Polyurethane resin composition, polyurethane resin, and molded article

Abstract

To provide a polyurethane resin composition, polyurethane resin, and molded article that can obtain a polyurethane resin having relatively good marine biodegradability and relatively reduced temperature dependence of storage modulus. [Solution] The polyurethane resin composition contains a first component containing a polyol and a second component containing a polyisocyanate. The polyol contains a polyester polyol. The saponification value of the polyester polyol is between 10 mg KOH / g and 210 mg KOH / g. The number-average molecular weight of the polyester polyol, measured by gel permeation chromatography (GPC) in terms of polystyrene, is 1,550 or higher. The polyisocyanate contains aliphatic polyisocyanates.

Description

[Technical Field]

[0001] This invention relates to polyurethane resin compositions, polyurethane resins, and molded articles. [Background technology]

[0002] Polyurethane resin compositions contain a polyol and a polyisocyanate. Polyurethane resin is produced by the reaction of the polyol and the polyisocyanate. Polyurethane resins are molded using various methods and are widely used in various industrial fields.

[0003] As a polyurethane resin composition, for example, the following two-component curing type coating composition has been proposed. That is, the two-component curing type coating composition contains an acrylic resin composition and a polyisocyanate-based curing agent. The acrylic resin composition contains a copolymer of (meth)acrylic acid ester monomer, a monomer having a vinyl group, a reactive silicone monomer, and a castor oil polyol. The polyisocyanate-based curing agent contains a 1,5-pentamethylene diisocyanate-based curing agent (see, for example, Patent Document 1 (Example 1)). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-045410 [Overview of the project] [Problems that the invention aims to solve]

[0005] On the other hand, from an environmental standpoint, there is a demand for polyurethane resins that can be biodegraded in marine environments, and also for polyurethane resin compositions that can be used to obtain such polyurethane resins.

[0006] Furthermore, the storage modulus of polyurethane resins typically fluctuates with temperature. However, depending on the application, it may be required to suppress the temperature-dependent fluctuation of the storage modulus. In particular, it may be required to reduce the temperature dependence of the storage modulus between -10°C and 50°C.

[0007] The present invention provides a polyurethane resin composition, a polyurethane resin, and a molded article that can be obtained having relatively good marine biodegradability and relatively reduced temperature dependence of the storage modulus. [Means for solving the problem]

[0008] The present invention [1] comprises a polyurethane resin composition comprising a first component containing a polyol and a second component containing a polyisocyanate, wherein the polyol contains a polyester polyol, the saponification value of the polyester polyol is 10 mg KOH / g or more and 210 mg KOH / g or less, the number average molecular weight of the polyester polyol in terms of polystyrene, as measured by gel permeation chromatography (GPC), is 1,550 or more, and the polyisocyanate contains an aliphatic polyisocyanate.

[0009] The present invention [2] includes the polyurethane resin composition described in [1] above, wherein the saponification value of the polyester polyol is 100 mg KOH / g or more and 200 mg KOH / g or less.

[0010] The present invention [3] comprises the polyurethane resin composition described in [1] or [2] above, wherein the polyester polyol has structural units derived from a fatty acid, and the fatty acid is a C15 to C20 fatty acid containing one or more hydroxyl groups in one molecule.

[0011] The present invention [4] comprises the polyurethane resin composition described in [3] above, wherein the fatty acid is ricinoleic acid.

[0012] The present invention [5] comprises a polyurethane resin composition according to any one of the above [1] to [4], wherein the polyester polyol has a number-average molecular weight in terms of polystyrene, as measured by gel permeation chromatography (GPC), of 1,700 or more.

[0013] The present invention [6] includes a polyurethane resin composition according to any one of the above [1] to [5], wherein the polyisocyanate contains at least one selected from the group consisting of 1,5-pentamethylene diisocyanate, a derivative of 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and a derivative of 1,6-hexamethylene diisocyanate.

[0014] The present invention [7] includes a polyurethane resin composition described in any one of the above [1] to [6], which is a raw material for a polyurethane resin.

[0015] The present invention [8] includes a polyurethane resin composition according to any one of the above [1] to [7], wherein the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate in the second component to the hydroxyl groups of the polyol in the first component is 0.70 or more and 1.60 or less.

[0016] The present invention [9] further includes a polyurethane resin composition according to any one of the above [1] to [7], wherein the third component contains a chain extender, and the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate in the second component to the hydroxyl groups of the polyol in the first component is 2.0 or more and 20.0 or less.

[0017] The present invention

[10] includes a polyurethane resin containing a reaction product of a polyurethane resin composition described in any one of the above [1] to [9].

[0018] The present invention

[11] includes a molded article comprising the polyurethane resin described in

[10] above. The present invention

[12] includes the molded body described in

[11] above, which is a powder.

Advantages of the Invention

[0019] The polyurethane resin composition of the present invention contains a first component containing a predetermined polyol and a second component containing a predetermined polyisocyanate. Therefore, according to the above polyurethane resin composition, a polyurethane resin having relatively excellent marine biodegradability and a reduced temperature dependence of the storage modulus can be obtained.

[0020] The polyurethane resin and the molded body of the present invention have relatively excellent marine biodegradability, and the temperature dependence of the storage modulus of the above polyurethane resin is relatively low.

Brief Description of the Drawings

[0021] [Figure 1] Figure 1 is a photograph of the powder (8 grains) of the polyurethane resin of Example 6 taken with a 100-fold magnifying glass. [Figure 2] Figure 2 is a photograph of the powder (8 grains) of the polyurethane resin of Example 9 taken with a 100-fold magnifying glass.

Modes for Carrying Out the Invention

[0022] Hereinafter, embodiments of the present disclosure will be described. These descriptions and examples are illustrative of the embodiments and do not limit the scope of the embodiments. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In the present disclosure, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. In numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced by the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. When referring to the amount of each component in a composition in this disclosure, if there are multiple types of the substance corresponding to each component in the composition, it means the total amount of those multiple types of substances present in the composition unless otherwise specified. In this disclosure, "mass%" and "weight%" are synonymous, and "parts by mass" and "parts by weight" are synonymous. In this disclosure, the "%" indicating the amount of contained components is based on mass unless otherwise specified. In this disclosure, the term “layer” includes cases where, when observing the region in which the layer exists, it is formed not only over the entire region but also over only a portion of the region. In the notation of groups (atomic groups) in this disclosure, the notation that does not specify substitution or unsubstituted includes both those with and without substituents.

[0023] 1. First Embodiment 1) Polyurethane resin composition In the first embodiment, the polyurethane resin composition is a raw material for a polyurethane resin (described later) and a molded article (described later). The polyurethane resin composition contains a first component containing a polyol and a second component containing a polyisocyanate, and does not contain a third component (i.e., a chain extender) as described later. Preferably, the polyurethane resin composition consists of the first component and the second component. Each of these will be described in detail below.

[0024] [1] Component 1 The first component contains a polyol, and preferably consists of a polyol. A polyol is an organic compound having two or more hydroxyl groups in one molecule.

[0025] [1.1] Polyol The polyol contains a polyester polyol, and preferably consists of a polyester polyol. The polyester polyol has a predetermined saponification value and a predetermined number-average molecular weight, which will be described in detail later.

[0026] [1.1.1] Polyester polyol Examples of polyester polyols include polyester polyols having structural units derived from polyhydric alcohols (polyhydric alcohol units) and structural units derived from carboxylic acids (carboxylic acid units).

[0027] [Polyhydric alcohols] 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-octen-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, isitol, dalucitol, althritol, inositol, and dipentaerythritol. Examples of heptahydric alcohols include perseitol. Examples of octahydric alcohols include sucrose. These can be used alone or in combination of two or more.

[0028] Furthermore, examples of polyhydric alcohols include polyoxyalkylene (C2-C3) polyols, and more specifically, polyoxyethylene polyols, polyoxypropylene polyols, and oxyethylene-oxypropylene copolymers (random or block copolymers). The average number of functional groups (average number of hydroxyl groups) of polyoxyalkylene (C2-C3) polyols is, for example, 2-6. The number-average molecular weight (GPC measurement) of polyoxyalkylene (C2-C3) polyols is, for example, 200-2000, preferably 400-1000, and more preferably 500-1000. These can be used alone or in combination of two or more types.

[0029] Preferably, polyhydric alcohols include dihydric to hexahydric alcohols. Also, preferably, polyoxyalkylene (C2-3) polyols with an average of 2 to 6 functional groups are also included as polyhydric alcohols.

[0030] Preferably, the polyhydric alcohols include dihydric to hexahydric alcohols and polyoxyalkylene (C2-3) polyols with an average number of functional groups of 2 to 6. From the viewpoint of reducing the temperature dependence of the storage modulus of the polyurethane resin in the range of -10°C to 50°C, more preferably, the polyhydric alcohols are dihydric to hexahydric alcohols.

[0031] In particular, as polyhydric alcohols, trihydric alcohols are more preferably, and glycerin is especially preferably.

[0032] In other words, the polyester polyol preferably contains structural units derived from trihydric alcohols (trihydric alcohol units) as polyhydric alcohol units, and more preferably contains only trihydric alcohol units. To put it another way, the polyhydric alcohol units preferably contain trihydric alcohol units, and more preferably consist of trihydric alcohol units. The polyester polyol even more preferably contains structural units derived from glycerin (glycerin units) as polyhydric alcohol units, and particularly preferably contains only glycerin units. To put it another way, the polyhydric alcohol units even more preferably contain glycerin units, and particularly preferably consist of glycerin units.

