Method for manufacturing polyurethane-forming compositions, potting materials, and sealants.

Abstract

To provide a urethane-based potting material that can achieve both high heat resistance and flexibility in low-temperature environments, along with high reliability that can maintain these properties over a long period of time. [Solution] A polyurethane-forming composition comprising a liquid polycarbonate polyol at 25°C and a non-aromatic polyisocyanate, wherein the polycarbonate polyol comprises a polycondensate of a polyol component containing a glycol with 8 or more carbon atoms and a carbonate component.

Description

Technical Field

[0001] The present invention relates to a polyurethane-forming composition, a potting material, and a method for manufacturing a sealing body.

Background Art

[0002] Conventionally, potting materials have been used to protect electrical and electronic components from an atmosphere containing moisture, dust, etc., vibration, shock, etc. Potting materials are required to have a wide variety of characteristics depending on their applications. Among them, potting materials applied to automotive use, particularly electrical and electronic components (such as electrical components like ECU (Electronic Control Unit), etc.) mounted in an engine room where the environment is harsh, require high heat resistance, flexibility in a low-temperature environment, and high reliability to maintain this over a long period.

[0003] As potting materials, urethane-based potting materials composed of a polyurethane-forming composition containing a polyol and a polyisocyanate are known. Urethane-based potting materials have the advantage that, with abundant raw materials, it is easy to control functions and economy, have high adhesiveness to adherents, and can satisfy the characteristics required for potting materials applied to electrical and electronic components such as water vapor barrier properties and electrical insulation properties. Therefore, in recent years, using urethane-based potting materials as the above-mentioned potting materials for automotive use has been under consideration.

[0004] However, generally, polyurethane is likely to cause a shape change due to a decrease in hardness or hardening due to an increase in hardness in a high-temperature environment. Also, flexibility in a low-temperature environment is likely to be insufficient, which may cause cracks, etc. Therefore, in order to apply urethane-based potting materials to the above-mentioned potting materials for automotive use, it is essential to improve heat resistance and flexibility in a low-temperature environment.

[0005] In contrast, for example, Patent Document 1 proposes a curable resin composition comprising a (meth)acrylic polyol, a castor oil polyol, and a polyisocyanate, wherein the (meth)acrylic polyol is composed of a polymer having a hydroxyl value of 5 mg KOH / g or more and 150 mg KOH / g or less, a glass transition temperature of -70°C or more and -40°C or less, a number average molecular weight of 500 or more and 20000 or less, and is liquid at 25°C. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2019-99595 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the cured product formed by the curable resin composition described in Patent Document 1 does not exhibit sufficient flexibility in low-temperature environments, particularly in low-temperature environments after prolonged exposure to high-temperature environments. Therefore, even with this curable resin composition, it is difficult to satisfy the characteristics required for potting materials in recent years.

[0008] Therefore, the main objective of the present invention is to provide a urethane-based potting material that can achieve both high heat resistance, flexibility in low-temperature environments, and high reliability that can maintain these properties over a long period of time. [Means for solving the problem]

[0009] In several aspects, the present invention provides the following [1] to

[19] .

[0010] [1] A polyurethane-forming composition comprising a polycarbonate polyol that is liquid at 25°C and a non-aromatic polyisocyanate, wherein the polycarbonate polyol comprises a polycondensate of a polyol component having 8 or more carbon atoms and a carbonate component.

[0011] [2] The polyurethane-forming composition according to [1], wherein the polyol component comprises a linear glycol and a branched glycol as the glycol having 8 or more carbon atoms.

[0012] [3] The polyurethane-forming composition according to [1] or [2], wherein the polyol component comprises a branched glycol having 8 or more carbon atoms in its main chain, as the glycol having 8 or more carbon atoms.

[0013] [4] The polyurethane-forming composition according to any one of [1] to [3], wherein the content of glycol having 8 or more carbon atoms in the polyol component is 30% by mass or more based on the total mass of the polyol component.

[0014] [5] The polyurethane-forming composition according to any one of [1] to [4], wherein the polyol component further comprises a glycol having 6 or 7 carbon atoms.

[0015] [6] The polyurethane-forming composition according to any one of [1] to [5], wherein the content of glycols having 6 or more carbon atoms in the polyol component is 90% by mass or more based on the total mass of the polyol component.

[0016] [7] The polyurethane-forming composition according to any one of [1] to [6], wherein the average number of carbon atoms in the polyol component is 6.5 or more.

[0017] [8] The polyurethane-forming composition according to any one of [1] to [7], wherein the polyol component further comprises a polyol having 3 or more hydroxyl groups.

[0018] [9] The polyurethane-forming composition according to any one of [1] to [8], wherein the hydroxyl value of the polycondensate is 30 to 180 mg KOH / g.

[0019]

[10] The polyurethane-forming composition according to any one of [1] to [9], wherein the non-aromatic polyisocyanate contains a derivative of an aliphatic polyisocyanate.

[0020]

[11] The polyurethane-forming composition according to any one of [1] to

[10] , wherein the non-aromatic polyisocyanate contains an isocyanurate-modified product of an aliphatic polyisocyanate.

[0021]

[12] The polyurethane-forming composition according to any one of [1] to

[11] , wherein the non-aromatic polyisocyanate contains an allophanate-modified product of an aliphatic polyisocyanate.

[0022]

[13] The polyurethane-forming composition according to any one of [1] to

[12] , wherein the non-aromatic polyisocyanate does not have a urethane group.

[0023]

[14] The polyurethane-forming composition according to any one of [1] to

[13] , which is a one-component type composition in which the polycarbonate polyol and the non-aromatic polyisocyanate are mixed in one liquid, and forms a polyurethane having a urethane group concentration of 1.7 mmol / g or less.

[0024]

[15] The polyurethane-forming composition according to any one of [1] to

[14] , which is a one-component type polyurethane-forming composition in which the polycarbonate polyol and the non-aromatic polyisocyanate are mixed in one liquid, and the content of the polycarbonate polyol in the polyurethane-forming composition is 60% by mass or more.

[0025]

[16] A two-component type polyurethane-forming composition comprising a first liquid containing the polycarbonate polyol and a second liquid containing the non-aromatic polyisocyanate, and when the first liquid and the second liquid are mixed and reacted so that the NCO index is 50 to 120, forms a polyurethane having a urethane group concentration of 1.7 mmol / g or less. The polyurethane-forming composition according to any one of [1] to

[13] .

[0026]

[17] A two-component composition comprising a first liquid containing the polycarbonate polyol and a second liquid containing the non-aromatic polyisocyanate, wherein when the first liquid and the second liquid are mixed so that the NCO index is 50 to 120, the content of the polycarbonate polyol in the resulting mixed liquid is 60% by mass or more, the polyurethane-forming composition according to any one of [1] to

[13] or

[16] .

