[0001]The present invention relates to a polyurethane resin composition.
Background technique
[0002]Polyurethane resin, flexibility, abrasion resistance, low-temperature curability, the electrical characteristics to be good, are used in electrical insulation sealant, and the like.
[0003]This polyurethane resin, moisture electric and electronic parts, can be protected atmosphere containing dust, vibration, etc. from the impact.
[0004]In addition to the electrically insulating sealing material, a polyurethane-based resin, electrical, electronic, automotive, civil engineering, in various fields of architecture etc., coating agents, have been widely used as an adhesive or the like.
[0005]
　Such a polyurethane-based resin, when used in various fields mentioned above, the selection of the polyisocyanate compound is important, the study has been variously conducted.
[0006]
　For example, Japanese Patent No. 5535529 (Patent Document 1), heat dissipation, and a polyurethane resin composition having excellent heat resistance in a sealed environment is disclosed.
[0007]
　However, polyurethane resin, due to the influence of the structure of the isocyanurate ring, the flexibility of the resin is impaired, there is a problem that elongation of the resin is poor.
[0008]
　Accordingly, the polyurethane resin composition excellent in elongation of the polyurethane resin is desired.
CITATION
Patent Document
[0009]
Patent Document 1: JP Patent No. 5535529
Summary of the Invention
Problems that the Invention is to Solve
[0010]
　The present invention aims at providing excellent elongation indicates (flexibility), and excellent compatibility, moisture resistance, and a polyurethane resin composition of heat radiation (thermal conductivity).
Means for Solving the Problems
[0011]
　The present inventors have in view of the above problems, intensively studied. As a result, the hydroxyl group-containing compound, a polyisocyanate compound, a polyurethane resin composition containing a plasticizer and an inorganic filler, the hydroxyl group-containing compound comprises a polybutadiene polyol, and the polyisocyanate compound, isocyanurate of hexamethylene diisocyanate including a isocyanurate modified product, of 4,4'-diphenylmethane diisocyanate and a hydrogenated product, if the polyurethane resin composition was found that the object can be achieved. By further conducting research based on this finding, the present invention has been completed.
[0012]
　That is, the present invention, the following polyurethane resin composition, provides a sealing material and electrical electronic components.
Section 1.
Hydroxyl group-containing compound (A), polyisocyanate compound (B), a polyurethane resin composition containing a plasticizer (C) and the inorganic filler (D),
the hydroxyl group-containing compound (A), polybutadiene polyol (A- include 1), and
the polyisocyanate compound (B) comprises an isocyanurate-modified product of hexamethylene diisocyanate and (B-1), 4,4'-diphenylmethane diisocyanate hydrogenated product and (B-2), polyurethane resin composition.
Section 2.
The content of the isocyanurate-modified product of hexamethylene diisocyanate (B-1) is a hydrogenated product of 4,4'-diphenylmethane diisocyanate with respect to (B-2) 100 parts by weight, is 10 to 1,000 parts by mass, Section polyurethane resin composition according to 1.
Section 3.
The content of the isocyanurate-modified product of hexamethylene diisocyanate (B-1) is 4,4'-diphenylmethane hydrogenated product of a diisocyanate (B-2) per 100 parts by weight of a 40 to 800 parts by weight, Section 1 or the polyurethane resin composition according to 2.
Section 4.
Inorganic filler (D) is, in the polyurethane resin, 50 to 85 mass%, a polyurethane resin composition according to any one of claim 1-3.
Section 5.
Polyurethane resin composition according to any one of claim 1 to 4, characterized in that the electric encapsulating electronic components.
Section 6.
Sealing material made of a polyurethane resin composition according to any one of claim 1-5.
Section 7.
Resin sealed electric and electronic parts using the sealing material according to claim 6.
Effect of the invention
[0013]
　Polyurethane resin composition of the present invention is directed to excellent elongation indicates (flexibility), and excellent compatibility, moisture resistance, and to provide a polyurethane resin composition of heat radiation (thermal conductivity) . Polyurethane resin composition of the present invention, for example, can be suitably used in various insulated electrical and electronic components. Further, the sealing material of the present invention contains the above-described polyurethane resin composition, elongation (flexibility), the compatibility is excellent in moisture resistance, and heat radiation (thermal conductivity). Further, electric and electronic parts of the present invention, since the resin-sealed using the sealing material exhibits high reliability.