[0033] Furthermore, as polyhydric alcohols, tetrahydric alcohols are more preferably mentioned, and diglycerin is particularly preferred.

[0034] In other words, the polyester polyol preferably contains structural units derived from tetrahydric alcohols (tetrahydric alcohol units) as polyhydric alcohol units, and more preferably contains only tetrahydric alcohol units. To put it another way, the polyhydric alcohol units preferably contain tetrahydric alcohol units, and more preferably consist of tetrahydric alcohol units. The polyester polyol is even more preferably containing structural units derived from diglycerin (diglycerin units) as polyhydric alcohol units, and particularly preferably contains only diglycerin units. To put it another way, the polyhydric alcohol units are even more preferably containing diglycerin units, and particularly preferably consist of diglycerin units.

[0035] Furthermore, as polyhydric alcohols, hexahydric alcohols are more preferably included, and sorbitol and pentaerythritol are particularly preferred.

[0036] In other words, the polyester polyol preferably contains structural units derived from hexahydric alcohols (hexahydric alcohol units) as polyhydric alcohol units, and more preferably contains only hexahydric alcohol units. To put it another way, the polyhydric alcohol units preferably contain hexahydric alcohol units, and more preferably consist of hexahydric alcohol units. The polyester polyol is even more preferably containing structural units derived from sorbitol (sorbitol units) and / or structural units derived from pentaerythritol (pentaerythritol units) as polyhydric alcohol units, and particularly preferably contains only sorbitol units and / or pentaerythritol units. To put it another way, the polyhydric alcohol units are even more preferably containing sorbitol units and / or pentaerythritol units, and particularly preferably consist of sorbitol units and / or pentaerythritol units.

[0037] [Carboxylic acid] Examples of carboxylic acids include fatty acids. That is, polyester polyols have structural units derived from fatty acids, for example.

[0038] Examples of fatty acids include saturated fatty acids and unsaturated fatty acids. Fatty acids are classified into, for example, fatty acids that do not contain hydroxyl groups 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).

[0039] Examples of hydroxyl-free fatty acids include hydroxyl-free fatty acids with 4 to 30 carbon atoms.

[0040] Examples of hydroxyl-free fatty acids with 4 to 30 carbon atoms include hydroxyl-free saturated fatty acids and hydroxyl-free unsaturated fatty acids with 4 to 30 carbon atoms. Examples of hydroxyl-free saturated fatty acids with 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 hydroxyl-free saturated fatty acids with 4 to 30 carbon atoms include oleic acid, linoleic acid, and linolenic acid. These can be used individually or in combination of two or more types.

[0041] Examples of hydroxyl group-containing fatty acids include hydroxyl group-containing fatty acids with 15 to 20 carbon atoms.

[0042] More specifically, 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).

[0043] Examples of monohydroxy fatty acids include monohydroxy fatty acids with 15 to 20 carbon atoms. Examples of monohydroxy fatty acids with 15 to 20 carbon atoms include monohydroxy saturated fatty acids and monohydroxy unsaturated fatty acids with 15 to 20 carbon atoms. Examples of monohydroxy saturated fatty acids with 15 to 20 carbon atoms include hydroxypentadecanoic acid, hydroxyhexadecanoic acid (hydroxypalmitic acid), hydroxyheptadecanoic acid, hydroxyoctadecanoic acid (hydroxystearic acid), hydroxynonadecanoic acid, and hydroxyeicosanoic acid (hydroxyarachidic acid). Examples of monohydroxy unsaturated fatty acids with 15 to 20 carbon atoms include hydroxyoleic acid (ricinoleic acid), hydroxylinoleic acid, and hydroxylinolenic acid. These can be used individually or in combination of two or more types.

[0044] Examples of polyhydroxy fatty acids include polyhydroxy fatty acids with 15 to 20 carbon atoms. Examples of polyhydroxy fatty acids with 15 to 20 carbon atoms include polyhydroxy saturated fatty acids and polyhydroxy unsaturated fatty acids with 15 to 20 carbon atoms. Examples of polyhydroxy saturated fatty acids with 15 to 20 carbon atoms include dihydroxypentadecanoic acid, dihydroxyhexadecanoic acid (dihydroxypalmitic acid), dihydroxyheptadecanoic acid, dihydroxyoctadecanoic acid (dihydroxystearic acid), dihydroxynonadecanoic acid, and dihydroxyeicosanoic acid (dihydroxyarachidic acid). Examples of polyhydroxy unsaturated fatty acids with 15 to 20 carbon atoms include dihydroxyoleic acid, dihydroxylinoleic acid, and dihydroxylinolenic acid. These can be used individually or in combination of two or more types.

[0045] Preferably, fatty acids include hydroxyl group-containing fatty acids, more preferably hydroxyl group-containing fatty acids having 15 to 20 carbon atoms (i.e., fatty acids having 15 to 20 carbon atoms that contain one or more hydroxyl groups in one molecule), even more preferably monohydroxy fatty acids having 15 to 20 carbon atoms, and particularly preferably ricinoleic acid.

[0046] In other words, polyester polyols contain, for example, structural units derived from fatty acids (hereinafter referred to as fatty acid units), preferably containing hydroxyl group-containing fatty acid units, more preferably containing hydroxyl group-containing fatty acid units having 15 to 20 carbon atoms, even more preferably containing monohydroxy fatty acid units having 15 to 20 carbon atoms, and particularly preferably containing ricinoleic acid units.

[0047] The fatty acid unit content is, for example, 80 to 99% by mass, preferably 90 to 95% by mass, relative to the total amount of polyester polyol.

[0048] [Method for producing polyester polyol] The method for producing polyester polyols is not particularly limited. For example, polyester polyols can be produced by ester condensation of the above polyhydric alcohol and the above carboxylic acid using a known method. Preferably, polyester polyols can be produced by ester condensation of the above dihydric to hexahydric alcohol and / or the above polyoxyalkylene (C2-3) polyol having an average number of functional groups of 2 to 6 and the above fatty acid using a known method.

[0049] The ratio of polyhydric alcohol to carboxylic acid is adjusted as appropriate depending on the purpose and application. For example, the ratio of carboxylic acid units to 1 mole of polyhydric alcohol units is, for example, 1 to 20 moles, preferably 5 to 18 moles, and more preferably 10 to 16 moles.

[0050] The above reaction yields a polyester polyol as a condensate of a polyhydric alcohol and a carboxylic acid. The reaction conditions between the polyhydric alcohol and the carboxylic acid are not particularly limited and can be set appropriately according to the purpose and application.

[0051] Furthermore, naturally derived polyester polyols can also be mentioned as polyester polyols. Examples of naturally derived polyester polyols include natural oils and natural oil derivatives. Examples of natural oils include vegetable oils and / or animal oils, with vegetable oils being preferred. 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. Preferably, ester condensates of castor oil and fatty acids are used as natural oil derivatives. Fatty acids that undergo ester condensation with castor oil are preferably fatty acids derived from natural oils, and 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, and examples include palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and dihydroxystearic acid, with ricinoleic acid being preferred. Natural oil derivatives are not particularly limited and are produced by esterifying natural oils and fatty acids in known ways.

[0052] Natural oils and natural oil derivatives have, for example, polyhydric alcohol units and fatty acid units. In natural oils and natural oil derivatives, the ratio of fatty acid units to 1 mole of polyhydric alcohol units is, for example, 1 to 10 moles, preferably 2 to 8 moles, and more preferably 3 to 6 moles.

[0053] Polyether polyester polyols are also examples of polyester polyols. Examples of polyether polyester polyols include addition polymers obtained by ring-opening addition polymerization of alkylene oxide to an initiator having an ester bond and a hydroxyl group. Examples of initiators having an ester bond and a hydroxyl group include the above-mentioned natural oils and natural oil derivatives, preferably natural oils, and more preferably castor oil. Examples of alkylene oxides include ethylene oxide (EO) and propylene oxide (PO), preferably propylene oxide (PO). The method for ring-opening addition polymerization of alkylene oxide to the initiator is not particularly limited, and known methods can be used. For example, ring-opening addition polymerization of alkylene oxide is carried out by contacting an initiator having an ester bond and a hydroxyl group with alkylene oxide in the presence of a known composite metal cyanide (DMC) catalyst and heating them. The polymerization conditions for ring-opening addition polymerization are not particularly limited and can be set as appropriate according to the purpose and application.

[0054] Furthermore, the polyester polyol is not limited to the above-mentioned polyester polyol, as long as it has the saponification value and number-average molecular weight described later. In addition to the above, other examples of polyester polyols include ring-opening polyester polyols. Examples of ring-opening polyester polyols include ring-opening polymers of lactones and / or lactides.

[0055] Polyester polyols are used alone or in combination of two or more types. From the viewpoint of obtaining relatively excellent marine biodegradability, naturally derived polyester polyols are preferred, more preferably natural oil derivatives, and even more preferably castor oil derivatives.

[0056] [1.2] Physical properties of polyester polyols The polyester polyol has a predetermined saponification value and number-average molecular weight. That is, a polyester polyol having a predetermined saponification value and number-average molecular weight is selected as the polyester polyol. When two or more types of polyester polyols are used in combination, preferably each polyester polyol has a predetermined saponification value and number-average molecular weight.