[0027]

[18] A potting material comprising the polyurethane-forming composition according to any one of [1] to

[17] .

[0028]

[19] A method for manufacturing a sealed body, comprising a step of sealing at least a part of an electrical component or an electronic component with the potting material according to

[18] . [Effect of the Invention]

[0029] According to the present invention, it is possible to provide a urethane-based potting material that can achieve both high heat resistance and flexibility in a low-temperature environment and high reliability that can be maintained over a long period of time. Further, according to the present invention, it is also possible to provide a polyurethane-forming composition that can be used for the potting material and a method for manufacturing a sealed body using the potting material. [Embodiments for Carrying out the Invention]

[0030] In this specification, a numerical range indicated using "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value of a certain stepwise numerical range may be replaced with the upper limit value or the lower limit value of another stepwise numerical range. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Also, the individually described upper limit value and lower limit value can be arbitrarily combined. [[ID=​Preferred embodiments of the present invention will be described below. However, the present invention is not limited in any way to the embodiments described below.

[0032] <Polyurethane-forming composition> One embodiment of the polyurethane-forming composition comprises a polycarbonate polyol (hereinafter also simply referred to as "polycarbonate polyol") that is liquid at 25°C and a non-aromatic polyisocyanate, wherein the polycarbonate polyol contains a polycondensate (hereinafter referred to as "polycondensate A") of a polyol component containing a glycol with 8 or more carbon atoms and a carbonate component.

[0033] The polyurethane-forming composition contains the polycarbonate polyol and the non-aromatic polyisocyanate, and reacts with heating or other means to form polyurethane (a composition containing polyurethane). Therefore, the reactants (reaction products) of the polyurethane-forming composition can be rephrased as a composition containing polyurethane. In one embodiment, the polyurethane-forming composition becomes a curable composition and hardens upon the formation of the polyurethane. Therefore, the reactants (reaction products) of the polyurethane-forming composition can, in one embodiment, be a cured body containing polyurethane.

[0034] The polyurethane-forming composition described above may be a one-component composition in which the polycarbonate polyol and the non-aromatic polyisocyanate are mixed in one liquid, or it may be a two-component polyurethane-forming composition comprising a first liquid containing the polycarbonate polyol and a second liquid containing the non-aromatic polyisocyanate. If the polyurethane-forming composition contains an active hydrogen group-containing compound other than the polycarbonate polyol, the active hydrogen group-containing compound may be included in the first liquid. If the polyurethane-forming composition contains an isocyanate group-containing compound other than the non-aromatic polyisocyanate, the isocyanate group-containing compound may be included in the second liquid.

[0035] The polyurethane-forming composition described above can be used as a potting material for sealing electrical and / or electronic components (hereinafter referred to as "electrical and electronic components") and the like. The polyurethane-forming composition described above can achieve both high heat resistance and flexibility in low-temperature environments, as well as high reliability that can maintain these properties over a long period of time. For this reason, the polyurethane-forming composition can maintain good potting performance even after repeating a cold cycle of -40°C to 150°C for a long period of time (e.g., 2000 cycles), and is therefore suitable for use as a potting material for automobiles, especially for electrical and electronic components (e.g., ECUs and other electrical components) mounted in engine compartments where the environment is harsh.

[0036] (Polycarbonate polyol) Polycarbonate polyols contain at least a polycondensate A of a polyol component containing a glycol with 8 or more carbon atoms (hereinafter referred to as "first glycol") and a carbonate component. Here, "glycol" means a compound having a structure in which two carbon atoms of a chain aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon are each substituted with one hydroxyl group. "Polycondensate A" means a reaction product or reaction mixture obtained by a transesterification reaction (polycondensation reaction) of the polyol component and the carbonate component. Therefore, polycondensate A may include multiple compounds. Polycarbonate polyols may also consist only of polycondensate A.

[0037] The carbon number of the first glycol is, for example, 8 to 20, and may be 8 to 12 or 8 to 10. The aliphatic hydrocarbon in the first glycol may be a chain-type aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon, but a chain-type aliphatic hydrocarbon is preferred from the viewpoint of superior flexibility in low-temperature environments. When the aliphatic hydrocarbon in the first glycol is a chain-type aliphatic hydrocarbon, the first glycol may be linear or branched.

[0038] Examples of the linear first glycol include 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, and 1,20-eicosanediol. These linear first glycols may be used individually or in combination of two or more.

[0039] The content of the linear first glycol in the polyol component may be 3% by mass or more, 10% by mass or more, 30% by mass or more, or 50% by mass or more, from the viewpoint of superior flexibility in low-temperature environments, and may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 60% by mass or less, 50% by mass or less, 35% by mass or less, or 20% by mass or less, from the viewpoint of further lowering the crystallinity of the polycarbonate polyol and further improving reliability (from the viewpoint of being able to maintain flexibility in low-temperature environments for a longer period of time). From these viewpoints, the content of the first glycol may be 3 to 99% by mass, 10 to 95% by mass, 30 to 90% by mass, 50 to 90% by mass, 3 to 60% by mass, 3 to 50% by mass, 3 to 35% by mass, or 3 to 20% by mass. Note that the above content is based on the total mass of the polyol component.

[0040] The branched first glycol preferably has 8 or more carbon atoms in its main chain, from the viewpoint of superior flexibility in low-temperature environments. Here, the main chain of the branched first glycol refers to the straight-chain portion having hydroxyl groups at both ends. The number of carbon atoms in the main chain is, for example, 8 to 20, and may also be 8 to 12 or 8 to 10.

[0041] The branched main chain of the first glycol has at least one side chain group attached to it. The number of side chain groups is, for example, 1 to 4, and may be 1 to 3 or 1 to 2. The side chain group is, for example, a hydrocarbon group having 1 to 7 carbon atoms, preferably an alkyl group. Specifically, examples include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and the like.

[0042] Examples of the branched first glycol include 2-methyl-1,8-octanediol and 1,12-octadecanediol. These branched first glycols may be used individually or in combination of two or more.

[0043] The content of the branched first glycol in the polyol component may be 5% by mass or more, 20% by mass or more, or 50% by mass or more, from the viewpoint of further lowering the crystallinity of the polycarbonate polyol and further improving reliability (from the viewpoint of being able to maintain flexibility in low-temperature environments for a longer period of time), or 99% by mass or less, 95% by mass or less, or 90% by mass or less, from the viewpoint of superior flexibility in low-temperature environments. From these viewpoints, the content of the branched first glycol may be 5 to 99% by mass, 20 to 95% by mass or 50 to 90% by mass. Note that the above content is based on the total mass of the polyol component.

