin,
The total content of Fe 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less with respect to the total solid content of the talc, and the total content of Fe 2 O 3 and Al 2 O 3 is 1 More than 0.0 mass% and 2.0 mass% or less, and the CaO content is less than 0.5 mass%.
（２）前記タルクの、レーザー回折法で測定した粒子径（Ｄ５０％）が、４．０～２０．０μｍである前記（１）に記載の液晶性樹脂組成物。
(2) The liquid crystalline resin composition according to (1), wherein the talc has a particle size (D50%) measured by a laser diffraction method of 4.0 to 20.0 μm.
（３）前記液晶性樹脂が、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、及び芳香族ジアミンの群から選ばれる少なくとも１種の化合物を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドである前記（１）又は（２）に記載の液晶性樹脂組成物。
(3) The liquid crystal resin is an aromatic polyester or an aromatic polyester amide having at least one compound selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines as a constituent component The liquid crystalline resin composition according to (1) or (2).
（４）前記Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が１．０質量％以上２．０質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超１．７質量％以下であり、かつＣａＯの含有量が０．０１質量％以上０．４質量％以下である前記（１）～（３）のいずれかに記載の液晶性樹脂組成物。
(4) The total content of the Fe 2 O 3 , Al 2 O 3 and CaO is 1.0 mass% or more and 2.0 mass% or less, and the total content of Fe 2 O 3 and Al 2 O 3 is 1 The liquid crystal property according to any one of the above (1) to (3), which is more than 0.0% by mass and 1.7% by mass or less and the CaO content is 0.01% by mass or more and 0.4% by mass or less. Resin composition.
本発明によれば、成形加工性及び耐熱性に優れた液晶性樹脂組成物を提供することができる。
According to the present invention, a liquid crystalline resin composition having excellent molding processability and heat resistance can be provided.
本発明の液晶性樹脂組成物は、液晶性樹脂１００質量部に対してタルクを５～２００質量部含有してなる液晶性樹脂組成物であって、前記タルクの全固形分量に対して、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超２．０質量％以下であり、かつＣａＯの含有量が０．５質量％未満であることを特徴としている。
以下に各成分について詳述する。 The liquid crystalline resin composition of the present invention is a liquid crystalline resin composition comprising 5 to 200 parts by mass of talc with respect to 100 parts by mass of the liquid crystalline resin, and Fe based on the total solid content of the talc. The total content of 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less, and the total content of Fe 2 O 3 and Al 2 O 3 is more than 1.0% by mass and 2.0% by mass or less. And the CaO content is less than 0.5% by mass.
Each component is described in detail below.
以下に各成分について詳述する。 The liquid crystalline resin composition of the present invention is a liquid crystalline resin composition comprising 5 to 200 parts by mass of talc with respect to 100 parts by mass of the liquid crystalline resin, and Fe based on the total solid content of the talc. The total content of 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less, and the total content of Fe 2 O 3 and Al 2 O 3 is more than 1.0% by mass and 2.0% by mass or less. And the CaO content is less than 0.5% by mass.
Each component is described in detail below.
［液晶性樹脂］
本発明において使用する液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージに載せた溶融試料を窒素雰囲気下で４０倍の倍率で観察することにより実施できる。本発明に適用できる液晶性樹脂は直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。 [Liquid crystal resin]
The liquid crystalline resin used in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase. The property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. When the liquid crystalline resin applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in a molten stationary state, and optically anisotropic.
本発明において使用する液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージに載せた溶融試料を窒素雰囲気下で４０倍の倍率で観察することにより実施できる。本発明に適用できる液晶性樹脂は直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。 [Liquid crystal resin]
The liquid crystalline resin used in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase. The property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. When the liquid crystalline resin applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in a molten stationary state, and optically anisotropic.
上記のような液晶性樹脂の種類としては特に限定されないが、芳香族ポリエステル又は芳香族ポリエステルアミドであることが好ましい。また、芳香族ポリエステル又は芳香族ポリエステルアミドを同一分子鎖中に部分的に含むポリエステルもその範囲にある。これらは６０℃でペンタフルオロフェノールに濃度０．１質量％で溶解したときに、好ましくは少なくとも約２．０ｄｌ／ｇ、さらに好ましくは２．０～１０．０ｄｌ／ｇの対数粘度（Ｉ．Ｖ．）を有するものが好ましく使用される。
The type of liquid crystalline resin as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide. Moreover, the polyester which partially contains aromatic polyester or aromatic polyester amide in the same molecular chain is also in that range. These have a logarithmic viscosity (IV) of preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by mass. .) Are preferably used.
本発明に適用できる液晶性樹脂としての芳香族ポリエステル又は芳香族ポリエステルアミドとして特に好ましくは、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミンの群から選ばれた少なくとも１種の化合物を構成成分として有する芳香族ポリエステル、芳香族ポリエステルアミドである。
The aromatic polyester or aromatic polyester amide as the liquid crystalline resin applicable to the present invention is particularly preferably constituted of at least one compound selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines and aromatic diamines. Aromatic polyesters and aromatic polyester amides as components.
