Polyurea resin composition

Abstract

To provide a polyurea resin composition which has good workability such as a long working time (pot life), and is excellent in electric insulation property.SOLUTION: A polyurea resin composition contains (A) an isocyanate group-containing compound, (B) an aromatic amine compound, and (C) a plasticizer, wherein (A) the isocyanate group-containing compound contains (A1) an isocyanate group-containing compound having at least one aromatic ring selected from the group consisting of an aromatic isocyanate compound, its polynuclear, its modifier, and its urethane prepolymer, (B) the aromatic amine compound contains (B1) polytetramethylene oxide-di-p-aminobenzoate, an equivalent ratio (NCO / NH2) of an isocyanate group in (A1) the isocyanate group-containing compound having the aromatic ring to an amino group in (B1) the polytetramethylene oxide-di-p-aminobenzoate is 0.5 to 2.0, and a content of (C) the plasticizer is 40 pts.mass or more with respect to 100 pts.mass of (A1) the isocyanate group-containing compound having the aromatic ring.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyurea resin composition. [Background technology]

[0002] In order to protect electrical and electronic components from the effects of external environmental factors (e.g., physical factors such as heat, vibration, and dropping; ultraviolet rays; chemical factors such as moisture and salt); they are sometimes encapsulated using thermosetting resin encapsulants. In particular, for electrical and electronic components used in automobile engines, water heaters, etc., polyurethane resin potting sealing has been mainly used so far because of its excellent performance such as moisture resistance, low-temperature curing property, and electrical properties.

[0003] However, in recent years, in addition to the conventional properties described above, sealing materials used in electric and electronic parts are required to have properties such as low-temperature rapid curing and short-time curing. Such polyurethane resins, characterized by low-temperature, fast curing, contain large amounts of tin catalysts to enhance reactivity, which has the problem of short usable life.Furthermore, polyurethane resins containing large amounts of tin catalysts have the problem of being prone to deterioration under high temperature and humidity.

[0004] On the other hand, in addition to polyurethane resins, polyurea resins are also known as thermosetting resins. These polyurea resins are produced by the reaction of an amino group-containing compound with an isocyanate group-containing compound, and are known to have higher reactivity and durability than polyurethane resins.

[0005] However, due to its high reactivity, polyurea resins are difficult to mold, and when they are compounded with, for example, plasticizers, fillers, etc., they suffer from problems such as a decrease in electrical insulation, and therefore polyurea resins have rarely been used in electrical and electronic component applications.

[0006] For example, Patent Document 1 describes a two-component room temperature curing urethane coating waterproofing material composition containing a polyurea resin. In Patent Document 1, the pot life is defined as the time until the viscosity of the composition exceeds 30 Pa s under conditions of a rotation speed of 10 rpm and 20°C, and a pot life of 30 minutes or more is determined to be excellent in workability (paragraph

[0049] of Patent Document 1).

[0007] However, in the casting process of potting agents for general electronic components, workability is significantly reduced when the viscosity of the composition exceeds 10 Pa·s, and therefore the pot life in Patent Document 1 cannot be said to be sufficient for potting work. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-113370 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to provide a polyurea resin composition that has a long pot life and excellent touch curability at room temperature, as well as excellent electrical insulation properties and durability in high-temperature, high-humidity environments. [Means for solving the problem]

[0010] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a polyurea resin composition containing an isocyanate group-containing compound, an aromatic amine compound, and a plasticizer, wherein the isocyanate group-containing compound has an aromatic ring, the aromatic amine compound is polytetramethylene oxide-di-p-aminobenzoate, the amount of the plasticizer is 40 parts by mass or more per 100 parts by mass of the isocyanate group-containing compound having an aromatic ring, and the equivalent ratio (NCO / NH2) of the isocyanate groups in the isocyanate group-containing compound having an aromatic ring to the amino groups in the aromatic amine compound is 0.5 to 2.0. The present invention was completed based on this finding.

[0011] That is, the present invention relates to the following polyurea resin composition, etc. Section 1. (A) an isocyanate group-containing compound, (B) an aromatic amine compound, and (C) Plasticizer A polyurea resin composition comprising: the (A) isocyanate group-containing compound includes at least one (A1) isocyanate group-containing compound having an aromatic ring selected from the group consisting of aromatic isocyanate compounds, polynuclear isocyanate compounds, modified isocyanate compounds, and urethane prepolymers thereof; the (B) aromatic amine compound includes (B1) polytetramethylene oxide-di-p-aminobenzoate, the equivalent ratio (NCO / NH2) of the isocyanate group in the (A1) isocyanate group-containing compound having an aromatic ring to the amino group in the (B1) polytetramethylene oxide-di-p-aminobenzoate is 0.5 to 2.0, and The polyurea resin composition, wherein the content of the (C) plasticizer is 40 parts by mass or more per 100 parts by mass of the (A1) aromatic ring-containing isocyanate group-containing compound. Section 2. Item 2. The polyurea resin composition according to Item 1, wherein the (C) plasticizer includes an ester-based plasticizer. Section 3. Item 2. The polyurea resin composition according to Item 1, wherein the (C) plasticizer comprises at least one selected from the group consisting of a phthalate ester, a trimellitate ester, and an adipic acid ester. Section 4. Item 1. The polyurea resin composition according to Item 1, further comprising (D) a filler. Section 5. Item 2. The polyurea resin composition according to Item 1, wherein the (D) filler contains aluminum hydroxide. Section 6. Item 2. The polyurea resin composition according to Item 1, wherein the (C) plasticizer in the polyurea resin composition is 7% by mass to 41% by mass. Section 7. Volume resistivity is 1.0×10 10 Item 2. The polyurea resin composition according to Item 1, wherein the modulus of elasticity is Ω·m or more. Section 8. Item 1. An encapsulant comprising the polyurea resin composition according to item 1. Section 9. Item 9. An electric / electronic component having the encapsulant according to item 8.

[0012] In addition, among the present inventions, inventions of products such as polyurea resin compositions and cured products defined by a manufacturing process are described as product-by-process claims because it is currently impossible or impractical to specify all of the components contained or the structure of the products. [Effects of the Invention]

[0013] According to the present invention, a polyurea resin composition having a long pot life and excellent tactile curing property at room temperature, and therefore excellent workability, can be provided. Furthermore, according to the present invention, a polyurea resin composition having excellent electrical insulation properties and high-temperature and high-humidity resistance can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0014] The polyurea resin composition of the present invention will be described in detail below. In this specification, the expressions "contain" or "comprise" include the concepts of "contain," "comprise," "substantially consist," and "consist only of."

[0015] 1. Polyurea resin composition The polyurea resin composition of the present invention comprises: (A) an isocyanate group-containing compound, (B) an aromatic amine compound, and (C) Plasticizer A polyurea resin composition comprising: the (A) isocyanate group-containing compound includes at least one (A1) isocyanate group-containing compound having an aromatic ring selected from the group consisting of aromatic isocyanate compounds, polynuclear isocyanate compounds, modified isocyanate compounds, and urethane prepolymers thereof; the (B) aromatic amine compound includes (B1) polytetramethylene oxide-di-p-aminobenzoate, an isocyanate group in the (A1) isocyanate group-containing compound having an aromatic ring; The equivalent ratio (NCO / NH2) of the amino group in the (B1) polytetramethylene oxide-di-p-aminobenzoate is 0.5 to 2.0, and The polyurea resin composition has a content of the (C) plasticizer of 40 parts by mass or more per 100 parts by mass of the (A1) aromatic ring-containing isocyanate group-containing compound. The polyurea resin includes a pure polyurea resin and a hybrid polyurea resin. Pure polyurea resin is a compound primarily composed of urea bonds formed by the chemical reaction of an isocyanate-containing compound with an amine compound. It cures to the touch in just a few seconds, is solvent-free, and requires no catalysts, making it environmentally friendly. It also has excellent chemical resistance, including acid and alkali resistance, and durability. The hybrid polyurea resin is a compound mainly composed of urethane bonds and urea bonds formed by a chemical reaction between an isocyanate group-containing compound, an amine compound, and an alcohol compound. In this specification, the hybrid polyurea resin may be any resin containing both urea bonds and urethane bonds in its molecular structure, and may also be referred to as polyurethane polyurea resin, polyurethane urea resin, polyurea urethane resin, etc.