[0044] From the viewpoint of achieving a higher degree of compatibility between heat resistance and flexibility in low-temperature environments, it is preferable to use a branched first glycol in combination with a linear first glycol. Specifically, for example, it is preferable to use 2-methyl-1,8-octanediol in combination with at least one glycol selected from the group consisting of 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

[0045] The mass ratio of the branched first glycol content to the linear first glycol content (branched first glycol / linear first glycol) may be 0.01 or more, 1 or more, or 5 or more from the viewpoint of superior flexibility in low-temperature environments, and may be 100 or less, 50 or less, or 10 or less from the viewpoint of further reducing the crystallinity of the polycarbonate polyol and further improving reliability (from the viewpoint of being able to maintain flexibility in low-temperature environments for a longer period of time). From these viewpoints, the above mass ratio may be 0.01 to 100, 1 to 50, or 5 to 10.

[0046] The content of the first glycol in the polyol component may be 30% by mass or more, 40% by mass or more, or 50% by mass or more, from the viewpoint of superior flexibility in low-temperature environments. From the above viewpoint, the content of the first glycol may be 30-100% by mass, 40-100% by mass or 50-100% by mass. Note that the above content is based on the total mass of the polyol component.

[0047] The polyol component may contain a glycol with 7 or fewer carbon atoms (hereinafter referred to as "second glycol"). The carbon number of the second glycol may be, for example, 1 to 7, 2 to 6 or 3 to 6, or 6 or 7. The polyol component may contain one type of second glycol or two or more types.

[0048] The aliphatic hydrocarbon in the second glycol may be a chain-type aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon chain. If the aliphatic hydrocarbon in the second glycol is a chain-type aliphatic hydrocarbon, the second glycol may be linear or branched.

[0049] Examples of the second glycol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanediol.

[0050] The content of the second glycol in the polyol component may be 70% by mass or less, 50% by mass or less, or 30% by mass or less, from the viewpoint of superior flexibility in low-temperature environments. From these viewpoints, the content of the second glycol may be 0 to 70% by mass, 0 to 50% by mass, or 0 to 30% by mass. Note that the above content is based on the total mass of the polyol component.

[0051] The mass ratio of the content of the second glycol to the content of the first glycol in the polyol component (second glycol / first glycol) may be 3 or less, 2 or less, 1 or less, or 0.5 or less, from the viewpoint of superior flexibility in low-temperature environments. From the above viewpoint, the above mass ratio may be 0 to 3, 0 to 2, 0 to 1, or 0 to 0.5.

[0052] In this embodiment, the greater the number of carbon atoms in the glycol contained in the polyol component, the more flexible it tends to be in low-temperature environments. From this viewpoint, the content of glycol with 6 or more carbon atoms in the polyol component may be 90% by mass or more, 95% by mass or more, or 100% by mass, based on the total mass of the polyol component.

[0053] The polyol component may include polyols other than glycols, such as polyols having three or more hydroxyl groups (polyols with three or more hydroxyl groups). The number of hydroxyl groups in the polyol may be, for example, 3 to 6, and may be 3 to 5 or 3 to 4. The number of carbon atoms in the polyol may be, for example, 3 to 15, and may be 3 to 10 or 3 to 6. The polyol may have an aromatic ring (e.g., a benzene ring), but from the viewpoint of superior flexibility in low-temperature environments, it is preferable that it does not have an aromatic ring, and it is more preferable that it is a compound having a structure in which one hydroxyl group is substituted on each of the three carbon atoms of an aliphatic hydrocarbon.

[0054] Specific examples of polyols having three or more hydroxyl groups include trimethylolethane, trimethylolpropane, 2-hydroxy-2-methyl-1,4-butanediol, glycerin, ditrimethylolethane, ditrimethylolpropane, diglycerin, pentaerythritol, xylitol, dipentaerythritol, sorbitol, and 1,3,5-tris(hydroxymethyl)benzene.

[0055] The content of polyols having three or more hydroxyl groups in the polyol component may be 3% by mass or more, 4% by mass or more, or 5% by mass or more from the viewpoint of superior heat resistance, and may be 22% by mass or less, 19% by mass or less, or 16% by mass or less from the viewpoint of superior flexibility in low-temperature environments. From these viewpoints, the content of polyols having three or more hydroxyl groups may be 3 to 22% by mass, 4 to 19% by mass, or 5 to 16% by mass. Note that the above content is based on the total mass of the polyol component.

[0056] The average carbon number of the polyol component may be 6.5 or more, or 7 or more, or 8 or more, from the viewpoint of superior flexibility in low-temperature environments. Here, the average carbon number of the polyol component is the molar average carbon number, which is a weighted average value weighted by the amount of polyol content (mol%) for each carbon number. From the viewpoint of superior heat resistance, the average carbon number of the polyol component may be 20 or less, or 15 or less, or 12 or less. From these viewpoints, the average carbon number of the polyol component may be 6.5 to 20, 7 to 15, or 8 to 12.

[0057] The carbonate component includes one type of carbonate or two or more types of carbonates. The carbonate can be any compound capable of condensing with a polyol to produce a polycarbonate polyol. Examples of carbonate components include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dipropyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; and diaryl carbonates such as diphenyl carbonate, dinaphthyl carbonate, diantlyl carbonate, diphenanthryl carbonate, diindanyl carbonate, and bistetrahydronaphthyl carbonate.

[0058] Polycondensate A contains a polycarbonate polyol having at least a carbonate group (-OCOO-) derived from the reaction (polycondensation reaction) between the polyol component and the carbonate component, and a residue (polyol residue) derived from the polyol component. The polyol residue is, for example, an n-valent residue obtained by removing n hydroxyl groups from the polyol. n is determined by the number of hydroxyl groups contained in the polyol. If the polyol is a diol (glycol), n is 1 or 2, and if the polyol is a triol, n is an integer from 1 to 3.

[0059] The hydroxyl value of polycondensate A is preferably 30 to 180 mgKOH / g. When the hydroxyl value of polycondensate A is 30 mgKOH / g or higher, it tends to have better heat resistance. Also, when the hydroxyl value of polycondensate A is 30 mgKOH / g or higher, sufficient fluidity is easily obtained, making mixing and composition formation easier. When the hydroxyl value of polycondensate A is 180 mgKOH / g or lower, it tends to have better flexibility in low-temperature environments. From these viewpoints, the hydroxyl value of polycondensate A may be 40 mgKOH / g or higher or 50 mgKOH / g or higher, or 150 mgKOH / g or lower or 130 mgKOH / g or lower. In this specification, hydroxyl value means the number of milligrams (mg) of potassium hydroxide equivalent to hydroxyl groups in 1 g of sample, and is measured in accordance with JIS K1557-1.

