WO2023188031A1 - Composition de résine de polyuréthane - Google Patents

Composition de résine de polyuréthane Download PDF

Info

Publication number
WO2023188031A1
WO2023188031A1 PCT/JP2022/015669 JP2022015669W WO2023188031A1 WO 2023188031 A1 WO2023188031 A1 WO 2023188031A1 JP 2022015669 W JP2022015669 W JP 2022015669W WO 2023188031 A1 WO2023188031 A1 WO 2023188031A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane resin
resin composition
value
containing compound
plasticizer
Prior art date
Application number
PCT/JP2022/015669
Other languages
English (en)
Japanese (ja)
Inventor
辰己 農宗
奈津美 葉狩
Original Assignee
サンユレック株式会社
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=85277859&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2023188031(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by サンユレック株式会社 filed Critical サンユレック株式会社
Priority to PCT/JP2022/015669 priority Critical patent/WO2023188031A1/fr
Priority to JP2022550014A priority patent/JP7227675B1/ja
Publication of WO2023188031A1 publication Critical patent/WO2023188031A1/fr

Links

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
    • C08G18/08—Processes
    • 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
    • C08G18/40—High-molecular-weight compounds
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a polyurethane resin composition.
  • urethane resins used for sealing members have a problem in that their flexibility decreases and cracks occur due to long-term heat cycles, and there is a need to reduce the temperature dependence of the elastic modulus.
  • Patent Document 1 A polyurethane resin composition that exhibits the above-mentioned heat resistance and heat cycle properties has been proposed (see Patent Document 1). Although the polyurethane resin composition is also an excellent polyurethane resin composition, there is still room for further improvement. Patent Document 1 discloses the use of DUP (diundecyl phthalate) or DIDA (diisodecyl adipate) as a plasticizer used in a polyurethane resin composition.
  • DUP diundecyl phthalate
  • DIDA diisodecyl adipate
  • DIDA has room for consideration in terms of heat resistance.
  • DUP may not have sufficient compatibility with specific hydroxyl group-containing compounds such as polybutadiene polyols and polyester polyols, so there is room for consideration regarding the decrease in elastic modulus at -20°C to -30°C.
  • An object of the present invention is to provide a polyurethane resin composition that has excellent compatibility, heat resistance, and heat cycle properties.
  • the present invention relates to the following polyurethane resin compositions, sealing materials, and electrical and electronic components.
  • a polyurethane resin composition containing an isocyanate group-containing compound, a hydroxyl group-containing compound, and a plasticizer The SP value of the mixture of the hydroxyl group-containing compound and the plasticizer is 8.75 or more.
  • the polyurethane resin composition according to Item 1 or 2 wherein the plasticizer contains a plasticizer A having an embrittlement temperature of less than -30°C and a plasticizer B having an embrittlement temperature of -30°C or higher and -20°C or lower. thing. 4.
  • Item 5 The polyurethane resin composition according to any one of Items 1 to 4, wherein the hydroxyl group-containing compound contains a polyolefin polyol. 6.
  • a sealing material comprising the polyurethane resin composition according to any one of Items 1 to 8. 10.
  • the polyurethane resin composition of the present invention has excellent compatibility, heat resistance, and heat cycle properties. Moreover, since the sealing material of the present invention is also made of the above polyurethane resin composition, it has excellent heat resistance and heat cycle properties. Furthermore, since the electrical/electronic component of the present invention has the above-mentioned sealing material, it can be sufficiently resin-sealed and exhibit high reliability.
  • the polyurethane resin composition of the present invention is a polyurethane resin composition containing an isocyanate group-containing compound, a hydroxyl group-containing compound, and a plasticizer, the composition comprising a mixture of the hydroxyl group-containing compound and the plasticizer. It is characterized by an SP value of 8.75 or more.
  • the elastic modulus of polyester polyols tends to increase in the low temperature range of -20°C to -30°C, and the heat cycleability tends to decrease.
  • Polyolefin polyols such as polybutadiene polyols are used in combination to improve heat cycle characteristics, but because the polybutadiene polyols have poor compatibility with polyester polyols, they can be used at a lower temperature of -20°C to -30°C than when polybutadiene polyols are used alone. There is a problem that the elastic modulus increases in the region.
  • the elastic modulus of polyurethane resin blended with polybutadiene polyol and polyester polyol increases in the -20°C to -30°C range, so the results of measuring the elastic modulus due to temperature changes in the -20°C to -30°C temperature range , a bump-like region with high elastic modulus appears.
  • polybutadiene polyol is used alone as the hydroxyl group-containing compound, the above region of high elastic modulus does not appear in the results of measuring the elastic modulus due to temperature changes, resulting in a smooth curve.
