WO2015104918A1 - Polyurethane resin composition - Google Patents

Polyurethane resin composition Download PDF

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Publication number
WO2015104918A1
WO2015104918A1 PCT/JP2014/081679 JP2014081679W WO2015104918A1 WO 2015104918 A1 WO2015104918 A1 WO 2015104918A1 JP 2014081679 W JP2014081679 W JP 2014081679W WO 2015104918 A1 WO2015104918 A1 WO 2015104918A1
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Prior art keywords
polyurethane resin
resin composition
castor oil
metal hydroxide
containing compound
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PCT/JP2014/081679
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French (fr)
Japanese (ja)
Inventor
成相 廣瀬
梓 金井
俊樹 野田
丈範 森
望 繁中
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第一工業製薬株式会社
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Publication of WO2015104918A1 publication Critical patent/WO2015104918A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6547—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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

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 which 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).
  • resin cases may be used for 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 inventors of the present invention have made extensive studies to solve the above problems, and as a result, by using a polyol having a specific structure and an isocyanate group-containing compound and a specific amount of metal hydroxide as the polyurethane resin composition, It has been found that the problems can be solved, and the present invention has been completed.
  • the polyurethane resin composition of the present invention is characterized in that the isocyanate group-containing compound contains an isocyanurate-modified product (D) of a polyisocyanate compound.
  • the polyurethane resin composition of the present invention is used for electric and electronic parts.
  • the polyurethane resin composition of the present invention 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.
  • the polyurethane resin composition of the present invention contains a hydroxyl group-containing compound, an isocyanate group-containing compound, and a metal hydroxide (C).
  • the hydroxyl group-containing compound used in the present invention contains polybutadiene polyol (A) and castor oil-based polyol (B). Since it contains two types of polyol compounds, the polybutadiene polyol (A) and the castor oil-based polyol (B), the compatibility during mixing of the polyurethane resin composition is excellent.
  • polybutadiene polyol (A) 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 (A) is preferably 3 to 25% by mass and more preferably 5 to 20% by mass with respect to the polyurethane resin composition.
  • the blending amount of the polybutadiene polyol (A) is less than the above range, the heat and moisture resistance and the electrical insulation tend to be lowered. There is a tendency to decrease.
  • castor oil-based polyol (B) 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 (B) at 25 ° C. is preferably 800 mPa ⁇ s or less, and more preferably 700 mPa ⁇ s or less.
  • the average number of hydroxyl groups calculated from the charged amount is preferably 1.0 to 3.0, and more preferably 1.0 to 2.7. If it is these ranges, the mixing viscosity at the time of manufacture of a polyurethane resin composition will become suitable, and workability
  • the amount of castor oil-based polyol (B) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, based on the polyurethane resin composition.
  • the blending amount of the castor oil-based polyol (B) is less than the above range, the mixing viscosity at the time of production of the polyurethane resin composition tends to be high, and the workability tends to be lowered. There is.
  • the polybutadiene polyol (A) and the castor oil-based polyol (B) are a hydroxyl group-terminated urethane prepolymer obtained by reacting with a polyisocyanate compound isocyanurate-modified product (D) and / or another polyisocyanate compound (E). Also good.
  • the mixing ratio of the polybutadiene polyol (A) and the castor oil-based polyol (B) 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.
  • the metal hydroxide (C) is aluminum hydroxide and / or magnesium hydroxide.
  • the compounding amount of the metal hydroxide (C) is 55 to 80 parts by mass, and more preferably 63 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 castor oil-based polyol (B) is more than the above range, the heat and humidity resistance tends to decrease, and when the castor oil-based polyol (B) is small, the mixing viscosity at the time of production of the polyurethane resin composition tends to increase, and the workability tends to decrease. There is.
  • the isocyanate group-containing compound used in the present invention preferably contains a modified product of a polyisocyanate compound, and isocyanurate-terminated urethane prepolymer obtained by reacting an isocyanurate-modified product (D) and / or a polyisocyanate compound with a polyol. It is more preferable to contain.
  • the isocyanate group-containing compound contains the isocyanurate-modified product (D) 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.
  • polyisocyanate compound (E) 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.
  • polyisocyanate compound examples include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds.
