JP5828950B1 - Polyurethane resin composition, sealing material and electric / electronic component - Google Patents

Abstract

An object of the present invention is to provide a polyurethane resin composition which is excellent in high temperature and high humidity durability and flame retardancy and excellent in workability. A polyurethane resin composition comprising a polyurethane resin obtained by reacting an isocyanate group-containing compound and a hydroxyl group-containing compound, an inorganic filler, and a petroleum hydrocarbon, wherein the isocyanate group-containing compound is a polyisocyanate compound. A polyurethane resin composition, wherein the content of the inorganic filler is 50 to 85% by mass with respect to 100% by mass of the polyurethane resin composition. [Selection figure] None

Description

  The present invention relates to a polyurethane resin composition, a sealing material, and an electric / electronic component.

  In recent years, the density and integration of electric and electronic parts have been increased, and improvement of reliability is required for each part. In particular, electrical and electronic parts used in car engines, water heaters, and the like are required to have high reliability even in a high temperature and high humidity environment.

  These electric and electronic parts are sealed with a sealing material in order to impart moisture resistance, and a polyurethane resin composition is used as the sealing material. The polyurethane resin composition used for such a sealing material is required to have high temperature and high humidity durability.

  As a polyurethane resin composition exhibiting thermal durability, for example, a polyurethane resin composition containing a specific hydroxyl group-containing compound, an isocyanate group-containing compound, and an inorganic filler (D), the blending of the inorganic filler (D) A polyurethane resin composition whose amount is 50 to 95% by mass with respect to the polyurethane resin composition has been proposed (see Patent Document 1).

  However, the polyurethane resin composition described in Patent Document 1 describes that an ester plasticizer is used as a plasticizer, and is used for electric and electronic parts used in a high-temperature and high-humidity environment as described above. As a polyurethane resin composition to be obtained, there is a problem that durability at high temperature and high humidity is not sufficient.

  In addition, the polyurethane resin composition used for electrical and electronic parts used in a high temperature environment is required to have flame retardancy in order to suppress ignition. However, Patent Document 1 does not discuss flame retardancy. The polyurethane resin composition of Patent Document 1 has a problem that flame retardancy is not sufficient.

  Furthermore, Patent Document 1 does not discuss the viscosity of the polyurethane resin composition before curing, and there is room for improvement in workability during coating and molding.

  Therefore, development of a polyurethane resin composition that is excellent in high-temperature and high-humidity durability and flame retardancy and excellent in workability is demanded.

Japanese Patent No. 5550161

  An object of the present invention is to provide a polyurethane resin composition that is excellent in high-temperature and high-humidity durability and flame retardancy and excellent in workability.

As a result of intensive studies, the inventor of the present invention, in a polyurethane resin composition comprising an isocyanate group-containing compound and a hydroxyl group-containing compound, a polyurethane resin composition containing an inorganic filler and a petroleum hydrocarbon, When the compound contains an isocyanurate-modified product of a polyisocyanate compound and the content of the inorganic filler is in a specific range, the inventors have found that the above object can be achieved, and have completed the present invention.
That is, this invention relates to the following polyurethane resin compositions, sealing materials, and electric / electronic parts.
1. A polyurethane resin composition comprising an isocyanate group-containing compound and a hydroxyl group-containing compound, a polyurethane resin composition containing an inorganic filler and a petroleum hydrocarbon,
The isocyanate group-containing compound includes a polyisocyanate compound isocyanurate-modified product,
Content of the said inorganic filler is 50-85 mass% with respect to 100 mass% of polyurethane resin compositions.
A polyurethane resin composition characterized by that.
2. Item 2. The polyurethane resin composition according to Item 1, wherein the content of the petroleum hydrocarbon is 5 to 45% by mass with respect to 100% by mass of the polyurethane resin composition.
3. Item 3. The polyurethane resin composition according to Item 1 or 2, wherein the petroleum hydrocarbon is an aromatic hydrocarbon.
4). Item 4. A sealing material comprising the polyurethane resin composition according to any one of Items 1 to 3.
5. Item 5. An electrical and electronic component sealed with a resin using the sealing material according to Item 4.