  • polyester polyol when polyester polyol is used alone as the hydroxyl group-containing compound, the elastic modulus increases from the temperature range of -20°C to -30°C because the glass transition temperature is not low enough.
  • the present inventors have determined that in a polyurethane resin composition, by setting the SP value of a mixture of a hydroxyl group-containing compound and a plasticizer within a specific range, the compatibility of these compounds is excellent, and the temperature between -20°C and -30°C is achieved. It has been found that the increase in the elastic modulus of polyurethane resin can be suppressed even in the range of Usually, when lowering the elastic modulus and glass transition temperature of polyurethane resin at low temperatures, a plasticizer with a brittle temperature of -30° C. or lower, such as DUP and DIDA, is used.
  • DIDA does not have sufficient heat resistance
  • a polyurethane resin composition containing DUP, polybutadiene polyol, and polyester polyol does not have sufficient compatibility when made into a polyurethane resin, resulting in -40%
  • the elastic modulus below °C decreases, but the elastic modulus between -20 °C and -30 °C does not decrease.
  • the polyurethane resin composition by adjusting the SP value of the mixture of the hydroxyl group-containing compound and the plasticizer to 8.75 or more, it has excellent compatibility, and has excellent heat resistance and heat cycle property.
  • An excellent polyurethane resin composition can be provided.
  • the isocyanate group-containing compound is not particularly limited, and known isocyanate group-containing compounds used for polyurethane resins can be used. Examples of such isocyanate group-containing compounds include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and araliphatic polyisocyanate compounds. Moreover, in order to further improve the heat resistance of the polyurethane resin composition, an isocyanurate modified product of the above-mentioned isocyanate group-containing compound may be used.
  • aliphatic polyisocyanate compounds include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2- Examples include methylpentane-1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
  • HDI hexamethylene diisocyanate
  • 2- Examples include methylpentane-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(isocyanatemethyl)cyclohexane, etc. can be mentioned.
  • Aromatic polyisocyanate compounds 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, 1,4-phenylene diisocyanate, and the like.
  • aromatic aliphatic polyisocyanate compound examples include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate, and the like.
  • the above isocyanate group-containing compounds may be used alone or in combination of two or more.
  • the amount of the isocyanate group-containing compound used is not particularly limited, and is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass based on 100% by mass of the polyurethane resin composition. , more preferably 1 to 10% by mass.
  • the upper limit of the content of the isocyanate group-containing compound is within the above range, curing failure of the polyurethane resin composition is further suppressed.
  • the lower limit of the content of the isocyanate group-containing compound is within the above range, the heat resistance of the cured polyurethane resin composition is further improved.
  • the SP value of the isocyanate group-containing compound is preferably 8.70 or more, more preferably 9.00 or more, even more preferably 9.50 or more, particularly preferably 10.00 or more, and most preferably 10.50 or more. Further, the SP value of the isocyanate group-containing compound is preferably 14.00 or less, more preferably 13.50 or less, even more preferably 13.00 or less, and particularly preferably 12.00 or less.
  • the hydroxyl group-containing compound used in the polyurethane resin composition of the present invention is not particularly limited as long as the SP value of the mixture of the hydroxyl group-containing compound and the plasticizer can be adjusted to 8.75 or more. It is possible to use various types of materials that are used as Examples of the polyol component include polyolefin polyols, castor oil polyols, polyester polyols, and hydrogenated products thereof.
  • polybutadiene polyol ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1 , 4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,2-hexanediol, 2,5-hexanediol, octanediol, nonanediol, decanediol, Diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanediol, trimethylolpropane, glycerin, 2-methylpropane-1,2,3-triol, 1,2,6-hexanetriol, pentaerythritol, polylactone diol, poly Lactone dio
  • polyolefin polyols polyolefin polyols, polyester polyols, and hydrides thereof are preferred.
  • polybutadiene polyol and polyester polyol it is more preferable to contain polybutadiene polyol and polyester polyol, and it is even more preferable to use polybutadiene polyol, castor oil, and its hydrogenated product.
  • castor oil and its hydride examples include castor oil, castor oil derivatives, and the like.
  • the castor oil derivatives include castor oil fatty acids; hydrogenated castor oil obtained by hydrogenating castor oil or castor oil fatty acids; transesterified products of castor oil and other fats and oils; reaction products of castor oil and polyhydric alcohols; esterification of castor oil fatty acids and polyhydric alcohols.
