TW201422714A - Composite resin composition and flat connector molded from same - Google Patents
Composite resin composition and flat connector molded from same Download PDFInfo
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- TW201422714A TW201422714A TW102130410A TW102130410A TW201422714A TW 201422714 A TW201422714 A TW 201422714A TW 102130410 A TW102130410 A TW 102130410A TW 102130410 A TW102130410 A TW 102130410A TW 201422714 A TW201422714 A TW 201422714A
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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
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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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
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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
- C08K7/14—Glass
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
- H01R43/18—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing bases or cases for contact members
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Abstract
Description
本發明關於複合樹脂組合物以及由該複合樹脂組合物成形之平面狀連接器。 The present invention relates to a composite resin composition and a planar connector formed from the composite resin composition.
液晶性聚合物，係尺寸精度、流動性等優良的熱塑性樹脂。由於具有如此之特徵，液晶性聚合物，先前被採用作為各種電子元件的材料。 The liquid crystalline polymer is a thermoplastic resin excellent in dimensional accuracy and fluidity. Due to such characteristics, liquid crystalline polymers have been previously employed as materials for various electronic components.
特別是，隨著近幾年的電子機器的高性能化，有對高耐熱性等的電子零件(連接器等)的需求。例如，於專利文獻1，揭示有藉由玻璃纖維強化之液晶性聚合物組合物成形之平面狀連接器。此外，於專利文獻2，揭示有藉由玻璃纖維以及滑石強化的液晶性聚合物組合物成形之平面狀連接器。如此之連接器，採用於要求很高的高耐熱性等，於外框內部具有柵格構造之平面狀連接器(CPU插座等)。 In particular, with the increase in the performance of electronic devices in recent years, there is a demand for electronic components (connectors, etc.) having high heat resistance. For example, Patent Document 1 discloses a planar connector formed by a glass fiber reinforced liquid crystalline polymer composition. Further, Patent Document 2 discloses a planar connector formed by a glass fiber and a talc-reinforced liquid crystalline polymer composition. Such a connector is a planar connector (CPU socket or the like) having a grid structure inside the outer frame for requiring high heat resistance and the like.
近幾年，隨著平面狀連接器的積集度的增加，平面狀連接器的形狀亦要求變化。例如，平面狀連接器的形狀，因連接插針數的增加，而要求柵格部的寬度更薄壁之形狀等。 In recent years, as the degree of integration of planar connectors has increased, the shape of planar connectors has also required changes. For example, the shape of the planar connector requires a shape of a thinner wall of the grid portion due to an increase in the number of connection pins.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2005-276758號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-276758
[專利文獻2]日本特開2010-3661號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-3661
但是，由包含先前的液晶性聚合物，成形配合上述需求之平面狀連接器，則組合物之流動性並不充分，而不但加工性差，且有在所得平面狀連接器之柵格部發生破裂(亦稱為「龜裂」)之情形。因此，難以得到耐龜裂性高的平面狀連接器。此外，難以得到具有充分的平面度，減低翹曲變形之平面狀連接器。 However, the fluidity of the composition is not sufficient by the planar connector including the prior liquid crystal polymer formed to meet the above requirements, and the workability is poor, and cracking occurs in the grid portion of the resulting planar connector. (also known as "cracking"). Therefore, it is difficult to obtain a planar connector having high crack resistance. Further, it is difficult to obtain a planar connector having sufficient flatness and reducing warpage.
本發明係有鑑於該等情形而完成者，以提供可得平面度以及流動性良好、抑制翹曲變形、耐龜裂性優良的平面狀連接器之複合樹脂組合物以及由該複合樹脂組合物成形之平面狀連接器為目標。 The present invention has been made in view of such circumstances, and provides a composite resin composition having a flat connector having excellent flatness and fluidity, excellent warpage resistance and crack resistance, and a composite resin composition. The formed planar connector is targeted.
本發明者們，發現藉由組合包含既定量特定構成單位之液晶性聚合物、玻璃纖維、及既定的無機填充材可解決上述課題。具體而言，本發明提供如下者。 The present inventors have found that the above problems can be solved by combining a liquid crystalline polymer containing a specific constituent unit, a glass fiber, and a predetermined inorganic filler. Specifically, the present invention provides the following.
(1)一種複合樹脂組合物，包含：(A)液晶性聚合物；(B)玻璃纖維；及(C)選自由滑石及研磨纖維所組成之群之1以上之無機填充材，上述(A)液晶性聚合物，包含下述構成單位：(I)4-羥基安息香酸；(II)2-羥基-6-萘酸；(III)對苯二甲酸；(IV)間苯二甲酸； 及(V)4,4'-二羥基聯苯，作為必須的構成成分，(I)的構成單位對全構成單位為35~75莫耳%，(II)的構成單位對全構成單位為2~8莫耳%，(III)的構成單位對全構成單位為4.5~30.5莫耳%，(IV)的構成單位對全構成單位為2~8莫耳%，(V)的構成單位對全構成單位為12.5~32.5莫耳%，(II)及(IV)的構成單位的總量對全構成單位為4~10莫耳%，上述(A)液晶性聚合物對複合樹脂組合物全體為45~60質量%，上述(B)玻璃纖維對複合樹脂組合物全體為35~50質量%，上述(C)選自由滑石及研磨纖維所組成之群之1以上之無機填充材，對複合樹脂組合物全體為0~15質量%。 (1) A composite resin composition comprising: (A) a liquid crystalline polymer; (B) a glass fiber; and (C) an inorganic filler selected from the group consisting of talc and abrasive fibers, the above (A) a liquid crystalline polymer comprising the following constituent units: (I) 4-hydroxybenzoic acid; (II) 2-hydroxy-6-naphthoic acid; (III) terephthalic acid; (IV) isophthalic acid; And (V) 4,4'-dihydroxybiphenyl, as an essential constituent component, the constituent unit of (I) is 35 to 75 mol% for the total constituent unit, and the constituent unit of (II) is 2 for the total constituent unit. ~8 mol%, the constituent unit of (III) is 4.5 to 30.5 mol% for the total constituent unit, and the constituent unit of (IV) is 2 to 8 mol% for the total constituent unit, and the constituent unit of (V) is The constituent unit is 12.5 to 32.5 mol%, and the total amount of the constituent units of (II) and (IV) is 4 to 10 mol% for the total constituent unit, and the liquid crystal polymer (A) is a composite resin composition as a whole. 45 to 60% by mass, the (B) glass fiber is 35 to 50% by mass based on the entire composite resin composition, and the above (C) is selected from the group consisting of inorganic fillers of 1 or more of the group consisting of talc and abrasive fibers, and a composite resin. The composition was 0 to 15% by mass in total.
(2)根據(1)之複合樹脂組合物，其中上述(B)玻璃纖維之纖維長及上述(C)研磨纖維之纖維長之平均玻璃纖維長為200~500μm。 (2) The composite resin composition according to (1), wherein the fiber length of the (B) glass fiber and the fiber length of the (C) abrasive fiber are 200 to 500 μm.
