Patent Application
20190367662
The present invention relates to a polyurethane resin composition and a sealed article.
Polyurethane resin compositions are used to seal objects such as electrical and electronic components in order to provide protection from condensation and contamination (PTL 1). Such polyurethane resin compositions are often used in high-temperature environments.
PTL 1: Japanese Unexamined Patent Application Publication No. 2008-231348
PTL 2: Japanese Unexamined Patent Application Publication No. 2001-352156
However, if a polyurethane resin composition is softened or melted when exposed to a high-temperature environment, the polyurethane resin composition may fail to properly protect an object to be sealed.
This invention has been made to solve the above problem, and an object thereof is to provide a polyurethane resin composition having high heat resistance.
To solve the above problem, the present inventors have intensively studied and found that the above problem can be solved by using a raw material having a specific structure, thereby completing the present invention.
Specifically, a polyurethane resin composition of the present invention is obtained by reacting a hydroxyl-group-containing compound (A) with an isocyanate-group-containing compound (B) and contains an antioxidant (C) having an alkylthio group.
In the present invention, the polyurethane resin composition is meant to include those during and after being cured by the reaction between the hydroxyl-group-containing compound (A) and the isocyanate-group-containing compound (B).
The present invention can provide a polyurethane resin composition having high heat resistance.
First, embodiments of the present invention will be enumerated.
(1) A polyurethane resin composition according to an embodiment of the present invention is obtained by reacting a hydroxyl-group-containing compound (A) with an isocyanate-group-containing compound (B) and contains an antioxidant (C) having an alkylthio group. Due to this configuration, the heat resistance of the polyurethane resin composition can be improved.
(2) Preferably, the antioxidant (C) is a phenol compound having the alkylthio group. Due to this configuration, the heat resistance of the polyurethane resin composition can be more effectively improved.
(3) Preferably, the polyurethane resin composition further contains an inorganic filler (D), and the sodium content of the inorganic filler (D) is 0.15 mass % or less of the inorganic filler (D) on a Na2O basis. Due to this configuration, the heat resistance of the polyurethane resin composition can be further improved.
(4) Preferably, the polyurethane resin composition further contains an inorganic filler (D), and the polyurethane resin composition contains the inorganic filler (D) in an amount of 20 parts by mass to 80 parts by mass based on 100 parts by mass of the polyurethane resin composition. Due to this configuration, for example, the polyurethane resin composition can be provided with high thermal conductivity, and mixing viscosity during the preparation of the polyurethane resin composition can be controlled to be in a range suitable for use.
(5) Preferably, the polyurethane resin composition contains the antioxidant (C) in an amount of 0.05 parts by mass to 2.0 parts by mass based on 100 parts by mass of the polyurethane resin composition. Due to this configuration, precipitation of the antioxidant on a surface of the polyurethane resin composition can be prevented while reducing deterioration of the polyurethane resin composition.
(6) A sealed article according to an embodiment of the present invention is sealed by the polyurethane resin composition according to any one of (1) to (5) above. Due to this configuration, an object to be sealed by the polyurethane resin composition having high heat resistance can properly be protected.
The embodiments of the present invention will now be described in detail.
The hydroxyl-group-containing compound (A) in the embodiments may be, for example, but is not limited to, a castor oil polyol, a polyether polyol, a polymer polyol, a low-molecular-weight glycol, a polyester polyol, a polybutadiene polyol, a polyisoprene polyol, a dimer acid polyol, a hydrogenated polybutadiene polyol, or a hydrogenated polyisoprene polyol. Two or more of them may be used in combination.
For improved heat resistance, a castor oil polyol is preferably contained as the hydroxyl-group-containing compound (A). When a castor oil polyol and other polyols are used in combination, the amount of castor oil polyol is preferably 60 mass % or more, more preferably 70 mass % or more, still more preferably 80 mass % or more, based on the total amount of the polyols used.
Examples of usable castor oil polyols include, but are not limited to, castor oil, hydrogenated castor oil, transesterification products of castor oil and other fatty oils, reaction products of castor oil and polyhydric alcohols, esterification reaction products of castor oil fatty acids and polyhydric alcohols, and addition polymerization products thereof with alkylene oxides. Two or more of them may be used in combination.
Examples of usable polyether polyols include, but are not limited to, ring-opening polymerization products obtained from alkylene oxides (hereinafter also referred to as “AOs”) and initiators such as water, propylene glycol, ethylene glycol, glycerol, trimethylolpropane, hexanetriol, triethanolamine, diglycerol, pentaerythritol, ethylenediamine, methyl glucoside, aromatic diamines, sorbitol, sucrose, and phosphoric acid. Two or more of them may be used in combination. Preferred initiators are those obtained by using water, propylene glycol, ethylene glycol, glycerol, trimethylolpropane, or hexanetriol as a starting material, and preferred AOs are ethylene oxide, propylene oxide, and butylene oxide.
