CN105778051B - Resin composition, sensor casting, and temperature sensor - Google Patents
Resin composition, sensor casting, and temperature sensor Download PDFInfo
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- CN105778051B CN105778051B CN201610009623.4A CN201610009623A CN105778051B CN 105778051 B CN105778051 B CN 105778051B CN 201610009623 A CN201610009623 A CN 201610009623A CN 105778051 B CN105778051 B CN 105778051B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
- G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- Epoxy Resins (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides a resin composition, a casting for a sensor and a temperature sensor, and aims to provide a casting for a sensor having excellent thermal shock resistance and moisture resistance and a resin composition for manufacturing the casting for the sensor, wherein in the resin composition containing an epoxy resin and a polyoxyalkylene polyamine as a curing agent, the amine equivalent of the polyoxyalkylene polyamine is 225g/eq or less, and the amine equivalent of the polyoxyalkylene polyamine is 0.40 to 0.75 relative to the epoxy equivalent 1 of the epoxy resin, and the polyoxypropylene diamine is used as the polyoxyalkylene polyamine.
Description
Technical Field
The invention relates to a resin composition, a sensor casting and a temperature sensor.
Background
Sensors such as temperature sensors are used in a wide range of fields such as automobiles, home appliances, and industrial equipment. For example, as a temperature sensor of a thermistor, a resin-molded thermistor sensor is known in which a thermistor element to which an insulated wire is connected is inserted into a protective case (case), and an insulating liquid resin such as epoxy resin is injected into the protective case and cured.
In recent years, the use environment of these sensors has become more severe, and the requirement for reliability of the sensors has also increased. The thermistor sensor is required to maintain high reliability without deterioration of the resin part and without interfacial separation between the resin part and the wire even under such severe use conditions.
[ patent document 1] Japanese unexamined patent publication No. 2012-59731
[ patent document 2] Japanese patent application laid-open No. Hei 6-248059
Disclosure of Invention
The sensor casting resin also needs to have excellent adhesion (thermal shock resistance) to prevent separation from a protective case such as a copper case during heat cycle use and shape retention to retain the shape even in long-term use under high humidity. In particular, shape retention is recently required to retain a shape for a longer period of time under a higher humidity condition.
The resin compositions for sensor potting of patent documents 1 and 2 have excellent adhesion to the case, but further improvement in shape retention is required.
Accordingly, an object of the present invention is to provide a resin composition which can maintain excellent adhesion to a case and can further improve shape retention under high humidity conditions, and a temperature sensor and a cast product for a sensor using the resin composition.
The present inventors have conducted extensive studies and as a result, have found that the above problems can be solved by specifying the amine equivalent of a polyoxyalkylene polyamine in a resin composition containing an epoxy resin and a polyoxyalkylene polyamine, and have completed the present invention.
(1) That is, the resin composition of the present invention is a resin composition containing an epoxy resin and a polyoxyalkylene polyamine having an amine equivalent of 225g/eq or less.
(2) The amine equivalent is preferably 200g/eq or less.
(3) Further, the amine equivalent of the polyoxyalkylene polyamine of the resin composition is preferably in the range of 0.40 to 0.75 equivalent to 1 epoxy equivalent of the epoxy resin.
(4) The polyoxyalkylene polyamine is preferably a polyoxypropylene diamine.
(5) The resin composition preferably further contains an inorganic filler.
(6) The inorganic filler preferably contains at least one selected from the group consisting of alumina, boron nitride, and silicon nitride.
(7) The resin composition is preferably usable for molding a sensor.
(8) The temperature sensor of the present invention includes a temperature sensor element, a case that encloses the temperature sensor element, and the resin composition that is formed by casting between the temperature sensor element and the case.
The present inventors have also found that the above-mentioned problems can be solved by adjusting the boiling water absorption of a cured product of a resin composition to a certain value in a cast product for a sensor using the resin composition containing an epoxy resin and a polyoxyalkylene polyamine.
