WO2009141996A1 - 平面状コネクター - Google Patents
平面状コネクター Download PDFInfo
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- WO2009141996A1 WO2009141996A1 PCT/JP2009/002190 JP2009002190W WO2009141996A1 WO 2009141996 A1 WO2009141996 A1 WO 2009141996A1 JP 2009002190 W JP2009002190 W JP 2009002190W WO 2009141996 A1 WO2009141996 A1 WO 2009141996A1
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- WIPO (PCT)
- Prior art keywords
- mol
- planar connector
- liquid crystalline
- phenylene
- crystalline polymer
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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
-
- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
Definitions
- the present invention relates to a planar connector having a lattice structure inside an outer frame such as a CPU socket.
- the liquid crystalline polymer is known as a material that is excellent in dimensional accuracy, vibration damping, and fluidity among thermoplastic resins, and generates very little burrs during molding. Conventionally, taking advantage of such characteristics, liquid crystal polymers have been widely used as materials for various electronic components.
- the recently required pitch interval of the lattice portion is 2 mm or less, and the width of the resin portion of the lattice portion holding the terminals is 0.5 mm or less.
- the performance was insufficient for use as a very thin planar connector. That is, in such a planar connector having a very thin grid portion, filling the lattice portion with resin increases the filling pressure due to insufficient fluidity, resulting in the resulting planar connector. There is a problem that the amount of warp deformation increases.
- liquid crystalline polymer composition having good fluidity with a small amount of glass fiber added.
- a composition is insufficient in strength and deforms due to reflow during mounting. The problem arises.
- the present situation is that a planar connector made of a liquid crystalline polymer having an excellent performance balance has not yet been obtained.
- JP-A-2005-276758 a planar connector composed of a specific composite resin composition in which the weight average length of the fibrous filler to be blended and the blending amount have a certain relationship. Proposed. Summary of the Invention
- a thin flat connector can be obtained that is excellent in performance such as moldability, flatness, warp deformation, and heat resistance.
- the above-mentioned Japanese Patent Application Laid-Open No. 2005-276758 deals with a change in shape accompanying an increase in the integration rate of a recent planar connector, particularly an increase in the number of connector pins and further thinning of the width of the lattice portion. It turns out that there are cases where it cannot be completed.
- the present inventors conducted extensive search and examination to provide a flat connector made of a liquid crystalline polymer with an excellent performance balance that can cope with the shape change of recent planar connectors.
- a composite resin composition in which (A) a liquid crystalline polymer is combined with (B) a plate-like inorganic filler and (C) a specific fibrous filler in a specific ratio, good moldability, flatness.
- the inventors have found that a flat connector excellent in all of the performances such as warp deformation and heat resistance can be obtained, and the present invention has been completed.
- the present invention relates to (A) a liquid crystalline polymer having a p-hydroxybenzoic acid residue of 55 mol% or less and a melting point of 330 ° C. or more, (B) a plate-like inorganic filler, and (C) a weight average fiber length. Consists of a fibrous filler of 250 to 600 ⁇ m, the component (B) is 25 to 35% by weight with respect to the whole composition, the component (C) is 10 to 25% by weight with respect to the whole composition, and (C) is formed from a composite resin composition having a total of 40 to 50% by weight of the total composition, It has a lattice structure inside the outer frame, and further has an opening inside the lattice structure. The pitch interval of the lattice part is 1.5mm or less,
- the planar connector is characterized by a structure in which the ratio of the thickness of the outer frame portion to the lattice portion is 0.8 or less.
- the liquid crystalline polymer (A) soot used in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic melt 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 polymer applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in the molten stationary state, and optically anisotropic.
- the liquid crystalline polymer (A) is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide, and is an aromatic polyester or a polyester partially containing the aromatic polyester amide in the same molecular chain. Is also in that range. They preferably have a logarithmic viscosity (IV) of at least about 2.0 dl / g, more preferably 2.0-10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by weight. .) Are used.
