Polyol composition, polyurethane resin composition, and polyurethane resin

Abstract

The polyol composition contains polyols (A) to (B). The polyol (A) is a polyester polyol. The polyol (A) has an average number of functional groups of 1.1-5.0 and a hydroxyl value of 50-170 mgKOH / g. The polyol (B) has an average number of functional groups of 2.0-4.0 and a hydroxyl value of 600-1200 mgKOH / g. The polyester polyol has a 15-20 C fatty acid (X) unit containing one hydroxyl group. The ratio of the fatty acid (X) to the polyol (B) is 0.08-0.90.

Description

Polyol composition, polyurethane resin composition, and polyurethane resin

[0001] The present invention relates to a polyol composition, a polyurethane resin composition, and a polyurethane resin.

[0002] Polyurethane resins are obtained by the reaction of a polyisocyanate component and a polyol component. Polyurethane resins are molded by various methods and are widely used in various industrial fields. Examples of molding methods for polyurethane resins include cast molding, injection molding, RIM molding, blow molding, and extrusion molding.

[0003] In recent years, from the viewpoint of environmental friendliness, there has been a demand for improving the biomass content of polyurethane resins. Therefore, the use of plant-derived polyols as polyol components has been investigated. Examples of plant-derived polyols include castor oil.

[0004] More specifically, a method has been proposed in which a polyisocyanate (A) and a polyol mixture (B) are reacted and molded by reaction injection molding. In this method, the polyol mixture contains a polyol, a crosslinking agent, and a catalyst. The polyol contains castor oil (polyol C) (see, for example, Example 4 of Patent Document 1).

[0005] JP 2012-111073 A

[0006] On the other hand, depending on the application, polyurethane resins may be required to have excellent mechanical properties, and in particular, polyurethane resins having relatively high hardness may be required.

[0007] Furthermore, the storage modulus of a polyurethane resin usually varies depending on temperature. However, depending on the application, it may be required to suppress the temperature-dependent variation in the storage modulus. In particular, it may be required to reduce the temperature dependence of the storage modulus at 0°C to 50°C. More specifically, it may be required to bring the average value of "E'24 / E'0" (described later) and "E'50 / E'24" (described later) closer to 1.0.

[0008] The present invention provides a polyol composition, a polyurethane resin composition, and a polyurethane resin that can provide a polyurethane resin having excellent mechanical properties (high hardness) and reduced temperature dependence of the storage modulus.

[0009] The present invention [1] is a polyol composition containing polyol (A) and polyol (B), wherein the polyol (A) is a polyester polyol, the polyol (A) has an average functionality of 1.1 to 5.0, a hydroxyl value of 50 mgKOH / g to 170 mgKOH / g, the polyol (B) has an average functionality of 2.0 to 4.0, and a hydroxyl value of 600 mgKOH / g to 1,200 mgKOH / g, the polyester polyol has a fatty acid (X) unit having 15 to 20 carbon atoms and containing one hydroxyl group, and the ratio ((X) / (B)) of the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) to the mass of the polyol (B) is 0.08 to 0.90.

[0010] The present invention [2] includes the polyol composition according to the above [1], in which the ratio ((B) / ((B)+(X))) of the mass of the polyol (B) to the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) and the polyol (B) is 0.55 to 0.95.

[0011] The present invention [3] includes the polyol composition according to the above [1] or [2], in which the ratio ((X) / (B)) of the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) to the mass of the polyol (B) is 0.15 to 0.50.

[0012] The present invention [4] includes the polyol composition according to any one of the above [1] to [3], wherein the polyol (A) has a hydroxyl value of 55 mg KOH / g to 170 mg KOH / g.

[0013] The present invention [5] includes the polyol composition according to any one of the above [1] to [4], wherein the polyol (A) has a hydroxyl value of 55 mg KOH / g to 140 mg KOH / g.

[0014] The present invention [6] includes the polyol composition according to any one of the above [1] to [5], wherein the fatty acid (X) is ricinoleic acid.

[0015] The present invention [7] includes the polyol composition according to any one of the above [1] to [6], which is a polyurethane resin raw material.

[0016] The present invention [8] includes a polyurethane resin composition containing a polyol component containing the polyol composition according to any one of the above [1] to [7] and a polyisocyanate component, and having an NCO index of 0.70 to 1.30.

[0017] The present invention [9] includes the polyurethane resin composition according to the above [8], wherein the polyisocyanate component contains at least one selected from the group consisting of diphenylmethane diisocyanate, diphenylmethane diisocyanate derivatives, phenylene diisocyanate, phenylene diisocyanate derivatives, and polymethylene polyphenyl polyisocyanate.

[0018] The present invention

[10] includes the polyurethane resin composition according to the above [9], in which the polyisocyanate component contains a diphenylmethane diisocyanate derivative.

[0019] The present invention

[11] is a polyurethane resin containing a reaction product of the polyurethane resin composition according to any one of the above [8] to

[10] , wherein the Shore D hardness of the polyurethane resin is 60 or more, and the density of the polyurethane resin is 1.0 g / cm ３ The polyurethane resin is as described above.

[0020] The polyol composition and polyurethane resin composition of the present invention provide a polyurethane resin having excellent mechanical properties (high hardness) and reduced temperature dependence of storage modulus. The polyurethane resin of the present invention also has excellent mechanical properties (high hardness) and can reduce temperature dependence of storage modulus.

[0021] In particular, the polyol composition and polyurethane resin composition described above can reduce the temperature dependency of the storage modulus at 0° C. to 50° C. More specifically, the average value of "E'24 / E'0" (described later) and "E'50 / E'24" (described later) (E'AVE) can be made closer to 1.0.

[0022] The following describes embodiments of the present disclosure. These descriptions and examples are illustrative of embodiments and do not limit the scope of the embodiments. In the present disclosure, a combination of two or more preferred aspects is a more preferred embodiment. In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​described before and after "to" as the lower and upper limits. In the present disclosure, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In the numerical ranges described in the present disclosure, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple corresponding substances. In the present disclosure, when the amount of each component in a composition is referred to, if multiple substances corresponding to each component are present in the composition, the total amount of the multiple substances present in the composition is meant, unless otherwise specified. In the present disclosure, "mass %" and "wt %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. In the present disclosure, "%" indicating the amount of a component is based on mass unless otherwise specified. In the present disclosure, the term "layer" includes a case where the layer is formed over the entire region when the region in which the layer exists is observed, as well as a case where the layer is formed only in a part of the region. In the notation of groups (atomic groups) in the present disclosure, a notation that does not indicate substituted or unsubstituted includes both those that have no substituent and those that have a substituent.

[0023] [1] Polyol Composition The polyol composition contains a polyol (A) and a polyol (B). Each of these will be described in detail below.

[0024] [1.1] Polyol (A) The polyol (A) is a polyester polyol. That is, the polyol (A) is composed of a polyester polyol. Examples of the polyester polyol include polyester polyols having a number average molecular weight of 900 to 4,000. The number average molecular weight can be determined as a polyethylene glycol-equivalent molecular weight by a known gel permeation chromatography method (the same applies hereinafter).

[0025] More specifically, the polyester polyol has a structural unit derived from a polyhydric alcohol (a polyhydric alcohol unit) and a structural unit derived from a carboxylic acid (a carboxylic acid unit).

[0026] <Polyhydric Alcohol Unit> Examples of polyhydric alcohols include dihydric alcohols, trihydric alcohols, tetrahydric alcohols, pentahydric alcohols, hexahydric alcohols, heptahydric alcohols, and octahydric alcohols. Examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of trihydric alcohols include glycerin, trimethylolpropane, and triisopropanolamine. Examples of tetrahydric alcohols include tetramethylolmethane (pentaerythritol) and diglycerin. Examples of pentahydric alcohols include xylitol. Examples of hexahydric alcohols include sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol. Examples of heptahydric alcohols include perseitol. Examples of octahydric alcohols include sucrose. These may be used alone or in combination.

[0027] Further, examples of polyhydric alcohols include polyoxyalkylene (carbon number (C) 2 to 3) polyols, and more specific examples include polyoxyethylene polyols, polyoxypropylene polyols, and oxyethylene-oxypropylene copolymers (random or block copolymers). The number average molecular weight (measured by GPC) of the polyoxyalkylene (C2 to C3) polyol is, from the viewpoint of the mechanical properties of the polyurethane resin, for example, 200 to 2,000, preferably 400 to 1,000, and more preferably 500 to 1,000. These may be used alone or in combination of two or more types.

[0028] The polyhydric alcohol is preferably a dihydric to hexahydric alcohol. Furthermore, the polyhydric alcohol is preferably a polyoxyalkylene (C2-C3) polyol. From the viewpoint of reducing the temperature dependency of the storage modulus of the polyurethane resin at 0°C to 50°C, the polyhydric alcohol is more preferably a trihydric to hexahydric alcohol.

[0029] In particular, from the viewpoint of reducing the temperature dependency of the storage modulus of the polyurethane resin at 0°C to 24°C, a more preferred example of the polyhydric alcohol is a trihydric alcohol, and particularly preferred is glycerin.

[0030] That is, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin at 0°C to 24°C, the polyester polyol preferably contains, as the polyhydric alcohol unit, a structural unit derived from a trihydric alcohol (trihydric alcohol unit), and more preferably contains only trihydric alcohol units. In other words, the polyhydric alcohol unit preferably contains a trihydric alcohol unit, and more preferably consists of a trihydric alcohol unit. The polyester polyol further preferably contains, as the polyhydric alcohol unit, a structural unit derived from glycerin (glycerin unit), and particularly preferably contains only glycerin units. In other words, the polyhydric alcohol unit further preferably contains a glycerin unit, and particularly preferably consists of a glycerin unit.