[0016] (A) Isocyanate group-containing compound In the present invention, the (A) isocyanate group-containing compound includes (A1) an isocyanate group-containing compound having an aromatic ring.

[0017] (A1) Aromatic ring-containing isocyanate group-containing compound The (A1) isocyanate group-containing compound having an aromatic ring is not particularly limited as long as it has two or more aromatic isocyanate groups, and various components that are used or can be used in polyurea resin compositions can be used.

[0018] Specifically, examples of the (A1) isocyanate group-containing compound having an aromatic ring include: (A1-1) Aromatic polyisocyanate compound (aromatic polyisocyanate compound that is not a polynuclear compound and is not a modified compound), (A1-2) a polynuclear product of the aromatic polyisocyanate compound (A1-1); (A1-3) A modified product of the aromatic polyisocyanate compound (A1-1) (for example, (A1-3a) isocyanurate compound, (A1-3b) carbodiimide compound, (A1-3c) adduct, (A1-3d) Biuret form, (A1-3e) allophanate, etc.); (A1-4) Urethane prepolymers of the aromatic polyisocyanate compounds (A1-1) above are exemplified.

[0019] Examples of the aromatic polyisocyanate compound (A1-1) include tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate, and preferred are 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI). A specific example of such an agent is Millionate (registered trademark) MR-200 (a mixture of MDI and its polynuclear derivatives) manufactured by Tosoh Corporation.

[0020] (A1-3) Examples of modified aromatic polyisocyanate compounds include carbodiimide derivatives of 4,4'-diphenylmethane diisocyanate (MDI). In the present invention, polyisocyanates having carbodiimide groups derived from 4,4'-diphenylmethane diisocyanate (carbodiimide-modified MDI) can be used. A specific example of such a polyisocyanate is Millionate (registered trademark) MTL manufactured by Tosoh Corporation.

[0021] The aromatic polyisocyanate compound (A1-1) described above can be used as is, or it can be used as a urethane prepolymer (A1-4) obtained by reacting the aromatic isocyanate compound (A1-1) described above with a hydroxyl group-containing compound (G) described below. The urethane prepolymer (A1-4) is not particularly limited, and may be a urethane prepolymer obtained by reacting a hydroxyl group-containing compound (G) with the aromatic polyisocyanate compound (A1-1). In this case, the isocyanate groups (NCO groups) may be in excess relative to the hydroxyl groups (OH groups). The urethane prepolymer (A1-4) may contain 0.5 to 20% by mass of NCO groups.

[0022] The polyurea resin composition of the present invention preferably contains, as the (A) isocyanate group-containing compound, only (A1-1) an aromatic polyisocyanate compound; or (A1-1) an aromatic polyisocyanate compound and (A1-4) a urethane prepolymer.

[0023] (G) Hydroxyl group-containing compounds The (G) hydroxyl group-containing compound is not particularly limited, and examples thereof include (G1) polyether polyol, (G2) polyester polyol, (G3) polycarbonate diol, (G4) polyolefin polyol, and (G5) silicone polyol.

[0024] (G1) Polyether polyol The polyether polyol (G1) is not particularly limited, and examples thereof include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide using as initiators water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), and dihydroxybenzenes (catechol, resorcinol, hydroquinone, etc.). Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, propylene oxide adducts of bisphenol A (bisphenol ether polyols), and polyether carbonate diols.

[0025] The hydroxyl value of the polyether polyol (G1) is preferably from 1 to 600 mgKOH / g, more preferably from 10 to 400 mgKOH / g, and particularly preferably from 25 to 150 mgKOH / g.

[0026] The average number of functional groups of the polyether polyol (G1) is usually 1.5 to 5, preferably 2 to 4, and more preferably 1.8 to 2.3.

[0027] The number average molecular weight (Mn) of the polyether polyol (G1) is usually in the range of 100 to 5,000, preferably in the range of 300 to 4,000, and more preferably in the range of 500 to 3,500.

[0028] The (G1) polyether polyols can be used alone or in combination of two or more. Among these, polypropylene diol, polytetramethylene glycol, and propylene oxide adduct of bisphenol A (bisphenol ether polyol) are preferred as the polyether polyol (G1).

[0029] (G2) Polyester polyol The polyester polyol (G2) is not particularly limited, and examples thereof include condensation type polyester polyols and castor oil-based polyols.

[0030] Condensation type polyester polyols include aliphatic dicarboxylic acids (succinic acid (C4H6O4), adipic acid (C6H 10 O4), azelaic acid (C9H 16 O4), sebacic acid (C 10 H 18Examples of suitable condensation polyester polyols include polycarboxylic acids having 2 to 10 carbon atoms or esters thereof, and more preferred condensation polyester polyols include polycarboxylic acids obtained by reacting a polycarboxylic acid such as adipic acid, sebacic acid, or isophthalic acid with a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, or polypropylene glycol.

[0031] Specific examples of condensation type polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyethylene terephthalate diol, polyhexamethylene isophthalate diol, polyethylene terephthalate diol, polyhexamethylene terephthalate diol, polyneopentyl terephthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene Examples of the copolymer include hexamethylene adipate diol, polydiethylene adipate diol, poly(polytetramethylene ether) adipate diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, poly(butylene adipate / butylene terephthalate) copolymer diol, and poly(3-methylpentylene adipate / 3-methylpentylene terephthalate) copolymer diol.

[0032] Commercially available condensation polyester polyols include, for example, Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, and OD-X-2420 (adipate) manufactured by DIC Corporation. Polyester polyols), OD-X-2523, OD-X-2555, OD-X-2560, Kuraray Co., Ltd. polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016; Sun-Estar 2610 [polyethylene adipate diol with Mn=1,000, manufactured by Sanyo Chemical Industries, Ltd.], Sun-Estar 4620 [polytetramethylene adipate diol with Mn=2,000], Sun-Estar 2620 [polyethylene adipate diol with Mn=2,000, manufactured by Sanyo Chemical Industries, Ltd.], Kuraray Polyol P-2010 [poly-3-methyl-1,5-pentylene adipate diol with Mn=2,000], Kuraray Polyol P-3010 [poly-3-methyl-1,5-pentylene adipate diol with Mn=3,000], Kuraray Polyol Kuraray Polyol P-6010 [poly-3-methyl-1,5-pentylene adipate diol with Mn=6000], Kuraray Polyol P-520 [poly-3-methyl-1,5-pentylene terephthalate diol with Mn=500], Kuraray Polyol P-1020 [poly-3-methyl-1,5-pentylene terephthalate diol with Mn=1000], Kuraray Polyol P-2020 [poly-3-methyl-1,5-pentylene terephthalate diol with Mn=2000], Kuraray Polyol P-530 [poly-3-methyl-1,5-pentylene isoflurane diol with Mn=500] diol], Kuraray Polyol P-1030 [poly-3-methyl-1,5-pentylene isophthalate diol with Mn=1000], Kuraray Polyol P-2030 [poly-3-methyl-1,5-pentylene isophthalate diol with Mn=2000], Kuraray Polyol P-1011 [poly(3-methyl-1,5-pentylene adipate / 3-methyl-1,5-pentylene terephthalate) copolymer diol with Mn=1,000], Kuraray Polyol P-2011 [poly(3-methyl-1,5-pentylene adipate / 3- Examples of suitable poly(3-methyl-1,5-pentylene adipate / 3-methyl-1,5-pentylene isophthalate) copolymer diols include Kuraray Polyol P-1012 [poly(3-methyl-1,5-pentylene adipate / 3-methyl-1,5-pentylene isophthalate) copolymer diols with Mn=1000], Kuraray Polyol P-1012 [poly(3-methyl-1,5-pentylene adipate / 3-methyl-1,5-pentylene isophthalate) copolymer diols with Mn=2000], and Kuraray Polyol P-2050 [poly-3-methyl-1,5-pentylene sebacate diol with Mn=2000].

[0033] The castor oil-based polyol is not particularly limited, and examples thereof include castor oil, castor oil derivatives, etc. As the (G2) polyester polyol, a castor oil-based polyol is preferred.

[0034] Commercially available castor oil-based polyols include URIC H-1824, URIC H-30, and URIC Y-403 manufactured by Ito Oil Mills, Ltd.

