CN115725163A - Liquid crystalline polymer composition - Google Patents
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- CN115725163A CN115725163A CN202211047121.2A CN202211047121A CN115725163A CN 115725163 A CN115725163 A CN 115725163A CN 202211047121 A CN202211047121 A CN 202211047121A CN 115725163 A CN115725163 A CN 115725163A
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- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
The purpose of the present invention is to provide a liquid crystal polymer composition which can reduce the generation of particles during ultrasonic cleaning of a molded article and can suppress the generation of warpage in the molded article. The present invention relates to a liquid crystal polymer composition comprising 100 parts by mass of a liquid crystal polymer, 1 to 50 parts by mass of titanium oxide and 1 to 50 parts by mass of mica, wherein the ratio of the content (parts by mass) of titanium oxide to the content (parts by mass) of mica is 0.1 to 10.
Description
Technical Field
The present invention relates to a liquid crystal polymer composition which reduces the generation of particles (particles) during ultrasonic cleaning and suppresses the occurrence of warpage in a molded article.
Background
Liquid crystal polymers are excellent in mechanical properties, moldability, chemical resistance, gas barrier properties, moisture resistance, electrical properties, and the like, and therefore are used in parts in various fields. In particular, since they are excellent in heat resistance and thin-wall moldability, they have been widely used in electronic components such as precision instruments.
On the other hand, it is known that a molded article of a liquid crystal polymer is peeled off from the surface of a resin by ultrasonic cleaning or sliding with other members to cause a fluffing phenomenon (hereinafter, referred to as "fibrillation"). In the case of precision instruments, particularly such optical instruments having lenses, a small amount of dirt or dust can have an effect on the instrument performance. For example, in a component used in an optical apparatus such as a camera module, if fine dirt, oil, dust, or the like adheres to a lens, it becomes a cause of a significant decrease in optical characteristics of the camera module.
In order to prevent such a decrease in optical characteristics, components constituting the camera module (hereinafter, also referred to as "camera module components") such as a lens barrel portion, a mounting support portion, a frame of a CMOS (image sensor), a shutter, and a shutter release lever portion are generally subjected to ultrasonic cleaning before assembly to remove fine dirt, dust, and the like adhering to the surface.
However, a molded article made of the liquid crystal polymer composition is easily peeled from the surface of the molded article, and if ultrasonic cleaning is performed, fibrillation in which the surface is peeled off and fluffing is easily caused occurs. In addition, fine powder or dust (hereinafter, referred to as particles) made of the resin composition is easily generated from the fibrillated portion. In addition, even if the particles generated are extremely fine, they become foreign matter at the time of assembling the camera module or at the time of using the camera module, and there is a problem that the optical characteristics of the camera module are significantly degraded.
As a liquid crystal polymer composition in which generation of particles is suppressed, a resin composition in which a specific filler (talc, glass fiber, carbon black, or the like) or an olefin copolymer is contained in a liquid crystal polymer has been proposed (patent documents 1 to 6).
Documents of the prior art
Patent literature
Patent document 1: japanese patent No. 5826411;
patent document 2: japanese patent laid-open publication No. 2015-021110;
patent document 3: japanese patent laid-open publication No. 2015-000949;
patent document 4: japanese patent laid-open publication No. 2012-193270;
patent document 5: japanese patent laid-open publication No. 2009-242453;
patent document 6: japanese patent laid-open No. 2009-242456.
Disclosure of Invention
Problems to be solved by the invention
However, these inorganic fillers have poor wettability with the liquid crystal polymer, and the effect of suppressing the generation of particles during ultrasonic cleaning is insufficient. Further, there is a problem that the molded product is warped depending on the filler contained therein.
Therefore, there is a demand for a liquid crystal polymer composition which is reduced in the generation of particles during ultrasonic cleaning and is reduced in the generation of warpage in a molded article. The purpose of the present invention is to provide a liquid crystal polymer composition which can reduce the generation of particles during ultrasonic cleaning of a molded article and can suppress the generation of warpage in the molded article.
Means for solving the problems
In view of the above problems, the present inventors have conducted extensive studies and, as a result, have found that: the present inventors have found that by containing titanium oxide and mica in a specific ratio with respect to a liquid crystal polymer, the generation of particles is reduced and warpage is improved when a molded article of a liquid crystal polymer composition is subjected to ultrasonic cleaning, and have completed the present invention.
That is, the present invention includes the following preferable embodiments.
[1] A liquid crystal polymer composition comprising 100 parts by mass of a liquid crystal polymer, 1 to 50 parts by mass of titanium oxide and 1 to 50 parts by mass of mica, wherein the ratio of the content (parts by mass) of titanium oxide to the content (parts by mass) of mica is 0.1 to 10.
[2]According to [1]The liquid crystal polymer composition, wherein the titanium oxide has an average particle diameter of 0.5μm is less than or equal to m.
