JP2015040248A - Liquid crystal polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal polymer composition that excels in fluidity during molding and causes little warpage even when the composition is treated at high temperature.SOLUTION: The liquid crystal polymer composition is prepared by compounding, in 100 parts by weight of a liquid crystal polymer, the following talc (A) and talc (B) by 10 to 250 parts by weight in a total amount of (A) and (B), with a weight ratio (A)/(B) controlled to 1/9 to 9/1. The talc (A) has an average particle diameter of 5 to 100 μm; and the talc (B) has an average particle diameter of 0.1 to 5 μm.

Description

  The present invention relates to a liquid crystal polymer composition which is excellent in fluidity and mechanical properties during molding and has little warpage.

  Thermotropic liquid crystal polymer (hereinafter abbreviated as liquid crystal polymer or LCP) is excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc. Its use is expanding in various applications.

  Especially in the field of information and communication such as personal computers and mobile phones, high integration of parts, miniaturization, thinning, and low profile are rapidly progressing, resulting in the formation of very thin parts. There are many cases. Therefore, the amount of LCP is greatly increased by taking advantage of its excellent moldability, that is, good fluidity and no characteristics of other resins such as no burrs.

  However, in recent years, the lead-free solder has led to higher reflow temperatures in electronic component applications such as connectors, and even in LCP molded products, warpage of molded products caused by reflow treatment at high temperatures has become a problem. .

  As a method for solving such a problem of warping of a molded product, a method of blending a liquid crystal polymer with a plate-like filler is known. For example, the average particle diameter is 0.5 to 100 μm, and D / A method of blending a liquid crystal polymer with a plate-like filler such as talc satisfying W ≦ 5 and 3 ≦ W / H ≦ 200 has been proposed (Patent Document 1, D is the maximum particle size of the plate-like filler) The direction is the x direction, W is the particle diameter in the direction perpendicular to the x direction (y direction), and H is the particle thickness in the z direction perpendicular to the xy plane).

  However, although the shape of talc proposed in Patent Document 1 is improved to some extent with respect to the occurrence of warpage, its effect is not sufficient, and further improvement of the occurrence of warpage is required.

JP 2001-106923 A

  An object of the present invention is to provide a liquid crystal polymer composition that is excellent in fluidity at the time of molding and has less warpage even when processed at a high temperature.

  As a result of intensive studies on the filler to be blended in the liquid crystal polymer, the present inventors have obtained a liquid crystal polymer composition obtained by blending two types of talc having a specific particle diameter into the liquid crystal polymer in a predetermined quantitative ratio. The present inventors have found that the fluidity and warpage are remarkably improved and have completed the present invention.

That is, the present invention provides the following talc (A) and talc (B) with respect to 100 parts by weight of the liquid crystal polymer, the total amount of (A) and (B) being 10 to 250 parts by weight, and (A) Provided is a liquid crystal polymer composition that is blended so that the weight ratio of / (B) is 1/9 to 9/1:
(A) Talc with an average particle diameter of 5 to 100 μm (B) Talc with an average particle diameter of 0.1 to 5 μm.

  The liquid crystal polymer composition of the present invention is excellent in fluidity at the time of molding and has a property that warpage is hardly generated even at high temperatures, and therefore can be suitably used as a molding material processed at high temperatures such as reflow.

  The liquid crystal polymer used in the liquid crystal polymer composition of the present invention is a liquid crystal polyester resin or liquid crystal polyester amide resin that forms an anisotropic molten phase called a thermotropic liquid crystal polymer by those skilled in the art.

  The property of the anisotropic molten phase of the liquid crystal polymer can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere.

  The liquid crystal polymer used in the present invention may be a blend of two or more liquid crystal polyester resins and / or liquid crystal polyester amide resins.

  As the liquid crystal polymer used in the present invention, either a semi-aromatic liquid crystal polymer having an aliphatic group in a molecular chain or a wholly aromatic liquid crystal polymer in which all molecular chains are composed of aromatic groups may be used. Among these liquid crystal polymers, it is preferable to use a wholly aromatic liquid crystal polymer, particularly a wholly aromatic liquid crystal polyester resin, because of good flame retardancy and mechanical properties.

  As the repeating unit constituting the liquid crystal polymer used in the present invention, aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic aminooxy repeating unit, aromatic diamino repeating unit, aromatic amino Examples thereof include a carbonyl repeating unit, an aromatic oxydicarbonyl repeating unit, and an aliphatic dioxy repeating unit.