[0060] When polycondensate A is a polycarbonate diol, the hydroxyl value of polycondensate A is preferably 30 to 130 mgKOH / g. Similarly, when the polyol component does not contain a polyol having three or more hydroxyl groups, the hydroxyl value of polycondensate A is preferably 30 to 130 mgKOH / g. When polycondensate A is a polycarbonate triol, the hydroxyl value of polycondensate A is preferably 40 to 180 mgKOH / g. Similarly, when the polyol component contains a polyol having three or more hydroxyl groups (for example, when the polyol component contains a triol), the hydroxyl value of polycondensate A is preferably 40 to 180 mgKOH / g.

[0061] The molecular weight of polycondensate A may be 600 or more, 1000 or more, or 1500 or more, from the viewpoint of superior flexibility in low-temperature environments. The molecular weight of polycondensate A may be 4000 or less, 3500 or less, or 3000 or less, from the viewpoint of superior heat resistance and sufficient fluidity, making mixing and composition formation easy. From these viewpoints, the molecular weight of polycondensate A may be 600 to 4000, 1000 to 3500, or 1500 to 3000. The above molecular weights are values ​​calculated from the hydroxyl value and number of hydroxyl groups of polycondensate A.

[0062] Polycondensate A can be used individually or in combination of two or more types.

[0063] Polycondensate A can be obtained, for example, by polycondensing the polyol component and carbonate component described above by a transesterification reaction. Specifically, polycondensate A can be obtained by carrying out a polycondensation reaction between the polyol component and the carbonate component in a reaction apparatus equipped with a stirrer, thermometer, heating device and distillation column, under a nitrogen stream, while gradually increasing the temperature to 190°C under a catalyst such as tetrabutoxytitanium, distilling off ethanol, and then gradually reducing the pressure to below 0.5 kPa, and reacting at a pressure of below 0.5 kPa for 4 hours or more. The mixing ratio of the polyol component and the carbonate component can be adjusted as appropriate from the viewpoint of hydroxyl value.

[0064] The polycarbonate polyol containing the polycondensate A described above is liquid at 25°C. Here, "liquid at 25°C" means that after heating to 100°C or higher, followed by standing at 25°C for 24 hours, visual observation reveals at least slight fluidity when tilted. Note that crystallization of polycarbonate polyols may take time; therefore, visual observation of the polycarbonate polyol should be performed after heating and standing at 25°C for 24 hours.

[0065] A polycarbonate polyol that is liquid at 25°C can be obtained, for example, by using a polyol with low crystallinity as the polyol component. Since polyols tend to become more crystallinity as the carbon chain length increases, when the first glycol is used, the polycarbonate polyol tends to become non-liquid at 25°C. However, by combining a linear glycol and a branched glycol as the first glycol, or by combining the first glycol with the second glycol, a polycarbonate polyol that is liquid at 25°C can be obtained.

[0066] (Non-aromatic polyisocyanates) Non-aromatic polyisocyanates are compounds that lack an aromatic ring and have multiple isocyanate groups. Examples of non-aromatic polyisocyanates include aliphatic polyisocyanates and their derivatives.

[0067] Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, and 2,4,4-trimethylhexa Examples include methylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, bis(isocyanate ethyl) carbonate, bis(isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanate methyl ester, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, and 2-isocyanate propyl-2,6-diisocyanate hexanoate.

[0068] Examples of aliphatic polyisocyanate derivatives include isocyanurate-modified, allophanate-modified, biuret-modified, urethane-modified, urea-modified, carbodiimide-modified, uretonimine-modified, and uretdione-modified derivatives. Using aliphatic polyisocyanate derivatives as non-aromatic polyisocyanates makes it easier to achieve a higher level of both heat resistance and flexibility in low-temperature environments.

[0069] Among aliphatic polyisocyanate derivatives, it is preferable to use at least one selected from the group consisting of isocyanurate-modified and allophanate-modified derivatives. When isocyanurate-modified derivatives are used, higher heat resistance is more easily obtained, and when allophanate-modified derivatives are used, flexibility in low-temperature environments tends to be further improved. From these viewpoints, it is preferable to use isocyanurate-modified derivatives and allophanate-modified derivatives in combination.

[0070] In the non-aromatic polyisocyanate, the content of the isocyanurate modified material may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 50% by mass or more, from the viewpoint of obtaining higher heat resistance, and may be 99.99% by mass or less, 99.9% by mass or less, 99% by mass or less, or 95% by mass or less, from the viewpoint of superior flexibility in low-temperature environments. From these viewpoints, the content of the isocyanurate modified material may be 10-100% by mass, 10-99.9% by mass, 20-99% by mass, 30-99% by mass, 30-95% by mass or 50-95% by mass. Note that the above content is based on the total mass of the non-aromatic polyisocyanate.

[0071] In the non-aromatic polyisocyanate, the content of the allophanate modified material may be 0.01% by mass or more, 1% by mass or more, or 5% by mass or more from the viewpoint of superior flexibility in low-temperature environments, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 50% by mass or less from the viewpoint of obtaining higher heat resistance. From these viewpoints, the content of the allophanate modified material may be 0.01 to 90% by mass, 1 to 80% by mass, 1 to 70% by mass, 5 to 70% by mass, or 5 to 50% by mass. Note that the above content is based on the total mass of the non-aromatic polyisocyanate.

[0072] Non-aromatic polyisocyanates are preferable to be free of urethane groups, as this provides superior flexibility in low-temperature environments. From a similar viewpoint, it is more preferable that the polyurethane-forming composition does not contain polyurethane polyisocyanates.

[0073] In polyurethane-forming compositions (for example, one-component compositions), polycarbonate polyols and non-aromatic polyisocyanates may be blended such that the NCO index is 50-120, 70-120, 80-110, 60-110, 90-105, or 80-105. The NCO index is the percentage (NCO groups / active hydrogen groups × 100) of the total number of moles of isocyanate groups (NCO groups) in the isocyanate group-containing compound relative to the total number of moles of active hydrogen groups in the active hydrogen group-containing compound contained in the composition.

