JP5085897B2 - Clamp member and sensor device using the same - Google Patents

Description

  The present invention relates to a clamp member used in various sensor devices and a sensor device using the clamp member.

  In recent years, various sensor devices corresponding to various measurements have been developed. As such a sensor device, a proximity sensor that detects whether or not an object has approached is known. This proximity sensor includes an oscillation circuit having a coil as a resonance circuit element. By detecting a decrease in oscillation amplitude of the oscillation circuit or an oscillation stop caused by an object including a magnetic material approaching the coil, the proximity sensor is detected. Is detected without contact.

  Since the above-mentioned various sensor devices, particularly proximity sensors, are used in various environments, they are environmentally friendly (for example, oil resistance, chemical resistance, heat shock resistance, flame resistance, etc. It is necessary to adopt an excellent structure. For this reason, the structure which seals the various components accommodated in the inside of a main body case is often employ | adopted by filling the inside of a main body case using fillers, such as resin. In order to obtain complete sealing performance, it is necessary that the inside of the main body case be filled with a cured resin without a gap. However, since there are a large number of complicatedly shaped gaps inside the main body case, it is not easy to completely seal the internal components by filling the gaps without any gaps.

  As a conventional proximity sensor sealing method, for example, there is a sealing method disclosed in JP-A-9-92105 (Patent Document 1).

  The method for sealing a proximity sensor disclosed in Patent Document 1 includes forming a labyrinth-like air vent passage between a coil case and a main body case, and placing the main body case inside in a reduced pressure environment when injecting resin. The air inside the main body case is sucked outside the main body case through the air vent passage, and the inside of the main body case is filled with resin.

In such a proximity sensor, for example, a polyarylate resin disclosed in Japanese Patent Application Laid-Open No. 2004-158198 (Patent Document 2) is used for a clamp member that fixes a filler that seals the main body case of the sensor. It has been.
JP-A-9-92105 JP 2004-158198 A

  For example, proximity sensors are used for metal object detection in the machine tool industry and the automotive industry. In such a case, an oil such as a water-soluble cutting oil (for example, Yushiroken EC-50T5 manufactured by Yushiro Chemical Industry) or a motor oil (for example, Synthetic # 770TG manufactured by Yushiro Chemical Industry Co., Ltd.) is used in such a poor environment that the sensor is applied. Is done. Therefore, the clamp member fixing the sealing filler that seals the main body case of the sensor is eroded by the above oil, causing cracks, and the oil reaches the circuit board, and finally the sensor. Destroy.

  Moreover, the proximity sensor is used for detecting an object for food conveyance in the food industry, and detects a metal object such as an aluminum package for packing food. In the food industry, it is necessary to ensure a high sanitary environment for packaging food. Therefore, since the food conveying machine and the like must be frequently washed to keep the surrounding environment clean, the cleaning agent is necessarily applied to the sensor. As the cleaning agent, for example, TEX121 (pH is 13) manufactured by ABC Compounding is used. Therefore, when the sensor is exposed to a cleaning atmosphere, the resin component of the clamp member is attacked by the alkaline cleaning agent, deteriorates due to hydrolysis, cracks occur, and the sensor is poorly insulated.

  In addition, in recent years, proximity sensors are used in harsh ambient environments (for example, high temperature, low temperature, and high humidity atmosphere), and high durability (for example, heat shock resistance) is required. However, in the conventional proximity sensor, since the bending elastic modulus of the resin used for the clamp member is high as a main factor, the adhesiveness between the sealing filler and the clamp member is poor, and the clamp member is sealed due to a severe temperature environment change. Peeling or cracking from the stop filler occurs, leading to sensor destruction. If a large amount of flame retardant is added for the purpose of improving the flame retardancy of the clamp member, the transparency of the clamp member is lost, the visibility of the operation indicator lamp provided at the rear end of the circuit board is lowered, and the Heat shock properties are also significantly reduced. Therefore, the environmental resistance and durability of the sensor are reduced, and the production line where the sensor is used is costly.

  As a result, a sensor that satisfies market demands in a poor environment has not been realized, and the replacement frequency has been shortened to prevent sensor failure. As a result, the user who uses the sensor is forced to be very expensive. In addition, in terms of flame retardancy, flame retardancy can be improved by adding a large amount of flame retardant to the resin, but transparency cannot be maintained, heat resistance is reduced, and adhesion to other resins is reduced. There was a big problem and technology development was very difficult.

  Therefore, in order to solve the above problems, the present invention provides a clamp member for a sensor device having excellent environmental compatibility (for example, oil resistance, chemical resistance, heat shock resistance, etc.) and a sensor device using the same. The purpose is to provide.

