WO2016009716A1 - Polyurethane resin composition - Google Patents

Polyurethane resin composition Download PDF

Info

Publication number
WO2016009716A1
WO2016009716A1 PCT/JP2015/064434 JP2015064434W WO2016009716A1 WO 2016009716 A1 WO2016009716 A1 WO 2016009716A1 JP 2015064434 W JP2015064434 W JP 2015064434W WO 2016009716 A1 WO2016009716 A1 WO 2016009716A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane resin
resin composition
mass
containing compound
parts
Prior art date
Application number
PCT/JP2015/064434
Other languages
French (fr)
Japanese (ja)
Inventor
成相 廣瀬
梓 金井
敏樹 野田
泰範 藤本
望 繁中
Original Assignee
第一工業製薬株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2014144655A external-priority patent/JP5854534B2/en
Priority claimed from JP2014144654A external-priority patent/JP5854533B2/en
Application filed by 第一工業製薬株式会社 filed Critical 第一工業製薬株式会社
Priority to CN201580035477.6A priority Critical patent/CN106661182A/en
Publication of WO2016009716A1 publication Critical patent/WO2016009716A1/en

Links

Images

Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a polyurethane resin composition.
  • Patent Document 1 Conventionally, electronic circuit boards and electronic components have been sealed using polyurethane resin or the like in order to prevent external contamination (Patent Document 1). 2. Description of the Related Art In recent years, as electronic parts and the like have a longer life, they are used under a long period of time under wet heat, and therefore have been required to have excellent wet heat resistance.
  • the present inventors contain a polybutadiene polyol, a castor oil-based polyol, and an isocyanurate-modified product of a polyisocyanate compound that are sealed in a transformer case and have excellent thermal durability even in a high temperature environment.
  • a polyurethane resin composition has been disclosed (Patent Document 2).
  • a resin case may be used for the peripheral parts of the sealing material.
  • the chemical stress crack does not occur on the case such as the electronic substrate and the case material, but the chemical stress crack is generated in the polyurethane resin composition disclosed so far.
  • a chemical stress crack is a typical brittle fracture that occurs with a tensile stress that is less than the tensile strength of the resin case.
  • the chemical adheres to and contacts the location where the tensile stress occurs (where the load is applied). In some cases, this is a phenomenon in which cracks (crazes, cracks) occur due to the synergistic action of chemicals and stress over time.
  • the present invention has been made in view of the above-described problems, and provides a polyurethane resin composition that is excellent in moisture and heat resistance, flame retardancy, electrical insulation, and workability, and that does not easily cause chemical stress cracks in a resin case. This is the issue.
  • the polyurethane resin composition includes a polyol having a specific structure, an isocyanate group-containing compound, a specific and specific amount of metal hydroxide, and a specific amount. It has been found that the above-mentioned problems can be solved by using the plasticizer, and the present invention has been completed.
  • Polyurethane resin composition containing 1 part by mass to 30 parts by mass with respect to a total of 100 parts by mass of (2)
  • the isocyanate group-containing compound contains a polyisocyanate compound isocyanurate-modified product (B1), and 40 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X).
  • the hydroxyl group-containing compound (A) further contains a castor oil-based polyol (A2), and 40 parts by mass of the metal hydroxide (C) to 100 parts by mass of the polyurethane resin composition (X).
  • the polyurethane resin composition according to (1) which contains 80 parts by mass
  • (4) The polyurethane resin composition according to (3), wherein a mass ratio of the castor oil-based polyol (A2) and the metal hydroxide (C) is (A2) :( C) 1: 5 to 1:10
  • the polyurethane resin composition of the present invention contains a hydroxyl group-containing compound, an isocyanate group-containing compound, a metal hydroxide and a plasticizer.
  • the hydroxyl group-containing compound used in the present invention contains polybutadiene polyol (A1).
  • polybutadiene polyol (A1) used in the present invention those conventionally known for use in polyurethane resins can be used, and the average hydroxyl value is preferably 20 to 120 mgKOH / g.
  • the blending amount of the polybutadiene polyol (A1) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass with respect to the polyurethane resin composition.
  • the blending amount of the polybutadiene polyol (A1) is less than the above range, the moist heat resistance and electrical insulation tend to be lowered.
  • the blending amount is more than the above range, the mixing viscosity at the time of producing the polyurethane resin composition is increased, and the workability is improved. There is a tendency to decrease.
  • the isocyanate group-containing compound contains a polyisocyanate compound isocyanurate-modified product (B1), and 40 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X). Parts to 80 parts by weight, (Ii)
  • the hydroxyl group-containing compound (A) further contains a castor oil-based polyol (A2), Containing 40 to 80 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X); Can be given.
  • a castor oil-based polyol (A2) as the hydroxyl group-containing compound in any of the preferred embodiments (i) and (ii). In particularly preferred embodiment (ii), it is more preferred. Since it contains two types of polyol compounds, the polybutadiene polyol (A1) and the castor oil-based polyol (A2), it is preferable because the compatibility of the polyurethane resin composition is excellent.
  • castor oil-based polyol (A2) castor oil, castor oil fatty acid, and hydrogenated castor oil or hydrogenated castor oil fatty acid hydrogenated to these can be used.
  • examples of such polyols include castor oil, a transesterification product of castor oil and other natural fats, a reaction product of castor oil and polyhydric alcohol, an esterification reaction product of castor oil fatty acid and polyhydric alcohol, and alkylene oxide added thereto. Examples include polymerized polyols.
  • the viscosity of castor oil-based polyol (A2) at 25 ° C. is preferably 800 mPa ⁇ s or less, and more preferably 700 mPa ⁇ s or less.
  • the number of functional groups is preferably 1.0 to 3.0, more preferably 1.0 to 2.7. Preferably, it is 1.2 to 2.7. It is particularly preferable in the preferred embodiment (ii) that the number of functional groups is within these ranges.
  • the number of functional groups means the average number of hydroxyl groups calculated from the charged amount. If it is these ranges, the mixing viscosity at the time of manufacture of a polyurethane resin composition will become suitable, and workability
  • the blending amount of the castor oil-based polyol (A2) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass with respect to the polyurethane resin composition.
  • the blending amount of the castor oil-based polyol (A2) is less than the above range, the mixing viscosity at the production of the polyurethane resin composition tends to be high, and the workability tends to be lowered.
  • the blending amount is more than the above range, the heat and humidity resistance tends to be lowered. There is.
  • the polybutadiene polyol (A1) and castor oil-based polyol (A2) may be a hydroxyl group-terminated urethane prepolymer obtained by reacting with the isocyanate group-containing compound (B).
  • the mixing ratio of the polybutadiene polyol (A1) and the castor oil-based polyol (A2) is preferably 10/90 to 90/10 (mass ratio). By making it in the said range, the compatibility at the time of mixing of a polyurethane resin composition becomes more favorable.
  • polyols other than polybutadiene polyol (A1) and castor oil-based polyol (A2) can be blended with the polyol component used in the present invention to such an extent that the effects of the present invention are not impaired.
  • examples of such polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyisoprene polyols, polybutadiene polyol hydrides, and polyisoprene polyol hydrides.
  • an isocyanurate-modified product (B1) of a polyisocyanate compound it is preferable to contain an isocyanurate-modified product (B1) of a polyisocyanate compound.
  • the isocyanate group-containing compound contains an isocyanurate-modified product of a polyisocyanate compound, the thermal durability of the polyurethane resin becomes excellent.
  • another polyisocyanate compound (B2) can be included in an isocyanate group containing compound.
  • Other isocyanate compounds are not particularly limited as long as they are other than isocyanurate-modified products, and examples include biuret-modified products, adduct-modified products, bifunctional modified products, and monomers.
  • the preferred embodiment (ii) preferably contains a polyisocyanate compound isocyanurate-modified product (B1), isocyanurate, allophanate, burette, or adduct-modified product.
  • the isocyanate group-containing compound contains an isocyanurate-modified product of a polyisocyanate compound, the thermal durability of the polyurethane resin becomes excellent. Although the reason is not clear, it can be inferred to be due to the hydrolysis-inhibiting effect of the isocyanurate-modified polyisocyanate compound.
  • the isocyanate group-containing compound may include other polyisocyanate compounds such as a bifunctional modified product and a monomer.
  • polyisocyanate compound examples include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds.
  • the polyisocyanate compound is preferably an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound, more preferably an aliphatic polyisocyanate compound, and most preferably hexamethylene diisocyanate from the viewpoints of reactivity, durability, viscosity, and workability. .
  • Aliphatic polyisocyanate compounds include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane- Examples include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
  • alicyclic polyisocyanate compounds include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, and the like. Is mentioned.
  • aromatic polyisocyanate compound examples 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, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate.
  • the polyisocyanate compound is preferably an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound, more preferably an aliphatic polyisocyanate compound, and most preferably hexamethylene diisocyanate from the viewpoints of reactivity, durability, viscosity, and workability. .