[0035] Examples of castor oil derivatives include castor oil fatty acids, hydrogenated castor oils obtained by hydrogenating castor oil or castor oil fatty acids, transesterification products of castor oil and other fats and oils, reaction products of castor oil and polyhydric alcohols, esterification products of castor oil fatty acids and polyhydric alcohols, and compounds obtained by addition polymerization of these with alkylene oxides. Among the above castor oil-based polyols, it is preferable to use esterification products of castor oil or castor oil fatty acids and polyhydric alcohols.

[0036] Examples of the hydrogenated castor oil include those disclosed in Japanese Patent Application Laid-Open No. 2-298574. Hydrogenated castor oil can be obtained by hydrogenating the above-mentioned castor oil-based polyol.

[0037] The average hydroxyl value of the castor oil-based polyol is preferably 10 to 400 mgKOH / g, and more preferably 20 to 200 mgKOH / g.

[0038] The average number of functional groups in the castor oil-based polyol is usually 1.5 to 3.5, more preferably 1.7 to 3, and even more preferably 1.9 to 2.7.

[0039] The number average molecular weight (Mn) of the above castor oil-based polyol is usually in the range of 100 to 5,000, preferably in the range of 200 to 4,000, and more preferably in the range of 300 to 3,500.

[0040] In this specification, the number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC) (polystyrene equivalent). Specifically, the number average molecular weight by GPC is measured using a Shodex GPC System 21 measuring device manufactured by Showa Denko K.K., a Shodex LF-804 / KF-803 / KF-804 column manufactured by Showa Denko K.K., and NMP as the mobile phase at a column temperature of 40°C, and can be calculated using a calibration curve of standard polystyrene.

[0041] Examples of condensation polyester polyols include polyester polyols obtained by condensing a low-molecular-weight polyol having a number average molecular weight (Mn) of less than 300 with a polycarboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof. Among the low-molecular-weight polyols having a number-average molecular weight (Mn) of less than 300 used in the condensation polyester polyol, preferred are ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, low-molar adducts of bisphenol A with ethylene oxide (hereinafter abbreviated as "EO") or 1,2- or 1,3-propylene oxide (hereinafter abbreviated as "PO"), and mixtures thereof.

[0042] The average hydroxyl value of the condensation type polyester polyol is preferably from 10 to 400 mgKOH / g, and more preferably from 20 to 200 mgKOH / g.

[0043] The average number of functional groups of the condensation type polyester polyol is usually 1.5 to 3.5, more preferably 1.8 to 3, and even more preferably 2 to 2.7.

[0044] The number average molecular weight (Mn) of the condensation type polyester polyol is usually in the range of 100 to 6,000, preferably in the range of 200 to 5,000, and more preferably in the range of 300 to 4,000.

[0045] The polyester polyol (G2) can be used alone or in combination of two or more.

[0046] (G3) Polycarbonate polyol The polycarbonate polyol (G3) is not particularly limited, and examples thereof include reaction products of polyols with carbonate compounds such as dialkyl carbonates, alkylene carbonates, and diaryl carbonates.

[0047] Examples of dialkyl carbonates include dimethyl carbonate and diethyl carbonate. Examples of alkylene carbonates include ethylene carbonate. Examples of diaryl carbonates include diphenyl carbonate. Polycarbonate polyols obtained by polycondensation of the above polyol components with phosgene; polycarbonate polyols obtained by transesterification of the above polyol components with carbonate diesters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate; copolymer polycarbonate polyols obtained by combining two or more of the above polyol components; polycarbonate polyols obtained by esterification of the above various polycarbonate polyols with carboxyl group-containing compounds; and the above various polycarbonate polyols. Examples of the polycarbonate polyol include polycarbonate polyols obtained by etherifying the above-mentioned polycarbonate polyols with ester compounds, polycarbonate polyols obtained by transesterifying the above-mentioned polycarbonate polyols with hydroxyl group-containing compounds, polyester-based polycarbonate polyols obtained by polycondensation of the above-mentioned polycarbonate polyols with dicarboxylic acid compounds, and copolymerized polyether-based polycarbonate polyols obtained by copolymerizing the above-mentioned polycarbonate polyols with alkylene oxides. The polycarbonate polyol (G3) can also be called a polycarbonate diol.

[0048] (G4) Polyolefin polyol The polyolefin polyol (G4) is not particularly limited, and may be, for example, a polymer of a radically polymerizable monomer having two or more unsaturated double bonds, or a copolymer of such a radically polymerizable monomer with another radically polymerizable monomer, and has two or more hydroxyl groups.

[0049] (G4) Polyolefin polyols include polyolefin polyols (for example, polybutadiene polyols, polyisoprene polyols), hydrogenated polyolefin polyols (hydrogenated polyolefin polyols), and the like.

[0050] Examples of (G4) polyolefin polyols include polybutadiene polyols, polyisoprene polyols, etc. Commercially available polyolefin polyols include polybutadiene polyols (NISSO-PBG series (G-1000, G-2000, G-3000, etc.) manufactured by Nippon Soda Co., Ltd., Poly Bd (registered trademark) series (R-45M, R-45HT, CS-15, CN-15, etc.) manufactured by ARCO Corporation of the United States), and polyisoprene polyols (Poly ip manufactured by Idemitsu Kosan Co., Ltd.).

[0051] Examples of hydrogenated polyolefin polyols (hydrogenated polyolefin polyols) include hydrogenated polybutadiene polyols, hydrogenated polyisoprene polyols, etc. Commercially available hydrogenated polyolefin polyols include hydrogenated polybutadiene polyols (NISSO-PBGI series (GI-1000, GI-2000, GI-3000, etc.) manufactured by Nippon Soda Co., Ltd.), hydrogenated polyolefin polyols (EPOL manufactured by Idemitsu Kosan Co., Ltd.), etc.

[0052] The hydroxyl value of the (G4) polyolefin polyol is preferably from 10 to 120 mgKOH / g, more preferably from 25 to 110 mgKOH / g, and particularly preferably from 30 to 100 mgKOH / g.

[0053] The average number of functional groups of the polyolefin polyol (G4) is usually 1.5 to 5, preferably 1.6 to 3, and more preferably 1.7 to 2.5.

[0054] The number average molecular weight (Mn) of the polyolefin polyol (G4) is usually in the range of 100 to 5,000, preferably in the range of 1,000 to 4,000, and more preferably in the range of 1,500 to 3,500.

[0055] The hydroxyl group content of the (G4) polyolefin polyol is not particularly limited and is usually 0.001 to 3 mol / kg, preferably 0.01 to 2 mol / kg, and more preferably 0.1 to 1.2 mol / kg.

[0056] The viscosity of the (G4) polyolefin polyol (30° C.) is usually in the range of 0.01 to 500 Pa·s, preferably in the range of 0.1 to 300 Pa·s, and more preferably in the range of 1 to 150 Pa·s. do.

[0057] The iodine value of the (G4) polyolefin polyol is usually in the range of 1 to 1000 g / 100 g, preferably in the range of 5 to 500 g / 100 g, and more preferably in the range of 10 to 100 g / 100 g.

[0058] The (G4) polyolefin polyols can be used alone or in combination of two or more. Among these, the (G4) polyolefin polyol is preferably a polybutadiene polyol, and more preferably a polybutadiene polyol having a number average molecular weight (Mn) of 1200 or more and a hydroxyl value of 20 to 150 mgKOH / g.

[0059] (G5) Silicone polyol The silicone polyol (G5) is not particularly limited, and examples thereof include those in which two or more hydroxyl groups and / or organic groups having hydroxyl groups are introduced into the terminals and / or side chains of dimethylpolysiloxane.Preferred examples of the silicone polyol (G5) include carbinol-modified silicone oil, polyether-modified silicone oil, and silanol-terminated silicone oil. Examples of commercially available silicone polyols (G5) include "Silaplane FMDA26" manufactured by JNC Corporation, and "Shin-Etsu Silicones" carbinol-modified KF-6000, KF-6001, KF-6002, KF-6003, X-22-170BX, silanol-modified X-21-5841, KF-9701, and diol-modified X-22-176F manufactured by Shin-Etsu Chemical Co., Ltd.

[0060] The (G) hydroxyl group-containing compound used in the present invention may further contain polyol compounds other than the above (G1) to (G5) (sometimes referred to as other polyols).

[0061] Examples of other polyols include dimer acid polyols; (G3) polycarbonate polyols; polycaprolactone polyols; acrylic polyols; amine polyols; and hydrogenated versions of these polyols.