  • 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 (A) and / or a castor oil-based polyol (B) 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 polyurethane resin composition of the present invention preferably contains substantially no plasticizer, and more preferably contains substantially no plasticizer comprising a phthalate ester or trimellitic acid ester.
  • substantially not contained means that the content of a plasticizer made of a plasticizer, a phthalate ester or a trimellitic acid ester in the polyurethane resin composition (X) is 0.01% by mass or less. This is because chemical stress cracks are likely to occur in the resin case due to bleed out over time.
  • polyols other than polybutadiene polyol (A) and castor oil-based polyol (B) 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.
  • 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 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 insulating property 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, and more preferably 0.7% or more at a critical strain after 85 ° C. ⁇ 85% 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.
  • 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 more and volume resistivity value of 10 9 ⁇ ⁇ cm or more ⁇ : Hardness or volume resistivity value does not satisfy the above. (Flame retardance) The flame retardancy was measured according to UL standard UL94 (flame retardance of plastic materials).
  • ⁇ critical strain value a: ellipse major axis 100 mm b: Ellipse minor axis 40mm X: Crack initiation point Distance from the fixed end to the crack initiation point relative to the long axis of the test piece mm t: Test piece thickness 2.0 mm ⁇ Evaluation> ⁇ (Fully practical): Critical strain value ( ⁇ ) 1.0% or more ⁇ (practical): critical strain value ( ⁇ ) 0.5% or more and less than 1.0% ⁇ (practical): critical strain value ( ⁇ ) less than 0.5%
  • the polyurethane resin composition of the present invention has a range in which the mixed viscosity can be used, is excellent in workability, heat and humidity 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 composition (X ) In a system with a large amount of metal hydroxide (C), workability is inferior.
  • the polyurethane resin obtained from the polyurethane resin composition of the present invention has heat-and-moisture resistance, it can be suitably used for electrical 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

Provided is a polyurethane resin composition having excellent moist-heat resistance, flame retardance, electrical insulation properties, and workability and being unlikely to have chemical stress cracks occurring in a resin case. The polyurethane resin composition contains a hydroxyl group-containing compound, an isocyanate group-containing compound, and a metal hydroxide. The hydroxyl group-containing compound contains a polybutadiene polyol and a castor oil-based polyol. The polyurethane resin composition contains 55-80 parts by mass metal hydroxide to 100 parts by mass polyurethane resin composition. The mass ratio ((B):(C)) between castor oil-based polyol (B) and metal hydroxide (C) is 1:5-1:10.

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 which 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, resin cases may be used for 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およびイソシアネート基含有化合物、特定量の金属水酸化物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 problems, and as a result, by using a polyol having a specific structure and an isocyanate group-containing compound and a specific amount of metal hydroxide as the polyurethane resin composition, It has been found that the problems can be solved, and the present invention has been completed.
　即ち、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および金属水酸化物（Ｃ）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（Ａ）およびひまし油系ポリオール（Ｂ）を含有し、前記金属水酸化物（Ｃ）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、ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、５５質量部～８０質量部含有し、前記ひまし油系ポリオール（Ｂ）および前記金属水酸化物（Ｃ）の質量比が（Ｂ）：（Ｃ）＝１：５～１：１０である。 That is, the polyurethane resin composition of the present invention is a polyurethane resin composition (X) containing a hydroxyl group-containing compound, an isocyanate group-containing compound and a metal hydroxide (C), wherein the hydroxyl group-containing compound is a polybutadiene polyol ( A) and castor oil-based polyol (B), wherein the metal hydroxide (C) is aluminum hydroxide and / or magnesium hydroxide, and 100 parts by mass of the polyurethane resin composition (X), It is contained in an amount of 55 to 80 parts by mass, and the mass ratio of the castor oil-based polyol (B) and the metal hydroxide (C) is (B) :( C) = 1: 5 to 1:10.
　本発明のポリウレタン樹脂組成物は、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（Ｄ）を含有することを特徴とする。 The polyurethane resin composition of the present invention is characterized in that the isocyanate group-containing compound contains an isocyanurate-modified product (D) of a polyisocyanate compound.
　本発明のポリウレタン樹脂組成物は、電気電子部品用であることを特徴とする。 The polyurethane resin composition of the present invention is used for electric and electronic parts.
　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および金属水酸化物（Ｃ）を含有する。 The polyurethane resin composition of the present invention contains a hydroxyl group-containing compound, an isocyanate group-containing compound, and a metal hydroxide (C).