  • Reactants Examples include addition polymerization of alkylene oxide to these.
  • the above hydroxyl group-containing compounds may be used alone or in combination of two or more.
  • the weight average molecular weight Mw of the hydroxyl group-containing compound is preferably 500 to 5,000, more preferably 800 to 4,800, even more preferably 900 to 4,000, and particularly preferably 1,000 to 3,000.
  • the number weight average molecular weight Mn of the hydroxyl group-containing compound is preferably 600 to 6,000, more preferably 900 to 5,000, even more preferably 1,000 to 4,000, and particularly preferably 1,200 to 3,500.
  • the average hydroxyl value of the hydroxyl group-containing compound is preferably 40 mgKOH/g or more, more preferably 70 mgKOH/g or more. Moreover, the average hydroxyl value is preferably 170 mgKOH/g or less, more preferably 120 mgKOH/g or less.
  • the average hydroxyl value of the above-mentioned hydroxyl group-containing compound is a value measured by the following measuring method.
  • the average hydroxyl value is the value of the hydroxyl group value of the single hydroxyl group-containing compound, and when two or more types are used together, the hydroxyl value of the multiple hydroxyl group-containing compounds is calculated as the blending ratio. This is the average value of the hydroxyl value calculated by multiplying and adding the results. Note that in this specification, the above hydroxyl value is a value measured by a measuring method based on method A of JIS K1557-1:2007.
  • the glass transition temperature of the hydroxyl group-containing compound is preferably -40°C or lower, more preferably -50°C or lower. Further, the glass transition temperature is preferably -90°C or higher, more preferably -85°C or higher.
  • the glass transition temperature is a value measured using a DSC (differential scanning calorimeter).
  • the content of the hydroxyl group-containing compound is preferably 3 to 40 mass%, more preferably 5 to 35 mass%, and 7 to 30 mass%, based on 100 mass% of the polyurethane resin composition. More preferably, 7 to 20% by mass is particularly preferred.
  • the upper limit of the content of the hydroxyl group-containing compound is within the above range, curing failure of the polyurethane resin composition is further suppressed.
  • the lower limit of the content of the hydroxyl group-containing compound is within the above range, the elastic modulus of the polyurethane resin composition can be further reduced, and an increase in the glass transition temperature can be further suppressed.
  • the SP value of the hydroxyl group-containing compound is preferably 8.70 or more, more preferably 8.75 or more, even more preferably 8.80 or more, and particularly preferably 8.85 or more. Further, the SP value of the hydroxyl group-containing compound is preferably 14.00 or less, more preferably 13.00 or less, even more preferably 12.00 or less, and particularly preferably 11.30 or less.
  • the SP value of the hydroxyl group-containing compound is measured by the Fedors method described in Examples below.
  • the NCO/OH ratio between the isocyanate group-containing compound and the hydroxyl group-containing compound is preferably 0.6 to 2.0, more preferably 0.7 to 1.5. is more preferable.
  • the heat resistance of the polyurethane resin composition is further improved.
  • the upper limit of the NCO/OH ratio is within the above range, curing failure of the polyurethane resin composition is further suppressed.
  • the plasticizer used in the polyurethane resin composition of the present invention is not particularly limited as long as the SP value of the mixture of the hydroxyl group-containing compound and the plasticizer can be adjusted to 8.75 or more. It is possible to use a variety of conventional ones.
  • the above plasticizers include phthalic acid esters such as dioctyl phthalate, diisononyl phthalate, and diundecyl phthalate; adipic acid esters such as dioctyl adipate and diisononyl adipate; methyl acetyl ricinoleate, butylacetyl ricinoleate, acetylated ricinoleic acid triglyceride, and acetylated ricinoleic acid triglyceride.
  • phthalic acid esters such as dioctyl phthalate, diisononyl phthalate, and diundecyl phthalate
  • adipic acid esters such as dioctyl adipate and diisononyl adipate
  • methyl acetyl ricinoleate butylacetyl ricinoleate
  • Castor oil-based esters such as polyricinoleic triglyceride; tricresyl phosphate; trimellitic acid esters such as trioctyl trimellitate and triisononyl trimellitate; Examples include mellitic acid esters. It has a boiling point of 250°C or higher, a freezing point of -20°C or lower, a viscosity of 500 mPa ⁇ s or lower at room temperature, and excellent compatibility with hydroxyl group-containing compounds of various SP values. Mellitic acid ester and tricresyl phosphate are preferred.
  • the content of the plasticizer in the polyurethane resin composition of the present invention is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and even more preferably 15 to 30% by mass, based on 100% by mass of the polyurethane resin composition. , 20 to 25% by weight is particularly preferred.
  • the upper limit of the content of the plasticizer is within the above range, curing failure of the polyurethane resin composition is further suppressed.
  • the lower limit of the plasticizer content is within the above range, the heat resistance of the cured polyurethane resin composition is further improved.