(9) That is, the sensor casting of the present invention is a sensor casting using a resin composition containing an epoxy resin and a polyoxyalkylene polyamine, and is characterized in that the boiling water absorption of a cured product of the resin composition is 1.9% or less.
(10) The cured product of the resin composition has a tensile modulus of elasticity of 1X 10 at-60 ℃ to-40 ℃9Pa～1×1010Pa, tensile modulus of elasticity of 1X 10 at 80-100 ℃6Pa～2×107Pa is preferred.
(11) Further, the polyoxyalkylene polyamine of the sensor casting is preferably a polyoxypropylene diamine.
The resin composition or the sensor casting of the present invention can improve moisture resistance while maintaining excellent thermal shock resistance of the cured resin, and therefore can maintain excellent reliability of the sensor for a long period of time even in a severe use environment.
Drawings
Fig. 1 is a schematic cross-sectional view showing a thermistor sensor according to an embodiment of the present invention.
FIG. 2 is a graph showing the relationship between the amine equivalent of the curing agent for a resin composition of the present invention and the shape retention time in a moisture resistance test.
Detailed Description
The following describes embodiments of the present invention in detail.
The resin composition of the present invention is characterized by containing an epoxy resin and a polyoxyalkylene polyamine.
The resin composition of the present invention will be described in detail below.
(1) Epoxy resin
Specific examples of the epoxy resin used in the present invention include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ether type epoxy resin such as phenol novolac type epoxy resin and cresol novolac epoxy resin, glycidyl ester type epoxy resin such as glycidyl hexahydrophthalate and dimer acid glycidyl ester, glycidyl amine type epoxy resin such as triglycidyl isocyanurate and tetraglycidyl diaminodiphenylmethane, alcohol ether type epoxy resin composed of 1-valent or polyvalent alcohol such as neopentyl glycol, trimethylolpropane, 1, 6-hexanediol and 1, 4-butanediol, brominated bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, epoxy resin having biphenyl skeleton, epoxy resin having naphthalene skeleton, epoxy resin having no hydroxyl group, epoxy resin having no hydroxyl group, and the like, Alicyclic epoxy resins, and the like.
Among these, an epoxy resin which is liquid at room temperature is preferable, but even an epoxy resin which is solid at room temperature can be used by dissolving it into an epoxy resin which is liquid at room temperature. These epoxy resins may be used alone or in combination of two or more.
(2) Polyoxyalkylene polyamines
In the present invention, polyoxyalkylene polyamine having an amine equivalent of 225g/eq or less is used as the curing agent. The polyoxyalkylene polyamine is a flexible amine, and a flexible portion in the molecule can relax thermal shock. Therefore, the present invention using the polyoxyalkylene polyamine can provide a cured product having excellent thermal shock resistance. Further, by using the polyoxyalkylene polyamine, a resin composition having a low viscosity and a good pot life can be obtained, and workability such as casting can be improved.
The amine equivalent is the number of grams of amine containing 1 equivalent of active hydrogen and is determined by dividing the number of active hydrogens by the molecular weight of the amine.
Specifically, according to JIS 7237: 1995, the total amine value was calculated by substituting the calculated total amine value into the following formula.
(amine equivalent) [1/{ (full amine value) x n } ] x 56.11x 1000
(here, the 1-stage amine n is 2, and the 2-stage amine n is 1)
By using a polyoxyalkylene polyamine having an amine equivalent of 225g/eq or less, a resin cured product having excellent thermal shock resistance and moisture resistance can be obtained. When the amine equivalent of the polyoxyalkylene polyamine exceeds 225g/eq or more, the moisture resistance of the resulting resin cured product is low, and sufficient shape retention cannot be obtained when the resin cured product is used under high humidity conditions for a long period of time. The amine equivalent of the polyoxyalkylene polyamine is more preferably 200g/eq or less. This further improves the thermal shock resistance and moisture resistance of the resulting resin cured product.