　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（Ａ）およびひまし油系ポリオール（Ｂ）を含有する。前記ポリブタジエンポリオール（Ａ）と前記ひまし油系ポリオール（Ｂ）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。 The hydroxyl group-containing compound used in the present invention contains polybutadiene polyol (A) and castor oil-based polyol (B). Since it contains two types of polyol compounds, the polybutadiene polyol (A) and the castor oil-based polyol (B), the compatibility during mixing of the polyurethane resin composition is excellent.
　本発明に用いるポリブタジエンポリオール（Ａ）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 (A) 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（Ａ）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（Ａ）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 (A) is preferably 3 to 25% by mass and more preferably 5 to 20% by mass with respect to the polyurethane resin composition. When the blending amount of the polybutadiene polyol (A) is less than the above range, the heat and moisture resistance and the electrical insulation tend to be lowered. There is a tendency to decrease.
　ひまし油系ポリオール（Ｂ）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 (B), 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（Ｂ）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。仕込み量から算出される平均水酸基数は、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い。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 (B) at 25 ° C. is preferably 800 mPa · s or less, and more preferably 700 mPa · s or less. The average number of hydroxyl groups calculated from the charged amount is preferably 1.0 to 3.0, and more preferably 1.0 to 2.7. 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（Ｂ）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（Ｂ）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 amount of castor oil-based polyol (B) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, based on the polyurethane resin composition. When the blending amount of the castor oil-based polyol (B) is less than the above range, the mixing viscosity at the time of production of the polyurethane resin composition tends to be high, and the workability tends to be lowered. There is.
　ポリブタジエンポリオール（Ａ）とひまし油系ポリオール（Ｂ）は、ポリイソシアネート化合物のイソシアヌレート変性体（Ｄ）および／または他のポリイソシアネート化合物（Ｅ）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 (A) and the castor oil-based polyol (B) are a hydroxyl group-terminated urethane prepolymer obtained by reacting with a polyisocyanate compound isocyanurate-modified product (D) and / or another polyisocyanate compound (E). Also good.
　前記ポリブタジエンポリオール（Ａ）と前記ひまし油系ポリオール（Ｂ）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 (A) and the castor oil-based polyol (B) 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.
　金属水酸化物（Ｃ）は、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) is 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、５５～８０質量部であり、６３～７８質量部であることがさらに好ましい。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 55 to 80 parts by mass, and more preferably 63 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.
　前記ひまし油系ポリオール（Ｂ）および前記金属水酸化物（Ｃ）の質量比は（Ｂ）：（Ｃ）＝１：５～１：１０である。上記範囲よりひまし油系ポリオール（Ｂ）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（Ｂ）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。 The mass ratio of the castor oil-based polyol (B) and the metal hydroxide (C) is (B) :( C) = 1: 5 to 1:10. When the castor oil-based polyol (B) is more than the above range, the heat and humidity resistance tends to decrease, and when the castor oil-based polyol (B) is small, the mixing viscosity at the time of production of the polyurethane resin composition tends to increase, and the workability tends to decrease. There is.
　本発明に用いるイソシアネート基含有化合物は、ポリイソシアネート化合物の変性体を含有することが好ましく、イソシアヌレート変性体（Ｄ）および／またはポリイソシアネート化合物とポリオール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を含有することがさらに好ましい。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（Ｄ）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（Ｅ）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。 The isocyanate group-containing compound used in the present invention preferably contains a modified product of a polyisocyanate compound, and isocyanurate-terminated urethane prepolymer obtained by reacting an isocyanurate-modified product (D) and / or a polyisocyanate compound with a polyol. It is more preferable to contain. When the isocyanate group-containing compound contains the isocyanurate-modified product (D) 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, other polyisocyanate compound (E) 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.
　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。 Examples of the polyisocyanate compound include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds.
　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（Ａ）及び／又はひまし油系ポリオール（Ｂ）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 (A) and / or a castor oil-based polyol (B) 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.