[0062] The dimer acid polyol is not particularly limited, and for example, known dimer acid polyols can be used.

[0063] The polycaprolactone polyol is not particularly limited, and examples thereof include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and δ-valerolactone.

[0064] Examples of acrylic polyols include copolymers obtained by copolymerizing a hydroxyl group-containing acrylate with a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.

[0065] Examples of hydroxyl group-containing acrylates include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, and polyhydroxyalkyl fumarate, and preferably 2-hydroxyethyl (meth)acrylate.

[0066] Examples of copolymerizable vinyl monomers include C monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl acrylate. 1-12 Alkyl (meth)acrylate; For example, aromatic vinyls such as styrene, vinyltoluene, and α-methylstyrene; For example, vinyl cyanides such as (meth)acrylonitrile; For example, vinyl monomers containing a carboxyl group, such as (meth)acrylic acid, fumaric acid, maleic acid, and itaconic acid, or alkyl esters thereof; For example, alkane polyol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and trimethylolpropane tri(meth)acrylate; For example, vinyl monomers containing an isocyanate group such as 3-(2-isocyanate-2-propyl)-α-methylstyrene can be used.

[0067] The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylates and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator.

[0068] The acrylic polyols include, for example, (G5) silicone polyols, fluorine polyols, and the like.

[0069] Examples of the fluorine polyol include acrylic polyols blended with a fluorine compound containing a vinyl group, such as tetrafluoroethylene or chlorotrifluoroethylene, as a copolymerizable vinyl monomer in the copolymerization of the acrylic polyol described above.

[0070] The vinyl monomer-modified polyol can be obtained by reacting the above-mentioned high molecular weight polyol with a vinyl monomer.

[0071] The amine polyol is not particularly limited, and examples thereof include diethanolamine, triethanolamine, aliphatic amine polyols, etc. Commercially available aliphatic amine polyols include "Sannyx NP-300" manufactured by Sanyo Chemical Industries, Ltd.

[0072] The (G) hydroxyl group-containing compounds can be used either alone or in combination of two or more. Of these, (G1) polyether polyol, (G2) polyester polyol, polybutadiene polyol, and castor oil polyol are preferred.

[0073] Examples of the combination of the (A1) aromatic ring-containing isocyanate group-containing compound and the (G) hydroxyl group-containing compound when producing the (A1-4) urethane prepolymer include: 4,4'-diphenylmethane diisocyanate, Examples include a combination with at least one polyol selected from the group consisting of polypropylene glycol, polybutadiene polyol, and polyester polyol.

[0074] When producing the urethane prepolymer (A1-4), the amounts of the aromatic ring-containing isocyanate group-containing compound (A1) and the hydroxyl group-containing compound (G) are such that the NCO group / OH group (equivalent ratio) is preferably 2 to 10, and more preferably 4 to 8.

[0075] The method for producing the urethane prepolymer (A1-4) is not particularly limited, and it can be produced, for example, by heating and stirring the hydroxyl group-containing compound (G) and the isocyanate group-containing compound having an aromatic ring (A1) in the above-mentioned equivalent ratio at 50 to 130° C. If necessary, a urethane catalyst such as an organotin compound, organobismuth, or amine can be used. The urethane prepolymers (A1-4) can be used either alone or in combination of two or more.

[0076] The viscosity of the (A1) isocyanate group-containing compound having an aromatic ring varies depending on the type of isocyanate compound, whether it is modified, etc., but is not particularly limited. For example, in the case of (A1-1) aromatic polyisocyanate compound, (A1-3) its modified product, and (A1-2) polynuclear compound (preferably a carbodiimide compound and polynuclear compound of an aromatic polyisocyanate compound), the viscosity at 25°C is, for example, 5 to 200 mPa·s, preferably 10 to 150 mPa·s, more preferably 15 to 100 mPa·s, and even more preferably 20 to 80 mPa·s.

[0077] The NCO content of the (A1) aromatic ring-containing isocyanate group-containing compound is not particularly limited, but is, for example, 5 to 45%, more preferably 10 to 40%, and even more preferably 20 to 35%.

[0078] As the (A1) aromatic ring-containing isocyanate group-containing compound, from the viewpoint of extending the usable time and suppressing the deterioration of electrical insulation, preferably (A1-3) allophanate-modified or urethane-modified aromatic polyisocyanate compounds, (A1-1) an aromatic polyisocyanate compound or (A1-2) a polynuclear aromatic polyisocyanate compound (more preferably, 4,4'-diphenylmethane diisocyanate (MDI) or a polynuclear MDI, and a mixture of MDI and a polynuclear MDI), (A1-3) Carbodiimide derivatives of aromatic polyisocyanate compounds (more preferably, polyisocyanates having carbodiimide groups derived from 4,4'-diphenylmethane diisocyanate (carbodiimide-modified MDI)) are included.

[0079] The (A1) aromatic ring-containing isocyanate group-containing compound is preferably 4,4'-diphenylmethane diisocyanate or a modified or polynuclear compound thereof, specifically 4,4'-diphenylmethane diisocyanate (MDI) or a polynuclear compound of MDI, a mixture of MDI and a polynuclear compound of MDI, and More preferred are carbodiimide-modified products of 4,4'-diphenylmethane diisocyanate, i.e., polyisocyanates having carbodiimide groups derived from 4,4'-diphenylmethane diisocyanate (carbodiimide-modified MDI), and the urethane prepolymer (A1-4) obtained by reacting the above-mentioned (A1) isocyanate group-containing compound having an aromatic ring with (G) a hydroxyl group-containing compound.

[0080] Among these, preferred commercially available products of the (A1) isocyanate group-containing compound having an aromatic ring include Millionate (registered trademark) MT (manufactured by Tosoh Corporation), Millionate (registered trademark) NM (manufactured by Tosoh Corporation), Millionate (registered trademark) MR-200 (manufactured by Tosoh Corporation), and Millionate (registered trademark) MTL (manufactured by Tosoh Corporation), with Millionate (registered trademark) MR-200 (manufactured by Tosoh Corporation) and Millionate (registered trademark) MTL (manufactured by Tosoh Corporation) being more preferred. Commercially available products of the (A1-4) urethane prepolymer having an isocyanate group terminal include Coronate 4088 (manufactured by Tosoh Corporation) and RU-42B (manufactured by Nisshin Resin Co., Ltd.), with N-2047U (manufactured by Ito Oil Mills Co., Ltd.) being more preferred.

[0081] The (A1) aromatic ring-containing isocyanate group-containing compound may be used alone or in any combination of two or more. Among these, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), a mixture of 2,4-TDI and 2,6-TDI, a dimer of 2,4-TDI, xylylene diisocyanate (XDI), metaxylylene diisocyanate (MXDI), tetramethylxylylene diisocyanate, m-phenylene diisocyanate, 4,4'-biphenyl diisocyanate, diphenyl ether-4,4'-diisocyanate, 3,3'-ditoluene-4,4'-diisocyanate (TODI), dianisidine diisocyanate (DADI), 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, and the like are preferred, with 4,4'-diphenylmethane diisocyanate (MDI) being more preferred.

[0082] The content of the (A1) aromatic ring-containing isocyanate group-containing compound is not particularly limited as long as it is an amount that can be used in a polyurea resin composition, and the content is, for example, usually 10 to 700 parts by mass, preferably 15 to 300 parts by mass, and more preferably 20 to 200 parts by mass, per 100 parts by mass of the (B) aromatic amine compound. The content of the (A1) isocyanate group-containing compound having an aromatic ring is, for example, usually 4 to 90 mass %, preferably 5 to 75 mass %, and more preferably 6 to 30 mass %, relative to 100 mass % of the polyurea resin composition.

[0083] The polyurea resin composition of the present invention may further contain (A) an isocyanate group-containing compound other than (A1) an isocyanate group-containing compound having an aromatic ring.

[0084] Examples of the (A) isocyanate group-containing compound other than the (A1) isocyanate group-containing compound having an aromatic ring include (A2) aliphatic isocyanate compounds and (A3) alicyclic isocyanate compounds.

[0085] The (A2) aliphatic isocyanate compound is not particularly limited, and examples thereof include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHMDI), dodecamethylene diisocyanate, lysine diisocyanate (LDI), and lysine triisocyanate (LTI), and modified compounds thereof may also be used.