  The polyurethane resin composition of the present invention is excellent in high-temperature and high-humidity durability and flame retardancy, and is excellent in workability. Moreover, since the sealing material of this invention also consists of the said polyurethane resin composition, it is excellent in high temperature high humidity durability and a flame retardance. Furthermore, since the electrical / electronic component of the present invention is resin-sealed using the sealing material, it exhibits high reliability even in a high-temperature and high-humidity environment.

  Hereinafter, the polyurethane resin composition, the sealing material and the electric / electronic component of the present invention will be described in detail.

  The polyurethane resin composition of the present invention contains a polyurethane resin formed by a reaction between a hydroxyl group-containing compound and an isocyanate group-containing compound.

  The isocyanate group-containing compound includes an isocyanurate-modified product of a polyisocyanate compound. When the isocyanate group-containing compound contains an isocyanurate-modified product of a polyisocyanate compound, the polyurethane resin composition exhibits excellent heat resistance and excellent flame retardancy.

  Examples of the isocyanurate-modified product of the polyisocyanate compound include those obtained by isocyanurate-modifying aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2- Examples thereof include methylpentane-1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.

  Examples of the alicyclic polyisocyanate compound include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Is mentioned.

  Examples of the aromatic polyisocyanate compound include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1, Examples include 5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

  Examples of the araliphatic polyisocyanate compound include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α, α, α, α-tetramethylxylylene diisocyanate.

  As the isocyanurate-modified product of the polyisocyanate compound, an isocyanurate-modified product of an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, or an aromatic polyisocyanate compound is preferable, and among them, an isocyanate of hexamethylene diisocyanate or diphenylmethane diisocyanate. A nurate modified product is more preferable.

  The above-mentioned polyisocyanate compound isocyanurate-modified products may be used alone or in admixture of two or more.

  Examples of commercially available isocyanate group-containing compounds including the isocyanurate-modified polyisocyanate compound include Coronate HX (trade name HDI isocyanurate manufactured by Nippon Polyurethane Co., Ltd.), Duranate TLA-100 (trade name HDI isocyanurate), and the like. It is done.

  The isocyanate group-containing compound may contain other isocyanato group-containing compounds in addition to the isocyanurate-modified product of the polyisocyanate compound. Examples of the other isocyanate group-containing compounds include the above-mentioned aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds, and these polyisocyanate compounds. And allophanate-modified products thereof.

  In the polyurethane resin composition of the present invention, the amount of the isocyanate group-containing compound used is preferably 1 to 30% by mass, more preferably 4 to 20% by mass, based on 100% by mass of the polyurethane resin composition. When the content of the isocyanate group-containing compound is too large, the polyurethane resin composition may cause poor curing, and when it is too small, the high temperature and high humidity durability of the cured polyurethane resin composition may be decreased.

  In the polyurethane resin composition of this invention, it does not specifically limit as a hydroxyl-containing compound used, It is possible to use what was conventionally used as a polyol component in a polyurethane resin composition. Examples of the polyol component include polybutadiene polyol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, and 1,3-butanediol. 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,2-hexanediol, 2,5-hexanediol, octanediol, nonanediol, decanediol , Diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanediol, trimethylolpropane, glycerin, 2-methylpropane-1,2,3-triol, 1,2,6-hexanetriol, pentaerythritol, polylactone diol Polylactone triol, ester glycol, polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, silicone polyol, fluorine polyol, polytetramethylene glycol, polypropylene glycol, polyethylene glycol, polycaprolactone polyol, hydroxyl group-containing liquid polyisoprene hydride, Examples include hydrides of hydroxyl-containing liquid polybutadiene.

  Among the polyol components, polybutadiene polyol is preferably used. The polybutadiene polyol has, for example, a repeating unit composed of polybutadiene having 60 to 90 mol% of 1,4 bonds and 10 to 40 mol% of 1,2 bonds, the number of repetitions being 10 to 14, Examples thereof include a polyol having a hydroxyl group at the terminal.

