JP6679283B2 - Cleaning member and ultrasonic cleaning machine including the cleaning member - Google Patents

Description

  The present invention relates to a cleaning member used for ultrasonic cleaning and an ultrasonic cleaning machine including the cleaning member.

  Ultrasonic cleaning is a cleaning method that removes dirt adhering to the object to be cleaned (object to be cleaned) by the action of ultrasonic waves, and there is little cleaning unevenness regardless of the shape of the object, and precision cleaning is possible. It is widely used for cleaning industrial products, general products, and electric and electronic parts such as semiconductors.

  The ultrasonic cleaning is usually performed by a cleaning container, an ultrasonic vibrator including a piezoelectric element provided on the outer wall surface of the cleaning container, and an ultrasonic oscillator that drives the ultrasonic vibrator. The object to be cleaned is put into a cleaning container containing the cleaning liquid, and ultrasonic waves are applied.

  During cleaning, when a modulation voltage with a frequency corresponding to the natural frequency of the ultrasonic vibrator is applied by the ultrasonic oscillator, the ultrasonic vibrator vibrates at the natural frequency and ultrasonic vibrations occur in the cleaning liquid contained in the cleaning container. Is propagated, the object to be cleaned is cleaned.

Ultrasonic cleaning is generally considered to be performed by the following three actions.
(1) Cavitation When ultrasonic waves are applied to the cleaning liquid, depressurizing force and pressure are repeatedly applied to the cleaning liquid due to ultrasonic vibration. Due to this decompression force, bubbles are generated in the cleaning liquid (cavitation). The shock wave generated when the bubbles disappear due to the pressing force removes the dirt adhering to the object to be cleaned.
(2) Acceleration When ultrasonic waves are applied to the cleaning liquid, the cleaning liquid vibrates due to ultrasonic vibration. Due to the acceleration force of the vibration of the cleaning liquid, the dirt adhering to the object to be cleaned is removed. The higher the frequency of the ultrasonic waves applied to the cleaning liquid, the stronger the cleaning power due to acceleration.
(3) Straight flow When ultrasonic waves are applied to the cleaning liquid, the cleaning liquid flows in the direction in which the ultrasonic waves propagate. By this flow of the cleaning liquid, the cleaning liquid near the surface of the article is agitated, and the dirt adhering to the object to be cleaned is removed.

  In such ultrasonic cleaning, it is required to equalize the sound pressure of the ultrasonic waves transmitted to the cleaning liquid in order to reduce uneven cleaning, but on the other hand, in order to reduce the output and increase the frequency, it is necessary to use an efficient ultrasonic wave. Sound wave propagation is desired.

  In the case of ultrasonic cleaning, cleaning members such as a cleaning container and a diaphragm have been conventionally made of metal such as stainless steel or glass (Patent Document 1 and Patent Document 2), and recently, they are lightweight and difficult to break. Resin products are also used because they are easy to handle.

JP, 9-1094, A JP, 2010-125372, A

  However, in a cleaning container made of metal such as stainless steel or a cleaning member made of glass, the sound pressure of ultrasonic waves transmitted to the cleaning liquid may become non-uniform, resulting in uneven cleaning. Further, although a non-uniform sound pressure is somewhat alleviated in a cleaning member made of a resin such as polyethylene or polypropylene, ultrasonic wave propagation efficiency may be reduced and cleaning may be insufficient.

  Therefore, an object of the present invention is to provide a cleaning member capable of suppressing uneven cleaning and insufficient cleaning during ultrasonic cleaning.

  The present inventors, as a result of diligent examination of the cleaning member constituting the ultrasonic cleaner, found that the cleaning effect is improved by configuring the cleaning member such as the cleaning container and the diaphragm with a liquid crystal polymer, The present invention has been completed.

  That is, the present invention provides a cleaning member used for ultrasonic cleaning, which is composed of a liquid crystal polymer.