より具体的には、
（１）主として芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上からなるポリエステル；
（２）主として（ａ）芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上と、（ｂ）芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の１種又は２種以上と、（ｃ）芳香族ジオール、脂環族ジオール、脂肪族ジオールおよびその誘導体の少なくとも１種又は２種以上、とからなるポリエステル；
（３）主として（ａ）芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミンおよびその誘導体の１種又は２種以上と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の１種又は２種以上、とからなるポリエステルアミド；
（４）主として（ａ）芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミンおよびその誘導体の１種又は２種以上と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の１種又は２種以上と、（ｄ）芳香族ジオール、脂環族ジオール、脂肪族ジオールおよびその誘導体の少なくとも１種又は２種以上、とからなるポリエステルアミド等が挙げられる。さらに上記の構成成分に必要に応じ分子量調整剤を併用してもよい。 More specifically,
(1) A polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2) mainly (a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof; and (b) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof; c) Polyester comprising at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof;
(3) mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof; (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof; and (c). A polyesteramide comprising one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof;
(4) mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof; (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof; and (c). One or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof; and (d) at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof, and And polyester amides composed of Furthermore, you may use a molecular weight modifier together with said structural component as needed.
（１）主として芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上からなるポリエステル；
（２）主として（ａ）芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上と、（ｂ）芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の１種又は２種以上と、（ｃ）芳香族ジオール、脂環族ジオール、脂肪族ジオールおよびその誘導体の少なくとも１種又は２種以上、とからなるポリエステル；
（３）主として（ａ）芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミンおよびその誘導体の１種又は２種以上と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の１種又は２種以上、とからなるポリエステルアミド；
（４）主として（ａ）芳香族ヒドロキシカルボン酸およびその誘導体の１種又は２種以上と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミンおよびその誘導体の１種又は２種以上と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸およびその誘導体の１種又は２種以上と、（ｄ）芳香族ジオール、脂環族ジオール、脂肪族ジオールおよびその誘導体の少なくとも１種又は２種以上、とからなるポリエステルアミド等が挙げられる。さらに上記の構成成分に必要に応じ分子量調整剤を併用してもよい。 More specifically,
(1) A polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2) mainly (a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof; and (b) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof; c) Polyester comprising at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof;
(3) mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof; (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof; and (c). A polyesteramide comprising one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof;
(4) mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof; (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof; and (c). One or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivatives thereof; and (d) at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof, and And polyester amides composed of Furthermore, you may use a molecular weight modifier together with said structural component as needed.
本発明に適用できる液晶性樹脂を構成する具体的化合物の好ましい例としては、ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸等の芳香族ヒドロキシカルボン酸；２，６－ジヒドロキシナフタレン、１，４－ジヒドロキシナフタレン、４，４’－ジヒドロキシビフェニル、ハイドロキノン、レゾルシン、下記一般式（Ｉ）および下記一般式（ＩＩ）で表される化合物等の芳香族ジオール；テレフタル酸、イソフタル酸、４，４’－ジフェニルジカルボン酸、２，６－ナフタレンジカルボン酸および下記一般式（ＩＩＩ）で表される化合物等の芳香族ジカルボン酸；ｐ－アミノフェノール、ｐ－フェニレンジアミン等の芳香族アミン類が挙げられる。
Specific examples of the specific compound constituting the liquid crystalline resin applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6-dihydroxynaphthalene, 1 , 4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, aromatic diols such as compounds represented by the following general formula (I) and the following general formula (II); terephthalic acid, isophthalic acid, 4, Aromatic dicarboxylic acids such as 4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol and p-phenylenediamine It is done.
本発明に用いられる液晶性樹脂の合成は、上記のモノマー化合物（又はモノマーの混合物）から直接重合法やエステル交換法を用いて公知の方法で行うことができるが、通常は溶融重合法やスラリー重合法等が用いられる。エステル形成能を有する上記化合物類はそのままの形で重合に用いてもよく、又、重合の前段階で前駆体から該エステル形成能を有する誘導体に変性されたものでもよい。これらの重合に際しては種々の触媒の使用が可能であり、代表的なものとしては、ジアルキル錫酸化物、ジアリール錫酸化物、二酸化チタン、アルコキシチタンけい酸塩類、チタンアルコラート類、カルボン酸のアルカリ及びアルカリ土類金属塩類、ＢＦ３の如きルイス酸塩等があげられる。触媒の使用量は一般にはモノマーの全質量に対して約０．００１～１質量％、特に約０．０１～０．２質量％が好ましい。これらの重合方法により製造されたポリマーはさらに必要があれば、減圧又は不活性ガス中で加熱する固相重合により分子量の増加を図ることができる。
The liquid crystalline resin used in the present invention can be synthesized by a known method using a direct polymerization method or a transesterification method from the above monomer compound (or a mixture of monomers), but usually a melt polymerization method or a slurry. A polymerization method or the like is used. The above compounds having ester-forming ability may be used for polymerization as they are, or may be modified from a precursor to a derivative having ester-forming ability in the previous stage of polymerization. In the polymerization, various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, carboxylic acid alkalis and Examples include alkaline earth metal salts and Lewis acid salts such as BF 3 . The amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.01 to 0.2% by weight, based on the total weight of the monomers. If the polymers produced by these polymerization methods are further necessary, the molecular weight can be increased by solid-phase polymerization by heating in a reduced pressure or an inert gas.