(3)一種平面狀連接器，由(1)或(2)之複合樹脂組合物成形，於外框部的內部具有柵格構造，於上述柵格構造的內部具有開口部，於上述柵格構造之柵格部之間距間隔為1.5mm以下，上述外框部與上述柵格部之厚度比例為1.0以下，插針插入孔係異形孔。 (3) A planar connector formed of the composite resin composition of (1) or (2), having a lattice structure inside the outer frame portion, and having an opening inside the grid structure, in the grid The distance between the grid portions of the structure is 1.5 mm or less, and the thickness ratio of the outer frame portion to the grating portion is 1.0 or less, and the pin insertion holes are shaped holes.
(4)根據(3)之平面狀連接器，其中遵照ISO178測 定之歪曲彈性模數為17GPa以上。 (4) A planar connector according to (3), which is tested in accordance with ISO178 The flexural modulus of elasticity is determined to be 17 GPa or more.
根據本發明，可提供可得平面度及流動性良好，抑制翹曲變形，耐龜裂性優良的平面狀連接器之複合樹脂組合物以及由該複合樹脂組合物成形之平面狀連接器。 According to the present invention, it is possible to provide a composite resin composition which is excellent in flatness and fluidity, and which is excellent in warpage deformation and crack resistance, and a planar connector formed from the composite resin composition.
第1圖係表示於實施例成形之平面狀連接器之圖，(a)係平面圖(b)係右側面圖。再者，圖中的數值單位係mm。 Fig. 1 is a view showing a planar connector formed in the embodiment, and (a) is a plan view (b) showing a right side view. Furthermore, the numerical unit in the figure is mm.
第2圖係表示於實施例成形之平面狀連接器之澆口位置之圖，(a)係平面圖，(b)係右側面圖。再者，圖中的數值單位係mm。 Fig. 2 is a view showing a gate position of a planar connector formed in the embodiment, (a) is a plan view, and (b) is a right side view. Furthermore, the numerical unit in the figure is mm.
第3圖係表示在於實施例進行之連接器平面度之測定之測定點之圖。再者，圖中的數值單位係mm。 Fig. 3 is a view showing measurement points of the measurement of the flatness of the connector performed in the embodiment. Furthermore, the numerical unit in the figure is mm.
第4圖係表示在於實施例進行之耐龜裂性之評估所使用之評估用射出成形品之圖。再者，圖中的數值單位係mm。 Fig. 4 is a view showing the injection molded article for evaluation used for the evaluation of crack resistance in the examples. Furthermore, the numerical unit in the figure is mm.
第5圖係表示在於本發明之平面狀連接器之柵格部之異形孔之插針插入孔之形狀之例之圖。 Fig. 5 is a view showing an example of the shape of the pin insertion hole of the shaped hole of the grid portion of the planar connector of the present invention.
以下，具體說明本發明之實施形態。 Hereinafter, embodiments of the present invention will be specifically described.
[複合樹脂組合物] [Composite resin composition]
本發明之複合樹脂組合物，各包含既定量特定的液晶性聚合物、玻璃纖維及無機填充材。以下，說明構成本發明之複合樹脂組合物之成分。 The composite resin composition of the present invention each contains a specific amount of a liquid crystal polymer, a glass fiber, and an inorganic filler. Hereinafter, the components constituting the composite resin composition of the present invention will be described.
(液晶性聚合物) (liquid crystalline polymer)
在於本發明之液晶性聚合物，包含下述構成單位：(I)4-羥基安息香酸(亦稱為「HBA」)、(II)2-羥基-6-萘酸(亦稱為「HNA」)、(III)對苯二甲酸(亦稱為「TA」)、(IV)間苯二甲酸(亦稱為「IA」)、及(V)4,4'-二羥基聯苯(亦稱為「BP」)，作為必須的構成成分。 The liquid crystalline polymer of the present invention comprises the following constituent units: (I) 4-hydroxybenzoic acid (also referred to as "HBA"), and (II) 2-hydroxy-6-naphthoic acid (also referred to as "HNA"). ), (III) terephthalic acid (also known as "TA"), (IV) isophthalic acid (also known as "IA"), and (V) 4,4'-dihydroxybiphenyl (also known as "BP") is an essential component.
在於本發明之液晶性聚合物，以特定的比例包含上述構成單位。即，(I)的構成單位對全構成單位為35~75莫耳%(以40~65莫耳%為佳)，(II)的構成單位對全構成單位為2~8莫耳%(以3~7莫耳%為佳)，(III)的構成單位對全構成單位為4.5~30.5莫耳%(以13~26莫耳%為佳)，(IV)的構成單位對全構成單位為2~8莫耳%(以3~7莫耳%為佳)，(V)的構成單位對全構成單位為12.5~32.5莫耳%(以15.5~29莫耳%為佳)，(II)與(IV)的構成單位對全構成單位之總量為4~10莫耳%(以5~10莫耳%為佳)。 The liquid crystalline polymer of the present invention contains the above constituent units in a specific ratio. That is, the constituent unit of (I) is 35 to 75 mol% (more preferably 40 to 65 mol%) for the total constituent unit, and the constituent unit of (II) is 2 to 8 mol% for the total constituent unit ( 3~7 mol% is better), the constituent unit of (III) is 4.5~30.5 mol% for the total constituent unit (13~26 mol% is preferred), and the constituent unit of (IV) is the total constituent unit. 2~8 mol% (3~7 mol% is preferred), and the constituent unit of (V) is 12.5~32.5 mol% (more preferably 15.5~29 mol%), (II) The total amount of the constituent units of (IV) is 4 to 10 mol% (more preferably 5 to 10 mol%).
(I)的構成單位對全構成單位未滿35莫耳%或超過75莫耳%，則液晶性聚合物的熔點顯著地變高，於製造平面狀連接器等的成形品時，液晶性聚合物在反應器內固化，而有無法製造所期望的分子量的液晶性聚合物的可能性而不佳。 When the constituent unit of (I) is less than 35 mol% or more than 75 mol% of the total constituent unit, the melting point of the liquid crystalline polymer is remarkably high, and when a molded article such as a planar connector is produced, liquid crystal polymerization is carried out. It is not preferable that the substance is solidified in the reactor, and there is a possibility that a liquid crystalline polymer having a desired molecular weight cannot be produced.
(II)的構成單位對全構成單位，未滿2莫耳%，則在於製造平面狀連接器的成形品時，有柵格部發生破裂的可能性而不佳。此外(II)的構成單位對全構成單位超過8莫耳%，則液晶性聚合物的耐熱性變低而不佳。 When the constituent unit of (II) is less than 2 mol% for the entire constituent unit, it is not preferable that the grid portion is broken when the molded article of the planar connector is manufactured. Further, when the constituent unit of (II) exceeds 8 mol% of the total constituent unit, the heat resistance of the liquid crystalline polymer is lowered.
(III)的構成單位對全構成單位未滿4.5莫耳%或超 過30.5莫耳%，則液晶性聚合物的熔點顯著地變高，於製造平面狀連接器等的成形品時，液晶性聚合物在反應器內固化，而有無法製造所期望的分子量的液晶性聚合物的可能性而不佳。 The constituent unit of (III) is less than 4.5% or more than the total constituent unit When the content is more than 30.5 mol%, the melting point of the liquid crystalline polymer is remarkably high. When a molded article such as a planar connector is produced, the liquid crystalline polymer is solidified in the reactor, and liquid crystal having a desired molecular weight cannot be produced. The possibility of a polymer is not good.
