Polyol composition, two-component curing polyurethane resin composition, and cured product

Abstract

Provided are a polyol composition and a two-component curing polyurethane resin composition which give a cured product having high elastic modulus at room temperature while suppressing an excessive increase in elastic modulus at low temperatures, and which have excellent storage stability. [Solution] The polyol composition according to the embodiment is a composition for producing a polyurethane resin by reacting with a polyisocyanate, and contains a polybutadiene polyol, a trifunctional polyether polyol, an ether ester-based plasticizer, and a phthalate ester-based plasticizer.

Description

[Technical field]

[0001] An embodiment of the present invention relates to a polyol composition, a two-component curing polyurethane resin composition using the polyol composition, and a cured product thereof. [Background technology]

[0002] 2. Description of the Related Art Two-component curing polyurethane resin compositions comprising a first component containing a polyol and a second component containing a polyisocyanate are used in a variety of applications, such as electrical and electronic component applications.

[0003] For example, Patent Document 1 discloses a two-component curing polyurethane resin composition comprising a first liquid containing, as a polyol, a polyether polyol obtained by adding an alkylene oxide including propylene oxide and / or butylene oxide to an active hydrogen compound having 3 to 6 functional groups, and a second liquid containing a polyisocyanate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 7209890 Summary of the Invention [Problem to be solved by the invention]

[0005] In some cases, the two-component curing polyurethane resin composition is required to have a cured product with moisture and heat resistance depending on the application. In addition, the cured product is required to have a high elastic modulus at room temperature while suppressing an excessive increase in elastic modulus at low temperatures. In order to meet such requirements, the present inventors have devised a combination of polybutadiene polyol and trifunctional polyether polyol as polyols. However, it has been found that the combination of polybutadiene polyol and trifunctional polyether polyol results in poor compatibility, and the storage stability of the polyol composition, which is the first component, is impaired.

[0006] In view of the above, an object of an embodiment of the present invention is to provide a polyol composition which can give a cured product that has a high elastic modulus at room temperature while suppressing an excessive increase in elastic modulus at low temperatures and has excellent storage stability, and a two-component curing polyurethane resin composition including the polyol composition. [Means for solving the problem]

[0007] The present invention includes the embodiments set forth below. [1] A polyol composition for use in reacting with a polyisocyanate to obtain a polyurethane resin, the polyol composition comprising a polybutadiene polyol, a trifunctional polyether polyol, an ether ester plasticizer, and a phthalate ester plasticizer. [2] The polyol composition according to [1], wherein a mass ratio of the polybutadiene polyol to the trifunctional polyether polyol is 1 / 1 to 5 / 1. [3] The polyol composition according to [1] or [2], wherein a mass ratio of the ether ester plasticizer to the phthalate ester plasticizer is 1 / 3 to 3 / 1. [4] The polyol composition according to any one of [1] to [3], wherein the trifunctional polyether polyol has a number average molecular weight of 1,500 or less. [5] The polyol composition according to any one of [1] to [4], wherein the trifunctional polyether polyol comprises a polyether polyol obtained by adding an alkylene oxide containing 70 mol% or more of propylene oxide to an active hydrogen compound having three functional groups. [6] A two-component curing polyurethane resin composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate, wherein the first liquid is the polyol composition according to any one of [1] to [5]. [7] The two-component curing polyurethane resin composition according to [6], which is for use in electric and electronic parts. [8] A cured product obtained by curing the two-component curing polyurethane resin composition described in [6] or [7]. Effect of the Invention

[0008] According to an embodiment of the present invention, it is possible to provide a polyol composition and a two-component curing polyurethane resin composition that can give a cured product that has a high elastic modulus at room temperature while suppressing an excessive increase in elastic modulus at low temperatures and has excellent storage stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The two-component curing polyurethane resin composition according to this embodiment includes a first liquid containing a polyol (A) and a second liquid containing a polyisocyanate (B). The polyol composition according to this embodiment is used as the first liquid, and contains a polybutadiene polyol (A1), a trifunctional polyether polyol (A2), an ether ester plasticizer (C1), and a phthalate ester plasticizer (C2), and is reacted with the polyisocyanate (B) to obtain a polyurethane resin.