[0031] Furthermore, from the viewpoint of reducing the temperature dependency of the storage modulus of the polyurethane resin at 24°C to 50°C, the polyhydric alcohol is more preferably a tetrahydric alcohol, and particularly preferably diglycerin.

[0032] That is, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin at 24°C to 50°C, the polyester polyol preferably contains, as the polyhydric alcohol unit, a structural unit derived from a tetrahydric alcohol (tetrahydric alcohol unit), and more preferably contains only tetrahydric alcohol units. In other words, the polyhydric alcohol unit preferably contains a tetrahydric alcohol unit, and more preferably consists of a tetrahydric alcohol unit. The polyester polyol further preferably contains, as the polyhydric alcohol unit, a structural unit derived from diglycerin (diglycerin unit), and particularly preferably contains only diglycerin units. In other words, the polyhydric alcohol unit further preferably contains a diglycerin unit, and particularly preferably consists of a diglycerin unit.

[0033] Furthermore, from the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistance, the polyhydric alcohol is more preferably a hexahydric alcohol, and particularly preferably sorbitol and pentaerythritol.

[0034] That is, from the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistance, the polyester polyol preferably contains, as the polyhydric alcohol unit, a structural unit derived from a hexahydric alcohol (hexahydric alcohol unit), and more preferably contains only hexahydric alcohol units. In other words, the polyhydric alcohol unit preferably contains a hexahydric alcohol unit, and more preferably consists of a hexahydric alcohol unit. The polyester polyol further preferably contains, as the polyhydric alcohol unit, a structural unit derived from sorbitol (sorbitol unit) and / or a structural unit derived from pentaerythritol (pentaerythritol unit), and particularly preferably contains only sorbitol units and / or pentaerythritol units. In other words, the polyhydric alcohol unit further preferably contains a sorbitol unit and / or a pentaerythritol unit, and particularly preferably consists of a sorbitol unit and / or a pentaerythritol unit.

[0035] <Carboxylic Acid Unit> Examples of carboxylic acids include fatty acids. Examples of fatty acids include saturated fatty acids and unsaturated fatty acids. Fatty acids are classified into fatty acids that do not contain a hydroxyl group in one molecule (hereinafter referred to as "hydroxyl-free fatty acids") and fatty acids that contain one or more hydroxyl groups in one molecule (hereinafter referred to as "hydroxyl-containing fatty acids").

[0036] Examples of non-hydroxyl group-containing fatty acids include non-hydroxyl group-containing fatty acids having 4 to 30 carbon atoms.

[0037] Examples of non-hydroxyl group-containing fatty acids having 4 to 30 carbon atoms include non-hydroxyl group-containing saturated fatty acids having 4 to 30 carbon atoms and non-hydroxyl group-containing unsaturated fatty acids having 4 to 30 carbon atoms. Examples of non-hydroxyl group-containing saturated fatty acids having 4 to 30 carbon atoms include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, and triacontanoic acid. Examples of non-hydroxyl group-containing saturated fatty acids having 4 to 30 carbon atoms include oleic acid, linoleic acid, and linolenic acid. These can be used alone or in combination of two or more.

[0038] Examples of hydroxyl group-containing fatty acids include fatty acids containing one hydroxyl group per molecule (hereinafter referred to as monohydroxy fatty acids) and fatty acids containing multiple hydroxyl groups per molecule (hereinafter referred to as polyhydroxy fatty acids).

[0039] Examples of monohydroxy-fatty acids include monohydroxy-fatty acids having 15 to 20 carbon atoms. Examples of monohydroxy-fatty acids having 15 to 20 carbon atoms include monohydroxy-saturated fatty acids having 15 to 20 carbon atoms and monohydroxy-unsaturated fatty acids having 15 to 20 carbon atoms. Examples of monohydroxy-saturated fatty acids having 15 to 20 carbon atoms include hydroxypentadecanoic acid, hydroxyhexadecanoic acid (hydroxypalmitic acid), hydroxyheptadecanoic acid, hydroxyoctadecanoic acid (hydroxystearic acid), hydroxynonadecanoic acid, and hydroxyicosanoic acid (hydroxyarachidic acid). Examples of monohydroxy-unsaturated fatty acids having 15 to 20 carbon atoms include hydroxyoleic acid (ricinoleic acid), hydroxylinoleic acid, and hydroxylinolenic acid. These can be used alone or in combination of two or more types.

[0040] Examples of polyhydroxy fatty acids include polyhydroxy fatty acids having 15 to 20 carbon atoms. Examples of polyhydroxy fatty acids having 15 to 20 carbon atoms include polyhydroxy saturated fatty acids having 15 to 20 carbon atoms and polyhydroxy unsaturated fatty acids having 15 to 20 carbon atoms. Examples of polyhydroxy saturated fatty acids having 15 to 20 carbon atoms include dihydroxypentadecanoic acid, dihydroxyhexadecanoic acid (dihydroxypalmitic acid), dihydroxyheptadecanoic acid, dihydroxyoctadecanoic acid (dihydroxystearic acid), dihydroxynonadecanoic acid, and dihydroxyicosanoic acid (dihydroxyarachidic acid). Examples of polyhydroxy unsaturated fatty acids having 15 to 20 carbon atoms include dihydroxyoleic acid, dihydroxylinoleic acid, and dihydroxylinolenic acid. These can be used alone or in combination of two or more types.

[0041] The fatty acid contains, as an essential component, a hydroxyl group-containing fatty acid, more specifically, a monohydroxy fatty acid having 15 to 20 carbon atoms. Hereinafter, the monohydroxy fatty acid having 15 to 20 carbon atoms will be referred to as fatty acid (X).

[0042] That is, the polyol (A) (polyester polyol) has, as an essential structural unit, a structural unit (i.e., a fatty acid (X) unit) derived from a fatty acid having 15 to 20 carbon atoms and containing one hydroxyl group (i.e., a fatty acid (X)).

[0043] The fatty acid (X) is preferably an unsaturated fatty acid (i.e., a monohydroxy-unsaturated fatty acid having 15 to 20 carbon atoms), more preferably ricinoleic acid. That is, the fatty acid (X) is more preferably ricinoleic acid, and the polyol (A) (polyester polyol) more preferably has a ricinoleic acid unit as the fatty acid (X) unit.

[0044] The content of the fatty acid (X) relative to the total amount of the polyol (A) (polyester polyol) is, for example, 80 to 99 mass %, or preferably 90 to 95 mass %.

[0045] <Method for producing polyester polyol> The method for producing the polyester polyol is not particularly limited. For example, the polyester polyol can be produced by ester condensation of the polyhydric alcohol and the carboxylic acid containing the fatty acid (X) by a known method.

[0046] The ratio of polyhydric alcohol to carboxylic acid is appropriately adjusted from the viewpoint of obtaining a polyurethane resin having a well-balanced hardness, density, and electrical resistance. Specifically, from the viewpoint of obtaining a polyurethane resin having a well-balanced hardness, density, and electrical resistance, the ratio of carboxylic acid units to 1 mole of polyhydric alcohol units is, for example, 1 to 10 moles, preferably 1.5 to 6 moles, and more preferably 1.5 to 3 moles.

[0047] The polyester polyol may also be a naturally derived polyester polyol. Examples of naturally derived polyester polyols include natural oils and natural oil derivatives. Examples of natural oils include vegetable oils and / or animal oils, preferably vegetable oils. Examples of vegetable oils include castor oil, soybean oil, palm oil, sesame oil, rapeseed oil, coconut oil, and hydrogenated versions thereof. Examples of natural oil derivatives include ester condensates of the above natural oils and the above fatty acids. Examples of natural oil derivatives include ester condensates of castor oil and fatty acids. Fatty acids that undergo ester condensation with castor oil are preferably fatty acids derived from natural oils, more preferably fatty acids derived from castor oil (castor oil fatty acids). Castor oil fatty acids are fatty acids obtained by saponification of castor oil, such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and dihydroxystearic acid, with ricinoleic acid being preferred. The natural oil derivative is not particularly limited, and can be produced by ester condensation of a natural oil with a fatty acid by a known method.

[0048] The polyester polyols may be used alone or in combination of two or more. From the viewpoint of improving the biomass content and achieving excellent environmental friendliness, the polyester polyol preferably contains a naturally derived polyester polyol, and more preferably consists of a naturally derived polyester polyol. From the viewpoint of obtaining a polyurethane resin having an excellent balance of hardness, density, and electrical resistance, the naturally derived polyester polyol is preferably a natural oil or a natural oil derivative, more preferably a natural oil derivative, and particularly preferably a castor oil derivative.

[0049] <Properties of Polyol (A)> The polyol (A) has a predetermined hydroxyl value and average functionality. That is, a polyester polyol having a predetermined hydroxyl value and average functionality is selected as the polyol (A). When two or more polyester polyols are used in combination, each polyester polyol preferably has a predetermined hydroxyl value and average functionality.

[0050] More specifically, the hydroxyl value of the polyol (A) is 50 mgKOH / g to 170 mgKOH / g from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin. Furthermore, the hydroxyl value of the polyol (A) is preferably 55 mgKOH / g to 170 mgKOH / g, more preferably 55 mgKOH / g to 150 mgKOH / g, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin. Furthermore, the hydroxyl value of the polyol (A) is even more preferably 55 mgKOH / g to 140 mgKOH / g, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin.

[0051] That is, the lower limit of the hydroxyl value of the polyol (A) is 50 mgKOH / g or more from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin, and is preferably 55 mgKOH / g or more from the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistivity.