The present invention is a clamp member used in a sensor device, and the material of the clamp member is selected from the group consisting of 10 to 50 parts by mass of a polyarylate resin, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and diphenyldicarboxylic acid. 90 to 50 parts by mass of a polyester formed from at least one aromatic dicarboxylic acid and at least one diol selected from the group consisting of 1,4-cyclohexanedimethanol, 1,4-butanediol and ethylene glycol polyarylate resin composition der containing is, the flexural modulus of the polyarylate resin composition is der Ru clamping member below 2.0 GPa. By including polyester in addition to polyarylate resin as the material of the clamp member, the oil resistance, chemical resistance, and heat shock resistance of the clamp member are improved.

  In the clamp member according to the present invention, it is preferable that the polyarylate resin composition further includes at least one compound selected from an organic phosphorus compound and a bromine compound. By further including an organic phosphorus compound and / or bromine compound as the material of the clamp member, the heat discoloration and / or flame retardancy of the clamp member is improved.

  In the clamp member according to the present invention, the polyarylate resin composition preferably further contains a polycarbonate resin. The fluidity at the time of heating of the resin composition is improved, and the workability at the time of forming the clamp member is improved.

  Further, the present invention is a sensor device using the above-described clamp member, a main body case having both ends opened, a detection unit that closes a front end opening of the main body case, and a circuit board that is accommodated in the main body case A sealing member that closes the rear end opening of the main body case, a sealing material that is filled in the main body case that contains the circuit board and is closed at both ends by the detection portion and the clamping member, and the clamp member It is a sensor apparatus which has a protector member to do. The sensor device including the clamp member has improved oil resistance, chemical resistance, heat shock resistance, and the like.

  ADVANTAGE OF THE INVENTION According to this invention, the clamp member for sensor apparatuses provided with the outstanding environmental compatibility (for example, oil resistance, chemical resistance, heat shock resistance, etc.) and a sensor apparatus using the same can be provided.

  The clamp member according to the present invention is a clamp member 40 used in the sensor device 1 with reference to FIG. 1 and FIG. 2. The material of the clamp member 40 is 10 to 50 parts by mass of polyarylate resin, terephthalate. Selected from the group consisting of at least one aromatic dicarboxylic acid selected from the group consisting of acids, isophthalic acid, naphthalenedicarboxylic acid and diphenyldicarboxylic acid, 1,4-cyclohexanedimethanol, 1,4-butanediol and ethylene glycol A polyarylate resin composition comprising 90 to 50 parts by mass of a polyester formed from at least one diol. By including polyester in addition to polyarylate resin as the material of the clamp member, the oil resistance, chemical resistance, and heat shock resistance of the clamp member are improved.

  Here, referring to FIG. 1 and FIG. 2, the sensor device 1 in which the clamp member according to the present invention is used includes a main body case 10 whose both ends are open, and a detection unit 20 that closes the front end opening of the main body case 10. The circuit board 30 accommodated in the body case 10, the clamp member 40 that closes the rear end opening of the body case 10, and the circuit board 30 is housed and both ends are blocked by the detection unit 20 and the clamp member 40. It has the sealing filler 50 with which the main body case 10 is filled, and the protector member 60 which contacts the clamp member 40. Here, the detection unit 20 refers to a part of the sensor device that detects a change due to the presence of an object to be detected. In the case of a proximity sensor, a part including a detection coil and its surrounding detection circuit is a photoelectric sensor. Denotes a portion including the light receiving element and its peripheral detection circuit portion. The circuit board 30 includes a circuit that processes a signal from the detection unit. Thus, the clamp member 40 is a member that fixes the sealing filler 50 that seals the main body case of the sensor, and is in contact with the sealing filler 50 and the protector member 60.

  In the sensor device according to the present invention, the electronic component 31 and the operation confirmation lamp 32 can be mounted on the circuit board 30. Here, the operation confirmation lamp 32 is arranged inside the clamp member 40 so that the blinking can be confirmed. Further, the cord 70 can be electrically connected to the rear end portion of the circuit board 30. The electrical connection between the circuit board 30 and the cord 70 is normally performed within the cord protector member 60.

  Moreover, with reference to FIG. 1 and FIG. 2, said sensor apparatus 1 is generally manufactured as follows. First, the front end opening of the main body case 10 whose both ends are opened is closed by the detection unit 20 to which the circuit board 30 is fixed, and the circuit board 30 is accommodated in the main body case 10. Next, the rear end opening of the main body case 10 is closed with a clamp member 40 having an opening (not shown). At this time, it is preferable that the rear end portion of the circuit board 30 protrudes through the clamp member 40.

  Next, the sealing material 50 is filled into the main body case 10 in which the circuit board 30 is accommodated from an opening (not shown) of the clamp member 40. Although there is no restriction | limiting in particular as the filler 50 for sealing, It is preferable that it is a transparent resin from a viewpoint which confirms blinking of the operation confirmation lamp | ramp 32, From a viewpoint which can perform resin filling on mild conditions, an epoxy resin, A thermosetting resin such as a urethane resin is preferable, and an epoxy resin is particularly preferable. Further, when an epoxy resin or the like is used as a sealing filler, volume shrinkage occurs during curing, and therefore it is preferable to fill the sealing filler sequentially in several times. For example, in FIG. 2, the sealing filler 50 is used for filling the primary casting sealing filler 51 for filling the vicinity of the detection unit 20 and the central portion and the rear end portion of the main body case 10. The secondary casting sealing filler 52 is filled separately. In addition, as shown in FIG. 2, a secondary casting sealing filler 52 is provided by providing a protective layer 53 in advance with a silicon resin, a urethane resin, or the like on the portion of the circuit board 30 where the electronic component 31 is mounted. The thermal stress applied to the electronic component 31 when filling can be relaxed.