[0057] [Saponification value] The saponification value of the polyester polyol is 10 mg KOH / g or more, preferably 100 mg KOH / g or more, more preferably 120 mg KOH / g or more, even more preferably 150 mg KOH / g or more, and particularly preferably 170 mg KOH / g or more. Alternatively, the saponification value of the polyester polyol is 210 mg KOH / g or less, preferably 205 mg KOH / g or less, more preferably 200 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and particularly preferably 190 mg KOH / g or less.

[0058] In other words, the saponification value of the polyester polyol is 10 mg KOH / g or more and 210 mg KOH / g or less, preferably 100 mg KOH / g or more and 205 mg KOH / g or less, more preferably 100 mg KOH / g or more and 200 mg KOH / g or less, even more preferably 120 mg KOH / g or more and 200 mg KOH / g or less, even more preferably 150 mg KOH / g or more and 200 mg KOH / g or less, and particularly preferably 170 mg KOH / g or more and 190 mg KOH / g or less.

[0059] The saponification value of a polyester polyol indicates the amount of carboxylic acid contained in the composition obtained by saponifying and decomposing the polyester polyol (i.e., the saponified decomposition composition). The saponification value is measured in accordance with JIS K 0070 (1992) (the same applies hereafter).

[0060] When two or more types of polyester polyols are used in combination, the overall saponification value of the polyester polyols can be calculated by apportioning the saponification value of each polyester polyol based on the formulation.

[0061] [Number average molecular weight] The number-average molecular weight (polystyrene equivalent) of the polyester polyol is 1,550 or more, preferably 1,700 or more, and more preferably 1,800 or more. Alternatively, the number-average molecular weight (polystyrene equivalent) of the polyester polyol may be, for example, 10,000 or less, or 8,000 or less.

[0062] In other words, the number-average molecular weight (in terms of polystyrene) of the polyester polyol is, for example, 1,550 to 10,000, preferably 1,700 to 10,000, and more preferably 1,800 to 8,000.

[0063] The number-average molecular weight is the polystyrene-equivalent number-average molecular weight measured by gel permeation chromatography (GPC). That is, the number-average molecular weight is measured as polystyrene-equivalent molecular weight by gel permeation chromatography (GPC) in accordance with the examples described later. Alternatively, the number-average molecular weight can also be calculated from the hydroxyl group equivalent and average number of hydroxyl groups using known methods.

[0064] [Hydroxyl value] The hydroxyl value of the polyester polyol is, for example, 20 mg KOH / g or more, preferably 30 mg KOH / g or more, and more preferably 40 mg KOH / g or more. Alternatively, the hydroxyl value of the polyester polyol is, for example, 200 mg KOH / g or less, preferably 180 mg KOH / g or less, and more preferably 150 mg KOH / g or less.

[0065] In other words, the hydroxyl value of the polyester polyol is, for example, 20 mg KOH / g or more and 200 mg KOH / g or less, preferably 30 mg KOH / g or more and 180 mg KOH / g or less, and more preferably 40 mg KOH / g or more and 150 mg KOH / g or less.

[0066] The hydroxyl value is measured in accordance with the phthalation method of Method B of JIS K 1557-1 (2007) (the same applies hereafter).

[0067] When two or more types of polyester polyols are used in combination, the total hydroxyl value of the polyester polyols can be calculated by apportioning the hydroxyl value of each polyester polyol based on the formulation.

[0068] [Average number of functional groups (average number of hydroxyl groups)] The average number of functional groups (average number of hydroxyl groups) of polyester polyols is, for example, 2.0 or more, preferably 2.2 or more. Alternatively, the average number of functional groups (average number of hydroxyl groups) of polyester polyols is, for example, 6.0 or less, preferably 5.0 or less, and more preferably 4.8 or less.

[0069] In other words, the average number of functional groups (average number of hydroxyl groups) of the polyester polyol is, for example, 2.0 or more and 6.0 or less, preferably 2.2 or more and 5.0 or less, and more preferably 2.2 or more and 4.8 or less.

[0070] The average number of functional groups in polyester polyols is calculated according to the following formula (the same applies hereafter). Average number of functional groups = number of moles of hydroxyl groups (amount of substance) / number of moles of polyester polyol (amount of substance)

[0071] In the above formula, the number of moles (amount of substance) of hydroxyl groups and the number of moles (amount of substance) of polyester polyol are calculated from the raw material preparation (amount of blending and number of functional groups) and the hydroxyl value mentioned above, respectively (the same applies hereinafter).

[0072] When two or more types of polyester polyols are used in combination, the total number-average molecular weight of the polyester polyols can be calculated by allocating the number-average molecular weight of each polyester polyol based on the formulation.

[0073] [1.1.3] Other polyols The polyol may contain other polyols as optional components, if necessary. These other polyols are polyols other than the polyester polyols mentioned above.

[0074] Other polyols include, for example, other high molecular weight polyols and low molecular weight polyols.

[0075] [Other high molecular weight polyols] High molecular weight polyols are relatively high molecular weight organic compounds that have two or more hydroxyl groups in one molecule. The number-average molecular weight of high molecular weight polyols is, for example, greater than 400 and, for example, 20,000 or less. Other high molecular weight polyols are high molecular weight polyols other than the polyester polyols mentioned above. Examples of other high molecular weight polyols include polyether polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. These can be used individually or in combination of two or more types.

[0076] [Low molecular weight polyols] Low molecular weight polyols are organic compounds with relatively low molecular weight, possessing two or more hydroxyl groups in a single molecule. The number-average molecular weight of low molecular weight polyols is, for example, between 40 and 400. Examples of low molecular weight polyols include the polyhydric alcohols mentioned above, more specifically, the dihydric, trihydric, tetrahydric, pentahydric, hexahydric, heptahydric, and octahydric alcohols. These can be used individually or in combination of two or more types.

[0077] [Content percentage] The content of other polyols is, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 0% by mass, relative to the total amount of polyols. In other words, the polyol preferably does not contain other polyols.

[0078] In other words, the polyester polyol content is, for example, 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass, relative to the total amount of polyol. That is, the polyol is more preferably polyester polyol.

[0079] [1.1.4] Physical properties of polyols [Saponification value] The saponification value of the polyol is, for example, 10 mg KOH / g or more, preferably 100 mg KOH / g or more, more preferably 120 mg KOH / g or more, even more preferably 150 mg KOH / g or more, and particularly preferably 170 mg KOH / g or more. Alternatively, the saponification value of the polyol is, for example, 210 mg KOH / g or less, preferably 205 mg KOH / g or less, more preferably 200 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and particularly preferably 190 mg KOH / g or less.

[0080] In other words, the saponification value of the polyol is, for example, 10 mg KOH / g or more and 210 mg KOH / g or less, preferably 100 mg KOH / g or more and 205 mg KOH / g or less, more preferably 100 mg KOH / g or more and 200 mg KOH / g or less, even more preferably 120 mg KOH / g or more and 200 mg KOH / g or less, even more preferably 150 mg KOH / g or more and 200 mg KOH / g or less, and particularly preferably 170 mg KOH / g or more and 190 mg KOH / g or less.

[0081] [Number average molecular weight] The number-average molecular weight (polystyrene equivalent) of the polyol is, for example, 1,550 or more, preferably 1,700 or more, and more preferably 1,800 or more. Alternatively, the number-average molecular weight (polystyrene equivalent) of the polyol may be, for example, 10,000 or less, or 8,000 or less.

[0082] In other words, the number-average molecular weight (in polystyrene terms) of the polyol is, for example, 1,550 to 10,000, preferably 1,700 to 10,000, and more preferably 1,800 to 8,000. The number-average molecular weight is the number-average molecular weight in polystyrene terms measured by gel permeation chromatography (GPC).

[0083] [Hydroxyl value] The hydroxyl value of the polyol is, for example, 20 mg KOH / g or more, preferably 30 mg KOH / g or more, and more preferably 40 mg KOH / g or more. Alternatively, the hydroxyl value of the polyol is, for example, 200 mg KOH / g or less, preferably 180 mg KOH / g or less, and more preferably 150 mg KOH / g or less.

[0084] In other words, the hydroxyl value of the polyol is, for example, 20 mg KOH / g or more and 200 mg KOH / g or less, preferably 30 mg KOH / g or more and 180 mg KOH / g or less, and more preferably 40 mg KOH / g or more and 150 mg KOH / g or less.

[0085] [Average number of functional groups (average number of hydroxyl groups)] The average number of functional groups (average number of hydroxyl groups) of the polyol is, for example, 2.0 or more, preferably 2.2 or more. Alternatively, the average number of functional groups (average number of hydroxyl groups) of the polyol is, for example, 6.0 or less, preferably 5.0 or less, and more preferably 4.8 or less.

[0086] In other words, the average number of functional groups (average number of hydroxyl groups) of the polyol is, for example, 2.0 or more and 6.0 or less, preferably 2.2 or more and 5.0 or less, and more preferably 2.2 or more and 4.8 or less.

[0087] [2] Second component The second component contains a polyisocyanate, and preferably consists of a polyisocyanate. A polyisocyanate is, for example, a compound having two or more isocyanate groups in one molecule.