[0052] The upper limit of the hydroxyl value of the polyol (A) is 170 mgKOH / g or less, preferably 160 mgKOH / g or less, more preferably 150 mgKOH / g or less, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin, and is even more preferably 140 mgKOH / g or less, from the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistivity.

[0053] The hydroxyl value is measured in accordance with the phthalation method of Method B of JIS K 1557-1 (2007) (the same applies hereinafter).

[0054] When two or more types of polyester polyols are used in combination, the hydroxyl value of the entire polyol (A) can be calculated by proportionally dividing the hydroxyl values ​​of the individual polyester polyols based on the blending recipe.

[0055] The average number of functional groups (average number of hydroxyl groups) of the polyol (A) is 1.1 to 5.0, preferably 1.5 to 4.5, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin. The average number of functional groups (average number of hydroxyl groups) of the polyol (A) is more preferably 1.5 to 4.0, and even more preferably 2.5 to 3.5, from the viewpoint of increasing the storage modulus of the polyurethane resin at a relatively high temperature (50°C).

[0056] That is, the lower limit of the average number of functional groups of the polyol (A) is 1.1 or more, preferably 1.5 or more, and more preferably 2.5 or more, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin.

[0057] Furthermore, the upper limit of the average number of functional groups of the polyol (A) is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less, and even more preferably 3.5 or less, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin.

[0058] The average functionality of a polyol is calculated according to the following formula (hereinafter the same): Average functionality = Number of moles of hydroxyl groups (amount of substance) / Number of moles of polyol (amount of substance)

[0059] In the above formula, the number of moles of hydroxyl groups (amount of substance) and the number of moles of polyol (amount of substance) are calculated from the raw material charge (amount blended and number of functional groups) of each polyol and the above hydroxyl value (the same applies hereinafter).

[0060] When two or more types of polyester polyols are used in combination, the number average molecular weight of the entire polyol (A) can be calculated by dividing the number average molecular weights of the individual polyester polyols proportionally based on the blending recipe.

[0061] <Content of polyol (A)> Since the polyol (A) is a polyester polyol having a fatty acid (X) unit, the fatty acid (X) is obtained when the polyol (A) is saponified and decomposed. In the polyol composition, the content of the polyol (A) is adjusted based on the ratio between the amount of the fatty acid (X) obtained by the saponification and decomposition of the polyol (A) and the amount of the polyol (B) described below. Details of the content of the polyol (A) will be described later.

[0062] [1.2] Polyol (B) <Polyether polyol not containing an aromatic ring> Examples of the polyol (B) include non-aromatic polyether polyols. Non-aromatic polyether polyols are polyether polyols that do not contain an aromatic ring. In other words, the polyol (B) is preferably composed of a polyether polyol that does not contain an aromatic ring. Examples of the non-aromatic polyether polyol include non-aromatic polyether polyols with relatively short chains (e.g., number average molecular weight of 160 to 220).

[0063] More specific examples of non-aromatic polyether polyols include non-aromatic polyoxyalkylene (carbon number (C) 2 to 3) polyols and non-aromatic polytetramethylene ether polyols.

[0064] Non-aromatic polyoxyalkylene (C2-3) polyols are polyether polyols having oxyalkylene groups having 2 to 3 carbon atoms and no aromatic rings. Non-aromatic polyoxyalkylene (C2-3) polyols can be obtained, for example, by addition polymerization of an alkylene oxide having 2 to 3 carbon atoms to an initiator that does not contain an aromatic ring. Examples of initiators that do not contain an aromatic ring include known aliphatic alcohols and known aliphatic amines. Preferred initiators include aliphatic alcohols, and more preferably the above-mentioned dihydric alcohols and trihydric alcohols. Examples of alkylene oxides having 2 to 3 carbon atoms include ethylene oxide and propylene oxide.

[0065] More specific examples of non-aromatic polyoxyalkylene (C2-3) polyols include non-aromatic polyoxyethylene polyols, non-aromatic polyoxypropylene polyols, and non-aromatic propylene oxide-ethylene oxide copolymers (random copolymers and / or block copolymers).

[0066] The non-aromatic polyoxyethylene polyol is a non-aromatic polyoxyalkylene (C2-3) polyol having oxyethylene units (EO) but no oxypropylene units (PO).

[0067] The non-aromatic polyoxypropylene polyol is a non-aromatic polyoxyalkylene (C2-3) polyol having oxypropylene units (PO) but no oxyethylene units.

[0068] The non-aromatic propylene oxide-ethylene oxide copolymer is a non-aromatic polyoxyalkylene (C2-3) polyol having an oxyethylene unit (EO) and an oxypropylene unit (PO). More specifically, the non-aromatic propylene oxide-ethylene oxide copolymer includes a non-aromatic polyoxypropylene polyol whose molecular terminals are modified with ethylene oxide (oxyethylene-terminated propylene oxide-ethylene oxide copolymer). The non-aromatic propylene oxide-ethylene oxide copolymer may contain polyoxyethylene in the middle of the polyoxypropylene.

[0069] In the non-aromatic propylene oxide-ethylene oxide copolymer, the ratio of oxyethylene units (EO) to oxypropylene units (PO) is not particularly limited and is appropriately set depending on the purpose and application. From the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistance, the oxyethylene units (EO) are, for example, 1 to 50% by mass, preferably 5 to 40% by mass, and more preferably 10 to 30% by mass, based on the total amount of oxyethylene units (EO) and oxypropylene units (PO). Furthermore, the oxypropylene units (PO) are, for example, 50 to 99% by mass, preferably 60 to 95% by mass, and more preferably 70 to 90% by mass, based on the total amount of oxyethylene units (EO) and oxypropylene units (PO).

[0070] Non-aromatic polytetramethylene ether polyols are polyether polyols that have polytetramethylene units but no aromatic rings. Examples of non-aromatic polytetramethylene ether polyols include ring-opening polymers of tetrahydrofuran (crystalline polytetramethylene ether glycol). Examples of non-aromatic polytetramethylene ether polyols include copolymers of ring-opening polymers of tetrahydrofuran and polyhydric alcohols (amorphous polytetramethylene ether glycol). These can be used alone or in combination of two or more.

[0071] The non-aromatic polyether polyols can be used alone or in combination of two or more. From the viewpoint of reducing the temperature dependency of the storage modulus of the polyurethane resin, the non-aromatic polyether polyol is preferably a non-aromatic polyoxyalkylene (C2-3) polyol.

[0072] In particular, from the viewpoint of improving the storage modulus of the polyurethane resin at 0° C. to 50° C., the non-aromatic polyoxyalkylene (C2-3) polyol is preferably a non-aromatic polyoxypropylene polyol. That is, from the viewpoint of improving the storage modulus of the polyurethane resin at 0° C. to 50° C., the non-aromatic polyoxyalkylene (C2-3) polyol preferably contains a non-aromatic polyoxypropylene polyol.

[0073] Furthermore, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin at 24° C. to 100° C., the non-aromatic polyoxyalkylene (C2-3) polyol is preferably a non-aromatic polyoxyethylene polyol. That is, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin at 24° C. to 100° C., the non-aromatic polyoxyalkylene (C2-3) polyol preferably contains a non-aromatic polyoxyethylene polyol.

[0074] Furthermore, from the viewpoint of reducing the variation in storage modulus (ratio of standard deviation to average value) at −50° C. to 50° C., the non-aromatic polyoxyalkylene (C2-3) polyol preferably includes a combination of a non-aromatic polyoxypropylene polyol and a non-aromatic polyoxyethylene polyol. That is, from the viewpoint of reducing the variation in storage modulus (ratio of standard deviation to average value) at −50° C. to 50° C., the non-aromatic polyoxyalkylene (C2-3) polyol preferably contains a non-aromatic polyoxypropylene polyol and a non-aromatic polyoxyethylene polyol.

[0075] When the non-aromatic polyoxyalkylene (C2-3) polyol contains a non-aromatic polyoxypropylene polyol and a non-aromatic polyoxyethylene polyol, the ratio of the total mass of the non-aromatic polyoxyethylene polyols to the total mass of the non-aromatic polyoxypropylene polyols (non-aromatic polyoxyethylene polyol / non-aromatic polyoxypropylene polyol) is, for example, 0.05 to 2.0, preferably 0.05 to 1.5, more preferably 0.05 to 1.0, and even more preferably 0.05 to 0.5. In other words, the upper limit of the ratio of the total mass of the non-aromatic polyoxyethylene polyols to the total mass of the non-aromatic polyoxypropylene polyols (non-aromatic polyoxyethylene polyol / non-aromatic polyoxypropylene polyol) is, for example, 2.0 or less, preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.5 or less. Furthermore, the lower limit of the ratio of the total mass of non-aromatic polyoxyethylene polyols to the total mass of non-aromatic polyoxypropylene polyols (non-aromatic polyoxyethylene polyol / non-aromatic polyoxypropylene polyol) is not particularly set, but may be, for example, 0.05 or more.

[0076] In particular, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin at 24°C to 100°C and also reducing the variation in the storage modulus (ratio of standard deviation to the average value) at -50°C to 50°C, non-aromatic polyoxyalkylene (C2-3) polyols having oxypropylene chains (PO chains) are more preferred. Specific examples include non-aromatic polyoxypropylene polyols and non-aromatic propylene oxide-ethylene oxide copolymers. A preferred example of the non-aromatic propylene oxide-ethylene oxide copolymer is an EO-capped non-aromatic polyoxypropylene polyol.

[0077] <Physical properties of polyol (B)> The polyol (B) has a predetermined hydroxyl value and average functionality. Preferably, a non-aromatic polyether polyol having a predetermined hydroxyl value and average functionality is selected as the polyol (B). When two or more polyols (preferably non-aromatic polyether polyols) are used in combination, preferably, each polyol (preferably non-aromatic polyether polyol) has a predetermined hydroxyl value and average functionality.