(IV)的構成單位對全構成單位未滿2莫耳%，則在於製造平面狀連接器等的成形品時，有柵格部發生破裂的可能性而不佳。此外，(IV)的構成單位對全構成單位超過8莫耳%，則液晶性聚合物的耐熱性變低而不佳。 When the constituent unit of (IV) is less than 2 mol% of the total constituent unit, when a molded article such as a planar connector is manufactured, there is a possibility that the grid portion may be broken. Further, when the constituent unit of (IV) exceeds 8 mol% of the total constituent unit, the heat resistance of the liquid crystalline polymer is lowered.
(V)的構成單位對全構成單位未滿12.5莫耳%或超過32.5莫耳%，則液晶性聚合物的熔點顯著地變高，於製造平面狀連接器等的成形品時，液晶性聚合物在反應器內固化，而有無法製造所期望的分子量的液晶性聚合物的可能性而不佳。 When the constituent unit of (V) is less than 12.5 mol% or more than 32.5 mol% of the total constituent unit, the melting point of the liquid crystalline polymer is remarkably high, and when a molded article such as a planar connector is produced, liquid crystal polymerization is carried out. It is not preferable that the substance is solidified in the reactor, and there is a possibility that a liquid crystalline polymer having a desired molecular weight cannot be produced.
(II)與(IV)的構成單位對全構成單位之總量未滿4莫耳%，則液晶性聚合物之結晶化熱可成2.5J/g以上。此種情形在於製造包含平面狀連接器等的成形品時，有柵格部發生破裂的可能性而不佳。液晶性聚合物的結晶化熱之較佳之值為2.3J/g以下，以2.0J/g以下更佳。再者，結晶化熱係表示液晶性聚合物之結晶化狀態，藉由示差熱量測定所求得之值。具體而言，係將液晶性聚合物由室溫以20℃/分的升溫條件測定時所觀測之吸熱波峰溫度(Tm1)之觀測後，以Tm1+40℃的溫度保持2分鐘之後，以20℃/分的降溫條件測定時所觀測之發熱波峰溫度之波峰所求得之發熱波峰的熱量。 When the constituent units of (II) and (IV) are less than 4 mol% of the total amount of the total constituent units, the heat of crystallization of the liquid crystalline polymer may be 2.5 J/g or more. In this case, when a molded article including a planar connector or the like is manufactured, there is a possibility that the grid portion may be broken. The crystallization heat of the liquid crystalline polymer is preferably 2.3 J/g or less, more preferably 2.0 J/g or less. Further, the crystallization heat indicates the crystallization state of the liquid crystalline polymer, and the value obtained by the differential calorimetry measurement. Specifically, after observing the endothermic peak temperature (Tm1) observed when the liquid crystalline polymer is measured at a room temperature of 20 ° C /min, the temperature is maintained at a temperature of Tm1 + 40 ° C for 2 minutes, and then 20 The heat of the heat generation peak obtained by the peak of the heat peak temperature observed during the measurement of the temperature drop condition of °C/min.
此外，(II)與(IV)的構成單位對全構成單位之總量超過10莫耳%，則液晶性聚合物的耐熱性變低而不佳。 Further, when the constituent units of (II) and (IV) exceed 10 mol% of the total amount of the total constituent units, the heat resistance of the liquid crystalline polymer is lowered.
再者，在於本發明之液晶性聚合物，在不阻礙本 發明之目的的範圍，可導入習知之其他構成單位。 Furthermore, the liquid crystalline polymer of the present invention does not hinder the present invention. The scope of the object of the invention can be imported into other constituent units of the prior art.
在於本發明之液晶性聚合物，可將上述構成單位，以直接聚合法、酯交換法、熔融聚合法、溶液聚合法、淤漿聚合法、固相聚合法等聚合而得。 The liquid crystalline polymer of the present invention can be obtained by polymerization of the above constituent units by a direct polymerization method, a transesterification method, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method or the like.
在於上述構成單位的聚合，加上上述構成單位，可並用活性化的單體，作為對上述構成單位之醯化劑、或酸氯化物衍生物。醯化劑，可舉無水醋酸等的酸酐等。 In the polymerization of the above-mentioned constituent unit, the above-mentioned constituent unit may be used, and the activated monomer may be used in combination as a deuteration agent or an acid chloride derivative to the above constituent unit. The halogenating agent may, for example, be an acid anhydride such as anhydrous acetic acid.
在於上述構成單位的聚合，可使用各種觸媒，可舉例如二烷基錫氧化物、二芳基錫氧化物、二氧化鈦、烷氧基鈦矽酸鹽類、鈦醇鹽、羧酸的鹼金屬鹽類、鹼土金屬鹽類、路易斯酸鹽(BF3等)等。觸媒的使用量，對上述構成單位的總量，可為0.001~1質量%，以0.003~0.2質量%為佳。 In the polymerization of the above constituent units, various catalysts can be used, and examples thereof include dialkyl tin oxides, diaryl tin oxides, titanium oxides, alkoxytitanium silicates, titanium alkoxides, and alkali metals of carboxylic acids. Salts, alkaline earth metal salts, Lewis salts (BF 3, etc.), and the like. The amount of the catalyst used may be 0.001 to 1% by mass, and preferably 0.003 to 0.2% by mass, based on the total amount of the above constituent units.
聚合反應的條件，只要是可進行上述構成單位之聚合之條件，並無特別限定，可為例如，反應溫度200~380℃、最終到達壓力0.1~760Torr(即，13~101,080Pa)。 The conditions of the polymerization reaction are not particularly limited as long as the polymerization can be carried out in the above-mentioned constituent units, and may be, for example, a reaction temperature of 200 to 380 ° C and a final arrival pressure of 0.1 to 760 Torr (that is, 13 to 101,080 Pa).
聚合反應，可為將全原料單體、醯化劑以及觸媒放入同一反應容器開始反應之方法(一段模式)，亦可將對應原料單體(I)、(II)及(V)之羥基，以醯化劑使之醯化之後，使對應於(III)及(IV)之羧基反應之方法(二段模式)。 The polymerization reaction may be a method in which the whole raw material monomer, the oximation agent and the catalyst are put into the same reaction vessel to start the reaction (a mode), and the corresponding raw materials monomers (I), (II) and (V) may also be used. A method in which a hydroxyl group is deuterated with a deuteration agent to react a carboxyl group corresponding to (III) and (IV) (two-stage mode).
由上述構成單位(I)或(V)所得之液晶性聚合物，根據構成成分及液晶性聚合物中序列分佈，亦存在有不成形異向性熔融相者，但在兼具熱穩定性與易加工性之點，在於本發明之液晶性聚合物，以成形異向性熔融相，即，於熔融時顯示光學異向性之液晶性聚合物為佳。 The liquid crystalline polymer obtained by the above-mentioned structural unit (I) or (V) may have an anisotropic melting phase depending on the composition distribution and the liquid crystal polymer, but it has thermal stability and The ease of processing is that the liquid crystalline polymer of the present invention is preferably formed by forming an anisotropic molten phase, that is, a liquid crystalline polymer which exhibits optical anisotropy upon melting.