  • the SP value of the plasticizer is preferably 8.70 or more, more preferably 8.75 or more, even more preferably 8.80 or more, and particularly preferably 8.90 or more. Further, the SP value of the plasticizer is preferably 12.00 or less, more preferably 11.00 or less, even more preferably 10.00 or less, and particularly preferably 9.70 or less.
  • the SP value of the plasticizer is measured by the Small method described in Examples below.
  • the content of the plasticizer having an SP value of 8.70 or more in the polyurethane resin composition of the present invention is preferably 5.3% by mass or more, more preferably 10% by mass or more, and 15% by mass or more. More preferably, it is at least % by mass. Further, the content in the polyurethane resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.
  • the content of the plasticizer having an SP value of 8.75 or more in the polyurethane resin composition of the present invention is preferably 5.3% by mass or more, more preferably 6% by mass or more, and 8.7% by mass or more. More preferably, the amount is % by mass or more. Further, the above content is preferably 40% by mass or less in the polyurethane resin composition, more preferably 30% by mass or less, even more preferably 25% by mass or less, particularly preferably 20% by mass or less.
  • the content of the plasticizer having an SP value of 8.80 or more in the polyurethane resin composition of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more. Further, the content in the polyurethane resin composition is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • the above plasticizer preferably contains a plasticizer A whose embrittlement temperature is less than -30°C and a plasticizer B whose embrittlement temperature is between -30°C and 0°C as measured in accordance with JIS K7216.
  • a plasticizer A whose embrittlement temperature is less than -30°C
  • a plasticizer B whose embrittlement temperature is between -30°C and 0°C as measured in accordance with JIS K7216.
  • the polyurethane resin composition of the present invention may contain an inorganic filler.
  • the above-mentioned inorganic filler is not particularly limited, and conventionally known inorganic fillers can be used.
  • examples of such inorganic fillers include calcium carbonate, fused silica, amorphous silica, talc, alumina, aluminum hydroxide, aluminum nitride, boron nitride, magnesium hydroxide, and magnesium oxide.
  • metal hydrated compounds such as aluminum hydroxide and magnesium hydroxide are preferred because they have excellent flame retardancy and thermal conductivity.
  • examples of inorganic fillers with excellent thermal conductivity include alumina, magnesium hydroxide, aluminum hydroxide, and the like.
  • an inorganic filler with a low Mohs hardness is preferable.
  • the Mohs hardness of such an inorganic filler is preferably 4 or less, more preferably 3 or less.
  • examples of such inorganic fillers include aluminum hydroxide (Mohs hardness: 3), magnesium hydroxide (Mohs hardness: 2.5), and talc (Mohs hardness: 1).
  • the Mohs hardness of the inorganic filler is a value measured by a Mohs hardness test method using standard minerals. Specifically, the Mohs hardness of the inorganic filler is a value determined by relative comparison from the Mohs hardness of the standard mineral when scratches are created by rubbing the standard mineral and the sample material together.
  • the content of the inorganic filler is preferably 20 to 80% by mass, more preferably 50 to 80% by mass, based on 100% by mass of the polyurethane resin composition.
  • the flame retardancy of the polyurethane resin composition is further improved.
  • the upper limit of the inorganic filler content within the above range, the mixing viscosity during the production of the polyurethane resin composition is suppressed, the workability is further improved, and the fluidity and flexibility after mixing are not impaired.
  • the heat resistance, moisture resistance, strength, and flame retardance are further improved, and furthermore, the linear expansion coefficient is lowered, so the heat cycle property is further improved.
  • additives such as an antioxidant, a polymerization catalyst, a moisture absorbent, a fungicide, a silane coupling agent, and the like can be added to the polyurethane resin composition of the present invention as necessary.
  • the antioxidant is not particularly limited, but conventionally known antioxidants used in urethane resin compositions can be used.
  • the polymerization catalyst is not particularly limited, but conventionally known polymerization catalysts used in urethane resin compositions can be used.
  • Such polymerization catalysts include tin catalysts such as dioctyltin dilaurate, dibutyltin dilaurate, and dioctyltin diacetate; lead catalysts such as lead octylate, lead octenoate, and lead naphthenate; bismuth octylate, bismuth neodecanoate, etc.
  • Examples include bismuth catalysts and amine catalysts such as diethylenetriamine.
  • an organic metal compound, a metal complex compound, etc. may be used as the above-mentioned catalyst.
  • the amount of these additives to be used may be appropriately determined according to the purpose of use, from the usual addition amount and specified range, so as not to impede the desired properties of the polyurethane resin composition.