- the constitution of aromatic polyester and aromatic polyester amide is as follows: (1) 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; (2) 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; (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). 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
- the polyesteramide which consists of, etc. are mentioned. Furthermore, you may use a molecular weight modifier together with said structural component as needed.
- specific examples of the specific compound constituting the applicable liquid crystalline polymer (A) include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and 2,6-dihydroxy.
- Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, compounds represented by the following general formula (1) and the following general formula (2); terephthalic acid, isophthalic acid 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and aromatic dicarboxylic acids such as compounds represented by the following general formula (3); aromatic amines such as p-aminophenol and p-phenylenediaminekind.
- the liquid crystalline polymer (A) to which the present invention is applied is such that the proportion of p-hydroxybenzoic acid residue as a terminal hydroxycarboxylic acid is 55 mol% with respect to all structural unit components of the liquid crystalline polymer. It is the following liquid crystalline polymer.
- the melting point of the liquid crystalline polymer needs to be 330 ° C. or higher.
- a planar connector is mounted on a circuit board, and soldering having a fixing and circuit forming function is performed to form an electronic circuit. The soldering is realized by passing through an infrared reflow furnace. In order not to change the shape and the like through infrared reflow, the melting point of the liquid crystalline polymer needs to be 330 ° C. or higher.
- liquid crystalline polymer those having a deflection temperature under load measured in accordance with ISO 75-1, 2 are preferably 250 ° C. or more.
- liquid crystalline polymer includes structural units represented by the following general formulas (I), (II), (III) and (IV) as essential structural components, and (I) ) Is 40 to 75 mol%, (II) is 8.5 to 30 mol%, (III) IV is 8.5 to 30 mol%, and (IV) is 0.1 to 8 mol%. It is a certain liquid crystalline polyester resin.
- Ar 1 is 2,6-naphthalene
- Ar 2 is one or more selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene
- Ar 3 is 1,3-
- Ar 4 is 1,4-phenylene.
- the raw material compounds necessary for forming such a liquid crystalline polyester will be described in detail step by step.
- various compounds having ordinary ester forming ability are used.
- the structural unit (I) is introduced from 6-hydroxy-2-naphthoic acid.
- the structural unit (II) is a dicarboxylic acid unit, and Ar 2 is selected from 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene, preferably from terephthalic acid in terms of heat resistance. It is to be introduced.
- the structural unit (III) is a diol unit, and hydroquinone, dihydroxybiphenyl or the like is used as the raw material compound, and dihydroxybiphenyl, particularly 4,4′-dihydroxybiphenyl is preferred from the viewpoint of heat resistance.
- the structural unit (IV) is introduced from 4-hydroxybenzoic acid.
- the structural units (I) to (IV) are contained, and the structural unit of (I) is 40 to 75 mol% (preferably 40 to 60 mol%, more preferably 45 to 60 mol%) with respect to all the structural units. Mol%), (II) constituent unit is 8.5 to 30 mol% (preferably 17.5 to 30 mol%), (III) constituent unit is 8.5 to 30 mol% (preferably 17.5 to 30 mol%), (IV ) In the range of 0.1 to 8 mol% (preferably 1 to 6 mol%).
- the constituent unit of (IV) is 3 to 6 mol% because a strong lattice portion is obtained and a connector with good flatness (small warpage deformation) can be obtained.
- the wholly aromatic polyester of the present invention is polymerized using a direct polymerization method or a transesterification method, and a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method or the like is used for the polymerization.
- an acylating agent for the polymerization monomer or a monomer having an activated terminal as an acid chloride derivative can be used.
- the acylating agent include acid anhydrides such as acetic anhydride.
- catalysts can be used for these polymerizations, and typical ones include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, alkali and alkaline earth of carboxylic acids. Metal salts, Lewis acid salts such as BF 3 and the like.
- the amount of catalyst used is generally about 0.001 to 1% by weight, particularly about 0.003 to 0.2% by weight, based on the total weight of the monomers.