  Next, the cord 70 is electrically connected to the rear end portion of the circuit board 30 protruding from the clamp member 40. Next, a cord protect member 60 is injection molded near the connection portion between the circuit board 30 and the cord 70. The material used for molding the cord protector member 60 is not particularly limited, but from the viewpoint of ensuring the flexibility of the cord, a thermoplastic elastomer (TPE) is preferable, and the blinking of the operation confirmation lamp 32 can be confirmed. From the viewpoint of ensuring high adhesion between the cord protector member 60, the clamp member 40, and the cord 70, a thermoplastic polyester elastomer (TPEE) having transparency is particularly preferable.

  As described above, the material of the clamp member according to the present invention is at least one aromatic selected from the group consisting of 10 to 50 parts by mass of polyarylate resin and terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and diphenyldicarboxylic acid. Polyarylate resin composition comprising 90-50 parts by mass of polyester formed from dicarboxylic acid and at least one diol selected from the group consisting of 1,4-cyclohexanedimethanol, 1,4-butanediol and ethylene glycol It is.

  Here, the polyarylate resin is an aromatic polyester polymer in which an aromatic dicarboxylic acid residue unit and a bisphenol residue unit are repeated.

  The polyarylate resin raw material for introducing the bisphenol residue unit is a bisphenol derivative. Specifically, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-) 3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4 ′ -Dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) And cyclohexane. These compounds may be used alone or in combination of two or more. Among these compounds, it is preferable to use at least 2,2-bis (4-hydroxyphenyl) propane, and more preferably the compound is used alone.

  On the other hand, the polyarylate resin raw material for introducing the aromatic dicarboxylic acid residue unit is an aromatic dicarboxylic acid derivative. Specifically, terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 5-tert-butylisophthalic acid, diphenic acid, 4,4′-dicarboxydiphenyl ether, bis (4-carboxyphenyl) alkane, 4,4′-dicarboxyphenyl sulfone, etc. . These divalent carboxylic acids can be used alone or in combination of two or more. A dicarboxylic acid that can be used particularly preferably is a mixture having a molar ratio of terephthalic acid to isophthalic acid of 1: 1. Further, the polyarylate of the present invention does not necessarily need to be a linear resin, and a branched structure may be introduced by adding a trifunctional or higher functional substance at the time of polymerization as long as the amount is small.

  The intrinsic viscosity of the polyarylate resin is preferably 0.4 to 1.0, more preferably 0.4 to 0.8, and still more preferably 0.5 to 0.7. Here, the intrinsic viscosity is a value measured using a solution having a temperature of 20 ° C. prepared using a mixture of phenol and ethane tetrachloride in a mass ratio of 1: 1 as a solvent.

  The polyester includes at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and diphenyldicarboxylic acid, 1,4-cyclohexanedimethanol, and 1,4-butanediol. In addition, a condensation polyester with at least one diol selected from ethylene glycol is used.

  As the dicarboxylic acid constituting the polyester, the mixing molar ratio (terephthalic acid / isophthalic acid / naphthalenedicarboxylic acid / diphenyldicarboxylic acid) can be arbitrarily selected, but the viewpoint of improving the adhesion with the sealing resin Therefore, the total molar fraction of terephthalic acid and isophthalic acid in the dicarboxylic acid component is preferably 50 to 100%. Further, from the viewpoint of improving the adhesion with the sealing resin, the molar ratio of terephthalic acid / isophthalic acid is preferably in the range of 99/1 to 1/99. The total molar fraction of naphthalenedicarboxylic acid and diphenyldicarboxylic acid is preferably 0 to 50%. When naphthalenedicarboxylic acid or diphenyldicarboxylic acid is contained in the dicarboxylic acid component, the heat resistance is improved, but if the total molar fraction thereof exceeds 50%, the adhesiveness with the sealing resin is lowered. However, these aromatic dicarboxylic acids are not in the above range as a single resin, but may be adjusted so as to fall within the above range as a result of blending. Although it does not restrict | limit especially adding another dicarboxylic acid component to such an extent that the performance of this invention is not impaired, Preferably aromatic dicarboxylic acid is used.