  Specific examples of the monomer that gives an aromatic oxycarbonyl repeating unit include, for example, parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid. 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, their alkyl, alkoxy or halogen Substituents and ester-forming derivatives thereof such as acylated products, ester derivatives, acid halides and the like can be mentioned. Among these, parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable from the viewpoint of easy adjustment of characteristics and melting point of the liquid crystal polymer.

  Specific examples of the monomer giving the aromatic dicarbonyl repeating unit include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1, Examples thereof include aromatic dicarboxylic acids such as 4-naphthalenedicarboxylic acid and 4,4′-dicarboxybiphenyl, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives such as ester derivatives and acid halides thereof. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because the liquid crystal polymer from which terephthalic acid and 2,6-naphthalenedicarboxylic acid are obtained can easily adjust the mechanical properties, heat resistance, melting point temperature, and moldability to appropriate levels.

  Specific examples of the monomer that gives an aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4 Aromatic diols such as 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituents thereof, and Examples thereof include ester-forming derivatives such as acylated products. Among these, hydroquinone and 4,4'-dihydroxybiphenyl are preferable from the viewpoint of reactivity during polymerization, characteristics of the obtained liquid crystal polymer, and the like.

  Specific examples of the monomer giving an aromatic aminooxy repeating unit include, for example, p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, and 8-amino-2- Examples thereof include aromatic hydroxyamines such as naphthol and 4-amino-4′-hydroxybiphenyl, alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof such as acylated products thereof.

  Specific examples of the monomer giving an aromatic diamino repeating unit include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, alkyls thereof, Examples include amide-forming derivatives such as alkoxy or halogen-substituted products, and acylated products thereof.

  Specific examples of the monomer that gives an aromatic aminocarbonyl repeating unit include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, and 6-amino-2-naphthoic acid, their alkyls, Examples thereof include alkoxy- or halogen-substituted products, and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides.

  Specific examples of the monomer that gives an aromatic oxydicarbonyl repeating unit include hydroxy aromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid. And alkyl-substituted, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof.

  Specific examples of the monomer giving the aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. In addition, polymers containing aliphatic dioxy repeating units such as polyethylene terephthalate and polybutylene terephthalate are converted into the above-mentioned aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and their acylated products, ester derivatives, acid halides. A liquid crystal polymer containing an aliphatic dioxy repeating unit can also be obtained by reacting with the above.

  The liquid crystal polymer used in the present invention may contain a thioester bond as long as the object of the present invention is not impaired. Examples of the monomer that gives such a bond include mercapto aromatic carboxylic acid, aromatic dithiol, and hydroxy aromatic thiol. The amount of these monomers used is aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic aminooxy repeating unit, aromatic diamino repeating unit, aromatic aminocarbonyl repeating unit, The amount is preferably 10 mol% or less based on the total amount of monomers giving the aromatic oxydicarbonyl repeating unit and the aliphatic dioxy repeating unit.

  Polymers that combine the above repeating units may or may not form an anisotropic melt phase depending on the monomer composition and composition ratio, and the sequence distribution of each repeating unit in the polymer. The liquid crystal polymer used is limited to those forming an anisotropic melt phase.

［式中、Ａｒ_１およびＡｒ_２はそれぞれ２価の芳香族基を表す。］
ここで、「芳香族基」は、６員の単環または環数２の縮合環である芳香族基を示す。 As the liquid crystal polymer used in the liquid crystal polymer composition of the present invention, a wholly aromatic liquid crystal polyester resin composed of repeating units of the following formulas (I) to (IV) is preferably used.

[Wherein, Ar ₁ and Ar ₂ each represent a divalent aromatic group. ]
Here, the “aromatic group” refers to an aromatic group which is a 6-membered monocyclic ring or a condensed ring having 2 rings.

Ar ₁ and Ar ₂ are more preferably one or more selected from the following aromatic groups (1) to (4), and Ar ₁ is represented by the formula (1) and / or (4): It is particularly preferred that Ar ₂ is an aromatic group represented by the formula (1) and / or (3).