[0074] In polyurethane-forming compositions, the content of polycarbonate polyol may be 50-95% by mass, 60-95% by mass, 50-90% by mass, 60-85% by mass, or 70-80% by mass. From the viewpoint of superior flexibility in low-temperature environments, the content of polycarbonate polyol is preferably 60% by mass or more, and from the viewpoint of superior heat resistance, it is preferably 95% by mass or less. In polyurethane-forming compositions, the content of non-aromatic polyisocyanate may be 5-50% by mass, 5-40% by mass, 10-50% by mass, 15-40% by mass, or 20-30% by mass. Here, the content of polycarbonate polyol and non-aromatic polyisocyanate is, if the polyurethane-forming composition is a one-component composition, based on the total mass of the polyurethane-forming composition, and if the polyurethane-forming composition is a two-component composition, based on the total mass of the mixture obtained when the first liquid and the second liquid are mixed so that the NCO index is 50 to 120 (for example, 100). In the case of a two-component polyurethane-forming composition, the above range for the polycarbonate polyol content means that the polycarbonate polyol content in the mixture is within the above range when the NCO index is any value between 50 and 120 (for example, 100). The same applies to the content of non-aromatic polyisocyanate.

[0075] (Other ingredients) The polyurethane-forming composition described above may further contain components other than polycarbonate polyol and non-aromatic polyisocyanate (other components). Examples of other components include chain extenders, crosslinking agents, antioxidants, catalysts, and plasticizers. If the polyurethane-forming composition is a two-component type, the chain extender and crosslinking agent may be included in the first liquid. Antioxidants, catalysts, and plasticizers may be included in the first liquid, the second liquid, or both.

[0076] [Chain extender] Chain extenders are bifunctional components used for chain extension (increasing molecular weight). Examples of chain extenders include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and dimer diol. These can be used individually or in combination of two or more.

[0077] The content of the chain extender may be 0.1 to 10% by mass, based on the total mass of the polyurethane-forming composition, when the polyurethane-forming composition is a one-component type. When the polyurethane-forming composition is a two-component type, the content of the chain extender in the mixture obtained when the first liquid and the second liquid are mixed so that the NCO index is 100 may be 0.1 to 10% by mass, relative to the total amount of the mixture. A content of 0.1% by mass or more tends to result in superior heat resistance, while a content of 10% by mass or less tends to result in superior flexibility in low-temperature environments.

[0078] [Crosslinking agent] Crosslinking agents are components with three or more functionalities used to form three-dimensional network crosslinks. Examples of crosslinking agents include trimethylolethane, trimethylolpropane, 2-hydroxy-2-methyl-1,4-butanediol, glycerin, ditrimethylolethane, ditrimethylolpropane, diglycerin, and pentaerythritol. These can be used individually or in combination of two or more.

[0079] The crosslinking agent content may be 1 to 10% by mass based on the total mass of the polyurethane-forming composition if the polyurethane-forming composition is a one-component type. If the polyurethane-forming composition is a two-component type, the amount of crosslinking agent in the mixture obtained when the first liquid and the second liquid are mixed so that the NCO index is 100 may be 1 to 10% by mass relative to the total amount of the mixture. A content of 1% by mass or more tends to result in superior heat resistance, while a content of 10% by mass or less tends to result in superior flexibility in low-temperature environments.

[0080] [Antioxidant] Examples of antioxidants include phenolic antioxidants, hindered amine antioxidants, thioether antioxidants, and phosphite antioxidants.

[0081] Examples of phenolic antioxidants include pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3 Examples include ,5-triazine-2,4,6(1H,3H,5H)-trione, N,N'-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate stearyl, and 2,6-di-t-butyl-p-cresol.

[0082] Examples of hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2,2,6,6-tetramethyl-4-piperidinol, bis-(1,2,2,6,6-pentamethylpiperidyl)-(3',5'-di-t-butyl-4'-hydroxybenzyl)butylmalonate, and bis-(2,2,6,6-tetramethyl-4-piperidinyl)succinate. , bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine, N-butyl-2,2,6,6- Tetramethyl-4-piperidineamine, 2,2'-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-bis-[ethanol], poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino), 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-un Examples include decyl oxazole, 1,1'-(1,2-ethane-diyl)-bis-(3,3',5,5'-tetramethyl-piperazinone), 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione, and 1,2,3,4-butane-tetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester.

[0083] Examples of thioether-based antioxidants include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, and trilauryl trithiophosphite.

[0084] Phosphate antioxidants include triisodecyl phosphite, tetra-(C12~15 alkyl)-4,4'-isopropylidenediphenyl diphosphite (e.g., tetra(tridecyl-4,4'-isopropylidenediphenyldiphosphite), triphenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol Examples include litol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, distearyl pentaerythritol diphosphite, and cyclic neopentanetetraylbis(2,6-di-t-butyl-4-methylphenyl phosphite).

[0085] The antioxidant content may be 0.01 to 3% by mass based on the total mass of the polyurethane-forming composition when the polyurethane-forming composition is a one-component type. When the polyurethane-forming composition is a two-component type, the antioxidant content in the mixture obtained when the first liquid and the second liquid are mixed so that the NCO index is 100 may be 0.01 to 3% by mass relative to the total amount of the mixture. A content of 0.01% by mass or more tends to further improve heat resistance, while a content of 3% by mass or less tends to suppress deterioration due to the effect of the antioxidant itself. From these viewpoints, the content may be 0.1% by mass or more, or 0.2% by mass or more, or 2% by mass or less, or 1% by mass or less.

[0086] [catalyst] Examples of catalysts include organotin compounds such as dioctyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin dioctoate, and tin 2-ethylhexanoate; iron compounds such as iron acetylacetonate and iron chloride; lithium compounds such as lithium acetylacetonate; lead compounds such as lead octoate; bismuth compounds such as bismuth octoate; and tertiary amine catalysts such as triethylamine and triethylenediamine.

[0087] If the polyurethane-forming composition is a one-component type, the catalyst content may be 0.001 to 1.000% by mass, based on the total mass of the polyurethane-forming composition. If the polyurethane-forming composition is a two-component type, the catalyst content in the mixture obtained when the first liquid and the second liquid are mixed so that the NCO index is 100 may be 0.001 to 1.000% by mass, relative to the total amount of the mixture.

[0088] [Plasticizer] Examples of plasticizers include trimellitic acid-based plasticizers such as tris(2-ethylhexyl) trimellitic acid, phthalate ester-based plasticizers represented by dioctyl phthalate and dinonyl phthalate, adipate ester-based plasticizers represented by dioctyl adipate and dinonyl adipate, and phosphate ester-based plasticizers such as triethyl phosphate.