[0010] <Polyol composition> [Polybutadiene polyol (A1)] The polybutadiene polyol (A1) is a polybutadiene having a hydroxy group, and is a non-hydrogenated (i.e., non-hydrogenated) polybutadiene polyol. The polybutadiene polyol (A1) is preferably one having a polybutadiene structure of 1,4-bond type, 1,2-bond type or a mixture thereof in the molecule and at least two hydroxy groups, more preferably one having a hydroxy group at each end of the polybutadiene structure.

[0011] The number average molecular weight (Mn) of the polybutadiene polyol (A1) is not particularly limited, but is preferably 700 to 5,000, more preferably 1,000 to 4,000, and may be 1,500 to 3,800, 2,000 to 3,500, or 2,500 to 3,300.

[0012] In this specification, the number average molecular weight (Mn) is a value measured by GPC (gel permeation chromatography) and calculated using a calibration curve of standard polystyrene. In detail, the GPC conditions are as follows: column: "TSKgel G4000HXL+TSKgel G3000HXL+TSKgel G2000HXL+TSKgel G1000HXL+TSKgel G1000HXL" manufactured by Tosoh Corporation, mobile phase: THF (tetrahydrofuran), mobile phase flow rate: 1.0 mL / min, column temperature: 40°C, sample injection amount: 50 μL, sample concentration: 0.2 mass%.

[0013] The hydroxyl value of the polybutadiene polyol (A1) is not particularly limited, but is preferably from 10 to 200 mgKOH / g, more preferably from 15 to 150 mgKOH / g, and further preferably from 20 to 120 mgKOH / g, and may be from 25 to 100 mgKOH / g, 30 to 90 mgKOH / g, or 35 to 70 mgKOH / g.

[0014] In this specification, the hydroxyl value is measured in accordance with Method A of JIS K1557-1:2007.

[0015] [Trifunctional polyether polyol (A2)] The trifunctional polyether polyol (A2) is a polyether polyol having a plurality of ether bonds in the molecule and having three hydroxyl groups. The trifunctional polyether polyol (A2) is preferably one obtained by adding an alkylene oxide to an active hydrogen compound having three functional groups.

[0016] The active hydrogen compound having three functional groups is a compound having an active hydrogen atom capable of undergoing an addition reaction with an alkylene oxide, and has three functional groups, i.e., a compound having three active hydrogen atoms in one molecule. Examples of the active hydrogen compound include polyhydric alcohols and alkanolamines. Examples of the polyhydric alcohol include trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, butanetriol, and hexanetriol. Examples of the alkanolamine include ethanolamine, diethanolamine, triethanolamine, methanolamine, and isopropanolamine. These active hydrogen compounds may be used alone or in combination of two or more.

[0017] Examples of the alkylene oxide to be added to the active hydrogen compound include ethylene oxide, propylene oxide, butylene oxide, etc., and any one of these may be used alone or two or more of them may be used in combination.

[0018] Such an alkylene oxide adduct can be produced by using the above-mentioned active hydrogen compound having three functional groups as a starting material (initiator) and subjecting the starting material to a ring-opening addition reaction with an alkylene oxide in the presence of a catalyst.

[0019] The number average molecular weight (Mn) of the trifunctional polyether polyol (A2) is preferably 1500 or less, and the elastic modulus at room temperature can be further increased. The number average molecular weight of the trifunctional polyether polyol (A2) is more preferably 300 to 1200, more preferably 300 to 1000, and further preferably 350 to 700.

[0020] The hydroxyl value of the trifunctional polyether polyol (A2) is not particularly limited and may be, for example, 100 to 600 mgKOH / g, 140 to 500 mgKOH / g, or 200 to 450 mgKOH / g.

[0021] In one embodiment, the trifunctional polyether polyol (A2) is preferably a polyether polyol (A2-1) obtained by adding an alkylene oxide containing 70 mol% or more of propylene oxide to an active hydrogen compound having a functionality of 3. In this way, 70 mol% or more of the total alkylene oxide units (100 mol%) constituting the polyether polyol are propylene oxide units, thereby improving compatibility with the polybutadiene polyol (A1). The alkylene oxide preferably contains 80 mol% or more of propylene oxide, more preferably contains 90 mol% or more, and even more preferably contains 100 mol%.