DESCRIPTION OF THE INVENTION
[0014]
　Polyurethane resin composition of the present invention, the sealing material and electrical and electronic components, will be described in detail. In the present specification, "contains" or "containing" The expression includes the concept of "containing", "including", "consisting essentially" and "consisting only of".
[0015]
　 1. Polyurethane resin composition
　polyurethane resin composition of the present invention, hydroxyl group-containing compound (A), polyisocyanate compound (B), a polyurethane resin composition containing a plasticizer (C) and the inorganic filler (D), the hydroxyl group-containing compound (a) comprises a polybutadiene polyol (a-1), and wherein the polyisocyanate compound (B) is an isocyanurate modified product of hexamethylene diisocyanate and (B-1), 4,4'- diphenylmethane diisocyanate It contains the hydrogenated product and (B-2).
[0016]
　 1-1. Hydroxyl group-containing compound (A)
　hydroxyl group-containing compound (A) used in the present invention contains a polybutadiene polyol (A-1).
[0017]
　Examples of commercially available products of polybutadiene polyol (A-1), for example, polybutadiene polyol [manufactured by Nippon Soda Co., Ltd. "NISSO-PBG Series" (G-1000, G-2000, G-3000, etc.), the United States ARCO Co., Ltd. "Poly Bd Series "(R-45M, R-45HT, CS-15, CN-15, etc.)], and the like.
[0018]
　The polybutadiene polyol (A-1) may be used alone, or two or more may be mixed.
[0019]
　Hydroxyl group-containing compound (A) used in the present invention may further contain the polybutadiene polyol (A-1) other than the hydroxyl group-containing compound (A-2).
[0020]
　Polybutadiene polyol (A-1) other than the hydroxyl group-containing compound (A-2) include, for example, polyols dimer acid; castor oil-based polyol; polydiene polyol (polyisoprene polyol); polyether polyol; polyester polyol; polycarbonate polyol ; polycaprolactone polyol; these hydrides (e.g., hydrides polydiene polyols etc.) and the like.
[0021]
　The dimer acid polyol, is not particularly limited and includes, known dimer acid polyol may be used.
[0022]
　The castor oil-based polyol is not particularly limited, for example, castor oil, castor oil derivatives and the like.
[0023]
　As the castor oil derivatives, e.g., castor oil fatty acids; hydrogenated castor oil was added hydrogen castor oil or castor oil fatty acid; transesterification product of castor oil and other oils; reaction product of castor oil and a polyhydric alcohol; esterification reaction products of castor oil fatty acids with polyhydric alcohols; these compounds by addition polymerization of alkylene oxide, and the like. Among the castor oil-based polyol, it is preferable to use the castor oil.
[0024]
　As the water-added castor oil, for example, those disclosed in JP-A-2-298574. Incidentally, hydrogenated castor oil is obtained by hydrogenation of the castor oil-based polyol.
[0025]
　The number average molecular weight of the castor oil-based polyol (Mn) of usually in the range of 100 to 4,000, preferably from 300 to 2,500.
[0026]
　The castor oil-based polyol has an average hydroxyl value was determined according to JIS K1557-1 of preferably a 20 ~ 250 mgKOH / g, and more preferably 50 ~ 120mgKOH / g.
[0027]
　In the present specification, the number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC) method (in terms of polystyrene). The number average molecular weight by the GPC method, specifically, as the measuring device Showa Denko K.K. Shodex GPC SYSTEM 21, manufactured by Showa Denko Co., Ltd. Shodex LF-804 / KF-803 / KF-804 as a column , using NMP as the mobile phase, measured at a column temperature of 40 ° C., it can be calculated using a calibration curve of standard polystyrene.
[0028]
　The polydiene polyol is not particularly limited, for example, polyisoprene polyol [manufactured by Idemitsu Kosan Co., Ltd. "Poly ip"], and the like.