　本発明のポリウレタン樹脂組成物には、可塑剤を実質的に含有しないことが好ましく、特にフタル酸エステルまたはトリメリット酸エステルからなる可塑剤を実質的に含有しないことがより好ましい。ここで、実質的に含有しないとは、可塑剤またはフタル酸エステルまたはトリメリット酸エステルからなる可塑剤のポリウレタン樹脂組成物（Ｘ）中の含有量が０．０１質量％以下のものをいう。経時的なブリードアウトにより、樹脂ケースにケミカルストレスクラックが生じ易くなるからである。 The polyurethane resin composition of the present invention preferably contains substantially no plasticizer, and more preferably contains substantially no plasticizer comprising a phthalate ester or trimellitic acid ester. Here, “substantially not contained” means that the content of a plasticizer made of a plasticizer, a phthalate ester or a trimellitic acid ester in the polyurethane resin composition (X) is 0.01% by mass or less. This is because chemical stress cracks are likely to occur in the resin case due to bleed out over time.
　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（Ａ）およびひまし油系ポリオール（Ｂ）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 (A) and castor oil-based polyol (B) 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.
　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 insulating property 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、８５℃×８５％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, and more preferably 0.7% or more at a critical strain after 85 ° C. × 85% 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。
（ポリブタジエンポリオール（Ａ））
　Ａ１：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）
　Ａ２：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（Ｂ））
　Ｂ１： ひまし油脂肪酸－多価アルコールエステル
　　　（商品名：ＵＲＩＣ　Ｙ－４０３、伊藤製油社製）
　Ｂ２： ひまし油
　　（商品名：ひまし油、伊藤製油社製）
　Ｂ３： ひまし油脂肪酸－多価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）
　Ｂ４： ひまし油脂肪酸－多価アルコールエステル
　　　　　（商品名：ＵＲＩＣ　Ｙ－４０６、伊藤製油社製）
　Ｂ５： ひまし油脂肪酸－多価アルコールエステル（官能基数 １価）
　　　　　（商品名：ＨＳ１－１６０、豊国製油社製）
（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）
（ポリイソシアネート化合物のイソシアヌレート変性体（Ｄ））
　Ｄ１：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（Ｅ））
　Ｅ１：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）
　Ｅ２：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Ａ－２０１Ｈ、旭化成ケミカルズ社製）
（可塑剤）
　　　ジイソノニルフタレート
　　　　　（商品名：サンソサイザーＤＩＮＰ、新日本理化社製）
＜実施例１～１３及び比較例１～５＞
　表１および表２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、ポリイソシアネート化合物のイソシアヌレート変性体（Ｄ）および他のポリイソシアネート化合物（Ｅ）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℃に調整したポリイソシアネート化合物のイソシアヌレート変性体（Ｄ）および他のポリイソシアネート化合物（Ｅ）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。 The raw materials used in Examples and Comparative Examples are shown below.
(Polybutadiene polyol (A))
A1: Polybutadiene polyol having an average hydroxyl value of 103 mgKOH / g (trade name: Poly bd R-15HT, manufactured by Idemitsu Kosan Co., Ltd.)
A2: 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 (B))
B1: Castor oil fatty acid-polyhydric alcohol ester (trade name: URIC Y-403, manufactured by Ito Oil Co., Ltd.)
B2: Castor oil (Brand name: Castor oil, Ito Oil Co., Ltd.)
B3: Castor oil fatty acid-polyhydric alcohol ester (functional group monovalent)
(Product name: URIC H-31, manufactured by Ito Oil)
B4: Castor oil fatty acid-polyhydric alcohol ester (trade name: URIC Y-406, manufactured by Ito Oil Co., Ltd.)
B5: Castor oil fatty acid-polyhydric alcohol ester (functional group monovalent)
(Product name: HS1-160, manufactured by Toyokuni Oil)
(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.)
(Isocyanurate-modified polyisocyanate compound (D))
D1: Isocyanurate modified product of hexamethylene diisocyanate (trade name: Duranate TLA-100, manufactured by Asahi Kasei Chemicals)
(Other polyisocyanate compounds (E))
E1: Bifunctional modified product of hexamethylene diisocyanate (trade name: Duranate D201, manufactured by Asahi Kasei Chemicals)
E2: Bifunctional modification of hexamethylene diisocyanate (trade name: Duranate A-201H, manufactured by Asahi Kasei Chemicals Corporation)
(Plasticizer)
Diisononyl phthalate (trade name: Sansosizer DINP, manufactured by Shin Nippon Rika Co., Ltd.)