  As the diol constituting the polyester, the mixing molar ratio (1,4-cyclohexanedimethanol / 1,4-butanediol / ethylene glycol) can be arbitrarily selected, but 1,4-cyclohexane in the diol component can be selected. It is preferable that the molar fraction of dimethanol is 20 to 100% because of excellent oil resistance and chemical resistance. Further, the molar fraction of 1,4-butanediol is preferably 0 to 30%. If 1,4-butanediol is contained in the diol component, the chemical resistance is improved, but if it is too much, the heat resistance is lowered. The molar fraction of ethylene glycol is preferably 0 to 80%. If ethylene glycol is contained in the diol component, the fluidity is improved, but if too much, the chemical resistance and heat resistance are lowered. However, these diols are not in the above range as a single resin, but may be prepared so as to fall within the above range as a result of blending. Regarding the diol component, addition of another diol component to the extent that the performance of the present invention is not impaired is not particularly limited, but an aliphatic diol is preferably used.

  The polyester made of the above raw materials is excellent in mechanical strength and molding processability, and therefore has an intrinsic viscosity of 0.5 to 1.2, preferably 0.6 to 1.0.

  Since the compounding ratio of the polyarylate resin and the polyester is excellent in molding processability, heat resistance, and chemical resistance of the resin composition, the mass ratio (polyarylate resin / polyester) is 10/50 to 90 /. 50 is preferable, 5/45 to 85/55 is more preferable, and 20/40 to 80/60 is further preferable. Two or more kinds of polyarylate resins and polyesters may be used in combination, and in this case, the blending ratio of the total of all polyarylate resins and the total of all polyesters may be in the above range.

  In the present invention, when a polyarylate resin and a polyester are mixed and used as the polyarylate resin composition, the resulting polyarylate resin composition has excellent melt processability and adhesion to a sealing resin, and the sensor It is suitable as a component of equipment.

  In the clamp member according to the present invention, the polyarylate resin composition which is a material of the clamp member may contain polycarbonate as a polymer in addition to the above polyarylate resin and polyester as desired. By including the polycarbonate in the polyarylate resin composition, the fluidity at the time of heating the resin composition is further improved, and the workability at the time of molding the clamp member is further improved.

  Polycarbonate is a polycarbonate formed by repeating bisphenol residue units and carbonate residue units.

  Examples of bisphenols as raw materials for introducing bisphenol residue units include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) Cyclohexane, 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis (4-hydroxyphenyl) propane, 1,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy) Phenyl) cyclododecane, 4,4′-dihydroxydiphenyl ether, 4,4′-dithiodiphenol, 4,4 - dihydroxy-3,3'-dichloro-diphenyl ether, 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether and the like. In addition, diphenols described in US Pat. Nos. 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used. These may be used alone or in combination of two or more. Among these compounds, it is preferable to use at least 2,2-bis (4-hydroxyphenyl) propane, and more preferably, this compound is used alone. Examples of the raw material for introducing the carbonate residue unit include phosgene and diphenyl carbonate.

  Moreover, it is preferable that the intrinsic viscosity of a polycarbonate is 0.3-0.7. When the intrinsic viscosity is lower than 0.3, the mechanical strength of the resin composition is lowered. On the other hand, when the intrinsic viscosity is higher than 0.7, the fluidity is lowered. In addition, the content of the polycarbonate is 30% by mass or less based on the total amount of all polymer components (polyarylate resin, polyester, and optionally contained polycarbonate, the same shall apply hereinafter), which has excellent chemical resistance. It is preferable. Moreover, from a viewpoint of improving the fluidity | liquidity at the time of the heating of a resin composition, 10 mass% or more is preferable with respect to the total amount of all the polymer components.

  In the clamp member according to the present invention, the polyarylate resin composition that is a material of the clamp member preferably further contains at least one compound selected from an organic phosphorus compound and a bromine compound.

  The polyarylate resin composition containing the above polyarylate resin and polyester is excellent in moldability, heat resistance, impact resistance and transparency, but tends to turn brown during melt processing. If the organophosphorus compound is further contained in such a resin composition, the above-mentioned discoloration can be effectively suppressed.

  As the organic phosphorus compound, a phosphate compound and / or a phosphite compound can be used, and at least a phosphate compound is preferably used. By using the phosphate compound, discoloration during melt processing can be more effectively suppressed.

Here, the phosphate compound is not particularly limited, but as represented by the following chemical formula (1), at least one OH group exhibiting acidity and at least one —OR group (—OR ¹ group and —OR group). An acid phosphate compound having ² groups) is preferable from the viewpoint of suppressing discoloration due to heat during melt processing.

In the chemical formula (1), R ¹ and R ² are each independent, and R ¹ is hydrogen or an alkyl or alkenyl group having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, more preferably 4 to 18 carbon atoms. . R ² is an alkyl or alkenyl group having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, more preferably 4 to 18 carbon atoms. When either R ¹ or R ² is an alkyl group or alkenyl group having 25 or more carbon atoms, discoloration of the resin composition during melt processing cannot be suppressed. R ¹ is preferably hydrogen or the same alkyl group or alkenyl group as R ² . Here, examples of the alkyl group or alkenyl group having 1 to 24 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. Pentyl group, hexyl group, octyl group, 2-ethylhexyl group, lauryl group, myristyl group, stearyl group, oleyl group, behenyl group, tetracosyl group and the like.