  The molecular weight of the polybutadiene polyol is preferably 800 to 4800, and more preferably 1200 to 3000.

  As the polyol component, a castor oil-based polyol can be used. Examples of the castor oil-based polyol include castor oil or castor oil derivatives.

  Castor oil fatty acid: castor oil fatty acid; hydrogenated castor oil hydrogenated to castor oil or castor oil fatty acid; transesterification product of castor oil and other fats and oils; reaction product of castor oil and polyhydric alcohol; Reaction products: those obtained by addition polymerization of alkylene oxides.

  As the castor oil-based polyol, hydrogenated castor oil is preferably used.

  The polyol component may contain a polybutadiene polyol and a castor oil-based polyol. In this case, the compounding ratio of the polybutadiene polyol and the castor oil-based polyol is such that the total amount of the polybutadiene polyol and the castor oil-based polyol is 100% by mass, and (polybutadiene polyol) :( castor oil-based polyol) = 90: 10% by mass to 50% : 50% by mass is preferable, and 90: 10% by mass to 70: 30% by mass is more preferable. When the polyol component having the above blending ratio is used, the compatibility with the polyisocyanate component is excellent, the viscosity of the polyurethane resin composition is lowered, and the workability can be further improved.

  As a commercial item of the said polyol component, Idemitsu Kosan Chemical Co., Ltd. hydroxyl-containing liquid polybutadiene Poly bd (trademark) R-15HT (brand name), R-45HT (brand name), etc. are mentioned.

  In the polyurethane resin composition of the present invention, the amount of the hydroxyl group-containing compound used is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, with the polyurethane resin composition as 100% by mass. When there is too much content of a hydroxyl-containing compound, there exists a possibility of producing poor curing, and when there is too little, there exists a possibility that the heat resistance of the polyurethane resin composition obtained may become low.

  In the polyurethane resin composition of the present invention, the NCO / OH ratio between the isocyanate group-containing compound and the hydroxyl group-containing compound is preferably 0.6 to 2.0, and preferably 0.7 to 1.5. Is more preferable. If the NCO / OH ratio is too small, the heat resistance of the polyurethane resin composition may be reduced. If the NCO / OH ratio is too large, the polyurethane resin composition may cause poor curing.

  The polyurethane resin composition of the present invention contains an inorganic filler. Although it does not specifically limit as said inorganic filler, A conventionally well-known inorganic filler can be used. Examples of such inorganic fillers include alumina, aluminum hydroxide, aluminum nitride, boron nitride, magnesium hydroxide, and magnesium oxide. Among these, since it is excellent in heat dissipation, examples thereof include alumina, magnesium oxide, aluminum nitride, boron nitride, zeolite, etc., but in terms of excellent flame retardancy, metal hydrated compounds such as aluminum hydroxide and magnesium hydroxide. Is preferred.

  In the polyurethane resin composition of the present invention, the content of the inorganic filler is 50 to 85% by mass with respect to 100% by mass of the polyurethane resin composition. When the content of the inorganic filler is less than 50% by mass, the polyurethane resin composition is inferior in flame retardancy. When the amount of the inorganic filler exceeds 85% by mass, the mixing viscosity at the time of producing the polyurethane resin composition becomes high, and the workability is lowered.

  The polyurethane resin composition of the present invention contains petroleum hydrocarbons. Petroleum hydrocarbons are hydrocarbons derived from petroleum such as gasoline, heavy oil, and light oil. Examples of petroleum hydrocarbons include paraffin hydrocarbons, olefin hydrocarbons, naphthene hydrocarbons, and aromatic hydrocarbons.