Specific examples of preferable liquid crystal polymers used in the present invention include those composed of the following monomer structural units.
1) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid copolymer 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 3) 4-hydroxybenzoic acid / terephthalic acid / Isophthalic acid / 4,4'-dihydroxybiphenyl copolymer 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 5) 4-hydroxybenzoic acid / terephthalic acid / Hydroquinone copolymer 6) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 7) 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer 8) 4- Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydride Roxybiphenyl copolymer 9) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 10) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone Copolymer 11) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone / 4,4'-dihydroxybiphenyl copolymer 12) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer 13) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 14) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / Hydroquinone copolymer 15) 4-hydroxybenzoic acid / 2-hydroxy-6- Futheic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 16) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4′-dihydroxybiphenyl copolymer 17) 4- Hydroxybenzoic acid / terephthalic acid / 4-aminophenol copolymer 18) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 19) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoene Acid / terephthalic acid / 4-aminophenol copolymer 20) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / 4-aminophenol copolymer 21) 4-hydroxybenzoic acid / terephthalic acid / ethylene Glycol copolymer 22) 4-hydroxybenzoic acid / terephthalic acid / , 4'-dihydroxybiphenyl / ethylene glycol copolymer 23) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / ethylene glycol copolymer 24) 4-hydroxybenzoic acid / 2-hydroxy-6 -Naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 25) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer.

Hereafter, the manufacturing method of the liquid crystal polymer used for this invention is demonstrated.
There are no particular restrictions on the method for producing the liquid crystal polymer used in the present invention, and known polycondensation methods for forming the above-mentioned monomers into ester bonds or amide bonds between the monomers, such as melt acidolysis methods and slurry polymerization methods. For example, the liquid crystal polymer used in the present invention can be obtained.

  The melt acidolysis method is a preferable method for producing the liquid crystal polymer used in the present invention. In this method, a monomer is first heated to form a melt of a reactant, and then a condensation polymerization reaction is continued to obtain a molten polymer. Note that a vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of the condensation.

  The slurry polymerization method is a method in which monomers are reacted in the presence of a heat exchange fluid, and a solid product is obtained in a state suspended in a heat exchange medium.

  In both the melt acidification method and the slurry polymerization method, the monomer component used in producing the liquid crystal polymer is a modified form in which a hydroxyl group and / or an amino group are acylated at room temperature, that is, a lower acylated product. Can also be used for the reaction. The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method using an acetylated product of the monomer in the reaction.

  The acylated product of the monomer may be prepared by separately acylating and synthesized in advance, or it may be generated in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during the production of the liquid crystal polymer. it can.

  In any case of the melt acidification method or the slurry polymerization method, the polymerization reaction is carried out at a temperature of 150 to 400 ° C., preferably 250 to 370 ° C. under normal pressure and / or reduced pressure. May be used.

  Specific examples of the catalyst include organic tin compounds such as dialkyltin oxide (eg dibutyltin oxide) and diaryltin oxide; metal oxides such as titanium dioxide; antimony compounds such as antimony trioxide; organics such as alkoxytitanium silicate and titanium alkoxide. Gaseous compounds such as titanium compounds; alkali or alkaline earth metal salts of carboxylic acids (eg potassium acetate); inorganic acid salts (eg potassium sulfate); Lewis acids (eg boron trifluoride); hydrogen halides (eg hydrogen chloride) Examples include acid catalysts.

  When a catalyst is used, the amount of the catalyst is preferably 1 to 1000 ppm, more preferably 2 to 100 ppm, based on the total amount of monomers.

  The liquid crystal polymer obtained by the polycondensation reaction is usually extracted from the polymerization reaction tank in a molten state, and then processed into a pellet, flake, or powder.

  The liquid crystal polymer in the form of pellets, flakes, or powders is subjected to heat treatment in a substantially solid state under reduced pressure, vacuum, or inert gas atmosphere for the purpose of increasing molecular weight and improving heat resistance. May be.

  The temperature of the heat treatment performed in the solid phase is not particularly limited as long as the liquid crystal polymer is not melted, but is preferably 260 to 350 ° C, more preferably 280 to 320 ° C.

  Moreover, the load deflection temperature measured according to ASTM D648 of the liquid crystal polymer used for this invention becomes like this. Preferably it is 200-310 degreeC, More preferably, it is 210-300 degreeC, More preferably, it is 220-290 degreeC.

The load deflection temperature is measured by the method described below.

<Load deflection temperature measurement method>
A strip-shaped test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm is formed using an injection molding machine (for example, UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), and this is used to comply with ASTM D648. Then, the temperature at which a predetermined amount of deflection (0.254 mm) is reached at a load of 1.82 MPa and a heating rate of 2 ° C./min is measured.