  • the SP value of the mixture of the hydroxyl group-containing compound and the plasticizer is 8.75 or more. If the SP value of the mixture is less than 8.75, the heat resistance and heat cycle properties of the polyurethane resin composition will decrease.
  • the SP value of the above mixture is preferably 8.80 or more, more preferably 8.85 or more.
  • the SP value of the above mixture is preferably 10.80 or less, more preferably 10.70 or less, and even more preferably 9.20 or less.
  • the SP value of the above mixture is measured by the method described in Examples below.
  • the SP value of the mixture of the isocyanate group-containing compound, the hydroxyl group-containing compound, and the plasticizer is not particularly limited, and is preferably 8.76 or more, more preferably 8.80 or more, and 8. More preferably .85 or more. Further, the SP value of the above mixture is preferably 11.00 or less, more preferably 10.80 or less, and even more preferably 10.50 or less. When the SP value of the mixture is within the above range, the heat resistance and heat cycle properties of the polyurethane resin composition are further improved, and the adhesion to members constituting electrical and electronic components is further improved.
  • the SP value of the above mixture is measured by the method described in Examples below.
  • the polyurethane resin composition of the present invention When the polyurethane resin composition of the present invention is in a liquid state before curing, its viscosity is preferably 500 to 100,000 mPa ⁇ s, more preferably 1,000 to 10,000 mPa ⁇ s, and even more preferably 1,500 to 5,000 mPa ⁇ s.
  • the polyurethane resin composition of the present invention can exhibit higher workability, and also improves flow into components, improving adhesion with electrical and electronic components and eliminating voids. This makes it difficult for resin to occur, and resin strength, thermal conductivity, and waterproofness are further improved.
  • the upper limit of the viscosity is within the above range, a large amount of inorganic filler can be blended, which further improves flame retardancy, lowers the coefficient of linear expansion, and further improves heat cycle performance.
  • the viscosity of the polyurethane resin composition before curing is a value measured by a Brookfield BH type viscometer described in the Examples below.
  • the glass transition temperature of the polyurethane resin composition of the present invention which is calculated from the maximum peak point of the loss modulus (E'': 10Hz) measured by DMA (dynamic mechanical analysis), is preferably -40°C or lower. , -60°C or lower is more preferable. Further, the glass transition temperature is preferably as low as possible, and may be, for example, about -80°C.
  • the glass transition temperature (Tg) calculated from the maximum peak point of the loss modulus (E'': 10Hz) measured by DMA (dynamic mechanical analysis) is the same as that described in the Examples below. Measure by method. Note that tan ⁇ is normally used to determine Tg in DMA. However, since tan ⁇ tends to have a broad peak point and a large measurement error, it is more accurate to determine it using the loss modulus (E''). Therefore, in this specification, the glass transition temperature (Tg) is calculated from the maximum peak point of the loss modulus (E'': 10 Hz).
  • the method for producing the polyurethane resin composition of the present invention is not particularly limited, and it can be produced by any conventionally known method used as a method for producing polyurethane resin compositions.
  • a component containing an isocyanate group-containing compound is prepared as component A (polyisocyanate component), a component containing a hydroxyl group-containing compound is prepared as component B (polyol component), and component A and component A are prepared.
  • component A polyisocyanate component
  • component B polyol component
  • component A and component A are prepared.
  • a method of producing a polyurethane resin composition containing the polyurethane resin by reacting the polyurethane resin with component B can be mentioned.
  • the above-mentioned A component contains an isocyanate group-containing compound and the above-mentioned B component contains a hydroxyl group-containing compound
  • other components may be contained in either the A component or the B component.
  • a configuration in which the B component contains an inorganic filler is preferable. With such a configuration, it is possible to suppress curing failure of the polyurethane resin due to reaction between moisture contained in the inorganic filler and the polyisocyanate group-containing compound.
  • the blending ratio of component A and component B approaches 1:1, making it easier to mix the components A and B. Also, by converting a portion of the component into urethane, the blending ratio of component A and component B approaches 1:1. The difference between the SP value and the SP value of component B becomes smaller, the compatibility is further improved, and the reaction is faster.
  • component A contains only an isocyanate group-containing compound
  • component B contains a hydroxyl group-containing compound, a plasticizer, and, if necessary, an inorganic filler.
  • a configuration containing an antioxidant and a polymerization catalyst is preferred. With such a configuration, component A and component B have excellent liquid stability.
  • the polyurethane resin composition may be in a liquid state before curing or may be a cured product, and the cured product is also referred to as a polyurethane resin.