[0088] [2.1] Polyisocyanates Polyisocyanates contain aliphatic polyisocyanates, and preferably consist of aliphatic polyisocyanates. The aliphatic polyisocyanates are linear aliphatic polyisocyanates.

[0089] [2.1.1] Aliphatic polyisocyanates Examples of aliphatic polyisocyanates include aliphatic polyisocyanate monomers and aliphatic polyisocyanate derivatives.

[0090] Examples of aliphatic polyisocyanate monomers include aliphatic diisocyanates. Examples of aliphatic diisocyanates include tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate. These can be used individually or in combination of two or more types.

[0091] Examples of aliphatic polyisocyanate derivatives include derivatives of the aliphatic polyisocyanate monomers described above. Examples of derivatives include polymers, isocyanurate-modified derivatives, allophanate-modified derivatives, polyol-modified derivatives, biuret-modified derivatives, urea-modified derivatives, oxadiazinetrione-modified derivatives, and carbodiimide-modified derivatives. These can be used individually or in combination of two or more types.

[0092] Furthermore, aliphatic polyisocyanates also include isocyanate-terminated prepolymers (hereinafter referred to as aliphatic isocyanate-terminated prepolymers) derived from aliphatic polyisocyanate monomers and / or aliphatic polyisocyanate derivatives.

[0093] Aliphatic isocyanate-terminated prepolymers can be obtained, for example, by reacting the above-mentioned aliphatic polyisocyanate monomer and / or aliphatic polyisocyanate derivative with a high molecular weight polyol in a ratio in which isocyanate groups are in excess of hydroxyl groups. Examples of high molecular weight polyols include known polyether polyols, known polyester polyols, known polycarbonate polyols, known polyurethane polyols, known epoxy polyols, known vegetable oil polyols, known polyolefin polyols, known acrylic polyols, and known vinyl monomer-modified polyols. The high molecular weight polyol may also be the above-mentioned polyester polyol. These can be used individually or in combination of two or more types.

[0094] In the production of aliphatic isocyanate-terminated prepolymers, the equivalent ratio (NCO / OH) of the isocyanate groups of the aliphatic polyisocyanate monomer and / or the aliphatic polyisocyanate derivative to the hydroxyl groups of the high molecular weight polyol is, for example, 1.01 to 100, preferably 2 to 50.

[0095] Aliphatic polyisocyanates can be used alone or in combination of two or more types. Preferred aliphatic polyisocyanates include aliphatic polyisocyanate monomers and aliphatic polyisocyanate derivatives, and more preferably 1,5-pentamethylene diisocyanate, derivatives of 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and derivatives of 1,6-hexamethylene diisocyanate. In other words, the polyisocyanate preferably contains aliphatic polyisocyanate monomers and / or aliphatic polyisocyanate derivatives, and more preferably contains at least one selected from the group consisting of 1,5-pentamethylene diisocyanate, derivatives of 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and derivatives of 1,6-hexamethylene diisocyanate.

[0096] More preferably, the aliphatic polyisocyanate is 1,5-pentamethylene diisocyanate and derivatives of 1,5-pentamethylene diisocyanate, and particularly preferably, a derivative of 1,5-pentamethylene diisocyanate. In other words, the polyisocyanate more preferably contains 1,5-pentamethylene diisocyanate and / or a derivative of 1,5-pentamethylene diisocyanate.

[0097] From the viewpoint of marine biodegradability and storage modulus, 1,5-pentamethylene diisocyanate is particularly preferred as the aliphatic polyisocyanate. In other words, the polyisocyanate more preferably contains 1,5-pentamethylene diisocyanate, and particularly preferably consists of 1,5-pentamethylene diisocyanate.

[0098] [2.1.2] Other polyisocyanates Polyisocyanates may optionally contain other polyisocyanates as optional components. These other polyisocyanates are polyisocyanates other than the aliphatic polyisocyanates mentioned above. Examples of other polyisocyanates include alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

[0099] Examples of alicyclic polyisocyanates include alicyclic polyisocyanate monomers and alicyclic polyisocyanate derivatives.

[0100] Examples of alicyclic polyisocyanate monomers include alicyclic diisocyanates. Examples of alicyclic diisocyanates include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane. These can be used individually or in combination of two or more.

[0101] Examples of alicyclic polyisocyanate derivatives include the derivatives of the alicyclic polyisocyanate monomers described above. These can be used individually or in combination of two or more types.

[0102] Furthermore, examples of alicyclic polyisocyanates include isocyanate-terminated prepolymers (hereinafter referred to as alicyclic isocyanate-terminated prepolymers) derived from alicyclic polyisocyanate monomers and / or alicyclic polyisocyanate derivatives. Alicyclic isocyanate-terminated prepolymers can be obtained, for example, by reacting the above-mentioned alicyclic polyisocyanate monomers and / or alicyclic polyisocyanate derivatives with the above-mentioned high molecular weight polyols in a ratio in which isocyanate groups are in excess of hydroxyl groups.

[0103] Examples of aromatic polyisocyanates include aromatic polyisocyanate monomers and aromatic polyisocyanate derivatives.

[0104] Examples of aromatic polyisocyanate monomers include aromatic diisocyanates. Examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate. These can be used individually or in combination of two or more types.

[0105] Examples of aromatic polyisocyanate derivatives include the aforementioned derivatives of the aromatic polyisocyanate monomers. Other examples of aromatic polyisocyanate derivatives include polymethylene polyphenylene polyisocyanates (crude MDI, polymeric MDI). These can be used individually or in combination of two or more types.

[0106] Furthermore, aromatic polyisocyanates also include isocyanate-terminated prepolymers (hereinafter referred to as aromatic isocyanate-terminated prepolymers) derived from aromatic polyisocyanate monomers and / or aromatic polyisocyanate derivatives. Aromatic isocyanate-terminated prepolymers can be obtained, for example, by reacting the above aromatic polyisocyanate monomers and / or aromatic polyisocyanate derivatives with the above high molecular weight polyol in a ratio in which isocyanate groups are in excess of hydroxyl groups.

[0107] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic polyisocyanate monomers and aromatic aliphatic polyisocyanate derivatives.

[0108] Examples of aromatic aliphatic polyisocyanate monomers include aromatic aliphatic diisocyanates. Examples of aromatic aliphatic diisocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and tetramethylxylylene diisocyanate. These can be used individually or in combination of two or more types.

[0109] Examples of aromatic aliphatic polyisocyanate derivatives include the derivatives of the aromatic aliphatic polyisocyanate monomers described above. These can be used individually or in combination of two or more types.

[0110] Furthermore, examples of aromatic aliphatic polyisocyanates include isocyanate-terminated prepolymers (hereinafter referred to as aromatic aliphatic isocyanate-terminated prepolymers) derived from aromatic aliphatic polyisocyanate monomers and / or aromatic aliphatic polyisocyanate derivatives. Aromatic aliphatic isocyanate-terminated prepolymers can be obtained, for example, by reacting the above aromatic aliphatic polyisocyanate monomers and / or the above aromatic aliphatic polyisocyanate derivatives with the above high molecular weight polyol in a ratio in which isocyanate groups are in excess of hydroxyl groups.

[0111] Other polyisocyanates can be used alone or in combination of two or more types.

[0112] [Content percentage] The content of other polyisocyanates is, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 0% by mass, relative to the total amount of polyisocyanates. In other words, the polyisocyanates preferably do not contain other polyisocyanates.

[0113] In other words, the content of aliphatic polyisocyanate is, for example, 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass, relative to the total amount of polyisocyanate. That is, the polyisocyanate is more preferably aliphatic polyisocyanate.

[0114] [2.2] Physical properties of polyisocyanates [Isocyanate group concentration] The isocyanate group concentration (based on solid content) of the polyisocyanate is, for example, 20.0% by mass or more and 35.0% by mass or less, preferably 22.0% by mass or more and 30.0% by mass or less.

[0115] [Average number of functional groups (number of isocyanate groups)] The isocyanate group concentration (based on solid content) of the polyisocyanate is, for example, 1.5 to 8.0, preferably 2.0 to 6.0.

[0116] [3] Additives Polyurethane resin compositions may contain additives as needed. Examples of additives include crosslinking agents, heat stabilizers, light stabilizers, UV absorbers, antioxidants, surfactants, pH adjusters, defoamers, rust inhibitors, viscosity modifiers, chelating agents, antistatic agents, binders, fragrances, dyes, and pigments. These can be used individually or in combination of two or more. The amount and timing of additive addition are determined appropriately depending on the type of additive.

[0117] [4] Method for producing polyurethane resin composition The polyurethane resin composition is manufactured, for example, by preparing a first component and a second component separately. That is, the polyurethane resin composition is preferably a two-component curable resin composition.

[0118] In a polyurethane resin composition, the ratio of the first component to the second component is adjusted based on the equivalent ratio (NCO / OH) of the isocyanate groups (NCO) of the polyisocyanate in the second component to the hydroxyl groups (OH) of the polyol in the first component. Preferably, the ratio of the first component to the second component is adjusted based on the equivalent ratio (NCO / OH) in the one-shot method described later. The specific equivalent ratio values ​​will be described later.

[0119] Industrially, the ratio of the first and second components can also be adjusted based on their masses. For example, the amount of polyisocyanate in the second component is, for example, 1 to 50 parts by mass, preferably 5 to 30 parts by mass, relative to 100 parts by mass of polyol in the first component.