Examples of usable polymer polyols include, but are not limited to, polymer polyols obtained by reacting the above polyether polyols with ethylenically unsaturated monomers (e.g., butadiene, acrylonitrile, and styrene) in the presence of radical polymerization catalysts. Two or more of them may be used in combination.
Examples of usable low-molecular-weight glycols include, but are not limited to, aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2-methyl-1,3-propanediol; alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A; and tri- or higher functional hydroxyl-group-containing compounds such as glycerol, trimethylolpropane, and pentaerythritol. Two or more of them may be used in combination.
Examples of usable polyester polyols include, but are not limited to, condensation reaction products of polyhydroxyl-group-containing compounds and polycarboxylic acids (aromatic polycarboxylic acids and aliphatic polycarboxylic acids) or ester-forming derivatives (e.g., phthalic anhydride and dimethyl terephthalate) such as anhydrides and lower alkyl (C1 to C4 alkyl) esters thereof; polylactone polyols; polycarbonate polyols; and castor oil derivatives [e.g., polyester polyols formed from castor oil fatty acids and polyhydric alcohols or polyoxyalkylene polyols (e.g., mono- or diglycerides formed from castor oil fatty acids, mono-, di-, or triesters formed from castor oil fatty acids and trimethylolpropane, and mono- or diesters formed from castor oil fatty acids and polyoxypropylene glycols); alkylene (C2 to C4) oxide adducts of castor oil; and hydroxyl-group-terminated prepolymers derived from castor oil and diphenylmethane diisocyanate]. Two or more of them may be used in combination.
Examples of usable dimer acid polyols include, but are not limited to, reaction products of dimer acids and diols, triols, polyalkylene glycols, or polyalkylene triols. Two or more of them may be used in combination. A dimer acid polyol having a weight-average molecular weight (Mw) of 300 to 50000 is preferred. The average number of functional groups per molecule of the dimer acid polyol is preferably 2 to 4. The hydroxyl value of the dimer acid polyol is preferably 2 mgKOH/g or more, more preferably 30 mgKOH/g or more. The hydroxyl value of the dimer acid polyol is preferably 800 mgKOH/g or less, more preferably 500 mgKOH/g or less, still more preferably 300 mgKOH/g or less.
Examples of usable polybutadiene polyols, polyisoprene polyols, hydrogenated polybutadiene polyols, and hydrogenated polyisoprene polyols include, but are not limited to, those which are commonly used for polyurethane resin compositions.
In the embodiments, the hydroxyl-group-containing compound (A) may be, for example, a hydroxyl-group-terminated urethane prepolymer obtained by reacting a hydroxyl-group-containing compound with an isocyanate-group-containing compound.
In view of moldability of molded products, the content of the hydroxyl-group-containing compound (A) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, based on 100 parts by mass of the polyurethane resin composition. In view of moldability of molded products, the content of the hydroxyl-group-containing compound (A) is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, based on 100 parts by mass of the polyurethane resin composition.
The isocyanate-group-containing compound (B) in the embodiments may be, for example, but is not limited to, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, an araliphatic polyisocyanate compound, or a modified product of any of these isocyanate compounds. Two or more of them may be used in combination. The isocyanate-group-containing compound (B) is preferably an aliphatic polyisocyanate compound, an aromatic polyisocyanate compound, or a modified product of any of these isocyanate compounds.
Examples of usable aliphatic polyisocyanate compounds include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1, 5-diisocyanate, and 3-methylpentane-1,5-diisocyanate. Two or more of them may be used in combination.
Examples of usable alicyclic polyisocyanate compounds include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane. Two or more of them may be used in combination.
Examples of usable aromatic polyisocyanate compounds include dialkyl diphenylmethane diisocyanate, tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (monomeric MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), 4,4′-dibenzyl diisocyanate, l,5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate. Two or more of them may be used in combination.
Examples of usable araliphatic polyisocyanate compounds include xylylene diisocyanate, tetraalkyl diphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate. Two or more of them may be used in combination.
Examples of usable modified products of polyisocyanate compounds include isocyanurate-modified products, biuret-modified products, adduct-modified products, carbodiimide-modified products, and bifunctional-modified products. Two or more of them may be used in combination.
In the embodiments, the isocyanate-group-containing compound (B) may be, for example, an isocyanate-group-terminated urethane prepolymer obtained by reacting a hydroxyl-group-containing compound with an isocyanate-group-containing compound.