Paraffinic hydrocarbons are saturated chain compounds represented by the molecular formula C _n H _{2n + 2} . Examples of commercially available paraffinic hydrocarbons used in the polyurethane resin composition of the present invention include Diana Process Oil PW-32 (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

The olefinic hydrocarbon is a chain hydrocarbon having a double bond. For example, when one double bond is present in the molecule, it is represented by a general formula of C _n H _2n . Examples of commercially available olefinic hydrocarbons used in the polyurethane resin composition of the present invention include DURASYN (registered trademark) 170 Polyolefins (trade name, manufactured by Ineos Oligomers Japan).

  Naphthenic hydrocarbons are hydrocarbons containing at least one saturated ring (naphthene ring) in one molecule, and examples thereof include cyclopentane and cyclohexane. As a commercial item of the naphthene type hydrocarbon used for the polyurethane resin composition of the present invention, for example, SUN No. 6 INSULATING OIL (trade name, manufactured by Nippon San Oil Co., Ltd.)

  The aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring in one molecule, and examples thereof include aromatic compounds having benzene as a basic structure. More specifically, examples include benzene and monocyclic compounds having a side chain attached to benzene, but also bicyclic and tricyclic polycyclic fused aromatic compounds and compounds containing both aromatic rings and naphthene rings. It is done. Examples of the aromatic hydrocarbon used in the polyurethane resin composition of the present invention include benzene and naphthalene. Moreover, as a commercial item of the aromatic hydrocarbon used for the polyurethane resin composition of this invention, Diana process oil AC-460 (brand name Idemitsu Kosan Co., Ltd. product) etc. are mentioned, for example.

  The petroleum hydrocarbon used in the polyurethane resin composition of the present invention is preferably an aromatic hydrocarbon or a naphthene hydrocarbon, and more preferably an aromatic hydrocarbon in terms of excellent compatibility with the hydroxyl group-containing compound.

  The content of petroleum hydrocarbon is preferably 0.1 to 45% by mass, more preferably 5 to 45% by mass, and still more preferably 5 to 30% by mass with respect to 100% by mass of the polyurethane resin composition. When there is too little petroleum hydrocarbon, there exists a possibility that the compatibility of a polyurethane resin composition may fall.

  The polyurethane resin composition of the present invention may contain a plasticizer in addition to the polyurethane resin obtained by the reaction of the isocyanate group-containing compound and the hydroxyl group-containing compound, an inorganic filler, and a petroleum hydrocarbon. It is preferable not to contain a plasticizer in that it can exhibit higher high temperature and high humidity durability. When the polyurethane resin composition of the present invention contains a plasticizer, the upper limit of the plasticizer content is preferably 20% by mass, more preferably 15% by mass, based on 100% by mass of the polyurethane resin composition.

  Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, diisononyl phthalate, and diundecyl phthalate; Castor oil esters such as triglyceride triglycerides, trimellitic esters such as trioctyl trimellitate, triisononyl trimellitate, pyromellitic esters such as tetraoctyl pyromellitate, tetraisononyl pyromellitate, etc. Can be mentioned. Of these, trimellitic acid ester is more preferable.

  The polyurethane resin composition of the present invention may also contain a phosphate ester flame retardant. The phosphate ester flame retardant is not particularly limited as long as it is a phosphorus-containing flame retardant. For example, trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricresyl phosphate (TCP ), Trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), cresyl di 2,6-xylenyl phosphate, and the like; non-halogen condensed phosphates such as the aromatic condensed phosphate, etc. Can be mentioned. Of these, tricresyl phosphate and trixylenyl phosphate are preferable.

  15-40 mass% is preferable with respect to 100 mass% of polyurethane resin compositions, and, as for content of a phosphate ester type flame retardant, 20-35 mass% is more preferable. If the content of the phosphate ester flame retardant in the polyurethane resin composition of the present invention is too large, the durability at high temperature and high humidity may be lowered, and if it is too small, sufficient flame retardancy may not be exhibited.

  Various additives such as a catalyst, an antioxidant, a hygroscopic agent, an antifungal agent, and a silane coupling agent can be added to the polyurethane resin composition of the present invention as necessary.