[0022] The trifunctional polyether polyol (A2) preferably contains 50% by mass or more of the polyether polyol (A2-1), more preferably 70% by mass or more, further preferably 90% by mass or more, and may be 100% by mass.

[0023] [Polyol (A)] The polyol (A) may be composed of only the polybutadiene polyol (A1) and the trifunctional polyether polyol (A2), or may further contain another polyol (A3) in addition to these.

[0024] The other polyol (A3) is a compound having multiple hydroxyl groups in the molecule, and includes various polyols other than the polybutadiene polyol (A1) and the trifunctional polyether polyol (A2). Specific examples include polyester polyol, polycarbonate polyol, dimer acid polyol, castor oil polyol, polycaprolactone polyol, acrylic polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, hydrogenated polybutadiene polyol, and bifunctional polyether polyol. In addition, low molecular weight polyols generally used as crosslinking agents may be used, and examples thereof include polyhydric alcohols having a molecular weight of less than 300, specifically, aliphatic alcohols such as ethylene glycol, 1,4-butanediol, octanediol, trimethylolpropane, triisopropanolamine, and octanediol, and aromatic alcohols such as N,N-bis(2-hydroxypropyl)aniline, hydroquinone-bis(β-hydroxyethyl)ether, and resorcinol-bis(β-hydroxyethyl)ether.

[0025] In the polyol (A), the mass ratio (A1) / (A2) of the polybutadiene polyol (A1) to the trifunctional polyether polyol (A2) is preferably 1 / 1 to 5 / 1. When the mass ratio (A1) / (A2) is 5 / 1 or less (i.e., 5 or less), the proportion of the trifunctional polyether polyol (A2) is increased, making it easier to maintain a high elastic modulus at room temperature. When the mass ratio (A1) / (A2) is 1 / 1 or more (i.e., 1 or more), the proportion of the polybutadiene polyol (A1) is increased, making it easier to suppress an increase in the elastic modulus at low temperatures. The mass ratio (A1) / (A2) is preferably 5 / 4 to 4 / 1, more preferably 3 / 2 to 7 / 2, and even more preferably 9 / 5 to 3 / 1.

[0026] The content of the polybutadiene polyol (A1) in 100% by mass of the polyol (A) is not particularly limited, but is preferably 50% by mass or more, more preferably 55 to 83% by mass, more preferably 60 to 80% by mass, and even more preferably 65 to 75% by mass.

[0027] The content of the trifunctional polyether polyol (A2) in 100% by mass of the polyol (A) is not particularly limited, but is preferably 50% by mass or less, more preferably 18 to 45% by mass, more preferably 20 to 40% by mass, and even more preferably 25 to 35% by mass.

[0028] The total amount of the polybutadiene polyol (A1) and the trifunctional polyether polyol (A2) in 100% by mass of the polyol (A) is preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass.

[0029] The amount of polyol (A) in the polyol composition is not particularly limited, and may be, for example, 5 to 90 mass%, 6 to 75 mass%, 7 to 40 mass%, 8 to 30 mass%, 9 to 25 mass%, or 10 to 20 mass% based on 100 mass% of the polyol composition.

[0030] [Ether ester plasticizers (C1)] The ether ester plasticizer (C1) is a plasticizer containing a polyether structure and an ester structure. Examples of the ether ester plasticizer (C1) include an ester compound of a polyalkylene glycol and a monocarboxylic acid, and an ester compound of a polyalkylene glycol and a polycarboxylic acid. The polyalkylene glycol preferably contains polyethylene glycol as a main component (preferably 80 mol% or more).