溶熔融異向性之性質，可藉由利用正交偏光片之慣用的偏光檢查方法確認。具體而言，熔融異向性，係使用偏光顯微鏡(奧林巴斯(股)製等)，將載置於加熱台(Linkam公司製等)的試料熔融，於氮氣氛下，以150倍的倍率觀察而確認。於熔融時顯示光學異向性的液晶性聚合物，係光學異向性，而插入正交的偏光片之間時，可使光穿透。試料係光學異向性，則例如即使是熔融靜止液態，亦會使偏光穿透。 The nature of the melt-melting anisotropy can be confirmed by a conventional polarizing inspection method using a crossed polarizer. Specifically, the melting anisotropy is melted by a polarizing microscope (Olympus Co., Ltd.), and the sample placed on a heating stage (manufactured by Linkam Co., Ltd.) is melted in a nitrogen atmosphere at 150 times. Confirmed by magnification observation. The liquid crystalline polymer exhibiting optical anisotropy upon melting is optically anisotropic, and when inserted between orthogonal polarizers, light can be transmitted. The sample is optically anisotropic, and for example, even if it is a molten stationary liquid, the polarized light is transmitted.
再者，以較熔點高10~40℃的溫度，以剪斷速度1000/秒之液晶性聚合物之熔融黏度，在1×105Pa．s以下(以5Pa．s以上1×102Pa．s以下更佳)，在於平面狀連接器的柵格部之成形時，可確保複合樹脂組合物之流動性，不會使填充壓力過度之點而佳。 Further, the melting viscosity of the liquid crystalline polymer having a shear rate of 1000/sec at a temperature higher by 10 to 40 ° C than the melting point is 1 × 10 5 Pa. s or less (more preferably 5 Pa.s or more and 1 × 10 2 Pa.s or less), in the molding of the grid portion of the planar connector, the fluidity of the composite resin composition can be ensured, and the filling pressure is not excessive. Good point.
本發明之複合樹脂組合物，將上述的液晶性聚合物，於複合樹脂組合物中，對複合樹脂組合物全體包含45~60質量%。液晶性聚合物，對複合樹脂組合物全體之含量，未滿45質量%，則流動性會惡化而不佳。液晶性聚合物，對複合樹脂組合物全體的含量，超過60質量%，則包含由複合樹脂組合物所得之平面狀連接器等之成形品之翹曲彈性模數及耐龜裂性降低而不佳。在於本發明之複合樹脂組合物，將上述液晶性聚合物，於複合樹脂組合物中，對複合樹脂組合物全體包含50~60質量%為佳。 In the composite resin composition of the present invention, the liquid crystalline polymer is contained in the composite resin composition in an amount of 45 to 60% by mass based on the entire composite resin composition. When the content of the liquid crystal polymer is less than 45% by mass in the entire content of the composite resin composition, the fluidity may be deteriorated. When the content of the liquid crystal polymer is more than 60% by mass in the entire composite resin composition, the warp elastic modulus and crack resistance of the molded article including the planar connector obtained from the composite resin composition are not lowered. good. In the composite resin composition of the present invention, the liquid crystalline polymer is preferably contained in the composite resin composition in an amount of 50 to 60% by mass based on the total of the composite resin composition.
(玻璃纖維) (glass fiber)
本發明之複合樹脂組合物，由於包含上述液晶性聚合物及玻璃纖維，故成形該複合樹脂組合物而得之成形品具有很高的 耐龜裂性。 Since the composite resin composition of the present invention contains the liquid crystalline polymer and the glass fiber, the molded article obtained by molding the composite resin composition has a high modulus. Resistance to cracking.
本發明之複合樹脂組合物，係於複合樹脂組合物中，對複合樹脂組合物全體，包含35~50質量%之玻璃纖維。玻璃纖維之含量，對複合樹脂組合物全體未滿35質量%，則由複合樹脂組合物所得之成形品之歪曲彈性模數低，成形品為平面狀連接器時，其柵格部等有發生破裂的可能性而不佳。玻璃纖維之含量，對複合樹脂組合物全體超過50質量%，則組合物之流動會惡化而不佳。在於本發明之玻璃纖維，於複合樹脂組合物中，對複合樹脂組合物全體包含40~50質量%為佳。 The composite resin composition of the present invention is a composite resin composition, and contains 35 to 50% by mass of glass fibers to the entire composite resin composition. When the content of the glass fiber is less than 35% by mass based on the total amount of the composite resin composition, the molded article obtained from the composite resin composition has a low flexural modulus, and when the molded article is a flat connector, the grid portion or the like occurs. The possibility of rupture is not good. When the content of the glass fiber exceeds 50% by mass based on the total amount of the composite resin composition, the flow of the composition may be deteriorated. In the composite resin composition, the glass fiber of the present invention preferably contains 40 to 50% by mass of the entire composite resin composition.
(無機填充材) (inorganic filler)
在於本發明之複合樹脂組合物，進一步包含選自由滑石及研磨纖維所組成之群之1以上之無機填充材。藉由使該等成分與玻璃纖維同時包含於複合樹脂組合物中，可不使複合樹脂組合物之流動性惡化，得到抑制翹曲變形之成形體。該等成分之總量，對複合樹脂組合物全體，包含0~15質量%。 The composite resin composition of the present invention further comprises an inorganic filler selected from the group consisting of talc and abrasive fibers. By including these components in the composite resin composition at the same time as the glass fibers, it is possible to obtain a molded body which suppresses warpage without deteriorating the fluidity of the composite resin composition. The total amount of these components is 0 to 15% by mass based on the entire composite resin composition.
在於本發明之複合樹脂組合物，玻璃纖維之纖維長，及，由上述無機填充材中的研磨纖維之纖維長算出之平均玻璃纖維長，以200~500μm為佳。平均纖維長未滿200μm，則由於由複合樹脂組合物所得之平面狀連接器等的成形品之柵格部等有發生破裂的可能性而不佳。平均纖維長超過500μm，則流動性會惡化，而有難以將複合樹脂組合物成形的可能性而不佳。 In the composite resin composition of the present invention, the fiber length of the glass fiber and the average glass fiber length calculated from the fiber length of the polishing fiber in the inorganic filler are preferably 200 to 500 μm. When the average fiber length is less than 200 μm, the lattice portion of the molded article such as a planar connector obtained from the composite resin composition may be broken. When the average fiber length exceeds 500 μm, the fluidity is deteriorated, and there is a possibility that it is difficult to form the composite resin composition.
此外，在於本發明之玻璃纖維及研磨纖維之纖維徑，並無特別限制，一般可使用5~15μm程度者。 Further, the fiber diameter of the glass fiber and the abrasive fiber of the present invention is not particularly limited, and generally 5 to 15 μm can be used.
(其他的成分) (other ingredients)
本發明之複合樹脂組合物，於上述成分之外，亦可調合核劑、碳黑、無機鍛燒顏料等的顏料、氧化防止劑、穩定劑、可塑劑、滑劑、脫模劑、難燃劑及習知之無機填充劑中之1種以上。 The composite resin composition of the present invention may be blended with a pigment, a carbon black, an inorganic calcined pigment, a pigment, an oxidation inhibitor, a stabilizer, a plasticizer, a slip agent, a mold release agent, and a flame retardant in addition to the above components. One or more of the agent and the conventional inorganic filler.