- liquid paraffin high heat resistant synthetic oil, inert mineral oil, or the like is used as a solvent.
- the reaction conditions are a reaction temperature of 200 to 380 ° C. and a final ultimate pressure of 0.1 to 760 torr (ie 13 to 101,080 Pa). Particularly in the melt reaction, the reaction temperature is 260 to 380 ° C., preferably 300 to 360 ° C., and the final ultimate pressure is 1 to 100 torr (ie 133 to 13,300 ° Pa), preferably 1 to 50 torr (ie 133 to 6,670 ° Pa). is there.
- all the raw material monomers, the acylating agent and the catalyst can be charged in the same reaction vessel to start the reaction (one-stage system), or the raw material monomers (I), (III) IV and (IV) hydroxyl groups are acylated. After acylating with an agent, it can also be reacted with the carboxyl group of (II) (two-stage system).
- the melt polymerization is performed after the inside of the reaction system has reached a predetermined temperature, and the pressure reduction is started to a predetermined degree of pressure reduction. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the polymer is discharged from the reaction system through a normal pressure from a reduced pressure state to a predetermined pressure state.
- the polymer produced by the above polymerization method can be further increased in molecular weight by solid-phase polymerization that is heated at normal pressure or reduced pressure in an inert gas.
- the preferred conditions for the solid state polymerization reaction are a reaction temperature of 230 to 350 ° C., preferably 260 to 330 ° C., and a final ultimate pressure of 10 to 760 Torr (ie, 1,330 to 101,080 Pa).
- the composite resin composition used in the present invention comprises the above (A) liquid crystalline polymer, (B) a plate-like inorganic filler, and (C) a fibrous filler having a weight average fiber length of 250 to 600 ⁇ m. .
- Examples of the (B) plate-like filler used in the present invention include talc, mica, glass flakes, various metal foils, and the like, and preferably one or more selected from talc and mica.
- the average particle diameter of the (B) plate-like filler is not particularly limited, but it is desirable to be small in consideration of the fluidity of the thin-walled portion, but in order to reduce warpage deformation, a certain size is maintained. Need to be. Specifically, 1 to 100 ⁇ m, desirably 5 to 50 ⁇ m is preferable.
- Examples of the (C) fibrous filler used in the present invention include glass fibers, carbon fibers, whiskers, inorganic fibers, ore fibers, and glass fibers are preferred.
- the fibrous filler must have a weight average fiber length of 250 to 600 ⁇ m. If the weight average fiber length exceeds 600 ⁇ m, the fluidity deteriorates and molding is impossible, or even if molding is possible, a connector with excellent flatness cannot be obtained. When the weight average fiber length is less than 250 ⁇ m, the reinforcing effect is small, and the strength (mesh strength) of the lattice portion holding the terminals is not preferable.
- the fiber diameter of the (B) fibrous filler is not particularly limited, but generally about 5 to 15 ⁇ m is used.
- the component (B) is 25 to 35% by weight with respect to the whole composition
- the component (C) is 10 to 25% by weight with respect to the whole composition
- the component (B) And the sum of components (C) must be 40 to 50% by weight based on the total composition.
- the pitch interval of the lattice portion is 1.5 mm or less This is particularly effective for a very thin planar connector in which the width of the resin portion of the lattice portion holding the terminals is 0.5 mm or less and the total height of the product is 5.0 mm or less.
- FIG. 1 it is a connector as shown in FIG. 1 formed in the embodiment, and comprises an outer frame portion having a thickness of 5.0 mm or less and a lattice portion having a thickness of 4.0 mm or less.
- the lattice part has a number of pin holes of several hundreds in a product of about 40 mm ⁇ 40 mm ⁇ 1 mm.
- the planar connector referred to in the present invention has an opening of an appropriate size in the lattice portion. Therefore, the pitch interval of the grid part is 1.5 mm or less, the width of the resin part holding the terminal is 0.5 mm or less, and the thickness ratio between the outer frame part and the grid part is 0.8 or less, which makes the injection molding very difficult. ing.