  Specific examples of preferable acid phosphate compounds include, for example, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate and the like. . Among these specific examples, butyl acid phosphate, 2-ethylhexyl acid phosphate, and oleyl acid phosphate are more preferable. Two or more phosphate compounds may be used in combination.

  Specific examples of the phosphite compound include, for example, trisnonyl phosphite, trisphenyl phosphite, tristridecyl phosphite, tris (monononylphenyl) phosphite, tris (monodinonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (2,5- Di-t-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) phenyl] phosphite, tris [2,4-di- (1, 1-dimethylpropyl) phenyl] phosphite, tris (2-cyclohex Ruphenyl) phosphite, trisphenyl phosphite, tris (octylthioethyl) phosphite, tris (octylthiopropyl) phosphite, tris (cresylthiopropyl) phosphite, tris (3,5-di-t-butyl-4 -Hydroxyphenyl) phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 4,4'-butylidene-bis (3-methyl-6-t -Butylphenyl-di-octyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane, bis (2,4-di-t-butyl) Phenyl) spiropentaerythritol diphosphite, bis (2,6-di-t-butyl- -Methylphenyl) spiropentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) spiropentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) Examples include spiropentaerythritol diphosphite and bis (nonylphenyl) spiropentaerythritol diphosphite.

  Among these specific examples, bis (nonylphenyl) spiropentaerythritol diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) spiropentaerythritol diphosphite are combined with the above phosphate compounds. Are preferably used.

  The content of the organophosphorus compound is preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total polymer components (total amount of polyarylate resin and polyester, and optionally contained polycarbonate), 0.03 to 0.3 parts by mass is more preferable. If the polycarbonate content is too small, the effect of preventing discoloration of the resin composition when molding the clamp member will be poor, and the transparency will tend to decrease slightly. If the content is too large, discoloration of the resin composition occurs when molding the clamp member, and the transparency tends to be slightly reduced. When two or more types of organophosphorus compounds are used in combination, the total amount thereof may be within the above range.

  In the clamp member of the present invention, the yellow index of the resin composition is preferably 30 or less, and more preferably 25 or less. Further, the total light transmittance of the resin composition is preferably 80% or more, and more preferably 85% or more. When the yellow index and the total light transmittance are within the above ranges, it is possible to visually recognize the operation indicator lamps provided on the circuit board of the sensor device, but it is difficult to visually recognize when either of these is out of the range.

  In addition, in the clamp member according to the present invention, if the polyarylate resin composition, which is the material of the clamp member, further contains a bromine compound, flame retardancy can be improved. Here, as the bromine compound, brominated polystyrene, brominated crosslinked aromatic polymer, brominated styrene / maleic anhydride copolymer, brominated polyphenylene ether, brominated epoxy resin, brominated diphenylethane, brominated polycarbonate, Examples thereof include ethylene bistetrabromophthalamide and brominated phenoxy resin. Of these bromine compounds, brominated diphenylethane and brominated polycarbonate are preferred.

  Further, in the clamp member according to the present invention, the polyarylate resin composition as the material of the clamp member is not limited to the ultraviolet absorber, the bluing agent, the flame retardant aid, the release agent, the charging, as long as the effect of the present invention is obtained. An inhibitor, a lubricant, a compatibilizing agent, an impact resistant material and the like may be included.

  The polyarylate resin composition used for molding the clamp member of the present invention is obtained by mixing the above-mentioned predetermined materials. Mixing may be achieved by simply dry blending the materials or by melting and kneading the materials. From the viewpoint of easy handling when molding the clamp member, the polyarylate resin composition is preferably a kneaded material in the form of pellets.

  From the viewpoint of high adhesiveness between the sealing filler and the clamp member, the flexural modulus of the polyarylate resin composition used for molding the clamp member of the present invention is preferably 2.0 GPa or less.

  The polyarylate resin composition used for molding the clamp member of the present invention preferably has a deflection temperature under load at 0.45 MPa of 80 ° C. or higher. If the deflection temperature under load is less than 80 ° C., the clamping member may be deformed by heat and stress when the sealing filler is filled and cured.

  The clamp member concerning this invention and the sensor apparatus using the same are demonstrated based on a following example and a comparative example. The raw materials of the polyarylate resin composition used in Examples and Comparative Examples are as follows. Unitika L powder was used as the polyarylate resin. Polyesters PE-1, PE-2, PE-3, PE-4, PE-5, and PE-6 synthesized as follows were used as the polyester. As the polycarbonate, Caliber 200-3 manufactured by Sumitomo Dow was used. As the organic phosphorus compound, butyl acid phosphate as a phosphate compound and bis (2,6-di-t-butyl-4-methylphenyl) spiropentaerythritol diphosphite as a phosphite compound were used. As the bromine compound, brominated polycarbonate (FG-8500, manufactured by Teijin Chemicals Ltd.) and brominated diphenylethane (8010, manufactured by Albemarle) were used.