<Examples 1 to 13 and Comparative Examples 1 to 5>
The polyurethane resin compositions of the examples and comparative examples were prepared according to the formulations shown in Table 1 and Table 2. In the preparation, among the components shown in Table 1, components other than the polyisocyanate compound isocyanurate-modified (D) and other polyisocyanate compounds (E) were mixed (trade name: Awatori Netaro, manufactured by Shinky Corporation) ) For 3 minutes at 2000 rpm and adjusted to 25 ° C. Subsequently, the polyisocyanate compound isocyanurate-modified product (D) adjusted to 25 ° C. and another polyisocyanate compound (E) were added to this mixture, and mixed at 2000 rpm for 60 seconds using the same mixer. The polyurethane resin composition of each Example was obtained.
　＜評価方法＞
（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。
（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。
（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。
（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５００
Ｖの測定電圧を印加し、６０秒後の数値を測定する。
（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、 ８５℃×８５％ＲＨ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、数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-M000001
 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＞
○（十分に実用可能）：臨界ひずみ値（ε）１．０％以上　
△（実用可能）：臨界ひずみ値（ε）０．５％以上、１．０％未満
×（実用不可）：臨界ひずみ値（ε）０．５％未満 <Evaluation method>
(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.
(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 more and volume resistivity value of 10 9 Ω · cm or more ×: Hardness or volume resistivity value does not satisfy the above.
(Flame retardance)
The flame retardancy was measured according to UL standard UL94 (flame retardance of plastic materials).
(Volume resistivity)
Using SE-10E manufactured by Toa Denpa Kogyo Co., Ltd., the specimen is 500 at 25 ± 5 ° C and 65 ± 5% RH.
A measurement voltage of V is applied and the value after 60 seconds is measured.
(Chemical stress crack resistance)
An ABS test piece 1 (trade name: Koube Poly Sheet ABS, manufactured by Shin-Kobe Electric Machinery Co., Ltd.) was attached to a 1/4 oval jig shown in FIG. 1 having a major axis of 100 mm and a minor axis of 40 mm, and the resin sheet of the example (sheet manufacturing method) After being attached to the surface of the test piece, it was left in an environment of 85 ° C. × 85% RH for 48 hours, the position X at which a crack was generated 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-M000001
 ε: critical strain value a: ellipse major axis 100 mm
b: Ellipse minor axis 40mm
X: Crack initiation point Distance from the fixed end to the crack initiation point relative to the long axis of the test piece mm
t: Test piece thickness 2.0 mm
<Evaluation>
○ (Fully practical): Critical strain value (ε) 1.0% or more
Δ (practical): critical strain value (ε) 0.5% or more and less than 1.0% × (practical): critical strain value (ε) less than 0.5%
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　なお、比較例２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。 In Comparative Example 2, the viscosity was extremely high and a homogeneous urethane resin could not be obtained.
　＜評価結果＞
　実施例１～１３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。一方、比較例１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および耐ケミカルストレスクラック性、比較例２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３のように、ひまし油系ポリオール（Ｂ）に変えてフタル酸エステル系可塑剤を用いた系では、耐ケミカルストレスクラック性が著しく劣る。比較例４のように、ひまし油系ポリオール（Ｂ）および前記金属水酸化物（Ｃ）の質量比の金属水酸化物（Ｃ）の割合が低い系では耐湿熱性が劣り、比較例５のように、ひまし油系ポリオール（Ｂ）および前記金属水酸化物（Ｃ）の質量比の金属水酸化物（Ｃ）の割合が高い系では作業性が劣ることがわかる。 <Evaluation results>
As can be seen from Examples 1 to 13, the polyurethane resin composition of the present invention has a range in which the mixed viscosity can be used, is excellent in workability, heat and humidity 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. On the other hand, in the system having a small amount of metal hydroxide (C) in the polyurethane resin composition (X) as in Comparative Example 1, flame retardancy and chemical stress crack resistance, and as in Comparative Example 2, the polyurethane resin composition (X ) In a system with a large amount of metal hydroxide (C), workability is inferior. As in Comparative Example 3, the chemical stress crack resistance is remarkably inferior in a system using a phthalate plasticizer instead of the castor oil-based polyol (B). As in Comparative Example 4, in a system in which the ratio of the castor oil-based polyol (B) and the metal hydroxide (C) in the mass ratio of the metal hydroxide (C) is low, the heat and moisture resistance is inferior. It can be seen that the workability is inferior in a system in which the ratio of the castor oil-based polyol (B) and the metal hydroxide (C) in the mass ratio of the metal hydroxide (C) is high.