  According to the ultrasonic cleaning machine provided with the cleaning member of the present invention, uneven cleaning and insufficient cleaning can be suppressed.

It is a schematic sectional drawing explaining the 1st embodiment of the ultrasonic cleaning machine provided with the cleaning member of the present invention. It is a schematic sectional drawing explaining the 2nd embodiment of the ultrasonic cleaning machine provided with the cleaning member of this invention. It is a schematic sectional drawing explaining the 3rd embodiment of the ultrasonic cleaning machine provided with the cleaning member of this invention.

  The cleaning member of the present invention is composed of a liquid crystal polymer. The cleaning member of the present invention is used for ultrasonic cleaning, that is, it can be used as a member constituting an ultrasonic cleaning machine. Hereinafter, examples of the ultrasonic cleaning machine provided with the cleaning member of the present invention (hereinafter, also referred to as “the ultrasonic cleaning machine of the present invention”) will be described, but the configuration of the ultrasonic cleaning machine of the present invention is limited to these. It is not intended to be.

  FIG. 1 shows a first embodiment of an ultrasonic cleaning machine equipped with the cleaning member of the present invention. The ultrasonic cleaning machine 1 mainly includes a cleaning container 2, an ultrasonic oscillator 3 attached to the bottom surface of the cleaning container 2, and an ultrasonic oscillator 4 that drives the ultrasonic oscillator 3. The ultrasonic oscillator 3 may be attached to the side surface of the cleaning container 2.

  At the time of cleaning, the object 6 to be cleaned is put into the cleaning container 2 containing the cleaning liquid 5, and the ultrasonic oscillator 3 vibrates the ultrasonic vibrator 3 to generate ultrasonic vibration. The ultrasonic vibration generated from the ultrasonic vibrator 3 is transmitted to the cleaning liquid 5 in the cleaning container 2 and the object 6 to be cleaned is cleaned. The shape of the ultrasonic transducer 3 is not particularly limited, but a piezoelectric piezoelectric element is preferably used and is fixed to the cleaning container 2 by bolting or an adhesive.

  As the cleaning liquid 5, water, an organic solvent, a mixed solvent of water and an organic solvent, an acidic solution, an alkaline solution, or the like is preferably used depending on the type of dirt attached to the article. A cleaning component such as a surfactant may be added to the cleaning liquid 5 in order to further improve the cleaning power.

  In the first embodiment of the present invention, the cleaning container 2, which is one of the cleaning members, is made of a liquid crystal polymer. The shape of the cleaning container 2 is not particularly limited as long as it is an open-type or closed-type container capable of containing a cleaning liquid and an object to be cleaned. A cup-shaped, bottle-shaped or tube-shaped material is appropriately used.

  By configuring the cleaning container 2 with a liquid crystal polymer, the ultrasonic vibration generated from the ultrasonic vibrator 3 is transmitted to the cleaning liquid with a uniform sound pressure, and the propagation efficiency is improved. Can be suppressed. Therefore, the precise cleaning of the object to be cleaned can be performed efficiently in a short time.

  Further, since the liquid crystal polymer has excellent chemical resistance, even when an organic solvent, an acidic solution or an alkaline solution is used as a cleaning liquid, it can be stably used without being corroded.

  The frequency of the ultrasonic waves applied in the present invention may be any frequency range from low frequency to high frequency, but from the viewpoint of improving cleaning power and suppressing cleaning unevenness, preferably 20 kHz to 5 MHz, more preferably 50 kHz. -4 MHz, more preferably 100 kHz-3 MHz.

  FIG. 2 shows a second embodiment of the ultrasonic cleaning machine provided with the cleaning member of the present invention. In the second embodiment, the vibrating plate 7 is attached inside the cleaning container 2, the ultrasonic vibration generated from the ultrasonic vibrator 3 is transmitted to the cleaning liquid 5 through the vibrating plate 7, and the cleaning target 6 is cleaned. To be done.