[0078] More specifically, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin, the hydroxyl value of the polyol (B) is 600 mgKOH / g to 1,200 mgKOH / g, preferably 700 mgKOH / g to 1,100 mgKOH / g, more preferably 800 mgKOH / g to 1,000 mgKOH / g, and even more preferably 850 mgKOH / g to 950 mgKOH / g.

[0079] That is, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin, the lower limit of the hydroxyl value of the polyol (B) is 600 mgKOH / g or more, preferably 700 mgKOH / g or more, more preferably 800 mgKOH / g or more, and even more preferably 850 mgKOH / g or more.

[0080] The upper limit of the hydroxyl value of the polyol (B) is 1,200 mgKOH / g or less, preferably 1,100 mgKOH / g or less, more preferably 1,000 mgKOH / g or less, and even more preferably 950 mgKOH / g or less, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin.

[0081] When two or more types of polyols (preferably, non-aromatic polyether polyols) are used in combination, the hydroxyl value of each polyol (preferably, non-aromatic polyether polyol) can be proportionally divided based on the blending recipe to calculate the overall hydroxyl value of polyol (B).

[0082] The average number of functional groups (average number of hydroxyl groups) of the polyol (B) is 2.0 to 4.0, preferably 2.5 to 3.5, and more preferably 2.8 to 3.2, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin.

[0083] That is, the lower limit of the average number of functional groups of the polyol (B) is 2.0 or more, preferably 2.5 or more, and more preferably 2.8 or more, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin.

[0084] The upper limit of the average number of functional groups of the polyol (B) is 4.0 or less, preferably 3.5 or less, and more preferably 3.2 or less, from the viewpoint of reducing the temperature dependency of the storage modulus of the polyurethane resin.

[0085] When two or more types of polyols (preferably, non-aromatic polyether polyols) are used in combination, the number average molecular weight of the entire polyol (B) can be calculated by proportionally dividing the number average molecular weights of the polyols (preferably, non-aromatic polyether polyols) based on the blending recipe.

[0086] <Content of Polyol (B)> In the polyol composition, the content of the polyol (B) is adjusted based on the ratio between the amount of the fatty acid (X) obtained by the saponification decomposition of the polyol (A) and the amount of the polyol (B). Details of the content of the polyol (B) will be described later.

[0087] [1.3] Polyol (C) The polyol composition can contain polyol (C) as needed. Polyol (C) is a polyol different from the polyol (A) and the polyol (B). Polyol (C) will be described in detail below. <Polyether polyol containing aromatic ring> Polyol (C) is an aromatic polyether polyol. The aromatic polyether polyol is a polyether polyol containing an aromatic ring. In other words, polyol (C) is composed of a polyether polyol containing an aromatic ring.

[0088] More specifically, examples of aromatic polyether polyols include aromatic polyoxyalkylene (carbon number (C) 2 to 3) polyols.

[0089] The aromatic polyoxyalkylene (C2-3) polyol may be a polyether polyol having an oxyalkylene group having 2 to 3 carbon atoms and an aromatic ring. The aromatic polyoxyalkylene (C2-3) polyol can be obtained, for example, by addition polymerization of an alkylene oxide having 2 to 3 carbon atoms to an initiator containing an aromatic ring. Examples of initiators containing an aromatic ring include known aromatic alcohols, known aromatic aliphatic alcohols, known aromatic amines, and known aromatic aliphatic amines.

[0090] <Physical Properties of Polyol (C)> The polyol (C) has a predetermined hydroxyl value and average functionality. The hydroxyl value of the polyol (C) is, for example, 200 mg KOH / g to 550 mg KOH / g. The average functionality (average number of hydroxyl groups) of the polyol (C) is, for example, 2.0 to 4.0.

[0091] For example, the polyol (C) may be mixed with the polyol (A) and the polyol (B) simultaneously when the polyol (A) and the polyol (B) are mixed.

[0092] <Content of Polyol (C)> The polyol composition preferably does not contain the polyol (C).

[0093] [1.4] Other Polyol (D) The polyol composition may contain another polyol (D) in addition to the polyol (A), the polyol (B), and the polyol (C). The other polyol (D) is a polyol other than the polyol (A), the polyol (B), and the polyol (C).

[0094] Examples of the other polyols (D) include low-molecular-weight polyols and high-molecular-weight polyols.

[0095] A low-molecular-weight polyol is a compound having two or more hydroxyl groups and a relatively low molecular weight. A relatively low molecular weight refers to a molecular weight of less than 400 (preferably less than 300). Examples of low-molecular-weight polyols include the polyhydric alcohols described above. More specifically, examples include the dihydric alcohols, trihydric alcohols, tetrahydric alcohols, pentahydric alcohols, hexahydric alcohols, heptahydric alcohols, and octahydric alcohols. A high-molecular-weight polyol is a compound having two or more hydroxyl groups and a relatively high molecular weight. A relatively high molecular weight refers to a number-average molecular weight of 400 or more (preferably 500 or more). These can be used alone or in combination of two or more types. The low-molecular-weight polyols and high-molecular-weight polyols are not particularly limited and can be produced by known methods.

[0096] <Content of Other Polyol (D)> The polyol composition preferably does not contain other polyol (D).

[0097] [1.5] Production of Polyol Composition The production method of the polyol composition is not particularly limited. For example, the polyol (A) and the polyol (B) are each prepared. If necessary, the polyol (C) and another polyol (D) are also prepared. Then, the polyol (A) and the polyol (B) are mixed by a known method. If necessary, the polyol (C) and another polyol (D) are also mixed together by a known method. As a result, a polyol composition is obtained.

[0098] <Content of Polyol (A) and Content of Polyol (B)> In the polyol composition, the content of polyol (A) and the content of polyol (B) are adjusted based on the ratio between the amount of fatty acid (X) obtained by saponification decomposition of polyol (A) and the amount of polyol (B) described below.

[0099] The amount of fatty acid (X) obtained by saponification decomposition of polyol (A) can be obtained as a theoretical value by calculation based on the molecular structure and molecular weight of polyol (A).

[0100] The amount of fatty acid (X) obtained by saponification decomposition of polyol (A) can be obtained as an actual measured value by the absolute calibration curve method of gas chromatography (GC / MS) in accordance with the examples described later.

[0101] The amount of fatty acid (X) obtained by saponification decomposition of polyol (A) is a theoretical value.

[0102] More specifically, the ratio of the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) to the mass of the polyol (B) (fatty acid (X) / polyol (B)) is 0.08 to 0.90, preferably 0.10 to 0.70.

[0103] In particular, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin in the range of 24 to 50° C., the ratio of the total mass of the fatty acids (X) obtained by saponification decomposition of the polyol (A) to the mass of the polyol (B) (fatty acid (X) / polyol (B)) is more preferably 0.15 to 0.50. Furthermore, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin in the range of 24 to 100° C., the ratio of the total mass of the fatty acids (X) obtained by saponification decomposition of the polyol (A) to the mass of the polyol (B) (fatty acid (X) / polyol (B)) is even more preferably 0.15 to 0.30.

[0104] Furthermore, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin, the ratio of the mass of the polyol (B) to the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) and the polyol (B), ((B) / ((B)+(X))), is, for example, 0.55 to 0.95, or preferably 0.60 to 0.90.

[0105] In particular, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin in the range of 24 to 50°C, the ratio of the mass of the polyol (B) to the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) and the polyol (B), ((B) / ((B)+(X))), is more preferably 0.70 to 0.90. Furthermore, from the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin in the range of 24 to 100°C, the ratio of the mass of the polyol (B) to the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) and the polyol (B), ((B) / ((B)+(X))), is even more preferably 0.80 to 0.88.

[0106] The content of the polyol (A) is, for example, 5 to 60 mass%, or preferably 10 to 50 mass%, based on the total amount of the polyol (A), the polyol (B), the polyol (C) blended as needed, and the other polyol (D) blended as needed.

[0107] The content of the polyol (B) is, for example, 40 to 95 mass%, or preferably 50 to 90 mass%, based on the total amount of the polyol (A), the polyol (B), the polyol (C) blended as needed, and the other polyol (D) blended as needed.

[0108] <Content of Polyol (C)> As described above, the polyol composition preferably does not contain the polyol (C). From the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin, the content of the polyol (C) is, for example, 30% by mass or less, preferably 15% by mass or less, and more preferably 0% by mass, relative to the total amount of the polyol (A), the polyol (B), the polyol (C) blended as needed, and the other polyol (D) blended as needed.

[0109] <Content of Other Polyol (D)> As described above, the polyol composition preferably does not contain the other polyol (D). From the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin, the content of the other polyol (D) is, for example, 30% by mass or less, preferably 15% by mass or less, and more preferably 0% by mass, relative to the total amount of the polyol (A), the polyol (B), the polyol (C) blended as needed, and the other polyol (D) blended as needed.

[0110] [1.6] Effects of Polyol Composition The polyol composition contains a polyol (A) having specific physical properties and a polyol (B) having specific physical properties, and the ratio of fatty acid (X) to polyol (B) is within a specific range.

[0111] Therefore, the polyol composition can provide a polyurethane resin having excellent mechanical properties and reduced temperature dependency of the storage modulus.

[0112] In particular, the polyol composition can reduce the temperature dependency of the storage modulus at 0° C. to 50° C. More specifically, the average value of "E'24 / E'0" (described later) and "E'50 / E'24" (described later) (E'AVE) can be made closer to 1.0.