  • an isocyanate group-terminated urethane prepolymer obtained by reacting a polyisocyanate compound with a polybutadiene polyol (A1) and / or a castor oil-based polyol (A2) can also be used as the polyisocyanate compound.
  • the molar ratio of isocyanate groups to hydroxyl groups is preferably 0.6 to 1.5, more preferably 0.7 to 1.3. This is because if the molar ratio of isocyanate group to hydroxyl group is smaller than this range, curing failure may occur or the heat resistance of the resulting resin may be reduced, and if it exceeds this range, curing failure may occur.
  • the metal hydroxide (C) used in the present invention is, for example, aluminum hydroxide and / or magnesium hydroxide.
  • the compounding amount of the metal hydroxide (C) is preferably 40 to 80 parts by mass, and more preferably 45 to 78 parts by mass with respect to 100 parts by mass of the polyurethane resin composition (X). If the blending amount of the metal hydroxide (C) is less than the above range, the flame retardancy tends to decrease, and if it is more than the above range, the mixing viscosity at the time of production of the polyurethane resin composition increases and the workability decreases. Tend to.
  • the amount of castor oil-based polyol (A2) is larger than the above range, the heat and humidity resistance tends to decrease.
  • the amount of castor oil-based polyol (A2) is small, the mixed viscosity at the time of production of the polyurethane resin composition increases, and the workability tends to decrease. There is.
  • plasticizer (D) used in the present invention those conventionally known for use in polyurethane resins can be used.
  • examples of such a plasticizer include phthalic acid such as dioctyl phthalate, diisononyl phthalate, and diundecyl phthalate.
  • Esters such as dioctyl adipate and diisononyl adipate, castor oil esters such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, acetylated ricinoleic acid triglyceride, acetylated polyricinoleic acid triglyceride, trioctyl trimellitate, triisononyl Trimellitic acid esters such as trimellitate, pyromellitic acid esters such as tetraoctyl pyromellitate, tetraisononyl pyromellitate, tricresyl phosphate, triski Les nil phosphate, cresyl diphenyl phosphate, carboxymethyl Les sulfonyl phosphate, and phosphoric acid esters such as triphenyl phosphate.
  • castor oil esters such as methyl acetyl ricino
  • phthalic acid ester, trimellitic acid ester, and phosphoric acid ester are preferred from the viewpoints of excellent heat and humidity resistance, flame resistance, electrical insulation, workability, and economic efficiency, and resistance to chemical stress cracks in the resin case.
  • a phthalic acid ester and a phosphoric acid ester are more preferable.
  • the compounding amount of the plasticizer (D) is 1 to 30 parts by mass with respect to a total of 100 parts by mass of the hydroxyl group-containing compound (A) and the plasticizer (D). From the viewpoints of excellent workability and workability and resistance to the occurrence of chemical stress cracks in the resin case, it is preferably 1 part by weight to 28 parts by weight, and more preferably 5 parts by weight to 25 parts by weight.
  • the mixing ratio of the polybutadiene polyol (A1) and the plasticizer (D) is preferably 100/4 to 100/35 (mass ratio), and preferably 100/7 to 100/30 (mass ratio). More preferred. By setting it within the above range, it is possible to obtain a polyurethane resin which has good workability and hardly causes chemical stress cracks in the resin case.
  • silane coupling agent examples include alkoxysilanes, vinyl group-containing silane coupling agents, epoxy group-containing silane coupling agents, methacryl group-containing silane coupling agents, and acrylic group-containing silane coupling agents.
  • the mixed viscosity of the present invention is preferably 40,000 mPa.s or less, more preferably 30,000 mPa.s or less. Within these ranges, the workability is good. In addition, mixing viscosity is measured by the method as described in an Example.
  • the moisture and heat resistance of the present invention preferably retains a hardness of type A5 or more, more preferably retains a hardness of type A10 or more after 85 ° C. ⁇ 85% RH ⁇ 3000 hours. These ranges are good in terms of maintaining the resin shape.
  • the flame retardancy of the present invention is preferably V-1 level flame retardancy, more preferably V-0 level flame retardancy in the UL94 standard.
  • the electrical insulation of the present invention is preferably 10 8 ⁇ ⁇ cm or more, more preferably 10 9 ⁇ ⁇ cm or more after 85 ° C. ⁇ 85% RH ⁇ 3000 hours. Within these ranges, it is favorable in terms of electrical insulation.
  • the chemical stress crack resistance of the present invention is preferably 0.5% or more, more preferably 0.7% or more, at a critical strain after 25 ° C. ⁇ 60% RH ⁇ 48 hours. Within these ranges, it is favorable in that cracks do not occur in the housing and case material of the substrate.
  • polyurethane resin composition of the present invention and the polyurethane resin raw material composition of the present invention will be described in detail based on Examples and Comparative Examples.
  • “parts” and “%” represent “parts by mass” and “mass%”, respectively, unless otherwise specified.
  • A1-1 Polybutadiene polyol having an average hydroxyl value of 103 mgKOH / g (trade name: Poly bd R-15HT, manufactured by Idemitsu Kosan Co., Ltd.)
  • A1-2 Polybutadiene polyol having an average hydroxyl value of 47 mgKOH / g (trade name: Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd.)
  • A2-1 Castor oil fatty acid-polyhydric alcohol ester (divalent functional group) (Product name: URIC Y-403, manufactured by Ito Oil)
  • A2-2 Castor oil (2.7 functional groups) (Product name: castor oil, manufactured by Ito Oil Co., Ltd.)
  • A2-3 Castor oil fatty acid-alcohol ester (monovalent functional group) (Product name: URIC H-31, manufactured by Ito Oil)
  • B1 Isocyanurate modified product of hexamethylene diisocyanate (trade name: Duranate TLA-100, manufactured by Asahi Kasei Chemicals) (Other polyisocyanate compound (B2))
  • B2-1 Bifunctional modified product of hexamethylene diisocyanate (trade name: Duranate D201, manufactured by Asahi Kasei Chemicals Corporation)
  • B2-2 A modified burette of hexamethylene diisocyanate (trade name: Duranate 24A-100, manufactured by Asahi Kasei Chemicals Corporation)
  • B2-3 Adduct modified product of hexamethylene diisocyanate (trade name: Duranate AE700-100, manufactured by Asahi Kasei Chemicals Corporation)
  • B2-4 Polymeric MDI (Product name: Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • Metal hydroxide (C)) C1: Aluminum hydroxide (trade name: Aluminum hydroxide C-305, manufactured by Sumitomo Chemical Co., Ltd.)
  • C2 Magnesium hydroxide (manufactured by Tateho Chemical Co., Ltd.)
  • D1 Diundecyl phthalate (Brand name: SUNSOSIZER DUP, manufactured by Shin Nippon Rika Co., Ltd.)
  • D2 Trisoxylenyl phosphate (trade name: TXP, manufactured by Daihachi Chemical Industry Co., Ltd.)
  • Examples 1 to 23 and Comparative Examples 1 to 6 The polyurethane resin composition of each Example and each comparative example was prepared according to the formulation shown in Table 1.
  • components other than the isocyanate group-containing compound (B) among the components shown in Table 1 were mixed for 3 minutes at 2000 rpm using a mixer (trade name: Aritori Nertaro, manufactured by Shinky Corp.), then 25 Adjusted to ° C. Then, the isocyanate group containing compound (B) adjusted to 25 degreeC was added to this mixture, and the polyurethane resin composition of each Example was obtained by mixing for 60 second at 2000 rpm using the mixer same as the above.
  • the flame retardancy was measured according to UL standard UL94 (flame retardance of plastic materials).
  • ABS test piece 1 (trade name: Kobe Poly Sheet ABS, manufactured by Shin-Kobe Electric Machinery Co., Ltd.) was attached to a 1/4 oval jig shown in FIG. After being attached to the surface of the test piece, the specimen was left in an environment of 25 ° C. ⁇ 60% for 48 hours, the position X at which a crack occurred was measured, and the critical strain value was obtained using Equation 1. Based on the critical strain value, the chemical stress crack resistance was evaluated by ranking as follows.
  • ⁇ critical strain value a: ellipse major axis 100 mm b: Ellipse minor axis 40mm
  • X Crack generation point Distance from the fixed end to the crack generation point with respect to the long axis of the test piece mm t: Test piece thickness 2.0 mm ⁇ Evaluation> ⁇ (The possibility of occurrence of crazes or cracks is small and can be used practically): Critical strain value ( ⁇ ) 0.7% or more ⁇ (The possibility of cracking is high in parts where molding strain is large or where stress concentration is high): Critical strain value ( ⁇ ) less than 0.7%
  • the polyurethane resin composition of the present invention has a range in which the mixed viscosity can be used, is excellent in workability, moist heat resistance, flame resistance, and electrical insulation, and is suitable for a resin case. It can be seen that chemical stress cracks are less likely to occur.
  • the polyurethane resin obtained from the polyurethane resin composition of the present invention has heat and moisture resistance, it can be suitably used for electric and electronic parts that generate heat.
  • electric and electronic parts include transformers such as transformer coils, choke coils, and reactor coils, and device control boards.
  • the electric and electronic parts using the polyurethane resin of the present invention can be used in electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, solar panels, electric tools, automobiles, motorcycles and the like.
  • the resulting polyurethane resin is less likely to cause chemical stress cracks in the resin case, and thus can be suitably used particularly in the field of electrical and electronic parts in which the resin case material is used.

Abstract

The purpose of the present invention is to provide a polyurethane resin composition with excellent moist heat resistance, flame retardance, electrical insulation and workability and with which chemical stress cracks do not occur easily in a resin case thereof. A polyurethane resin composition (X) comprising a hydroxyl group-containing compound (A), an isocyanate group-containing compound (B), a metal hydroxide (C), and a plasticizer (D), wherein: the hydroxyl group-containing compound comprises a polybutadiene polyol (A1); the metal hydroxide is aluminum hydroxide and/or magnesium hydroxide; and the composition comprises 1 part by mass - 30 parts by mass of the plasticizer (D) with respect to 100 parts by mass of the sum of the hydroxyl group-containing compound (A) and the plasticizer (D).