[0031] Examples of the ester compound of polyalkylene glycol and monocarboxylic acid include aliphatic polyether ester plasticizers such as aliphatic carboxylic acid monoester compounds of polyalkylene glycol and aliphatic carboxylic acid diester compounds of polyalkylene glycol. In the case of the monoester compound, for example, an ester compound obtained by reacting an aliphatic monocarboxylic acid with a polyethylene glycol monoalkyl ether in which an aliphatic alcohol is added to one end of polyethylene glycol may be used. Specific examples of the aliphatic polyether ester plasticizer include polyethylene glycol butanoic acid ester, polyethylene glycol isobutanoic acid ester, polyethylene glycol (2-ethylhexanoic acid) ester, polyethylene glycol decanoic acid ester, polyethylene glycol dibutanoic acid ester, polyethylene glycol diisobutanoic acid ester, polyethylene glycol di(2-ethylbutyric acid) ester, polyethylene glycol di(2-ethylhexanoic acid) ester, and polyethylene glycol didecanoic acid ester. Any one of these may be used, or two or more may be used in combination.

[0032] The ester compound of polyalkylene glycol and polycarboxylic acid may be an ester compound obtained by reacting an aliphatic dicarboxylic acid with a polyethylene glycol monoalkyl ether in which an aliphatic alcohol is added to one end of polyethylene glycol. Specific examples of the ester compound of polyalkylene glycol and polycarboxylic acid include adipic acid ether ester plasticizers such as dibutoxyethanol adipate, di(butyl diglycol) adipate, di(butyl polyglycol) adipate, di(2-ethylhexyloxyethanol) adipate, di(2-ethylhexyl diglycol) adipate, di(2-ethylhexyl polyglycol) adipate, dioctoxyethanol adipate, di(octyl diglycol) adipate, and di(octyl polyglycol) adipate. Any one of these may be used, or two or more may be used in combination.

[0033] The molecular weight of the ether ester plasticizer (C1) is not particularly limited, and may be, for example, 300-2,000, 350-1,000, or 400-900 in terms of molecular weight or number average molecular weight (Mn).

[0034] Examples of commercially available ether ester plasticizers (C1) include polyether ester plasticizers such as "ADEKACIZER RS-700", "ADEKACIZER RS-735", "ADEKACIZER RS-966", and "ADEKACIZER RS-1000" (all manufactured by ADEKA CORPORATION). Examples of commercially available adipic acid ether ester plasticizers include "ADEKACIZER RS-107" (manufactured by ADEKA CORPORATION).

[0035] [Phthalate ester plasticizers (C2)] Examples of the phthalate ester plasticizer (C2) include dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, ethyl benzyl phthalate, butyl benzyl phthalate, isobutyl benzyl phthalate, heptyl benzyl phthalate, (2-ethylhexyl) benzyl phthalate, n-octyl benzyl phthalate, nonyl benzyl phthalate, isononyl benzyl phthalate, isodecyl benzyl phthalate, undecyl benzyl phthalate, tridecyl benzyl phthalate, cyclohexyl benzyl phthalate, benzyl-3-(isobutyryloxy)-1-isopropyl-2,2-dimethylpropyl phthalate, and myristyl benzyl phthalate. These may be used alone or in combination of two or more.

[0036] In one embodiment, the phthalate ester plasticizer (C2) is preferably a dialkyl phthalate, more preferably a diester of an alkanol having 4 to 18 carbon atoms and phthalic acid, and even more preferably a diester of an alkanol having 6 to 15 carbon atoms and phthalic acid.

[0037] [Plasticizer (C)] In this embodiment, the ether ester plasticizer (C1) and the phthalate ester plasticizer (C2) are used in combination as the plasticizer (C), which improves the compatibility of the polyol composition containing the polybutadiene polyol (A1) and the trifunctional polyether polyol (A2), thereby improving the storage stability of the polyol composition. In addition, in combination with the use of the polybutadiene polyol (A1) and the trifunctional polyether polyol (A2) as the polyol (A), a cured product can be obtained that has a high elastic modulus at room temperature while suppressing an excessive increase in the elastic modulus at low temperatures. It is preferable that the plasticizer (C) is composed only of the ether ester plasticizer (C1) and the phthalate ester plasticizer (C2), but other plasticizers may be used in combination within a range that does not impair the purpose of this embodiment.