[0113] Therefore, the polyol composition is preferably used as a raw polyol for a polyurethane resin (a polyurethane resin raw material). More preferably, the polyol composition is used as a raw polyol for a polyurethane resin (i.e., a polyurethane resin raw material) described later.

[0114] [2] Polyurethane Resin and Polyurethane Resin Composition [2.1] Polyurethane Resin A polyurethane resin is a polyurethane resin having a relatively high hardness and a relatively high density. That is, a polyurethane resin is defined by its hardness and density. More specifically, a polyurethane resin has a Shore D hardness of 60 or more and a viscosity of 1.0 g / cm ３ It is a polyurethane resin having a density of 1000 or more.

[0115] It should be noted that foamed polyurethane resins (polyurethane foams and foamed elastomers) do not usually have the above hardness and / or density. That is, the above polyurethane resins are non-foamed polyurethane resins (non-foams, non-foamed elastomers) and are distinguished from foamed polyurethane resins.

[0116] The polyurethane resin can be obtained, for example, by reacting a polyurethane resin composition as a polyurethane resin raw material.

[0117] [2.2] Polyurethane Resin Composition The polyurethane resin composition is a raw material composition for producing the polyurethane resin described above. The polyurethane resin composition contains a polyol component and a polyisocyanate component.

[0118] <Polyol Component> The polyol component contains the polyol composition described above. That is, the polyol component contains the polyol (A) and the polyol (B), and also optionally contains the polyol (C) and optionally another polyol (D) in the proportions described above.

[0119] <Polyisocyanate Component> Examples of the polyisocyanate component include polyisocyanates commonly used industrially. Examples of polyisocyanates include linear aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Examples of linear aliphatic polyisocyanates include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and derivatives thereof. Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), hydrogenated diphenylmethane diisocyanate (HDI), and derivatives thereof. １２ MDI), hydrogenated xylylene diisocyanate (H ６Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), phenylene diisocyanate, and derivatives thereof. Examples of aralkyl polyisocyanates include xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and derivatives thereof. Examples of derivatives include polymers, isocyanurate-modified products, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, and carbodiimide-modified products. Examples of derivatives include polymethylene polyphenyl polyisocyanate (polymeric MDI). These can be used alone or in combination of two or more types.

[0120] From the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistance, the polyisocyanate component is preferably an aromatic polyisocyanate, more preferably diphenylmethane diisocyanate (MDI), phenylene diisocyanate, or a derivative thereof, and also preferably polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0121] In other words, the polyisocyanate component preferably contains at least one selected from the group consisting of diphenylmethane diisocyanate, diphenylmethane diisocyanate derivatives, phenylene diisocyanate, phenylene diisocyanate derivatives, and polymethylene polyphenyl polyisocyanate.

[0122] From the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistance, the polyisocyanate component is more preferably a diphenylmethane diisocyanate derivative, and particularly preferably a carbodiimide-modified diphenylmethane diisocyanate. In other words, the polyisocyanate component more preferably contains a diphenylmethane diisocyanate derivative, and particularly preferably contains a carbodiimide-modified diphenylmethane diisocyanate.

[0123] Furthermore, from the viewpoint of obtaining a polyurethane resin having a good balance of hardness, density, and electrical resistance, the polyisocyanate component preferably comprises at least one selected from the group consisting of diphenylmethane diisocyanate, diphenylmethane diisocyanate derivatives, phenylene diisocyanate, phenylene diisocyanate derivatives, and polymethylene polyphenyl polyisocyanate, more preferably comprises a diphenylmethane diisocyanate derivative, and particularly preferably comprises a carbodiimide-modified product of diphenylmethane diisocyanate.

[0124] The isocyanate group concentration (NCO content) of the polyisocyanate component is, for example, 20.0 to 35.0 mass%, preferably 25.0 to 29.5 mass%, more preferably 27.0 to 29.5 mass%, and even more preferably 27.5 to 28.5 mass%.

[0125] <Preparation of Polyurethane Resin Composition> The polyurethane resin composition may be, for example, a two-component resin composition containing a polyisocyanate component and a polyol component, which are mixed together at the time of use.

[0126] The polyurethane resin composition may also be a one-component resin composition containing a mixture of a polyisocyanate component and a polyol component, in which the polyisocyanate component and the polyol component are mixed together before use.

[0127] In the polyurethane resin composition, the ratio of the polyisocyanate component to the polyol component is adjusted based on the isocyanate index (NCO index), which is calculated by the following formula:

[0128] Isocyanate index = [(number of moles of isocyanate groups in the polyisocyanate component) / (number of moles of hydroxyl groups in the polyol component)]

[0129] The isocyanate index (NCO index) of the polyurethane resin composition is, for example, 0.70 to 1.30, preferably 0.80 to 1.20, more preferably 0.90 to 1.10, still more preferably 1.00 to 1.08, and particularly preferably 1.01 to 1.07.

[0130] <Additives> The polyurethane resin composition may contain additives. Examples of additives include catalysts and antifoaming agents. Examples of catalysts include known urethane catalysts, more specifically known amine catalysts and known organometallic catalysts. Examples of amine catalysts include tertiary amine catalysts, quaternary ammonium salts, and imidazoles. Examples of tertiary amine catalysts include triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl)ether, and N-methylmorpholine. Examples of quaternary ammonium salts include tetraethylhydroxylammonium. Examples of imidazoles include imidazole and 2-ethyl-4-methylimidazole. Examples of organometallic catalysts include organotin compounds, organolead compounds, organonickel compounds, organocobalt compounds, organocopper compounds, and organobismuth compounds. Examples of organotin compounds include tin acetate, tin octoate (stannous octoate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride. Examples of organolead compounds include lead octoate and lead naphthenate. Examples of organonickel compounds include nickel naphthenate. Examples of organocbalt compounds include cobalt naphthenate. Examples of organocopper compounds include copper octenate. Examples of organobismuth compounds include bismuth octoate (bismuth octoate) and bismuth neodecanoate. These compounds may be used alone or in combination. Examples of the defoaming agent include known silicone-based defoaming agents. Examples of the additives include crosslinkers, plasticizers, fillers, antioxidants, compatibilizers, colorants, stabilizers, and ultraviolet absorbers. These may be used alone or in combination.

[0131] The additives may be prepared separately from the polyol component and the polyisocyanate component and added at the time of use. Alternatively, the additives may be added in advance to the polyol component and / or the polyisocyanate component. Preferably, the additives are added in advance to the polyol component. In other words, the polyol component is preferably prepared as a premix containing the polyol composition and the additives. The amount and timing of addition of the additives are appropriately determined depending on the purpose and application.

[0132] Furthermore, the additive preferably does not contain a foaming agent. However, as a common technique in known resin molding methods, it is known to dissolve or disperse a small amount of foaming gas in the resin raw material in order to fill the minute spaces that occur when the resin raw material is injected into a mold and to suppress shrinkage of the molded product, thereby suppressing molding defects and variations. The foaming gas used for such purposes is distinguished from the foaming agent used to obtain a foamed polyurethane resin (polyurethane foam and foamed elastomer), and is allowed to be used as an additive, so long as the hardness and density of the cured product (polyurethane resin) of the polyurethane resin composition are within the above-mentioned ranges.

[0133] Such a polyurethane resin composition contains the polyol composition, and therefore, the polyurethane resin composition has excellent mechanical properties and exhibits reduced temperature dependence of the storage modulus.

[0134] [2.3] Production of Polyurethane Resin The polyurethane resin is produced as a cured product of the polyurethane resin composition by reacting and molding the polyurethane resin composition described above.

[0135] The method for reacting and molding the polyurethane resin composition is not particularly limited, and a known resin molding method can be used. Examples of the resin molding method include the molding method for rigid polyurethane resins described in paragraph

[0171] of WO 2017 / 014178, more specifically, cast molding, injection molding, RIM molding, blow molding, and extrusion molding.

[0136] For example, in the case of a cast molding method, when the polyurethane resin composition is a two-component resin composition, a polyisocyanate component and a polyol component are mixed and the mixture is heated in a predetermined mold during the production of the polyurethane resin, and when the polyurethane resin composition is a one-component resin composition, a pre-mixed one-component resin composition is prepared and the one-component resin composition is heated in a predetermined mold.

[0137] The heating conditions are not particularly limited, but for example, the heating temperature is, for example, 40 to 200° C., preferably 60 to 150° C., and more preferably 80 to 100° C. The heating time is, for example, 3 minutes to 24 hours, preferably 30 minutes to 12 hours, and more preferably 1 hour to 6 hours.

[0138] The polyurethane resin composition is cured by the heating, and a polyurethane resin is obtained. The polyurethane resin is, for example, demolded and aged as necessary. The aging conditions are not particularly limited and are appropriately set depending on the purpose and application.

[0139] [2.4] Physical Properties of Polyurethane Resin The polyurethane resin described above is obtained using the polyol composition and polyurethane resin composition described above. Therefore, the polyurethane resin described above has excellent mechanical properties (hardness) and can reduce the temperature dependence of the storage modulus.

[0140] <Storage Modulus> The storage modulus (E') of a polyurethane resin is measured in accordance with the Examples described later. As described in the Examples below, the ratio of the storage modulus E' at 100°C (this E' is defined as "E'100") to the storage modulus E' at 24°C (this E' is defined as "E'24") is defined as E'100 / E'24. The ratio of the storage modulus E' at 50°C (this E' is defined as "E'50") to the storage modulus E' at 24°C is defined as E'50 / E'24. The ratio of the storage modulus E' at 24°C to the storage modulus E' at 0°C (this E' is defined as "E'0") is defined as E'24 / E'0. The average value of the above "E'24 / E'0" and "E'50 / E'24" is defined as "E'AVE".