[0029]
　The hydride polydiene polyol is not particularly limited, for example, hydrides of polybutadiene polyol [manufactured by Nippon Soda Co., Ltd., "NISSO-PBGI series" (GI-1000, GI-2000, and GI-3000, etc.)], hydrides polyisoprene polyol [manufactured by Idemitsu Kosan Co., Ltd. "Epol"], and the like.
[0030]
　The polyether polyol is not particularly limited, for example, water, low molecular polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol and the like), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin as initiator hydroquinone) such as ethylene oxide, propylene oxide, alkylene oxide addition polymerization is a polyether polyol obtained by causing such as butylene oxide. Specifically, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
[0031]
　The polyester polyol is not particularly limited, for example, can be obtained by esterification reaction of a polyol component and an acid component.
[0032]
　As the polyol component is not particularly limited, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl - 2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol diol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecane diol, glycerol, trimethylol propane, pentaerythritol, hexanetriol, polypropylene glycol, and the like.
[0033]
　The acid component is not particularly limited, for example, succinic acid, methyl succinic acid, adipic acid, Pimerikku acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecane diacid, dimer acid, 2 - methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 4,4 ' - biphen El dicarboxylic acid, and their acid anhydrides.
[0034]
　The polycarbonate polyol is not particularly limited, for example, polycarbonate polyol obtained by polycondensation reaction between the polyol component and phosgene; and the polyol component, dimethyl carbonate, diethyl carbonate, Jipurobiru, diisopropyl carbonate, dibutyl carbonate, ethylbutyl the various polycarbonates; copolymeric polycarbonate polyol obtained in combination of two or more of the polyol component; carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, a polycarbonate polyol obtained by the carbonic acid diester such as dibenzyl carbonate engaged transesterification condensation polycarbonate polyols resulting polyol and a carboxyl group-containing compound is reacted esterified; the various polycarbonate polyols and hydroxyl Polycarbonate polyols obtained and containing compound is reacted etherification; the various polycarbonate polyol and polycarbonate polyol obtained by the ester compound is an ester exchange reaction; the various polycarbonate polyol and the hydroxyl-containing compound with an ester exchange reaction to obtain are polycarbonate polyols; the various polycarbonate polyols and polyester obtained and a dicarboxylic acid compound with a polycondensation reaction polycarbonate polyols; the various polycarbonate polyol copolymerized polyether polycarbonate polyols obtained the alkylene oxide are copolymerized; etc. and the like.
[0035]
　The polycaprolactone polyol is not particularly limited, for example, .epsilon.-caprolactone, etc. caprolactone based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as δ- valerolactone.
[0036]
　Hydroxyl group-containing compound (A) used in the present invention can be used in polybutadiene polyol (A-1) alone, or polybutadiene polyol (A-1) and polybutadiene polyol (A-1) other than the hydroxyl group-containing compound (A -2) and it can be used as a mixture. The polybutadiene polyol (A-1) has a molecular weight can be used two or more different polybutadiene polyol. Hydroxyl group-containing compounds other than polybutadiene polyol (A-2) can also be used as a mixture of two or more.
[0037]
　Polyurethane resin composition of the present invention, as the hydroxyl group-containing compounds, by the inclusion of polybutadiene polyol (A-1), it is possible to improve the moisture resistance and heat cycle resistance of the polyurethane resin composition.
[0038]
　Content of polybutadiene polyol used in the present invention (A-1) is not particularly limited, the polyurethane resin composition 100 wt%, usually 0.01 to 25% by weight, preferably 0.1 a ~ 20 wt%, more preferably 1 to 15 mass%.
[0039]
　 1-2. Polyisocyanate compound (B)
　a polyisocyanate compound (B) used in the present invention, isocyanurate-modified product of hexamethylene diisocyanate and (B-1), a hydrogenated product of 4,4'-diphenylmethane diisocyanate and (B-2) It contains.
[0040]
　Examples of commercially available isocyanurate-modified hexamethylene diisocyanate (B-1), for example, (manufactured HDI-based isocyanurate Asahi Kasei Chemicals Corporation) Duranate TLA-100, include Coronate HX (manufactured by Tosoh Corporation) or the like.