In view of moldability of molded products, the content of the isocyanate-group-containing compound (B) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more, based on 100 parts by mass of the polyurethane resin composition. In view of moldability of molded products, the content of the isocyanate-group-containing compound (B) is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, further more preferably 50 parts by mass or less, based on 100 parts by mass of the polyurethane resin composition.
In the embodiments, the molar ratio (NCO/OH) of the isocyanate group in the isocyanate-group-containing compound (B) to the hydroxyl group in the hydroxyl-group-containing compound (A) is preferably 0.6 or more, more preferably 0.8 or more. If the molar ratio is below this range, insufficient curing may occur, and a resin having low heat resistance may be provided. The molar ratio is preferably 1.5 or less, more preferably 1.3 or less. If the molar ratio is above this range, insufficient curing may occur.
The antioxidant (C) in the embodiments has an alkylthio group. In view of the heat resistance of the polyurethane resin composition, the number of carbon atoms in the alkylthio group is preferably 6 or more, more preferably 7 or more, still more preferably 8 or more. The antioxidant (C) having an alkylthio group may be, for example, 2,2-bis[[3-(dodecylthio)-1-oxopropyloxy]methyl]-1,3-propanediyl bis[3-(dodecylthio)propionate] (SUMILIZER TP-D manufactured by Sumitomo Chemical Co., Ltd.), 2,4-bis(octylthiomethyl)-6-methylphenol (IRGANOX 1520L manufactured by BASF), or 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol (IRGANOX 565 manufactured by BASF). Two or more of them may be used in combination.
For improved heat resistance, the antioxidant (C) is preferably a phenol compound. Examples of the antioxidant (C) that has an alkylthio group and is also a phenol compound include IRGANOX 1520L and IRGANOX 565.
For improved heat resistance, the antioxidant (C) preferably has a triazine ring. Examples of the antioxidant (C) having an alkylthio group and a triazine ring include IRGANOX 565. For improved heat resistance, the antioxidant (C) is more preferably a phenol compound having an alkylthio group and a triazine ring. The antioxidant (C) may be used in combination with another antioxidant.
The amount of the antioxidant (C) is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, based on 100 parts by mass of the polyurethane resin composition. The amount of the antioxidant (C) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the polyurethane resin composition.
The inorganic filler (D) can be added to the polyurethane resin composition in the embodiments. The inorganic filler (D) is used in order, for example, to increase thermal conductivity and heat dissipation properties of the polyurethane resin composition. When the object to be sealed by the polyurethane resin composition is an exothermic body such as an electrical or electronic component, the polyurethane resin composition is required to have thermal conductivity and heat dissipation properties at or above certain levels. The inorganic filler (D) may be, for example, alumina, aluminum hydroxide, aluminum nitride, boron nitride, magnesium hydroxide, or magnesium oxide.
The sodium content of the inorganic filler (D) is preferably 0.3 mass % or less, more preferably 0.2 mass % or less, still more preferably 0.15 mass % or less, further more preferably 0.10 mass % or less, of the inorganic filler (D) on a Na2O basis. When the sodium content of the inorganic filler (D) is not more than these values, the heat resistance can be more effectively increased.
To increase the thermal conductivity and heat dissipation properties of the polyurethane resin composition, the amount of the inorganic filler (D) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the polyurethane resin composition. To reduce the mixing viscosity during the production of the polyurethane resin composition, the amount of the inorganic filler (D) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, based on 100 parts by mass of the polyurethane resin composition. When the mixing viscosity during the production is high, the workability tends to be low.
A plasticizer (E) can be added to the polyurethane resin composition in the embodiments. The plasticizer (E) may be a known one used for polyurethane resins. For example, phthalates such as dioctyl phthalate, diisononyl phthalate, and diundecyl phthalate; non-phthalate compounds such as diisononyl 1,2-cyclohexanedicarboxylate; adipates such as dioctyl adipate and diisononyl adipate; castor oil esters such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, acetylricinoleic triglyceride, and acetylpolyricinoleic triglyceride; trimellitates such as trioctyl trimellitate and triisononyl trimellitate; pyromellitates such as tetraoctyl pyromellitate and tetraisononyl pyromellitate; and phosphates such as tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, xylenyl phosphate, and triphenyl phosphate can be used.
The amount of the plasticizer (E) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the polyurethane resin composition. A large amount of plasticizer may degrade physical properties, such as strength, of the polyurethane resin composition.
Optionally, various additives such as catalysts, antioxidants, moisture absorbents, antifungal agents, and silane coupling agents can be added to the polyurethane resin composition in the embodiments. Examples of silane coupling agents include alkoxysilanes, vinyl-group-containing silane coupling agents, epoxy-group-containing silane coupling agents, methacrylic-group-containing silane coupling agents, and acrylic-group-containing silane coupling agents.