[0141] The E'100 / E'24 of the polyurethane resin is, for example, 0.4 to 1.0, preferably 0.6 to 1.0, more preferably 0.64 to 1.0, even more preferably 0.66 to 1.0, and particularly preferably 0.68 to 1.0. That is, the lower limit of the E'100 / E'24 of the polyurethane resin is, for example, 0.4 or more, preferably 0.6 or more, more preferably 0.64 or more, even more preferably 0.66 or more, and particularly preferably 0.68 or more. Furthermore, the E'100 / E'24 of the polyurethane resin is, for example, 1.0 or less.

[0142] The E'50 / E'24 of the polyurethane resin is, for example, 0.75 to 1.0, preferably 0.8 to 1.0, more preferably 0.85 to 1.0, and even more preferably 0.89 to 1.0. That is, the lower limit of the E'50 / E'24 of the polyurethane resin is, for example, 0.75 or more, preferably 0.8 or more, more preferably 0.85 or more, and even more preferably 0.89 or more. Furthermore, the E'50 / E'24 of the polyurethane resin is, for example, 1.0 or less.

[0143] The E'24 / E'0 ratio of the polyurethane resin is, for example, 0.8 to 1.0, preferably 0.9 to 1.0, and more preferably 0.93 to 1.0. That is, the lower limit of the E'24 / E'0 ratio of the polyurethane resin is, for example, 0.8 or more, preferably 0.9 or more, and more preferably 0.93 or more. Furthermore, the E'24 / E'0 ratio of the polyurethane resin is, for example, 1.0 or less.

[0144] The E'AVE of the polyurethane resin is, for example, 0.8 to 1.0, preferably 0.85 to 1.0, more preferably 0.88 to 1.0, and even more preferably 0.90 to 1.0. That is, the lower limit of the E'AVE of the polyurethane resin is, for example, 0.8 or more, preferably 0.85 or more, more preferably 0.88 or more, and even more preferably 0.90 or more. The upper limit of the E'AVE of the polyurethane resin is, for example, 1.0 or less.

[0145] <Hardness> The lower limit of the Shore D hardness of the polyurethane resin is, for example, 60 or more, preferably 65 or more, more preferably 70 or more, even more preferably 75 or more, and particularly preferably 80 or more. The upper limit of the Shore D hardness of the polyurethane resin is not particularly limited, but may be 90 or less, 85 or less, or 80 or less.

[0146] That is, the Shore D hardness of the polyurethane resin is, for example, 60 to 90, preferably 65 to 90, more preferably 70 to 85, even more preferably 75 to 85, and particularly preferably 80 to 85. The Shore D hardness is measured in accordance with the examples described later.

[0147] <Density> The density of the polyurethane resin is, for example, 1.0 g / cm ３ or more, and 1.05 g / cm ３ or more, and 1.1 g / cm ３ or more, 1.12 g / cm ３ The upper limit of the density of the polyurethane resin may be, for example, 1.5 g / cm from the viewpoint of lightness. ３ Preferably, 1.3 g / cm or less ３ More preferably, 1.2 g / cm or less３ The following is the result.

[0148] That is, the density of the polyurethane resin is, for example, 1.0 to 1.5 g / cm ３ The density is measured in accordance with the examples described below.

[0149] <Electrical Resistivity> The lower limit of the volume resistivity of the polyurethane resin is, for example, 1.0 × 10 １６ Ω cm or more, preferably 1.5 × 10 １６ The upper limit of the volume resistivity of the polyurethane resin is not particularly limited, but is, for example, 9.0×10 １６ Ω cm or less, and may be 5.0 × 10 １６ It may be Ω·cm or less.

[0150] That is, the volume resistivity of the polyurethane resin is, for example, 1.0×10 １６ ~9.0 x 10 １６ Ω cm, preferably 1.5×10 １６ ~5.0 x 10 １６ The volume resistivity density is Ω·cm. The volume resistivity density is measured in accordance with the examples described later.

[0151] <Balance of hardness, density and electrical resistance> Polyurethane resins have a relatively high electrical resistance (volume resistivity), a relatively high hardness (Shore D hardness), and a relatively low density (1.0 g / cm ３ The balance between hardness, density and electrical resistance can be confirmed, for example, by the balance index of the following formula.

[0152] Balance index [Ω cm ４ / (g / 10 １８ ) ] = volume resistivity (Ω cm) × Shore D hardness (-) × 10 －１８ / density (g / cm ３ )

[0153] A polyurethane resin having a large value as the balance index in the above formula has a good balance of relatively high electrical resistance, relatively high hardness, and relatively low density.

[0154] In the polyurethane resin described above, the lower limit of the balance index in the above formula is, for example, 0.3 [Ω cm ４ / (g / 10 １８ ) )] or more, preferably 0.5 [Ω cm ４ / (g / 10 １８ ) )] or more, more preferably 0.9 [Ω cm ４ / (g / 10 １８ ) )] or more, more preferably 0.95 [Ω cm ４ / (g / 10 １８ The upper limit of the balance index in the above formula is not particularly limited, but is, for example, 30 [Ω cm ４ / (g / 10 １８ ) )] or less, and ４ / (g / 10 １８ ) )] or less, and may be 10 [Ω cm ４ / (g / 10 １８ ) )] or less, and 5 [Ω cm ４ / (g / 10 １８ ) or less.

[0155] That is, in the polyurethane resin described above, the balance index of the above formula is, for example, 0.3 to 30 [Ω cm ４ / (g / 10 １８ )], preferably 0.5 to 20 [Ω cm ４ / (g / 10 １８ )], more preferably 0.9 to 10 [Ω cm ４ / (g / 10 １８ )], more preferably 0.95 to 5 [Ω cm ４ / (g / 10 １８ )].

[0156] The polyurethane resins described above are suitable for use in various products in which resin molded articles are used, including, but not limited to, buildings, structures, robot parts, electrical and electronic parts, office supplies, and healthcare products.

[0157] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The materials, amounts used, ratios, and processing procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention.

[0158] [1] Measurement and Evaluation Methods Various physical properties were measured and evaluated by the following methods.

[0159] [1.1] Volume Resistivity The volume resistivity (Ω cm) of the polyurethane resin was measured using a digital ultra-high resistance / microcurrent meter Model 8340A (manufactured by ADC) in accordance with JIS K6911 (1995), at a temperature of 23°C and a relative humidity (RH) of 50%.

[0160] [1.2] D Hardness A polyurethane resin was pressed horizontally against an ASKER D hardness tester in accordance with JIS K7215 (1986). The maximum indicated value of the indicator was read within 1 second.

[0161] [1.3] Density The density of the polyurethane resin was measured according to the water displacement method of JIS K7112 (2023).

[0162] [1.4] Balance of Electrical Properties, Hardness, and Lightness Polyurethane resins are required to have high volume resistivity, high hardness, and moderate density. Therefore, the following formula was created as an index showing the balance of these properties.

[0163] Balance index [Ω cm ４ / (g / 10 １８ ) ] = volume resistivity (Ω cm) × Shore D hardness (-) × 10 －１８ / density (g / cm ３ )

[0164] The balance between electrical properties, hardness, and lightness was calculated using the above formula.

[0165] [1.5] Dynamic Viscoelasticity (E') A polyurethane resin was cut into a rectangular parallelepiped sample measuring 4 mm wide x 2 mm thick x 35 mm long.

[0166] Next, the dynamic viscoelasticity of the rectangular parallelepiped sample was measured using a dynamic viscoelasticity measuring device (manufactured by IT Measurement & Control Co., Ltd., Model: DVA-200). The measurement conditions were as follows. From the obtained data, the value of the storage modulus E' was calculated.

[0167] Tensile mode Measurement temperature: -100°C to 250°C Heating rate: 5°C / min Measurement frequency: 10Hz Set strain: 0.18% Gauge distance: 20mm Number of measurement points: every 1°C

[0168] The ratio of the storage modulus E' at 100°C (this E' is defined as "E'100") to the storage modulus E' at 24°C (this E' is defined as "E'24") was defined as E'100 / E'24.

[0169] The ratio of the storage modulus E' at 50°C (this E' is defined as "E'50") to the storage modulus E'24 at 24°C was defined as E'50 / E'24.

[0170] The ratio of the storage modulus E'24 at 24°C to the storage modulus E' at 0°C (this E' is defined as "E'0") was defined as E'24 / E'0.

[0171] Furthermore, the average value of the above "E'24 / E'0" and the above "E'50 / E'24" ([(E'50 / E'24)+(E'24 / E'0)] / 2) was defined as "E'AVE".

[0172] Then, the temperature dependency of the storage modulus was evaluated based on the above "E'100 / E'24", "E'50 / E'24", "E'24 / E'0" and "E'AVE".

[0173] In the table, "E±" indicates exponential notation. More specifically, "E+n" means "×10 ｎ " means "E-n" and "x10 －ｎ " means.

[0174] [1.6] (Composition Ratio) In the polyol (A) described below, the only fatty acid (X) having 15 to 20 carbon atoms and 1 hydroxyl group is ricinoleic acid. Other fatty acids (palmitic acid (16 carbon atoms, 0 hydroxyl groups), stearic acid (18 carbon atoms, 0 hydroxyl groups), oleic acid (18 carbon atoms, 0 hydroxyl groups), linoleic acid (18 carbon atoms, 0 hydroxyl groups), linolenic acid (18 carbon atoms, 0 hydroxyl groups), and dihydroxystearic acid (18 carbon atoms, 2 hydroxyl groups)) are fatty acids other than the fatty acid (X).