[0041]
　Examples of commercially available hydrogenated product of 4,4'-diphenylmethane diisocyanate (B-2), for example, HMDI (manufactured Manhanasha), and the like.
[0042]
　The polyisocyanate compound (B) is an isocyanurate modified product of hexamethylene diisocyanate (B-1), and 4,4'-diphenylmethane hydrogenated product of a diisocyanate (B-2) can be used only. Further, the polyisocyanate compound (B), the isocyanurate-modified hexamethylene diisocyanate (B-1), and 4,4'-diphenylmethane hydrogenated product of a diisocyanate (B-2), further said (B-1 ) and it may also include (B-2) other than the polyisocyanate compound (B-3). The isocyanurate-modified product of hexamethylene diisocyanate (B-1) may be used alone, or two or more may be mixed. The 4,4'-diphenylmethane hydrogenated product of a diisocyanate (B-2) may be used alone, or two or more may be mixed.
[0043]
　Examples of the (B-1) and (B-2) other than the polyisocyanate compound (B-3), for example, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, aromatic aliphatic poly isocyanate compounds and the like.
[0044]
　Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methyl 1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.
[0045]
　Examples of the alicyclic polyisocyanate compound include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methyl cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane.
[0046]
　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, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like.
[0047]
　Examples of the aromatic aliphatic polyisocyanate compounds, e.g., dialkyl diphenyl methane diisocyanate, tetraalkyl diphenylmethane diisocyanate, alpha, alpha, alpha, alpha-tetramethyl xylylene diisocyanate.
[0048]
　Polyurethane resin composition of the present invention, isocyanurate-modified hexamethylene diisocyanate (B-1), by containing a hydrogenated product of 4,4'-diphenylmethane diisocyanate (B-2), the polyurethane resin elongation of objects (flexibility), compatibility, moisture resistance, and becomes the heat radiation (thermal conductivity) is excellent.
[0049]
　The content of the isocyanurate-modified product of hexamethylene diisocyanate in the polyurethane resin composition of the present invention (B-1) include, but are not particularly limited, a hydrogenated product of 4,4'-diphenylmethane diisocyanate (B-2 ) with respect to 100 parts by weight, for example, from 10 to 1,000 parts by mass, preferably 25-800 parts by weight, more preferably 40 to 800 parts by weight,
　the content of the polyisocyanate compound (B) used in the present invention is, There is no particular limitation with respect to the polyurethane resin composition 100 wt%, usually 0.01 to 30 mass%, preferably 0.1 to 25 mass%, more preferably 1 to 20 mass% .
[0050]
　Polyurethane resin composition of the present invention, the polyisocyanate compound (B), NCO / OH ratio of the hydroxyl group-containing compound (A) is preferably 0.6 to 2.0 0.7 to and more preferably 1.5.
[0051]
　 1-3. Plasticizer (C)
　a polyurethane resin composition of the present invention includes the plasticizer (C).
[0052]
　The plasticizer (C) used in the present invention is not particularly limited, for example, dioctyl phthalate, diisononyl phthalate (diisononyl phthalate), phthalic acid esters such as diundecyl phthalate; dioctyl adipate, adipic acid esters such as diisononyl adipate; trimellitic acid esters trioctyl trimellitate, tri isononyl trimellitate, etc.; methyl acetyl ricinoleate, butyl acetyl ricinoleate, acetyl ricinoleic acid triglyceride, castor oil-based esters, such as acetylated polyricinoleate triglyceride tetraoctyl pyromellitate, pyromellitic acid esters such as tetra isononyl pyromellitate and the like. Among these, diisononyl phthalate is preferable.
[0053]
　The content of the plasticizer (C), is not particularly limited, for example, the polyurethane resin composition 100 wt%, is usually 0.01-40 wt%, preferably from 0.1 to 30 mass% There, more preferably from 5 to 25 mass%.
[0054]
　The plasticizer (C) may be used alone, or two or more may be mixed.