  Although it does not specifically limit as a catalyst, The conventionally well-known catalyst used for a urethane resin composition can be used. Examples of such catalysts include tin catalysts such as dioctyltin dilaurate, dibutyltin dilaurate and dioctyltin diacetate; lead catalysts such as lead octylate, lead octenoate and lead naphthenate; bismuth such as bismuth octylate and bismuth neodecanoate. Examples of the catalyst include amine catalysts such as diethylenetriamine. In addition, as the catalyst, an organometallic compound, a metal complex compound, or the like may be used.

  The amount of these additives to be used may be appropriately determined according to the purpose of use from the range of normal addition amounts and identification so as not to inhibit the desired properties of the polyurethane resin composition.

  When the polyurethane resin composition of the present invention is in a liquid state before curing, the viscosity is preferably 500 to 200,000 mPa · s, more preferably 500 to 100,000 mPa · s. By setting the viscosity within the above range, the polyurethane resin composition of the present invention can exhibit higher workability. In addition, in this specification, the viscosity of the polyurethane resin composition before hardening is a value measured by the measuring method shown below. That is, a component containing a hydroxyl group-containing compound is prepared and used as component B. After mixing for 3 minutes at 2000 rpm using a mixer (trade name: Awatori Nertaro, Shinki Co., Ltd.), the temperature is adjusted to 23 ° C. Separately, a component containing an isocyanate group-containing compound is prepared as component A and adjusted to 23 ° C. Subsequently, A component is added to B component, and it mixes for 60 seconds at 2000 rpm using the said mixer. The viscosity of the mixed solution after 2 minutes from the start of mixing is measured using a BH type viscometer to obtain a measured value of the viscosity of the polyurethane resin composition before curing.

  It does not specifically limit as a method to manufacture the polyurethane resin composition of this invention, It can manufacture by the conventionally well-known method used as a method of manufacturing a polyurethane resin composition.

  As such a production method, for example, a component containing an isocyanate group-containing compound is prepared, a component A, a component containing a hydroxyl group-containing compound is prepared as a component B, and the reaction is performed by mixing the component A and the component B. Examples of the polyurethane resin include a method for producing a polyurethane resin composition containing the polyurethane resin.

  As long as the A component contains an isocyanate group-containing compound and the B component contains a hydroxyl group-containing compound, the other component may be contained in either the A component or the B component. Especially, the structure by which the inorganic filler is contained in B component is preferable. By setting it as such a structure, the hardening defect of the polyurethane resin by the reaction of the water | moisture content contained in an inorganic filler and a polyisocyanate group containing compound can be suppressed.

  As a combination of the composition of the A component and the B component, specifically, the A component contains only an isocyanate group-containing compound, the B component contains a hydroxyl group-containing compound, an inorganic filler, a petroleum hydrocarbon, and as necessary. Accordingly, the composition containing the plasticizer, phosphate ester flame retardant, and the above-mentioned additives, the A component contains the isocyanate group-containing compound and the phosphate ester flame retardant, the B component is the hydroxyl group-containing compound, inorganic A configuration containing a filler, a petroleum-based hydrocarbon, and, if necessary, a plasticizer and the above-described additives is preferable. By setting it as such a structure, A component and B component are excellent in liquid stability. More specifically, the component A contains an isocyanate group-containing compound and a plasticizer, and the component B contains a hydroxyl group-containing compound, a phosphate ester flame retardant, an inorganic filler, and a petroleum hydrocarbon, A The component may contain an isocyanate group-containing compound, a petroleum hydrocarbon, a phosphate ester flame retardant, a plasticizer and an inorganic filler, and the component B may contain a hydroxyl group-containing compound and a plasticizer. Moreover, except an isocyanate group containing compound and a hydroxyl group containing compound, it is not contained in A component and B component, but may be separately prepared and added as C component.

  The polyurethane resin composition may be liquid before curing or may be cured. As a method of curing the polyurethane resin composition, the polyurethane resin composition is changed over time by mixing the A component and the B component to react the isocyanate group-containing compound with the hydroxyl group-containing compound to obtain a polyurethane resin. Although the method of making it harden | cure is mentioned, you may make it harden | cure by heating. In this case, the heating temperature is preferably about 40 to 120 ° C., and the heating time is preferably about 0.1 to 24 hours.