本發明之複合樹脂組合物之製造方法，只要可將上述的液晶性聚合物與玻璃纖維等均勻地混合，並無特別限定，可由先前已知的樹脂組合物之製造方法適宜選擇。可舉例如，使用單軸或雙軸擠出機等的熔融混練裝置，將各成分熔融混練擠出之後，將所得複合樹脂組合物加工成粉末、碎片、膠粒等所期望的形態之方法。 The method for producing the composite resin composition of the present invention is not particularly limited as long as it can uniformly mix the above-mentioned liquid crystalline polymer with glass fibers or the like, and can be suitably selected from a conventionally known method for producing a resin composition. For example, a method in which a melt-kneading device such as a uniaxial or biaxial extruder is used, and each component is melt-kneaded and extruded, and the obtained composite resin composition is processed into a desired form such as a powder, a chip, or a colloidal particle.
本發明之複合樹脂組合物，由於流動性優良，成形時的最小填充壓力不容易變得過度，可良好地成形，如平面狀連接器之柵格部等的具有複雜形狀的部分。最小填充壓力，係於成形複合樹脂組合物時，特定在365℃可得良好的成形品之最小射出填充壓。 In the composite resin composition of the present invention, since the fluidity is excellent, the minimum filling pressure at the time of molding is not easily excessive, and it can be favorably molded, such as a portion having a complicated shape such as a grid portion of a planar connector. The minimum filling pressure is a minimum injection filling pressure of a molded article which is excellent at 365 ° C when the composite resin composition is formed.
(平面狀連接器) (flat connector)
藉由成形本發明之複合樹脂組合物，可得本發明之平面狀連接器。平面狀連接器之形狀，並無特別限定，可係於外框部的內部具有柵格構造，於上述柵格構造之內部具有開口部，在於上述柵格構造的柵格部之間距間隔為1.5mm以下，上述外框部與上述柵格部之厚度比例為1.0以下之平面狀連接器。此外，以在於平面狀連接器，保持端子之柵格部之樹脂部分之寬度為0.5mm以下，製品全體的高度為5.0mm以下之非常薄壁 的平面狀連接器亦可。 The planar connector of the present invention can be obtained by molding the composite resin composition of the present invention. The shape of the planar connector is not particularly limited, and may have a grid structure inside the outer frame portion, and has an opening inside the grid structure, and the interval between the grid portions of the grid structure is 1.5. Below mm, a planar connector in which the thickness ratio of the outer frame portion to the grating portion is 1.0 or less. Further, in the planar connector, the width of the resin portion of the grid portion of the holding terminal is 0.5 mm or less, and the height of the entire product is 5.0 mm or less. The planar connector is also available.
本發明之平面狀連接器之形狀，可舉例如，第1圖所示者。該平面狀連接器，全體的大小為43.88mm×43.88mm×3mmt、厚度為3mm以下的外框部，及厚度為1.5mm以下的柵格部，於中部具有13.88mm×13.88mm的開口部。此外，該平面狀連接器之插針插入孔，為防止插入平面狀連接器之插針的脫落，插針插入孔的寬度的一部分亦可變窄。 The shape of the planar connector of the present invention may be, for example, as shown in Fig. 1. The planar connector has an overall outer frame portion having a size of 43.88 mm × 43.88 mm × 3 mmt and a thickness of 3 mm or less, and a grid portion having a thickness of 1.5 mm or less, and has an opening portion of 13.88 mm × 13.88 mm in the middle portion. Further, in the pin insertion hole of the planar connector, a part of the width of the pin insertion hole can be narrowed in order to prevent the pin inserted into the planar connector from coming off.
在於本發明之平面狀連接器之柵格部之插針插入孔之形狀，並無特別限定，可為四方形，亦可為圓形。在於本發明之較佳的插針插入孔之形狀，於四方形、圓形之外的形狀(在於本發明稱為「異形」)，可舉例如，第5圖所示之形狀、星形的形狀等。具有如此之形狀之插針插入孔(於本發明稱為「異形孔」)，不僅成形非常的困難，且容易發生破裂，容易降低成形品之耐龜裂性。但是，本發明之平面狀連接器插針插入孔，即使是異形孔，亦可具有優良的耐龜裂性。此外，本發明之平面狀連接器，不只在柵格部之中具有開口部者，亦包含在柵格部之中沒有開口部者。 The shape of the pin insertion hole of the grid portion of the planar connector of the present invention is not particularly limited, and may be a square or a circular shape. The shape of the preferred pin insertion hole of the present invention is a shape other than a square or a circle (referred to as "a shape" in the present invention), and for example, a shape shown in FIG. Shape and so on. The pin insertion hole having such a shape (referred to as "amorphous hole" in the present invention) is not only extremely difficult to form, but also easily broken, and it is easy to reduce the crack resistance of the molded article. However, the flat connector pin insertion hole of the present invention can have excellent crack resistance even in the case of a special-shaped hole. Further, the planar connector of the present invention includes not only an opening portion in the grid portion but also an opening portion in the grid portion.
得到本發明之平面狀連接器之成形方法，並無特別限定，選擇可防止所得平面狀連接器之變形，可得具有良好的平面度(後述)之平面狀連接器，不會有殘留內部應力之成形條件為佳。以填充壓力低，為降低所得平面狀連接器之殘留內部應力，成形機之料管溫度以液晶性聚合物之熔點以上的溫度為佳。 The method for forming the planar connector of the present invention is not particularly limited, and it is selected to prevent deformation of the obtained planar connector, and a planar connector having a good flatness (described later) can be obtained without residual internal stress. The forming conditions are preferred. The filling pressure is low, and in order to reduce the residual internal stress of the obtained planar connector, the temperature of the tube of the molding machine is preferably a temperature higher than the melting point of the liquid crystalline polymer.
此外，金屬模具溫度以70~100℃為佳。金屬模具溫度低，則有引起填充於金屬模具之複合樹脂組合物流動不良的可能性而不佳。金屬模具溫度高，則有發生毛邊等的問題的可能性而不佳。關於射出速度，以150mm/秒以上成形為佳。射出速度低，則有只能得到未填充成形品的可能性，即使得到完全填充的成形品，亦有成為填充壓力高且殘留內部應力大的成形品，而只能得到平面度低的連接器的可能性。 In addition, the temperature of the metal mold is preferably 70 to 100 ° C. When the temperature of the metal mold is low, there is a possibility that the composite resin composition filled in the metal mold may flow poorly. When the temperature of the metal mold is high, there is a possibility that problems such as burrs occur. Regarding the injection speed, it is preferable to form it at 150 mm/sec or more. When the injection speed is low, there is a possibility that only an unfilled molded article can be obtained, and even if a fully filled molded article is obtained, a molded article having a high filling pressure and a large residual internal stress can be obtained, and only a connector having a low flatness can be obtained. The possibility.
本發明之平面狀連接器，具有良好的歪曲彈性模數，耐龜裂性優良。本發明之平面狀連接器之歪曲彈性模數，可為17GPa以上。彈性模數在17GPa以上的平面狀連接器，即使係具有薄壁的柵格部者，亦不容易發生破裂，而耐龜裂性優良。再者，歪曲彈性模數，係遵照ISO178測定。 The planar connector of the present invention has a good flexural modulus and is excellent in crack resistance. The flat connector of the present invention has a flexural modulus of elasticity of 17 GPa or more. A planar connector having a modulus of elasticity of 17 GPa or more does not easily break even if it has a thin-walled grid portion, and is excellent in crack resistance. Furthermore, the flexural modulus is measured in accordance with ISO178.