[0055]
　 1-4. Inorganic filler (D)
　a polyurethane resin composition of the present invention includes an inorganic filler (D).
[0056]
　The inorganic filler (D) used in the present invention is not particularly limited, for example, metal hydroxides, metal oxides, metal nitrides, and zeolite.
[0057]
　As the metal hydroxide, for example, aluminum hydroxide and magnesium hydroxide.
[0058]
　As the metal oxide, for example, aluminum oxide (alumina), magnesium oxide, silicon oxide (silica), titanium oxide, and the like.
[0059]
　As the metal nitride, for example, boron nitride, aluminum nitride, silicon nitride, and the like.
[0060]
　Zeolite is not particularly limited, it is possible to use those used in the known polyurethane resin composition.
[0061]
　Among them, zeolite, alkali metal or alkaline earth metal crystalline hydrated aluminosilicates are preferred.
[0062]
　Crystalline form of the zeolite is not particularly limited, for example, A-type, X-type, LSX type, and the like. Among these, preferred crystalline form is form A.
[0063]
　Alkali metal or alkaline earth metal in the zeolite is not particularly limited, for example, potassium, sodium, calcium, and lithium. Among these, potassium is preferred.
[0064]
　Preferred inorganic fillers are metal hydroxides and metal oxides, more preferably, an aluminum hydroxide and alumina, particularly preferably aluminum hydroxide.
[0065]
　The inorganic filler (D) may be used alone, or two or more may be mixed.
[0066]
　The content of the inorganic filler (D), is not particularly limited, for example, the polyurethane resin composition 100% by weight, usually 50 to 80 wt%, preferably 60-78 wt%, more preferably 65 to 70 mass%.
[0067]
　The shape of the inorganic filler (D) is spherical, it may be any of irregular shape.
[0068]
　 1-5. Polymerization catalyst (E)
　in the polyurethane resin composition of the present invention, it is possible if necessary to include a polymerization catalyst (E).
[0069]
　The polymerization catalyst (E), can be used known polymerization catalyst, for example, organotin catalysts, organic lead catalysts, metal catalysts such as organic bismuth catalyst; and the like amine catalyst.
[0070]
　Organotin catalysts, for example, dioctyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin diacetate, and the like.
[0071]
　The organic lead catalysts, e.g., lead octylate, lead octenoate, naphthenate lead, and the like.
[0072]
　The organic bismuth catalyst, e.g., bismuth octoate, bismuth neodecanoate, and the like.
[0073]
　The amine catalysts, for example, diethylene triamine, triethylamine, N,, N-dimethylcyclohexylamine, N, N N ', N' tetramethylethylenediamine, N, N, N ', N ", N" - pentamethyldiethylenetriamine, tri diamine, dimethylamino ethanoate - le, bis (2-dimethylaminoethyl) d - ether, and the like. Further, as the catalyst, an organometallic compound, it may be used a metal complex compound or the like.
[0074]
　When containing a polymerization catalyst (E), the content thereof is not particularly limited, for example, the polyurethane resin composition 100 wt%, is usually 0.00001 to 10% by weight, preferably 0.0001 to 5 is the mass%, more preferably from 0.001 to 1 mass%.
[0075]
　The polymerization catalyst (E) may be used alone, or two or more may be mixed.
[0076]
　 1-6. Antifoam (F)
　in the polyurethane resin composition of the present invention may contain an antifoaming agent (F), if necessary.
[0077]
　As the antifoaming agent used in the present invention is not particularly limited, for example, silicones (oil type, compound type, self-emulsifying, emulsion type, etc.), alcohols and the like.
[0078]
　Preferred silicone antifoams are modified silicone anti-foaming agent (particularly, those modified with hydrophilic groups to the polysiloxane lipophilic group).
[0079]
　Antifoaming agent (F) may be used alone, or two or more may be mixed.
[0080]
　When containing antifoam (F), the content thereof is not particularly limited, specially with respect to the polyurethane resin composition 100 wt%, preferably 0.001 to 10 mass%, 0.01 to 5 wt% It is more preferable.