Description

ポリウレタン樹脂組成物Polyurethane resin composition
　本発明は、ポリウレタン樹脂組成物に関する。 The present invention relates to a polyurethane resin composition.
　従来、電子回路基板や電子部品は、外部からの汚染を防ぐためにポリウレタン樹脂等を用いて封止することが行われている（特許文献１）。近年、電子部品などの長寿命化に伴って、長期にわたって湿熱下で使用されることから、優れた耐湿熱性を有することも求められている。 Conventionally, electronic circuit boards and electronic components have been sealed using polyurethane resin or the like in order to prevent external contamination (Patent Document 1). 2. Description of the Related Art In recent years, as electronic parts and the like have a longer life, they are used under a long period of time under wet heat, and therefore have been required to have excellent wet heat resistance.
　このような点に鑑み、本発明者らは、変圧器のケース内部のような密閉かつ高温環境下でも熱的耐久性に優れるポリブタジエンポリオール、ひまし油系ポリオールおよびポリイソシアネート化合物のイソシアヌレート変性体を含有するポリウレタン樹脂組成物について開示してきた（特許文献２）。 In view of such points, the present inventors contain a polybutadiene polyol, a castor oil-based polyol, and an isocyanurate-modified product of a polyisocyanate compound that are sealed in a transformer case and have excellent thermal durability even in a high temperature environment. A polyurethane resin composition has been disclosed (Patent Document 2).
　一方、封止材の周辺部品には樹脂ケースが使用される場合がある。この場合に、電子基板等の筐体(きょうたい)やケース材に対して、ケミカルストレスクラックが発生しないことが求められるが、これまでに開示されていたポリウレタン樹脂組成物ではケミカルストレスクラックの生じにくさが、十分でない場合があった。ケミカルストレスクラックとは、樹脂ケースの引張強度以下の引張応力で発生する、典型的な脆性破壊をいい、成形品において、引張応力発生箇所（荷重がかかっている箇所）に薬品が付着・接触した場合等に、時間経過を伴って薬品と応力との相乗作用にて割れ(クレーズ、クラック)が起る現象である。 On the other hand, a resin case may be used for the peripheral parts of the sealing material. In this case, it is required that the chemical stress crack does not occur on the case such as the electronic substrate and the case material, but the chemical stress crack is generated in the polyurethane resin composition disclosed so far. There were cases where the bitterness was not enough. A chemical stress crack is a typical brittle fracture that occurs with a tensile stress that is less than the tensile strength of the resin case. In the molded product, the chemical adheres to and contacts the location where the tensile stress occurs (where the load is applied). In some cases, this is a phenomenon in which cracks (crazes, cracks) occur due to the synergistic action of chemicals and stress over time.
特開２００８－２３１３４８号公報JP 2008-231348 A 特開２０１１－１４２６号公報JP 2011-1426 A
　本発明は、上記問題点に鑑みて為されたものであり、耐湿熱性、難燃性、電気絶縁性、作業性に優れ、かつ樹脂ケースにケミカルストレスクラックが生じにくいポリウレタン樹脂組成物を提供することを課題とする。 The present invention has been made in view of the above-described problems, and provides a polyurethane resin composition that is excellent in moisture and heat resistance, flame retardancy, electrical insulation, and workability, and that does not easily cause chemical stress cracks in a resin case. This is the issue.
　本発明の発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、ポリウレタン樹脂組成物として、特定の構造のポリオール、イソシアネート基含有化合物、特定かつ特定量の金属水酸化物および特定量の可塑剤を用いることにより、上記課題を解決できることを見いだし、本発明を完成させるに至った。 The inventors of the present invention have made extensive studies to solve the above-mentioned problems. As a result, the polyurethane resin composition includes a polyol having a specific structure, an isocyanate group-containing compound, a specific and specific amount of metal hydroxide, and a specific amount. It has been found that the above-mentioned problems can be solved by using the plasticizer, and the present invention has been completed.
　即ち、本発明は下記に掲げる事項に関する。
（１）　水酸基含有化合物（Ａ）、イソシアネート基含有化合物（Ｂ）、金属水酸化物（Ｃ）および可塑剤（Ｄ）を含有するポリウレタン樹脂組成物（Ｘ）であって、前記水酸基含有化合物が、ポリブタジエンポリオール（Ａ１）を含有し、前記金属水酸化物が水酸化アルミニウムおよび／または、水酸化マグネシウムであって、前記可塑剤（Ｄ）が、水酸基含有化合物（Ａ）および可塑剤（Ｄ）の合計１００質量部に対して、１質量部～３０質量部含有する、ポリウレタン樹脂組成物、
（２）　前記イソシアネート基含有化合物が、ポリイソシアネート化合物のイソシアヌレート変性体（Ｂ１）を含有し、ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、前記金属水酸化物（Ｃ）を４０質量部～８０質量部含有するものである、（１）記載のポリウレタン樹脂組成物、
（３）　前記水酸基含有化合物（Ａ）が、さらにひまし油系ポリオール（Ａ２）を含有し、ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、前記金属水酸化物（Ｃ）を４０質量部～８０質量部含有するものである、（１）記載のポリウレタン樹脂組成物、
（４）　前記ひまし油系ポリオール（Ａ２）および前記金属水酸化物（Ｃ）の質量比が（Ａ２）：（Ｃ）＝１：５～１：１０である（３）記載のポリウレタン樹脂組成物、
（５）　前記イソシアネート基含有化合物が、ヘキサメチレンジイソシアネートのイソシアヌレート、アロファネート、ビュレットまたはアダクト変性体を含有するものである（３）または（４）記載のポリウレタン樹脂組成物、
（６）　前記ひまし油系ポリオール（Ａ２）が、１．０～２．７官能のひまし油系ポリオールを含有することを特徴とする（３）～（５）のいずれか１項記載のポリウレタン樹脂組成物、
（７）　電気電子部品用であることを特徴とする（１）～（６）のいずれか１項に記載のポリウレタン樹脂組成物、
に関する。 That is, this invention relates to the matter hung up below.
(1) A polyurethane resin composition (X) containing a hydroxyl group-containing compound (A), an isocyanate group-containing compound (B), a metal hydroxide (C) and a plasticizer (D), wherein the hydroxyl group-containing compound is Polybutadiene polyol (A1), the metal hydroxide is aluminum hydroxide and / or magnesium hydroxide, and the plasticizer (D) is a hydroxyl group-containing compound (A) and a plasticizer (D). Polyurethane resin composition containing 1 part by mass to 30 parts by mass with respect to a total of 100 parts by mass of
(2) The isocyanate group-containing compound contains a polyisocyanate compound isocyanurate-modified product (B1), and 40 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X). Part to 80 parts by weight of the polyurethane resin composition according to (1),
(3) The hydroxyl group-containing compound (A) further contains a castor oil-based polyol (A2), and 40 parts by mass of the metal hydroxide (C) to 100 parts by mass of the polyurethane resin composition (X). The polyurethane resin composition according to (1), which contains 80 parts by mass,
(4) The polyurethane resin composition according to (3), wherein a mass ratio of the castor oil-based polyol (A2) and the metal hydroxide (C) is (A2) :( C) = 1: 5 to 1:10,
(5) The polyurethane resin composition according to (3) or (4), wherein the isocyanate group-containing compound contains an isocyanurate, allophanate, burette or adduct modified product of hexamethylene diisocyanate,
(6) The polyurethane resin composition according to any one of (3) to (5), wherein the castor oil-based polyol (A2) contains a castor oil-based polyol having a functionality of 1.0 to 2.7. ,
(7) The polyurethane resin composition according to any one of (1) to (6), wherein the polyurethane resin composition is for electric and electronic parts,
About.
　本発明のポリウレタン樹脂組成物を用いることにより、耐湿熱性、難燃性、電気絶縁性、作業性に優れ、かつ樹脂ケースにケミカルストレスクラックが生じにくいポリウレタン樹脂を得ることかできる。 By using the polyurethane resin composition of the present invention, it is possible to obtain a polyurethane resin that is excellent in moisture and heat resistance, flame retardancy, electrical insulation, and workability and that is resistant to chemical stress cracks in the resin case.
耐ケミカルストレスクラック性評価に用いる１／４楕円治具の横断面図である。It is a cross-sectional view of a 1/4 elliptical jig used for chemical stress crack resistance evaluation.
　本発明のポリウレタン樹脂組成物は、水酸基含有化合物、イソシアネート基含有化合物、金属水酸化物および可塑剤を含有する。 The polyurethane resin composition of the present invention contains a hydroxyl group-containing compound, an isocyanate group-containing compound, a metal hydroxide and a plasticizer.
　本発明に用いる水酸基含有化合物は、ポリブタジエンポリオール（Ａ１）を含有する。 The hydroxyl group-containing compound used in the present invention contains polybutadiene polyol (A1).
　本発明に用いるポリブタジエンポリオール（Ａ１）としてはポリウレタン樹脂に使用される従来公知のものを使用することができ、平均水酸基価が２０～１２０ｍｇＫＯＨ／gであることが好ましい。 As the polybutadiene polyol (A1) used in the present invention, those conventionally known for use in polyurethane resins can be used, and the average hydroxyl value is preferably 20 to 120 mgKOH / g.
　ポリブタジエンポリオール（Ａ１）の配合量は、ポリウレタン樹脂組成物に対して３～２５質量％であることが好ましく、５～２０質量％であることがより好ましい。ポリブタジエンポリオール（Ａ１）の配合量が上記範囲より少ないと、耐湿熱性、電気絶縁性が低下する傾向があり、上記範囲より多いとポリウレタン樹脂組成物の製造時の混合粘度が高くなり、作業性が低下する傾向がある。 The blending amount of the polybutadiene polyol (A1) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass with respect to the polyurethane resin composition. When the blending amount of the polybutadiene polyol (A1) is less than the above range, the moist heat resistance and electrical insulation tend to be lowered. When the blending amount is more than the above range, the mixing viscosity at the time of producing the polyurethane resin composition is increased, and the workability is improved. There is a tendency to decrease.