[0089] When the polyurethane-forming composition is a one-component type, the plasticizer content may be 0.1% by mass or more, 20% by mass or less, or 0.1 to 20% by mass, based on the total mass of the polyurethane-forming composition. When the polyurethane-forming composition is a two-component type, the plasticizer content in the mixture obtained when the first liquid and the second liquid are mixed so that the NCO index is 100 may be 0.1% by mass or more, 20% by mass or less, or 0.1 to 20% by mass, based on the total amount of the mixture. From the viewpoint of maintaining high flexibility in low-temperature environments for a longer period of time, the above content may be 10% by mass or less, 1% by mass or less, or 0.1% by mass or less, or 0% by mass.

[0090] The polyurethane-forming composition may or may not contain aromatic polyisocyanates, but the content of aromatic polyisocyanates is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the total of aromatic polyisocyanates and non-aromatic polyisocyanates.

[0091] The polyurethane-forming composition described above may be a composition that forms polyurethane with a urethane group concentration of 1.7 mmol / g or less. For example, if the polyurethane-forming composition is a two-component composition, the polyurethane-forming composition may be a composition that forms polyurethane with a urethane group concentration of 1.7 mmol / g or less when the first liquid and the second liquid are mixed and reacted so that the NCO index is 50 to 120 (e.g., 100). Here, the urethane group concentration refers to the number of moles of urethane groups (-NHCOO-) contained in the polyurethane, based on the total mass of the polyurethane formed. Therefore, the urethane group concentration can be calculated from the blending amounts of the active hydrogen group-containing compound and the isocyanate group-containing compound contained in the polyurethane-forming composition. When the urethane group concentration of the formed polyurethane is within the above range, it tends to have better flexibility in low-temperature environments. From a similar viewpoint, the above urethane group concentration may be 1.5 mmol / g or less or 1.2 mmol / g or less. From the viewpoint of superior heat resistance, the urethane group concentration may be 0.3 mmol / g or more, 0.4 mmol / g or more, or 0.5 mmol / g or more. From these viewpoints, the urethane group concentration may be 0.3 to 1.7 mmol / g, 0.4 to 1.5 mmol / g, or 0.5 to 1.2 mmol / g. Note that if the polyurethane-forming composition is a two-component composition, a urethane group concentration within the above range means that when the NCO index is any value between 50 and 120 (for example, 100), a polyurethane having a urethane group concentration within the above range is formed.

[0092] <Potting materials and sealants> The potting material in one embodiment consists of the polyurethane-forming composition of the above embodiment. By using the polyurethane-forming composition of the above embodiment as a potting material, electrical and electronic components can be sealed. That is, the present invention provides, as one embodiment, a method for manufacturing a sealed body, comprising a step (sealing step) of sealing at least a part of an electrical and electronic component with a potting material consisting of the polyurethane-forming composition of the above embodiment.

[0093] The sealing step includes a step of reacting a polycarbonate polyol contained in the polyurethane-forming composition of the above embodiment with a non-aromatic polyisocyanate to form a polyurethane.

[0094] If the polyurethane-forming composition is a one-component type, the polycarbonate polyol and non-aromatic polyisocyanate are reacted by, for example, heating the composition. If the polyurethane-forming composition is a two-component type, the polycarbonate polyol and non-aromatic polyisocyanate are reacted by mixing the first liquid and the second liquid. The mixing of the first liquid and the second liquid may be performed, for example, after heating or cooling at least one of the liquids. Alternatively, the mixture may be heated after mixing the first and second liquids. The first and second liquids may be mixed so that the NCO index is 50-120, 70-120, 80-110, 60-110, 90-105, or 80-105.

[0095] In the sealing process, at least a portion of the electrical / electronic component is sealed by a sealing portion containing polyurethane. This results in a sealed body comprising the electrical / electronic component and a sealing portion that seals at least a portion of the electrical / electronic component. If the polyurethane-forming composition is a one-component type, the sealing portion can be described as a cured body of the polyurethane-forming composition, and if the polyurethane-forming composition is a two-component type, it can be described as a cured body of a mixture of the first and second liquids. [Examples]

[0096] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0097] <Synthesis Examples 1-17 and 19-22> Polycarbonate polyols of Synthesis Examples 1-17 and 19-22 were synthesized by polycondensation of polyol and carbonate components. Specifically, in a reaction apparatus equipped with a stirrer, thermometer, heating device, and distillation column, 684 g of 1,6-hexanediol, 293 g of ND-15 (a mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol in a mass ratio of 15:85), and 791 g of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged as glycols, and 0.06 g of tetrabutyl titanate was added as a reaction catalyst. The temperature inside the apparatus was gradually increased to 190°C under a nitrogen stream. When the distillation of ethanol slowed and the top temperature of the distillation column fell below 50°C, the temperature inside the apparatus was kept at 190°C and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at a pressure of 0.1 kPa for a further 5 hours to distill off the ethanol. This resulted in the synthesis of the polycarbonate polyol in Synthesis Example 1. Furthermore, the polycarbonate polyols in Synthesis Examples 2-17 and 19-22 were synthesized in the same manner as in Synthesis Example 1, except that the polyol components (mixtures of polyols) were used as the polyol components to have the compositions shown in Tables 1-4, and the amounts of the polyol components and carbonate components were adjusted to achieve the desired hydroxyl value.

[0098] <Synthesis Example 18> In a reactor equipped with a stirrer, thermometer, heating device, and distillation column, 865 g of ND-15 (a mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol in a mass ratio of 15:85) as glycol, 60 g of TMP as a polyol having three or more hydroxyl groups, and 702 g of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged. Furthermore, 0.08 g of lithium acetylacetonate (manufactured by Sigma-Aldrich) was charged as a reaction catalyst, and the temperature inside the reactor was gradually increased to 150°C under a nitrogen stream. When the distillation of ethanol slowed and the top temperature of the distillation column fell below 50°C, the temperature inside the reactor was kept at 150°C, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at a pressure of 0.1 kPa for a further 5 hours to distill off the ethanol. This synthesized the polycarbonate polyol of Synthesis Example 18.

[0099] The details of the polyol components shown in Tables 1-4 are as follows. • 1,5-PG:1,5-pentanediol · 1,6-HD: 1,6-hexanediol MPD: 3-methyl-1,5-pentanediol · 1,8-OD:1,8-octanediol • 1,9-ND:1,9-nonanediol MOD:2-methyl-1,8-octanediol · 1,10-DD: 1,10-decanediol TMP: Trimethylolpropane Products manufactured by Tokyo Chemical Industry Co., Ltd. were used as the 1,5-PG source, 1,6-HD source, 1,8-OD source, 1,10-DD source, and TMP source, and a product manufactured by Kuraray Co., Ltd. was used as the MPD source. ND or ND-15 (both product names) manufactured by Kuraray Co., Ltd. were used as the 1,9-ND source, and ND-15 (product name) manufactured by Kuraray Co., Ltd. was used as the MOD.