　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 electrical 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 (3)

  1. 　水酸基含有化合物、イソシアネート基含有化合物および金属水酸化物（Ｃ）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（Ａ）およびひまし油系ポリオール（Ｂ）を含有し、
    　前記金属水酸化物（Ｃ）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、ポリウレタン樹脂組成物（Ｘ）１００質量部に対して、５５質量部～８０質量部含有し、
    　前記ひまし油系ポリオール（Ｂ）および前記金属水酸化物（Ｃ）の質量比が（Ｂ）：（Ｃ）＝１：５～１：１０であるポリウレタン樹脂組成物。     A polyurethane resin composition (X) containing a hydroxyl group-containing compound, an isocyanate group-containing compound and a metal hydroxide (C),
    The hydroxyl group-containing compound contains a polybutadiene polyol (A) and a castor oil-based polyol (B),
    The metal hydroxide (C) is aluminum hydroxide and / or magnesium hydroxide and contains 55 to 80 parts by mass with respect to 100 parts by mass of the polyurethane resin composition (X).
    A polyurethane resin composition in which a mass ratio of the castor oil-based polyol (B) and the metal hydroxide (C) is (B) :( C) = 1: 5 to 1:10.
  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（Ｄ）を含有する請求項１に記載のポリウレタン樹脂組成物。 The polyurethane resin composition according to claim 1, wherein the isocyanate group-containing compound contains an isocyanurate-modified product (D) of a polyisocyanate compound.
  3. 　電気電子部品用であることを特徴とする請求項１または２に記載のポリウレタン樹脂組成物。
          The polyurethane resin composition according to claim 1 or 2, wherein the polyurethane resin composition is used for electrical and electronic parts.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016009716A1 (en) * 2014-07-15 2016-01-21 第一工業製薬株式会社 Polyurethane resin composition
JP5989219B1 (en) * 2015-12-04 2016-09-07 サンユレック株式会社 Polyurethane resin composition
WO2017056766A1 (en) * 2015-09-30 2017-04-06 第一工業製薬株式会社 Polyurethane resin forming composition and polyurethane resin
JP2017066252A (en) * 2015-09-30 2017-04-06 第一工業製薬株式会社 Polyurethane resin-formable composition and polyurethane resin
EP3424721A1 (en) * 2017-06-09 2019-01-09 Canon Kabushiki Kaisha Liquid ejection head

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3357947A4 (en) 2015-09-30 2019-04-17 Sekisui Chemical Co., Ltd. Flame-retardant rigid polyurethane foam
JP7108757B1 (en) 2021-07-13 2022-07-28 第一工業製薬株式会社 Polyurethane resin composition
JP7108756B1 (en) * 2021-07-13 2022-07-28 第一工業製薬株式会社 Polyurethane resin composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893717A (en) * 1981-11-30 1983-06-03 Nippon Zeon Co Ltd Potting agent for electrical insulation
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893717A (en) * 1981-11-30 1983-06-03 Nippon Zeon Co Ltd Potting agent for electrical insulation
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

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016009716A1 (en) * 2014-07-15 2016-01-21 第一工業製薬株式会社 Polyurethane resin composition
WO2017056766A1 (en) * 2015-09-30 2017-04-06 第一工業製薬株式会社 Polyurethane resin forming composition and polyurethane resin
JP2017066252A (en) * 2015-09-30 2017-04-06 第一工業製薬株式会社 Polyurethane resin-formable composition and polyurethane resin
JP5989219B1 (en) * 2015-12-04 2016-09-07 サンユレック株式会社 Polyurethane resin composition
WO2017094358A1 (en) * 2015-12-04 2017-06-08 サンユレック株式会社 Polyurethane resin composition
CN107041141A (en) * 2015-12-04 2017-08-11 三悠瑞克株式会社 Polyurethane resin composition
EP3424721A1 (en) * 2017-06-09 2019-01-09 Canon Kabushiki Kaisha Liquid ejection head
US10661563B2 (en) 2017-06-09 2020-05-26 Canon Kabushiki Kaisha Liquid ejection head

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