  • a method for curing the polyurethane resin composition by mixing the above A component and B component, an isocyanate group-containing compound and a hydroxyl group-containing compound are reacted to form a polyurethane resin, and the polyurethane resin composition is cured over time.
  • a method of curing may be mentioned, it may be hardened by heating. In this case, the heating temperature is preferably about 40° C. to 120° C., and the heating time is preferably about 0.1 hour to 24 hours.
  • the elastic modulus (E': 10 Hz) at -30°C of the polyurethane resin composition (cured product thereof) is preferably 40 MPa or less, more preferably 25 MPa or less. Further, the elastic modulus is preferably 5 MPa or more.
  • the difference between the elastic modulus at 120°C and the elastic modulus at -30°C of the polyurethane resin composition (cured product thereof) is preferably 25 MPa or less, more preferably 20 MPa or less.
  • the coefficient of linear expansion is constant, the heat cycle property is affected by the stress generated from the difference between the elastic modulus at high temperatures and the elastic modulus at low temperatures. For this reason, it is preferable that the difference between the elastic modulus at high temperature and the elastic modulus at low temperature is small.
  • the elastic modulus of (the cured product of) the polyurethane resin composition is measured by a measuring method using a dynamic viscoelasticity measuring device described in Examples below.
  • the polyurethane resin composition of the present invention has an SP value of a mixture of a hydroxyl group-containing compound and a plasticizer of 8.75 or more and 9.20 or less, and a modulus of elasticity at 120°C and a modulus of elasticity at -30°C. It is preferable that the difference is 25 MPa or less.
  • the hydroxyl group-containing compound contains a polyolefin polyol
  • the plasticizer contains a plasticizer a having an SP value of 8.75 or more and a plasticizer b having an SP value of less than 8.75. It is preferable to do so. With the above configuration, the glass transition temperature of the polyurethane resin composition is lowered and the heat cycle properties are further improved.
  • the present invention also provides an encapsulant made of the above-mentioned polyurethane resin composition.
  • the encapsulant made of the polyurethane resin composition has excellent compatibility, heat resistance, and heat cycle properties, and is therefore suitable for electrical and electronic components used in high-temperature environments and electrical and electronic components that generate heat. It can be used for.
  • the sealing material made of the polyurethane resin composition has excellent flexibility in a low temperature range, and therefore can be suitably used for electrical and electronic components used in low temperature environments. Examples of such electrical and electronic components include transformers such as transformer coils, choke coils, and reactor coils, equipment control boards, and various sensors. Such electrical and electronic components are also part of the present invention.
  • the electrical and electronic components of the present invention can be used in electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, power tools, automobiles, motorcycles, and the like.
  • the polyurethane resin composition of the present invention can be usefully used as an adhesive.
  • the polyurethane resin composition of the present invention can be usefully used as a gap filler used for the purpose of heat dissipation in electrical and electronic components.
  • Isocyanate group-containing compound TPA-100 HDI isocyanurate modified product, trade name: Duranate TPA-100, manufactured by Asahi Kasei Chemicals, molecular weight 546, specific gravity 1.16, SP value 11.74 (value calculated by Fedors method) )
  • A201H HDI allophanate modified product, trade name: Duranate A201H, manufactured by Asahi Kasei Chemicals, molecular weight 466, specific gravity 1.05, SP value 12.29 (value calculated by Fedors method)
  • HMDI Hydrogenated MDI, product name: WANNATE HMDI, manufactured by Wanka Chemical Japan Co., Ltd., molecular weight 262, specific gravity 1.08, SP value 10.74 (value calculated by Fedors method)
  • ⁇ MTL Carbodiimide modified MDI, trade name: Millionate MTL, manufactured by Tosoh Corporation, molecular weight 250, specific gravity 1.22, SP value 12.66 (value calculated by Fedors method)
  • (B) Hydroxyl group-containing compound /R-45HT polybutadiene polyol, trade name: Poly bd R-45 HT, manufactured by Idemitsu Petrochemical Co., Ltd., number average molecular weight 2800, SP value 8.86 (value calculated by Fedors method) ⁇ R-15HT: Polybutadiene polyol, trade name: Poly bd R-15 HT, manufactured by Idemitsu Petrochemical Co., Ltd., number average molecular weight 1200, SP value 9.16 (value calculated by Fedors method) ⁇ H-30: Polyester polyol (castor oil polyol), trade name: URIC H-30, manufactured by Fuji Oil Co., Ltd., number average molecular weight 933, SP value 10.86 (value calculated by Fedors method) ⁇ P-2050: Polyester polyol, trade name: Kuraray Polyol P-2050, manufactured by Kuraray Co., Ltd., number average molecular weight 2000, SP value 11.29 (value calculated by Fedors method) ⁇ Polyes