In the case of, for example, raw materials at 25° C. are mixed together, the mixing viscosity during the production of the polyurethane resin composition in the embodiments is preferably 5 Pa·s or less, more preferably 4 Pa·s or less. A mixing viscosity of not more than these values provides good workability. The mixing viscosity is measured by a method described in EXAMPLES.
When the object to be sealed is an exothermic body such as an electrical or electronic component, the thermal conductivity of the polyurethane resin composition in the embodiments is preferably 0.3 W/m·K or more, more preferably 0.4 W/m·K or more. The thermal conductivity is measured by a method described in EXAMPLES.
The polyurethane resin composition in the embodiments can seal articles such as electrical and electronic components, medical supplies, toys, and housewares. Articles in the state of being sealed by the polyurethane resin composition are also referred to as sealed articles.
The polyurethane resin composition in the embodiments will now be described in more detail with reference to Examples and Comparative Examples. It should be understood that the present invention is not limited to the examples. “Parts” and “%” in this DESCRIPTION indicate “parts by mass” and “mass %”, respectively, unless otherwise specified.
Raw materials used in Examples and Comparative Examples will be described.
Table 1 shows raw materials used to form polyurethane resin compositions of Examples 1 to 15 and Comparative Examples 1 to 3, the amount thereof (parts by mass), and results of evaluations described below.
A mixture of raw materials excluding the isocyanate-group-containing compound (B) was mixed using a disperser (manufactured by PRIMIX Corporation, model name: TK HOMOGENIZING DISPER Model 2.5) for 30 minutes. Thereafter, the isocyanate-group-containing compound (B) was added so as to achieve NCO/OH=1 to 1.1, and mixing and defoaming were performed. Using the polyurethane resin composition thus prepared, heat resistance, thermal conductivity, and mixing viscosity were evaluated as described below.
1. Production of Test Piece for Heat Resistance Evaluation
The uncured polyurethane resin composition prepared was poured into a cylindrical mold with a diameter of 5 cm to a level of 3 cm and allowed to stand in an environment at 80° C. for 16 hours, thereby curing the polyurethane resin composition. Thereafter, the cured polyurethane resin composition was demolded to obtain a test piece for heat resistance evaluation.
2. Evaluation of Heat Resistance
A test piece (hereinafter also referred to as an unheated test piece) allowed to stand in a room-temperature environment for 24 hours and a test piece (hereinafter also referred to as a heated test piece) allowed to stand in a high-temperature environments at 150° C. for 24 hours were prepared. The unheated test piece and the heated test piece were then measured for their surface hardness (type A) in accordance with JIS K6253. Hardness retention (%), as defined as the percentage of the hardness of the heated test piece relative to the hardness of the unheated test piece, was evaluated according to the following evaluation criteria. ⊙: Hardness retention is 70% or more, and neither melting nor appearance change is observed in heated test piece. ◯: Hardness retention is less than 70%, and neither melting nor appearance change is observed in heated test piece. x: Melting or appearance change is observed in heated test piece (hardness is not measured).
1. Production of Test Piece for Thermal Conductivity Evaluation
The uncured polyurethane resin composition prepared was poured into a box-shaped mold with a bottom of 6 cm×12 cm to a level of 1 cm and allowed to stand in an environment at 80° C. for 16 hours, thereby curing the polyurethane resin composition. Thereafter, the cured polyurethane resin composition was demolded to obtain a test piece for thermal conductivity evaluation.
2. Evaluation of Thermal Conductivity
The thermal conductivity of the test piece was measured by a probe method using a thermal conductivity meter (QTM-D3 manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
The mixing viscosity in preparing the polyurethane resin composition was measured. Specifically, the isocyanate-group-containing compound (B) was added to the mixture of raw materials excluding the isocyanate-group-containing compound (B), and mixing was started. The mixing viscosity after five minutes was measured using a BH type viscometer. The temperature of the raw materials and the ambient temperature during the mixing are 25° C.
Referring to the evaluation results in Table 1, the polyurethane resin compositions of Examples 1 to 15 each have high heat resistance, a good thermal conductivity, and, in addition, a mixing viscosity in a range suitable for use. Comparison of Examples 1 to 13 and Examples 14 and 15 shows that combined use of an antioxidant containing an alkylthio group and an inorganic filler with a sodium content (on a Na2O basis) of 0.10 mass % or less can more effectively increase the heat resistance of the polyurethane resin composition. It can also be seen that the heat resistance is significantly worse when an antioxidant not containing an alkylthio group is used as in Comparative Examples 1 to 3 than when an antioxidant containing an alkylthio group is used.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-067361 | Mar 2017 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2018/003865 | 2/5/2018 | WO | 00 |