[0086] The alicyclic isocyanate compound (A3) is not particularly limited, and examples thereof include isophorone diisocyanate (IPDI), cyclohexylene diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate, hydrogenated XDI (H6XDI), hydrogenated MDI (H 12 Examples of the diisocyanate include norbornene diisocyanate (MDI), norbornene diisocyanate (NBDI), and modified compounds thereof may also be used.

[0087] When (A) an isocyanate group-containing compound other than (A1) an isocyanate group-containing compound having an aromatic ring is contained, the content thereof is not particularly limited and may be, for example, 0.01 to 30 mass %.

[0088] (B) Aromatic amine compounds The aromatic amine compound (B) used in the present invention is (B1) polytetramethylene oxide-di-p-aminobenzoate. There are no particular limitations on the polytetramethylene oxide-di-p-aminobenzoate (B1). The number of amino groups in the polytetramethylene oxide-di-p-aminobenzoate (B1) is preferably 2 to 3. The molecular weight of the polytetramethylene oxide-di-p-aminobenzoate (B1) is preferably 400 to 2,000. The molecular weight of (B1) polytetramethylene oxide-di-p-aminobenzoate is a number average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and converted into standard polystyrene.

[0089] (B1) Polytetramethylene oxide-di-p-aminobenzoate is represented by the following general formula (1):

[0090] [ka]

[0091] The compound is represented by the formula: where x can be in a range corresponding to the molecular weight (e.g., 400 to 2000) of (B1) polytetramethylene oxide-di-p-aminobenzoate. The substitution position of the amino group (NH2) in the formula may be any position (ortho-, meta-, or para-position) on the benzene ring. The substitution positions of the two amino groups may be the same or different.

[0092] (B1) Specific examples of polytetramethylene oxide-di-p-aminobenzoate include polytetramethylene glycol di-p-aminobenzoate.

[0093] From the viewpoint of extending the usable time and improving the electrical insulation, the molecular weight of (B1) polytetramethylene oxide-di-p-aminobenzoate is preferably 480 to 1500, more preferably 700 to 1250. The molecular weight of (B1) polytetramethylene oxide-di-p-aminobenzoate is a number average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. Regarding the molecular weight of (B1) polytetramethylene oxide-di-p-aminobenzoate, a higher molecular weight leads to a longer pot life than a lower molecular weight. Also, a lower molecular weight leads to a higher hardness than a higher molecular weight.

[0094] The equivalent ratio (isocyanate group / amino group (active hydrogen group)) of the isocyanate group in the isocyanate group-containing compound having an aromatic ring (A1) to the amino group (active hydrogen group) in the aromatic amine compound (B) is usually 0.5 to 2.0, preferably 0.7 to 1.8, and more preferably 1.1 to 1.3.

[0095] The content of the (B) aromatic amine compound is, for example, usually 10 to 85 mass %, preferably 20 to 75 mass %, and more preferably 35 to 70 mass %, relative to 100 mass % of the polyurea resin composition.

[0096] The polyurea resin composition of the present invention may further contain (B) an aromatic amine compound other than (B1) polytetramethylene oxide-di-p-aminobenzoate (hereinafter referred to as "(B2) other aromatic amine compound"). (B2) The other aromatic amine compound is preferably an aromatic compound containing two amino groups (diamine) or an aromatic compound containing two or more amino groups (for example, triamine, tetraamine, polyamine, etc.). Examples of the (B2) other aromatic amine compounds include low molecular weight aromatic amines such as metaphenylenediamine, diethyltoluenediamine, 4,4'-diamino-3,3'-dichlorodiphenylmethane, and trimethylene-bis(4-aminobenzoate); Examples include (B1) polymeric aromatic amines other than polytetramethylene oxide-di-p-aminobenzoate, such as poly(tetramethylene / 3-methyltetramethylene ether) glycol bis(4-aminobenzoate).

[0097] When (B2) another aromatic amine compound is contained, the content thereof is not particularly limited, and may be, for example, 0.01 to 10% by mass.

[0098] (C) Plasticizer The polyurea resin composition of the present invention contains (C) a plasticizer.

[0099] The plasticizer used in the present invention is not particularly limited, and examples thereof include ester-based plasticizers and hydrocarbon-based plasticizers.

[0100] The ester-based plasticizer is not particularly limited as long as it contains an ester group, and examples of the ester-based plasticizer include phthalates, adipates, castor oil esters, trimellitates, pyromellitates, phosphates, terephthalates, citrates, and benzoates.

[0101] Examples of phthalate esters include dioctyl phthalate, diisononyl phthalate (diisononyl phthalate) (DINP), and diundecyl phthalate. Examples of adipate esters include dioctyl adipate, diisononyl adipate, and diisodecyl adipate. Examples of castor oil esters include methyl acetylricinoleate, butyl acetylricinoleate, acetylated ricinoleic acid triglyceride, and acetylated polyricinoleic acid triglyceride. Examples of trimellitic acid esters include trioctyl trimellitate (TOTM) and triisononyl trimellitate. Examples of phosphate esters include pyromellitic acid esters such as tetraoctyl pyromellitate and tetraisononyl pyromellitate; triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), and the like. Examples of terephthalic acid esters include bis(2-ethylhexyl) terephthalate. Examples of citrate esters include tributyl acetyl citrate. Examples of benzoic acid esters include glycol benzoate.

[0102] As the ester-based plasticizer, phthalate ester, trimellitate ester, and adipate ester are preferred, and phthalate ester and trimellitate ester are more preferred.

[0103] Examples of hydrocarbon plasticizers include naphthenic hydrocarbons, aromatic hydrocarbons, paraffinic hydrocarbons, and olefinic hydrocarbons.

[0104] The naphthenic hydrocarbon is not particularly limited as long as it has at least one saturated ring in the molecule, and examples of naphthenic hydrocarbons include dicyclopentadiene. Specific examples of naphthenic hydrocarbons include SUN 6 INSULATING OIL (Japan Sun Oil Co., Ltd.), Diana Process Oil NS (90S, 100), Diana Process Oil NM (280), Diana Process Oil NP (24, 90S, 100), Diana Process Oil NR (26) (all of which are manufactured by Idemitsu Kosan Co., Ltd.), the SUNTHENE series (e.g., 410, 450, 4240, 250J), the SUPURE series (e.g., N90, NX90) (all of which are manufactured by Japan Sun Oil Co., Ltd.), and the SNH series (e.g., SNH3, SNH46) (all of which are manufactured by Sankyo Yuka Kogyo Co., Ltd.).

[0105] The aromatic hydrocarbon is not particularly limited as long as it has at least one aromatic ring in the molecule. Specific examples of aromatic hydrocarbons include Diana Process Oil AC (460), Diana Process Oil AH (16) (both manufactured by Idemitsu Kosan Co., Ltd.), and JSO AROMA 790 (Japan Sun Oil Co., Ltd.).

[0106] Examples of paraffinic hydrocarbons include normal paraffinic hydrocarbons and isoparaffinic hydrocarbons, and include isoprene, piperylene, styrene, vinyltoluene, indene, terpene resins (α-pinene, β-pinene, dipentene, etc.), aromatic modified terpene resins, and terpene phenol resins. The paraffinic hydrocarbon is not particularly limited, and specific examples include Diana Process Oil PW (90, 380) (Idemitsu Kosan Co., Ltd.), SUNPAR series (e.g., 107, 150, 2280), and SUPURE series (e.g., LW70, P100) (all Nippon Sun Oil Co., Ltd.). The hydrocarbon plasticizer may be a paraphene-naphthene hydrocarbon mixture.

[0107] Examples of olefin hydrocarbons include ethylene and α-olefin co-oligomers, poly-α-olefins, hydrogenated poly-α-olefins, etc. The hydrogenation method is not particularly limited, and known methods can be used. The olefin hydrocarbon is not particularly limited, and specific examples include α-olefins sold as Linearene 10, Linearene 12, etc. (Idemitsu Kosan Co., Ltd.), Durasyn (INEOS Oligomers), polyisoprene sold as Kurapren (registered trademark) LIR-30, Kurapren (registered trademark) LIR-410, Kurapren (registered trademark) UC-102M, Kurapren (registered trademark) LIR-290, etc. (Kuraray Co., Ltd.), polybutadienes sold as Kurapren (registered trademark) LBR-302, Kurapren (registered trademark) LBR-307, Kurapren (registered trademark) LBR-820, etc. (Kuraray Co., Ltd.), polystyrene butadiene sold as Kurapren (registered trademark) L-SBR-820, etc. (Kuraray Co., Ltd.), and 1,2-polybutadiene homopolymer B series (e.g., B-1000, B-3000, etc.) (Nippon Soda Co., Ltd.).