  • polyester polyol (X) was manufactured by the following method. That is, 1220 g (4 moles) of hydrogenated castor oil fatty acid with an acid value of 178 and 60 mL of xylene for reflux assistance were charged into a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser with a test tube. The reaction was carried out for 6 hours at 180°C to 220°C under air flow. During this time, water produced by the condensation reaction was distilled out of the system by azeotropy. As a result, an oxycarboxylic acid oligomer having an acid value of 46 was obtained.
  • liquid polyester polyol (X) which was liquid at room temperature, had an acid value of 3.3, an OH value of 105, an iodine value of 3.2, and a viscosity of 2.1 Pa ⁇ s/23°C.
  • C Inorganic filler /H-32: Aluminum hydroxide, product name: Hygilite H-32, manufactured by Showa Denko K.K.
  • TCP Tricresyl phosphate
  • SP value 9.70 value calculated by Small method
  • freezing point -35°C molecular weight 368
  • IrganoX1010 manufactured by BASF
  • Polymerization catalyst /U-810 Dioctyltin dilaurate, trade name: Neostan U-810, manufactured by Nitto Kasei Co., Ltd.
  • the embrittlement temperature is a value measured by a measuring method based on JIS K7216. Specifically, the temperature at which 50% of the test piece breaks into two or more pieces at a certain temperature point is measured under the following conditions.
  • Test piece Size 38.0 ⁇ 2.0 ⁇ 6.0 ⁇ 0.4 ⁇ 2.0 ⁇ 0.2 (mm) The test piece is left at room temperature of 23°C ⁇ 2 and relative humidity 50 ⁇ 5% for 40 hours or more before use. Five levels of testing are carried out by changing the temperature for each sample. The number of tests at each level was 10 times.
  • Heat transfer solvent Ethanol Test method: After placing the test piece in the test atmosphere temperature for 3 minutes, impact it once with a hammer at a speed of 2 ⁇ 0.2 m/s from a moving distance of 5 mm to check for damage. and evaluate.
  • Measuring equipment Embrittlement temperature tester FS (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
  • SP values are values measured by the Fedors method for (A) isocyanate group-containing compounds and (B) hydroxyl group-containing compounds, and by the Small method for (D) plasticizers.
  • the SP value of the mixture ((1) SP value of (A) isocyanate group-containing compound + (B) hydroxyl group-containing compound + (D) plasticizer; 2) SP value of (B) hydroxyl group-containing compound + (D) plasticizer; (3) SP value of mixture of multiple (D) plasticizers) were calculated.
  • the SP value of the mixture was calculated using the following formula with reference to the calculation method of formula (3) described in paragraph 0020 of JP-A No. 2011-194508.
  • the isocyanate group-containing compound (A) was prepared as a polyisocyanate component.
  • a polyurethane resin composition was obtained by adding a polyisocyanate component to the above polyol component, stirring, defoaming, and mixing so that the blending amount was as shown in Table 1.
  • the polyol component and the polyisocyanate component were mixed by adjusting the polyol component to 23°C, then adding the polyisocyanate component adjusted to 23°C, and using a rotation/revolution mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.). The mixture was stirred for 1 minute at a rotational speed of 2000 rpm.
  • test piece A (Creation of test piece)
  • the prepared polyurethane resin composition was injected into a mold A with a size of 100 mm x 100 mm x 3 mm, a mold B with an inner diameter of 30 mm and a height of 10 mm, and a mold C with a size of 10 mm x 80 mm x 3 mm.
  • the polyurethane resin composition in the mold was heated at 80° C. for 16 hours, and then left at room temperature for one day to be cured.
  • test piece A (100 mm x 100 mm x 3 mm)
  • test piece B (inner diameter 30 mm, height 10 mm)
  • test piece C (10 mm x 80 mm x 3 mm) were prepared.
  • test piece A was cut into a No. 3 dumbbell test piece to prepare test piece A-1.
  • Viscosity The polyurethane resin composition was adjusted to 23° C., and the viscosity was measured using a Brookfield BH viscometer 3 minutes after mixing the polyol component, polyisocyanate component, inorganic filler, and plasticizer.
  • the temperature of the initial hardness test piece B was adjusted to 23 ° C., and the hardness (type A) was measured using a hardness meter (manufactured by Kobunshi Keiki Co., Ltd., Asker Rubber Hardness Meter Type A) according to a measurement method based on JIS K 6253. .
  • the volume resistivity of the volume resistivity test piece A was measured using a resistance measuring device (manufactured by HIOKI, DSM-8104). The measured value of the volume resistivity was taken as the volume resistivity value.
  • Elastic modulus (E'10Hz), glass transition temperature (E'') The elastic modulus E' (10 Hz) of the test piece C at each temperature of -40°C, -30°C, -20°C, 23°C, and 120°C was measured using a dynamic viscoelasticity measuring machine: DMA (manufactured by SII Nano Technology: DMS6100). ). Further, the glass transition temperature (° C.) was calculated from the peak point of the “loss modulus E'' (10 Hz).
  • the polyurethane resin composition of the present invention has excellent compatibility, heat resistance, and heat cycle properties. Therefore, it can be used in fields such as electrical products. Furthermore, the polyurethane resin composition of the present invention can be used in the fields of adhesives and gap fillers used for heat dissipation purposes in electrical and electronic components.