  The present invention is also a sealing material comprising the polyurethane resin composition. The sealing material comprising the polyurethane resin composition is excellent in high temperature and high humidity durability and flame retardancy, and has excellent workability. It can be suitably used for accompanying electric and electronic parts. Examples of such electric and electronic parts include transformers such as transformer coils, choke coils, and reactor coils, equipment control bases, various sensors, and the like. Such electric and electronic parts are also one aspect of the present invention. The electric and electronic parts of the present invention can be used in electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, electric tools, automobiles, motorcycles, and the like.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

The raw material used for an Example and a comparative example is shown below.
・ Hydroxyl-containing compound: Polybutadiene polyol Product name; Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.)
・ Inorganic filler 1: Aluminum hydroxide Product name: Heidilite H-32 (manufactured by Showa Denko KK)
・ Inorganic filler 2: Aluminum hydroxide Product name: Heidilite H-42 (manufactured by Showa Denko KK)
-Petroleum hydrocarbons 1: Aromatic hydrocarbons Product name; Diana Process Oil AC-460 (made by Idemitsu Kosan Co., Ltd.)
-Petroleum hydrocarbons 2: Naphthenic hydrocarbons Product name; SUN No.6 INSULATING OIL (manufactured by Sun Japan Oil Company)
Petroleum hydrocarbons 3: Olefin hydrocarbons Product name: DURASYN (registered trademark) 170 Polyalphaolefins (Duracin 170) (manufactured by Ineos Oligomers Japan)
・ Plasticizer: Diundecyl phthalate Product name: Sansocizer DINP (manufactured by Shin Nippon Chemical Co., Ltd.)
・ Catalyst: Dioctyltin dilaurate Product name; Neostan U-810 (manufactured by Nitto Kasei Co., Ltd.)
・ Antioxidant: Trade name; Irganox 1010 (Ciba Specialty Chemicals)
・ Isocyanate group-containing compound: HDI-based isocyanurate Product name: Duranet TLA-100 (manufactured by Asahi Kasei Chemicals)

(Preparation of polyurethane resin composition)
The raw materials blended with the B agent shown in Table 1 are charged into a reaction kettle equipped with heating, cooling and decompression devices, dehydrated at 100 ° C. and a pressure of 10 mmHg or less for 2 hours, and a polyol component (B agent) is obtained. Prepared.

  As the polyisocyanate component, the isocyanate group-containing compound as a raw material was prepared and used as agent A.

  A polyurethane resin composition was obtained by adding the A agent to the B agent, stirring, defoaming and mixing in the blending amounts shown in Table 1. Mixing agent B and agent A is prepared by adjusting the polyol component (agent B) to 23 ° C. and then adding the polyisocyanate component (agent A) adjusted to 23 ° C. , Manufactured by Shinky Corp.) and stirring for 1 minute at a rotational speed of 2000 rpm.

  In addition, the compounding ratio of A agent and B agent was prepared so that the active hydrogen in a polyol component might be 1 equivalent with respect to 1 equivalent of isocyanate groups in a polyisocyanate component.

(Creation of specimen)
The prepared polyurethane resin composition was poured into a molding die A having a size of 130 × 130 × 1.5 mm and a molding die B having an inner diameter of 30 mm and a height of 10 mm. Each was heated at 60 ° C. for 16 hours and then allowed to stand at room temperature for 1 day to be cured to prepare test pieces A and B. Using the prepared test pieces A and B, the compatibility, high-temperature and high-humidity durability, and flame retardancy tests were performed by the following methods.

  The following tests were performed using the polyurethane resin compositions of Examples and Comparative Examples prepared as described above.