  In the second embodiment of the present invention, the diaphragm 7, which is one of the cleaning members, is made of liquid crystal polymer. The shape of the vibrating plate 7 is not particularly limited, but a plate-shaped, rod-shaped, net-shaped or block-shaped one is appropriately used depending on the shape of the cleaning container, the shape of the object to be cleaned and the purpose of cleaning. The vibration plate 7 may be fixed to the bottom surface or the side surface of the cleaning container 2 by bolting or an adhesive agent, or may be mounted on the bottom surface of the cleaning container 2 without being fixed.

  By configuring the vibrating plate 7 with a liquid crystal polymer, the same effect as that of the first embodiment can be obtained. As shown in the second embodiment of the present invention, when the vibrating plate 7 is made of a liquid crystal polymer, the cleaning container 2 does not necessarily have to be made of a liquid crystal polymer. Alternatively, it may be made of another resin such as polyethylene.

  In the first and second embodiments, the case where the ultrasonic transducer 3 is attached to the outside of the cleaning container 2 is shown, but the ultrasonic transducer 3 is arranged in a state of being immersed in the cleaning liquid inside the cleaning container. You may.

  FIG. 3 shows a third embodiment of the ultrasonic cleaning machine provided with the cleaning member of the present invention. In the third embodiment, the net-shaped placing member 10 is installed inside the outer tank 9 that contains the medium 8, and the cleaning container 2 is placed on the placing member 10. The ultrasonic vibrator 3 is attached to the bottom surface of the outer tank 9, and the ultrasonic vibration generated from the ultrasonic vibrator 3 cleans the object 6 to be cleaned in the cleaning container 2 through the medium 8 in the outer tank 9.

  In the third embodiment, the ultrasonic cleaning machine includes a cleaning container 2, an outer tank 9 and a mounting member 10 as cleaning members, and the cleaning container 2 is made of a liquid crystal polymer. It is desirable that at least one of the outer tank 9 and the mounting member 10 is made of a liquid crystal polymer. By configuring these cleaning members with a liquid crystal polymer, the same effect as that of the first embodiment can be obtained.

  As the medium 8 contained in the outer tank 9, the same medium as the cleaning liquid 5 described above is used.

The cleaning member is not particularly limited as long as it is a member included in the ultrasonic cleaner. In the first to third embodiments of the present invention, as the cleaning member, a cleaning container, a vibration plate, an outer tank, a mounting member, and the like are illustrated, but in addition to these, the object to be cleaned is immersed in the cleaning liquid. The carrying member for carrying the same, the holding member and the supporting member attached to the bottom portion and the side wall portion inside the washing container are also included in the washing member of the present invention, and these members are also preferably made of a liquid crystal polymer. When the cleaning member is the cleaning container and / or the vibration plate, ultrasonic waves from the ultrasonic vibrator easily propagate to the object to be cleaned through the liquid crystal polymer, so that the cleaning power tends to be improved. It is preferable that the washing container or the diaphragm is composed of the liquid crystal polymer of the present invention.
The thickness of the cleaning member is not particularly limited, but is, for example, 0.1 to 10 mm.

  Since the cleaning member included in the ultrasonic cleaning machine is made of a liquid crystal polymer, ultrasonic waves from the ultrasonic vibrator easily propagate to the object to be cleaned through the liquid crystal polymer, so that the cleaning power is improved. Presumed. Further, a standing wave is less likely to be generated, and the sound pressure of ultrasonic waves transmitted to the cleaning liquid is likely to be uniform, so that it is assumed that cleaning unevenness is suppressed.

  In the present invention, the liquid crystal polymer is a polyester or a polyesteramide that forms an anisotropic melt phase, and is not particularly limited as long as it is called 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 polarization inspection method using a crossed polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarization microscope and observing the sample mounted on the Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere. The liquid crystal polymer in the present invention is optically anisotropic, that is, it transmits light when inspected between orthogonal polarizers. If the sample is optically anisotropic, polarized light will be transmitted even if it is stationary.