On the other hand, the lower limit of the amine equivalent of the polyoxyalkylene polyamine is not particularly limited, but is preferably 100g/eq or more, more preferably 120g/eq or more, in view of workability such as uniform dispersion with an epoxy resin or the like.
The polyoxyalkylene polyamine used in the present invention may, for example, be a polyoxypropylene triamine, a polyoxypropylene diamine, a polyoxyethylene diamine, a polytetramethylene ether glycol/polypropylene glycol copolymer diamine, a polypropylene glycol/polyethylene glycol copolymer diamine or the like. Among these, polyoxypropylene diamine is particularly preferable from the viewpoint of flexibility and moisture resistance.
The polyoxyalkylene polyamine described above can be used alone, or a plurality of the polyoxyalkylene polyamines can be used in combination. The amine equivalent when a plurality of polyoxyalkylene polyamines are used is expressed as the average amine equivalent per unit mass of the polyoxyalkylene polyamine present. For example, an amine equivalent of a1g/eq of amine 1 with an amine equivalent of a2g/eq of amine 2 is m1And m2The average amine equivalent of the resin composition thus prepared was calculated by the following equation.
Average amine equivalent weight ═ m1+m2)/[(m1/a1)+(m2/a2)]
In the present invention, it is preferable that the amine equivalent of the polyoxyalkylene polyamine is in the range of 0.40 to 0.75 equivalent relative to 1 equivalent of the epoxy resin. When the equivalent ratio is within the above range, the thermal shock resistance and moisture resistance of the resulting resin cured product are further improved. When the amine equivalent of the polyoxyalkylene polyamine exceeds 0.75 equivalent based on 1 equivalent of the epoxy resin, the heat shock resistance tends to be lowered. On the other hand, when the amine equivalent of the polyoxyalkylene polyamine is less than 0.40 equivalent based on 1 equivalent of the epoxy resin, although excellent thermal shock resistance can be obtained, the plasticity of the cured resin is high and there is a possibility that the cured resin is dissolved in oil or the like.
(3) Filler
In the resin composition of the present invention, an inorganic filler is preferably added as a filler. Examples of the inorganic filler include silica, calcium carbonate, and bicarbonates of calcium and magnesium (Ca. Mg (CO)3)2) Alumina, aluminum hydroxide, magnesium hydroxide, clay, talc, mica, wollastonite, boron nitride, silicon nitride, and the like. Among these inorganic fillers, alumina, boron nitride, silicon nitride and the like having high thermal conductivity are preferable, and alumina is particularly preferable. As the alumina, any crystal form of α alumina, β alumina, and γ alumina can be used, but α alumina is preferably used from the viewpoint of stability.
The average particle size of the inorganic filler is preferably 1 to 100 μm, more preferably 1 to 10 μm. In the present invention, a part of the inorganic filler may be alumina having a particle size of 1 μm or less (hereinafter referred to as "fine alumina"). In this case, the fine alumina functions as a sedimentation preventing agent for other inorganic fillers, and a cast product in which the inorganic fillers are uniformly dispersed can be obtained. The proportion of the fine alumina used as the anti-settling agent is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, based on the total amount of the inorganic filler (the total amount of the fine alumina and the inorganic filler other than the fine alumina). The amount of the inorganic filler added is preferably 55% by mass or more, more preferably 65% by mass or more, based on the total composition. When the amount of the inorganic filler added is 55% by mass or more, the thermal conductivity is 0.5W/mK or more, and therefore the performance of the sensor is further improved. The upper limit of the amount of the inorganic filler to be used is not particularly limited, but is preferably 80 mass% or more in view of workability in casting work.
(4) Other additives
The resin composition of the present invention may further contain other various additives as necessary within a range not impairing the effects of the present invention. The additives include colorants, flame retardants, defoaming agents, coupling agents, adhesion improvers, impact moderators, sedimentation preventives, thickening reducers, diluents, and the like.