[0120] [5] Effects The above polyurethane resin composition contains a first component comprising the above polyol and a second component comprising the above polyisocyanate. Therefore, the above polyurethane resin composition makes it possible to obtain a polyurethane resin that has relatively good marine biodegradability and reduced temperature dependence of its storage modulus.

[0121] As a result, the above polyurethane resin composition is suitably used as a raw material for polyurethane resin. Examples of raw materials for polyurethane resin include molding materials, paints, adhesives, and coating agents (e.g., aqueous dispersions), with molding materials being preferred.

[0122] 2) Polyurethane resin The polyurethane resin contains the reaction product of the polyurethane resin composition. More specifically, the polyurethane resin can be obtained as a cured product of the polyurethane resin composition by reacting it with the polyurethane resin composition as a polyurethane resin raw material.

[0123] The method for obtaining polyurethane resin is not particularly limited, but one example is the one-shot method. In the one-shot method, for example, the first component (i.e., polyol) and the second component (i.e., polyisocyanate) are mixed in a predetermined equivalent ratio and reacted.

[0124] More specifically, in the one-shot method, the equivalent ratio (NCO / OH) of the isocyanate groups (NCO) of the polyisocyanate in the second component to the hydroxyl groups (OH) of the polyol in the first component is, for example, 0.70 to 1.60, preferably 0.80 to 1.50, more preferably 0.85 to 1.45, and even more preferably 0.95 to 1.35.

[0125] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, 40 to 200°C, preferably 60 to 150°C, and more preferably 80 to 100°C. The reaction time is, for example, 3 minutes to 24 hours, preferably 30 minutes to 12 hours. The reaction method is not particularly limited and includes known solution polymerization and known bulk polymerization. In addition, a known urethane catalyst may be added to the above reaction as needed. The amount and timing of addition of the urethane catalyst should be appropriately set according to the purpose and application.

[0126] The above reaction yields a polyurethane resin as a reaction product of the first component (i.e., polyol) and the second component (i.e., polyisocyanate). The polyurethane resin is then aged by known methods as needed. The aging conditions are set appropriately according to the purpose and application.

[0127] The polyurethane resin described above is obtained using the polyurethane resin composition described above. Therefore, the polyurethane resin described above has relatively good marine biodegradability and can also relatively reduce the temperature dependence of its storage modulus.

[0128] As a result, the above-mentioned polyurethane resin is suitably used in the manufacture of molded articles.

[0129] 3) Molded body The molded article contains the above-mentioned polyurethane resin. Preferably, the molded article is made of the above-mentioned polyurethane resin.

[0130] A molded article can be obtained, for example, by molding the above-mentioned polyurethane resin using a known molding method. Examples of molding methods include injection molding, extrusion molding, press molding, and cast molding. Alternatively, a molded article can also be obtained, for example, by machining the above-mentioned polyurethane resin using a known machining method. Examples of machining methods include crushing, cutting, and polishing.

[0131] The shape of the molded article is not particularly limited and is set as appropriate according to the purpose and application. Examples of molded article shapes include powder, microcapsules, pellets, plates, fibers, strands, films, sheets, and pipes. Powder is preferred. In other words, the molded article is preferably a powder.

[0132] Powders can be obtained, for example, by crushing polyurethane resin using a known method. Examples of powders include powders and beads. The size of the powder is not particularly limited and is set appropriately according to the purpose and application. For example, the particle size (maximum particle length) of the powder is, for example, 10 nm to 1000 μm, preferably 50 nm to 500 μm.

[0133] Furthermore, the above-mentioned molded article contains the above-mentioned polyurethane resin. Therefore, the above-mentioned molded article has relatively good marine biodegradability and can also relatively reduce the temperature dependence of its storage modulus.

[0134] 2. Second Embodiment 1) Polyurethane resin composition In the second embodiment, the polyurethane resin composition is a raw material for the polyurethane resin and molded article, similar to the first embodiment described above. The same explanation as in the first embodiment will be omitted below. The polyurethane resin composition contains a first component containing a polyol, a second component containing a polyisocyanate, and a third component containing a chain extender. Preferably, the polyurethane resin composition consists of the first, second, and third components. Each of these will be described in detail below.

[0135] [1] Component 1 The first component is the same as the first component of the first embodiment described above. That is, the first component contains the above polyol, and preferably consists of the above polyol. The polyol contains the above polyester polyol, and preferably consists of the above polyester polyol. The polyester polyol has the above saponification value and the above number average molecular weight.

[0136] [2] Second component The second component is the same as the second component of the first embodiment described above. That is, the second component contains the polyisocyanate, and preferably consists of the polyisocyanate. The polyisocyanate contains the aliphatic polyisocyanate, and preferably consists of the aliphatic polyisocyanate.

[0137] [3] Third component [3.1] Chain extenders The third component contains a chain extender, preferably a chain extender. The chain extender is a compound that causes a chain extension reaction of an isocyanate-terminated prepolymer (described later) in the prepolymerization method described later. Examples of chain extenders include organic compounds having hydroxyl groups and / or amino groups as active hydrogen groups, and more specifically, low molecular weight polyols and low molecular weight polyamines. Water can also be used as a chain extender.

[0138] [Low molecular weight polyols] Examples of low molecular weight polyols include the polyhydric alcohols mentioned above, and more specifically, the dihydric alcohols, trihydric alcohols, tetrahydric alcohols, pentahydric alcohols, hexahydric alcohols, heptahydric alcohols, and octahydric alcohols mentioned above. These can be used individually or in combination of two or more types.

[0139] [Low molecular weight polyamines] Examples of low molecular weight polyamines include low molecular weight diamines and low molecular weight triamines. Examples of low molecular weight diamines include ethylenediamine, 1,3-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, hydrazine, and tolylenediamine. Examples of low molecular weight triamines include triethylenetetramine and tetraethylenepentamine. These can be used alone or in combination of two or more.

[0140] [water] As mentioned above, in addition to low molecular weight polyols and low molecular weight polyamines, water can also be used as a chain extender. Water reacts with the isocyanate group of an isocyanate-terminated prepolymer (described later) to produce an amine. The resulting amine then reacts with the isocyanate group to cause the isocyanate-terminated prepolymer (described later) to undergo a chain extension reaction.

[0141] Chain extenders can be used alone or in combination of two or more. Preferred chain extenders include water, dihydric alcohols, trihydric alcohols, and low molecular weight diamines, with water being more preferred.

[0142] [4] Additives The polyurethane resin composition may contain the above-mentioned additives as needed. The amount and timing of additive addition are determined appropriately according to the purpose and application.

[0143] [5] Method for producing polyurethane resin composition A polyurethane resin composition can be manufactured, for example, by preparing a first component, a second component, and a third component individually. Alternatively, in a polyurethane resin composition, the first component and the second component may be pre-mixed.

[0144] In a polyurethane resin composition, the ratio of the first component to the second component is adjusted based on the equivalent ratio (NCO / OH) of the isocyanate groups (NCO) of the polyisocyanate in the second component to the hydroxyl groups (OH) of the polyol in the first component. Preferably, the ratio of the first component to the second component is adjusted based on the equivalent ratio (NCO / OH) in the prepolymer method described later. The specific equivalent ratio values ​​will be described later.

[0145] Industrially, the ratio of the first and second components can also be adjusted based on their masses. For example, the amount of polyisocyanate in the second component is, for example, 1.3 parts by mass or more and 21.4 parts by mass or less, preferably 2.0 parts by mass or more and 19.8 parts by mass or less, and more preferably 2.6 parts by mass or more and 17.4 parts by mass or less, per 100 parts by mass of polyol in the first component.

[0146] Furthermore, in the polyurethane resin composition, the ratio of the first, second, and third components is adjusted based on the equivalent ratio (NCO / active hydrogen group) of the isocyanate group-terminated prepolymer (described later) obtained by the reaction of the first and second components with respect to the active hydrogen groups (i.e., hydroxyl groups and / or amino groups) of the chain extender in the third component. The specific equivalent ratio values ​​will be described later.

[0147] Industrially, the ratio of the first, second, and third components can also be adjusted based on their masses. For example, for every 100 parts by mass of the total amount of polyol in the first component and isocyanate in the second component, the amount of chain extender in the third component is, for example, 0.5 parts by mass or more and 300.0 parts by mass or less, preferably 0.9 parts by mass or more and 230.0 parts by mass or less, and more preferably 1.2 parts by mass or more and 190.0 parts by mass or less.

[0148] [6] Effects The above polyurethane resin composition contains a first component comprising the above polyol and a second component comprising the above polyisocyanate. Therefore, the above polyurethane resin composition makes it possible to obtain a polyurethane resin that has relatively good marine biodegradability and reduced temperature dependence of its storage modulus.

[0149] As a result, the above polyurethane resin composition is suitably used as a raw material for polyurethane resin.

[0150] 2) Polyurethane resin The polyurethane resin contains the reaction product of the polyurethane resin composition described above. More specifically, the polyurethane resin can be obtained as a cured product of the polyurethane resin composition by reacting it with the polyurethane resin composition used as a polyurethane resin raw material.

[0151] The method for obtaining polyurethane resin is not particularly limited, but one example is the prepolymerization method. In the prepolymerization method, for example, first, the first component (i.e., polyol) and the second component (i.e., polyisocyanate) are reacted in a predetermined equivalent ratio (prepolymer synthesis step).