[3] The liquid crystal polymer composition according to [1] or [2], wherein the liquid crystal polymer is a liquid crystal polyester resin comprising repeating units represented by formula (I) and formula (II):
[ chemical formula 1]
[4] The liquid-crystalline polymer composition according to any one of [1] to [3], wherein the liquid-crystalline polymer is a wholly aromatic liquid-crystalline polyester resin composed of repeating units represented by formulae (I) to (IV):
[ chemical formula 2]
In the formula, ar 1 And Ar 2 Each represents a 2-valent aromatic group.
[5]According to [4]]The liquid crystal polymer composition wherein the repeating units represented by the formulae (III) to (IV) are Ar 1 And Ar 2 1 or more kinds of repeating units each independently selected from the aromatic groups represented by the formulae (1) to (4):
[ chemical formula 3]
[6]According to [4]]Or [ 5]]The liquid crystal polymer composition, wherein the repeating unit represented by the formula (III) is Ar 1 Is a repeating unit of an aromatic group represented by the formula (1) wherein the repeating unit represented by the formula (IV) is Ar 2 Is a repeating unit of an aromatic group represented by the formula (1) and/or Ar 2 Is a repeating unit of an aromatic group represented by the formula (3).
[7] The liquid-crystalline polymer composition according to any one of [1] to [6], which further comprises graphite.
[8] A molded article comprising the liquid crystal polymer composition according to any one of [1] to [7 ].
[9] The molded article according to item [8], which is a component constituting 1 type selected from a connector, a switch, a relay, a capacitor, a coil, a transformer, a camera module and an antenna.
Effects of the invention
The liquid crystal polymer composition of the present invention can reduce the generation of particles when a molded article is subjected to ultrasonic cleaning, and can suppress the generation of warpage in the molded article, and therefore, can be suitably used as a molding resin for parts requiring ultrasonic cleaning, particularly electronic parts.
Drawings
FIG. 1 is a schematic view showing a planar test piece prepared for measuring the amount of warpage.
Detailed Description
The liquid crystal polymer (hereinafter, also referred to as LCP) used in the liquid crystal polymer composition of the present invention is not particularly limited as long as it is a polyester or a polyesteramide forming an anisotropic melt phase, and is a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyesteramide in the technical field.
The properties of the anisotropic molten phase can be confirmed by a conventional polarized light inspection method using crossed polarizers. More specifically, confirmation of the anisotropic molten phase can be carried out by observing a sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. The liquid crystal polymer in the present invention is a liquid crystal polymer showing optical anisotropy, that is, a liquid crystal polymer which transmits light when an inspection is performed between crossed polarizers. If the sample is optically anisotropic, polarized light transmits even in a stationary state, for example.
Examples of the polymerizable monomer constituting the constituent unit of the liquid crystal polymer in the present invention include: aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic hydroxylamines, aromatic diamines, aliphatic diols and aliphatic dicarboxylic acids. Only 1 type of such polymerizable monomer may be used, or 2 or more types of polymerizable monomers may be used in combination. It is suitable to use at least 1 kind of polymerizable monomer having a hydroxyl group and a carboxyl group.
The polymerizable monomer constituting the constituent unit of the liquid crystal polymer may be an oligomer in which 1 or more of the above-mentioned compounds are bonded, that is, an oligomer composed of 1 or more of the above-mentioned compounds.
Specific examples of the aromatic hydroxycarboxylic acid include: 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4' -hydroxyphenyl-4-benzoic acid, 3' -hydroxyphenyl-4-benzoic acid, 4' -hydroxyphenyl-3-benzoic acid and their alkyl, alkoxy or halogen substituents, and their acyl compounds, ester derivatives, acyl halide and other ester forming derivatives. Among these, from the viewpoint of easy adjustment of the heat resistance, mechanical strength and melting point of the resulting liquid crystal polymer, 1 or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable.
Specific examples of the aromatic dicarboxylic acid include: terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4' -dicarboxybiphenyl, 3,4' -dicarboxybiphenyl and 4,4' -dicarboxybiphenyl, alkyl-, alkoxy-or halogen-substituted compounds thereof, and ester-forming derivatives such as ester derivatives and acid halides thereof. Among these, from the viewpoint of effectively improving the heat resistance of the resulting liquid crystal polymer, 1 or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2, 6-naphthalenedicarboxylic acid are preferable, and terephthalic acid and 2, 6-naphthalenedicarboxylic acid are more preferable.
As specific examples of the aromatic diol, there may be mentioned: ester-forming derivatives such as hydroquinone, resorcinol, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 3 '-dihydroxybiphenyl, 3,4' -dihydroxybiphenyl, 4 '-dihydroxybiphenyl ether, 2' -dihydroxybiphenyl, alkyl-, alkoxy-, or halogen-substituted compounds thereof, and acyl-substituted compounds thereof. Among these, from the viewpoint of excellent reactivity at the time of polymerization, 1 or more compounds selected from hydroquinone, resorcinol, 4 '-dihydroxybiphenyl and 2, 6-dihydroxynaphthalene are preferable, and 1 or more compounds selected from hydroquinone, 4' -dihydroxybiphenyl and 2, 6-dihydroxynaphthalene are more preferable.