　本発明のポリウレタン樹脂組成物の好ましい実施形態としては、
（i）　前記イソシアネート基含有化合物が、ポリイソシアネート化合物のイソシアヌレート変性体（Ｂ１）を含有し、ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、前記金属水酸化物（Ｃ）を４０質量部～８０質量部含有するもの、
（ii）　前記水酸基含有化合物（Ａ）が、さらにひまし油系ポリオール（Ａ２）を含有し、
　ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、前記金属水酸化物（Ｃ）を４０質量部～８０質量部含有するもの、
があげられる。 As a preferred embodiment of the polyurethane resin composition of the present invention,
(I) The isocyanate group-containing compound contains a polyisocyanate compound isocyanurate-modified product (B1), and 40 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X). Parts to 80 parts by weight,
(Ii) The hydroxyl group-containing compound (A) further contains a castor oil-based polyol (A2),
Containing 40 to 80 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X);
Can be given.
　本発明においては、前記好ましい実施形態（i）および（ii）のいずれにおいても、水酸基含有化合物として、さらにひまし油系ポリオール（Ａ２）を用いることが好ましい。特に好ましい実施形態（ii）において、より好ましい。前記ポリブタジエンポリオール（Ａ１）と前記ひまし油系ポリオール（Ａ２）の２種類のポリオール化合物を含有していることから、ポリウレタン樹脂組成物の混合時の相溶性が優れることから好ましい。 In the present invention, it is preferable to use a castor oil-based polyol (A2) as the hydroxyl group-containing compound in any of the preferred embodiments (i) and (ii). In particularly preferred embodiment (ii), it is more preferred. Since it contains two types of polyol compounds, the polybutadiene polyol (A1) and the castor oil-based polyol (A2), it is preferable because the compatibility of the polyurethane resin composition is excellent.
　ひまし油系ポリオール（Ａ２）としては、ひまし油、ひまし油脂肪酸、及びこれらに水素付加した水添ひまし油や水添ひまし油脂肪酸を用いて製造されたポリオールを使用することができる。このようなポリオールとしては、ひまし油、ひまし油とその他の天然油脂とのエステル交換物、ひまし油と多価アルコールとの反応物、ひまし油脂肪酸と多価アルコールとのエステル化反応物及びこれらにアルキレンオキサイドを付加重合したポリオールなどが挙げられる。 As the castor oil-based polyol (A2), castor oil, castor oil fatty acid, and hydrogenated castor oil or hydrogenated castor oil fatty acid hydrogenated to these can be used. Examples of such polyols include castor oil, a transesterification product of castor oil and other natural fats, a reaction product of castor oil and polyhydric alcohol, an esterification reaction product of castor oil fatty acid and polyhydric alcohol, and alkylene oxide added thereto. Examples include polymerized polyols.
　ひまし油系ポリオール（Ａ２）の２５℃における粘度は、８００ｍＰａ・ｓ以下であることが好ましく、７００ｍＰａ・ｓ以下であることがより好ましい。　本発明においては、前記好ましい実施形態（i）および（ii）のいずれにおいても、官能基数は、１．０～３．０であることが好ましく、１．０～２．７であることがより好ましく、１．２～２．７であることがさらに好ましい。官能基数がこれらの範囲であることは、特に、好ましい実施形態（ii）において好ましい。本発明において官能基数は仕込み量から算出される平均水酸基数をいう。これらの範囲であれば、ポリウレタン樹脂組成物の製造時の混合粘度が好適なものとなり、作業性が良好なものとなる。 The viscosity of castor oil-based polyol (A2) at 25 ° C. is preferably 800 mPa · s or less, and more preferably 700 mPa · s or less. In the present invention, in any of the preferred embodiments (i) and (ii), the number of functional groups is preferably 1.0 to 3.0, more preferably 1.0 to 2.7. Preferably, it is 1.2 to 2.7. It is particularly preferable in the preferred embodiment (ii) that the number of functional groups is within these ranges. In the present invention, the number of functional groups means the average number of hydroxyl groups calculated from the charged amount. If it is these ranges, the mixing viscosity at the time of manufacture of a polyurethane resin composition will become suitable, and workability | operativity will become favorable.
　ひまし油系ポリオール（Ａ２）の配合量は、ポリウレタン樹脂組成物に対して３～２５質量％であることが好ましく、５～２０質量％であることがより好ましい。ひまし油系ポリオール（Ａ２）の配合量が上記範囲より少ないと、ポリウレタン樹脂組成物の製造時の混合粘度が高くなり、作業性が低下する傾向があり、上記範囲より多いと耐湿熱性が低下する傾向がある。 The blending amount of the castor oil-based polyol (A2) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass with respect to the polyurethane resin composition. When the blending amount of the castor oil-based polyol (A2) is less than the above range, the mixing viscosity at the production of the polyurethane resin composition tends to be high, and the workability tends to be lowered. When the blending amount is more than the above range, the heat and humidity resistance tends to be lowered. There is.
　ポリブタジエンポリオール（Ａ１）とひまし油系ポリオール（Ａ２）は、イソシアネート基含有化合物（Ｂ）と反応させて得られる水酸基末端ウレタンプレポリマーであってもよい。 The polybutadiene polyol (A1) and castor oil-based polyol (A2) may be a hydroxyl group-terminated urethane prepolymer obtained by reacting with the isocyanate group-containing compound (B).
　前記ポリブタジエンポリオール（Ａ１）と前記ひまし油系ポリオール（Ａ２）の混合割合は、１０／９０～９０／１０（質量比）であることが好ましい。上記範囲内とすることにより、ポリウレタン樹脂組成物の混合時の相溶性がより良好となる。 The mixing ratio of the polybutadiene polyol (A1) and the castor oil-based polyol (A2) is preferably 10/90 to 90/10 (mass ratio). By making it in the said range, the compatibility at the time of mixing of a polyurethane resin composition becomes more favorable.
　なお、本発明に用いるポリオール成分には、本発明の効果を損なわない程度に、ポリブタジエンポリオール（Ａ１）およびひまし油系ポリオール（Ａ２）以外のポリオールを配合することができる。このようなポリオールとしては、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリイソプレンポリオール、ポリブタジエンポリオールの水素化物およびポリイソプレンポリオールの水素化物などが挙げられる。 In addition, polyols other than polybutadiene polyol (A1) and castor oil-based polyol (A2) can be blended with the polyol component used in the present invention to such an extent that the effects of the present invention are not impaired. Examples of such polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyisoprene polyols, polybutadiene polyol hydrides, and polyisoprene polyol hydrides.
　本発明においては、前記好ましい実施形態（i）において、ポリイソシアネート化合物のイソシアヌレート変性体（Ｂ１）を含有することが好ましい。イソシアネート基含有化合物がポリイソシアネート化合物のイソシアヌレート変性体を含有することにより、ポリウレタン樹脂の熱的耐久性が優れたものとなる。その理由は明らかではないが、ポリイソシアネート化合物のイソシアヌレート変性体の加水分解抑制効果によるものと推察できる。また、イソシアネート基含有化合物には、他のポリイソシアネート化合物（Ｂ２）を含めることが出来る。他のイソシアネート化合物としては、イソシアヌレート変性体以外であれば特に限定されることなく、ビウレット変性体、アダクト変性体、二官能変性体、単量体等が挙げられる。 In the present invention, in the preferred embodiment (i), it is preferable to contain an isocyanurate-modified product (B1) of a polyisocyanate compound. When the isocyanate group-containing compound contains an isocyanurate-modified product of a polyisocyanate compound, the thermal durability of the polyurethane resin becomes excellent. Although the reason is not clear, it can be inferred to be due to the hydrolysis-inhibiting effect of the isocyanurate-modified polyisocyanate compound. Moreover, another polyisocyanate compound (B2) can be included in an isocyanate group containing compound. Other isocyanate compounds are not particularly limited as long as they are other than isocyanurate-modified products, and examples include biuret-modified products, adduct-modified products, bifunctional modified products, and monomers.
　本発明においては、前記好ましい実施形態（ii）において、ポリイソシアネート化合物のイソシアヌレート変性体（Ｂ１）、イソシアヌレート、アロファネート、ビュレットまたはアダクト変性体を含有することが好ましい。イソシアネート基含有化合物がポリイソシアネート化合物のイソシアヌレート変性体を含有することにより、ポリウレタン樹脂の熱的耐久性が優れたものとなる。その理由は明らかではないが、ポリイソシアネート化合物のイソシアヌレート変性体の加水分解抑制効果によるものと推察できる。また、イソシアネート基含有化合物には、二官能変性体、単量体等の他のポリイソシアネート化合物を含めることが出来る In the present invention, the preferred embodiment (ii) preferably contains a polyisocyanate compound isocyanurate-modified product (B1), isocyanurate, allophanate, burette, or adduct-modified product. When the isocyanate group-containing compound contains an isocyanurate-modified product of a polyisocyanate compound, the thermal durability of the polyurethane resin becomes excellent. Although the reason is not clear, it can be inferred to be due to the hydrolysis-inhibiting effect of the isocyanurate-modified polyisocyanate compound. In addition, the isocyanate group-containing compound may include other polyisocyanate compounds such as a bifunctional modified product and a monomer.
　ポリイソシアネート化合物としては、脂肪族ポリイソシアネート化合物、脂環族ポリイソシアネート化合物、芳香族ポリイソシアネート化合物および芳香脂肪族ポリイソシアネート化合物が挙げられる。ポリイソシアネート化合物としては、反応性、耐久性、粘度および作業性の観点から、脂肪族ポリイソシアネート化合物、脂環族ポリイソシアネート化合物が好ましく、脂肪族ポリイソシアネート化合物がより好ましく、ヘキサメチレンジイソシアネートが最も好ましい。 Examples of the polyisocyanate compound include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds. The polyisocyanate compound is preferably an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound, more preferably an aliphatic polyisocyanate compound, and most preferably hexamethylene diisocyanate from the viewpoints of reactivity, durability, viscosity, and workability. .