此外，本發明之平面狀連接器，抑制了變形。平面狀連接器之變形程度，係以平面狀連接器之平面度作為指標判斷。具體而言，靜置於水平的桌上，將平面狀連接器以影像測定器測定平面狀連接器的高度，由連接器端面，將0.5mm的位置以10mm間隔測定，將最大高度與最小高度的差作為平面度。本發明之平面狀連接器，在於進行IR回焊前後，抑制了平面度的變化。 Further, the planar connector of the present invention suppresses deformation. The degree of deformation of the planar connector is judged by the flatness of the planar connector as an index. Specifically, the table is placed on a horizontal table, and the flat connector is used to measure the height of the planar connector by an image measuring device. The position of the connector is measured at an interval of 10 mm from the end face of the connector, and the maximum height and the minimum height are measured. The difference is as flatness. The planar connector of the present invention suppresses variations in flatness before and after IR reflow.
[實施例] [Examples]
以下，以實施例具體說明本發明，惟本發明不應限定於該等。 Hereinafter, the present invention will be specifically described by way of examples, but the invention should not be construed as limited thereto.
(液晶性聚合物1製造方法) (Method for Producing Liquid Crystalline Polymer 1)
於具有攪拌機、回焊管、單體投入口、氮導入口、減壓/ 流出線的聚合容器，放入以下原料單體、金屬觸媒，醯化劑，開始氮置換。 With mixer, reflow tube, monomer inlet, nitrogen inlet, decompression / The polymerization vessel of the outflow line was placed in the following raw material monomer, metal catalyst, and oxime agent to start nitrogen substitution.
(I)2-羥基-6-萘酸：166g(48莫耳%)(HNA) (I) 2-hydroxy-6-naphthoic acid: 166 g (48 mol%) (HNA)
(II)對苯二酸：76g(25莫耳%)(TA) (II) terephthalic acid: 76 g (25 mol%) (TA)
(III)4,4'-二羥基聯苯：86g(25莫耳%)(BP) (III) 4,4'-dihydroxybiphenyl: 86 g (25 mol%) (BP)
(IV)4-羥安息香酸：5g(2莫耳%)(HBA) (IV) 4-hydroxybenzoic acid: 5 g (2 mol %) (HBA)
醋酸鉀觸媒：22.5mg Potassium acetate catalyst: 22.5mg
無水醋酸：191g Anhydrous acetic acid: 191g
對聚合容器放入原料之後，將反應系的溫度提升到140℃，以140℃反應1小時。之後，進一步花5.5小時升溫到360℃，由此，花30分鐘減壓至5Torr(即，667Pa)，邊將醋酸、過剩的無水醋酸、其他的低沸份餾除邊進行熔融聚合。攪拌轉矩達到既定之值之後，導入氮由減壓狀態經由常壓成加壓狀態，由聚合容器下部排出聚合物，將膠條膠粒化成膠粒。將所得膠粒，於氮氣流下，以300℃進行8小時熱處理。膠粒的熔點為349℃，結晶化熱為5.6J/g、熔融黏度為23Pa．s。 After the raw material was placed in the polymerization vessel, the temperature of the reaction system was raised to 140 ° C, and the reaction was carried out at 140 ° C for 1 hour. Thereafter, the temperature was further increased to 360 ° C for 5.5 hours, whereby the pressure was reduced to 5 Torr (i.e., 667 Pa) for 30 minutes, and acetic acid, excess anhydrous acetic acid, and other low boiling portions were distilled off and melt-polymerized. After the stirring torque reaches a predetermined value, the introduced nitrogen is pressurized in a reduced pressure state via normal pressure, and the polymer is discharged from the lower portion of the polymerization vessel to pelletize the rubber strip into colloidal particles. The obtained micelles were heat-treated at 300 ° C for 8 hours under a nitrogen stream. The melting point of the colloidal particles is 349 ° C, the heat of crystallization is 5.6 J / g, and the melt viscosity is 23 Pa. s.
再者，在於本實施例，熔融黏度之測定係以下述條件進行。 Further, in the present embodiment, the measurement of the melt viscosity was carried out under the following conditions.
使用L=20mm、d=1mm之(股)東洋精機製毛細管流變儀1B型，以較液晶性聚合物之熔點高10~20℃的溫度，以剪斷速度1000/秒，遵照ISO11443，測定液晶性聚合物之熔融黏度。 Use L=20mm, d=1mm (Feed) Toyo Seiki Capillary Rheometer Model 1B, at a temperature 10 to 20 ° C higher than the melting point of the liquid crystalline polymer, with a shear rate of 1000 / sec, in accordance with ISO11443, The melt viscosity of the liquid crystalline polymer.
(液晶性聚合物2之製造方法) (Method of Manufacturing Liquid Crystalline Polymer 2)
於具備攪拌機、回焊管、單體投入口、氮導入口、減壓/流出線的聚合容器放入以下的原料單體、金屬觸媒，醯化劑， 開始氮置換。 The following raw material monomers, metal catalysts, and oximation agents are placed in a polymerization vessel equipped with a stirrer, a reflow tube, a monomer inlet, a nitrogen inlet, and a reduced pressure/outflow line. Start nitrogen replacement.
(I)4-羥基安息香酸：188.4g(60莫耳%)(HBA) (I) 4-hydroxybenzoic acid: 188.4 g (60 mol%) (HBA)
(II)6-羥基-2-萘酸：21.4g(5莫耳%)(HNA) (II) 6-Hydroxy-2-naphthoic acid: 21.4 g (5 mol%) (HNA)
(III)對苯二酸：66.8g(17.7莫耳%)(TA) (III) terephthalic acid: 66.8 g (17.7 mol%) (TA)
(IV)4,4'-二羥基聯苯：52.2g(12.3莫耳%)(BP) (IV) 4,4'-dihydroxybiphenyl: 52.2 g (12.3 mol%) (BP)
(V)4-乙酸基胺基酚：17.2g(5莫耳%)(APAP) (V) 4-acetoxyaminophenol: 17.2 g (5 mol%) (APAP)
醋酸鉀觸媒：15mg Potassium acetate catalyst: 15mg
無水醋酸：226.2g Anhydrous acetic acid: 226.2g
對聚合容器放入原料之後，將反應系的溫度提升到140℃上，以140℃反應1小時。之後，進一步花4.5小時升溫到340℃，由此花15分鐘減壓至10Torr(即，667Pa)，邊將醋酸、過剩的無水醋酸、其他的低沸份餾除邊進行熔融聚合。攪拌轉矩達到既定之值之後，導入氮，由減壓狀態經由常壓成為加壓狀態，由聚合容器下部排出聚合物，將膠條膠粒化成膠粒。所得的膠粒的熔點為334℃，結晶化熱為2.7J/g，熔融黏度為18Pa．s。 After the raw material was placed in the polymerization vessel, the temperature of the reaction system was raised to 140 ° C, and the reaction was carried out at 140 ° C for 1 hour. Thereafter, the temperature was further increased to 340 ° C for 4.5 hours, and the pressure was reduced to 10 Torr (i.e., 667 Pa) over 15 minutes, and acetic acid, excess anhydrous acetic acid, and other low boiling portions were distilled off and melt-polymerized. After the stirring torque reaches a predetermined value, nitrogen is introduced, and the pressure is reduced to a pressurized state by a normal pressure from a reduced pressure state, and the polymer is discharged from the lower portion of the polymerization vessel to pelletize the rubber into a colloidal particle. The obtained rubber particles have a melting point of 334 ° C, a heat of crystallization of 2.7 J / g, and a melt viscosity of 18 Pa. s.