上記のような方法で得られた液晶性樹脂の溶融粘度は特に限定されない。一般には成形温度での溶融粘度が剪断速度１０００ｓｅｃ－１で１０Ｐａ・ｓ以上６００Ｐａ・ｓ以下のものが使用可能である。しかし、それ自体あまり高粘度のものは流動性が非常に悪化するため好ましくない。なお、上記液晶性樹脂は２種以上の液晶性樹脂の混合物であってもよい。
The melt viscosity of the liquid crystalline resin obtained by the above method is not particularly limited. In general, those having a melt viscosity at a molding temperature of 10 Pa · s to 600 Pa · s at a shear rate of 1000 sec −1 can be used. However, those having a very high viscosity are not preferable because the fluidity is extremely deteriorated. The liquid crystalline resin may be a mixture of two or more liquid crystalline resins.
［タルク］
本発明に使用するタルクとしては、当該タルクの全固形分量に対して、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超２．０質量％以下であり、かつＣａＯの含有量が０．５質量％未満であるものを用いる。すなわち、本発明に使用するタルクは、その主成分たるＳｉＯ２及びＭｇＯの他、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯのうちの少なくとも１種を含有し、各成分が上記の含有量範囲で含有するものである。 [talc]
As the talc used in the present invention, the total content of Fe 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less based on the total solid content of the talc, Fe 2 O 3 and Al The total content of 2 O 3 is more than 1.0% by mass and 2.0% by mass or less, and the content of CaO is less than 0.5% by mass. That is, the talc used in the present invention contains at least one of Fe 2 O 3 , Al 2 O 3 and CaO in addition to the main components SiO 2 and MgO, and each component has the above content range. It contains.
本発明に使用するタルクとしては、当該タルクの全固形分量に対して、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超２．０質量％以下であり、かつＣａＯの含有量が０．５質量％未満であるものを用いる。すなわち、本発明に使用するタルクは、その主成分たるＳｉＯ２及びＭｇＯの他、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯのうちの少なくとも１種を含有し、各成分が上記の含有量範囲で含有するものである。 [talc]
As the talc used in the present invention, the total content of Fe 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less based on the total solid content of the talc, Fe 2 O 3 and Al The total content of 2 O 3 is more than 1.0% by mass and 2.0% by mass or less, and the content of CaO is less than 0.5% by mass. That is, the talc used in the present invention contains at least one of Fe 2 O 3 , Al 2 O 3 and CaO in addition to the main components SiO 2 and MgO, and each component has the above content range. It contains.
前記タルクにおいて、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％を超えると、成形加工性及び耐熱性が悪化する。Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量は、１．０質量％以上２．０質量％以下が好ましい。
また、前記タルクにおいて、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％以下のタルクは入手が困難であり、２．０質量％を超えると、成形加工性及び耐熱性が悪化する。Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量は、１．０質量％超１．７質量％以下が好ましい。
さらに、前記タルクにおいて、ＣａＯの含有量が０．５質量％以上であると、成形加工性及び耐熱性が悪化する。ＣａＯの含有量は、０．０１質量％以上０．４質量％以下が好ましい。 In the talc, when the total content of Fe 2 O 3 , Al 2 O 3 and CaO exceeds 2.5% by mass, the moldability and heat resistance deteriorate. The total content of Fe 2 O 3 , Al 2 O 3 and CaO is preferably 1.0% by mass or more and 2.0% by mass or less.
Further, in the talc, the total content of 1.0 mass% of talc Fe 2 O 3 and Al 2 O 3 is difficult to obtain, exceeds 2.0 mass%, moldability and heat resistance Gets worse. The total content of Fe 2 O 3 and Al 2 O 3 is preferably more than 1.0 mass% and not more than 1.7 mass%.
Furthermore, in the talc, when the content of CaO is 0.5% by mass or more, moldability and heat resistance deteriorate. The content of CaO is preferably 0.01% by mass or more and 0.4% by mass or less.
また、前記タルクにおいて、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％以下のタルクは入手が困難であり、２．０質量％を超えると、成形加工性及び耐熱性が悪化する。Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量は、１．０質量％超１．７質量％以下が好ましい。
さらに、前記タルクにおいて、ＣａＯの含有量が０．５質量％以上であると、成形加工性及び耐熱性が悪化する。ＣａＯの含有量は、０．０１質量％以上０．４質量％以下が好ましい。 In the talc, when the total content of Fe 2 O 3 , Al 2 O 3 and CaO exceeds 2.5% by mass, the moldability and heat resistance deteriorate. The total content of Fe 2 O 3 , Al 2 O 3 and CaO is preferably 1.0% by mass or more and 2.0% by mass or less.
Further, in the talc, the total content of 1.0 mass% of talc Fe 2 O 3 and Al 2 O 3 is difficult to obtain, exceeds 2.0 mass%, moldability and heat resistance Gets worse. The total content of Fe 2 O 3 and Al 2 O 3 is preferably more than 1.0 mass% and not more than 1.7 mass%.
Furthermore, in the talc, when the content of CaO is 0.5% by mass or more, moldability and heat resistance deteriorate. The content of CaO is preferably 0.01% by mass or more and 0.4% by mass or less.
本発明において、前記タルクの、レーザー回折法で測定した粒子径（Ｄ５０％）は、そり変形の防止及び流動性の維持という観点から、４．０～２０．０μｍであることが好ましく、１０～１８μｍであることがより好ましい。
In the present invention, the particle size (D50%) of the talc measured by a laser diffraction method is preferably 4.0 to 20.0 μm from the viewpoint of preventing warpage deformation and maintaining fluidity. More preferably, it is 18 μm.