(5) Method for preparing resin composition
When the resin composition of the present invention is a one-pack type, it can be prepared by mixing an epoxy resin, a polyoxyalkylene polyamine, a predetermined amount of a filler added as needed, the above-mentioned other additives, and the like with a mixer or the like. In the case of the two-component type, a filler and other additives are added to the epoxy resin in a predetermined amount as required, and the mixture is mixed to prepare a base compound. On the other hand, the polyoxyalkylene polyamine is mixed with other curing agents and additives as needed to prepare a curing agent. In the production of a sensor or the like, the above-mentioned base compound and the curing agent are mixed by a mixer or the like and used.
(6) Cured product of resin composition
The resin composition of the present invention containing an epoxy resin and a polyoxyalkylene polyamine can be cured to be applied to sensor casting. The curing conditions are not particularly limited, but the curing temperature is preferably from 80 ℃ to 150 ℃ and the curing time is preferably from 0.5 hours to 10 hours. Here, the boiling water absorption of the cured product of the resin composition was adjusted to 1.9% or less. The boiling water absorption is a value representing the water absorption after the moisture resistance test of the resin cured product evaluated by the method described later. By adjusting the boiling water absorption of the cured resin to 1.9% or less, the shape retention after long-term use under high humidity can be significantly improved. Specifically, it was confirmed that the cured resin having a boiling water absorption of 1.9% or less retained its original shape after being left in an environment of 85 ℃ and a relative humidity of 85% for 4000 hours. The boiling water absorption of the cured resin is preferably 1.7% or less, more preferably 1.6% or less.
The tensile modulus of the cured product of the resin composition at-60 ℃ to-40 ℃ calculated by the method described later is preferably 1X 109Pa～1×1010Pa, the stretch modulus of the patient at 80 ℃ to 100 ℃ is preferably 1X 106Pa～2×107Pa. By reducing the modulus of elasticity at-60 to 40 ℃ and the modulus of elasticity at 80 to 100 ℃, the thermal shock resistance can be improved, and the adhesiveness to a protective case or the like can be maintained even after long-term use under severe thermal cycles.
(7) Manufacture of thermistor temperature sensor
The resin composition of the present invention is suitably used for casting between a temperature sensor element and a protective case of a temperature sensor such as a thermistor sensor. A method for manufacturing a thermistor sensor according to an embodiment of the present invention will be described below. As shown in fig. 1, in the thermistor sensor 1 of the present embodiment, the temperature element 2, the lead wire 3 made of a copper wire or the like connected to the temperature element 2, and the end portions of the external lead wires 4(4a, 4b) connected via the lead wire 3 are inserted into the protective case 5. Here, the resin composition of the present invention is injected into the protective case 5 and cured to form the resin portion 6.
As the protective case, a case made of resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or ABS resin may be used in addition to a metal case made of copper. In the case of using any of the cases, the effects of the resin composition and the sensor-use potting product of the present invention can be exhibited. The outer lead 4 is an insulated wire in which an insulating cover 4b made of soft vinyl chloride resin, bridged polyethylene, or the like is coated on the outer periphery of a conductor 4 a. In the manufacture of the thermistor sensor 1, after a resin composition is injected into the protective case 5, the temperature element 2 to which the lead 3 and the external lead 4 are connected may be inserted and the resin composition may be cured. The temperature element 2 to which the lead 3 and the external lead 4 are connected may be inserted into the protective case 5, and then a resin composition may be injected and cured. The curing temperature of the resin composition is preferably from 80 ℃ to 150 ℃ and the curing temperature is preferably from 0.5 hour to 10 hours.
In the thermistor sensor 1, by using the resin composition of the present invention, even when used under severe conditions of thermal cycle, the resin portion does not peel off from the protective case or the like, and the shape can be maintained even when used for a long period of time under high humidity, thereby realizing a sensor having high reliability.