[0038] The mass ratio (C1) / (C2) of the ether ester plasticizer (C1) to the phthalate ester plasticizer (C2) is preferably 1 / 3 to 3 / 1, which can enhance the effect of improving the compatibility of the polyol composition. The mass ratio (C1) / (C2) is preferably 2 / 5 to 5 / 2, more preferably 1 / 2 to 2 / 1, and even more preferably 2 / 3 to 3 / 2.

[0039] The total amount of the ether ester plasticizer (C1) and the phthalate ester plasticizer (C2) per 100 parts by mass of the polyol (A) is not particularly limited, but from the viewpoint of further enhancing the effects of this embodiment, it is preferably 40 to 180 parts by mass, more preferably 50 to 150 parts by mass, more preferably 60 to 130 parts by mass, more preferably 70 to 125 parts by mass, and even more preferably 80 to 115 parts by mass.

[0040] [Other ingredients] In addition to the above-mentioned components, various additives such as a catalyst, a filler, an active hydrogen compound other than polyol, an antioxidant, a foam stabilizer, a defoamer, a diluent, a flame retardant, an ultraviolet absorber, a colorant, a filler, and a plasticizer may be added to the polyol composition as needed, within a range that does not impair the object of the present embodiment.

[0041] The catalyst used is one that promotes the reaction between the polyol (A) and the polyisocyanate (B), and examples of the catalyst include metal catalysts such as organotin catalysts, organolead catalysts, and organobismuth catalysts, various urethane polymerization catalysts such as amine catalysts, and organic acid catalysts such as octylic acid. The amount of the catalyst is not particularly limited, and may be, for example, 0.001 to 0.02 parts by mass or 0.005 to 0.01 parts by mass relative to 100 parts by mass of the polyol (A).

[0042] The filler is preferably an inorganic filler. Examples of the inorganic filler include metal oxides such as silica, alumina, and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. The amount of the filler is not particularly limited, and in one embodiment, when the polyol composition contains a filler, the amount of the filler (preferably an inorganic filler) in 100% by mass of the polyol composition may be, for example, 20 to 92% by mass, 50 to 90% by mass, 60 to 85% by mass, or 65 to 80% by mass.

[0043] The polyol composition is a liquid at room temperature (25° C.), that is, a liquid composition having fluidity, and the viscosity thereof is not particularly limited.

[0044] <Two-component curing polyurethane resin composition> The two-component curing polyurethane resin composition is a combination of a first component containing a polyol (A) and a second component containing a polyisocyanate (B), and a polyurethane resin is formed by mixing and reacting the first and second components. Therefore, the composition is also called a two-component polyurethane-forming composition.

[0045] [1st liquid] As the first liquid, the above-mentioned polyol composition is used.

[0046] [Second liquid] The polyisocyanate (B) contained in the second liquid is not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used. For example, the polyisocyanate (B) can be an aromatic polyisocyanate (B1), an aliphatic polyisocyanate (B2), or an alicyclic polyisocyanate (B3), and any one of these can be used alone or in combination of two or more.

[0047] Examples of the aromatic polyisocyanate (B1) include tolylene diisocyanate (TDI, for example, 2,4-TDI, 2,6-TDI), diphenylmethane diisocyanate (MDI, for example, 2,2'-MDI, 2,4'-MDI, 4,4'-MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and modified and polynuclear products thereof.

[0048] Examples of the aliphatic polyisocyanate (B2) 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, 3-methylpentane-1,5-diisocyanate, and modified and polynuclear products thereof.

[0049] Examples of the alicyclic polyisocyanate (B3) include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, and modified products and polynuclear products thereof.

[0050] Examples of the modified product include an isocyanurate modified product, an allophanate modified product, a biuret modified product, an adduct modified product, and a carbodiimide modified product.

[0051] In one embodiment, the polyisocyanate (B) preferably contains an aromatic polyisocyanate (B1). More preferably, the polyisocyanate (B) is at least one selected from the group consisting of diphenylmethane diisocyanate (MDI) and its modified and polynuclear products (B11). The amount of the above (B1), preferably (B11), in 100% by mass of the polyisocyanate (B) is preferably 50% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.