Specific examples of the aromatic aminocarboxylic acid include: 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, alkyl, alkoxy or halogen substituted compounds thereof, and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof.
As specific examples of the aromatic hydroxylamine, there can be mentioned: ester-forming derivatives such as 4-aminophenol, N-methyl-4-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino-4 '-hydroxybiphenyl ether, 4-amino-4' -hydroxybiphenyl methane, 4-amino-4 '-hydroxybiphenyl sulfide, and 2,2' -diaminobinaphthyl, alkyl, alkoxy, or halogen substituents thereof, and acyl compounds thereof. Among these, from the viewpoint of easily obtaining a balance between the heat resistance and mechanical strength of the resulting liquid crystal polymer, 4-aminophenol is preferred.
As specific examples of the aromatic diamine, there may be mentioned: amide-forming derivatives such as 1, 4-phenylenediamine, 1, 3-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, alkyl-, alkoxy-, or halogen-substituted compounds thereof, and acyl-substituted compounds thereof.
As specific examples of the aliphatic diols, there may be mentioned: ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and acylates thereof. Further, an aliphatic diol-containing polymer such as polyethylene terephthalate or polybutylene terephthalate may be reacted with the above-mentioned aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and an acyl compound, ester derivative, acid halide compound, or the like thereof.
As specific examples of the aliphatic dicarboxylic acid, there may be mentioned: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid and hexahydroterephthalic acid. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid are preferable from the viewpoint of excellent reactivity at the time of polymerization.
The polymerizable monomer forming the constituent unit of the liquid crystal polymer in the present invention may contain, as other copolymerizable component, dihydroxyterephthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, 1,3, 5-benzenetricarboxylic acid, pyromellitic acid, or an alkyl-, alkoxy-, or halogen-substituted compound thereof, or an ester-forming derivative thereof such as an acyl compound, an ester derivative, or an acid halide thereof, as long as the object of the present invention is not impaired. The amount of the polymerizable monomer used is preferably, for example, 10 mol% or less based on the total constituent units constituting the liquid crystal polymer.
In the present invention, the liquid crystal polymer may be a polymer containing a thioester bond within a range not prejudicial to the object of the present invention. Examples of the polymerizable monomer to which such a bond is imparted include: mercapto aromatic carboxylic acids, aromatic dithiols and hydroxy aromatic thiols, and the like. The content of these polymerizable monomers is preferably 10 mol% or less with respect to the total constituent units constituting the liquid crystal polymer.
The polymer obtained by combining these repeating units has a polymer forming an anisotropic melt phase and a polymer not forming an anisotropic melt phase depending on the constitution or composition ratio of the monomers and the sequence distribution of the repeating units in the polymer, but the liquid crystal polymer used in the present invention is limited to the polymer forming an anisotropic melt phase.
As the liquid crystal polymer used in the present invention, a liquid crystal polyester resin containing repeating units represented by the formulae (I) and (II):
[ chemical formula 4]
Further, as the liquid crystal polymer used in the present invention, a wholly aromatic liquid crystalline polyester resin composed of repeating units represented by formulae (I) to (IV):
[ chemical formula 5]
In the formula, ar 1 And Ar 2 Each represents a 2-valent aromatic group.
Here, each of the formula (III) and the formula (IV) may contain Ar in plural kinds 1 And Ar 2 . That is, the repeating unit represented by the formula (III) may be Ar 1 And Ar as the other species 1 The repeating unit represented by the formula (IV) may be Ar as a certain kind of repeating unit 2 And Ar as the other species 2 And the like. Further, "aromatic group" means an aromatic group which is a 6-membered single ring or a condensed ring having 2 rings.
The repeating units represented by the formulae (III) to (IV) are more preferably Ar in terms of excellent flowability and mechanical properties 1 And Ar 2 Each independently selected from 1 or more kinds of repeating units of aromatic groups represented by the following formulae (1) to (4). It is particularly preferable that the repeating unit represented by the formula (III) is Ar 1 Is a repeating unit of an aromatic group represented by the formula (1) and the repeating unit represented by the formula (IV) is Ar 2 A repeating unit which is an aromatic group represented by the formula (1) and/or the formula (3):
[ chemical formula 6]
Specific examples of the combination of polymerizable monomers forming the constituent unit of the liquid crystal polymer used in the present invention include the following combinations.
1) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid;
2) 4-hydroxybenzoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl;
3) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4, 4' -dihydroxybiphenyl;
4) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4, 4' -dihydroxybiphenyl/hydroquinone;
5) 4-hydroxybenzoic acid/terephthalic acid/hydroquinone;
6) 6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone;
7) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl;
8) 6-hydroxy-2-naphthoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl;
9) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone;
10 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone/4, 4' -dihydroxybiphenyl;
11 4-hydroxybenzoic acid/2, 6-naphthalenedicarboxylic acid/4, 4' -dihydroxybiphenyl;
12 4-hydroxybenzoic acid/terephthalic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone;
13 4-hydroxybenzoic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone;
14 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone;
15 4-hydroxybenzoic acid/terephthalic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone/4, 4' -dihydroxybiphenyl;
16 4-hydroxybenzoic acid/terephthalic acid/4-aminophenol;
17 6-hydroxy-2-naphthoic acid/terephthalic acid/4-aminophenol;
18 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4-aminophenol;
19 4-hydroxybenzoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl/4-aminophenol;
20 4-hydroxybenzoic acid/terephthalic acid/ethylene glycol;
21 4-hydroxybenzoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl/ethylene glycol;
22 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/ethylene glycol;
23 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl/ethylene glycol;
24 4-hydroxybenzoic acid/terephthalic acid/2, 6-naphthalenedicarboxylic acid/4, 4' -dihydroxybiphenyl.
Among these, liquid crystal polymers composed of constituent units derived from polymerizable monomers of 1), 9), 10) and 14) are preferable, liquid crystal polymers composed of constituent units derived from polymerizable monomers of 9), 10) and 14) are more preferable, and liquid crystal polymers composed of constituent units derived from polymerizable monomers of 9) are particularly preferable from the viewpoint of further reducing the generation of particles and the occurrence of warpage in molded articles.
The liquid crystal polymer may be used alone, or may be used as a mixture of 2 or more liquid crystal polymers.
One of preferable embodiments of the liquid crystal polymer used in the present invention is a wholly aromatic liquid crystalline polyester resin comprising repeating units represented by the following formulae (a) to (D):
[ chemical formula 7]
Wherein p, q, r and s represent the composition ratio (mol%) of each repeating unit in the liquid-crystalline polyester resin, and satisfy the following conditions:
0.1≤q/(p+q)≤0.9；
8≤q≤34；
r is more than or equal to 10 and less than or equal to 25; and
10≤s≤25。
hereinafter, a method for producing a liquid crystal polymer used in the present invention will be described.
The method for producing the liquid crystal polymer used in the present invention is not particularly limited, and the liquid crystal polymer can be obtained by subjecting a polymerizable monomer to a known polycondensation method for forming an ester bond or an amide bond, for example, a melt acidolysis method, a slurry polymerization method, or the like.
The molten acid hydrolysis method is a preferred method for producing the liquid crystal polymer used in the liquid crystal polymer composition of the present invention. The method comprises the following steps: the polymerizable monomer is initially heated to form a molten solution of the reaction mass, and then the polycondensation reaction is continued to obtain a molten polymer. Vacuum may be applied to easily remove volatile substances (e.g., acetic acid, water, etc.) by-produced at the final stage of condensation.
The slurry polymerization method refers to a method of reacting polymerizable monomers in the presence of a heat exchange fluid, and a solid product is obtained in a state of being suspended in a heat exchange medium.
In the case of either the molten acid hydrolysis method or the slurry polymerization method, the polymerizable monomer used in the production of the liquid crystal polymer may be reacted as a modified form (lower acyl group) in which a hydroxyl group and/or an amino group is acylated at ordinary temperature, that is, a lower acylated compound.
The lower acyl group is preferably an acyl group having 2 to 5 carbon atoms, and more preferably an acyl group having 2 or 3 carbon atoms. In a preferred embodiment of the present invention, an acetylate of the above polymerizable monomer is supplied to the reaction.
The lower acyl compound of the polymerizable monomer may be an acyl compound synthesized in advance by acylation separately, or may be produced in a reaction system by adding an acylating agent such as acetic anhydride to the polymerizable monomer in the production of the liquid crystal polymer.
In the case of either the melt acidolysis method or the slurry polymerization method, the polycondensation reaction can be carried out at a temperature of usually 150 to 400 ℃, preferably 250 to 370 ℃, under normal pressure and/or reduced pressure, and a catalyst can be used as necessary.
Specific examples of the catalyst include: organic tin compounds (dialkyltin oxides such as dibutyltin oxide, diaryltin oxide, etc.), titanium dioxide, antimony trioxide, organic titanium compounds (titanium alkoxysilicate, titanium alkoxide, etc.), alkali and alkaline earth metal salts of carboxylic acids (potassium acetate, sodium acetate, etc.), lewis acids (BF) 3 Etc.), a gaseous acid catalyst such as hydrogen halide (HCl, etc.), etc.
When a catalyst is used, the amount of the catalyst is preferably 1 to 1000ppm, more preferably 2 to 100ppm, based on the total amount of the polymerizable monomers.
The liquid crystal polymer obtained by such a polycondensation reaction is usually taken out from a polymerization reaction tank in a molten state, and then processed into pellets, chips or powder, and subjected to melt kneading with other components.