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the case where no specific description is given in the examples, "%" and "part" represent mass% and mass part.
(Components of resin composition)
(A) Main agent
(A1) Bisphenol a type epoxy resin: JeR815, epoxy equivalent 184g/eq Mitsubishi chemical column Co., Ltd
(A2) Polyoxyalkylene bisphenol a diglycidyl ether (polyoxyalkylene bisphenol a type epoxy resin), epoxy equivalent: manufactured by ADEKA, 510g/eq
(B) Curing agent
(B1) Polyoxypropylene diamine: JEFFAMINE D-400, molecular weight of about 400, amine equivalent; 114g/eq HUNTSMAN
(B2) Polyoxypropylene diamine: JEFFAMINE D-2000, molecular weight: about 2000, amine equivalent: 500g/eq of Huntsman Co., Ltd
(B3) XTJ-542, molecular weight: about 1000, amine equivalent: 260g/eq HUNTSMAN manufactured by HUNTSMAN
(B4) Acid anhydride: methyl tetrahydrophthalic anhydride: HN-2000, anhydride equivalent: 166g/eq Hitachi chemical Industrial products, manufactured by Nishisha Kabushiki Kaisha
(B5)2,4, 6-tris (dimethylaminomethyl) phenol: manufactured by Ancamine K-54Air Products Chemicals, Inc
(examples 1 to 9, comparative examples 1 to 3, and reference example 1)
The epoxy resin, the coupling agent, the pigment and the filler were mixed in a mixer at the compounding ratios (by mass) shown in tables 1 and 2 to prepare a base compound. The curing agents shown in table 1 or table 2 were mixed singly or in a mixture of 2 or more, and then mixed with the base compound in the proportions (by mass) shown in table 1 and table 2 to prepare a resin composition. The obtained resin compositions were poured into a mold for preparing test pieces for evaluation of boiling water absorption, moisture resistance, tensile modulus and thermal shock resistance, and cured by heating at 100 ℃ for 5 hours. The boiling water absorption, moisture resistance, tensile elasticity and thermal shock resistance of the test pieces (cured products) obtained were evaluated by the methods described below, and the results are shown in tables 1 and 2.
(measurement of boiling Water absorption)
The resin composition was poured into a mold and heated at 100 ℃ for 5 hours to cure the resin composition, thereby obtaining a sample for measuring boiling water absorption of 45mm phi and 3mm in thickness. The sample was boiled in water at 100 ℃ for 24 hours, taken out, dried at 40 ℃ for 5 hours, dried at 100 ℃ for 5 hours, and the weights of the boiled and dried samples were measured. The boiling water absorption was calculated by the following formula.
(boiling water absorption [ { (weight of sample after boiling) - (weight of sample after drying) }/(weight of sample after drying) ] x100
(moisture resistance test: shape Retention test)
The resin compositions of examples and comparative examples were injected into a mold, and heated at 100 ℃ for 5 hours to cure the resin compositions, thereby preparing a sample for a moisture resistance test having a thickness of 3mm and a diameter of 45mm phi. Each sample was placed in a constant temperature and humidity cell at 85 ℃ and 85% relative humidity, and taken out every 500 hours to observe (visually) the shape retention property. The time at which the sample was found to elute was regarded as the elution time and evaluated.
(measurement of tensile modulus of elasticity)
The resin composition was injected into a mold, heated at 100 ℃ for 5 hours to cure the resin composition, and then cut into a sample having a width of 10mm, a length of 50mm and a thickness of 2mm to prepare a sample for measurement. The tensile modulus was measured by using a DMA measuring apparatus according to JIS K0129: 2005.
(thermal shock resistance test)
After the resin compositions of examples and comparative examples were deaerated, 2ml of the resin compositions were injected into a 4mm phi copper box (capacity: 2.5ml) into which an analog sensor was inserted, using a syringe needle. Then, the resin composition was cured by heating at 100 ℃ for 5 hours to obtain a sample for evaluation. In addition, 2 simulation wires with the diameter of 1.2mm are connected to the simulation sensor.