[0052] The amount of polyisocyanate (B) in the two-component curing polyurethane resin composition is not particularly limited, and may be, for example, 5 to 70 parts by mass, 10 to 60 parts by mass, or 15 to 50 parts by mass relative to 100 parts by mass of polyol (A).

[0053] The NCO / OH (index) is not particularly limited, and may be, for example, 0.60 to 1.60, 0.70 to 1.50, 0.80 to 1.40, or 0.90 to 1.30.

[0054] Here, NCO / OH is the molar ratio of isocyanate groups contained in polyisocyanate (B) to hydroxyl groups contained in polyol (A). NCO / OH is calculated using the hydroxyl value of polyol (A) and the isocyanate value of polyisocyanate (B). The isocyanate value is calculated by isocyanate value = {(isocyanate content) x 56110} / (42.02 x 100) using the isocyanate content measured in accordance with JIS K1603-1:2007 Method A.

[0055] In one embodiment, the second liquid may contain a plasticizer (D) together with the polyisocyanate (B). The plasticizer (D) contained in the second liquid is preferably the ether ester plasticizer (C1) and / or the phthalate ester plasticizer (C2) contained in the first liquid (polyol composition), and more preferably the phthalate ester plasticizer (C2). However, other plasticizers may be used.

[0056] When the second liquid contains a plasticizer (D), the amount thereof is not particularly limited, and may be, for example, 10 to 300 parts by mass, 50 to 250 parts by mass, or 80 to 200 parts by mass relative to 100 parts by mass of the polyisocyanate (B).

[0057] The second liquid may be composed of only the polyisocyanate (B), or may be composed of the polyisocyanate (B) and the plasticizer (D). Alternatively, various additives such as catalysts, fillers, antioxidants, foam stabilizers, defoamers, diluents, flame retardants, ultraviolet absorbers, colorants, bulking agents, and plasticizers may be added together with the polyisocyanate (B) as necessary within a range that does not impair the object of this embodiment.

[0058] The second liquid is liquid at room temperature (25° C.), that is, has fluidity, and its viscosity is not particularly limited.

[0059] The two-component curing polyurethane resin composition according to this embodiment is usually composed of the above-mentioned first and second liquids, but may also contain a third liquid containing the above-mentioned other components as optional components in addition to the first and second liquids.

[0060] The two-component curing polyurethane resin composition can be produced by preparing the first and second liquids, respectively, and the first and second liquids may be provided separately. That is, the two-component kit may be prepared in which the first and second liquids are filled in separate containers. The first and second liquids filled in separate containers are mixed at the time of use, whereby the polyol (A) and the polyisocyanate (B) react to produce a polyurethane resin, and a polyurethane resin cured product is obtained as a reaction product. That is, a cured product is obtained by curing the two-component curing polyurethane resin composition. At that time, the composition may be cured by heating, or may be cured at room temperature. The heating temperature and heating time are not particularly limited.

[0061] <Applications of two-component curing polyurethane resin composition> The use of the two-component curing polyurethane resin composition according to the present embodiment is not particularly limited. For example, it may be used as a resin material constituting a part of an electric / electronic component, for example, for sealing the electric / electronic component. Examples of the electric / electronic component include transformers such as transformer coils, choke coils, and reactor coils, device control boards, sensors, and wireless communication components. EXAMPLES

[0062] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited thereto.

[0063] Details of each component used in the examples and comparative examples are as follows.

[0064] [Polyol] Polybutadiene polyol 1: Hydroxyl value 47 mgKOH / g, number average molecular weight approx. 2900, product name "POLYVEST-HT", manufactured by Evonik Polybutadiene polyol 2: hydroxyl value 102.7 mgKOH / g, number average molecular weight approx. 1200, product name "Poly bd R-15HT", Idemitsu Kosan Co., Ltd. Polyether polyol 1: Trifunctional, hydroxyl value 420 mg KOH / g, number average molecular weight approx. 400, product name "EXCENOL 430", manufactured by AGC Inc. Polyether polyol 2: Trifunctional, hydroxyl value 160 mgKOH / g, number average molecular weight approx. 1000, product name "EXCENOL 1030", manufactured by AGC Inc. Polyether polyol 3: Bifunctional, hydroxyl value 280 mgKOH / g, product name "EXCENOL 420", manufactured by AGC Inc. Polyester polyol: Trifunctional, hydroxyl value 336mgKOH / g, product name "Kuraray Polyol F-510", manufactured by Kuraray Co., Ltd.