  Examples of the polymerizable monomer constituting the liquid crystal polymer in the present invention include aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, and aliphatic diol. And aliphatic dicarboxylic acids. The polymerizable monomer constituting the liquid crystal polymer may be only one kind of these compounds or may be a combination of two or more kinds of compounds, but a polymerizable monomer having at least one kind of hydroxy group or amino group. It is desirable to include a polymer. The polymerizable monomer that constitutes the liquid crystal polymer may be an oligomer in which one or more of the above compounds are bonded, that is, an oligomer composed of one or more of the above 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 and 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 Examples thereof include alkyl-, alkoxy- or halogen-substituted compounds and their acyl-derivatives, ester derivatives, ester-forming derivatives such as acid halides. Among these, one or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid from the viewpoint of easily controlling the heat resistance, mechanical strength and melting point of the obtained liquid crystal polymer. Is preferred.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl and 3 4,4'-dicarboxybiphenyl and 4,4'-dicarboxyterphenyl, alkyl, alkoxy or halogen substitution products thereof, and ester derivatives thereof, ester-forming derivatives such as acid halides. Among these, one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of effectively increasing the heat resistance of the obtained liquid crystal polymer, and terephthalic acid Is more preferable.

  Specific examples of the aromatic diol include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, Examples include ester-forming derivatives such as 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenol ether and 2,2′-dihydroxybinaphthyl, their alkyl, alkoxy or halogen-substituted compounds, and their acylated products. Among these, one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4′-dihydroxybiphenyl and 2,6-dihydroxynaphthalene are preferable from the viewpoint of excellent reactivity during polymerization, and hydroquinone, 4 More preferred is one or more compounds selected from the group consisting of 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene.

  Specific examples of the aromatic aminocarboxylic acid include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, alkyl, alkoxy or halogen substitution products thereof, and acylated products and ester derivatives thereof. And ester-forming derivatives such as acid halides.

  Specific examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol and 4-amino-. 4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide and 2,2'-diaminobinaphthyl, alkyls thereof , Alkoxy- or halogen-substituted compounds, and ester-forming derivatives such as acylated products thereof. Among these, 4-aminophenol is preferable from the viewpoint of easily balancing the heat resistance and mechanical strength of the obtained liquid crystal polymer.

  Specific examples of the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, alkyl, alkoxy or halogen-substituted products thereof, and their Examples thereof include amide-forming derivatives such as acylated products.

  Specific examples of the aliphatic diol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. Further, a polymer containing an aliphatic diol such as polyethylene terephthalate or polybutylene terephthalate is reacted with the above aromatic oxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol and their acylated products, ester derivatives, acid halides and the like. You may let me.

  Specific examples of the aliphatic dicarboxylic acid include 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 during polymerization.

  In the present invention, the liquid crystal polymer is dihydroxyterephthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid as long as the object of the present invention is not impaired. Alternatively, these alkyl-, alkoxy- or halogen-substituted compounds and their acyl-forming compounds, ester derivatives, ester-forming derivatives such as acid halides may be contained as the polymerizable monomer. The content of these polymerizable monomers is preferably 10 mol% or less based on the total amount of the other polymerizable monomers.

  In the present invention, the liquid crystal polymer may contain a thioester bond as long as the object of the present invention is not impaired. Examples of the polymerizable monomer that gives such a bond include mercapto aromatic carboxylic acids, and aromatic dithiols and hydroxyaromatic thiols. The content of these polymerizable monomers is preferably 10 mol% or less based on the total amount of the other polymerizable monomers.