The liquid crystal polymer composition of the present invention comprises the following talc (A) and talc (B) with respect to 100 parts by weight of the liquid crystal polymer obtained as described above, and the total amount of (A) and (B) is 10 It is obtained by blending so that the weight ratio of (A) / (B) is 1/9 to 9/1.
(A) Talc with an average particle diameter of 5 to 100 μm (B) Talc with an average particle diameter of 0.1 to 5 μm.

  In the present invention, the “average particle diameter” of talc is a median diameter measured by a laser diffraction method.

  The average particle diameter of talc (A) is preferably 10 to 50 μm, more preferably 15 to 30 μm.

  The average particle size of talc (B) is preferably 0.3 to 4 μm, more preferably 0.5 to 3 μm.

  The total amount of talc (A) and talc (B) with respect to 100 parts by weight of the liquid crystal polymer may be 10 to 250 parts by weight, preferably 15 to 100 parts by weight, and 30 to 70 parts by weight. Is more preferable. When the total amount of talc (A) and talc (B) with respect to 100 parts by weight of the liquid crystal polymer is less than 10 parts by weight, the warp suppressing effect in the molded product tends to be insufficient, and the total amount is 100 parts by weight of the liquid crystal polymer. On the other hand, if it exceeds 250 parts by weight, the fluidity of the liquid crystal polymer composition tends to decrease, such being undesirable.

  The weight ratio of talc (A) to talc (B) ((A) / (B)) may be 1/9 to 9/1, preferably 2/8 to 8/2, more preferably 3 /. 7-7 / 3. When the weight ratio of talc (A) to talc (B) is less than 1/9 or more than 9/1, the warp improving effect in the molded product tends to be insufficient.

  Further, in the liquid crystal polymer composition of the present invention, a further inorganic filler may be blended in addition to the above-described two types of talc (A) and (B) as long as the object of the present invention is not impaired.

  Further inorganic fillers that can be incorporated into the liquid crystal polymer composition of the present invention may be fibrous, plate-like or granular (powder), such as glass fiber, milled glass, silica alumina fiber, alumina fiber, Examples include carbon fibers, aramid fibers, potassium titanate whiskers, aluminum borate whiskers, wollastonite, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, barium sulfate, and titanium oxide. In these, glass fiber is preferable at the point which the balance of a physical property and cost is excellent. Two or more of these fillers may be used in combination.

  The total amount of further inorganic fillers in the liquid crystal polymer composition of the present invention is preferably 10 to 100 parts by weight, more preferably 15 to 50 parts by weight with respect to 100 parts by weight of the liquid crystal polymer.

  In the liquid crystal polymer composition of the present invention, other additives such as higher fatty acid, higher fatty acid ester, higher fatty acid amide, higher fatty acid metal salt (where higher fatty acid is carbon Release agents such as polysiloxanes and fluororesins; colorants such as dyes and pigments; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; surfactants Etc. may be blended. These additives may be blended alone or in combination of two or more.

  The total amount of other additives in the liquid crystal polymer composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the total amount of other additives exceeds 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease and the thermal stability tends to deteriorate.

  For additives having an external lubricant effect, such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants, the liquid crystal polymer composition is preliminarily attached to the surface of the pellet of the liquid crystal polymer composition. You may squeeze it.

  Moreover, you may mix | blend another resin component with the liquid-crystal polymer composition of this invention in the range which does not impair the objective of this invention. Examples of other resin components include polyamide, polyester, polyacetal, polyphenylene ether, and modified products thereof, and thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, phenol resin, epoxy resin, and polyimide resin. And other thermosetting resins. Other resin components can be blended alone or in combination of two or more. The blending amount of the other resin components is not particularly limited, and may be appropriately determined according to the use and purpose of the liquid crystal polymer composition. In one typical example, the total amount of the other resin components is 0.1 to 100 parts by weight, particularly 0.1 to 80 parts by weight, based on 100 parts by weight of the liquid crystal polymer.

  The liquid crystal polymer composition of the present invention is obtained by adding the above-described talc (A) and talc (B) to a liquid crystal polymer together with further inorganic fillers, other additives, other resin components and the like as desired. Using a mixer, a kneader, a uniaxial or biaxial extruder, etc., it can be obtained by melt-kneading in the temperature range from the vicinity of the crystal melting temperature of the liquid crystal polymer to the crystal melting temperature + 20 ° C.