The granular, flaky or powdery liquid crystalline polyester may be subjected to heat treatment in a substantially solid phase state under reduced pressure, under vacuum or in an atmosphere of nitrogen or helium as an inert gas in order to increase the molecular weight and improve the heat resistance.
The liquid crystal polymer composition of the present invention contains titanium oxide and mica in addition to the above liquid crystal polymer.
The crystal structure of the titanium oxide used in the present invention is not particularly limited, and one or more selected from rutile type, anatase type, and brucite type can be used. Among them, rutile type and anatase type are preferable in terms of being excellent in the effect of reducing the generation of particles at the time of ultrasonic washing. In addition, in order to obtain good dispersion in the resin, the resin may be doped with other metal oxides such as magnesium and calcium.
The titanium oxide used in the present invention may be used after the surface thereof is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc.) or another surface treatment agent.
The average particle diameter of titanium oxide is preferably 0.5μm is less than or equal to, more preferably 0.03 to 0.48μm is more preferably 0.05 to 0.26μm is particularly preferably from 0.07 to 0.25μm, most preferably 0.08 to 0.20μm。
When the average particle diameter of titanium oxide exceeds 0.5μm, it tends to be difficult to reduce the generation of particles.
In the present specification and claims, "average particle diameter" means a volume-based cumulative 50% particle diameter of particles that can be determined by a laser diffraction scattering method. That is, the particle size distribution was measured by a laser diffraction scattering method, and a cumulative curve was obtained with the total volume of the particle groups as 100%, and the cumulative curve was the particle size of a point at which the cumulative volume was 50%.
The content of titanium oxide in the liquid crystal polymer composition of the present invention is 1 to 50 parts by mass, preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass, relative to 100 parts by mass of the liquid crystal polymer. When the content of titanium oxide is less than 1 part by mass, the effect of suppressing the generation of particles is insufficient, and when it exceeds 50 parts by mass, the fluidity becomes insufficient, and the abrasion of the cylinder or the die of the molding machine increases.
Mica used in the present invention is a ground product of a silicate mineral containing hydrous potassium aluminum silicate as a main component and containing magnesium, sodium, iron, etc. in addition to aluminum and potassium, and examples thereof include: muscovite, phlogopite, biotite, and synthetic mica. Among these, muscovite is preferable in terms of good hue and easy acquisition.
The mica used in the present invention may be surface-treated with a silane coupling agent or the like, or granulated with a binder to be granulated.
The mica used in the present invention preferably has an average particle diameter of 5 to 100μm mica, more preferably 10 to 80μmica of m, particularly preferably 20 to 60μm mica. The average particle diameter of mica means a cumulative 50% particle diameter on a volume basis of particles which can be determined by a laser diffraction scattering method.
The content of mica in the liquid crystal polymer composition of the present invention is 1 to 50 parts by mass, preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass, relative to 100 parts by mass of the liquid crystal polymer. If the content of mica is less than 1 part by mass, the effect of suppressing the generation of particles is insufficient, and if it exceeds 50 parts by mass, the fluidity becomes insufficient.
The content ratio of titanium oxide to mica (part by mass of titanium oxide/part by mass of mica) in the liquid crystal polymer composition of the present invention is 0.1 to 10, preferably 0.2 to 5, more preferably 0.3 to 3.5, further preferably 0.4 to 2.5, and particularly preferably 0.5 to 2.
When the content ratio of titanium oxide and mica is less than 0.1, the effect of suppressing the generation of particles cannot be obtained, and when the content ratio of titanium oxide and mica exceeds 10, the effect of improving warpage cannot be obtained.
The liquid crystal polymer composition of the present invention may further contain graphite in order to further suppress the occurrence of warpage in a molded article. The graphite used in the present invention may be natural graphite or artificial graphite, and 2 or more kinds thereof may be used in combination. Graphite having a high fixed carbon content, a low ash content such as silicon oxide, and a high crystallinity is preferable.
The average particle diameter of the graphite is usually 5 to 100μm is preferably 5 to 80μm is more preferably 5 to 60μAnd m is selected. The average particle diameter of graphite means a volume-based cumulative 50% particle diameter of particles which can be determined by a laser diffraction scattering method.
When graphite is contained, the content is 0.1 to 20 parts by mass, preferably 1 to 17 parts by mass, more preferably 3 to 15 parts by mass, and particularly preferably 5 to 10 parts by mass, based on 100 parts by mass of the liquid crystal polymer. If the content of graphite is less than 0.1 part by mass, it is difficult to obtain a further improvement effect of warpage, and if the content of graphite exceeds 20 parts by mass, fluidity tends to become insufficient.
The liquid crystal polymer composition of the present invention may further contain a higher fatty acid ester and/or a higher fatty acid metal salt.