- the pitch interval of the lattice portion is 1.5 mm or less (1.2 mm)
- the ratio of the thickness of the outer frame portion and the lattice portion is 0.8 or less (0.5)
- Molding a flat connector with a very thin resin part width in the grid part with a difference in thickness between the outer frame part and the grid part that the width of the resin part of the grid part holding the terminals is 0.5mm or less (0.18mm) It can be molded with good properties and its flatness is also excellent.
- the flatness before the IR reflow process for surface mounting at a peak temperature of 230 to 280 ° C is 0.15 mm or less, and the difference in flatness before and after reflow is 0.05. It can be said that what is mm or less has excellent flatness in practical use.
- the molding method for obtaining a connector having such excellent flatness is not particularly limited, but an economical injection molding method is preferably used.
- an economical injection molding method is preferably used.
- the cylinder temperature of the molding machine is preferably a temperature above the melting point T ° C. of the liquid crystalline polymer.
- the cylinder temperature is T ° C. to (T + 30) ° C., preferably T ° C. to (T + 15) ° C.
- the mold temperature is preferably 70 to 100 ° C. When the mold temperature is low, the filled resin composition is unfavorably caused by flow failure, and when the mold temperature is too high, problems such as generation of burrs are not preferable.
- the injection speed is preferably 150 mm / sec or more. If the injection speed is low, only unfilled molded products can be obtained, or even if a completely filled molded product is obtained, the molded product has a high filling pressure and a large residual internal stress, and only a connector with poor flatness can be obtained. It may not be possible.
- additives such as nucleating agents, carbon black, pigments such as inorganic fired pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, flame retardants, and the like are added to the composite resin composition.
- the composition imparted with the above characteristics is also included in the range of the composite resin composition referred to in the present invention.
- a special gate (overflow) shown in FIG. 2 was used.
- the gate uses a pin side that drops onto a tab beside the molded product with a pin gate and then obtains the molded product with a submarine gate.
- ⁇ Pin gate diameter ⁇ 1.0mm ⁇ Submarine gate; ⁇ 0.6mm ⁇ Number of gate points: 10 points ⁇ Pin gate part runner size; equivalent to ⁇ 3.0 mm ⁇ Submarine gate part runner size; equivalent to ⁇ 2.0 mm
- the obtained connector was placed on a horizontal desk, and the height of the connector was measured with Mitutoyo Quick Vision 404PRO CNC image measuring machine. At that time, the position of 0.5 mm from the end face of the connector was measured at 10 mm intervals, and the difference between the maximum height and the minimum height was defined as flatness (see FIG. 3).
- IR reflow was performed under the following conditions, and the flatness was measured by the above-described method to determine the difference in flatness before and after reflow.
- Measuring machine RF-300 (using far-infrared heater) Sample feed rate: 140mm / sec Reflow furnace transit time: 5 min Temperature conditions Preheat zone: 150 ° C, reflow zone: 225 ° C, peak temperature: 287 ° C [Molding condition] Molding machine; Sodick TR100EH Cylinder temperature; 350 ° C-350 ° C-350 ° C-350 ° C-350 ° C (Comparative Examples 5-8) 370 ° C-370 ° C-370 ° C-370 ° C-360 ° C (Examples 1-5, Comparative Examples 1-4) 380 ° C-380 ° C-380 ° C-380 ° C-370 ° C (Example 6) 360 ° C-360 ° C-360 ° C-360 ° C-
- the sample was once cooled to room temperature under a temperature drop condition of 20 ° C./min, and then measured again under a temperature rise condition of 20 ° C./min.
- Minimum Filling Pressure The minimum filling pressure at which a good molded product can be obtained when the planar connector of FIG. (5) Mesh Strength Using the planar connector shown in FIG. 1, the strength at the point (blacked portion) shown in FIG. 4 was measured to obtain the mesh strength.