[0175] Therefore, in each example and comparative example, ricinoleic acid was set as the fatty acid (X), and the composition ratio was calculated as follows.

[0176] [Amount of Fatty Acid (X) (Theoretical Value)] The content ratio of fatty acid (X) to the total amount of fatty acids obtained by saponification of castor oil (hereinafter simply referred to as the content ratio of ricinoleic acid, and the same applies hereinafter) was set to 89% by mass. The content ratio of ricinoleic acid to the total amount of fatty acids in castor oil was also set to 89% by mass.

[0177] Furthermore, for the highly purified castor oil fatty acids obtained by purifying the castor oil fatty acids, the content of ricinoleic acid relative to the total amount of fatty acids was set to 94 mass%.

[0178] The amounts of raw materials used to prepare the following polyol (A-2) were as follows: Castor oil 767.63 g Castor oil fatty acid 245.55 g (-28.28 g due to dehydration)

[0179] The content of ricinoleic acid obtained by saponification decomposition of polyol (A-2) was calculated from the above-mentioned charged amount, and as a result, the content of ricinoleic acid in polyol (A-2) was 90.2 mass% relative to the total mass of polyol (A-2).

[0180] In the same manner as above, the content of ricinoleic acid obtained by saponification decomposition of polyols A-3 to A-7 was calculated based on the charged amounts. The results were as follows.

[0181] Ricinoleic acid content in polyol (A-3): 76.6% by mass Ricinoleic acid content in polyol (A-4): 39.3% by mass Ricinoleic acid content in polyol (A-5): 77.7% by mass Ricinoleic acid content in polyol (A-6): 88.1% by mass Ricinoleic acid content in polyol (A-7): 88.7% by mass

[0182] Since the polyol (A-1) was castor oil, the content of ricinoleic acid in the polyol (A-1) was set to 89.0% by mass.

[0183] [Amount of Fatty Acid (X) (Measured Value)] The amount of fatty acid (X) obtained by saponification decomposition of polyol (A) was calculated as an actual measured value (reference value) by the absolute calibration curve method of gas chromatography (GC / MS) described below. That is, the saponification decomposition product obtained by saponification decomposition of polyol (A) was silylated and measured by GC / MS under the measurement conditions described below. In addition, a calibration curve was created using a ricinoleic acid reagent (purity >95%) as a standard sample. Then, the amount of fatty acid (X) obtained by saponification decomposition of polyol (A) was calculated by the absolute calibration curve method. As a result, the amount of fatty acid (X) obtained by saponification decomposition of polyol (A) was 79.6 mass%.

[0184] <GC / MS measurement conditions> Apparatus: Agilent 8890 / 5977B MSD (manufactured by Agilent) Column: HP-5MS 0.25 mm x 30 m x 0.25 μm film thickness Heating conditions: Heat from 120°C to 320°C at a rate of 10°C / min and hold for 3 min Measurement mode: SCAN m / z 30-900 Simultaneous measurement with FID

[0185] [(X) / (B)] Based on the formulation of each polyol composition, the mass ratio ((X) / (B)) of the amount (g) of fatty acid (X) contained in polyol (A) to the amount (g) of polyol (B) was calculated.

[0186] The amount of fatty acid (X) was determined based on a theoretical value, i.e., the mass ratio ((X) / (B)) was calculated based on the theoretical value.

[0187] Furthermore, in some examples, the mass ratio ((X) / (B)) was calculated based on the actual measured value using the actual measured value of the amount of fatty acid (X) as a reference value. Specifically, the mass ratio ((X) / (B)) was calculated based on the actual measured value in a formulation in which polyol (A-1) was used as polyol (A).

[0188] [(B) / (B)+(X)] Based on the formulation of each polyol composition, the mass ratio ((B) / (B)+(X)) of the amount (g) of polyol (B) to the total amount (g) of fatty acid (X) and polyol (B) was calculated.

[0189] The amount of fatty acid (X) was calculated based on the theoretical value, i.e., the mass ratio ((B) / (B)+(X)) was calculated based on the theoretical value.

[0190] [1.7] Hydroxyl value and average functionality The hydroxyl value of each polyol was measured in accordance with the phthalation method of JIS K 1557-1 (2007), Method B. The average functionality (average number of hydroxyl groups) of each polyol was calculated using the following formula: Average functionality = Number of moles of hydroxyl groups (amount of substance) / Number of moles of polyol (amount of substance).

[0191] In the above formula, the number of moles of hydroxyl groups (amount of substance) and the number of moles of polyol (amount of substance) were calculated from the raw material charge (amount blended and number of functional groups) of each polyol and the above hydroxyl value.

[0192] [2] Purification Example [2.1] Refined Castor Oil Fatty Acids Commercially available castor oil (manufactured by Ito Oil Mills, brand name: Diamond, polyester polyol, hydroxyl value 154.3 mg KOH / g, ricinoleic acid 89%) was hydrolyzed to obtain castor oil fatty acids (ricinoleic acid 89%).

[0193] Molecular distillation apparatus (evaporation surface area 0.03 m) ２ The castor oil fatty acids were purified using a purifying filter (Shibata Scientific Co., Ltd.), and the fatty acids not containing hydroxyl groups in the castor oil fatty acids were removed as low-boiling components. This resulted in high-purity castor oil fatty acids. The purification conditions were as follows:

[0194] Insertion speed: 200 g / h, evaporation surface temperature: 160°C, pressure: 15 Pa, wiper rotation speed: 300 rpm

[0195] The high-purity castor oil fatty acid had an acid value of 180.7 mg KOH / g, a hydroxyl value of 172.9 mg KOH / g, and a ricinoleic acid content (purity) of 94.0 mass%.

[0196] [3] Preparation Examples [3.1] Polyol Composition (1) Polyol (A-1) Commercially available castor oil (manufactured by Ito Oil Mills, brand name: Diamond, polyester polyol, hydroxyl value 154.3 mg KOH / g, ricinoleic acid 89%) was prepared as polyol (A-1).

[0197] (2) Polyol (A-2) The above polyol (A-1) was subjected to ester condensation with commercially available castor oil fatty acid (89% ricinoleic acid) to obtain a polyester polyol.

[0198] More specifically, 245.55 g of castor oil fatty acid (89% ricinoleic acid) and 767.63 g of polyol (A-1) were placed in a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and then subjected to a condensation reaction at 180°C under a nitrogen stream.

[0199] When the acid value of the content of the flask became 10 mgKOH / g or less, 0.1 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The content of the flask was then subjected to a condensation reaction at 180°C for a total of 40 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-2).

[0200] The polyol (A-2) had a hydroxyl value of 115.0 mgKOH / g and an average functionality of 2.7.

[0201] (3) Polyol (A-3) A commercially available polyoxypropylene polyol (trade name: Actocol D-400, average functionality 2, hydroxyl value 280.5 mg KOH / g, manufactured by Mitsui Chemicals) and high-purity castor oil fatty acid (94% ricinoleic acid) were subjected to ester condensation to obtain a polyester polyol.

[0202] More specifically, 815.05 g of high-purity castor oil fatty acid (94% ricinoleic acid) and 232.98 g of polyoxypropylene polyol (trade name Actocol D-400, average functionality 2, hydroxyl value 280.5 mgKOH / g, manufactured by Mitsui Chemicals) were placed in a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and a condensation reaction was carried out at 180°C under a nitrogen stream.

[0203] When the acid value of the content of the flask became 10 mgKOH / g or less, 0.21 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The content of the flask was then subjected to a condensation reaction at 180°C for a total of 45 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-3).

[0204] The polyol (A-3) had a hydroxyl value of 56.0 mgKOH / g and an average functionality of 1.7.

[0205] (4) Polyol (A-4) A commercially available polyoxypropylene polyol (trade name: Actocol D-1000, average functionality 2, hydroxyl value 112.2 mgKOH / g, manufactured by Mitsui Chemicals) and castor oil fatty acid (89% ricinoleic acid) were subjected to ester condensation to obtain a polyester polyol.

[0206] More specifically, 442.71 g of castor oil fatty acid (89% ricinoleic acid) and 581.01 g of polyoxypropylene polyol (trade name Actocol D-1000, average functionality 2, hydroxyl value 112.2 mgKOH / g, manufactured by Mitsui Chemicals) were placed in a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and a condensation reaction was carried out at 180°C under a nitrogen stream.

[0207] When the acid value of the content of the flask became 10 mgKOH / g or less, 0.2 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The content of the flask was then subjected to a condensation reaction at 180°C for a total of 49 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-4).

[0208] The polyol (A-4) had a hydroxyl value of 56.1 mgKOH / g and an average functionality of 1.7.

[0209] (5) Polyol (A-5) A commercially available polyoxypropylene polyol (trade name SOR-400, initiator sorbitol, average functionality 6, hydroxyl value 400 mgKOH / g, manufactured by Mitsui Chemicals) and castor oil fatty acid (89% ricinoleic acid) were subjected to ester condensation to obtain a polyester polyol.

[0210] More specifically, 873.0 g of castor oil fatty acid (89% ricinoleic acid) and 179.3 g of polyoxypropylene polyol (product name SOR-400, initiator sorbitol, average functionality 6, hydroxyl value 400 mgKOH / g, manufactured by Mitsui Chemicals) were placed in a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and a condensation reaction was carried out at 210°C under a nitrogen stream.

[0211] When the acid value of the content of the flask became 10 mgKOH / g or less, 0.6 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The content of the flask was then subjected to a condensation reaction at 210°C for a total of 56 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-5).

[0212] The polyol (A-5) had a hydroxyl value of 52.8 mgKOH / g and an average functionality of 4.4.