The content of the higher fatty acid ester and/or the higher fatty acid metal salt is 0.01 to 1.3 parts by mass, preferably 0.03 to 1.2 parts by mass, and more preferably 0.05 to 1.0 part by mass. If the content of the higher fatty acid ester is not less than the lower limit, the occurrence of swelling (bulging) can be further suppressed, and if the content of the higher fatty acid ester is not more than the upper limit, blistering (blistering) is more difficult to occur. If the content of the higher fatty acid ester and/or the higher fatty acid metal salt is less than 0.01 parts by mass, swelling tends to occur, and if it exceeds 1.3 parts by mass, foaming tends to occur.
The higher fatty acid to be a raw material of the higher fatty acid ester and/or the higher fatty acid metal salt used in the present invention is preferably a higher fatty acid having 10 or more carbon atoms. Examples of such higher fatty acids include: capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, montanic acid, and the like. Among them, stearic acid and montanic acid are preferable.
Examples of the alcohol to be a raw material of the ester include: stearyl alcohol, behenyl alcohol, glycerin, sorbitan, propylene glycol, pentaerythritol, polyoxyethylene bisphenol a, and the like.
Further, as the metal constituting the metal salt, there can be mentioned: alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as magnesium, calcium and barium; or zinc, etc., and alkaline earth metals are particularly preferably used. Specific examples of the higher fatty acid metal salt include: calcium stearate, barium stearate, zinc stearate, magnesium stearate, sodium montanate, calcium montanate, magnesium montanate, potassium montanate, lithium montanate, zinc montanate, barium montanate, aluminum montanate, calcium palmitate, magnesium palmitate, and barium palmitate, and the like. Among these, calcium stearate and calcium montanate are preferably used in terms of cost and maintenance of physical properties of molded articles.
The higher fatty acid ester and/or higher fatty acid metal salt used in the present invention is preferably in the form of powder or granules for easy mixing with the liquid crystal polyester resin composition.
The liquid crystal polymer composition of the present invention may contain other resin components within a range not to impair the object of the present invention. Examples of the other resin components include: polyamide, polyester, polyacetal, polyphenylene ether and modified products thereof, polysulfone, polyethersulfone, polyetherimide, polyamideimide and other thermoplastic resins, or phenolic resin, epoxy resin, polyimide resin and other thermosetting resins.
The other resin components may be contained singly or in combination of 2 or more. The content of the other resin component is not particularly limited as long as it is appropriately determined according to the use or purpose of the liquid crystal polymer composition. Typically, the total content of the other resins is preferably in the range of 0.1 to 100 parts by mass, more preferably 0.2 to 80 parts by mass, per 100 parts by mass of the liquid crystal polymer.
The liquid crystal polymer composition of the present invention may contain other fibrous, plate-like or granular inorganic fillers or organic fillers within a range not impairing the effects of the present invention.
When the liquid crystal polymer composition of the present invention contains another fibrous, plate-like, or granular inorganic filler or organic filler, the content thereof is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less, based on 100 parts by mass of the liquid crystal polyester. If the content of these other fillers exceeds the above upper limit, moldability tends to be lowered or thermal stability tends to be deteriorated.
Examples of other fibrous fillers include: milled glass (Milled glass), silica alumina fiber, carbon fiber, aramid fiber, polyarylate fiber, polybenzimidazole fiber, potassium titanate whisker, aluminum borate whisker and the like, and these may be used alone or in combination of 2 or more.
Examples of other plate-like fillers include: silicates such as kaolin, clay, vermiculite, feldspar powder, acid clay, agalmatolite clay, sericite, sillimanite, bentonite, glass flakes, slate flour, and silane; carbonates such as calcium carbonate, calcium carbonate (lead powder), barium carbonate, magnesium carbonate, and dolomite; sulfates such as barite powder, precipitated calcium sulfate, plaster of paris, and barium sulfate; hydroxides such as hydrated alumina; oxides such as alumina, antimony oxide, magnesium oxide, zinc white, silica sand, quartz, white carbon, and diatomaceous earth; sulfides such as molybdenum disulfide; tabular wollastonite and the like may be used alone or in combination of 2 or more.
Examples of other particulate fillers include: calcium carbonate, glass beads, barium sulfate, etc., and these may be used alone or in combination of 2 or more.
The liquid crystal polymer composition of the present invention may contain other additives than the above-described additives within a range not impairing the effects of the present invention.
Examples of other additives include: silicone, fluorine resin, etc. as a mold release modifier, dyes, pigments, carbon black, etc. as a colorant, flame retardants, antistatic agents, surfactants, phosphorus antioxidants, phenol antioxidants, sulfur antioxidants, etc. as antioxidants, weather resistance agents, heat stabilizers, neutralizing agents, etc. These additives may be used alone or in combination of 2 or more.
The content of the other additive is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the liquid crystal polymer. If the content of the other additive exceeds the upper limit, moldability tends to be lowered or thermal stability tends to be deteriorated.
The liquid crystal polymer composition of the present invention can be produced by blending a liquid crystal polymer, titanium oxide, mica, and, if necessary, graphite, a higher fatty acid ester or a higher fatty acid metal salt, other resin components, other fibrous, plate-like or granular inorganic or organic fillers, other additives, etc. in a predetermined composition and melt-kneading them by using a banbury mixer, a kneader, a single-screw or twin-screw extruder, etc.