  In the present invention, the liquid crystal polymer is an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol, an aromatic aminocarboxylic acid, an aromatic hydroxyamine, an aromatic diamine, an aliphatic diol, or an aliphatic diol from the viewpoint of improving the detergency. A copolymer composed of two or more compounds selected from the group consisting of dicarboxylic acids is preferable, and aromatic hydroxycarboxylic acid, aromatic aminocarboxylic acid, aromatic diol, aromatic hydroxyamine, aromatic More preferably, it is a copolymer composed of two or more compounds selected from the group consisting of diamines, aliphatic diols, aromatic dicarboxylic acids and aliphatic carboxylic acids.

Further, from the viewpoint of improving the detergency, it is particularly preferable that the polymerizable monomer constituting the liquid crystal polymer in the invention contains an aromatic hydroxycarboxylic acid, and the liquid phase polymer is an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid or A copolymer composed of two or more compounds selected from the group consisting of aromatic diols is highly preferred.
When the polymerizable monomer contains 4-hydroxybenzoic acid as the aromatic hydroxycarboxylic acid, the content of 4-hydroxybenzoic acid is 100 mol parts of all the polymerizable monomers from the viewpoint of improving detergency. On the other hand, the amount is preferably 30 to 100 mol parts, more preferably 40 to 95 mol parts, still more preferably 50 to 90 mol parts, particularly preferably 55 to 85 mol parts, and particularly preferably 60 to 80 mol parts.

Specific examples of the polymerizable monomer that constitutes the liquid crystal polymer that constitutes the cleaning member of the present invention include those composed of 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 the monomer constitutional units 1), 9), 10) and 14) are preferable.

  Hereinafter, a method for producing a liquid crystal polymer that constitutes the cleaning member of the present invention will be described.

  The method for producing the liquid crystal polymer constituting the cleaning member of the present invention is not particularly limited, and a known polycondensation method for forming a polymerizable monomer to form an ester bond or an amide bond, for example, a melt acidolysis method, a slurry polymerization method. The liquid crystal polymer can be obtained by subjecting the liquid crystal polymer to the above.

  The molten acidolysis method is a preferred method for producing the liquid crystal polymer that constitutes the cleaning member of the present invention. This method involves first heating the polymerizable monomer to form a molten solution of the reactants and then continuing the polycondensation reaction to obtain the molten polymer. A vacuum may be applied to facilitate removal of volatile substances (eg, acetic acid, water, etc.) that are by-produced in the final stage of condensation.

  The slurry polymerization method is a method of reacting a polymerizable monomer 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 both cases of the melt acidolysis method and the slurry polymerization method, the polymerizable monomer used for producing the liquid crystal polymer is modified at room temperature with a modified form obtained by acylating a hydroxy group and / or an amino group, that is, It can also be used in the reaction as an acylated product.

  The lower acyl group preferably has 2 to 5 carbon atoms, and more preferably has 2 or 3 carbon atoms. In a preferred embodiment of the present invention, the acetylated product of the polymerizable monomer is subjected to the reaction.

  The lower acylated product of the polymerizable monomer may be separately acylated and previously synthesized, or may be used in the reaction system by adding an acylating agent such as acetic anhydride to the polymerizable monomer during the production of the liquid crystal polymer. It can also be generated with.

  In either case of the melt acidolysis method or the slurry polymerization method, the polycondensation reaction is preferably carried out at a temperature of 150 to 400 ° C., preferably 250 to 370 ° C. under normal pressure and / or reduced pressure, and if necessary. A catalyst may be used.

Specific examples of the catalyst include organotin compounds such as dialkyltin oxide (eg, dibutyltin oxide) and diaryltin oxide; titanium dioxide; antimony trioxide; organotitanium compounds such as alkoxytitanium silicate and titanium alkoxide; alkali and alkali carboxylic acids. Examples thereof include earth metal salts (for example, potassium acetate); Lewis acids (for example, boron trifluoride), and gaseous acid catalysts such as hydrogen halides (for example, hydrogen chloride).
When a catalyst is used, the amount of the catalyst is preferably 1-1000 ppm, more preferably 2-100 ppm, based on the total amount of polymerizable monomers.