- Molding machine Sumitomo SE100DU Cylinder temperature; 350 ° C-350 ° C-350 ° C-350 ° C-350 ° C (Comparative Examples 5-8) 370 ° C-370 ° C-370 ° C-370 ° C-360 ° C (Examples 1-5, Comparative Examples 1-4) 380 ° C-380 ° C-380 ° C-380 ° C-370 ° C (Example 6) 360 ° C-360 ° C-360 ° C-360 ° C-350 ° C (Example 7) Mold temperature: 90 °C Injection speed: 2m / min Holding pressure: 50MPa Holding pressure time: 7 sec Cooling time: 10 sec Screw rotation speed: 120rpm Screw back pressure: 1MPa (7) Weight average fiber length 5 g of resin composition pellets were heated at 600 ° C.
- the pressure was reduced to 5 Torr (that is, 667 Pa) over 30 minutes, and melt polymerization was performed while distilling a low boiling point such as acetic acid.
- a low boiling point such as acetic acid.
- nitrogen was introduced to make a pressurized state, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to be pelletized.
- the obtained pellets were heat-treated at 300 ° C. for 8 hours under a nitrogen stream to obtain liquid crystalline polymer 1.
- the melting point of the liquid crystalline polymer 1 was 352 ° C., and the deflection temperature under load was 300 ° C.
- the temperature was raised to 340 ° C. over 5.5 hours while continuing stirring.
- the pressure was reduced to 5 Torr (that is, 667 Pa) over 30 minutes, and melt polymerization was performed while distilling a low boiling point such as acetic acid.
- nitrogen was introduced to make a pressurized state, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to be pelletized.
- the obtained pellets were heat-treated at 280 ° C. for 8 hours under a nitrogen stream to obtain liquid crystalline polymer 3.
- the liquid crystalline polymer 3 had a melting point of 335 ° C. and a deflection temperature under load of 235 ° C.
Abstract
Description
背景技術
発明の概要
外枠の内部に格子構造を有し、更に格子構造の内部に開口部を有する、
格子部のピッチ間隔が1.5mm以下、
外枠部と格子部の厚みの比率が0.8以下
の構造に特徴がある平面状コネクターである。
発明の詳細な説明
(1)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;
(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;
(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、(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などが挙げられる。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。