　脂肪族ポリイソシアネート化合物としては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、３－メチルペンタン－１，５－ジイソシアネートなどが挙げられる。 Aliphatic polyisocyanate compounds include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane- Examples include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
　脂環族ポリイソシアネート化合物としては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサンなどが挙げられる。 Examples of alicyclic polyisocyanate compounds include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, and the like. Is mentioned.
　芳香族ポリイソシアネート化合物としては、トリレンジイソシアネート、２，２’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、４，４’－ジベンジルジイソシアネート、１，５－ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネートなどが挙げられる。 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.
　芳香脂肪族ポリイソシアネート化合物としては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α，α－テトラメチルキシリレンジイソシアネートなどが挙げられる。 Examples of the araliphatic polyisocyanate compound include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate.
　ポリイソシアネート化合物としては、反応性、耐久性、粘度および作業性の観点から、脂肪族ポリイソシアネート化合物、脂環族ポリイソシアネート化合物が好ましく、脂肪族ポリイソシアネート化合物がより好ましく、ヘキサメチレンジイソシアネートが最も好ましい。 The polyisocyanate compound is preferably an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound, more preferably an aliphatic polyisocyanate compound, and most preferably hexamethylene diisocyanate from the viewpoints of reactivity, durability, viscosity, and workability. .
　また、上記ポリイソシアネート化合物には、ポリイソシアネート化合物と、ポリブタジエンポリオール（Ａ１）及び／又はひまし油系ポリオール（Ａ２）とを反応させてなるイソシアネート基末端ウレタンプレポリマーも使用することができる。 In addition, an isocyanate group-terminated urethane prepolymer obtained by reacting a polyisocyanate compound with a polybutadiene polyol (A1) and / or a castor oil-based polyol (A2) can also be used as the polyisocyanate compound.
　本発明のポリウレタン樹脂は、イソシアネート基と水酸基とのモル比（ＮＣＯ／ＯＨ）が、０．６～１．５であることが好ましく、０．７～１．３であることがより好ましい。イソシアネート基と水酸基のモル比がこの範囲より小さいと硬化不良が生じる場合や得られる樹脂の耐熱性が低くなる場合があり、この範囲より大きいと硬化不良が起こる場合があるからである。 In the polyurethane resin of the present invention, the molar ratio of isocyanate groups to hydroxyl groups (NCO / OH) is preferably 0.6 to 1.5, more preferably 0.7 to 1.3. This is because if the molar ratio of isocyanate group to hydroxyl group is smaller than this range, curing failure may occur or the heat resistance of the resulting resin may be reduced, and if it exceeds this range, curing failure may occur.
　本発明に用いる金属水酸化物（Ｃ）は、例えば、水酸化アルミニウムおよび／または、水酸化マグネシウムである。 The metal hydroxide (C) used in the present invention is, for example, aluminum hydroxide and / or magnesium hydroxide.
　金属水酸化物（Ｃ）の配合量は、ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、４０～８０質量部であることが好ましく、４５～７８質量部であることがより好ましい。金属水酸化物（Ｃ）の配合量が上記範囲より少ないと、難燃性が低下する傾向があり、上記範囲より多いとポリウレタン樹脂組成物の製造時の混合粘度が高くなり、作業性が低下する傾向がある。 The compounding amount of the metal hydroxide (C) is preferably 40 to 80 parts by mass, and more preferably 45 to 78 parts by mass with respect to 100 parts by mass of the polyurethane resin composition (X). If the blending amount of the metal hydroxide (C) is less than the above range, the flame retardancy tends to decrease, and if it is more than the above range, the mixing viscosity at the time of production of the polyurethane resin composition increases and the workability decreases. Tend to.
　本発明においては、前記好ましい実施形態（i）および（ii）のいずれにおいても、前記ひまし油系ポリオール（Ａ２）および前記金属水酸化物（Ｃ）の質量比は（Ａ２）：（Ｃ）＝１：５～１：１０であることが好ましい。（Ａ２）および（Ｃ）の質量比がこれらの範囲であることは、特に、好ましい実施形態（ii）において好ましい。上記範囲よりひまし油系ポリオール（Ａ２）が多いと耐湿熱性が低下する傾向があり、ひまし油系ポリオール（Ａ２）が少ないとポリウレタン樹脂組成物の製造時の混合粘度が高くなり、作業性が低下する傾向がある。 In the present invention, in any of the preferred embodiments (i) and (ii), the mass ratio of the castor oil-based polyol (A2) and the metal hydroxide (C) is (A2) :( C) = 1. : 5 to 1:10 are preferable. It is particularly preferable in the preferred embodiment (ii) that the mass ratio of (A2) and (C) is within these ranges. When the amount of castor oil-based polyol (A2) is larger than the above range, the heat and humidity resistance tends to decrease. When the amount of castor oil-based polyol (A2) is small, the mixed viscosity at the time of production of the polyurethane resin composition increases, and the workability tends to decrease. There is.
　本発明に用いる可塑剤（Ｄ）としてはポリウレタン樹脂に使用される従来公知のものを使用することができ、このような可塑剤としては例えば、ジオクチルフタレート、ジイソノニルフタレート、ジウンデシルフタレートなどのフタル酸エステル、ジオクチルアジペート、ジイソノニルアジペートなどのアジピン酸エステル、メチルアセチルリシノレート、ブチルアセチルリシノレート、アセチル化リシノール酸トリグリセリド、アセチル化ポリリシノール酸トリグリセリドなどのひまし油系エステル、トリオクチルトリメリテート、トリイソノニルトリメリテートなどのトリメリット酸エステル、テトラオクチルピロメリテート、テトライソノニルピロメリテートなどのピロメリット酸エステル、トリクレジルフォスフェート、トリスキシレニルフォスフェート、クレジルジフェニルホスフェート、キシレニルホスフェート、トリフェニルフォスフェートなどリン酸エステルなどが挙げられる。耐湿熱性、難燃性、電気絶縁性、作業性、経済性に優れ、かつ樹脂ケースにケミカルストレスクラックの生じにくさの観点から、これらのうちフタル酸エステル、トリメリット酸エステル、リン酸エステルが好ましく、フタル酸エステル、リン酸エステルがより好ましい。 As the plasticizer (D) used in the present invention, those conventionally known for use in polyurethane resins can be used. Examples of such a plasticizer include phthalic acid such as dioctyl phthalate, diisononyl phthalate, and diundecyl phthalate. Esters, adipates such as dioctyl adipate and diisononyl adipate, castor oil esters such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, acetylated ricinoleic acid triglyceride, acetylated polyricinoleic acid triglyceride, trioctyl trimellitate, triisononyl Trimellitic acid esters such as trimellitate, pyromellitic acid esters such as tetraoctyl pyromellitate, tetraisononyl pyromellitate, tricresyl phosphate, triski Les nil phosphate, cresyl diphenyl phosphate, carboxymethyl Les sulfonyl phosphate, and phosphoric acid esters such as triphenyl phosphate. Among these, phthalic acid ester, trimellitic acid ester, and phosphoric acid ester are preferred from the viewpoints of excellent heat and humidity resistance, flame resistance, electrical insulation, workability, and economic efficiency, and resistance to chemical stress cracks in the resin case. Preferably, a phthalic acid ester and a phosphoric acid ester are more preferable.
　可塑剤（Ｄ）の配合量は、水酸基含有化合物（Ａ）および可塑剤（Ｄ）の合計１００質量部に対して、１質量部～３０質量部であり、耐湿熱性、難燃性、電気絶縁性、作業性に優れ、かつ樹脂ケースにケミカルストレスクラックの生じにくさの観点から、１質量部～２８質量部がより好ましく、５質量部～２５質量部がさらに好ましい。 The compounding amount of the plasticizer (D) is 1 to 30 parts by mass with respect to a total of 100 parts by mass of the hydroxyl group-containing compound (A) and the plasticizer (D). From the viewpoints of excellent workability and workability and resistance to the occurrence of chemical stress cracks in the resin case, it is preferably 1 part by weight to 28 parts by weight, and more preferably 5 parts by weight to 25 parts by weight.
　前記ポリブタジエンポリオール（Ａ１）と前記可塑剤（Ｄ）の混合割合は、１００／４～１００／３５（質量比）であることが好ましく、１００／７～１００／３０（質量比）であることがより好ましい。上記範囲内とすることにより、良好な作業性を有しつつ、樹脂ケースにケミカルストレスクラックが生じにくいポリウレタン樹脂を得ることができる
。 The mixing ratio of the polybutadiene polyol (A1) and the plasticizer (D) is preferably 100/4 to 100/35 (mass ratio), and preferably 100/7 to 100/30 (mass ratio). More preferred. By setting it within the above range, it is possible to obtain a polyurethane resin which has good workability and hardly causes chemical stress cracks in the resin case.
　また、本発明のポリウレタン樹脂組成物には、触媒、酸化防止剤、吸湿剤、防黴剤、シランカップリング剤など、必要に応じて各種の添加剤を添加することができる。シランカップリング剤としては、例えばアルコキシシラン類、ビニル基含有シランカップリンク剤、エポキシ基含有シランカップリンク剤、メタクリル基含有シランカップリンク剤、アクリル基含有シランカップリンク剤などが挙げられる。 In addition, 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. Examples of the silane coupling agent include alkoxysilanes, vinyl group-containing silane coupling agents, epoxy group-containing silane coupling agents, methacryl group-containing silane coupling agents, and acrylic group-containing silane coupling agents.
　本発明の混合粘度は、４万mPa.s以下が好ましく、３万mPa.s以下がさらに好ましい。これらの範囲であると作業性の点で良好である。なお、混合粘度は実施例に記載の方法で測定される。 The mixed viscosity of the present invention is preferably 40,000 mPa.s or less, more preferably 30,000 mPa.s or less. Within these ranges, the workability is good. In addition, mixing viscosity is measured by the method as described in an Example.