  The liquid crystal polymer obtained by the polycondensation reaction in this manner is usually processed into pellets, flakes, or powders after being extracted from the polymerization reaction tank in a molten state.

  A liquid crystal polymer in the form of pellets, flakes, or powder is substantially solid phase under reduced pressure, under vacuum, or in an inert gas atmosphere such as nitrogen or helium for the purpose of increasing the molecular weight and improving heat resistance. You may heat-process in a state.

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

  The liquid crystal polymer obtained as described above may contain one or more selected from inorganic or organic fillers, other additives described below, and other resin components. A composition containing an inorganic or organic filler and other additives in addition to the liquid crystal polymer is also referred to as a liquid crystal polymer composition.

  The inorganic filler or organic filler which the liquid crystal polymer composition may contain may be fibrous, plate-like or granular, for example, glass fiber, milled glass, silica-alumina fiber, alumina fiber, carbon fiber, aramid fiber. , Potassium titanate whiskers, aluminum borate whiskers, wollastonite, talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide. Among these, glass fiber is preferable because it has an excellent balance between physical properties and cost. Two or more kinds of these fillers may be used in combination.

  The total amount of the inorganic filler or the organic filler in the liquid crystal polymer composition is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the total amount of the above-mentioned inorganic filler or organic filler exceeds 200 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the moldability of the liquid crystal polymer composition tends to be deteriorated, and the cylinder and the metal of the molding machine may be reduced. Mold wear tends to increase. When the total amount of the inorganic filler or the organic filler is equal to or more than the above lower limit value, the effect of improving the mechanical strength can be exhibited according to the content of the filler.

  In the present invention, the liquid crystal polymer composition includes other additives such as higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid metal salts (wherein higher fatty acid means carbon atom) within a range that does not impair the effects of the present invention. Mold release modifiers such as polysiloxane and fluororesin; coloring agents such as dyes and pigments; antioxidants; heat stabilizers; ultraviolet absorbers; antistatic agents; surfactants, etc. May be included. These additives may contain only 1 type, or may contain 2 or more types in combination.

  The total amount of other additives in the liquid crystal polymer composition is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the liquid crystal polymer. When the total amount of the other additives exceeds 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the moldability of the liquid crystal polymer composition tends to decrease and the thermal stability tends to deteriorate. When the total amount of the other additives is at least the above lower limit value, the function of the additive depending on the content of the additive can be exhibited.

  Further, in molding the liquid crystal polymer composition constituting the cleaning member of the present invention, an external lubricant effect such as a higher fatty acid, a higher fatty acid ester, a higher fatty acid metal salt, or a fluorocarbon-based surfactant among the above-mentioned other additives is exerted. The additive which it has may be made to adhere to the pellet surface of a liquid crystal polymer beforehand.

  The liquid crystal polymer composition constituting the cleaning member of the present invention may contain other resin components. Other resin components include, for example, polyamide, polyester, polyacetal, polyphenylene ether, and modified products thereof, and thermoplastic resins such as polysulfone, polyether sulfone, polyetherimide, and polyamideimide, and phenol resins, epoxy resins, and polyimide resins. Thermosetting resins such as Other resin components may be contained alone or in combination of two or more. The content of the other resin component is not particularly limited, but in one typical example, the total amount of the other resin component is usually 0.1 to 100 parts by weight, relative to 100 parts by weight of the liquid crystal polymer. In particular, it is 0.1 to 80 parts by weight.

  The liquid crystal polymer composition constituting the cleaning member of the present invention is an inorganic filler or an organic filler, other additives and other resin components and the like are added to the liquid crystal polymer, which is a Banbury mixer, kneader, uniaxial or It can be obtained by melt-kneading in a temperature range from near the crystal melting temperature of the liquid crystal polymer to the crystal melting temperature plus 100 ° C. using a twin-screw extruder or the like.