[0100] (Calculation of average carbon number) The average number of carbon atoms (molar average carbon atoms) of the polyol components used in synthesis examples 1 to 22 was calculated from the blending amounts. The results are shown in Tables 1 to 4. Note that the average number of carbon atoms of the polyol components can also be determined by analyzing the synthesized polycarbonate polyol. In synthesis examples 3, 8, and 19, the average number of carbon atoms of the polyol components was determined by analyzing the polycarbonate polyol using the method described below, and it was confirmed that the obtained analytical value (measured value) was the same as the calculated value derived from the blending amounts.

[0101] (Measurement of average carbon number) Approximately 0.1 g of polycarbonate polyol was accurately weighed and dissolved in 5 mL of tetrahydrofuran (THF) in a 300 mL round-bottom flask. Then, 5 mL of 6 mol / L potassium hydroxide aqueous solution, 45 mL of ethanol, and boiling chips were added, and the mixture was refluxed in a water bath for 1 hour. After refluxing, the mixture was cooled to room temperature, neutralized with 5 mL of 6 mol / L hydrochloric acid, and then 100 mL of ethanol was added. The solvent was then removed using an evaporator. Chloroform was added to the round-bottom flask, and the mixture was shaken well. While washing the flask, the filtrate after filtration was collected, and this process was repeated several times until the filtrate reached 100 mL. The resulting sample solution was analyzed by gas chromatography (GC) under the following conditions, and the molar ratio of each polyol component was calculated from a pre-prepared calibration curve for each polyol component. The average number of carbon atoms was calculated from the obtained molar ratios. Furthermore, even if the type of polyol component constituting the polycarbonate polyol is unknown, the type of polyol component can be identified from the mass information obtained by GC / MS analysis. In the case of special polyol components that cannot be identified by mass information alone, they can be identified by structural analysis (e.g., NMR analysis) of each polyol component separated by the GC analysis. [conditions] Equipment: Shimadzu GC-2010 Column: Restek Stabilwax (0.25mmI.D.×30m, df=0.25μm) Column oven temperature: 100℃ - 10℃ / min - 250℃ (5 min) Column flow rate: 1.0 mL / min Sample inlet: Split inlet (split ratio = 1 / 30), 250°C Sample injection volume: 1 μL Carrier gas: He Detector (FID) temperature: 250℃

[0102] (Condition evaluation) The polycarbonate polyols obtained in Synthesis Examples 1-22 were heated to 100°C, placed in transparent glass bottles, and left to stand at 25°C for 24 hours. The state of the polycarbonate polyols at 25°C after standing was then evaluated. Specifically, visual observation was performed; if there was even slight fluidity when tilted, it was judged to be liquid, and if there was no fluidity, it was judged to be solid. The evaluation results are shown in Tables 1-4.

[0103] (Hydroxyl value and molecular weight measurement) The hydroxyl values ​​of the polycarbonate polyols obtained in Synthesis Examples 1-22 were evaluated using an acetylation reagent in accordance with JIS K1557-1. The molecular weight of the polycarbonate polyols was also calculated based on the hydroxyl values. The results are shown in Tables 1-4.

[0104] (DSC measurement) Differential scanning calorimeter (DSC) measurements were performed on the polycarbonate polyols obtained in synthesis examples 1 to 22. The DSC measurements were performed using a PerkinElmer DSC8500 in the following order [1] to [5]. [1] The samples were rapidly cooled from room temperature (25°C) to -80°C and held at -80°C for 3 minutes. [2] The temperature was increased from -80°C to 100°C at a heating rate of 10°C / min. [3] It was held at 100°C for 3 minutes. [4] The temperature was lowered from 100°C to -80°C at a rate of 10°C / min. [5] -80°C was maintained for 3 minutes. [6] The temperature was increased from -80°C to 100°C at a heating rate of 10°C / min.

[0105] The glass transition temperature (Tg) was determined from the measurement results in step [6] of the DSC measurement described above. In addition, for samples where a crystallization peak (exothermic peak) and a melting peak (endothermic peak) were observed, the crystallization peak temperature and melting peak temperature were determined, and for samples where a crystallization peak (exothermic peak) was observed during cooling, the maximum crystallization temperature (crystallization onset temperature) was determined. Note that the crystallization peak temperature is the value observed during cooling in step [4] or during heating in step [6]. If no crystallization peak temperature was observed during cooling in step [4], but a crystallization peak temperature was observed in the temperature range below -20°C during heating, it can be said that solidification may occur at temperatures below -20°C after a long period of time. Also, if a crystallization peak was observed in the temperature range below 0°C during cooling in step [4], it can be said that solidification may occur at temperatures below 0°C in a relatively short time. Furthermore, if no crystallization peak was observed in either step [4] or step [6], it can be said that the sample will not solidify and will maintain its fluidity. Regardless of the above, if a melting peak is observed at 25°C or higher during the heating process in step [6], it can be said that the material is solid at 25°C.

[0106] [Table 1]

[0107] [Table 2]

[0108] [Table 3]

[0109] [Table 4]

[0110] <Examples 1-26 and Comparative Examples 1-11> Polyurethanes for Examples 1-26 and Comparative Examples 1-11 were synthesized using the components shown in Tables 5-10 in the amounts indicated in Tables 5-10. Specifically, each component was heated to 40-60°C and thoroughly mixed until homogeneous. After degassing under reduced pressure, the mixture was injected into a mold preheated to 100-120°C and cured by heating at 100-120°C for 30 minutes to 1 hour. After demolding, the mixture was subjected to secondary curing at 40-50°C for 12 hours to obtain the polyurethanes (polyurethane-containing compositions) for Examples 1-26 and Comparative Examples 1-11. The amounts of polyol (polycarbonate polyol, polyether polyol, or polybutadiene polyol) and polyisocyanate were adjusted so that the equivalent ratio of the active hydrogen groups (OH groups) of the polyol to the isocyanate groups (NCO groups) of the polyisocyanate was as shown in Tables 5-10. The urethane group concentration in the table was calculated from the blending amounts of active hydrogen group-containing compounds (polycarbonate polyols and crosslinking agents) and isocyanate group-containing compounds (polyisocyanates).