[0108] As the hydrocarbon-based plasticizer, aromatic hydrocarbons are preferred.

[0109] The above plasticizers can be used alone or in combination of two or more.

[0110] Among these, ester-based plasticizers are preferred, and phthalate esters, trimellitates, and adipates are more preferred. Addition of these ester-based plasticizers makes it possible to extend the usable time while maintaining the insulating properties.

[0111] The viscosity of the (C) plasticizer at 25°C is usually 5 to 6000 mPa·s, preferably 10 to 5000 mPa·s, and more preferably 20 to 4000 mPa·s. The viscosity is measured using a Brookfield viscometer. Specifically, the required amount of sample is placed in a container and the sample temperature is adjusted to 23±0.5°C. Next, the viscosity is measured after rotating the sample at a specified rotation speed for 60 seconds using a specified rotor.

[0112] The content of the (C) plasticizer is generally 40 to 400 parts by mass, preferably 45 to 350 parts by mass, and more preferably 50 to 300 parts by mass, per 100 parts by mass of the (A1) aromatic ring-containing isocyanate group-containing compound. The content of the (C) plasticizer is, for example, usually 7 to 60 mass %, preferably 10 to 50 mass %, and more preferably 15 to 40 mass %, relative to 100 mass % of the polyurea resin composition.

[0113] Other ingredients The polyurea resin composition of the present invention may further contain various additives, as needed, such as a filler, a polymerization catalyst, an antifoaming agent, a liquid flame retardant, a liquid flame retardant auxiliary, a crosslinking agent (chain extender), an antioxidant, a tackifier, a curing accelerator, a colorant, an ultraviolet absorber, a moisture absorber, an antifungal agent, and a silane coupling agent.

[0114] (D) Filler The polyurea resin composition of the present invention may contain a filler, such as an inorganic filler, an organic filler, a solid flame retardant, a solid flame retardant auxiliary, a filler, or a pigment, as long as the filler does not affect the effects of the present invention.

[0115] The inorganic filler used in the present invention is not particularly limited, and examples thereof include metal hydroxides, metal oxides, metal nitrides, natural minerals, zeolites, etc. Surface-treated metal oxides, etc. may also be used. Methods for treating the surface of the metal oxides, etc., include, for example, oxidation treatment and treatment with a surface treatment agent such as a silane coupling agent.

[0116] Examples of metal hydroxides include aluminum hydroxide, magnesium hydroxide, etc. Here, aluminum hydroxide and magnesium hydroxide also function as flame retardants.

[0117] Examples of metal oxides include aluminum oxide (alumina), magnesium oxide, silicon dioxide (silica, etc.), and titanium oxide.

[0118] Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride.

[0119] Examples of natural minerals include calcium carbonate, talc (silicate mineral), mica, and silica.

[0120] The zeolite is not particularly limited, and any zeolite used in known polyurethane resin compositions can be used.

[0121] Among these, the zeolite is preferably a crystalline hydrous aluminosilicate of an alkali metal or alkaline earth metal.

[0122] The crystal form of the zeolite is not particularly limited, and examples thereof include A-type, X-type, LSX-type, etc. Among these, the preferred crystal form is A-type.

[0123] The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples thereof include potassium, sodium, calcium, lithium, etc. Among these, potassium is preferred.

[0124] The inorganic fillers may be used alone or in combination of two or more. Among the inorganic fillers, aluminum hydroxide, magnesium hydroxide, alumina, magnesium oxide, and silica also function as solid flame retardants.

[0125] Examples of the flame retardant include phosphorus-based flame retardants, inorganic flame retardants, bromine-based flame retardants, and chlorine-based flame retardants. Examples of phosphorus-based flame retardants that can be used include red phosphorus, phosphate esters, condensed phosphate esters, aromatic condensed phosphate esters, aliphatic phosphate amidates, and phosphazenes. In addition to the aluminum hydroxide, magnesium hydroxide, alumina, magnesium oxide, and silica described above as inorganic fillers, for example, antimony trioxide, antimony pentoxide, ammonium borate, zinc borate, etc. can be used as the inorganic flame retardant. Examples of bromine-based flame retardants include hexabromobenzene, decabromodiphenyl oxide (DBDPO), tetrabromobisphenol A (TBBA), and ethylenebis(pentabromophenyl). Examples of chlorine-based flame retardants include chlorinated paraffin, perchlorocyclopentadecanone, and chlorendic acid.

[0126] The flame retardant aid is not particularly limited, and examples thereof include nitrogen-based compounds, radical trapping agents such as hindered amines, and the like. A flame retardant synergist can be blended together with the flame retardant. Examples of the nitrogen-based compound include melamine cyanurate, triazine compounds, and guanidine compounds. Examples of the hindered amine include monomeric amines such as bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 4-benzoyloxy-2,2',6,6'-tetramethylpiperidine, and bis(1,2,2,6,6-pentamethyl-4-piperidyl){[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl}butylmalonate; and poly{[6-(1,1,3,3-tetramethyl oligomer types such as (2,2,6,6-tetramethyl-4-piperidyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)iminol]}; polyester bond types such as a polyesterification product of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid; and those having a polymerizable unsaturated group such as 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

[0127] Commercially available examples of the hindered amine include "Tinuvin (registered trademark) 765," "Tinuvin (registered trademark) 770DF," "Tinuvin (registered trademark) 144," "Tinuvin (registered trademark) 622SF," and "Tinuvin (registered trademark) 152" (all manufactured by BASF), "ADK STAB (registered trademark) LA-52," "ADK STAB (registered trademark) LA-57," "ADK STAB (registered trademark) LA-63P," "ADK STAB (registered trademark) LA-72," "ADK STAB (registered trademark) LA-77Y," "ADK STAB (registered trademark) LA-81," "ADK STAB (registered trademark) LA-82," and "ADK STAB (registered trademark) LA-87" (all manufactured by ADEKA Corporation).

[0128] When the polyurea resin composition of the present invention contains a filler, the content of the filler (D) is preferably 0.1 to 80 mass %, more preferably 0.3 to 70 mass %, relative to 100 mass % of the polyurea resin composition.

[0129] (E) The antifoaming agent is not particularly limited, and examples thereof include silicones (oil type, compound type, self-emulsifying type, emulsion type, etc.), alcohols, and the like.

[0130] A preferred silicone-based antifoaming agent is a modified silicone-based antifoaming agent (particularly one in which polysiloxane has a lipophilic group and is modified with a hydrophilic group).

[0131] The (E) antifoaming agent can be used alone or in combination of two or more.

[0132] When (E) an antifoaming agent is contained, its content is not particularly limited, and is preferably from 0.001 to 10 mass %, more preferably from 0.005 to 5 mass %, relative to 100 mass % of the polyurea resin composition.

[0133] The crosslinking agent (chain extender) is not particularly limited, and examples thereof include aromatic alcohol crosslinking agents such as N,N-bis(2-hydroxypropyl)aniline, hydroquinone-bis(β-hydroxyethyl)ether, and resorcinol-bis(β-hydroxyethyl)ether; Aliphatic alcohol-based crosslinkers such as ethylene glycol, 1,3-butanediol (1,3-butylene glycol), 1,4-butanediol, octanediol, trimethylolpropane, and triisopropanolamine; aromatic amine-based crosslinking agents such as phenylenediamine, tolylenediamine, diphenyldiamine, 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 1,2-bis(2-aminophenylthio)ethane, and trimethylene glycol-p-aminobenzoate; Examples of the crosslinking agents include aliphatic amine-based crosslinking agents such as ethylenediamine, propylenediamine, hexamethylenediamine, and diethylenetriamine.

[0134] Among these, aromatic alcohol-based crosslinking agents and aliphatic alcohol-based crosslinking agents are preferred, and aliphatic alcohol-based crosslinking agents are more preferred.

[0135] The number average molecular weight of the crosslinking agent is usually 1,000 or less, preferably 500 or less, and more preferably 400 or less.

[0136] When the polyurea resin composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is not particularly limited and is, for example, usually 0.01 to 30 mass%, preferably 0.1 to 20 mass%, and more preferably 1 to 15 mass%, relative to 100 mass% of the polyurea resin composition.