　本発明の耐湿熱性は、８５℃×８５％ＲＨ×３０００時間後において、硬度ｔｙｐｅＡ５以上を保持することが好ましく、硬度ｔｙｐｅＡ１０以上を保持することがさらに好ましい。これらの範囲であると樹脂形状保持の点で良好である。 The moisture and heat resistance of the present invention preferably retains a hardness of type A5 or more, more preferably retains a hardness of type A10 or more after 85 ° C. × 85% RH × 3000 hours. These ranges are good in terms of maintaining the resin shape.
　本発明の難燃性は、ＵＬ９４規格において、Ｖ－１レベルの難燃性を有することが好ましく、Ｖ－０レベルの難燃性を有することがさらに好ましい。 The flame retardancy of the present invention is preferably V-1 level flame retardancy, more preferably V-0 level flame retardancy in the UL94 standard.
　本発明の電気絶縁性は、８５℃×８５％ＲＨ×３０００時間後において、１０の８乗Ω・cm以上であることが好ましく、１０の９乗 Ω・ｃｍ以上であることがさらに好ましい。これらの範囲であると電気絶縁性の点で良好である。 The electrical insulation of the present invention is preferably 10 8 Ω · cm or more, more preferably 10 9 Ω · cm or more after 85 ° C. × 85% RH × 3000 hours. Within these ranges, it is favorable in terms of electrical insulation.
　本発明の耐ケミカルストレスクラック性は、２５℃×６０％ＲＨ×４８時間後での臨界ひずみにおいて、０．５％以上であることが好ましく、０．７％以上であることがさらに好ましい。これらの範囲であると基板の筐体およびケース材にクラックが入らない点で良好である。 The chemical stress crack resistance of the present invention is preferably 0.5% or more, more preferably 0.7% or more, at a critical strain after 25 ° C. × 60% RH × 48 hours. Within these ranges, it is favorable in that cracks do not occur in the housing and case material of the substrate.
　以下、実施例及び比較例に基づいて、本発明のポリウレタン樹脂組成物および本発明のポリウレタン樹脂用原料組成物について詳細に説明する。なお、本明細書中に於ける「部」、「％」は、特に明示した場合を除き、「質量部」、「質量％」をそれぞれ表している。 Hereinafter, the polyurethane resin composition of the present invention and the polyurethane resin raw material composition of the present invention will be described in detail based on Examples and Comparative Examples. In the present specification, “parts” and “%” represent “parts by mass” and “mass%”, respectively, unless otherwise specified.
　実施例及び比較例において使用する原料を以下に示す。 The raw materials used in the examples and comparative examples are shown below.
（ポリブタジエンポリオール（Ａ１））
　Ａ１－１：平均水酸基価１０３ｍｇＫＯＨ／ｇのポリブタジエンポリオール
　　　　　（商品名：Ｐｏｌｙ　ｂｄ　Ｒ－１５ＨＴ、出光興産社製）
　Ａ１－２：平均水酸基価４７ｍｇＫＯＨ／ｇのポリブタジエンポリオール
　　　　　（商品名：Ｐｏｌｙ　ｂｄ　Ｒ－４５ＨＴ、出光興産社製）
（ひまし油系ポリオール（Ａ２－１））
　Ａ２－１： ひまし油脂肪酸－多価アルコールエステル（官能基数２価）
　　　　　（商品名：ＵＲＩＣ　Ｙ－４０３、伊藤製油社製）
　Ａ２－２： ひまし油（官能基数２．７価）
　　　　　（商品名：ひまし油、伊藤製油社製）
　Ａ２－３： ひまし油脂肪酸－アルコールエステル（官能基数１価）
　　　　　（商品名：ＵＲＩＣ　Ｈ－３１、伊藤製油社製） (Polybutadiene polyol (A1))
A1-1: Polybutadiene polyol having an average hydroxyl value of 103 mgKOH / g (trade name: Poly bd R-15HT, manufactured by Idemitsu Kosan Co., Ltd.)
A1-2: Polybutadiene polyol having an average hydroxyl value of 47 mgKOH / g (trade name: Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd.)
(Castor oil-based polyol (A2-1))
A2-1: Castor oil fatty acid-polyhydric alcohol ester (divalent functional group)
(Product name: URIC Y-403, manufactured by Ito Oil)
A2-2: Castor oil (2.7 functional groups)
(Product name: castor oil, manufactured by Ito Oil Co., Ltd.)
A2-3: Castor oil fatty acid-alcohol ester (monovalent functional group)
(Product name: URIC H-31, manufactured by Ito Oil)
（イソシアネート基含有化合物）
（ポリイソシアネート化合物のイソシアヌレート変性体（Ｂ１））
　Ｂ１：ヘキサメチレンジイソシアネートのイソシアヌレート変性体
　　　　　（商品名：デュラネートＴＬＡ－１００、旭化成ケミカルズ社製）
（他のポリイソシアネート化合物（Ｂ２））
　Ｂ２－１：ヘキサメチレンジイソシアネートの２官能型変性体
　　　　　（商品名：デュラネートＤ２０１、旭化成ケミカルズ社製）
　Ｂ２－２：ヘキサメチレンジイソシアネートのビュレット変性体
　　　　　（商品名：デュラネート２４Ａ－１００、旭化成ケミカルズ社製）
　Ｂ２－３：ヘキサメチレンジイソシアネートのアダクト変性体
　　　　　（商品名：デュラネートＡＥ７００－１００、旭化成ケミカルズ社製）
　Ｂ２－４：ポリメリックＭＤＩ　　
　　　　　（商品名：ミリオネートＭＲ－２００、日本ポリウレタン工業社製） (Isocyanate group-containing compound)
(Isocyanurate-modified polyisocyanate compound (B1))
B1: Isocyanurate modified product of hexamethylene diisocyanate (trade name: Duranate TLA-100, manufactured by Asahi Kasei Chemicals)
(Other polyisocyanate compound (B2))
B2-1: Bifunctional modified product of hexamethylene diisocyanate (trade name: Duranate D201, manufactured by Asahi Kasei Chemicals Corporation)
B2-2: A modified burette of hexamethylene diisocyanate (trade name: Duranate 24A-100, manufactured by Asahi Kasei Chemicals Corporation)
B2-3: Adduct modified product of hexamethylene diisocyanate (trade name: Duranate AE700-100, manufactured by Asahi Kasei Chemicals Corporation)
B2-4: Polymeric MDI
(Product name: Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.)
（金属水酸化物（Ｃ））
　Ｃ１：水酸化アルミニウム
　　　　　（商品名：水酸化アルミＣ－３０５、住友化学社製）
　Ｃ２：水酸化マグネシウム
　　　　　（タテホ化学工業社製） (Metal hydroxide (C))
C1: Aluminum hydroxide (trade name: Aluminum hydroxide C-305, manufactured by Sumitomo Chemical Co., Ltd.)
C2: Magnesium hydroxide (manufactured by Tateho Chemical Co., Ltd.)
（可塑剤（Ｄ））
　Ｄ１：ジウンデシルフタレート
　　　　　（商品名：サンソサイザーＤＵＰ、新日本理化社製）
　Ｄ２：トリスキシレニルフォスフェート
　　　　　（商品名：ＴＸＰ、大八化学工業社製） (Plasticizer (D))
D1: Diundecyl phthalate (Brand name: SUNSOSIZER DUP, manufactured by Shin Nippon Rika Co., Ltd.)
D2: Trisoxylenyl phosphate (trade name: TXP, manufactured by Daihachi Chemical Industry Co., Ltd.)
　＜実施例１～２３及び比較例１～６＞　
　表１に示す配合により、各実施例及び各比較例のポリウレタン樹脂組成物を調製した。調製に際しては、表１に示す成分のうち、イソシアネート基含有化合物（Ｂ）を除く成分を混合機（商品名：あわとり練太郎、シンキー社製）を用いて２０００ｒｐｍで３分間混合した後、２５℃に調整した。続いて、この混合物に２５℃に調整したイソシアネート基含有化合物（Ｂ）を加え、同上の混合機を用いて２０００ｒｐｍで６０秒間混合することにより、各実施例のポリウレタン樹脂組成物を得た。 <Examples 1 to 23 and Comparative Examples 1 to 6>
The polyurethane resin composition of each Example and each comparative example was prepared according to the formulation shown in Table 1. In the preparation, components other than the isocyanate group-containing compound (B) among the components shown in Table 1 were mixed for 3 minutes at 2000 rpm using a mixer (trade name: Aritori Nertaro, manufactured by Shinky Corp.), then 25 Adjusted to ° C. Then, the isocyanate group containing compound (B) adjusted to 25 degreeC was added to this mixture, and the polyurethane resin composition of each Example was obtained by mixing for 60 second at 2000 rpm using the mixer same as the above.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
 なお、比較例５は、粘度が著しく高く、均質なウレタン樹脂を得ることが出来なかった。
Figure JPOXMLDOC01-appb-T000002
 In Comparative Example 5, the viscosity was remarkably high and a homogeneous urethane resin could not be obtained.
　＜評価方法＞ <Evaluation method>
（混合粘度）
　得られたポリウレタン樹脂組成物を２５℃に調整し、混合開始から５分後の粘度をＢＨ型粘度計を用いて測定した。 (Mixed viscosity)
The obtained polyurethane resin composition was adjusted to 25 ° C., and the viscosity 5 minutes after the start of mixing was measured using a BH viscometer.
（耐湿熱性）
１．試験片の作成
　上記ポリウレタン樹脂組成物を５ｃｍ×５ｃｍ、厚み１ｃｍの金型に流し込み、８０℃で１６時間養生した後、これを脱型することにより、耐湿熱性評価用の試験片を作成した。
２．耐湿熱性の評価
　試験片を８５℃×８５％ＲＨ×３０００時間処理後、硬度（タイプＡ）をＪＩＳ　Ｋ６２５３で測定し、体積固有抵抗値を、東亜電波工業社製ＳＥ－１０Ｅを用い、２５±５℃、６５±５％ＲＨで５００Ｖの測定電圧を印加し、６０秒後の数値を測定した。下記の通り評価した。
　○：硬度ｔｙｐｅＡ１０以上かつ体積固有抵抗値が１０の９乗 Ω・ｃｍ以上
　×：硬度または体積固有抵抗値が上記を満たさない。 (Moisture and heat resistance)
1. Preparation of Test Pieces The polyurethane resin composition was poured into a 5 cm × 5 cm, 1 cm thick mold, cured at 80 ° C. for 16 hours, and then demolded to prepare a test piece for wet heat resistance evaluation.
2. Evaluation of wet heat resistance After the test piece was treated at 85 ° C. × 85% RH × 3000 hours, the hardness (type A) was measured according to JIS K6253, and the volume resistivity was 25 ± 25 using SE-10E manufactured by Toa Denpa Kogyo Co., Ltd. A measurement voltage of 500 V was applied at 5 ° C. and 65 ± 5% RH, and the value after 60 seconds was measured. Evaluation was performed as follows.
◯: Hardness type A10 or higher and volume resistivity value of 10 9 Ω · cm or more ×: Hardness or volume resistivity value does not satisfy the above.
（難燃性）
　難燃性は、ＵＬ規格のＵＬ９４（プラスチック材料の難燃性）に従って測定した。 (Flame retardance)
The flame retardancy was measured according to UL standard UL94 (flame retardance of plastic materials).
（体積固有抵抗値）
　東亜電波工業社製ＳＥ－１０Ｅを用い、２５±５℃、６５±５％ＲＨで、試験片を５００Ｖの測定電圧を印加し、６０秒後の数値を測定する。 (Volume resistivity)
Using SE-10E manufactured by Toa Denpa Kogyo Co., Ltd., a measurement voltage of 500 V is applied to the test piece at 25 ± 5 ° C. and 65 ± 5% RH, and the value after 60 seconds is measured.
（耐ケミカルストレスクラック性）
　ＡＢＳ試験片１（商品名：コウベポリシートＡＢＳ、新神戸電機社製）を長軸１００ｍｍ、短軸４０ｍｍの図１に示す１／４楕円治具に取り付け、実施例の樹脂シート（シートの製法）を試験片表面に貼り付けしたあと、 ２５℃×６０％の環境下に４８時間放置し、亀裂が発生する位置Ｘを測定し、式１を用いて臨界ひずみ値を求めた。当該臨界ひずみ値に基づき、耐ケミカルストレスクラック性を下記のようにランク分けして評価した。
Figure JPOXMLDOC01-appb-M000003
  