The liquid crystal polymer composition of the present invention exhibits an extremely small amount of warpage. In one preferred embodiment, the liquid crystal polymer composition of the present invention is a connector-shaped test piece having a length of 55.0 mm, a width of 9.0 mm, and a thickness of 0.5 mm, which is measured by the method for measuring a warpage described below. The amount of warpage before and after the treatment when the initial warpage amount is 0.1 mm or less, particularly preferably 0.08 mm or less, and the test piece is subjected to a reflow treatment at 250 ° C. or more for 20 to 30 seconds. The amount of change is 0.01 mm or less. The peak temperature in such reflow treatment is preferably 260 to 265 ° C.

<Definition and measurement method of warping amount>
In this specification, “warping amount” means a connector having a length of 55.0 mm, a width of 9.0 mm, and a thickness of 0.5 mm using an injection molding machine (for example, UH-1000-110 manufactured by Nissei Plastic Co., Ltd.). A shape test piece is formed, and the distance from the measuring instrument stage surface to the upper surface of the test piece is measured using a three-dimensional measuring instrument (for example, QHV250 manufactured by Mitutoyo Corporation), and the thickness of the test piece is 0.5 mm from the distance. The value after subtraction shall be said. Moreover, the value of the amount of warpage measured after the test piece was allowed to stand for 24 hours under conditions of 23 ° C. and 50% relative humidity is defined as “initial warp amount”. Next, using a reflow apparatus (for example, an IR reflow apparatus such as SAI-2604 manufactured by Senju Metal Industry Co., Ltd.), the test piece is subjected to a reflow process under desired conditions, and the amount of change in warpage before and after the reflow process (process) By calculating the difference between the amount of warpage before and after (absolute value), the degree of warpage due to high temperature can be evaluated.

  The liquid crystal polymer composition of the present invention is usually processed into a molded product, a film, a sheet, a nonwoven fabric, and the like by a known molding method using an injection molding machine, an extruder, or the like.

  Since the liquid crystal polymer composition of the present invention has excellent fluidity during molding and does not easily warp even under high temperature conditions, it can be processed under high temperatures such as reflow, switches, relays, connectors, chips, light It can be suitably used as a molding material for pickups, inverter transformers, coil bobbins, antennas, substrates and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

  First, synthesis examples of liquid crystal polymers used in Examples and Comparative Examples will be described.

Hereinafter, the abbreviations in the synthesis examples represent the following compounds.

[Monomers used for liquid crystal polymer synthesis]
POB: parahydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid HQ: hydroquinone BP: 4,4'-dihydroxybiphenyl TPA: terephthalic acid NDA: 2,6-naphthalenedicarboxylic acid

[Synthesis Example 1 (LCP-1)]
In a reaction vessel equipped with a stirrer with a torque meter and a distillation tube, POB: 386.0 g (43 mol%), BON 6: 183.5 g (15 mol%), HQ: 150.3 g (21 mol%) and TPA : 226.7 g (21 mol%) was charged, and 1.025 times moles of acetic anhydride was charged with respect to the amount of hydroxyl groups (mol) of all monomers, and deacetic acid polymerization was performed under the following conditions.
The temperature was raised from room temperature to 145 ° C. over 1 hour in a nitrogen gas atmosphere, and maintained at 145 ° C. for 30 minutes. Next, the temperature was raised to 350 ° C. over 7 hours while acetic acid produced as a by-product was distilled off, and then the pressure was reduced to 10 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical.

[Synthesis Example 2 (LCP-2)]
In a reaction vessel equipped with a stirrer with a torque meter and a distillation pipe, POB: 314.2 g (35 mol%), BON 6: 61.2 g (5 mol%), BP: 169.4 g (14 mol%), HQ : 114.5 g (16 mol%) and TPA: 323.9 g (30 mol%), and 1.03 times mol acetic anhydride with respect to the amount of hydroxyl groups (mol) of all monomers were charged under the following conditions: Deacetic acid polymerization was performed.
The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and maintained at 145 ° C. for 30 minutes. Next, the temperature was raised to 350 ° C. over 7 hours while acetic acid produced as a by-product was distilled off, and then the pressure was reduced to 5 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical.