The liquid crystal polymer composition of the present invention obtained in this manner can be molded or processed by a known molding method using an injection molding machine, an extruder, or the like to obtain a desired molded article.
A molded article made of a liquid crystal polymer composition is generally easy to peel off from its surface, and when ultrasonic cleaning is performed, fibrillation in which the surface is peeled off and fluffs is easily generated, and fine powder or dust (hereinafter referred to as "particles") made of a resin composition is easily generated from the fibrillated part.
According to the liquid crystal polymer composition of the present invention, since the generation of particles is suppressed, the molded article thereof does not become foreign matter during the assembly and use of an optical member such as a camera module, and excellent optical characteristics can be obtained.
In addition, the liquid crystalline polymer composition of the present invention shows a very small amount of warpage. The warpage amount can be measured by the warpage amount measuring method described below.
< definition of warpage amount and measuring method >
In the present specification, the "warpage amount" refers to a value obtained by molding a flat test piece (thickness 0.5mm, longitudinal and transverse length 17mm, width 3mm of central slit-shaped step difference, and thickness 0.25 mm) having a slit-shaped step difference in the central portion thereof by using an injection molding machine (for example, NEX15-1E manufactured by seiki resin co., ltd.) under the conditions described below, and subtracting the thickness (0.5 mm) of the test piece from the maximum warpage height by using a three-dimensional measuring instrument (for example, one Shot 3D VR-3000 manufactured by Keyence corporation).
Thus, the molded article comprising the liquid crystal polymer composition of the present invention can reduce the generation of particles during ultrasonic cleaning and suppress the generation of warpage in the molded article, and therefore, is suitably used for electronic components such as connectors, switches, relays, capacitors, coils, transformers, camera modules, antennas, and the like. Particularly for use in a camera module.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. The melt viscosity, tensile strength, flexural strength, number of generated particles, and amount of warpage in the examples were measured by the following methods.
< melt viscosity >
Using a melt viscosity measuring apparatus (Capillograp 1D manufactured by Toyo Seiki Seisaku-sho Co., ltd.), a capillary of 1.0mm 9811x 10mm was used, and the shear rate was 1000 seconds -1 Respectively, the melt viscosity of the sample at a temperature of crystal melting temperature (Tm) +20 ℃.
< tensile Strength >
An ASTM No. 4 dumbbell test piece was produced by injection molding using an injection molding machine (UH 1000-110 manufactured by Nichisu resin industries, ltd.) at a cylinder temperature of 350 ℃ and a mold temperature of 70 ℃. The measurement was carried out in accordance with ASTM D638 using INSTRON5567 (Universal testing machine manufactured by Instron Japan Company Limited).
< flexural Strength >
The same test piece as used for the measurement of deflection temperature under load was used, and the measurement was carried out in accordance with ASTM D790.
< number of particle generation >
The same test piece as the test piece used for measuring the deflection temperature under load was placed in a cylindrical glass container having an outer diameter of 50mm, an inner diameter of 45mm and a height of 100mm and containing 50mL of pure water, the gate portion was not immersed in water, and the cylindrical glass container was placed in an ultrasonic cleaning tank (US-102 manufactured by SND) having a length of 140mm, a width of 240mm and a depth of 100mm and containing 1000mL of water. After ultrasonic washing was performed at 38kHz and 100W for 10 minutes, the particle size 2 in 1mL of pure water was measured by a particle counter (LiQuilaz-05 manufactured by Spectris corporation)μm or more particles [ falling matter (particles) peeled off from test piece)]Counting 3 times, taking the measured average value as the measurement result, less than 500 are recorded as "good", more than 500 are recorded as "good", less than 1000 are recorded as "delta", more than 1000 are recorded as "good"Note as "x".
< amount of warpage >
A flat test piece (thickness 0.5mm, longitudinal and transverse lengths 17mm, width 3mm of the central slit-like step, and thickness 0.25 mm) having a slit-like step in the central portion shown in FIG. 1 was molded using an injection molding machine (NEX 15-1E, manufactured by Hitachi resin Co., ltd.) under the conditions described in Table 1. The test piece was left to stand at 23 ℃ and a relative humidity of 50% for 24 hours, and then the thickness (0.5 mm) of the test piece was subtracted from the maximum warpage height using a three-dimensional measuring instrument (One Shot 3D VR-3000 manufactured by Keyence corporation), and the obtained value was used as the warpage amount.