  The liquid crystal polymer or liquid crystal polymer composition thus obtained is molded into a cleaning member such as a cleaning container, a diaphragm, an outer tank, a mounting member, a holding member and a supporting member by a known method.

  The ultrasonic cleaning machine provided with the cleaning member of the present invention, the sound pressure is transmitted to the cleaning liquid in a uniform state, and by improving the propagation efficiency, uneven cleaning and insufficient cleaning are suppressed, so that the efficiency in a short time. Precise cleaning of objects to be cleaned becomes possible.

  Examples of the object to be cleaned, which is cleaned by the ultrasonic cleaner provided with the cleaning member of the present invention, include articles such as glass products, metal products, pottery, ceramics and plastics. Specifically, semiconductor wafers, electric and electronic parts such as liquid crystal glass substrates, precision machine parts used for cameras and watches, everyday items such as glasses, contact lenses, dentures, ornaments such as rings and accessories, press parts, piping, Examples include industrial products such as filters and cutlery, and household items such as tableware.

  Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Reference Example 1 (Synthesis of Liquid Crystal Polymer 1)
The following compound was charged into a reaction vessel equipped with a stirring blade and a distillation tube, heated in a nitrogen gas atmosphere between 40 and 170 ° C. over 1 hour, kept at 170 ° C. for 30 minutes, and then brought to 330 ° C. The temperature was raised over a period of time, the reaction was further performed at 330 ° C. for 10 minutes, and then the pressure was reduced at 330 ° C. Then, the pressure was reduced to 10 torr over 1.5 hours, and the polycondensation was completed when the predetermined stirring torque was reached. The contents were taken out of the reaction container, and liquid crystal polymer pellets were obtained by a pulverizer. The amount of acetic acid distilled during the polymerization was almost the theoretical amount.
4-Hydroxybenzoic acid: 655.3 g (73 parts by mol)
6-hydroxy-2-naphthoic acid: 330.3 g (27 parts by mole)
Acetic anhydride: 676.9 g (102 parts by mol)

Reference Example 2 (Synthesis of Liquid Crystal Polymer 2)
The following compounds were placed in a reaction vessel equipped with a stirring blade and a distillation tube, heated in a nitrogen gas atmosphere at a temperature between 40 and 170 ° C over 1 hour, kept at 170 ° C for 30 minutes, and then heated to 350 ° C at 7 ° C. The temperature was raised over a period of time, the reaction was further performed at 350 ° C. for 10 minutes, and then the pressure was reduced at 350 ° C. Then, the pressure was reduced to 5 torr over 1.5 hours, and when the predetermined stirring torque was reached, the polycondensation was completed. The contents were taken out of the reaction container, and liquid crystal polymer pellets were obtained by a pulverizer. The amount of acetic acid distilled during the polymerization was almost the theoretical amount.
4-Hydroxybenzoic acid: 628.4 g (70 parts by mole)
6-hydroxy-2-naphthoic acid: 24.5 g (2 parts by mole)
Hydroquinone: 100.2 g (14 parts by mole)
2,6-naphthalenedicarboxylic acid: 196.7 g (14 mole parts)
Acetic anhydride: 696.8 g (105 parts by mol)

<Sound pressure measurement>
Example 1
Using the liquid crystal polymer 1 synthesized in Reference Example 1, a test piece having a thickness of 0.8 mm, a length of 17 cm and a width of 12.7 cm was produced by injection molding.
The sound pressure was measured using the obtained test piece. A sound pressure of 2 V was applied to the test piece by a USB oscilloscope (Pico Technology Limited) via a ceramic oscillator. The ultrasonic wave transmitted through the test piece was received by a receiving element at a location 5 cm away from the transmitter, and the maximum receiving voltage was measured. The results are shown in Table 1.

Example 2
The maximum receiving voltage was measured in the same manner as in Example 1 except that a test piece was prepared using the liquid crystal polymer 2. The results are shown in Table 1.