[Synthesis Example 3 (LCP-3)]
In a reaction vessel equipped with a stirrer with a torque meter and a distillation tube, POB: 628.4 g (70 mol%), BON6: 24.5 g (2 mol%), HQ: 100.2 g (14 mol%) and NDA196 .7 g (14 mol%) was charged, and 1.03 times moles of acetic anhydride was charged with respect to the amount of hydroxyl groups (mol) of all monomers, and deacetic acid polymerization was performed under the following conditions.
The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and maintained at 145 ° C. for 30 minutes. Next, the temperature was raised to 345 ° C. over 7 hours while acetic acid produced as a by-product was distilled off, and then the pressure was reduced to 10 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical.

The talc (A), talc (B), and fibrous inorganic filler used in Examples and Comparative Examples are shown below.

<Talc (A)>
NK-64 manufactured by Fuji Talc Co., Ltd. (average particle size 19.0 μm, water content 0.50% by weight)
<Talc (B)>
Made by Nippon Talc Co., Ltd., D-800 (average particle size 0.8 μm, water content 0.60% by weight)
<Fibrous inorganic filler>
Glass fiber: ECS3010A (average fiber length 10.5 μm) manufactured by CPIC

[Examples 1-4, Comparative Examples 1-2]
Using LCP-1 as the liquid crystal polymer, the amount of talc (A), talc (B) and fibrous inorganic filler (glass fiber) shown in Table 1 are blended with respect to 100 parts by weight of the liquid crystal polymer. What was melt-kneaded with an extruder (manufactured by Ikegai Co., Ltd., PCM-30) was pelletized to prepare a liquid crystal polymer composition.
About the pellet of the obtained liquid crystal polymer composition, the load deflection temperature (DTUL), the tensile strength, the bending strength, the bending elastic modulus, the Izod strength, the flow length, and the warpage amount were measured by the methods shown below. The results are shown in Table 1.

(1) Load deflection temperature (DTUL)
Using an injection molding machine (UH-1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), strip-shaped test pieces having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm were molded under the conditions shown in Table 2. Using this, the temperature reaching a predetermined amount of deflection (0.254 mm) at a load of 1.82 MPa and a heating rate of 2 ° C./min was measured in accordance with ASTM D648.

(2) Tensile strength ASTM No. 4 dumbbell test piece was molded under the conditions shown in Table 2 using an injection molding machine (UH-1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), and conformed to ASTM D638 using this. And measured.

(3) Bending strength and flexural modulus Using the same test piece as the test piece used for measuring the load deflection temperature, the bending strength and the flexural modulus were measured in accordance with ASTM D790.

(4) Izod impact strength Using the same test piece as that used for the load deflection temperature measurement, the center of the test piece was cut perpendicularly to the length direction to obtain a length of 63.5 mm, a width of 12.7 mm, and a thickness. A strip-shaped test piece of 3.2 mm was obtained and measured according to ASTM D256.

(5) Fluidity Using a rectangular bar flow mold having a length of 127 mm, a width of 12.7 mm, and a thickness of 0.2 mm, molding shown in Table 3 using an injection molding machine (NEX-15-1E, manufactured by Nissei Plastic Industry Co., Ltd.) The flow length was measured when injection molding was performed under conditions and the bar flow mold was filled.

(6) Warpage amount Using an injection molding machine (manufactured by Nissei Plastic Co., Ltd., UH-1000-110), injection molding was performed under the molding conditions shown in Table 4, and the length was 55.0 mm × width 9.0 mm × thickness 0. A 5 mm connector-shaped test piece was molded. After this test piece was allowed to stand for 24 hours under conditions of 23 ° C. and 50% relative humidity, the distance from the measuring instrument stage surface to the upper surface of the test piece was measured using a three-dimensional measuring device (manufactured by Mitutoyo Corporation, QHV250). Then, a value obtained by subtracting 0.5 mm of the thickness of the test piece from the distance was defined as an initial warpage amount. Next, using an IR reflow device (SAI-2604, manufactured by Senju Metal Industry Co., Ltd.), the test piece was subjected to a reflow treatment under the following conditions, and then the amount of warpage was measured in the same manner as above, before and after the reflow treatment. The amount of change in warpage (that is, the difference in warpage before and after reflow treatment (absolute value)) was determined.
<Reflow processing conditions>
Preheating: 190 ° C., 30-50 seconds, main heating: 250 ° C. or more, 20-30 seconds, peak temperature: 260-265 ° C.