[0065] [Plasticizer] Ether ester plasticizer 1: Product name "Adeka Cizer RS-700", manufactured by ADEKA Corporation Ether ester plasticizer 2: Product name "ADEKA Cizer RS-966", manufactured by ADEKA Corporation Ether ester plasticizer 3: Product name: Monocizer W-260, manufactured by DIC Corporation Phthalate plasticizer 1: Diisononyl phthalate (DINP) Phthalate plasticizer 2: Diundecyl phthalate (DUP) Phosphorus-based plasticizer: Product name: Sanso Cizer TCP, manufactured by New Japan Chemical Co., Ltd.

[0066] [Polyisocyanate] HDI Isocyanurate 1: Isocyanate content 23.3%, product name "Duranate TLA-100", manufactured by Asahi Kasei Corporation HDI Isocyanurate 2: Isocyanate content 23.1%, product name "Duranate TPA-100-D", manufactured by Asahi Kasei Corporation Polymeric MDI: Isocyanate content 32%, product name "Formlite NE-5000B", manufactured by BASF INOAC Polyurethanes Ltd.

[0067] [Other ingredients] Tin-based catalyst: Product name "Neostan U-810", manufactured by Nitto Kasei Co., Ltd. Inorganic filler: Product name: Suisanka Aluminum C305-F, manufactured by Sumitomo Chemical Co., Ltd.

[0068] [Examples 1 to 17 and Comparative Examples 1 to 7] Two-component curing polyurethane resin compositions of each Example and Comparative Example were prepared according to the formulations (parts by mass) shown in Tables 1 to 4 below. In detail, the first and second components were weighed according to the formulations shown in Tables 1 to 4, respectively, and prepared by stirring and mixing them. The compatibility of the obtained first component (polyol composition) was evaluated. The evaluation method is as follows.

[0069] The first liquid and the second liquid were mixed by stirring according to the "first liquid / second liquid mass ratio" shown in Tables 1 to 4, and degassed. The degassed mixed liquid was poured into a 3 mm thick mold, cured at 80°C for 1 day, and hardened to produce a 3 mm thick resin sheet. The obtained resin sheet was used to measure the wet heat resistance and the elastic modulus at room temperature and low temperature. The measurement method is as follows.

[0070] [compatibility] Each component of the first liquid was weighed, stirred and mixed, and the state of the first liquid after that was checked to evaluate the compatibility according to the following criteria. A: It was transparent and did not separate even after one week. B: After mixing, the mixture was transparent and did not separate, but after one week, separation occurred. C: Separation occurred immediately after mixing.

[0071] [Moisture and heat resistance] The resin sheet was cut into sheets of 30 mm x 30 mm x 3 mm to be used as measurement samples. Measurements were performed using an Espec Corporation device (main body model: EHS-212M, name: highly accelerated life test device), and in unsaturated control (humidification water temperature control) mode, the state of the resin sheet was checked after a specified time of durability testing at a temperature of 85°C and a humidity of 85%, and the time until the resin melted and could no longer maintain the sheet shape was measured, and evaluation was performed according to the following criteria. Note that for those with a compatibility rating of "C", it was not possible to prepare a resin sheet, and therefore measurement was not possible. A: More than 3000 hours B: 2500 hours or more but less than 3000 hours C: Less than 2500 hours D: Not measurable

[0072] Elasticity Modulus The resin sheet was cut into sheets with a width of 5 mm, length of 30 mm, and thickness of 3 mm to be used as samples for measurement. Dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring instrument (body type: Rheogel E-4000) manufactured by UBM Co., Ltd., and the elastic modulus was measured with the deformation mode set to tensile mode, and the evaluation was performed according to the following criteria. As for the measurement conditions, the tensile mode conditions were a chuck distance of 20 mm, an initial strain of 0.2 mm, and a sinusoidal force with a frequency of 10 Hz and a strain amplitude of 2 μm was applied to the measurement sample. The measurement temperatures were 25° C. and −40° C. Note that for those with a compatibility rating of “C”, it was not possible to prepare a resin sheet, and therefore measurement was not possible.