The sample was immersed in liquid nitrogen for 1 minute and taken out, and then immersed in silicone oil maintained at 130 ℃ for 1 minute and taken out. After standing at room temperature for 2 minutes, the analog sensor was pulled by hand to confirm the presence or absence of pulling. This step was set as 1 cycle, and the number of cycles elapsed when the analog sensor element was pulled out was measured for each sample and evaluated.
As shown in Table 1, in example 1 and comparative example 2, a polyoxypropylene diamine having an amine equivalent of 114g/eq and a polytetramethylene ether glycol/polypropylene glycol copolymer diamine having an amine equivalent of 260g/eq were used alone as curing agents, respectively. In example 2, example 3, example 4, comparative example 1 and comparative example 3, the amine equivalent was changed by changing the mixing ratio of polyoxypropylene diamine having an amine equivalent of 114g/eq and polyoxypropylene diamine having an amine equivalent of 500 g/eq.
As shown in Table 1, it was found that the number of cycles from the pulling-out of the analog sensor element was 3 and the thermal shock resistance was at a level suitable for practical use in comparative example 1 having an amine equivalent of 248 g/eq. However, it was also confirmed that the boiling water absorption was as high as 2.0%, the shape retention time was 3500 hours, and the shape retention under high humidity conditions was insufficient. It is also found that comparative example 3, in which the amine equivalent is 298g/eq, can also obtain good thermal shock resistance, but the shape retention time is shorter than comparative example 1. Further, it was also confirmed that in comparative example 2 using a polytetramethylene ether glycol/polypropylene glycol copolymer type diamine having an amine equivalent of 260g/eade1, good thermal shock resistance was obtained in the same manner, but the shape retention property under high humidity conditions was insufficient. The boiling water absorption of comparative examples 2 and 3 was 2.0% as in comparative example 1.
On the other hand, it was found that in examples 1, 2, 3 and 4 having amine equivalent weights of 114, 148, 186 and 212g/eq, the number of cycles until the dummy sensor element was pulled out was 3 or more in any case, and it was possible to significantly increase the shape retention time while maintaining excellent thermal shock resistance. In addition, the boiling water absorption rates of examples 1, 2, 3 and 4 were 1.3%, 1.4%, 1.6% and 1.7%, respectively, and the boiling water absorption rate of the cured product of the resin composition containing the epoxy resin and the polyoxyalkylene polyamine was 1.7% or less, which satisfied both excellent thermal shock resistance and moisture resistance.
FIG. 2 shows the relationship between the amine equivalent of a cured resin and the shape retention time in a moisture resistance test. From FIG. 2, it was confirmed that the shape retention time increased as the amine equivalent decreased. When the amine equivalent is 225g/eq or less, the shape retention time increases sharply, and when the amine equivalent is 200g/eq or less, the shape retention time increases more remarkably.
Further, as reference example 1, a resin composition was prepared using an epoxy resin (polyoxyalkylene bisphenol A type epoxy resin, epoxy equivalent: 510g/eq), an acid anhydride (methyltetrahydrophthalic anhydride, acid anhydride equivalent: 166g/eq) and 2,4, 6-tris (dimethylaminomethyl) phenol in an equivalent ratio (acid anhydride equivalent/epoxy equivalent) of 0.9, and a cured resin was obtained under the same conditions as in the above examples. It was confirmed that the above cured resin had a boiling water absorption of 1.4%, a shape retention time of more than 8000 hours, and good moisture resistance. However, in the above reference example 1, the tensile modulus at 80 ℃ to 100 ℃ was as high as 28X 106Pa, in the thermal shock resistance test in a predetermined temperature range (-40 ℃ to-150 ℃), the number of cycles until the sensor element was pulled out was about 1/10 in the example, and thus it was found that sufficient thermal shock resistance could not be obtained.