[0081]
　 1-7. Other components
　polyurethane resin composition of the present invention, if necessary, tackifiers, accelerators, colorants, chain extenders, crosslinking agents, fillers, pigments, fillers, flame retardants, urethane catalyst, ultraviolet absorbers, antioxidants, water moisture absorbent can include antifungal, various additives such as a silane coupling agent.
[0082]
　The content of these components, depending on its intended use, so as not to inhibit the desired properties of the polyurethane resin composition may be suitably determined from the range of the normal amount and identification.
[0083]
　Incidentally, the polyurethane resin composition of the present invention is not adding a foaming agent. That is, the polyurethane resin composition of the present invention whereas it is an object of the heat radiation or the like with an inorganic filler, urethane foam containing blowing agent since it is the purpose of thermal insulation and the like, they are those different purposes .
[0084]
　 2. Method for producing a polyurethane resin composition
　as a method for producing the polyurethane resin composition of the present invention is not particularly limited, it can be prepared according to methods known to be used as a method of producing the polyurethane resin composition.
[0085]
　Examples of such a manufacturing method, for example, preparing a composition comprising a hydroxyl group-containing compound (A) (first component) (Step 1), polyisocyanate compound (B) composition containing a (second component) preparation step (step 2), and mixture of the foregoing second component and the first component, and a method comprising the step (step 3) to obtain a polyurethane resin composition.
[0086]
　The first component contains a hydroxyl group-containing compound (A), if the second component contained the polyisocyanate compound (B), other components, is contained in either of the second component or the first component it may be.
[0087]
　For example, the first component is hydroxyl group-containing compound (A), contain a plasticizer (C) and the inorganic filler (D), the second component can be given a configuration for containing polyisocyanate compound (B).
[0088]
　The first component is the hydroxyl group-containing compound (A), a plasticizer (C), contain an inorganic filler (D) and an antifoaming agent (F), the second component is a polyisocyanate compound (B) and a polymerization catalyst ( E) may be configured to contain;
first component hydroxyl group-containing compound (a), a plasticizer (C), an inorganic filler (D), and anti-foaming agent (F), and a catalyst, the may be configured to 2 component contains the polyisocyanate compound (B);
first component hydroxyl group-containing compound (a), contain a plasticizer (C) and antioxidants, the second component is a polyisocyanate compound (B), and it may be configured to contain an inorganic filler (D);
first component hydroxyl group-containing compound (a), a plasticizer (C), an inorganic filler (D) and the polymerization catalyst (E) containing the second component is a polyisocyanate compound (B), and an antifoaming agent (F) It may be configured to have.
[0089]
　In the polyurethane resin composition, hydroxyl group-containing compound (A) and a polyisocyanate compound (B) are reacted in part or whole may form a polyurethane resin. That is, the polyurethane resin composition may be a liquid before curing, or may be cured. As a method for curing the polyurethane resin composition, by mixing the second component and the first component, hydroxyl group-containing compound (A) and the polyisocyanate compound (B) and react, by a polyurethane resin, a method for time cure the polyurethane resin composition may be mentioned, it may be cured by heating. In this case, the heating temperature is preferably about 40 - 120 ° C., the heating time is preferably about 0.5 to 24 hours.
[0090]
　 3. Applications
　The present invention is also a sealing material made of the polyurethane resin composition. Sealing material made of the polyurethane resin composition, heat dissipation is excellent in hydrolysis resistance and flame retardancy, and, drops of flame retardance even when used in a high-temperature environment is suppressed since, it can be suitably used for electric and electronic parts, etc. with fever. Such electrical and electronic components, for example, transformer coil, choke coils, transformers such as a reactor coil, equipment control board, various sensors, and the like. Such electrical and electronic components is also one of the present invention. Electrical and electronic parts of the present invention, for example, electric washing machine, toilet, water heater, water purifier, bath, dishwasher, electric tools, automobiles, can be used for motorcycle or the like.
Example
[0091]
　Following by referring to Examples and Comparative Examples will be specifically described polyurethane resin composition of the present invention. However, examples are merely an example, the present invention is not limited to the examples.
[0092]
　 Test Example 1
　The raw materials used in Examples and Comparative Examples are shown below.