これら液晶性ポリマーの中で、本発明が適用される液晶性ポリマー(A) としては、末端ヒドロキシカルボン酸としてのp-ヒドロキシ安息香酸残基の液晶性ポリマー全構成単位成分に対する割合が55モル%以下である液晶性ポリマーである。
以下、かかる液晶性ポリエステルを形成するために必要な原料化合物について順を追って詳しく説明する。上記(I)~(IV)の構成単位を具現化するには通常のエステル形成能を有する種々の化合物が使用される。
(1) 見掛け溶融粘度
L=20mm、d=1mmのキャピラリー式レオメータ((株)東洋精機製キャピログラフ1B型)を使用し、温度360℃、剪断速度1000/sでISO11443に準拠して、見掛け溶融粘度を測定した。液晶性ポリマー1及び液晶性ポリマー2を使用した場合は380℃、液晶性ポリマー3を使用した場合は350℃、液晶性ポリマー4を使用した場合は360℃で測定した。
(2) コネクター平面度の測定
樹脂組成物ペレットから、下記成形条件で、図1に示すような、全体の大きさ43.88mm×43.88mm×3mmt、中央部に13.88mm×13.88mmの孔開きを有し、格子部ピッチ間隔1.0mm、格子部の樹脂部分の幅0.12mm(抜き勾配をつけ、中央部で0.12mmとした)、格子部の厚み1.5mm、外枠部の幅3.0mmの平面状コネクター(ピン孔数1248ピン)を射出成形した。
ゲートはピンゲートで成形品脇のタブに落とし、その後サブマリンゲートで成形品を得る、ピンサイドを採用。
・ピンゲート径; φ1.0mm
・サブマリンゲート; φ0.6mm
・ゲート点数; 10点
・ピンゲート部ランナーサイズ; φ3.0mm相当
・サブマリンゲート部ランナーサイズ; φ2.0mm相当
[IRリフロー条件]
測定機;日本パルス技術研究所製大型卓上リフローハンダ付け装置RF-300(遠赤外線ヒーター使用)
試料送り速度;140mm/sec
リフロー炉通過時間;5min
温度条件 プレヒートゾーン;150℃、リフローゾーン;225℃、ピーク温度;287℃
[成形条件]
成形機;ソディック TR100EH
シリンダー温度;
350℃-350℃-350℃-350℃-350℃(比較例5~8)
370℃-370℃-370℃-370℃-360℃(実施例1~5、比較例1~4)
380℃-380℃-380℃-380℃-370℃(実施例6)
360℃-360℃-360℃-360℃-350℃(実施例7)
金型温度;80℃
射出速度;300mm/sec
保圧力;50MPa
充填時間;0.09~0.11sec
保圧時間;1sec
冷却時間;10sec
スクリュー回転数;120rpm
スクリュー背圧;1MPa
(3) 液晶性ポリマーの融点
示差熱分析装置(TA Instruments Q-1000)を使用し、重合を完了したポリマーを室温から20℃/分の昇温条件で400℃の温度で3分間保持した後、20℃/分の降温条件で室温まで一旦冷却した後、再度20℃/分の昇温条件で測定した。
(4) 最小充填圧
図1の平面状コネクターを射出成形する際に良好な成形品を得られる最小の射出充填圧を最小充填圧とした。
(5) メッシュ強度
図1の平面状コネクターを用い、図4に示す地点(黒塗り部)の強度を測定し、メッシュ強度とした。
試験機;オリエンテック製テンシロンRTA-250
スパン距離;6mm
試験速度;1mm/min
(6) 荷重たわみ温度
下記成形条件で、液晶性ポリマーのみと、板状充填剤及び繊維状充填剤を含む液晶性ポリマー組成物をそれぞれ射出成形し、ISO75-1,2に準拠して測定した。
[成形条件]
成形機;住友 SE100DU
シリンダー温度;
350℃-350℃-350℃-350℃-350℃(比較例5~8)
370℃-370℃-370℃-370℃-360℃(実施例1~5、比較例1~4)
380℃-380℃-380℃-380℃-370℃(実施例6)
360℃-360℃-360℃-360℃-350℃(実施例7)
金型温度;90℃
射出速度;2m/min
保圧力;50MPa
保圧時間;7sec
冷却時間;10sec
スクリュー回転数;120rpm
スクリュー背圧;1MPa
(7) 重量平均繊維長
樹脂組成物ペレット5gを600℃で2時間加熱し灰化した。灰化残渣を5%ポリエチレングリコール水溶液に十分分散させた後、スポイトでシャーレに移し、顕微鏡でガラス繊維を観察した。同時に画像測定器((株)ニレコ製LUZEXFS)を用いてガラス繊維の重量平均繊維長を測定した。尚、50μm以下のガラス繊維は除外して測定した。
実施例1~7および比較例1~8
下記条件にて、板状充填剤及び繊維状充填剤を含む液晶性ポリマー組成物の上記試験片を作製し、評価したところ、表1に示す結果を得た。尚、比較例8は、射出成形により良好な試験片を得ることができなかった。
[製造条件]
(使用成分)
(A)液晶性ポリマー
・液晶性ポリマー1
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を投入した。
・(I)6-ヒドロキシ-2-ナフトエ酸1218g(48モル%)(HNA)
・(II)テレフタル酸560g(25モル%)(TA)
・(III) 4,4'-ジヒドロキシビフェニル628g(25モル%)(BP)
・(IV)4-ヒドロキシ安息香酸37g(2モル%)(HBA)