Polyoxyalkylene bisphenol a type epoxy resins are known as epoxy resins having very excellent thermal shock resistance. Although not shown in the table, when a polyoxyalkylene polyamine was used as the curing agent, a cured product having excellent thermal shock resistance and moisture resistance could be obtained. However, in reference example 1 using an acid anhydride as a curing agent, such a cured product was not obtained.
From the above results, it was confirmed that the resin composition of the present invention containing an epoxy resin and a polyoxyalkylene polyamine has the effects.
As shown in Table 2, in examples 2 and 5 to 9, a curing agent in which a polyoxypropylene diamine having an amine equivalent of 114g/eg and a polyoxypropylene diamine having an amine equivalent of 500g/eq were mixed at a mass ratio of 70:30 was used. Here, samples having different equivalent ratios were prepared by changing the mixing ratios of the main agent and the curing agent. In examples 7, 8 and 9 in which the equivalence ratio was increased, the number of cycles elapsed when the analog sensor element was pulled out was reduced, and in examples 5 and 6 in which the equivalence ratio was reduced, the number of cycles was increased, as compared with example 2 in which the equivalence ratio (amine equivalent/epoxy equivalent) was 0.6.
In example 5 in which the equivalent ratio was 0.4, although excellent thermal shock resistance could be obtained, the resin cured product had high plasticity and was likely to be dissolved in oil or the like, and therefore, it can be said that an equivalent ratio of 0.4 or more is preferable. On the other hand, in order to secure a sufficient number of cycles, it is said that the equivalence ratio is preferably 0.75 or less.
Further, it is understood from example 5 that since a sufficient shape retention time can be obtained with a boiling water absorption of 1.9%, the boiling water absorption of a cured product of the resin composition containing the epoxy resin and the polyoxyalkylene polyamine is 1.9% or less, and excellent thermal shock resistance and moisture resistance can be satisfied at the same time.
Description of reference numerals:
1. thermistor sensor
2. Temperature element
3. Lead wire
4. External lead wire
5. Protective box
6. Resin part
Claims (9)
1. A resin composition for sensor casting, which contains an epoxy resin and a polyoxyalkylene polyamine, characterized in that the amine equivalent of the polyoxyalkylene polyamine is 100g/eq to 225 g/eq;
the amine equivalent of the polyoxyalkylene polyamine is in the range of 0.50 to 0.70 equivalent relative to 1 equivalent of the epoxy resin.
2. The resin composition according to claim 1, wherein the amine equivalent is 200g/eq or less.
3. The resin composition according to claim 1 or 2, wherein the polyoxyalkylene polyamine is a polyoxypropylene diamine.
4. The resin composition according to claim 1, further comprising an inorganic filler.
5. The resin composition according to claim 4, wherein the inorganic filler comprises at least one selected from the group consisting of alumina, boron nitride and silicon nitride.
6. The resin composition according to claim 1, wherein the epoxy resin is a liquid epoxy resin at room temperature.
7. A temperature sensor comprising a temperature sensor element, a case enclosing the temperature sensor element, and the resin composition casting according to any one of claims 1 to 5 molded by casting between the temperature sensor element and the case.
8. The temperature sensor according to claim 7, wherein the resin composition casting has a boiling water absorption of 1.9% or less.