(液晶性聚合物3之製造方法) (Method of Manufacturing Liquid Crystalline Polymer 3)
於具備攪拌機、回焊管、單體投入口、氮導入口、減壓/流出線的聚合容器放入以下的原料單體、金屬觸媒，醯化劑，開始氮置換。 The following raw material monomers, metal catalysts, and oximation agents were placed in a polymerization vessel equipped with a stirrer, a reflow tube, a monomer inlet, a nitrogen inlet, and a reduced pressure/outflow line, and nitrogen substitution was started.
(I)4-羥安息香酸：1041g(48莫耳%)(HBA) (I) 4-hydroxybenzoic acid: 1041 g (48 mol%) (HBA)
(II)6-羥基-2-萘酸：89g(3莫耳%)(HNA) (II) 6-Hydroxy-2-naphthoic acid: 89 g (3 mol%) (HNA)
(III)對苯二酸：565g(21.7莫耳%)(TA) (III) terephthalic acid: 565 g (21.7 mol%) (TA)
(IV)間苯二甲酸：78g(3莫耳%)(IA) (IV) isophthalic acid: 78 g (3 mol%) (IA)
(V)4,4'-二羥基聯苯：711g(24.3莫耳%)(BP) (V) 4,4'-dihydroxybiphenyl: 711 g (24.3 mol%) (BP)
醋酸鉀觸媒：110mg Potassium acetate catalyst: 110mg
無水醋酸：1645g Anhydrous acetic acid: 1645g
對聚合容器放入原料之後，將反應系的溫度提升到140℃，以140℃反應1小時。之後，進一步花5.5小時升溫到360℃，由此，花20分鐘減壓至10Torr(即，1330Pa)，邊將醋酸、過剩的無水醋酸、其他的低沸份餾除邊進行熔融聚合。攪拌轉矩達到既定之值之後，導入氮由減壓狀態經由常壓成加壓狀態，由聚合容器下部排出聚合物，將膠條膠粒化成膠粒。所得的膠粒的熔點為358℃，結晶化熱為1.6J/g，熔融黏度為9Pa．s。 After the raw material was placed in the polymerization vessel, the temperature of the reaction system was raised to 140 ° C, and the reaction was carried out at 140 ° C for 1 hour. Thereafter, the temperature was further increased to 360 ° C for 5.5 hours, whereby the pressure was reduced to 10 Torr (i.e., 1330 Pa) for 20 minutes, and acetic acid, excess anhydrous acetic acid, and other low boiling portions were distilled off and melt-polymerized. After the stirring torque reaches a predetermined value, the introduced nitrogen is pressurized in a reduced pressure state via normal pressure, and the polymer is discharged from the lower portion of the polymerization vessel to pelletize the rubber strip into colloidal particles. The obtained rubber particles have a melting point of 358 ° C, a heat of crystallization of 1.6 J / g, and a melt viscosity of 9 Pa. s.
(液晶性聚合物之外的成分) (components other than liquid crystal polymer)
將上述所得各液晶性聚合物，使用雙軸擠出機與下述成分混合，得到複合樹脂組合物。各成分之調合量如第1表及第2表所示。再者，以下，表中的「%」係表示質量%。 Each of the liquid crystal polymers obtained above was mixed with the following components using a twin screw extruder to obtain a composite resin composition. The blending amount of each component is shown in Tables 1 and 2. In addition, in the following, "%" in the table indicates the mass %.
玻璃纖維：日本電氣硝子(股)ECS03T-786H，纖維徑10μm，長度3mm切條 Glass fiber: Nippon Electric Glass Co., Ltd. ECS03T-786H, fiber diameter 10μm, length 3mm slit
滑石：松村產業(股)製CROWNTALC PP，平均粒徑10μm Talc: CROWNTALC PP made by Matsumura Industry Co., Ltd., with an average particle size of 10 μm
研磨纖維：日本紡(股)製PF70E001，纖維徑10μm，纖維長70μm Grinding fiber: PF70E001 made of Japanese spinning (stock), fiber diameter 10μm, fiber length 70μm
根據下述方法，測定所得液晶性聚合物或平面狀連接器之物性。將評估結果示於第1表及第2表。 The physical properties of the obtained liquid crystalline polymer or planar connector were measured according to the following methods. The results of the evaluation are shown in Tables 1 and 2.
(平均玻璃纖維長) (average glass fiber length)
將5g複合樹脂組合物膠粒以600℃加熱，灰化2小時。將 灰化殘渣充分分散於5質量%聚乙二醇水溶液之後，以滴管移置培養皿，以顯微鏡觀察玻璃纖維。同時，使用影像測定器((股)Nicole製LUZEXFS)測定玻璃纖維的重量平均纖維長。再者，關於包含研磨纖維之組合物，所謂平均玻璃纖維長，係指玻璃纖維與研磨纖維之纖維長之平均。 5 g of the composite resin composition colloidal particles were heated at 600 ° C and ashed for 2 hours. will After the ashing residue was sufficiently dispersed in a 5 mass% polyethylene glycol aqueous solution, the petri dish was placed in a dropper, and the glass fiber was observed under a microscope. At the same time, the weight average fiber length of the glass fiber was measured using an image measuring device (LUZEXFS manufactured by Nicole). Further, regarding the composition containing the abrasive fiber, the average glass fiber length means the average of the fiber length of the glass fiber and the abrasive fiber.
(歪曲彈性模數) (distorted elastic modulus)
以如下成形條件，射出成形複合樹脂組合物，遵照ISO178測定歪曲彈性模數。 The molded composite resin composition was injected under the following molding conditions, and the flexural modulus was measured in accordance with ISO178.