・酢酸カリウム触媒(触媒量)
・無水酢酸(HNA、BP、HBAの総モル量に対して1.04倍モル)
次いで、窒素気流下、140℃で1時間撹拌後、撹拌を続けながら360℃まで5.5時間かけて昇温した。次に、30分かけて5Torr(即ち667Pa)まで減圧にし、酢酸等の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して加圧状態とし、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットを窒素気流下、300℃で8時間熱処理したものを液晶性ポリマー1とした。液晶性ポリマー1の融点は352℃、荷重たわみ温度は300℃であった。
・液晶性ポリマー2
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を投入した。
・(I)6-ヒドロキシ-2-ナフトエ酸76g(2.5モル%)(HNA)
・(II)テレフタル酸645g(23.9モル%)(TA)
・(III) 4,4'-ジヒドロキシビフェニル562g(18.6モル%)(BP)
・(IV)4-ヒドロキシ安息香酸1121g(50モル%)(HBA)
・(V)4-アセトアミドフェノール123g(5モル%)(APAP)
・酢酸カリウム触媒(触媒量)
・無水酢酸(HNA、BP、HBAの総モル量に対して1.03倍モル)
次いで、窒素気流下、140℃で1時間撹拌後、撹拌を続けながら350℃まで5.5時間かけて昇温した。次に、30分かけて5Torr(即ち667Pa)まで減圧にし、酢酸等の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して加圧状態とし、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットを窒素気流下、280℃で8時間熱処理したものを液晶性ポリマー2とした。液晶性ポリマー2の融点は367℃、荷重たわみ温度は260℃であった。
・液晶性ポリマー3
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を投入した。
・(I)6-ヒドロキシ-2-ナフトエ酸157g(5モル%)(HNA)
・(II)テレフタル酸490g(17.7モル%)(TA)
・(III) 4,4'-ジヒドロキシビフェニル382g(12.3モル%)(BP)
・(IV)4-ヒドロキシ安息香酸1381g(60モル%)(HBA)
・(V)4-アセトアミドフェノール126g(5モル%)(APAP)
・酢酸カリウム触媒(触媒量)
・無水酢酸(HNA、BP、HBAの総モル量に対して1.03倍モル)
次いで、窒素気流下、140℃で1時間撹拌後、撹拌を続けながら340℃まで5.5時間かけて昇温した。次に、30分かけて5Torr(即ち667Pa)まで減圧にし、酢酸等の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して加圧状態とし、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットを窒素気流下、280℃で8時間熱処理したものを液晶性ポリマー3とした。液晶性ポリマー3の融点は335℃、荷重たわみ温度は235℃であった。
・液晶性ポリマー4
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を投入した。
・(I)6-ヒドロキシ-2-ナフトエ酸157g(45モル%)(HNA)
・(II)テレフタル酸77g(25モル%)(TA)
・(III) 4,4'-ジヒドロキシビフェニル86g(25モル%)(BP)
・(IV)4-ヒドロキシ安息香酸13g(5モル%)(HBA)
・酢酸カリウム触媒(触媒量)
・無水酢酸(HNA、BP、HBAの総モル量に対して1.1倍モル)
次いで、窒素気流下、140℃で1時間撹拌後、撹拌を続けながら360℃まで5.5時間かけて昇温した。次に、30分かけて5Torr(即ち667Pa)まで減圧にし、酢酸等の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して加圧状態とし、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットを窒素気流下、300℃で8時間熱処理したものを液晶性ポリマー4とした。液晶性ポリマー4の融点は335℃、荷重たわみ温度は257℃であった。
(B)板状充填剤
・マイカ;(株)山口雲母工業製AB-25S、平均粒径25μm
・タルク;松村産業(株)製クラウンタルクPP、平均粒径10μm
(C)繊維状充填剤
・ガラス繊維;日本電気硝子(株)製ECS03T-786H、繊維径10μm、長さ3mmのチョプドストランド
・ミルドファイバー;日東紡(株)製PF70E001(繊維径10μm、繊維長70μm)
Claims (4)