[0093]
　 Polybutadiene polyol
(A-1) a-1: Average hydroxyl value 103mgKOH / g of polybutadiene polyol
(trade name: R-15HT, manufactured by Idemitsu Kosan Co., Ltd.)
　 castor oil based polyol
(A-2) a-2: Castor oil-based polyol
(trade name: castor oil, manufactured by Itoh oil Corporation)
　 polyisocyanate compound
(B) b-1: isocyanurate-modified hexamethylene diisocyanate
(trade name: DURANATE TLA-100, manufactured by Asahi Kasei Chemicals
Corporation) b-2 : a hydrogenated product of 4,4'-diphenylmethane diisocyanate
(trade name: HDMI, Wanhua Co., Ltd.)
　 plasticizer
(C) c1: diisononyl phthalate (DINP)
(trade name: DINP, Ltd. J plus)
　 inorganic filler
(D) d1: aluminum hydroxide
(trade name: Higilite H-32 Showa Denko
KK) d2: Aluminum hydroxide
(trade name: Higilite H-42I, manufactured by Showa Denko)
　 polymerization catalyst
(E) e1: dioctyltin dilaurate
(trade name: Neostann U-810, manufactured by Nitto Kasei Co., Ltd. Etsu Chemical Co., Ltd.)
　 anti-foaming agent (F)
f1: SC-5570 (silicone-based, Toray - Dow Silicone Co., Ltd.)
　 Preparation of the polyurethane resin composition
　
　The components in Composition (parts by weight) shown in Table 1 blended to prepare a variety of polyurethane resin composition by the following procedure.
[0094]
　First, in the amounts shown in Table 1, a hydroxyl group-containing compounds, plasticizers, antifoaming agents, inorganic fillers, and a polymerization catalyst was added, the mixer (Thinky Co., Ltd., trade name: Awatori Rentaro) using, 1 minute at 2000 rpm, after mixing at 23 ° C., to give mixture was cooled to room temperature (first component).
[0095]
　Subsequently, the mixture of the (first component), the polyisocyanate compound (second component) was added in the amounts shown in Table 1 was adjusted to 23 ° C., using a mixer of the same mixed for 1 minute at 2000 rpm, to obtain a polyurethane resin compositions of the examples and Comparative examples was defoamed.
[0096]
　Note that the second component and the blending ratio of the first component with respect to NCO groups 1 equivalent in the polyisocyanate compound (B), as the hydroxyl group-containing compound (A) in the active hydrogen (OH) is 1 equivalent did.
[0097]
[Table 1]

[0098]
　 Specimen (test piece) of Preparation
　130 × 130 × 3 mm mold of, or inner 30 mm, mold height 10 mm, and the mold of 6cm × 12cm × 1cm, injecting the polyurethane resin compositions prepared did. Then the polyurethane resin composition, was heated at 60 ° C. 16 h, allowed to cure for 1 day at room temperature. The resulting cured product A (130 × 130 × 3mm) , the cured product B (diameter 30mm and height 10 mm), and on specimens of the cured product C (6cm × 12cm × 1cm) , hardness, cured product appearance ( compatibility), moisture resistance, the test for elongation (flexibility) and flame retardancy were carried out by the following method. The results are shown in Table 1.
[0099]
　 Hardness
　In accordance with JIS K 6253 hardness of the cured product B, was measured using Asker A hardness meter (manufactured by Kobunshi Keiki Co., Ltd.).
[0100]
　 Cured product appearance (compatibility)
　for the polyurethane resin composition described in Examples and Comparative Examples after curing, were observed surface condition of the resulting cured product A the exterior visually evaluate the compatibility in accordance with the following evaluation criteria did.
A: After heating 80 ° C. for 16 hours, then, even after 168 hours of heating at 120 ° C., not seen droplets and fogging on the surface (bleed does not occur)
C: The after heating 80 ° C. for 16 hours, bleed Although not generated, bleed after 168 hours heating at 120 ° C. for generating
　 moisture resistance
　to the cured product B, 121 ° C., was subjected to pressure cooker test (PCT test) under the conditions of 100% RH 2 atm / 300 hours. According JIS K 6253 hardness after hardness and testing before the test was measured using Asker A hardness meter (manufactured by Kobunshi Keiki Co., Ltd.) to measure the hardness retention.