<Synthesis of Polyester PE-1 to PE-6>
Polyester PE-1 was charged with 35.5 kg of terephthalic acid, 26.5 kg of ethylene glycol, and 10.6 kg of 1,4-cyclohexanedimethanol having a cis / trans ratio of 30:70 in an esterification reactor. As a result, 2 × 10 ⁻⁴ mol of zinc acetate was added to 1 mol of terephthalic acid, and an esterification reaction was carried out under a nitrogen gas atmosphere at 0.35 MPa and 250 ° C. for 3 hours. After the obtained esterification reaction product was sent to a polycondensation reactor, 2 × 10 ⁻⁴ mol of antimony trioxide was added as a catalyst to 1 mol of terephthalic acid component, and 1700 Pa (1.3 torr), It was obtained by performing a polycondensation reaction at 280 ° C. for 3 hours. With reference to Table 1, this polyester PE-1 has an intrinsic viscosity of 0.82 dl / g (deciliter / gram, the same applies hereinafter), a molar fraction of terephthalic acid in the dicarboxylic acid component of 100%, The mole fraction of 1,4-cyclohexanedimethanol in the components was 30% and the mole fraction of ethylene glycol was 70%.

Polyester PE-2 was charged with 33.7 kg of terephthalic acid, 1.8 kg of isophthalic acid, and 75.8 kg of 1,4-cyclohexanedimethanol having a cis / trans ratio of 30:70 in an esterification reactor. The esterification reaction was carried out by adding 2 × 10 ⁻⁴ moles of zinc acetate to 1 mole of the total amount of terephthalic acid and isophthalic acid, and terephthalic acid and The polyester PE-1 was synthesized in the same manner as the synthesis of polyester PE-1, except that 2 × 10 ⁻⁴ mol of antimony trioxide was added to 1 mol of isophthalic acid to carry out a polycondensation reaction. With reference to Table 1, this polyester PE-2 has an intrinsic viscosity of 0.80 dl / g, a molar fraction of terephthalic acid in the dicarboxylic acid component of 95%, and a molar fraction of isophthalic acid of 5 mol%. Yes, the molar fraction of 1,4-cyclohexanedimethanol in the diol component was 100%.

Polyester PE-3 was charged with 26.6 kg of terephthalic acid, 8.9 kg of isophthalic acid, and 75.8 kg of 1,4-cyclohexanedimethanol having a ratio of cis isomer to trans isomer of 30:70 in an esterification reactor. The esterification reaction was carried out by adding 2 × 10 ⁻⁴ moles of zinc acetate to 1 mole of the total amount of terephthalic acid and isophthalic acid, and terephthalic acid and The polyester PE-1 was synthesized in the same manner as the synthesis of polyester PE-1, except that 2 × 10 ⁻⁴ mol of antimony trioxide was added to 1 mol of isophthalic acid to carry out a polycondensation reaction. With reference to Table 1, this polyester PE-3 had an intrinsic viscosity of 0.79 dl / g, a molar fraction of terephthalic acid in the dicarboxylic acid component of 75%, and a molar fraction of isophthalic acid of 25 mol%. The molar fraction of 1,4-cyclohexanedimethanol in the diol component was 100%.

Polyester PE-4 was charged with 25.5 kg of terephthalic acid, 21.5 kg of 1,4-butanediol and 22.3 kg of ethylene glycol in an esterification reactor, and 2 × 10 ⁻⁴ to 1 mol of terephthalic acid as a catalyst. Synthesize | combined by the method similar to the synthesis | combination of polyester PE-1 except having added molar zinc acetate and performing esterification reaction. With reference to Table 1, this polyester PE-4 has an intrinsic viscosity of 0.72 dl / g, a molar fraction of terephthalic acid in the dicarboxylic acid component of 100%, and 1,4-butane in the diol component. The mole fraction of diol was 40% and the mole fraction of ethylene glycol was 60%.

Polyester PE-5 was esterified by adding 42.0 kg of naphthalenedicarboxylic acid and 30.1 kg of ethylene glycol to the esterification reactor and adding 2 × 10 ⁻⁴ mol of zinc acetate as a catalyst to 1 mol of naphthalenedicarboxylic acid. Except that the reaction was performed, and that the resulting esterification product was subjected to a polycondensation reaction by adding 2 × 10 ⁻⁴ mol of antimony trioxide to 1 mol of naphthalenedicarboxylic acid as a catalyst. The polyester PE-1 was synthesized in the same manner as the synthesis of polyester PE-1. With reference to Table 1, this polyester PE-5 has an intrinsic viscosity of 0.83 dl / g, a mole fraction of naphthalenedicarboxylic acid in the dicarboxylic acid component of 100%, and a mole of ethylene glycol in the diol component. The fraction was 100%.