一方、本発明において、前記タルクは、液晶性樹脂１００質量部に対して、５～２００質量部含有する。当該含有量が５質量部未満であると、そり変形防止効果が少なく、２００質量部を超えると、流動性が悪化する。当該含有量は５～１００質量部であることが好ましく、１０～４０質量部であることがより好ましい。
On the other hand, in the present invention, the talc is contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the liquid crystalline resin. When the content is less than 5 parts by mass, the effect of preventing warping deformation is small, and when it exceeds 200 parts by mass, the fluidity is deteriorated. The content is preferably 5 to 100 parts by mass, and more preferably 10 to 40 parts by mass.
上記タルクとしては松村産業製クラウンタルクＰＰ及び日本タルク製ＭＳ－Ｋ等の市販品を使用することができる。
As the talc, commercially available products such as Crown Talc PP made by Matsumura Sangyo and MS-K made by Nippon Talc can be used.
［他の成分］
本発明においては、タルク以外の無機充填剤を配合してもよい。例えば、ガラス繊維、アスベスト繊維、シリカ繊維、シリカ・アルミナ繊維、チタン酸カリウム繊維、ボロン繊維、炭化珪素繊維、カーボン繊維、軽質炭酸カルシウム、重質ないし微粉化炭酸カルシウム、特殊カルシウム系充填材等の炭酸カルシウム、霞石、閃長石微粉末、モンモリロナイト、ベントナイト等の焼成クレー、シラン改質クレー等のクレー（珪酸アルミニウム粉末）、溶融シリカ、合成シリカ、結晶シリカ等のシリカ（二酸化珪素）粉末、珪藻土、珪砂等の珪酸含有化合物、軽石粉、軽石バルーン、スレート粉、雲母粉等の天然鉱物の粉砕品、アルミナ、アルミナコロイド（アルミナゾル）、アルミナ・ホワイト、硫酸アルミニウム等のアルミナ含有化合物、硫酸バリウム、リトポン、硫酸カルシウム、二硫化モリブデン、グラファイト（黒鉛）等の鉱物、ガラスビーズ、ガラス中空体、ガラスフレーク、発泡ガラスビーズ等のガラス系フィラー、フライアッシュ球、火山ガラス中空体、合成無機中空体、単結晶チタン酸カリウム、カーボンナノチューブ、炭素中空球、炭素６４フラーレン、無煙炭粉末、人造氷晶石（クリオライト）、酸化チタン、酸化マグネシウム、塩基性マグネシウム、ドロマイト、チタン酸カリウム、亜硫酸カルシウム、マイカ、アスベスト、珪酸カルシウム、アルモニウム粉、硫化モリブデン等が挙げられる。
これら無機充填剤は、単独で用いても、２種以上を併用して配合してもよい。 [Other ingredients]
In the present invention, an inorganic filler other than talc may be blended. For example, glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, boron fiber, silicon carbide fiber, carbon fiber, light calcium carbonate, heavy or finely powdered calcium carbonate, special calcium filler, etc. Calcium carbonate, meteorite, feldspar fine powder, montmorillonite, bentonite, etc., clay such as silane modified clay (aluminum silicate powder), silica (silicon dioxide) powder such as fused silica, synthetic silica, crystalline silica, diatomaceous earth Silica-containing compounds such as silica sand, pulverized natural minerals such as pumice powder, pumice balloon, slate powder, and mica powder, alumina-containing compounds such as alumina, alumina colloid (alumina sol), alumina white, aluminum sulfate, barium sulfate, Lithopone, calcium sulfate, molybdenum disulfide, Minerals such as phyto (graphite), glass beads such as glass beads, glass hollow bodies, glass flakes, foamed glass beads, fly ash spheres, volcanic glass hollow bodies, synthetic inorganic hollow bodies, single crystal potassium titanate, carbon nanotubes, Carbon hollow sphere, carbon 64 fullerene, anthracite powder, artificial cryolite, titanium oxide, magnesium oxide, basic magnesium, dolomite, potassium titanate, calcium sulfite, mica, asbestos, calcium silicate, aluminum powder, sulfide Examples include molybdenum.
These inorganic fillers may be used alone or in combination of two or more.