[0073] (Normal temperature: 25℃) A:25MPa or more B: 10MPa or more and less than 25MPa C: Less than 10MPa D: Not measurable

[0074] (Low temperature: -40℃) A: Less than 500MPa B: 500MPa or more and less than 2000MPa C:2000MPa or more D: Not measurable

[0075] [Table 1]

[0076] [Table 2]

[0077] [Table 3]

[0078] [Table 4]

[0079] The results are shown in Tables 1 to 4. Comparative Example 1 is a combination of polybutadiene polyol and bifunctional polyether polyol as polyols, and is inferior in moist heat resistance and has a low elastic modulus at room temperature, failing to satisfy the required characteristics. Comparative Example 2 is a combination of polybutadiene polyol and trifunctional polyester polyol as polyols, and has a high elastic modulus at room temperature while suppressing an excessive increase in elastic modulus at low temperatures, but is inferior in moist heat resistance.

[0080] In Comparative Example 3, the polyol was polybutadiene polyol alone, and no trifunctional polyether polyol was blended, so the elastic modulus at room temperature was low and the required properties could not be met.In Comparative Example 4, the polyol was trifunctional polyether polyol alone, and no polybutadiene polyol was blended, so the elastic modulus at low temperature was too high and the required properties could not be met.

[0081] In Comparative Examples 5 to 7, polybutadiene polyol and trifunctional polyether polyol were used as polyols, but ether ester plasticizers and phthalate ester plasticizers were not used as plasticizers. In Comparative Examples 5 to 7, separation was observed immediately after the first liquid was mixed and prepared, and the compatibility of the first liquid was poor. Therefore, it was not possible to measure the wet heat resistance and elastic modulus.

[0082] In contrast, Examples 1 to 17 used polybutadiene polyol and trifunctional polyether polyol in combination as the polyol, and used ether ester plasticizer and phthalate ester plasticizer in combination as the plasticizer, and had excellent compatibility with the first liquid and excellent storage stability. In addition, the cured product had excellent resistance to moist heat and had a high elastic modulus at room temperature while suppressing excessive increase in elastic modulus at low temperatures.

[0083] In addition, the various numerical ranges described in the specification can be arbitrarily combined with their upper and lower limits, and all such combinations are considered to be preferred numerical ranges described in the specification. In addition, a numerical range described as "X to Y" means from X to Y.

[0084] Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the gist of the invention. These embodiments and their omissions, substitutions, modifications, etc. are included in the scope and gist of the invention as well as the invention and its equivalents described in the claims.

Claims

1. A polyol composition for reacting with a polyisocyanate to obtain a polyurethane resin, comprising: The plasticizer comprises a polybutadiene polyol, a trifunctional polyether polyol, an ether ester plasticizer, and a phthalate ester plasticizer, the trifunctional polyether polyol comprises a polyether polyol obtained by adding an alkylene oxide containing 70 mol % or more and 100 mol % or less of propylene oxide to an active hydrogen compound having three functional groups, The polyol composition has a mass ratio of the polybutadiene polyol to the trifunctional polyether polyol of 1 / 1 to 5 / 1.

2. The polyol composition according to claim 1, wherein a mass ratio of the ether ester plasticizer to the phthalate ester plasticizer is 1 / 3 to 3 / 1.

3. The polyol composition according to claim 1, wherein the trifunctional polyether polyol has a number average molecular weight of 300 or more and 1,500 or less.

4. A two-component curing polyurethane resin composition comprising a first liquid containing a polyol and a second liquid containing a polyisocyanate, wherein the first liquid is the polyol composition according to any one of claims 1 to 3.

5. The two-component curing polyurethane resin composition according to claim 4, which is for use in electric and electronic parts.

6. A cured product obtained by curing the two-component curing polyurethane resin composition according to claim 4.

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