[Examples 5-7, Comparative Examples 3-4]
Using LCP-2 as the liquid crystal polymer, the amount of talc (A), talc (B) and fibrous inorganic filler (glass fiber) shown in Table 5 are blended with respect to 100 parts by weight of the liquid crystal polymer. What was melt-kneaded with an extruder (manufactured by Ikegai Co., Ltd., PCM-30) was pelletized to prepare a liquid crystal polymer composition.
About the pellet of the obtained liquid crystal polymer composition, it injection-molded on the conditions of Table 6 using the injection molding machine (Nissei Plastic Industries Co., Ltd. UH-1000-110), and carried out similarly to Example 1. The load deflection temperature (DTUL), tensile strength, bending strength, bending elastic modulus, and Izod strength were measured. Injection molding was performed under the molding conditions shown in Table 3 using an injection molding machine (Nex-15-1E, manufactured by Nissei Plastic Industry Co., Ltd.), and the flow length was measured in the same manner as in Example 1. Using an injection molding machine (manufactured by Nissei Plastic Co., Ltd., UH-1000-110), injection molding was performed under the molding conditions shown in Table 7, and the amount of warpage was measured in the same manner as in Example 1. The results are shown in Table 5.

[Examples 8 to 10, Comparative Examples 5 to 6]
Using LCP-3 as the liquid crystal polymer, the amount of talc (A), talc (B) and fibrous inorganic filler (glass fiber) shown in Table 8 are blended with respect to 100 parts by weight of the liquid crystal polymer, and biaxial What was melt-kneaded with an extruder (manufactured by Ikegai Co., Ltd., PCM-30) was pelletized to prepare a liquid crystal polymer composition.
About the pellet of the obtained liquid crystal polymer composition, it injection-molded on the conditions of Table 6 using the injection molding machine (Nissei Plastic Industries Co., Ltd. UH-1000-110), and carried out similarly to Example 1. The load deflection temperature (DTUL), tensile strength, bending strength, bending elastic modulus, and Izod strength were measured. Injection molding was performed under the molding conditions shown in Table 3 using an injection molding machine (Nex-15-1E, manufactured by Nissei Plastic Industry Co., Ltd.), and the flow length was measured in the same manner as in Example 1. Using an injection molding machine (manufactured by Nissei Plastic Co., Ltd., UH-1000-110), injection molding was performed under the molding conditions shown in Table 7, and the amount of warpage was measured in the same manner as in Example 1. The results are shown in Table 8.

Claims (8)

The total amount of (A) and (B) is 10 to 250 parts by weight of the following talc (A) and talc (B) with respect to 100 parts by weight of the liquid crystal polymer, and (A) / (B) Liquid crystal polymer composition formulated so that the weight ratio is 1/9 to 9/1:
(A) Talc with an average particle diameter of 5 to 100 μm (B) Talc with an average particle diameter of 0.1 to 5 μm.   Furthermore, the liquid crystal polymer composition of Claim 1 formed by mix | blending 10-100 weight part of glass fiber with respect to 100 weight part of liquid crystal polymer. The liquid crystal polymer composition according to claim 1 or 2, wherein the liquid crystal polymer is a liquid crystal polyester resin composed of repeating units of the formulas (I) to (IV).

[Wherein, Ar ₁ and Ar ₂ each represent a divalent aromatic group. ] The liquid crystal polymer composition according to claim 3, wherein Ar ₁ and Ar ₂ are one or more selected from the following aromatic groups (1) to (4).

Ar ₁ is an aromatic group represented by formula (1) and / or (4) according to claim 4, and Ar ₂ is represented by formula (1) and / or (3) according to claim 4. The liquid crystal polymer composition according to claim 4, which is an aromatic group.   6. The liquid crystal polymer composition according to claim 1, wherein (1) the liquid crystal polymer composition is obtained by molding the length 55.0 mm × width 9.0 mm × thickness 0.5 mm. The amount of warpage before and after the treatment when the initial warpage amount of the connector shape test piece is 0.1 mm or less and (2) the reflow treatment is performed on the test piece at 250 ° C. or higher for 20 to 30 seconds. The change amount of is 0.01 mm or less, A liquid crystal polymer composition,   A molded product obtained by molding the liquid crystal polymer composition according to claim 1.   The molded article according to claim 7, wherein the molded article is selected from the group consisting of a switch, a relay, a connector, a chip, an optical pickup, an inverter transformer, and a coil bobbin.