[0152] More specifically, in the prepolymer synthesis step of the prepolymer method, the equivalent ratio (NCO / OH) of the isocyanate groups (NCO) of the polyisocyanate in the second component to the hydroxyl groups (OH) of the polyol in the first component is, for example, 2.0 or more and 20.0 or less, preferably 4.0 or more and 15.0 or less, and more preferably 6.0 or more and 10.0 or less.

[0153] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, 40 to 200°C, preferably 60 to 150°C, and more preferably 80 to 100°C. The reaction time is, for example, 3 minutes to 24 hours, preferably 30 minutes to 12 hours. The reaction method is not particularly limited and includes known solution polymerization and known bulk polymerization. In addition, a known urethane catalyst may be added to the above reaction as needed. The amount and timing of addition of the urethane catalyst should be appropriately set according to the purpose and application.

[0154] As a result of the above reaction, an isocyanate-terminated prepolymer is obtained as a reaction product of the first component (i.e., polyol) and the second component (i.e., polyisocyanate).

[0155] Next, in this method, the isocyanate group-terminated prepolymer and the third component (i.e., the chain extender) are mixed in a predetermined equivalent ratio and reacted (chain extension step).

[0156] More specifically, for example, when a low molecular weight polyol and / or low molecular weight polyamine is used as the third component (i.e., chain extender), a polyurethane resin can be obtained by mixing the isocyanate group-terminated prepolymer and the low molecular weight polyol and / or low molecular weight polyamine in appropriate proportions and reacting them. In such a case, the equivalent ratio (NCO / active hydrogen group) of the isocyanate group (NCO) of the isocyanate group-terminated prepolymer to the active hydrogen group (i.e., hydroxyl group and / or amino group) of the chain extender in the third component is, for example, 0.70 to 1.60, preferably 0.80 to 1.50, more preferably 0.85 to 1.45, and even more preferably 0.95 to 1.35.

[0157] Furthermore, for example, when water is used as the third component (i.e., chain extender), a polyurethane resin can be obtained by, for example, dispersing the isocyanate-terminated prepolymer in water (or a water-containing dispersion medium) using a known method, and reacting the water with the isocyanate-terminated prepolymer. In such cases, the blending ratio of the isocyanate-terminated prepolymer to water is not particularly limited and can be set as appropriate. For example, the equivalent ratio (NCO / H2O) of the isocyanate group (NCO) of the isocyanate-terminated prepolymer to the water molecule as the third component is, for example, 0.50 to 1.60, preferably 0.50 to 1.50, more preferably 0.50 to 1.45, and even more preferably 0.50 to 1.35.

[0158] The reaction conditions are not particularly limited, but for example, the reaction temperature is, for example, 40 to 200°C, preferably 60 to 150°C, and more preferably 80 to 100°C. The reaction time is, for example, 3 minutes to 24 hours, preferably 30 minutes to 12 hours. The reaction method is not particularly limited and includes known solution polymerization and known bulk polymerization. In addition, a known urethane catalyst may be added to the above reaction as needed. The amount and timing of addition of the urethane catalyst should be appropriately set according to the purpose and application.

[0159] The above reaction yields a polyurethane resin as a reaction product between the isocyanate-terminated prepolymer and the third component (i.e., the chain extender). The polyurethane resin is then aged by known methods as needed. The aging conditions are set appropriately according to the purpose and application.

[0160] The polyurethane resin described above is obtained using the polyurethane resin composition described above. Therefore, the polyurethane resin described above has relatively good marine biodegradability and can also relatively reduce the temperature dependence of its storage modulus.

[0161] As a result, the above-mentioned polyurethane resin is suitably used in the manufacture of molded articles.

[0162] 3) Molded body The molded article contains the above-mentioned polyurethane resin. Preferably, the molded article is made of the above-mentioned polyurethane resin.

[0163] A molded article can be obtained, for example, by molding the polyurethane resin described above using the molding method described above. Alternatively, a molded article can also be obtained, for example, by machining the polyurethane resin described above using the machining method described above. The shape of the molded article is not particularly limited and can be set as appropriate according to the purpose and application. The molded article is preferably the powder described above.

[0164] And the above-mentioned molded body contains the above-mentioned polyurethane resin. Therefore, the above-mentioned molded body has relatively excellent marine biodegradability, and the temperature dependence of the storage elastic modulus can be relatively reduced.

[0165] 3. Physical Properties of Polyurethane Resin and Molded Body [Marine Biodegradability] The above-mentioned polyurethane resin and molded body have marine biodegradability. That is, the above-mentioned polyurethane resin and molded body can be decomposed by marine microorganisms. When marine microorganisms decompose the above-mentioned polyurethane resin and molded body, carbon dioxide is generated. Therefore, based on the amount of carbon dioxide generated when the above-mentioned polyurethane resin and molded body come into contact with marine microorganisms, the marine biodegradability of the polyurethane resin and molded body can be confirmed.

[0166] More specifically, in the above-mentioned polyurethane resin and molded body, the amount of carbon dioxide generated measured in accordance with the examples described later is, for example, 0.10 mg / cm 2 or more, preferably 0.2 mg / cm 2 or more, more preferably 0.4 mg / cm 2 or more. Also, in the above-mentioned polyurethane resin and molded body, the amount of carbon dioxide generated measured in accordance with the examples described later may be, for example, 1000 mg / cm 2 or less. That is, in the above-mentioned polyurethane resin and molded body, the amount of carbon dioxide generated measured in accordance with the examples described later is, for example, 0.10 mg / cm 2 or more and 1000 mg / cm 2 or less, preferably 0.2 mg / cm 2 or more and 1000 mg / cm 2 or less, more preferably 0.4 mg / cm 2 or more and 1000 mg / cm 2 or less.

[0167] [Temperature Dependence of Storage Elastic Modulus] The storage modulus (E') of the polyurethane resin and molded article described above is measured in accordance with the examples described later. The temperature dependence of the storage modulus is confirmed based on the variance of the storage modulus E' (variance is defined as "E'VAR") from -10°C to 50°C. The variance can be calculated using known methods.

[0168] The dispersion of the storage modulus E' (E'VAR) in the range of -10°C to 50°C is, for example, 1.0 × 10⁻⁶. 11 Pa or less, preferably 9.0 × 10 10 Pa or less, more preferably 7.0 × 10 10 Pa or less, more preferably 5.0 × 10 10 Pa or less, particularly preferably 2.0 × 10 10 It is below Pa.

[0169] [A hardness] The Shore A hardness of the polyurethane resin and molded article is, for example, 64 or less, preferably 62 or less, more preferably 60 or less, and even more preferably 58 or less. Also, the Shore A hardness of the polyurethane resin is, for example, 30 or more. That is, the Shore A hardness of the polyurethane resin and molded article is, for example, 30 to 64, preferably 30 to 62, more preferably 30 to 60, and even more preferably 30 to 58.

[0170] 4.Applications The above-mentioned polyurethane resin composition, polyurethane resin, and molded articles are particularly suitable for use in various industrial fields where marine biodegradability is required. Examples of industrial fields where marine biodegradability is required include the fragrance, agrochemical, pharmaceutical, paint, and adhesive fields. Furthermore, embodiments of the above-mentioned polyurethane resin composition, polyurethane resin, and molded articles can be appropriately selected according to the purpose and application. [Examples]

[0171] Hereinafter, the present invention will be described more specifically based on 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 appropriately changed without departing from the spirit of the present invention.

[0172] [1] Measurement method and evaluation method The following methods were used to measure and evaluate various physical properties.

[0173] [1.1] Number average molecular weight (measured value) It was measured under the following conditions by gel permeation chromatography (GPC). In the present invention, the molecular weight at the maximum frequency measured by GPC under these measurement conditions and converted to standard polystyrene was defined as the number average molecular weight (measured value).

[0174] <GPC measuring device> · Analytical device: HLC-8320GPC (Tosoh Corporation) · Analysis software: EcoSEC-WS (Tosoh Corporation) · Column: TSKgel guardcolumn HXL-L + TSKgel G3000HXL + TSKgel G2000HXL + TSKgel G1000HXL (Tosoh Corporation) · Solvent: THF (tetrahydrofuran, special grade, Junsei Chemical Co., Ltd.) · Flow rate: 0.8 ml / min · Converted polymer: polystyrene (TSKgel standard polystyrene, Tosoh Corporation) · Measurement temperature: 40 °C

[0175] [1.2] Hydroxyl value and average functionality number The hydroxyl value of each polyol was determined by the phthalation method in accordance with Method B of JIS K 1557-1 (2007).

[0176] Also, the theoretically calculated number average molecular weight (calculated value) of each polyol was calculated based on the charged amount of the raw materials of the polyol. Then, the average functionality number of each polyol was calculated by the following formula. Average number of functional groups = Number-average molecular weight (calculated value) × Hydroxyl value / (56.1 × 1000)

[0177] [1.3] Saponification value The saponification value of each polyol was measured in accordance with JIS K 0070 (1992). The saponification value indicates the carboxylic acid content of the decomposition composition obtained by the saponification of each polyol.