9. The temperature sensor according to claim 7 or 8, wherein the resin composition casting has a tensile modulus of elasticity of 1x 10 at-60 ℃ to-40 ℃9Pa～1×1010Pa, tensile modulus of elasticity at 80-100 ℃ of 1X 106Pa～2×107Pa。
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| JP (1) | JP6177940B2 (en) |
| CN (1) | CN105778051B (en) |
| TW (1) | TWI664231B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6558959B2 (en) * | 2015-06-02 | 2019-08-14 | ソマール株式会社 | Epoxy resin composition for thermistor sensor casting and thermistor sensor |
| CN113474395A (en) * | 2019-02-26 | 2021-10-01 | 富士胶片株式会社 | Adhesive for endoscope, cured product thereof, endoscope, and method for producing endoscope |
| JP7170901B2 (en) * | 2019-11-08 | 2022-11-14 | 三菱電機株式会社 | Elevator Suspension and Elevator |
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| JPH06248059A (en) * | 1993-02-25 | 1994-09-06 | Somar Corp | Liquid epoxy resin composition for casting |
| CN201289406Y (en) * | 2008-11-14 | 2009-08-12 | 常州市惠昌传感器有限公司 | Temperature sensor joint |
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| JPH07242796A (en) * | 1994-03-02 | 1995-09-19 | Nippon Kayaku Co Ltd | Epoxy resin composition for casting and its cured article |
| DE59610415D1 (en) * | 1995-04-04 | 2003-06-12 | Vantico Ag | Curable epoxy resin mixture containing wollastonite |
| JP2001122947A (en) * | 1999-10-28 | 2001-05-08 | Tosoh Corp | Curing accelerator for epoxy resin and epoxy resin composition using the same |
| JP2001151862A (en) * | 1999-11-22 | 2001-06-05 | Tosoh Corp | Epoxy resin composition |
| JP5111695B2 (en) * | 2001-04-03 | 2013-01-09 | 株式会社リコー | Epoxy resin composition for manufacturing inkjet head and method for manufacturing inkjet head |
| JP4864327B2 (en) * | 2005-01-21 | 2012-02-01 | 阪本薬品工業株式会社 | Epoxy resin composition |
| JP2007023134A (en) * | 2005-07-14 | 2007-02-01 | Sakamoto Yakuhin Kogyo Co Ltd | Epoxy resin composition |
| EP1904578B1 (en) * | 2005-07-15 | 2009-12-02 | Huntsman Advanced Materials (Switzerland) GmbH | Toughened compositon |
| JP2009114307A (en) * | 2007-11-06 | 2009-05-28 | Hitachi Chem Co Ltd | Thermosetting adhesive composition for ceramics substrate and adhesive film using the same composition |
| US9085658B2 (en) * | 2008-12-30 | 2015-07-21 | Blue Cube Ip Llc | Divinylarene dioxide formulations for vacuum resin infusion molding |
| JP5530313B2 (en) * | 2010-09-03 | 2014-06-25 | 京セラケミカル株式会社 | Thermistor sensor casting resin composition and thermistor sensor |
| JP6134089B2 (en) * | 2011-02-22 | 2017-05-24 | 積水化学工業株式会社 | Insulating material and laminated structure |
| JP5825734B2 (en) * | 2011-07-13 | 2015-12-02 | コニシ株式会社 | Model material or model manufacturing method |
| JP5913884B2 (en) * | 2011-09-27 | 2016-04-27 | 積水化学工業株式会社 | Insulating material and laminated structure |
| CN102964780A (en) * | 2012-12-11 | 2013-03-13 | 蓝星(北京)化工机械有限公司 | Epoxy resin composition for vacuum introduction formation of fibre reinforced composite material and preparation method of epoxy resin composition |
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- 2016-01-06 JP JP2016000761A patent/JP6177940B2/en active Active
- 2016-01-06 CN CN201610009623.4A patent/CN105778051B/en active Active
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| JPH06248059A (en) * | 1993-02-25 | 1994-09-06 | Somar Corp | Liquid epoxy resin composition for casting |
| CN201289406Y (en) * | 2008-11-14 | 2009-08-12 | 常州市惠昌传感器有限公司 | Temperature sensor joint |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI664231B (en) | 2019-07-01 |
| JP6177940B2 (en) | 2017-08-09 |
| CN105778051A (en) | 2016-07-20 |
| TW201625734A (en) | 2016-07-16 |
| JP2016130307A (en) | 2016-07-21 |
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