本発明においては、タルク以外の無機充填剤を配合してもよい。例えば、ガラス繊維、アスベスト繊維、シリカ繊維、シリカ・アルミナ繊維、チタン酸カリウム繊維、ボロン繊維、炭化珪素繊維、カーボン繊維、軽質炭酸カルシウム、重質ないし微粉化炭酸カルシウム、特殊カルシウム系充填材等の炭酸カルシウム、霞石、閃長石微粉末、モンモリロナイト、ベントナイト等の焼成クレー、シラン改質クレー等のクレー（珪酸アルミニウム粉末）、溶融シリカ、合成シリカ、結晶シリカ等のシリカ（二酸化珪素）粉末、珪藻土、珪砂等の珪酸含有化合物、軽石粉、軽石バルーン、スレート粉、雲母粉等の天然鉱物の粉砕品、アルミナ、アルミナコロイド（アルミナゾル）、アルミナ・ホワイト、硫酸アルミニウム等のアルミナ含有化合物、硫酸バリウム、リトポン、硫酸カルシウム、二硫化モリブデン、グラファイト（黒鉛）等の鉱物、ガラスビーズ、ガラス中空体、ガラスフレーク、発泡ガラスビーズ等のガラス系フィラー、フライアッシュ球、火山ガラス中空体、合成無機中空体、単結晶チタン酸カリウム、カーボンナノチューブ、炭素中空球、炭素６４フラーレン、無煙炭粉末、人造氷晶石（クリオライト）、酸化チタン、酸化マグネシウム、塩基性マグネシウム、ドロマイト、チタン酸カリウム、亜硫酸カルシウム、マイカ、アスベスト、珪酸カルシウム、アルモニウム粉、硫化モリブデン等が挙げられる。
これら無機充填剤は、単独で用いても、２種以上を併用して配合してもよい。 [Other ingredients]
In the present invention, an inorganic filler other than talc may be blended. For example, glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, boron fiber, silicon carbide fiber, carbon fiber, light calcium carbonate, heavy or finely powdered calcium carbonate, special calcium filler, etc. Calcium carbonate, meteorite, feldspar fine powder, montmorillonite, bentonite, etc., clay such as silane modified clay (aluminum silicate powder), silica (silicon dioxide) powder such as fused silica, synthetic silica, crystalline silica, diatomaceous earth Silica-containing compounds such as silica sand, pulverized natural minerals such as pumice powder, pumice balloon, slate powder, and mica powder, alumina-containing compounds such as alumina, alumina colloid (alumina sol), alumina white, aluminum sulfate, barium sulfate, Lithopone, calcium sulfate, molybdenum disulfide, Minerals such as phyto (graphite), glass beads such as glass beads, glass hollow bodies, glass flakes, foamed glass beads, fly ash spheres, volcanic glass hollow bodies, synthetic inorganic hollow bodies, single crystal potassium titanate, carbon nanotubes, Carbon hollow sphere, carbon 64 fullerene, anthracite powder, artificial cryolite, titanium oxide, magnesium oxide, basic magnesium, dolomite, potassium titanate, calcium sulfite, mica, asbestos, calcium silicate, aluminum powder, sulfide Examples include molybdenum.
These inorganic fillers may be used alone or in combination of two or more.
本発明の液晶性樹脂組成物を用いて成形品を得る方法としては特に限定はなく、公知の方法を採用することができる。例えば、本発明の液晶性樹脂組成物を押出機に投入して溶融混練してペレット化し、このペレットを所定の金型を装備した射出成形機に投入し、射出成形することで成形品を得ることができる。
ペレット化する際の溶融温度としては、２５０～４００℃とすることが好ましく、３００～３８０℃とすることがより好ましい。 There is no limitation in particular as a method of obtaining a molded article using the liquid crystalline resin composition of this invention, A well-known method is employable. For example, the liquid crystalline resin composition of the present invention is put into an extruder, melted and kneaded into pellets, and the pellets are put into an injection molding machine equipped with a predetermined mold and injection molded to obtain a molded product. be able to.
The melting temperature at the time of pelletization is preferably 250 to 400 ° C., more preferably 300 to 380 ° C.
ペレット化する際の溶融温度としては、２５０～４００℃とすることが好ましく、３００～３８０℃とすることがより好ましい。 There is no limitation in particular as a method of obtaining a molded article using the liquid crystalline resin composition of this invention, A well-known method is employable. For example, the liquid crystalline resin composition of the present invention is put into an extruder, melted and kneaded into pellets, and the pellets are put into an injection molding machine equipped with a predetermined mold and injection molded to obtain a molded product. be able to.
The melting temperature at the time of pelletization is preferably 250 to 400 ° C., more preferably 300 to 380 ° C.
以下に、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
［実施例１～６、比較例１～５］
液晶性樹脂（ＬＣＰ；ポリプラスチックス（株）製、ベクトラ（登録商標）ＬＣＰ Ｅ９５０ｉ）１００質量部と、ガラス繊維（日本電気硝子（株）製ＥＣＳ０４Ｔ－７９０ＤＥ（平均繊維径６μｍ、長さ３ｍｍのチョップドストランドファイバー）２７質量部と、タルク５５質量部と、離型剤（ペンタエリスリトールテトラベヘネート、日本油脂（株）製、ニッサンエレクトールWEP-5）０．５５質量部とを二軸押出機（（株）日本製鋼製ＴＥＸ－３０α）を用いて溶融混練し、ペレット化した。なお、各実施例・比較例において、タルクは表１に記載の組成のものを用いた。表１において、「Ｆｅ＋Ａｌ＋Ｃａ」及び「Ｆｅ＋Ａｌ」は、それぞれ、タルクの全固形分量に対するＦｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量を示す。また、タルクにおける各含有成分の含有率はＪＩＳ Ｍ ８８５１に則って分析して得た値であり、粒子径はレーザー回折法により測定して得た値である。 [Examples 1 to 6, Comparative Examples 1 to 5]
100 parts by mass of a liquid crystalline resin (LCP; manufactured by Polyplastics Co., Ltd., Vectra (registered trademark) LCP E950i) and glass fiber (ECS04T-790DE manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter 6 μm, length 3 mm) Biaxial extrusion of 27 parts by mass of chopped strand fiber), 55 parts by mass of talc, and 0.55 parts by mass of a release agent (pentaerythritol tetrabehenate, manufactured by Nippon Oil & Fats Co., Ltd., Nissan Electol WEP-5) The mixture was melt-kneaded and pelletized using a machine (Tex-30α manufactured by Nippon Steel Co., Ltd.) In each example and comparative example, talc having the composition shown in Table 1 was used. , “Fe + Al + Ca” and “Fe + Al” are the total content of Fe 2 O 3 , Al 2 O 3 and CaO with respect to the total solid content of talc, respectively, Fe 2 O 3 represents the total content of Al 2 O 3. Further, the content of each component in talc is a value obtained by analysis according to JIS M 8851, and the particle diameter is obtained by measurement by a laser diffraction method. Value.