[0178] [1.4] Ratio of CO2 emissions 600 ml of seawater and 100 g of sea sand were collected in a 1000 ml flask. Next, an ultrasonic irradiation device (AS ONE, Vs-F100) was used to irradiate the seawater and sea sand with ultrasound for 60 seconds. After that, the seawater was filtered using a filter bag (AS ONE, 420-10) to extract microorganisms into the seawater, and the seawater was placed in a glass bottle.

[0179] Next, two pieces of cellulose (ADVANTEC FILTER PAPER 5C) cut to 1.5 cm x 1.5 cm, or one piece of polyurethane resin cut to 1.5 cm x 3.0 cm, were placed in the aforementioned glass bottles and left for 63 days.

[0180] Next, the carbon dioxide generated in the glass bottle was reacted with an alkali (potassium hydroxide, described below) to produce a carbonate. Subsequently, the amount of carbon dioxide generated by the marine biodegradation of cellulose and the amount of carbon dioxide generated by the marine biodegradation of polyurethane resin were calculated by titrating the carbonate using the method described below.

[0181] More specifically, first, 5 ml of a 0.5 M potassium hydroxide solution for carbon dioxide absorption was placed in a centrifuge tube with holes drilled in it. Next, the centrifuge tube was attached to the aforementioned glass bottle and removed after a predetermined time had elapsed. After that, titration was performed with hydrochloric acid, and the amount of carbon dioxide generated by marine biodegradation was determined from the amount of potassium hydroxide consumed.

[0182] Furthermore, the amount of carbon dioxide emitted was measured twice, and the average value was calculated. Then, the ratio (%) of the amount of carbon dioxide emitted from the marine biodegradation of polyurethane resin to the amount of carbon dioxide emitted from the marine biodegradation of cellulose (average value) was calculated, with the amount of carbon dioxide emitted from the marine biodegradation of cellulose (average value) set to 100%. The results were used to evaluate the marine biodegradability.

[0183] During the titration, the container volume (measured value) was 1118 mL. The amount of seawater from which the microorganisms were extracted was 225 mL.

[0184] [1.5]A hardness In accordance with JIS K6253 (2012), a 2 mm thick polyurethane resin sheet was obtained as a test specimen. Using a rubber hardness tester (Tefloc Corporation, model number "GS-719N (A-TYPE)"), the pressure plate of the rubber hardness tester was brought into contact with the test specimen, and the measured value [Shore A hardness] after 10 seconds was read. Five measurements were taken at positions where the contact points were 6 mm or more apart, and the average value was calculated.

[0185] [1.6] Storage modulus (E') Polyurethane resin was cut into rectangular samples measuring 4 mm wide x 2 mm thick x 35 mm long. The dynamic viscoelasticity of these rectangular samples was then measured using a dynamic viscoelasticity measuring device (IT Measurement & Control Co., Ltd., Model: DVA-200). The measurement conditions were as follows. The storage modulus E' was determined from the obtained data.

[0186] Tension mode Measurement temperature: -100℃~100℃ Heating rate: 5°C / min Measurement frequency: 10Hz Setting distortion: 0.16% Distance between gauge lines: 20mm Number of measurement points: every 1°C

[0187] The storage modulus E' at -40°C was defined as "E'-40", the storage modulus E' at 10°C as "E'10", and the storage modulus E' at 50°C as "E'50".

[0188] The average value (defined as "E'AVE") and variance (defined as "E'VAR") of the storage modulus E' across all measurement points in the range of -10°C to 50°C were calculated according to conventional methods. The product of the average value (E'AVE) and the variance (E'VAR) of the storage modulus E' across all measurement points in the range of -10°C to 50°C was defined as "E'VAR × E'AVE". The variance was calculated using the VAR.P function in Microsoft Excel® spreadsheet software, covering all measurement points of the storage modulus E'.

[0189] However, in Comparative Example 3, the polyurethane resin fractured at around 15°C. Therefore, E'AVE, E'VAR, and E'VAR×E'AVE were not calculated.

[0190] Then, the temperature dependence of the storage modulus was evaluated based on the above-mentioned "E'-40", "E'10", "E'50", and "E'VAR×E'AVE".

[0191] Note that in the table, "E±" indicates exponential notation. More specifically, "E+n" means "×10 n " means "En" is "×10 -n It means "...".

[0192] [1.7] Average particle size (μm) Using a digital microscope (VHX6000 manufactured by Keyence Corporation), the polyurethane resin powder prepared by the methods described in Examples 6 and 9 below was observed with a 100x magnification microscope. Fifty particulate matter samples were randomly selected from the powder, and the long and short sides of each sample were measured. The average of these measurements was defined as the particle size. The average of the particle sizes (i.e., the average of the long and short sides) of these 50 samples was defined as the average particle size.

[0193] [2] Polyisocyanate components [2.1] Polyisocyanate (A-1) 1,5-pentamethylene diisocyanate (PDI, manufactured by Mitsui Chemicals, Inc.) was prepared as polyisocyanate (A-1). The isocyanate group concentration (based on solid content) of polyisocyanate (A-1) was 54.5% by mass.

[0194] [2.2] Polyisocyanate (A-2) As polyisocyanate (A-2), a derivative of 1,5-pentamethylene diisocyanate (isocyanurate modified, trade name Stavio D-370N, manufactured by Mitsui Chemicals, Inc.) was prepared. The isocyanate group concentration (based on solid content) of polyisocyanate (A-2) was 25.0% by mass.

[0195] [2.3] Polyisocyanate (A-3) An aliphatic isocyanate-terminated prepolymer, as polyisocyanate (A-3), was prepared by the following method.

[0196] Specifically, 178.2 parts by mass of the polyol (A-1), described later, as a polyester polyol, and 182.8 parts by mass of polyisocyanate (A-1) were placed in a flask (1 L), and the mixture was reacted at 80°C to obtain a reaction product solution (hereinafter referred to as prepolymer solution) containing an aliphatic isocyanate group-terminated prepolymer.

[0197] Furthermore, the equivalent ratio (NCO / OH) of isocyanate groups in the polyisocyanate component to hydroxyl groups in the polyol component was approximately 6.0, and the isocyanate group concentration in the prepolymer solution was 22.7% by mass.

[0198] Subsequently, the unreacted polyisocyanate (A-1) was removed under reduced pressure to obtain an aliphatic isocyanate-terminated prepolymer as polyisocyanate (A-3). The isocyanate group concentration (based on solid content) of polyisocyanate (A-3) was 7.46% by mass.

[0199] [3] Polyol [3.1] Polyol (A-1) A polyester polyol was obtained by esterifying castor oil (manufactured by Ito Oil Co., Ltd., brand name Dia, polyester polyol, hydroxyl value 163.5 mg KOH / g, number average molecular weight (measured value) 1,508, number average molecular weight (calculated value) 927, average number of functional groups 2.7, ricinoleic acid 89%) with commercially available castor oil fatty acid (ricinoleic acid 89%).

[0200] More specifically, 245.55 g of castor oil fatty acids (89% ricinoleic acid) and 767.63 g of the above-mentioned castor oil were charged into a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and these were condensed at 180°C under a nitrogen atmosphere. When the acid value of the flask contents fell below 10 mg KOH / g, 0.1 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The contents of the flask were then condensed at 180°C for 40 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-1).

[0201] The hydroxyl value of polyol (A-1) was 120.0 mgKOH / g, the number-average molecular weight (measured value) was 1,872, the number-average molecular weight (calculated value) was 1,213, and the average number of functional groups was 2.6.

[0202] [3.2] Polyol (A-2) A polyester polyol was obtained by esterifying a commercially available polyoxypropylene polyol (trade name SOR-400, initiator sorbitol, average number of functional groups 6, hydroxyl value 400 mg KOH / g, manufactured by Mitsui Chemicals) with castor oil fatty acid (ricinoleic acid 89%).

[0203] More specifically, 873.0 g of castor oil fatty acid (89% ricinoleic acid) and 179.3 g of polyoxypropylene polyol (trade name SOR-400, initiator sorbitol, average number of functional groups 6, hydroxyl value 400 mg KOH / g, manufactured by Mitsui Chemicals) were charged into a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and these were condensed at 210°C under a nitrogen atmosphere.

[0204] When the acid value of the flask contents fell below 10 mg KOH / g, 0.6 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The contents of the flask were then condensed at 210°C for a total of 56 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-2).

[0205] The hydroxyl value of polyol (A-2) was 52.5 mgKOH / g, the number-average molecular weight (measured value) was 5,064, the number-average molecular weight (calculated value) was 4,721, and the average number of functional groups was 4.4.

[0206] [3.3] Polyol (A-3) 3000g of castor oil (manufactured by Ito Oil Co., Ltd., brand name Dia, polyester polyol, hydroxyl value 163.5 mg KOH / g, number average molecular weight (measured value) 1508, number average molecular weight (calculated value) 927, average number of functional groups 2.7, ricinoleic acid 89%) and 0.6g of DMC (complex metal cyanide complex) catalyst were charged into a pressure reaction vessel equipped with a stirring device. After purging the reaction vessel with nitrogen, the temperature inside the reaction vessel was raised to 110°C, and 150g of propylene oxide (PO) was supplied to the reaction vessel. Subsequently, the contents of the reaction vessel were stirred at 300 rpm. After approximately 55 minutes, exothermic reaction of the contents and a decrease in the internal pressure of the reaction vessel were confirmed, confirming the activation of the DMC catalyst.