[成形條件] [forming conditions]
成形機：住友重機械工業SE100DU Forming machine: Sumitomo Heavy Machinery Industry SE100DU
料管溫度(表示由噴嘴側之溫度)：360℃ -370℃ -370℃ -360℃ -340℃ -330℃(實施例1~6、比較例3~7) Tube temperature (indicating the temperature from the nozzle side): 360 ° C -370 ° C -370 ° C -360 ° C -340 ° C -330 ° C (Examples 1 to 6, Comparative Examples 3 to 7)
370℃ -370℃ -370℃ -370℃ -370℃ -380℃(比較例1) 370 ° C -370 ° C -370 ° C -370 ° C -370 ° C -380 ° C (Comparative Example 1)
350℃ -350℃ -350℃ -350℃ -340℃ -330℃(比較例2) 350 ° C -350 ° C -350 ° C -350 ° C -340 ° C -330 ° C (Comparative Example 2)
金屬模具溫度：80℃ Metal mold temperature: 80 ° C
射出速度：2m/min Injection speed: 2m/min
保壓力：50MPa Pressure: 50MPa
保壓時間：2秒 Holding time: 2 seconds
冷卻時間：10秒 Cooling time: 10 seconds
螺桿旋轉數：120rpm Screw rotation number: 120rpm
螺桿背壓：1.2MPa Screw back pressure: 1.2MPa
(連接器平面度) (connector flatness)
將第1圖所示之複合樹脂組合物，射出成形為全體的大小 為43.88mm×43.88mm×3mmt，於中部具有13.88mm×13.88mm的開口部，柵格部間距間隔為1.0mm之平面狀連接器(針孔數1248針)。再者，澆口係使用如第2圖所示之特殊澆口(溢流)。 The composite resin composition shown in Fig. 1 is injection molded into the entire size. It is 43.88 mm × 43.88 mm × 3 mmt, and has a flat portion of 13.88 mm × 13.88 mm in the middle portion, and a planar connector having a grid portion pitch of 1.0 mm (the number of pinholes is 1248 stitches). Furthermore, the gate uses a special gate (overflow) as shown in Fig. 2.
將所得連接器靜置於水平的桌子上，將連接器的高度以MITSUTOYO製Quick Vision 404PROCNC影像測定機測定。此時，如第3圖表示，測定由連接器端面，0.5mm的位置，以10mm間隔測定，以由最小平方平面之最大高度與最小高度之差作為平面度。 The resulting connector was placed on a horizontal table, and the height of the connector was measured by a MITSUTOYO Quick Vision 404PROCNC image measuring machine. At this time, as shown in Fig. 3, the measurement was performed at a position of 0.5 mm from the end face of the connector at intervals of 10 mm, and the difference between the maximum height and the minimum height of the least square plane was taken as the flatness.
(連接器變形量) (connector deformation)
以下述條件進行IR回焊，以上述方法測定平面度，將在於回焊前後的平面狀連接器之平面度之差作為連接器變形量求得。 The IR reflow was performed under the following conditions, and the flatness was measured by the above method, and the difference in the flatness of the planar connector before and after the reflow was obtained as the amount of deformation of the connector.
[IR回焊條件] [IR reflow conditions]
測定器：日本脈衝技術研究所製之大型桌上回焊焊接裝置RF-300(使用遠紅外線加熱器) Measuring device: Large table reflow soldering device RF-300 manufactured by Japan Pulse Technology Research Institute (using far infrared heater)
試料輸送速度：140mm/秒 Sample conveying speed: 140mm / sec
反射爐通過時間：5分鐘 Reverberatory furnace passage time: 5 minutes
預熱區的溫度條件：150℃ Preheating zone temperature conditions: 150 ° C
回焊區的溫度條件：225℃ Temperature condition of reflow zone: 225 ° C
波峰溫度：287℃ Peak temperature: 287 ° C
[成形條件] [forming conditions]
成形機；住友重機械工業SE30DUZ Forming machine; Sumitomo Heavy Machinery Industry SE30DUZ
料管溫度(表示由噴嘴側之溫度)： 360℃ -365℃ -340℃ -330℃(實施例1~6、比較例3~7) Feed tube temperature (indicating the temperature from the nozzle side): 360 ° C -365 ° C -340 ° C -330 ° C (Examples 1 to 6, Comparative Examples 3 to 7)
370℃ -370℃ -370℃ -380℃(比較例1) 370 ° C -370 ° C -370 ° C -380 ° C (Comparative Example 1)
350℃ -350℃ -340℃ -330℃(比較例2) 350 ° C -350 ° C -340 ° C -330 ° C (Comparative Example 2)
金屬模具溫度：80℃ Metal mold temperature: 80 ° C
射出速度：300mm/秒 Injection speed: 300mm / sec
保壓力：50MPa Pressure: 50MPa
保壓時間：2秒 Holding time: 2 seconds
冷卻時間：10秒 Cooling time: 10 seconds
螺桿旋轉數：120rpm Screw rotation number: 120rpm
螺桿背壓：1.2MPa Screw back pressure: 1.2MPa
(連接器之最小填充壓力) (the minimum filling pressure of the connector)
將第1圖之平面狀連接器射出成形時，可得良好的成形品之最小射出填充壓力作為最小填充壓力測定。 When the planar connector of Fig. 1 is injection molded, the minimum injection filling pressure of a good molded article can be measured as the minimum filling pressure.
(耐龜裂性) (crack resistance)
第4圖所示評估用射出成形品，係外周直徑：23.6mm，於內部開有31個φ3.2mm之孔，孔間距離之最小壁厚為0.16mm。澆口係採用第4圖之箭頭部之3點澆口。成形品破裂觀察係使用實體顯微鏡，以倍率5倍觀察孔周圍之破裂的發生狀況，成形品發生破裂時以「×」，沒有發生時判斷為「○」。 In the evaluation injection molded article shown in Fig. 4, the outer peripheral diameter was 23.6 mm, and 31 holes of φ 3.2 mm were opened inside, and the minimum wall thickness between the holes was 0.16 mm. The gate is a 3-point gate of the arrow portion of Fig. 4. In the case of the fracture of the molded product, the occurrence of cracking around the hole was observed at a magnification of 5 times using a solid microscope, and "×" was observed when the molded product was broken, and "○" was determined when it did not occur.
[成形條件] [forming conditions]
成形機：住友重機械工業SE30DUZ Forming Machine: Sumitomo Heavy Machinery Industry SE30DUZ
料管溫度(表示由噴嘴側之溫度)： 370℃ -375℃ -360℃ -350℃(實施例1~6、比較例3~7) Feed tube temperature (indicating the temperature from the nozzle side): 370 ° C -375 ° C -360 ° C -350 ° C (Examples 1 to 6, Comparative Examples 3 to 7)
360℃ -360℃ -360℃ -370℃(比較例1) 360 ° C -360 ° C -360 ° C -370 ° C (Comparative Example 1)
350℃ -350℃ -340℃ -330℃(比較例2) 350 ° C -350 ° C -340 ° C -330 ° C (Comparative Example 2)
金屬模具溫度：140℃ Metal mold temperature: 140 ° C
射出速度：150mm/秒 Injection speed: 150mm / sec
保壓力：100MPa Pressure: 100MPa
保壓時間：2秒 Holding time: 2 seconds
冷卻時間：10秒 Cooling time: 10 seconds
螺桿旋轉數：120rpm Screw rotation number: 120rpm
螺桿背壓：1.2MPa Screw back pressure: 1.2MPa
如第1表及第2表所示，本發明之平面狀連接器，平面度、翹曲變形、流動性、耐龜裂性優良，歪曲彈性模數為17GPa以上。此外，對由本發明之複合樹脂組合物所得，插針插入孔為異形孔(具有第5圖之形狀之異形孔)之平面狀連接器，進行同樣的試驗，結果得到與上述同樣的良好的結果。 As shown in the first table and the second table, the planar connector of the present invention is excellent in flatness, warpage, fluidity, and crack resistance, and has a flexural modulus of 17 GPa or more. Further, the same test was carried out on the planar connector in which the pin insertion hole was a shaped hole (a shaped hole having the shape of Fig. 5) obtained from the composite resin composition of the present invention, and as a result, the same good results as described above were obtained. .
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