液晶性樹脂（ＬＣＰ；ポリプラスチックス（株）製、ベクトラ（登録商標）ＬＣＰ Ｅ９５０ｉ）１００質量部と、ガラス繊維（日本電気硝子（株）製ＥＣＳ０４Ｔ－７９０ＤＥ（平均繊維径６μｍ、長さ３ｍｍのチョップドストランドファイバー）２７質量部と、タルク５５質量部と、離型剤（ペンタエリスリトールテトラベヘネート、日本油脂（株）製、ニッサンエレクトールWEP-5）０．５５質量部とを二軸押出機（（株）日本製鋼製ＴＥＸ－３０α）を用いて溶融混練し、ペレット化した。なお、各実施例・比較例において、タルクは表１に記載の組成のものを用いた。表１において、「Ｆｅ＋Ａｌ＋Ｃａ」及び「Ｆｅ＋Ａｌ」は、それぞれ、タルクの全固形分量に対するＦｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量を示す。また、タルクにおける各含有成分の含有率はＪＩＳ Ｍ ８８５１に則って分析して得た値であり、粒子径はレーザー回折法により測定して得た値である。 [Examples 1 to 6, Comparative Examples 1 to 5]
100 parts by mass of a liquid crystalline resin (LCP; manufactured by Polyplastics Co., Ltd., Vectra (registered trademark) LCP E950i) and glass fiber (ECS04T-790DE manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter 6 μm, length 3 mm) Biaxial extrusion of 27 parts by mass of chopped strand fiber), 55 parts by mass of talc, and 0.55 parts by mass of a release agent (pentaerythritol tetrabehenate, manufactured by Nippon Oil & Fats Co., Ltd., Nissan Electol WEP-5) The mixture was melt-kneaded and pelletized using a machine (Tex-30α manufactured by Nippon Steel Co., Ltd.) In each example and comparative example, talc having the composition shown in Table 1 was used. , “Fe + Al + Ca” and “Fe + Al” are the total content of Fe 2 O 3 , Al 2 O 3 and CaO with respect to the total solid content of talc, respectively, Fe 2 O 3 represents the total content of Al 2 O 3. Further, the content of each component in talc is a value obtained by analysis according to JIS M 8851, and the particle diameter is obtained by measurement by a laser diffraction method. Value.
得られた樹脂組成物（ペレット）について、以下の評価試験を行った。
（１）溶融粘度
上記ペレットを、キャピラリー式レオメーター（（株）東洋精機製作所製キャピログラフ１D：ピストン径１０ｍｍ）を用いて、シリンダー温度が融点＋２０℃、せん断速度が１０００ｓｅｃ－１の条件で、ＩＳＯ １１４４３に準拠して、見かけの溶融粘度を測定した。なお、測定には、内径１ｍｍ、長さ２０ｍｍのオリフィスを用いた。測定結果を表１に示す。
（２）ブリスター試験
上記ペレットを、射出成形機（住友重機械工業（株）製、ＳＥ１００ＤＵ）を用いて、成形サイクルが２０秒となるような条件で、１／３２燃焼試験片（ウェルドあり）に成形した。得られた試験片を指定温度のホットプレスに５分間挟んだ後、表面を観察した。表面に膨れが出ない最大温度をＢＦＴ（Ｂｌｉｓｔｅｒ Ｆｒｅｅ Ｔｅｍｐ）として探索した。なお、ウェルド部で割ったものを１検体とし、上記指定温度は２５０～３００℃の範囲において１０℃刻みで設定し、測定を実施した。測定結果を表１に示す。
（３）計量時間
上記ペレットを、射出成形機（住友重機械工業（株）製、ＳＥ３０ＤＵＺ、スクリュー径φ：１８ｍｍ、計量ストローク長：５５ｍｍ）を用いて、スクリュー回転数が１５０ｒｐｍの条件で成形し、各２０ショットの計量時間を測定し平均値を得た。得られた数値を表１に示す。なお、計量時間が短いものは成形加工性が良好と判断される。 The following evaluation tests were performed on the obtained resin composition (pellet).
(1) Melt viscosity Using the capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd .: piston diameter 10 mm), the above pellets were subjected to ISO under the conditions of a cylinder temperature of melting point + 20 ° C. and a shear rate of 1000 sec −1. The apparent melt viscosity was measured according to 11443. For the measurement, an orifice having an inner diameter of 1 mm and a length of 20 mm was used. The measurement results are shown in Table 1.
(2) Blister test 1/32 combustion test piece (with weld) under the condition that the molding cycle is 20 seconds using an injection molding machine (SE100DU manufactured by Sumitomo Heavy Industries, Ltd.). Molded into. The obtained test piece was sandwiched between hot presses at a specified temperature for 5 minutes, and then the surface was observed. The maximum temperature at which the surface did not swell was searched as BFT (Blister Free Temp). The sample divided by the weld part was used as one sample, and the specified temperature was set in increments of 10 ° C. in the range of 250 to 300 ° C., and measurement was performed. The measurement results are shown in Table 1.
(3) Metering time The above pellets are molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SE30DUZ, screw diameter φ: 18 mm, measuring stroke length: 55 mm) under the condition of a screw speed of 150 rpm. The weighing time for each 20 shots was measured to obtain an average value. The obtained numerical values are shown in Table 1. In addition, it is judged that a thing with short measurement time has favorable moldability.