[0207] Next, while maintaining the temperature inside the reaction vessel below 120°C, 850 g of propylene oxide (PO) was continuously supplied to the reaction vessel. Then, while maintaining the temperature inside the reaction vessel below 120°C, the contents were stirred and matured for 60 minutes. After that, the mixture was degassed under reduced pressure for 30 minutes to remove unreacted propylene oxide (PO). The resulting reaction product (polyether polyester polyol) was designated as polyol (A-3).

[0208] The hydroxyl value of polyol (A-3) was 123.0 mgKOH / g, the number-average molecular weight (measured value) was 3,324, the number-average molecular weight (calculated value) was 1,231, and the average number of functional groups was 2.7.

[0209] [3.4] Polyol (A-4) A polyester polyol was obtained by esterifying a commercially available polyoxypropylene polyol (product name D-400, initiator propylene glycol (PG), average number of functional groups 2, hydroxyl value 280 mg KOH / g, manufactured by Mitsui Chemicals) with castor oil fatty acid (ricinoleic acid 94%).

[0210] More specifically, 815.05 g of castor oil fatty acid (94% ricinoleic acid) and 232.98 g of the above polyoxypropylene polyol (product name D-400, initiator propylene glycol (PG), average number of functional groups 2, hydroxyl value 280 mg KOH / g, manufactured by Mitsui Chemicals) were charged into a glass flask equipped with a thermometer, a stirrer, and a dehydrator, and these were condensed at 200°C under a nitrogen atmosphere.

[0211] When the acid value of the flask contents fell below 10 mg KOH / g, 0.1 g of tetrabutyl orthotitanate (catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask. The contents of the flask were then condensed at 200°C for 40 hours. The resulting reaction product (polyester polyol) was designated as polyol (A-4).

[0212] The hydroxyl value of polyol (A-4) was 56.0 mgKOH / g, the number-average molecular weight (measured value) was 2,753, the number-average molecular weight (calculated value) was 1,703, and the average number of functional groups was 1.7.

[0213] [3.4] Polyol (B-1) Polyoxypropylene polyol (hydroxyl value 120.0 mg KOH / g, number average molecular weight (measured value) 2,005, number average molecular weight (calculated value) 1,403, average number of hydroxyl groups 3.0, abbreviation T-1500, manufactured by Mitsui Chemicals, Inc.) was designated as polyol (B-1).

[0214] [3.5] Polyol (B-2) Castor oil (manufactured by Ito Oil Co., Ltd., brand name Dia, polyester polyol, hydroxyl value 163.5 mg KOH / g, number average molecular weight (measured value) 1,508, number average molecular weight (calculated value) 927, average number of functional groups 2.7, ricinoleic acid 89%) was used as polyol (B-2).

[0215] [3.6] Polyol (B-3) Castor oil polyol (manufactured by Ito Oil Co., Ltd., brand name URIC HF-2050, polyester polyol, hydroxyl value 92.9 mg KOH / g, number average molecular weight (measured value) 3,046, number average molecular weight (calculated value) 2,053, average number of functional groups 3.4) was designated as polyol (B-3).

[0216] [4] catalyst [4.1] Catalyst 1 As a catalyst, dibutyltin dilaurate (DBTDL, urethane catalyst, manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared.

[0217] [5] Polyurethane resin (first embodiment, one-shot method) [5.1] Examples 1-5, Examples 7-8 and Comparative Examples 1-3 According to the formulation described in Table 1, the polyol as the first component, the polyisocyanate as the second component, and the catalyst were weighed into 200 mL poly cups. The polyol, polyisocyanate, and catalyst were then stirred and mixed using a rotation-revolution type mixer (Sinky Co., Ltd., product name "Awatori Rentaro ARE-312") (2000 rpm, 30 seconds) to obtain a mixed solution.

[0218] Next, the above mixture was poured into a mold (32cm x 13cm x 2mm thick) and heated in an oven at 80°C for 2 to 16 hours to obtain polyurethane resin. After that, the mold was removed from the oven, cooled to room temperature, and a 32cm x 13cm x 2cm thick sheet of polyurethane resin was demolded from the mold.

[0219] [5.2] Example 6 A 0.9 g sample was taken from the polyurethane resin sheet obtained in Example 1. The sample was then crushed using a mortar and pestle until it was sufficiently fine. The crushed sample was then passed through a stainless steel sieve with a mesh size of 500 μm to obtain the pass-through material. This pass-through material was obtained as polyurethane resin powder. The CO2 emission ratio (relative to cellulose) of the polyurethane resin powder obtained from 0.9 g of the sample was 168%. Figure 1 shows a 100x magnified image of the polyurethane resin powder (8 particles). Figure 1 also shows the particle size of the polyurethane resin powder.

[0220] The long and short sides of the polyurethane resin powder were measured, and the average of these values ​​was determined as the particle size. The average of 50 of these particle sizes (i.e., the average of the long and short sides) was defined as the average particle size. The average particle size was 100.2 μm. The median of the 50 particle sizes was 94.0 μm, the maximum was 243.0 μm, and the minimum was 47.0 μm.

[0221] [6] Polyurethane resin (second embodiment, prepolymer method) [6.1] Example 9 A polyurethane resin was obtained by reacting a polyol (A-1) as the first component, a polyisocyanate (A-1) as the second component, and water (chain extender) as the third component.

[0222] More specifically, an isocyanate-terminated prepolymer was obtained by reacting polyol (A-1) with polyisocyanate (A-1) using the same method as the production of polyisocyanate (A-3) described above, and removing the unreacted polyisocyanate (A-1). The isocyanate-terminated prepolymer was dissolved in toluene to obtain a polyisocyanate solution.

[0223] Meanwhile, 490 g of water was added as the third component to a 1 L separable flask equipped with a stirrer, and 9.0 g of polyvinyl alcohol (PVA, commercially available) was dissolved in the water to obtain an aqueous PVA solution (dispersion medium). While stirring the dispersion medium at 600 rpm, the polyisocyanate solution was added to the dispersion medium and dispersed to obtain a suspension.

[0224] While stirring the suspension, 0.4 g of urethane catalyst (amine-based catalyst, trade name Dabco2040, manufactured by Evonik Japan) was added to the suspension. The suspension was then heated to 80°C, and the isocyanate-terminated prepolymer (reaction product of components 1 and 2) in the polyisocyanate solution was reacted with water in the dispersion medium (component 3) for 2.5 hours to obtain a reaction product solution containing polyurethane resin.

[0225] The reaction product was cooled to room temperature and separated into solid and liquid components to obtain the solid component. The solid component was thoroughly washed with water and dried at 70°C for 20 hours to obtain polyurethane beads.

[0226] Subsequently, the obtained polyurethane beads were passed through a stainless steel sieve with a mesh size of 500 μm to obtain the pass-through material. This pass-through material was used as polyurethane resin powder. The ratio of CO2 generation (to cellulose) of the polyurethane resin powder obtained from 0.9 g of polyurethane beads was 101%. Figure 2 shows a 100x magnified image of the polyurethane resin powder (8 particles). Figure 2 also shows the particle size of the polyurethane resin powder.

[0227] The diameter of polyurethane resin powder was measured, and the average of the diameters of 50 points was defined as the average particle diameter. The average particle diameter was 170 μm. The median of the 50 average particle diameters was 152 μm, the maximum value was 615 μm, and the minimum value was 101 μm.

[0228] [Table 1]

Claims

1. It contains a first component containing a polyol and a second component containing a polyisocyanate. The aforementioned polyol contains a polyester polyol, The saponification value of the polyester polyol is 10 mg KOH / g or more and 210 mg KOH / g or less. The number-average molecular weight of the polyester polyol, measured by gel permeation chromatography (GPC) in terms of polystyrene, is 1,550 or more. A polyurethane resin composition wherein the polyisocyanate contains an aliphatic polyisocyanate.

2. The polyurethane resin composition according to claim 1, wherein the saponification value of the polyester polyol is 100 mg KOH / g or more and 200 mg KOH / g or less.

3. The polyester polyol has structural units derived from fatty acids, The polyurethane resin composition according to claim 1 or 2, wherein the fatty acid is a fatty acid having 15 to 20 carbon atoms and containing one or more hydroxyl groups in one molecule.

4. The polyurethane resin composition according to claim 3, wherein the fatty acid is ricinoleic acid.

5. The polyurethane resin composition according to claim 1 or 2, wherein the number-average molecular weight of the polyester polyol, measured by gel permeation chromatography (GPC) on a polystyrene basis, is 1,700 or more.

6. The polyurethane resin composition according to claim 1 or 2, wherein the polyisocyanate contains at least one selected from the group consisting of 1,5-pentamethylene diisocyanate, a derivative of 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and a derivative of 1,6-hexamethylene diisocyanate.

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

8. The polyurethane resin composition according to claim 1 or 2, wherein the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate in the second component to the hydroxyl groups of the polyol in the first component is 0.70 or more and 1.60 or less.

9. Furthermore, it contains a third component which includes a chain extender, The polyurethane resin composition according to claim 1 or 2, wherein the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate in the second component to the hydroxyl groups of the polyol in the first component is 2.0 or more and 20.0 or less.

10. A polyurethane resin containing a reaction product of the polyurethane resin composition according to claim 1 or 2.

11. A molded article comprising the polyurethane resin described in claim 10.

12. The molded article according to claim 11, wherein the material is a powder.

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