[0137] The above crosslinking agents can be used alone or in combination of two or more.

[0138] The content of these components may be appropriately determined depending on the intended use from the range of the usual amounts and specifications so as not to impair the desired properties of the polyurea resin composition.

[0139] 2. Method for producing polyurea resin composition The method for producing the polyurea resin composition of the present invention is not particularly limited, and the composition can be produced according to any known method used for producing polyurea resin compositions. For example, a method for producing a polyurea resin composition of the present invention includes a step of mixing (A1) an isocyanate group-containing compound having an aromatic ring, (B1) polytetramethylene oxide-di-p-aminobenzoate, (C) a plasticizer, and, if necessary, (D) a filler.

[0140] More specifically, the polyurea resin composition of the present invention may have a structure in which the first component contains (A1) an isocyanate group-containing compound having an aromatic ring and (C) a plasticizer, and the second component contains (B1) polytetramethylene oxide-di-p-aminobenzoate and (D) a filler; A composition in which the first component contains (A1) an isocyanate group-containing compound having an aromatic ring, and the second component contains (B1) polytetramethylene oxide-di-p-aminobenzoate, (C) a plasticizer, and (D) a filler; A composition in which the first component contains (A1) an isocyanate group-containing compound having an aromatic ring and (D) a filler, and the second component contains (B1) polytetramethylene oxide-di-p-aminobenzoate and (C) a plasticizer; An example of such a configuration is one in which the first component contains (A1) an isocyanate group-containing compound having an aromatic ring, (C) a plasticizer, and (D) a filler, and the second component contains (B1) polytetramethylene oxide-di-p-aminobenzoate.

[0141] Also, a structure in which the first component contains (A1) an isocyanate group-containing compound having an aromatic ring and (C) a plasticizer, and the second component contains (B1) polytetramethylene oxide-di-p-aminobenzoate; A composition in which the first component contains (A1) an isocyanate group-containing compound having an aromatic ring and (C) a plasticizer, and the second component contains (B1) polytetramethylene oxide-di-p-aminobenzoate, (C) a plasticizer, and (D) a filler; A composition in which the first component contains (A1) an isocyanate group-containing compound having an aromatic ring and (C) a plasticizer, and the second component contains (B1) polytetramethylene oxide-di-p-aminobenzoate, (C) the plasticizer, (D) a filler, and (E) an antifoaming agent; The first component may contain (A1) an isocyanate group-containing compound having an aromatic ring, and the second component may contain (B1) polytetramethylene oxide-di-p-aminobenzoate, (C) a plasticizer, (D) a filler, and (E) an antifoaming agent.

[0142] When producing a polyurea resin composition, the first component (agent I) is generally used in an amount of 1 to 1,000 parts by mass, preferably 3 to 500 parts by mass, and more preferably 5 to 200 parts by mass per 100 parts by mass of the second component (agent II). The reason for blending other components with the first component is to lower the viscosity of the isocyanate compound and to match the ratio (blending ratio) of the first component to the second component. Therefore, the first component can be used without blending other components. If necessary, the first component or the second component may be diluted with an organic solvent (e.g., toluene, methyl ethyl ketone, butyl acetate, etc.).

[0143] The polyurea resin composition may be in a liquid state before curing, or may be cured. The polyurea resin composition may be cured by mixing the first and second components, causing the isocyanate group-containing compound (A) and the aromatic amine compound (B) to react with each other to form a polyurea resin, thereby curing the polyurea resin composition over time. Alternatively, the polyurea resin composition may be cured by heating. In this case, the heating temperature is preferably about 40 to 120°C, and the heating time is preferably about 0.1 to 24 hours.

[0144] 3. Uses of polyurea resin compositions and cured polyurea resins The polyurea resin composition and the cured polyurea resin of the present invention can be used for sealing materials, potting agents, coating agents, covering agents, sealing agents, adhesives, and the like.

[0145] The polyurea resin composition of the present invention has a long pot life and excellent finger-touch curability at room temperature. In this specification, the pot life is defined as the time until the reaction progresses at a temperature of 23°C and the viscosity reaches (increases to) 10 Pa·s. The usable time (pot life) of the polyurea resin composition of the present invention is preferably 5 to 180 minutes, more preferably 10 to 120 minutes, and particularly preferably 15 to 100 minutes. The viscosity of the polyurea resin composition of the present invention at a temperature of 23° C. is preferably 0.1 Pa·s to 8 Pa·s, more preferably 0.5 Pa·s to 7 Pa·s, and particularly preferably 0.8 Pa·s to 5 Pa·s.

[0146] The fingertip curability can be determined by the fingertip curing time at room temperature. Here, the "fingertip curing time" refers to the time required for the resin composition to no longer adhere to a finger, matchstick, glass rod, or the like when the surface of the resin composition is touched with the finger, matchstick, glass rod, or the like, although a mark remains on the surface. The touch-hardening time of the polyurea resin composition of the present invention is not particularly limited, but is preferably 5 to 180 minutes, more preferably 10 to 120 minutes, and particularly preferably 15 to 120 minutes at a temperature of 23°C.

[0147] The polyurea resin composition of the present invention is excellent in electrical insulation properties and durability in high-temperature, high-humidity environments. The volume resistivity of the cured product of the polyurea resin composition of the present invention is not particularly limited, but is preferably 1.0×10 8 Ω·m or more, and more preferably 1.0×10 10 Ω·m or more, particularly preferably 1.0×10 11 Ω·m or more. [Example]

[0148] The polyurea resin composition of the present invention will be specifically described below with reference to examples and comparative examples. However, the examples are merely illustrative and the present invention is not limited to these examples.

[0149] The raw materials used in the examples and comparative examples are shown below.

[0150] (A) Isocyanate group-containing compound MTL: Carbodiimide-modified MDI, trade name: Millionate MTL, manufactured by Tosoh Corporation, specific gravity 1.22 TSA: Aliphatic polyisocyanate, product name: Duranate TSA-100, manufactured by Asahi Kasei Corporation, specific gravity 1.13 Prepolymer 1: MDI-based isocyanate-terminated prepolymer, product name: URIC N-2047U, manufactured by Ito Oil Mills, specific gravity 1.05, number average molecular weight (Mn) 1050 Prepolymer 2: MDI-based isocyanate-terminated prepolymer 85 parts by mass of Millionate MT (manufactured by Tosoh Corporation) and 100 parts by mass of polybd R-45HT (manufactured by Idemitsu Kosan Co., Ltd.) were mixed and heated and stirred in an oil bath at 80°C for 3 hours to synthesize prepolymer 2 with an NCO% of 16%.

[0151] (B) Aromatic amine compounds Elasmer (registered trademark) 1000P: Polytetramethylene oxide-di-p-aminobenzoate (PTMDA), trade name; Elasmer 1000P, manufactured by Kumiai Chemical Industry Co., Ltd., molecular weight 1238, specific gravity 1.03 DETDA: Diethyltoluenediamine, trade name: LonzaCure DETDA80, manufactured by Lonza Co., Ltd., specific gravity 1.02

[0152] (C) Plasticizer DINP: Diisononyl phthalate, trade name: DINP, manufactured by J-Plus Corporation, specific gravity 0.97 TOTM: Trioctyl trimellitate, trade name: TOTM, manufactured by J-Plus Corporation, specific gravity 0.99 AC460: Process oil, product name: Diana Process Oil AC-460, manufactured by Idemitsu Kosan Co., Ltd., specific gravity 1.02 (D) Filler B143: Aluminum hydroxide, product name: Aluminum hydroxide (dry powder) B143, manufactured by Nippon Light Metal Co., Ltd., specific gravity 2.42

[0153] <Examples 1 to 13 and Comparative Examples 1 to 5> Method for preparing polyurea resin composition Various polyurea resin compositions were prepared according to the following procedure. (B) Aromatic amine compound, (C) plasticizer, and (D) filler were mixed for 1 minute at 2000 rpm using a planetary centrifugal mixer (Thinky Mixer). To the above mixed components, (A) an isocyanate group-containing compound was added, and the mixture was mixed at 2000 rpm for 1 minute using a planetary centrifugal mixer (Thinky Mixer). The resulting mixture was degassed to obtain polyurea resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5.