Abstract

La présente invention concerne une composition de résine de polyuréthane qui présente une excellente compatibilité, tout en présentant d'excellentes propriétés de résistance à la chaleur et de cycle thermique.　La présente invention concerne une composition de résine de polyuréthane qui contient un composé contenant un groupe isocyanate, un composé contenant un groupe hydroxyle et un plastifiant, et qui est caractérisée en ce que la valeur SP d'un mélange du composé contenant un groupe hydroxyle et du plastifiant est de 8,75 ou plus.
PCT/JP2022/015669 2022-03-29 2022-03-29 Composition de résine de polyuréthane WO2023188031A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2022/015669 WO2023188031A1 (fr) 2022-03-29 2022-03-29 Composition de résine de polyuréthane
JP2022550014A JP7227675B1 (ja) 2022-03-29 2022-03-29 ポリウレタン樹脂組成物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/015669 WO2023188031A1 (fr) 2022-03-29 2022-03-29 Composition de résine de polyuréthane

Publications (1)

Publication Number Publication Date
WO2023188031A1 true WO2023188031A1 (fr) 2023-10-05

Family

ID=85277859

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/015669 WO2023188031A1 (fr) 2022-03-29 2022-03-29 Composition de résine de polyuréthane

Country Status (2)

Country Link
JP (1) JP7227675B1 (fr)
WO (1) WO2023188031A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016098328A (ja) * 2014-11-21 2016-05-30 サンユレック株式会社 ポリウレタン樹脂組成物
JP2016204577A (ja) * 2015-04-27 2016-12-08 日本パーカライジング株式会社 固体潤滑剤、金属材料用潤滑皮膜剤、表面処理金属材料、及び金属材料の潤滑皮膜形成方法
JP2017137480A (ja) * 2016-01-28 2017-08-10 三洋化成工業株式会社 滑り止め用シート

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6905135B1 (ja) * 2020-09-29 2021-07-21 第一工業製薬株式会社 ポリウレタン樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016098328A (ja) * 2014-11-21 2016-05-30 サンユレック株式会社 ポリウレタン樹脂組成物
JP2016204577A (ja) * 2015-04-27 2016-12-08 日本パーカライジング株式会社 固体潤滑剤、金属材料用潤滑皮膜剤、表面処理金属材料、及び金属材料の潤滑皮膜形成方法
JP2017137480A (ja) * 2016-01-28 2017-08-10 三洋化成工業株式会社 滑り止め用シート

Also Published As

Publication number Publication date
JP7227675B1 (ja) 2023-02-22
JPWO2023188031A1 (fr) 2023-10-05

Similar Documents

Publication Publication Date Title
CN107041141B (zh) 聚氨酯树脂组合物
JP5535529B2 (ja) ポリウレタン樹脂組成物
JP5550161B1 (ja) ポリウレタン樹脂組成物
CN111699217B (zh) 聚氨酯树脂组合物
JP5568187B1 (ja) ポリウレタン樹脂組成物
JP5863934B1 (ja) ポリウレタン樹脂組成物
WO2019107199A1 (fr) Composition de résine durcissable et composant électrique obtenu en l'utilisant
JP6990999B2 (ja) ポリウレタン樹脂組成物、封止物、ポリオール組成物およびイソシアネート組成物
JP5854534B2 (ja) ポリウレタン樹脂組成物
JP3805752B2 (ja) ウレタンポリオール組成物およびポリウレタン組成物
JP6012821B1 (ja) ポリウレタン樹脂組成物、封止材及び電気電子部品
JP7227675B1 (ja) ポリウレタン樹脂組成物
JP5946574B1 (ja) ポリウレタン樹脂組成物
JP2015089941A (ja) ポリウレタン樹脂組成物
JP5787425B2 (ja) ポリウレタン樹脂
JP5784210B1 (ja) ポリウレタン樹脂組成物
WO2023053970A1 (fr) Composition contenant de l'isocyanate et composition de résine de polyuréthane réactive de type à deux composants
JP5707197B2 (ja) ポリオール組成物及びポリウレタン樹脂
JP5946555B1 (ja) ポリウレタン樹脂組成物
JP5854533B2 (ja) ポリウレタン樹脂組成物
JP7075735B2 (ja) 樹脂組成物および樹脂製造用組成物
JP5828950B1 (ja) ポリウレタン樹脂組成物、封止材及び電気電子部品
JP2005225959A (ja) コネクタ封止用硬化性組成物
JP6165204B2 (ja) 電子機器用封止材、及び、電子機器
JP2010254879A (ja) イソシアヌレート基含有ウレタンエラストマー形成性組成物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2022550014

Country of ref document: JP

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

Ref document number: 22935179

Country of ref document: EP

Kind code of ref document: A1