[0213] (6) Polyol (A-6) Commercially available diglycerin (trade name Diglycerin S, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and castor oil fatty acid (89% ricinoleic acid) were subjected to ester condensation to obtain a polyester polyol.

[0214] More specifically, 996.13 g of castor oil fatty acid (89% ricinoleic acid) and 71.35 g of diglycerin (trade name Diglycerin S, manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.) were placed in a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and a condensation reaction was carried out at 210°C under a nitrogen stream.

[0215] When the acid value of the content of the flask became 10 mgKOH / g or less, 0.12 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The content of the flask was then subjected to a condensation reaction at 210°C for a total of 42 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-6).

[0216] The polyol (A-6) had a hydroxyl value of 62.9 mgKOH / g and an average functionality of 3.0.

[0217] (7) Polyol (A-7) A polyester polyol was obtained by ester condensation of a commercially available polyoxypropylene polyol (trade name SOR-400, initiator sorbitol, average functionality 6, hydroxyl value 400 mgKOH / g, manufactured by Mitsui Chemicals), a polyoxypropylene polyol (trade name PE-450, initiator pentaerythritol, average functionality 4, hydroxyl value 450 mgKOH / g), and high-purity castor oil fatty acid (94% ricinoleic acid).

[0218] More specifically, 742.49 g of high-purity castor oil fatty acid (94% ricinoleic acid), 71.79 g of polyoxypropylene polyol (trade name SOR-400, initiator sorbitol, average functionality 6, hydroxyl value 400 mgKOH / g, manufactured by Mitsui Chemicals), and 30.13 g of polyoxypropylene polyol (trade name PE-450, initiator pentaerythritol, average functionality 4, hydroxyl value 450 mgKOH / g) were placed in a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and a condensation reaction was carried out at 180°C under a nitrogen stream.

[0219] When the acid value of the content of the flask became 10 mgKOH / g or less, 0.34 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The content of the flask was then subjected to a condensation reaction at 180°C for a total of 60 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-7).

[0220] The polyol (A-7) had a hydroxyl value of 47.6 mgKOH / g and an average functionality of 4.4.

[0221] (8) Polyol (B-1) As polyol (B-1), commercially available polyoxyalkylene polyols (non-aromatic polyether polyols, polyoxyethylene polyols) were prepared.

[0222] In polyol (B-1), the ratio of oxyethylene units to the total amount of oxyalkylene units was 100 mass%, the ratio of oxypropylene units to the total amount of oxyalkylene units was 0 mass%, the average number of functional groups was 3, and the hydroxyl value was 920 mgKOH / g.

[0223] (9) Polyol (B-2) As polyol (B-2), commercially available polyoxyalkylene polyols (non-aromatic polyether polyols, polyoxypropylene polyols) were prepared.

[0224] In polyol (B-2), the ratio of oxyethylene units to the total amount of oxyalkylene units was 0 mass%, the ratio of oxypropylene units to the total amount of oxyalkylene units was 100 mass%, the average number of functional groups was 3, and the hydroxyl value was 875 mgKOH / g.

[0225] (10) Polyol (C-1) A commercially available tolylenediamine-based polyether polyol (aromatic polyether polyol) was prepared as polyol (C-1).

[0226] In polyol (C-1), the ratio of oxyethylene units to the total amount of oxyalkylene units was 29 mass%, the ratio of oxypropylene units to the total amount of oxyalkylene units was 71 mass%, the average number of functional groups was 4, and the hydroxyl value was 400 mgKOH / g.

[0227] (11) Polyol (C-2) A commercially available tolylenediamine-based polyether polyol (aromatic polyether polyol) was prepared as polyol (C-2).

[0228] In polyol (C-2), the ratio of oxyethylene units to the total amount of oxyalkylene units was 0 mass%, the ratio of oxypropylene units to the total amount of oxyalkylene units was 100 mass%, the average number of functional groups was 4, and the hydroxyl value was 451 mgKOH / g.

[0229] (12) Other Polyol (D-1) Dipropylene glycol (DPG, manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared as other polyol (D-1).

[0230] (13) Other Polyols (D-2) As other polyols (D-2), commercially available polyoxyalkylene polyols (non-aromatic polyether polyols, propylene oxide-ethylene oxide block copolymers (oxyethylene-terminated)) were prepared.

[0231] In polyol (D-2), the ratio of oxyethylene units to the total amount of oxyalkylene units was 15 mass%, the ratio of oxypropylene units to the total amount of oxyalkylene units was 85 mass%, the average number of functional groups was 3, and the hydroxyl value was 33 mgKOH / g.

[0232] (14) Polyisocyanate A commercially available carbodiimide-modified diphenylmethane diisocyanate (NCO content measured by ASTM D1638: 28.5% by mass to 29.5% by mass, trade name: Cosmonate LL, manufactured by Kumho Mitsui Chemicals, Inc.) was prepared as the polyisocyanate.

[0233] [4] Examples and Comparative Examples Example 1 Polyol (A) and polyol (B) were mixed according to the formulation shown in Table 1 to obtain a polyol composition.

[0234] Next, additives were added to the polyol composition to obtain a polyol component (resin premix). More specifically, an antifoaming agent (additive, silicone-based antifoaming agent, manufactured by BYK Japan, product name: BYK-1799) was added to the polyol composition. The amount of antifoaming agent added was 5 ppm relative to the polyol component (resin premix).

[0235] Next, polyisocyanate (trade name: Cosmonate LL) was prepared as a polyisocyanate component, thereby obtaining a polyurethane resin composition (two-component resin composition) including a polyol component and a polyisocyanate component.

[0236] Next, the polyol component (resin premix) and the polyisocyanate component were stirred and degassed under vacuum using a hot stirrer set at 120°C and 500 rpm. After mixing, the polyol component (resin premix) and the polyisocyanate component were each cooled to 25°C.

[0237] The polyol component (resin premix) and the polyisocyanate component were then mixed so that the isocyanate index became the value shown in Table 1, and the mixture was stirred for 40 to 80 seconds using a planetary centrifugal mixer. The mixture was then degassed under reduced pressure in vacuum and poured into a one-sided open mold (thickness: 4 mm, depth: 100 mm, width: 300 mm) preheated to 90°C. The polyurethane resin composition was then cured by heating at 90°C for 30 minutes or more to obtain a molded polyurethane resin product. The polyurethane resin was then evaluated using the methods described above.

[0238] Examples 2 to 8 and Comparative Examples 1 to 7 Polyol compositions, polyurethane resin compositions, and polyurethane resins were obtained in the same manner as in Example 1, except that the formulations were changed as shown in Tables 1 and 2. The polyurethane resins were also evaluated by the methods described above.

[0239] In each Example and Comparative Example, a catalyst solution was appropriately added as necessary. The catalyst solution was prepared by diluting dibutyltin dilaurate (DBTDL, manufactured by Tokyo Chemical Industry Co., Ltd.) with diisononyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) to 20% by mass. In Comparative Example 7, the polyol component (resin premix) and the polyisocyanate component were mixed, and then stirred for 300 seconds using a planetary centrifugal mixer.

[0240]

[0241]

[0242] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the following claims.

[0243] The polyol composition, polyurethane resin composition, and polyurethane resin of the present invention are suitable for use in buildings, structures, robot parts, electric and electronic parts, office supplies, and health care products.

Claims

1. A polyol composition comprising a polyol (A) and a polyol (B), wherein the polyol (A) is a polyester polyol, the polyol (A) has an average functionality of 1.1 to 5.0, the polyol (A) has a hydroxyl value of 50 mgKOH / g to 170 mgKOH / g, the polyol (B) has an average functionality of 2.0 to 4.0, the polyol (B) has a hydroxyl value of 600 mgKOH / g to 1,200 mgKOH / g, the polyester polyol has a fatty acid (X) unit having 15 to 20 carbon atoms and containing one hydroxyl group, and the ratio ((X) / (B)) of the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) to the mass of the polyol (B) is 0.08 to 0.

90.

2. The polyol composition according to claim 1, wherein a ratio of the mass of the polyol (B) to the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) and the polyol (B), ((B) / ((B)+(X))), is 0.55 to 0.

95.

3. The polyol composition according to claim 1 or 2, wherein a ratio ((X) / (B)) of the total mass of the fatty acid (X) obtained by saponification decomposition of the polyol (A) to the mass of the polyol (B) is 0.15 to 0.

50.

4. The polyol composition according to claim 1 or 2, wherein the polyol (A) has a hydroxyl value of 55 mg KOH / g to 170 mg KOH / g.

5. The polyol composition according to claim 1 or 2, wherein the polyol (A) has a hydroxyl value of 55 mg KOH / g to 140 mg KOH / g.

6. The polyol composition according to claim 1 or 2, wherein the fatty acid (X) is ricinoleic acid.

7. The polyol composition according to claim 1 or 2, which is a raw material for a polyurethane resin.

8. A polyurethane resin composition comprising: a polyol component containing the polyol composition according to claim 1 or 2; and a polyisocyanate component, the polyurethane resin composition having an NCO index of 0.70 to 1.

30.

9. The polyurethane resin composition according to claim 8, wherein the polyisocyanate component contains at least one member selected from the group consisting of diphenylmethane diisocyanate, a diphenylmethane diisocyanate derivative, phenylene diisocyanate, a phenylene diisocyanate derivative, and a polymethylene polyphenyl polyisocyanate.

10. The polyurethane resin composition according to claim 9, wherein the polyisocyanate component contains a diphenylmethane diisocyanate derivative.

11. A polyurethane resin containing a reaction product of the polyurethane resin composition according to claim 8, the polyurethane resin having a Shore D hardness of 60 or more and a density of 1.0 g / cm ３ That's it, polyurethane resin.

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