- (A)p-ヒドロキシ安息香酸残基が55モル%以下であり、融点が330℃以上の液晶性ポリマー、(B)板状の無機充填剤及び(C)重量平均繊維長が250~600μmの繊維状充填剤からなり、(B)成分が組成物全体に対し25~35重量%、(C)成分が組成物全体に対し10~25重量%、且つ(B)成分と(C)成分の合計が組成物全体に対し40~50重量%である複合樹脂組成物から形成され、
外枠の内部に格子構造を有し、更に格子構造の内部に開口部を有する、
格子部のピッチ間隔が1.5mm以下、
外枠部と格子部の厚みの比率が0.8以下
の構造に特徴がある平面状コネクター。 - (A)液晶性ポリマーが、ISO75-1,2に準拠して測定した荷重たわみ温度が250℃以上のものである請求項1記載の平面状コネクター。
- (A)液晶性ポリマーが、必須の構成成分として下記一般式(I),(II),(III),(IV)で表される構成単位を含み、全構成単位に対して(I)の構成単位が40~75モル%、(II)の構成単位が8.5 ~30モル%、(III) の構成単位が8.5 ~30モル%、(IV)の構成単位が0.1 ~8モル%である液晶性ポリエステル樹脂であることを特徴とする請求項1又は2記載の平面状コネクター。
- (B)板状の無機充填剤が、タルク、マイカより選ばれる1種以上である請求項1~3の何れか1項記載の平面状コネクター。
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CN2009801187934A CN102037620B (zh) | 2008-05-23 | 2009-05-19 | 平面状连接器 |
US12/993,532 US8272879B2 (en) | 2008-05-23 | 2009-05-19 | Planar connector |
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JP2008-135405 | 2008-05-23 |
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Family
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PCT/JP2009/002190 WO2009141996A1 (ja) | 2008-05-23 | 2009-05-19 | 平面状コネクター |
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US (1) | US8272879B2 (ja) |
JP (1) | JP5165492B2 (ja) |
CN (1) | CN102037620B (ja) |
TW (1) | TWI449774B (ja) |
WO (1) | WO2009141996A1 (ja) |
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CN103460515A (zh) * | 2011-04-01 | 2013-12-18 | 宝理塑料株式会社 | 平面状连接器 |
JP2015117351A (ja) * | 2013-12-20 | 2015-06-25 | 東レ株式会社 | 液晶性ポリエステル樹脂組成物およびそれを用いた金属複合成形品 |
KR20180090808A (ko) | 2015-12-09 | 2018-08-13 | 스미또모 가가꾸 가부시끼가이샤 | 액정 폴리에스테르 조성물 및 성형체 |
WO2018020930A1 (ja) * | 2016-07-27 | 2018-02-01 | ポリプラスチックス株式会社 | 全芳香族ポリエステルアミド及びその製造方法 |
JP6345373B1 (ja) * | 2016-07-27 | 2018-06-20 | ポリプラスチックス株式会社 | 全芳香族ポリエステルアミド及びその製造方法 |
WO2021085240A1 (ja) * | 2019-10-31 | 2021-05-06 | ポリプラスチックス株式会社 | 樹脂組成物及びコネクター |
JP6944615B1 (ja) * | 2019-10-31 | 2021-10-06 | ポリプラスチックス株式会社 | 樹脂組成物及びコネクター |
Also Published As
Publication number | Publication date |
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US8272879B2 (en) | 2012-09-25 |
TWI449774B (zh) | 2014-08-21 |
CN102037620A (zh) | 2011-04-27 |
TW201006915A (en) | 2010-02-16 |
JP2010003661A (ja) | 2010-01-07 |
JP5165492B2 (ja) | 2013-03-21 |
CN102037620B (zh) | 2013-09-04 |
US20110086968A1 (en) | 2011-04-14 |
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