[Hardness retention] = - based on {[(pre-test hardness) (Hardness after test)] ÷ (pre-test hardness)} × 100 The calculated hardness reduction rate was evaluated moisture resistance according to the following evaluation criteria.
A: the hardness retention rate is more than 50%
B: the hardness retention rate is less than 20% ~ 50%
C: the hardness retention rate is less than 20%
　 elongation (flexibility )
　elongation of the cured product A (flexible) JIS K 6251 in accordance with, it was evaluated based on the following formula.
Wherein: elongation rate = {[(gauge length at break) - (gauge length)] ÷ (distance between bench marks)} × 100
A: elongation of 60% or more
C: elongation rate is less than 60%
　 The thermal conductivity
　of the thermal conductivity of the test piece C of 6cm × 12cm × 1cm, were measured using the Kyoto electronic device QTM-500.
[0101]
　
　From the results of Examples 1-3, the polyurethane resin composition of the present invention, elongation (flexibility), compatibility, found to satisfy all of moisture resistance, and heat radiation (thermal conductivity) It was.
[0102]
　On the other hand, from the results of Comparative Examples 1 and 2, a polyurethane resin composition containing no HMDI is elongation (flexibility), and compatibility were inferior.
[0103]
　From the results of Comparative Example 3, the polyurethane resin cured product that does not contain an isocyanurate modified product (TLA-100) of hexamethylene diisocyanate was inferior moisture resistance.
[0104]
　 Test Example 2
　by blending the components in the following composition shown in Table 2 (parts by weight), in the same manner as in Test Example 1, to create a polyurethane resin composition was evaluated each performance. In Table 2, TPA-100 is an isocyanurate modified product of Asahi Kasei Chemicals Corporation of hexamethylene diisocyanate (B-1), HMDI is 4,4'-diphenylmethane diisocyanate used in the present Example a hydrogenated product (B-2). The results are shown in Table 2. As shown in Table 2, the same results as in Test Example 1 were obtained.
[0105]
[Table 2]

Industrial Applicability
[0106]
　The use of the polyurethane resin composition of the present invention, the polyurethane resin cured product obtained, elongation (flexibility), compatibility, moisture resistance, and to satisfy all of the heat radiation (thermal conductivity), electrical products, use in the field of electronic components and the like are possible.

claims

[Claim 1]Hydroxyl group-containing compound (A), polyisocyanate compound (B), a polyurethane resin composition containing a plasticizer (C) and the inorganic filler (D),
the hydroxyl group-containing compound (A), polybutadiene polyol (A- include 1), and
the polyisocyanate compound (B) comprises an isocyanurate-modified product of hexamethylene diisocyanate and (B-1), 4,4'-diphenylmethane diisocyanate hydrogenated product and (B-2), polyurethane resin composition.
[Claim 2]
The content of the isocyanurate-modified product of hexamethylene diisocyanate (B-1) is a hydrogenated product of 4,4'-diphenylmethane diisocyanate with respect to (B-2) 100 parts by weight, is 10 to 1,000 parts by mass, wherein polyurethane resin composition according to claim 1.
[Claim 3]
The content of the isocyanurate-modified product of hexamethylene diisocyanate (B-1) is 4,4'-diphenylmethane hydrogenated product of a diisocyanate (B-2) per 100 parts by weight of a 40 to 800 parts by weight, wherein polyurethane resin composition according to claim 1 or 2.
[Claim 4]
Inorganic filler (D) is, in the polyurethane resin, 50 to 85 mass%, a polyurethane resin composition according to any one of claims 1 to 3.
[Claim 5]
Polyurethane resin composition according to any one of claims 1 to 4, characterized in that an electric sealed electronic component.
[Claim 6]
Sealing material made of a polyurethane resin composition according to any one of claims 1 to 5.
[Claim 7]
Resin sealed electric and electronic parts using the sealing material according to claim 6.