[ Table 1]
| Forming machine | NEX-15-1E manufactured by NITAMIN RESIN INDUSTRIAL CO., LTD |
| Barrel temperature | 350-350-310-280 (℃) |
| Temperature of the mold | 80 (℃) |
| Speed of injection moulding | 50 mm/sec |
| Pressure maintaining device | 30MPa |
| Time of injection molding | 3 seconds |
| Cooling time | 2 seconds |
| Screw rotation speed | 150rpm |
| Screw back pressure | 0.5MPa |
Synthesis example 1 (Synthesis of liquid Crystal Polymer)
A reaction vessel equipped with a stirrer equipped with a torquemeter and a distillation tube was charged with 431g (48 mol%) of p-hydroxybenzoic acid, 196g (16 mol%) of 6-hydroxy-2-naphthoic acid, 194g (18 mol%) of terephthalic acid and 129g (18 mol%) of hydroquinone to a total amount of 6.5 mol, and acetic anhydride was charged in an amount of 1.03 mol per mol of hydroxyl groups in the total monomers to conduct the deacetylation polymerization under the following conditions.
The temperature was raised from room temperature to 150 ℃ over 1 hour under a nitrogen atmosphere, and the temperature was maintained at this temperature for 30 minutes. Then, the temperature was raised to 350 ℃ over 7 hours while by-produced acetic acid was distilled off, and then the pressure was reduced to 5mmHg over 80 minutes. The polymerization reaction was terminated at a time point when a predetermined torque was exhibited, the contents of the reaction vessel were taken out, and particles of the liquid crystal polymer were obtained by a pulverizer. The amount of distilled acetic acid during polymerization was almost the same as the theoretical value.
The filler used in the following examples and comparative examples is given.
Titanium oxide 1: "A-100" (average particle diameter: 0.15) manufactured by Shiyu industries Ltdμm)；
Titanium oxide 2: "TIO20PB" (average particle diameter: 0.5) manufactured by high purity chemical researchμm)；
Mica: "AB-25S" manufactured by Yamaguchi-Mica;
talc: "RL119" manufactured by Fuji Talc;
graphite: "PC-30" made of Ito graphite;
higher fatty acid ester: licowax E flakes from Clariant Japan.
Examples 1 to 7 and comparative examples 1 to 5
LCP synthesized in example 1, titanium oxide, mica, talc, graphite and a higher fatty acid ester were blended and mixed so as to have the contents (parts by mass) shown in Table 2, and the resulting mixture was melt-kneaded at 350 ℃ using a twin-screw extruder (TEX-30 manufactured by Japan Steel works, ltd.) to obtain pellets of a liquid crystal polymer composition. The melt viscosity, tensile strength, flexural strength, number of generation of particles and amount of warpage were measured by the above-mentioned methods. The results are shown in Table 2.
As shown in Table 2, the liquid crystal polymer compositions of examples 1 to 7 each had a particle size of 2μThe number of particles having a particle size of m or more is less than 1000, and the amount of warpage is small.
On the other hand, the liquid crystal polymer compositions of comparative examples 1 to 5 are not preferable results in terms of at least one of generation of particles and an amount of warpage.
Claims (9)
1. A liquid crystal polymer composition comprising 100 parts by mass of a liquid crystal polymer, 1 to 50 parts by mass of titanium oxide and 1 to 50 parts by mass of mica, wherein the ratio of the content (parts by mass) of titanium oxide to the content (parts by mass) of mica is 0.1 to 10.
2. The liquid crystalline polymer composition according to claim 1, wherein the titanium oxide has an average particle diameter of 0.5μm is less than or equal to m.
3. The liquid-crystalline polymer composition according to claim 1 or 2, wherein the liquid-crystalline polymer is a liquid-crystalline polyester resin comprising repeating units represented by formulae (I) and (II):
[ chemical formula 8]
4. The liquid-crystalline polymer composition according to any one of claims 1 to 3, wherein the liquid-crystalline polymer is a wholly aromatic liquid-crystalline polyester resin composed of repeating units represented by formulae (I) to (IV):
[ chemical formula 9]
In the formula, ar 1 And Ar 2 Each represents a 2-valent aromatic group.
5. The liquid-crystalline polymer composition according to claim 4, wherein the repeating units represented by the formulae (III) to (IV) are Ar 1 And Ar 2 Each independently selected from 1 or more kinds of repeating units of the aromatic groups represented by the formulae (1) to (4):
[ chemical formula 10]
6. The liquid-crystalline polymer composition according to claim 4 or 5, wherein the repeating unit represented by formula (III) is Ar 1 Is a repeating unit of an aromatic group represented by the formula (1) wherein the repeating unit represented by the formula (IV) is Ar 2 Is a repeating unit of an aromatic group represented by the formula (1) and/or Ar 2 Is a repeating unit of an aromatic group represented by the formula (3).
7. A liquid crystalline polymer composition according to any one of claims 1 to 6 further comprising graphite.
8. A molded article comprising the liquid crystal polymer composition according to any one of claims 1 to 7.
9. The molded article according to claim 8, which is a component constituting 1 kind selected from a connector, a switch, a relay, a capacitor, a coil, a transformer, a camera module and an antenna.
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| JP5325442B2 (en) | 2008-03-28 | 2013-10-23 | Ｊｘ日鉱日石エネルギー株式会社 | Liquid crystalline polyester resin composition for camera modules |
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