The viscosity of the polyurethane resin composition before workability curing was measured by the following measurement method. That is, a component containing a hydroxyl group-containing compound was prepared and used as component B. After mixing for 3 minutes at 2000 rpm using a mixer (trade name: Awatori Netaro, manufactured by Shinki Co., Ltd.), the temperature was adjusted to 23 ° C. Moreover, the component containing an isocyanate group containing compound was prepared separately, and it was set as A component, and was adjusted to 23 degreeC. Subsequently, A component was added to B component, and it mixed for 60 second at 2000 rpm using the said mixer. The viscosity of the mixed solution after 2 minutes from the start of mixing was measured using a BH viscometer, and the viscosity of the polyurethane resin composition before curing was measured. Based on the measured viscosity, workability was evaluated according to the following evaluation criteria.
○: Viscosity is less than 120,000 mPa · s Δ: Viscosity is 120,000 to 200,000 mPa · s
X: Viscosity exceeds 200,000 mPa · s

Hardened product appearance (compatible)
The surface state of the test piece B, which is a polyurethane resin composition after curing, was visually observed, and the compatibility was evaluated according to the following evaluation criteria.
○: Droplets and cloudiness are not observed on the surface Δ: Droplets are hardly observed, but some cloudiness is generated ×: Droplets are generated from the surface (bleed out occurs)

High temperature and high humidity durability 1
Using the test piece B which is a polyurethane resin composition after curing, a pressure cooker test was performed under the conditions of 151 ° C. and 100% RH 5 atm / 200 hours. The appearance after the pressure cooker test was visually observed, and high temperature and high humidity durability 1 was evaluated according to the following evaluation criteria.
○: The shape is retained ×: The shape is not retained or swollen

High temperature and high humidity durability 2
Using the test piece B which is a polyurethane resin composition after curing, a pressure cooker test was performed under the conditions of 151 ° C. and 100% RH 5 atm / 200 hours. The hardness after pressure cooker test (type A) is measured according to JIS K6253, and the ratio (%) of hardness after pressure cooker test to the hardness before pressure cooker test is calculated as the hardness retention rate. Wet durability 2 was evaluated.
○: Hardness retention is 40% or more ×: Hardness retention is less than 40%

The heat conductivity measurement was performed by pouring the prepared polyurethane resin composition into a 6 cm × 12 cm × 1 cm mold, curing it at 60 ° C. for 16 hours, and then leaving it at 23 ° C. for 24 hours. Test specimens were prepared. Using the prepared test piece, the thermal conductivity was measured by QTM-500 manufactured by Kyoto Electronics Co., Ltd., and the heat dissipation was evaluated according to the following evaluation criteria.
○: Thermal conductivity is 0.6 W / m · k or more ×: Thermal conductivity is less than 0.6 W / m · k

A flame retardancy test was performed using test piece A which is a polyurethane resin composition after flame retardancy curing. The test was conducted by Underwriters Laboratories, Inc., USA. Based on the combustion test standard (UL94) established by Flame retardancy was evaluated according to the following evaluation criteria.
○: V-0
Δ: V-2
X: HB

  The results are shown in Table 1.

  The polyurethane resin composition of the present invention is excellent in high-temperature and high-humidity durability and flame retardancy, and is excellent in workability. For this reason, it can be used in the field of electrical products and the like.

Claims (3)

A polyurethane resin composition comprising an isocyanate group-containing compound and a hydroxyl group-containing compound, a polyurethane resin composition containing an inorganic filler and a petroleum hydrocarbon,
The isocyanate group-containing compound includes a polyisocyanate compound isocyanurate-modified product,
The content of the inorganic filler, the polyurethane resin composition 100% by mass, Ri 50-85% by mass,
The content of the petroleum hydrocarbon is 5 to 45% by mass with respect to 100% by mass of the polyurethane resin composition,
The petroleum hydrocarbon is an aromatic hydrocarbon or an olefin hydrocarbon,
A polyurethane resin composition characterized by that.   A sealing material comprising the polyurethane resin composition according to claim 1.   An electrical / electronic component sealed with a resin using the sealing material according to claim 2.