（１）溶融粘度
上記ペレットを、キャピラリー式レオメーター（（株）東洋精機製作所製キャピログラフ１D：ピストン径１０ｍｍ）を用いて、シリンダー温度が融点＋２０℃、せん断速度が１０００ｓｅｃ－１の条件で、ＩＳＯ １１４４３に準拠して、見かけの溶融粘度を測定した。なお、測定には、内径１ｍｍ、長さ２０ｍｍのオリフィスを用いた。測定結果を表１に示す。
（２）ブリスター試験
上記ペレットを、射出成形機（住友重機械工業（株）製、ＳＥ１００ＤＵ）を用いて、成形サイクルが２０秒となるような条件で、１／３２燃焼試験片（ウェルドあり）に成形した。得られた試験片を指定温度のホットプレスに５分間挟んだ後、表面を観察した。表面に膨れが出ない最大温度をＢＦＴ（Ｂｌｉｓｔｅｒ Ｆｒｅｅ Ｔｅｍｐ）として探索した。なお、ウェルド部で割ったものを１検体とし、上記指定温度は２５０～３００℃の範囲において１０℃刻みで設定し、測定を実施した。測定結果を表１に示す。
（３）計量時間
上記ペレットを、射出成形機（住友重機械工業（株）製、ＳＥ３０ＤＵＺ、スクリュー径φ：１８ｍｍ、計量ストローク長：５５ｍｍ）を用いて、スクリュー回転数が１５０ｒｐｍの条件で成形し、各２０ショットの計量時間を測定し平均値を得た。得られた数値を表１に示す。なお、計量時間が短いものは成形加工性が良好と判断される。 The following evaluation tests were performed on the obtained resin composition (pellet).
(1) Melt viscosity Using the capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd .: piston diameter 10 mm), the above pellets were subjected to ISO under the conditions of a cylinder temperature of melting point + 20 ° C. and a shear rate of 1000 sec −1. The apparent melt viscosity was measured according to 11443. For the measurement, an orifice having an inner diameter of 1 mm and a length of 20 mm was used. The measurement results are shown in Table 1.
(2) Blister test 1/32 combustion test piece (with weld) under the condition that the molding cycle is 20 seconds using an injection molding machine (SE100DU manufactured by Sumitomo Heavy Industries, Ltd.). Molded into. The obtained test piece was sandwiched between hot presses at a specified temperature for 5 minutes, and then the surface was observed. The maximum temperature at which the surface did not swell was searched as BFT (Blister Free Temp). The sample divided by the weld part was used as one sample, and the specified temperature was set in increments of 10 ° C. in the range of 250 to 300 ° C., and measurement was performed. The measurement results are shown in Table 1.
(3) Metering time The above pellets are molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SE30DUZ, screw diameter φ: 18 mm, measuring stroke length: 55 mm) under the condition of a screw speed of 150 rpm. The weighing time for each 20 shots was measured to obtain an average value. The obtained numerical values are shown in Table 1. In addition, it is judged that a thing with short measurement time has favorable moldability.
表１より、実施例１～６においては、いずれもブリスター試験の結果が２７０℃以上であることから耐熱性に優れ、また計量時間は最も長いものでも２１秒強であることから成形加工性に優れることが分かる。これに対して、比較例１～５においては、ブリスター試験の結果が比較例３を除き２６０℃と低く、また計量時間はいずれも２２秒を超えており、成形加工性及び耐熱性を同時に良好な結果とすることができなかった。
From Table 1, in Examples 1 to 6, all of the results of the blister test are 270 ° C. or higher, so the heat resistance is excellent, and the longest measuring time is just over 21 seconds. It turns out that it is excellent. In contrast, in Comparative Examples 1 to 5, the results of the blister test were as low as 260 ° C. except for Comparative Example 3, and the measurement time was over 22 seconds, and both the moldability and heat resistance were good at the same time. It was not possible to achieve a good result.
Claims (4)
- 液晶性樹脂１００質量部に対してタルクを５～２００質量部含有してなる液晶性樹脂組成物であって、
前記タルクの全固形分量に対して、Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が２．５質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超２．０質量％以下であり、かつＣａＯの含有量が０．５質量％未満であることを特徴とする液晶性樹脂組成物。 A liquid crystalline resin composition comprising 5 to 200 parts by mass of talc with respect to 100 parts by mass of a liquid crystalline resin,
The total content of Fe 2 O 3 , Al 2 O 3 and CaO is 2.5% by mass or less with respect to the total solid content of the talc, and the total content of Fe 2 O 3 and Al 2 O 3 is 1 More than 0.0 mass% and 2.0 mass% or less, and CaO content is less than 0.5 mass%, The liquid crystalline resin composition characterized by the above-mentioned. - 前記タルクの、レーザー回折法で測定した粒子径（Ｄ５０％）が、４．０～２０．０μｍである請求項１に記載の液晶性樹脂組成物。 2. The liquid crystalline resin composition according to claim 1, wherein the talc has a particle size (D50%) measured by a laser diffraction method of 4.0 to 20.0 μm.
- 前記液晶性樹脂が、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、及び芳香族ジアミンの群から選ばれる少なくとも１種の化合物を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドである請求項１又は２に記載の液晶性樹脂組成物。 The liquid crystal resin is an aromatic polyester or an aromatic polyester amide having at least one compound selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines as a constituent component. 2. The liquid crystalline resin composition according to 2.