 ε：臨界ひずみ値
 ａ：楕円長軸 １００ｍｍ
 ｂ：楕円短軸 ４０ｍｍ
 X：亀裂発生点 試験片の長軸に対する固定端から亀裂発生点までの距離 ｍｍ
 ｔ：試験片厚み ２．０ｍｍ
＜評価＞
○（クレーズまたはクラック発生の可能性が小さく、十分に実用可能）：臨界ひずみ値（ε）０．７％以上　
×（成形ひずみの大きな部分や応力集中の高い部分ではクラック発生の可能性が高い）：臨界ひずみ値（ε）０．７％未満 (Chemical stress crack resistance)
An ABS test piece 1 (trade name: Kobe Poly Sheet ABS, manufactured by Shin-Kobe Electric Machinery Co., Ltd.) was attached to a 1/4 oval jig shown in FIG. After being attached to the surface of the test piece, the specimen was left in an environment of 25 ° C. × 60% for 48 hours, the position X at which a crack occurred was measured, and the critical strain value was obtained using Equation 1. Based on the critical strain value, the chemical stress crack resistance was evaluated by ranking as follows.
Figure JPOXMLDOC01-appb-M000003
ε: critical strain value a: ellipse major axis 100 mm
b: Ellipse minor axis 40mm
X: Crack generation point Distance from the fixed end to the crack generation point with respect to the long axis of the test piece mm
t: Test piece thickness 2.0 mm
<Evaluation>
○ (The possibility of occurrence of crazes or cracks is small and can be used practically): Critical strain value (ε) 0.7% or more
× (The possibility of cracking is high in parts where molding strain is large or where stress concentration is high): Critical strain value (ε) less than 0.7%
　＜評価結果＞
　実施例１～２３から分かるように、本発明のポリウレタン樹脂組成物は、混合粘度が使用可能な範囲であり、また、作業性、耐湿熱性、難燃性、電気絶縁性に優れ、樹脂ケースにケミカルストレスクラックが生じにくいことが分かる。 <Evaluation results>
As can be seen from Examples 1 to 23, the polyurethane resin composition of the present invention has a range in which the mixed viscosity can be used, is excellent in workability, moist heat resistance, flame resistance, and electrical insulation, and is suitable for a resin case. It can be seen that chemical stress cracks are less likely to occur.
　一方、比較例１のように可塑剤が少ない系では、粘度が高くなり作業性が悪くなる。比較例２のように可塑剤が多い場合は、ケミカルストレスクラックが生じてしまう。また、比較例３のようにポリブタジエンポリオールを使用しない系では、耐湿熱性が低くなる。比較例４のようにポリウレタン樹脂組成物（Ｘ）中の金属水酸化物（Ｃ）が少ない系では難燃性、比較例５のようにポリウレタン樹脂組成物（Ｘ）中の金属水酸化物（Ｃ）が多い系では作業性が劣る。比較例６のように、可塑剤（Ｄ）が少ない系では、作業性が劣る。 On the other hand, in a system with few plasticizers as in Comparative Example 1, the viscosity becomes high and the workability deteriorates. When there are many plasticizers like the comparative example 2, a chemical stress crack will arise. Moreover, in the system which does not use polybutadiene polyol as in Comparative Example 3, the heat and humidity resistance is low. Flame retardancy is obtained in a system with a small amount of metal hydroxide (C) in the polyurethane resin composition (X) as in Comparative Example 4, and metal hydroxide (in the polyurethane resin composition (X) as in Comparative Example 5 ( Workability is inferior in a system with many C). As in Comparative Example 6, the workability is inferior in a system with little plasticizer (D).
　本発明のポリウレタン樹脂組成物から得られるポリウレタン樹脂は、耐湿熱性を有していることから、発熱を伴う電気電子部品に好適に使用することができる。このような電気電子部品としては、トランスコイル、チョークコイルおよびリアクトルコイルなどの変圧器や機器制御基板が挙げられる。本発明のポリウレタン樹脂を使用した電気電子部品は、電気洗濯機、便座、湯沸し器、浄水器、風呂、食器洗浄機、太陽光パネル、電動工具、自動車、バイクなどに使用できる。また、本発明のポリウレタン樹脂組成物を用いれば、得られるポリウレタン樹脂は樹脂ケースにケミカルストレスクラックが生じにくいため、特に、樹脂ケース材が使用される電気電子部品分野に好適に使用できる。 Since the polyurethane resin obtained from the polyurethane resin composition of the present invention has heat and moisture resistance, it can be suitably used for electric and electronic parts that generate heat. Examples of such electric and electronic parts include transformers such as transformer coils, choke coils, and reactor coils, and device control boards. The electric and electronic parts using the polyurethane resin of the present invention can be used in electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, solar panels, electric tools, automobiles, motorcycles and the like. In addition, when the polyurethane resin composition of the present invention is used, the resulting polyurethane resin is less likely to cause chemical stress cracks in the resin case, and thus can be suitably used particularly in the field of electrical and electronic parts in which the resin case material is used.