[0154] <Preparation of test pieces> The prepared polyurea resin composition was poured into a mold having dimensions of 100 × 100 × 3 mm and an inner diameter of 30 mm, and then allowed to stand at 23°C for 16 hours to obtain test piece A (100 × 100 × 3 mm) or test piece B (inner diameter 30 mm, height 10 mm). The prepared polyurea resin composition was poured into a molding die of 125 mm x 13 mm x 1.5 mm, and heated at 23°C for 16 hours to prepare a test piece C.

[0155] The polyurea resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5, or test pieces A to C, prepared as described above were used to carry out the following measurements and tests.

[0156] Test Example <Workability> The workability of the polyurea resin composition was evaluated based on the viscosity, the pot life, and the finger-touch hardness.

[0157] (1) Viscosity The polyurethane resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were each prepared according to the procedure described in the above-mentioned preparation method for the polyurea resin composition, and their viscosities were measured. The viscosities were measured at 23°C 3 minutes after preparation using a B-type viscometer (TV-25 viscometer, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm.

[0158] (2) Pot life The pot life was evaluated as follows: (1) After measuring the viscosity, the measurement was continued in an environment of 23°C, and the pot life was defined as the time until the viscosity increased due to the reaction and reached 10 Pa·s.

[0159] (3) Hardenable to touch The finger-touch curability was evaluated by pouring the composition into a molding die with an inner diameter of 30 mm and determining whether the resin adhered to a matchstick after 2 hours. Here, "finger-touch curability" refers to a state in which, when the surface of the resin composition is touched with a finger, matchstick, glass rod, etc., a mark remains on the surface, but the resin composition does not adhere to the finger, matchstick, glass rod, etc. The evaluation criteria were as follows: two hours after casting, the end of a matchstick was pressed against the surface of the resin composition and then pulled up; if the resin composition did not adhere to the matchstick, it was rated as "touchable"; if it did adhere, it was rated as "untouchable."

[0160] The measured viscosity, pot life, and tactile hardness were evaluated for workability according to the following criteria. The results are shown in Tables 1 and 2. [Workability evaluation] A: Viscosity is 100 mPa·s or more but less than 6000 mPa·s, pot life is 21 minutes or more but less than 100 minutes, and the product can be touched with fingers within 2 hours B: Viscosity is 100 mPa·s or more but less than 6000 mPa·s, pot life is 10 minutes or more but less than 21 minutes, and the product can be touched with fingers within 2 hours C: Viscosity cannot be measured, pot life cannot be measured, viscosity is 6000 mPa s or more, pot life is less than 10 minutes or more than 100 minutes, or the product cannot be touched within 2 hours

[0161] <Electrical insulation: volume resistivity> The volume resistivity of test piece A was measured using a resistance meter (HIOKI, DSM-8104). Based on the measurement results, the electrical insulation was evaluated according to the following evaluation criteria. The measured volume resistivity values ​​(Ω·m) are shown in Tables 1 and 2. [Evaluation criteria for electrical insulation] A: Volume resistivity is 1.0 x 10 11 (1.0E+11)Ω m or more B: Volume resistivity is 1.0 x 10 11 Less than (1.0E+11) Ω·m C: Not measurable

[0162] <High temperature and humidity test> A pressure cooker test (PCT) was performed using test piece B under conditions of 121°C, 100% RH (relative humidity), and 2 atmospheres. After the test, test piece B was cooled to room temperature, and the hardness was measured and the appearance was evaluated. Tables 1 and 2 show the time until the hardness became 50% or less, the appearance after 50 hours, and the evaluation score according to the following evaluation criteria.

[0163] [Time to reduce hardness to 50% or less] The hardness of the test piece B was measured in accordance with JISK 6253 using an Asker A-type hardness tester (manufactured by Kobunshi Keiki Co., Ltd.). [Hardness reduction rate] = (hardness after test) ÷ (hardness before test) × 100 The measurement was stopped when the hardness reduction rate reached 50% (half), and the time was recorded in Table 1. If the hardness reduction rate had not reached 50% after 200 hours, it was recorded as "200<".

[0164] [Appearance after 50 hours] If there was no abnormality in appearance after 50 hours had passed, the result was recorded as "No abnormality" in Tables 1 and 2. If a crack occurred in test piece B within 50 hours, the evaluation was terminated at that point, and the result was recorded as "crack" in Tables 1 and 2.

[0165] [Evaluation criteria for high temperature and high humidity testing] A: If no cracks occur within 50 hours and the time it takes for the hardness to drop to 50% or less of the initial hardness is 50 hours or more. B: No cracks occur within 50 hours, and the time it takes for the hardness to drop to 50% or less of the initial hardness is less than 50 hours. C: Measurement is not possible or cracks have occurred within 50 hours.

[0166] <Flame retardancy test> Flame retardancy tests were conducted in accordance with the UL94 test (combustion test for plastic materials for equipment parts) established by Underwriters Laboratories (UL) of the United States. UL94V testing was performed using test piece C, and the test piece was judged as "V-0," "V-1," or "V-2." If the test piece did not meet the UL94V criteria, the HB test was performed and evaluated. When the UL94V test was performed, the judgment results are shown in Tables 1 and 2, and when the HB test was performed, the results are shown as "HB" in Tables 1 and 2. The polyurea composition of Comparative Example 1 was not subjected to a flame retardancy test.

[0167] <Overall rating> The overall evaluation was based on the evaluation scores of workability, electrical insulation, and high-temperature, high-humidity test, and was made according to the following evaluation criteria. The results are shown in Tables 1 and 2. A: When all items are rated "A" B: There are less than one "C" and one or more "B" in each evaluation. C: If there is one or more "C" in each evaluation.

[0168] [Table 1]

[0169] [Table 2]

[0170] <Judgment result> The polyurea resin compositions of Examples 1 to 13 were excellent in workability, such as viscosity, usable time, and finger-touch curability, and the cured products obtained from these polyurea resin compositions exhibited excellent electrical insulation. Furthermore, the cured products of the polyurea resin compositions also exhibited excellent moisture resistance in a high-temperature, high-humidity test (accelerated environment). On the other hand, the polyurea resin compositions of Comparative Examples 1 to 5 showed poor results in workability, electrical insulation properties, high temperature and humidity tests, and the like. The cured product of the polyurea resin composition of Example 4, which contained a filler, was more flame retardant than the cured products of the polyurea resin compositions of the other Examples, which did not contain a filler. [Industrial Applicability]

[0171] The polyurea resin composition and cured polyurea resin of the present invention can be used as a sealing material, potting agent, coating agent, covering agent, sealing agent, adhesive, electronic component material, etc.

Claims

1. (A) an isocyanate group-containing compound, (B) an aromatic amine compound, and (C) Plasticizer A polyurea resin composition comprising: the (A) isocyanate group-containing compound includes at least one (A1) isocyanate group-containing compound having an aromatic ring selected from the group consisting of aromatic isocyanate compounds, polynuclear isocyanate compounds, modified isocyanate compounds, and urethane prepolymers thereof; the aromatic amine compound (B) includes polytetramethylene oxide-di-p-aminobenzoate (B1), The equivalent ratio (NCO / NH) of the isocyanate group in the isocyanate group-containing compound having an aromatic ring (A1) to the amino group in the polytetramethylene oxide-di-p-aminobenzoate (B1) is ２ ) is 0.5 to 2.0, and The polyurea resin composition, wherein the content of the plasticizer (C) is 40 parts by mass or more per 100 parts by mass of the isocyanate group-containing compound (A1) having an aromatic ring.

2. The polyurea resin composition according to claim 1 , wherein the plasticizer (C) comprises an ester-based plasticizer.

3. The polyurea resin composition according to claim 1 , wherein the plasticizer (C) comprises at least one selected from the group consisting of a phthalate ester, a trimellitate ester, and an adipic acid ester.

4. The polyurea resin composition according to claim 1 , further comprising (D) a filler.

5. The polyurea resin composition according to claim 1 , wherein the filler (D) comprises aluminum hydroxide.

6. The polyurea resin composition according to claim 1, wherein the (C) plasticizer in the polyurea resin composition is 7% by mass to 41% by mass.

7. Volume resistivity is 1.0 x 10 １０ The polyurea resin composition according to claim 1, having a modulus of elasticity of Ω·m or more.

8. A sealing material comprising the polyurea resin composition according to claim 1.

9. An electric / electronic component comprising the encapsulant according to claim 8.

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