- 前記Ｆｅ２Ｏ３、Ａｌ２Ｏ３及びＣａＯの合計含有量が１．０質量％以上２．０質量％以下であり、Ｆｅ２Ｏ３及びＡｌ２Ｏ３の合計含有量が１．０質量％超１．７質量％以下であり、かつＣａＯの含有量が０．０１質量％以上０．４質量％以下である請求項１～３のいずれか１項に記載の液晶性樹脂組成物。 The total content of Fe 2 O 3 , Al 2 O 3 and CaO is 1.0 mass% or more and 2.0 mass% or less, and the total content of Fe 2 O 3 and Al 2 O 3 is 1.0 mass%. The liquid crystalline resin composition according to any one of claims 1 to 3, wherein the content of CaO is 1.7% by mass or more and 1.7% by mass or less, and the CaO content is 0.01% by mass or more and 0.4% by mass or less.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201380041162.3A CN104520384A (en) | 2012-08-02 | 2013-07-30 | Liquid crystal resin composition |
| KR1020157003760A KR101646212B1 (en) | 2012-08-02 | 2013-07-30 | Liquid crystal resin composition |
| SG11201500803UA SG11201500803UA (en) | 2012-08-02 | 2013-07-30 | Liquid crystal resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-171784 | 2012-08-02 | ||
| JP2012171784A JP5869983B2 (en) | 2012-08-02 | 2012-08-02 | Liquid crystalline resin composition |
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| Publication Number | Publication Date |
|---|---|
| WO2014021300A1 true WO2014021300A1 (en) | 2014-02-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2013/070566 WO2014021300A1 (en) | 2012-08-02 | 2013-07-30 | Liquid crystal resin composition |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP5869983B2 (en) |
| KR (1) | KR101646212B1 (en) |
| CN (1) | CN104520384A (en) |
| MY (1) | MY158601A (en) |
| SG (1) | SG11201500803UA (en) |
| TW (1) | TWI551671B (en) |
| WO (1) | WO2014021300A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02147657A (en) * | 1988-11-30 | 1990-06-06 | Nippon Petrochem Co Ltd | Production of talc-filled thermoplastic polyester resin composition |
| JPH04202557A (en) * | 1990-11-30 | 1992-07-23 | Toray Ind Inc | Heat-resistant resin composition and heat-resistant tableware for oven produced by molding the resin |
| JPH0770422A (en) * | 1993-06-25 | 1995-03-14 | Sumitomo Chem Co Ltd | Liquid crystal polyester resin composition and lamp reflector |
| JP2009242453A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE54564B1 (en) | 1982-07-26 | 1989-11-22 | Dart Ind Inc | Polyester moulding compositions and ovenware therefrom |
| EP0630955B1 (en) * | 1993-06-25 | 1999-09-01 | Sumitomo Chemical Company Limited | Liquid crystal polyester resin composition and lamp reflector |
| JP2001207054A (en) * | 2000-01-24 | 2001-07-31 | Polyplastics Co | Molded article of liquid crystalline polymer |
| JP2005200595A (en) * | 2004-01-19 | 2005-07-28 | Polyplastics Co | Liquid crystal display part |
| WO2009119863A1 (en) * | 2008-03-28 | 2009-10-01 | 新日本石油株式会社 | Liquid-crystal polyester resin composition for camera modules |
-
2012
- 2012-08-02 JP JP2012171784A patent/JP5869983B2/en active Active
-
2013
- 2013-07-30 KR KR1020157003760A patent/KR101646212B1/en active IP Right Grant
- 2013-07-30 MY MYPI2015700251A patent/MY158601A/en unknown
- 2013-07-30 WO PCT/JP2013/070566 patent/WO2014021300A1/en active Application Filing
- 2013-07-30 SG SG11201500803UA patent/SG11201500803UA/en unknown
- 2013-07-30 CN CN201380041162.3A patent/CN104520384A/en active Pending
- 2013-08-01 TW TW102127571A patent/TWI551671B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02147657A (en) * | 1988-11-30 | 1990-06-06 | Nippon Petrochem Co Ltd | Production of talc-filled thermoplastic polyester resin composition |
| JPH04202557A (en) * | 1990-11-30 | 1992-07-23 | Toray Ind Inc | Heat-resistant resin composition and heat-resistant tableware for oven produced by molding the resin |
| JPH0770422A (en) * | 1993-06-25 | 1995-03-14 | Sumitomo Chem Co Ltd | Liquid crystal polyester resin composition and lamp reflector |
| JP2009242453A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
Non-Patent Citations (1)
| Title |
|---|
| HAYASHI-KASEI CO., LTD.: "Ippan Talc", 2006, Retrieved from the Internet <URL:http://www.hayashi-kasei.co.jp/chemistry/TALCAN.htm> [retrieved on 20130814] * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101646212B1 (en) | 2016-08-05 |
| MY158601A (en) | 2016-10-18 |
| JP5869983B2 (en) | 2016-02-24 |
| JP2014031410A (en) | 2014-02-20 |
| SG11201500803UA (en) | 2015-04-29 |
| CN104520384A (en) | 2015-04-15 |
| KR20150038061A (en) | 2015-04-08 |
| TW201420732A (en) | 2014-06-01 |
| TWI551671B (en) | 2016-10-01 |
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