Comparative Examples 1-3
The maximum receiving voltage was measured in the same manner as in Example 1 except that test pieces were prepared using a glass plate, SUS304, and polyethylene, respectively. The results are shown in Table 1.

<Evaluation of detergency>
Example 3
100 mL of distilled water was added to a 300 mL wide container (thickness: 0.5 mm) produced by injection molding using liquid crystal polymer 1, and an oily skin cream (“Aloe skin cream”, manufactured by Taisho Sangyo Co., Ltd.) 0 A metal screw, in which 1 g of the resin was evenly applied, was sunk. Then, the wide-mouthed container was placed in an ultrasonic cleaner (US-102 manufactured by NND Corp.) filled with water so that water did not enter the container, and ultrasonic waves of 38 kHz were applied at an output of 100 V for 10 minutes. And washed. When the screw part of the screw after washing was observed, the detachment of the cream was confirmed at the top part and the groove part of the screw thread.

Comparative Example 4
It was washed in the same manner as in Example 3 except that the wide-mouthed container was made of polyethylene. When the screw part of the screw after cleaning was confirmed, the cream at the top of the screw thread was detached, but the cream remaining in the groove part was confirmed.

As described above, it is understood that the liquid crystal polymer has a higher ultrasonic wave transmission rate and is superior in cleaning power as compared with the materials of Comparative Examples 1 to 3.
Preferred embodiments of the present invention include:
[1] A cleaning member used for ultrasonic cleaning, which is composed of a liquid crystal polymer.
[2] The cleaning member according to [1], wherein the cleaning member is a cleaning container and / or a vibration plate.
[3] The liquid crystal polymer is selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, aliphatic diol and aliphatic dicarboxylic acid. The cleaning member according to [1] or [2], which is a copolymer composed of two or more kinds of compounds described above.
[4] The liquid crystal polymer is a copolymer composed of two or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and aromatic diols, [1] or [2] The cleaning member according to.
[5] The cleaning according to [3] or [4], wherein the aromatic hydroxycarboxylic acid is one or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. Parts.
[6] The cleaning member according to [3] or [4], wherein the aromatic dicarboxylic acid is one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. .
[7] The aromatic diol is one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4′-dihydroxybiphenyl and 2,6-dihydroxynaphthalene, [3] or [4] Parts for cleaning.
[8] An ultrasonic cleaning machine comprising the cleaning member according to any one of [1] to [7].

1 Ultrasonic Cleaning Machine 2 Cleaning Container 3 Ultrasonic Transducer 4 Ultrasonic Oscillator 5 Cleaning Liquid 6 Cleaning Object 7 Vibration Plate 8 Medium 9 Outer Tank 10 Mounting Member

Claims (7)

A cleaning member used for ultrasonic cleaning, which is composed of a liquid crystal polymer, has an ultrasonic frequency of 20 kHz to 5 MHz, and the polymerizable monomer forming the liquid crystal polymer is 4-hydroxy as an aromatic hydroxycarboxylic acid. A cleaning member containing benzoic acid and 6-hydroxy-2-naphthoic acid and having a thickness of 0.1 to 10 mm . Cleaning member is a cleaning container, the cleaning member according to claim 1.   The liquid crystal polymer is selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic hydroxyamines, aromatic diamines, aliphatic diols and aliphatic dicarboxylic acids 2 The cleaning member according to claim 1, which is a copolymer composed of one or more kinds of compounds.   The cleaning liquid according to claim 1 or 2, wherein the liquid crystal polymer is a copolymer composed of two or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and aromatic diols. Element.   The cleaning member according to claim 3 or 4, wherein the aromatic dicarboxylic acid is one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid.   The cleaning member according to claim 3 or 4, wherein the aromatic diol is one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene. Ultrasonic cleaning machine having a cleaning member according to any one of claims 1-6.

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