Claims (7)

  1. 　水酸基含有化合物（Ａ）、イソシアネート基含有化合物（Ｂ）、金属水酸化物（Ｃ）および可塑剤（Ｄ）を含有するポリウレタン樹脂組成物（Ｘ）であって、
    　前記水酸基含有化合物が、ポリブタジエンポリオール（Ａ１）を含有し、
    　前記金属水酸化物が水酸化アルミニウムおよび／または、水酸化マグネシウムであって、
    　前記可塑剤（Ｄ）が、水酸基含有化合物（Ａ）および可塑剤（Ｄ）の合計１００質量部に対して、１質量部～３０質量部含有する、
    ポリウレタン樹脂組成物。     A polyurethane resin composition (X) containing a hydroxyl group-containing compound (A), an isocyanate group-containing compound (B), a metal hydroxide (C) and a plasticizer (D),
    The hydroxyl group-containing compound contains a polybutadiene polyol (A1),
    The metal hydroxide is aluminum hydroxide and / or magnesium hydroxide,
    The plasticizer (D) contains 1 part by mass to 30 parts by mass with respect to 100 parts by mass in total of the hydroxyl group-containing compound (A) and the plasticizer (D).
    Polyurethane resin composition.
  2. 　前記イソシアネート基含有化合物が、ポリイソシアネート化合物のイソシアヌレート変性体（Ｂ１）を含有し、
    ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、前記金属水酸化物（Ｃ）を４０質量部～８０質量部含有するものである、請求項１記載のポリウレタン樹脂組成物。     The isocyanate group-containing compound contains a polyisocyanate compound isocyanurate-modified product (B1),
    The polyurethane resin composition according to claim 1, comprising 40 to 80 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X).
  3. 　前記水酸基含有化合物（Ａ）が、さらにひまし油系ポリオール（Ａ２）を含有し、
    　ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、前記金属水酸化物（Ｃ）を４０質量部～８０質量部含有するものである、請求項１記載のポリウレタン樹脂組成物。     The hydroxyl group-containing compound (A) further contains a castor oil-based polyol (A2),
    The polyurethane resin composition according to claim 1, comprising 40 to 80 parts by mass of the metal hydroxide (C) with respect to 100 parts by mass of the polyurethane resin composition (X).
  4. 　前記ひまし油系ポリオール（Ａ２）および前記金属水酸化物（Ｃ）の質量比が（Ａ２）：（Ｃ）＝１：５～１：１０である請求項３記載のポリウレタン樹脂組成物。 The polyurethane resin composition according to claim 3, wherein a mass ratio of the castor oil-based polyol (A2) and the metal hydroxide (C) is (A2) :( C) = 1: 5 to 1:10.
  5. 　前記イソシアネート基含有化合物が、ヘキサメチレンジイソシアネートのイソシアヌレート、アロファネート、ビュレットまたはアダクト変性体を含有するものである請求項３または４記載のポリウレタン樹脂組成物。 The polyurethane resin composition according to claim 3 or 4, wherein the isocyanate group-containing compound contains an isocyanurate, allophanate, burette or adduct modified product of hexamethylene diisocyanate.
  6. 　前記ひまし油系ポリオール（Ａ２）が、１．０～２．７官能のひまし油系ポリオールを含有することを特徴とする請求項３～５のいずれか１項記載のポリウレタン樹脂組成物。 The polyurethane resin composition according to any one of claims 3 to 5, wherein the castor oil-based polyol (A2) contains a castor oil-based polyol having a functionality of 1.0 to 2.7.
  7. 　電気電子部品用であることを特徴とする請求項１～６のいずれか１項に記載のポリウレタン樹脂組成物。
     
     
     
     
          The polyurethane resin composition according to any one of claims 1 to 6, which is used for electrical and electronic parts.




PCT/JP2015/064434 2014-07-15 2015-05-20 Polyurethane resin composition WO2016009716A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580035477.6A CN106661182A (en) 2014-07-15 2015-05-20 Polyurethane resin composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014144655A JP5854534B2 (en) 2014-07-15 2014-07-15 Polyurethane resin composition
JP2014-144654 2014-07-15
JP2014144654A JP5854533B2 (en) 2014-07-15 2014-07-15 Polyurethane resin composition
JP2014-144655 2014-07-15

Publications (1)

Publication Number Publication Date
WO2016009716A1 true WO2016009716A1 (en) 2016-01-21

Family

ID=55078220

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/064434 WO2016009716A1 (en) 2014-07-15 2015-05-20 Polyurethane resin composition

Country Status (2)

Country Link
CN (1) CN106661182A (en)
WO (1) WO2016009716A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6755631B2 (en) * 2018-08-30 2020-09-16 第一工業製薬株式会社 Two-component curable resin composition for battery potting

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5562918A (en) * 1978-11-01 1980-05-12 Sanyurejin Kk Urethane resin composition
JPS5893717A (en) * 1981-11-30 1983-06-03 Nippon Zeon Co Ltd Potting agent for electrical insulation
JPH04209620A (en) * 1990-12-10 1992-07-31 Hayakawa Rubber Co Ltd Room-temperature-curable flame-retarding composition
JP2010150472A (en) * 2008-12-26 2010-07-08 Dai Ichi Kogyo Seiyaku Co Ltd Polyurethane resin composition and polyurethane resin
JP2011001426A (en) * 2009-06-17 2011-01-06 Dai Ichi Kogyo Seiyaku Co Ltd Polyurethane resin composition
WO2013054659A1 (en) * 2011-10-12 2013-04-18 サンユレック株式会社 Polyurethane resin composition for electrical insulation
JP2014084330A (en) * 2012-10-19 2014-05-12 Dai Ichi Kogyo Seiyaku Co Ltd Polyurethane resin-formable composition and polyurethane resin
WO2015104918A1 (en) * 2014-01-10 2015-07-16 第一工業製薬株式会社 Polyurethane resin composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7875149B2 (en) * 2005-06-08 2011-01-25 Ppg Industries Ohio, Inc. Aircraft adhesive
JP2009013237A (en) * 2007-07-02 2009-01-22 Dai Ichi Kogyo Seiyaku Co Ltd Exoergic polyurethane resin composition and exoergic polyurethane sheet
JP4517115B2 (en) * 2007-09-10 2010-08-04 第一工業製薬株式会社 Polyurethane resin electrical insulation composition
JP5161756B2 (en) * 2008-12-26 2013-03-13 第一工業製薬株式会社 Polyurethane resin composition and polyurethane resin
JP5216574B2 (en) * 2008-12-26 2013-06-19 第一工業製薬株式会社 Polyurethane resin composition and polyurethane resin
JP2010150475A (en) * 2008-12-26 2010-07-08 Dai Ichi Kogyo Seiyaku Co Ltd Polyurethane resin composition and polyurethane resin

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5562918A (en) * 1978-11-01 1980-05-12 Sanyurejin Kk Urethane resin composition
JPS5893717A (en) * 1981-11-30 1983-06-03 Nippon Zeon Co Ltd Potting agent for electrical insulation
JPH04209620A (en) * 1990-12-10 1992-07-31 Hayakawa Rubber Co Ltd Room-temperature-curable flame-retarding composition
JP2010150472A (en) * 2008-12-26 2010-07-08 Dai Ichi Kogyo Seiyaku Co Ltd Polyurethane resin composition and polyurethane resin
JP2011001426A (en) * 2009-06-17 2011-01-06 Dai Ichi Kogyo Seiyaku Co Ltd Polyurethane resin composition
WO2013054659A1 (en) * 2011-10-12 2013-04-18 サンユレック株式会社 Polyurethane resin composition for electrical insulation
JP2014084330A (en) * 2012-10-19 2014-05-12 Dai Ichi Kogyo Seiyaku Co Ltd Polyurethane resin-formable composition and polyurethane resin
WO2015104918A1 (en) * 2014-01-10 2015-07-16 第一工業製薬株式会社 Polyurethane resin composition

Also Published As

Publication number Publication date
CN106661182A (en) 2017-05-10

Similar Documents

Publication Publication Date Title
JP5568187B1 (en) Polyurethane resin composition
JP5550161B1 (en) Polyurethane resin composition
JP5854534B2 (en) Polyurethane resin composition
JP5535529B2 (en) Polyurethane resin composition
KR101787616B1 (en) Polyol composition for producing polyurethane resin composition
JP6990999B2 (en) Polyurethane resin compositions, encapsulants, polyol compositions and isocyanate compositions
JP5282214B1 (en) Flame retardant resin composition
JP5854533B2 (en) Polyurethane resin composition
JP5787425B2 (en) Polyurethane resin
JP2015089941A (en) Polyurethane resin composition
WO2016009716A1 (en) Polyurethane resin composition
JP2016098327A (en) Polyurethane resin composition, encapsulating material and electric and electronic component
JP6012837B1 (en) Polyurethane resin composition
TWI706005B (en) Polyurethane resin forming composition and polyurethane resin
JP7396193B2 (en) Urethane resin composition and cured product thereof
CN115720582A (en) Polyurethane resin composition
TWI703187B (en) Polyurethane resin forming composition and polyurethane resin
JP2021183702A (en) Polyurethane resin composition for sealing and sealed article
WO2017056766A1 (en) Polyurethane resin forming composition and polyurethane resin
JP6286085B1 (en) Polyurethane resin composition and sealing material
JP2019038974A (en) Resin composition and composition for producing resin
JP2018172631A (en) Polyurethane resin composition and sealed product
JP6273235B2 (en) Polyurethane resin composition
JPH1025413A (en) Flame-retardant liquid polymer composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15822614

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15822614

Country of ref document: EP

Kind code of ref document: A1