Polyester PE-6 was charged with 35.5 kg of terephthalic acid and 33.1 kg of ethylene glycol in an esterification reactor, and 2 × 10 ⁻⁴ mol of zinc acetate was added to 1 mol of terephthalic acid as a catalyst to carry out the esterification reaction. The synthesis was performed in the same manner as the synthesis of polyester PE-1, except that it was performed. With reference to Table 1, this polyester PE-6 has an intrinsic viscosity of 0.89 dl / g, a mole fraction of terephthalic acid in the dicarboxylic acid component of 100%, and a mole fraction of ethylene glycol in the diol component. The rate was 100%.

Example 1
<Preparation of Pellet of Polyarylate Resin Composition, Test Piece for Measuring Physical Properties, and Sample Plate>
Using 20 parts by mass of a polyarylate resin, 80 parts by mass of polyester and 0.06 parts by mass of a phosphate compound, the main direction of a twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.) using a continuous quantitative supply device manufactured by Kubota. The mixture was supplied to the supply port, melted and kneaded at a resin temperature of 300 ° C., and a discharge rate of 15 kg / hr. The resin composition taken into a strand from the die was passed through a water bath, solidified by cooling, and cut with a pelletizer, then 100 The pellets of the polyarylate resin composition were obtained by drying with hot air for 12 hours. Next, the obtained polyarylate resin composition pellets were molded at a resin temperature of 290 ° C. using an injection molding machine (IS100E-3S manufactured by Toshiba Machine Co., Ltd.) to prepare a test piece for measuring physical properties and a sample plate.

<Measurement of physical properties of polyarylate resin composition>
The intrinsic viscosity of the polyarylate resin composition was measured using the polyarylate resin composition pellets. Also, the bending strength, flexural modulus, deflection temperature under load, oil resistance, chemical resistance and adhesiveness of the polyarylate resin composition are as described above after standing at room temperature (23 ° C., relative humidity 50%) for 1 day or more. It measured using the test piece for physical property measurement. Further, the total light transmittance and the yellow index were further measured using a vapor sample plate.

Here, the specific measuring method of the said physical-property measurement and its evaluation criteria are as follows.
(1) Intrinsic viscosity was measured using a solution at a temperature of 20 ° C. obtained by using an equivalent mixture of phenol and ethane tetrachloride as a solvent, and expressed in units of dl / g.
(2) Flexural strength and flexural modulus were measured according to ASTM D790.
(3) The deflection temperature under load was measured at a load of 0.45 MPa according to ASTM D648.
(4) The total light transmittance (hereinafter also referred to as T%) was measured on a 3 mm thick sample plate according to JIS K7105 with a haze meter (Nippon Denshoku SZ-Σ90 colorimeter). Here, T% of 85% or more was evaluated as excellent, T% of 80% or more and less than 85% was evaluated as good, and T% of less than 80% was evaluated as defective.
(5) The yellow index (hereinafter also referred to as YI) was measured with a color tone measuring device (SE-2000 type colorimeter manufactured by Nippon Denshoku) based on JIS Z8722. . Here, those having a YI of 25 or less were judged to be excellent, those having a YI exceeding 25 and 30 or less were judged good, and those having a YI exceeding 30 were judged to be bad. It is considered that the smaller the YI, the higher the heat discoloration.
(6) Flame retardancy was measured using a test piece having a thickness of 1/8 inch (3.2 mm) based on UL standard 94. Here, the flame retardancy was evaluated according to UL standard 94 in grades of V-0, V-1, V-2 and HB.
(7) The oil resistance is a test piece having the shape shown in FIG. 3 using an injection molding machine (IS100E-3S manufactured by Toshiba Machine Co., Ltd.). As shown in FIG. Fixed to U shape with wire, immersed in oil (Yushiloken EC-50T5 manufactured by Yushiro Chemical Industry), and left to stand in a constant temperature bath at 50 ° C. for 100 hours to check for cracks and breakage did. Here, the thing which did not have a crack and destruction was made into good, and the thing with a crack or destruction was made into the defect. Here, the dimensions of the test piece shown in FIG. 3 are as follows: length L ₁ is 57 mm, length L ₂ is 115 mm, length L ₃ is 215 mm, width W ₁ is 13 mm, width W ₂ is 19 mm, radius of curvature R Is 76 mm and the thickness T is 3.2 mm.
(8) The chemical resistance was prepared by using an injection molding machine (IS100E-3S manufactured by Toshiba Machine Co., Ltd.) to produce a test piece having the shape shown in FIG. 3, and both ends of the test piece were as shown in FIG. , Fixed in a U-shape with a wire, and diluted with water an aqueous detergent (25% by weight sodium hydroxide and 5% by weight sodium hypochlorite TEX121, pH 13 made by ABC Compounding) The specimen was immersed in a cleaning liquid having a concentration of 1.13% by mass and allowed to stand for 100 hours in a thermostatic bath at 50 ° C., and the presence or absence of cracks or breakage of the test piece was confirmed. Here, the thing which did not have a crack and destruction was made into good, and the thing with a crack or destruction was made into the defect. Here, the dimensions of the test piece fixed to the U-shaped mold with the wire shown in FIG. 4 are as follows: the wire fixing distance L _{4 in} the length direction is 20 mm, the wire fixing distance W _{4 in the} width direction is 10 mm, and is fixed with the wire. The distance D between both ends is 80 mm.
(9) Adhesion was made by using an injection molding machine (IS100E-3S manufactured by Toshiba Machine Co., Ltd.) to produce a test piece having the shape shown in FIG. ) Was used as an adhesive, and an adhesive test piece shown in FIG. 5 was prepared, and a tensile shear test was performed in accordance with ASTM D1002 to confirm the adhesion state (fracture mode) at the fracture portion. Here, the case where the fracture portion was the material failure of the test piece or the cohesive failure of the adhesive was judged good, and the case where the fracture portion was the interface fracture between the test piece and the adhesive was judged as poor. The measurement results and evaluation results are summarized in Table 2.