[0111] <Rating> (Initial evaluation) The initial low-temperature properties (low-temperature flexibility) of the polyurethanes obtained in the above examples and comparative examples were evaluated by DMA measurement of the polyurethanes. Specifically, first, a measurement sample (test piece) of 200 mm × 5 mm × 2 mm (thickness) was prepared. Next, using a DMA7100 manufactured by Hitachi High-Tech Science Corporation, DMA measurement was performed on the measurement sample under the conditions of -80°C to 300°C, heating rate of 2°C / min, and frequency of 1 Hz, and the storage modulus (E') and tanδ peak temperature at -40°C were determined. The results are shown in Tables 5 to 10. When the storage modulus (E') at -40°C was 700 MPa or less, it was judged that the initial low-temperature properties were good.

[0112] Furthermore, the Shore A hardness of the polyurethane was measured using a Type A hardness tester in accordance with JIS K6253. The sample used for measurement was Φ30mm × 13m (height). A hardness of 5 or higher was considered to indicate that the polyurethane had sufficient hardness.

[0113] (Evaluation after heat resistance test) For measurement samples prepared in the same manner as the initial evaluation described above, a heat resistance test was conducted by heating at 150°C for 1000 hours or 2000 hours. After that, DMA measurement and Shore A hardness measurement were performed in the same manner as the initial evaluation described above, and the storage modulus (E') at -40°C, the storage modulus (E') at 25°C, the tanδ peak temperature, and the Shore A hardness were determined. Furthermore, the hardness change rate was calculated using the Shore A hardness obtained in the initial evaluation and the Shore A hardness obtained in the evaluation after the heat resistance test. The results are shown in Tables 5 to 10. After the heat resistance test of heating at 150°C for 1000 hours, if the storage modulus (E') at -40°C was 1100 MPa or less, the storage modulus (E') at 25°C was 5 MPa or less, and the hardness change rate was 50% or less, it was judged to have high heat resistance and high reliability in maintaining flexibility in low-temperature environments over a long period of time. In Comparative Example 4, it was confirmed that a portion of the sample melted during the heat resistance test, and in Comparative Example 8, it was confirmed that the entire sample melted during the heat resistance test. Therefore, evaluation after the heat resistance test was not performed for Comparative Example 4 and Comparative Example 8.

[0114] [Table 5]

[0115] [Table 6]

[0116] [Table 7]

[0117] [Table 8]

[0118] [Table 9]

[0119] [Table 10]

[0120] The details of the polycarbonate polyols, polyether polyols, polybutadiene polyols, polyisocyanates, catalysts, additives, and plasticizers listed in Tables 5 to 10 are as follows. [Polycarbonate polyol] • Polycarbonate polyols synthesized in Synthesis Examples 1-22 [Polyether polyol] • PTG-L3500 (manufactured by Hodogaya Chemical Industry Co., Ltd., product name) [Polybutadiene polyol] • R-45HT (manufactured by Idemitsu Kosan Co., Ltd., product name: Poly bd R-45HT) [Polyisocyanate] • Polyisocyanate 1: Isocyanurate modified form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, product name: Coronate HXLV ("Coronate" is a registered trademark), NCO content 23.1%) • Polyisocyanate 2: A mixture of isocyanurate-modified hexamethylene diisocyanate and allophanate-modified hexamethylene diisocyanate, synthesized by the following method. • Polyisocyanate 3: Hexamethylene diisocyanate (manufactured by Tosoh Corporation, NCO content 50.0%) • Polyisocyanate 4: Carbodiimide modified form of diphenylmethane diisocyanate (manufactured by Tosoh Corporation, product name: Myrionate MTL ("Millionate" is a registered trademark), NCO content 28.7%) [catalyst] • DOTDL: Dioctyl tin dilaurate (manufactured by Kishida Chemical Co., Ltd.) • U-600: Bismastris (2-ethylhexanoate) (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600 ("Neostan" is a registered trademark)) [Crosslinking agent] • TMP: Trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) [Additives] IRGANOX-1010: Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (manufactured by BASF, trade name) • Mixture C: A mixture of IRGANOX-1010, SANOL LS770 (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, Ciba Specialty Chemicals Co., Ltd., trade name), and ADEKA Stab AO-26 (thioether antioxidant, manufactured by ADEKA Corporation, trade name) (mass ratio = 1:1:1) Mixture D: A mixture of IRGANOX-1010, SANOL LS770 (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, Ciba Specialty Chemicals Co., Ltd., trade name), and ADEKA Stab 1500 (tetra-C12-15 alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), manufactured by ADEKA Corporation, trade name) (mass ratio = 1:1:1) [Plasticizer] • TOTM: Tris-2-ethylhexyl trimellitate (manufactured by J-Plus Co., Ltd.)

[0121] <Synthesis of Polyisocyanate 2> In a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 730 g of hexamethylene diisocyanate (manufactured by Tosoh Corporation) and 65 g of tridecanol (manufactured by KH Neochem Co., Ltd.) were charged and reacted at 80°C for 1 hour. Subsequently, 0.2 g of tin octoate (manufactured by Nippon Chemical Industrial Co., Ltd.) was added to the reaction solution and the reaction was carried out at 90°C until the desired NCO content was reached. Then, 0.2 g of acidic phosphate ester (manufactured by Johoku Chemical Industry Co., Ltd., product name: JP-508), a reaction stopper, was added and the reaction was stopped at 50°C for 1 hour. From this reaction product, excess HDI was removed by thin-film distillation (conditions: 140°C, 0.04 kPa) to obtain a modified polyisocyanate (polyisocyanate 2) with an NCO content of 17.7% by mass, a free HDI content of 0.1% by mass, and an isocyanurate modified form:allophanate modified form ratio of 45:55 (by mass). The mass ratio of isocyanurate-modified and allophanate-modified products was determined by the following measurement method. (Measurement method) 1 Using 1H-NMR (JEOL, JNM-ECZ400S / L1), the mass ratio of the isocyanurate-modified and allophanate-modified compounds was determined from the area ratio of the signal of the hydrogen atom bonded to the nitrogen atom of the allophanate group at approximately 8.5 ppm and the signal of the hydrogen atom of the methylene group adjacent to the nitrogen atom of the isocyanurate group at approximately 3.7 ppm. The specific measurement conditions are as follows. ·Measurement temperature: 23℃ • Sample concentration: 0.1g / 1ml • Total number of times: 16 • Relaxation time: 5 seconds • Solvent: Deuterium dimethyl sulfoxide • Chemical shift criterion: Signal of hydrogen atoms of the methyl group in deuterium dimethyl sulfoxide (2.5 ppm)

Claims

[Claim 1] It contains a polycarbonate polyol that is liquid at 25°C and a non-aromatic polyisocyanate. The polycarbonate polyol is a polyurethane-forming composition comprising a polycondensate of a polyol component containing a glycol with 8 or more carbon atoms and a carbonate component.

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