<Production of clamp member and proximity sensor>
When it was determined that the resin composition was good in the adhesion evaluation, a clamp member was molded from the above resin composition pellets using an injection molding machine (IS80G manufactured by Toshiba Machine Co., Ltd.). Next, the proximity sensor shown in FIGS. 1 and 2 was assembled using this clamp member.

<Evaluation of heat shock resistance of proximity sensor>
(10) The sheet shock resistance of the produced proximity sensor is a cycle of heating for 30 minutes in a 85 ° C. heating tank after cooling for 30 minutes in a −40 ° C. cooling tank using a thermal shock test. A heat shock resistance test was performed, and the number of cycles until the proximity sensor reached insulation failure was measured. Here, one having a cycle number of 150 or more was judged good, and one having a cycle number less than 150 was judged defective. The evaluation results are summarized in Table 2.

(Examples 2-18, Comparative Examples 1-3)
About each of Examples 2-18 and Comparative Examples 1-3, as a polyarylate resin composition, as described in Table 2 and Table 3, polyarylate resin, polyester PE-1 to PE-6, polycarbonate, organophosphorus compound And preparation of polyarylate resin composition pellets, physical property measurement specimens and sample plates, measurement of physical properties of polyarylate resin composition, clamping member and proximity The sensor was manufactured and the heat shock resistance of the proximity sensor was evaluated. The measurement results and evaluation results are summarized in Tables 2 and 3.

  As is apparent from Tables 2 and 3, the polyarylate resin composition forming the clamp member according to the present invention has excellent oil resistance, chemical resistance and flame resistance, A clamp member having chemical resistance and flame retardancy and a sensor device using the same can be provided. Further, by using the clamp member, a sensor device having high heat shock resistance and excellent environmental compatibility can be obtained.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

It is a model disassembled perspective view which shows the assembly structure of the sensor apparatus concerning this invention. It is a schematic cross section which shows the sensor apparatus concerning this invention. It is a schematic diagram which shows the shape of the test piece used for evaluation of the polyarylate resin composition of the clamp member concerning this invention. Here, (a) shows a schematic plan view of the test piece, and (b) shows a schematic side view of the test piece. It is a schematic diagram which shows the evaluation test method of the oil resistance or chemical resistance of the polyarylate resin composition of the clamp member concerning this invention. Here, (a) is a schematic top view of a test piece in which both ends are fixed with a wire, (b) is a schematic side view of a test piece in which both ends are fixed with a wire, and (c) is a wire in both ends. The model perspective view which shows the immersion state to the oil or cleaning agent of the fixed test piece is shown. It is a model side view which shows the evaluation test method of the adhesiveness of the polyarylate resin composition of the clamp member concerning this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Sensor apparatus, 10 Main body case, 20 Detection part, 30 Circuit board, 31 Electronic component, 32 Operation confirmation lamp, 40 Clamp member, 50,300 Sealing filler, 51 Primary casting sealing filler, 52 Secondary casting sealing filler, 53 protective layer, 60 protector member, 70 cord, 100 test piece, 101 wire, 200 oil or cleaning agent.

Claims (4)

A clamp member used in a sensor device,
The material of the clamp member is 10 to 50 parts by mass of polyarylate resin and at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and diphenyldicarboxylic acid, and 1,4-cyclohexane dimethanol, Ri polyarylate resin composition der comprising a polyester from 90 to 50 parts by mass formed from at least one diol selected from the group consisting of 1,4-butanediol and ethylene glycol,
The polyarylate resin composition of flexural modulus of Ru der less 2.0GPa clamping member.   The clamp member according to claim 1, wherein the polyarylate resin composition further contains at least one compound selected from an organic phosphorus compound and a bromine compound.   The clamp member according to claim 1 or 2, wherein the polyarylate resin composition further contains a polycarbonate resin. A sensor device using the clamp member according to any one of claims 1 to 3,
A main body case that is open at both ends; a detection unit that closes a front end opening of the main body case; a circuit board that is housed in the main body case; and the clamp member that closes a rear end opening of the main body case; A sensor device comprising: a sealing filler that is filled in the main body case in which the circuit board is accommodated and both ends are closed by the detection unit and the clamp member; and a protector member that contacts the clamp member.

Images