Polyester polyol, polyester polyurethane, resin composition, and coating agent

Abstract

The present invention relates to a polyester polyurethane (X) which is a reaction product (X) of a polyester polyol (AB) and a polyisocyanate, wherein: the polyester polyol (AB) is a reaction product (AB) that is obtained by reacting any glycol (A) among glycols represented by formulae (1-1) to (1-3) with a dicarboxylic acid (B) represented by formula (2); the polyester polyol (AB) does not contain a polymerization component derived from lactide; and the polyester polyol (AB) is (i) a reaction product with a dicarboxylic acid having 5 or more carbon atoms in formula (2) in cases where the glycol has 4 or fewer carbon atoms in formulae (1-1) to (1-3), or (ii) a reaction product with a dicarboxylic acid having 4 or fewer carbon atoms in formula (2) in cases where the glycol has 5 or more carbon atoms in formulae (1-1) to (1-3).

Description

Polyester polyol, polyester polyurethane, resin composition, coating agent

[0001] The present invention relates to a polyester polyol, a polyester polyurethane, a resin composition containing them, and a coating agent.

[0002] Many synthetic resins do not easily decompose in the natural environment. Therefore, the deterioration of the natural environment by synthetic resins has become a problem. For example, discarded synthetic resins become microplastics and pollute the marine environment.

[0003] In response to the social issue of global environmental degradation caused by the large-scale disposal of synthetic resins, the demand for sustainable product groups (packaging materials, films, etc.) made of resins having biodegradability in all environments (seawater, fresh water, soil, compost, etc.) is increasing.

[0004] In response to this growing environmental awareness, the replacement of non-biodegradable plastic products, which have been considered to have a large impact on the ecosystem, with plastic products made of biodegradable resins is particularly progressing in the consumer goods field. In the fields of food packaging and cosmetic pouches in consumer goods, various packaging materials have a multilayer structure for functional expression. Although packaging materials and food trays contained therein have been replaced with biodegradable plastic products, adhesives for joining each layer are those derived from conventional petrochemicals, and the entire packaging material and pouch have not yet been made biodegradable. Patent Document 1 discloses a polyester polyol, a polyester polyurethane that can exhibit biodegradability satisfying the required level in the market and has good handling properties (fluidity), and a laminate adhesive and a laminate excellent in adhesion using the same.

[0005] JP 2022-166901 A

[0006] However, the polyester polyurethane disclosed in Patent Document 1 is a polyester polyurethane obtained by reacting a polyisocyanate (E) with a polyester polyol (ABCD) containing a polyester polyol (AB), lactide (C), and a cyclic monomer (D). To obtain the polyester polyurethane of Patent Document 1, the polyester polyol reacted with the polyisocyanate must be a polyester polyol obtained by reacting a diol with a dicarboxylic acid and then polymerizing it with lactide and a cyclic monomer. If a biodegradable polyester polyurethane that meets the desired required level can be obtained using a polyester polyol that does not contain lactide or a cyclic monomer, the polymerization step with lactide and a cyclic monomer can be reduced from the process of producing the polyester polyol (ABCD) described in Patent Document 1. Reducing the number of steps is desirable from the viewpoint of cost reduction and productivity improvement. Furthermore, in Patent Document 1, in order to include lactide as an essential component, an organotin compound is used as a catalyst in the polymerization process of polyester polyol (AB), lactide (C), and cyclic monomer (D) (see Example 1 in paragraph

[0093] of Patent Document 1). Such organotin compounds are a cause for concern due to their environmental impact, and regulations on their use are increasing both domestically and internationally. On the other hand, organotitanium and organozirconium compounds, which have a lower environmental impact, are attracting attention as catalysts to replace organotin compounds. Therefore, it is desirable that polyester polyols be manufactured using organotitanium compounds or the like as catalysts. In addition, lactide contained in Patent Document 1 is known to contribute to biodegradability, and it is thought that the biodegradability performance in Patent Document 1 is enhanced by including lactide. However, if a polyester polyol that exhibits excellent biodegradability can be obtained using only the polyester polyol obtained by reacting a diol (glycol) and a dicarboxylic acid, even without containing lactide, it would be desirable as it would solve the above-mentioned problems.

[0007] Therefore, the present invention aims to provide a polyester polyol that exhibits excellent biodegradability using only a polyester polyol obtained by reacting a glycol with a dicarboxylic acid, without using a lactide-containing polyester polyol as described in Patent Document 1, and to provide a polyester polyurethane that exhibits excellent biodegradability produced using such a polyester polyol. Furthermore, the present invention aims to provide a resin composition or coating agent containing such a polyester polyol or polyester polyurethane that exhibits excellent biodegradability.

[0008] The inventors of this invention conducted diligent research to solve the above problems and, as a result, found that they could solve the above problems, and completed the present invention having the following gist.

[0009] In other words, the present invention encompasses the following embodiments: [1] A polyester polyurethane (X) which is a reaction product (X) of a polyester polyol (AB) and a polyisocyanate, wherein the polyester polyol (AB) is a reaction product (AB) obtained by reacting a glycol (A) from any of the glycols represented by the following formulas (1-1) to (1-3) with a dicarboxylic acid (B) represented by the following formula (2), the polyester polyol (AB) does not contain a polymerization component derived from lactide, and the polyester polyol (AB) is (i) a glycol in formulas (1-1) to (1-3) having 4 or fewer carbon atoms, that is, a glycol in formula (1-1) where m is 4 or less, or in formula (1-2) where p+q is 3 or less, or in formula (1-3) where r+s is 4 or less, or a reaction product with a dicarboxylic acid in formula (2) having 5 or more carbon atoms, that is, a dicarboxylic acid in formula (2) where n is 5 or more, or (ii) Polyester polyurethane (X) is a reaction product of a glycol having 5 or more carbon atoms in formulas (1-1) to (1-3), that is, a glycol in formula (1-1) where m is 5 or more, or in formula (1-2) where p+q is 4 or more, or in formula (1-3) where r+s is 5 or more, in formula (2) where n is 4 or less, in formula (2).

[0010] (In equation (1-1), m represents an integer greater than or equal to 1.)

[0011] (In formula (1-2), R １ (where represents an alkyl group having 1 to 4 carbon atoms, and p and q are each independently 0 or integers of 1 or greater, with p + q being 1 or greater.)

[0012] (In equation (1-3), r and s each represent an integer greater than or equal to 1, independently of each other.)

[0013] (In equation (2), n represents an integer greater than or equal to 1.)

[0014] [2] The polyester polyurethane (X) according to [1], wherein the polyester polyol (AB) is (i) a reaction product of any glycol selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and diethylene glycol and any dicarboxylic acid selected from the group consisting of heptanediol, suberic acid, azelaic acid, and sebacic acid, or (ii) a reaction product of any glycol consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol and any dicarboxylic acid consisting of glutaric acid and adipic acid. [3] A resin composition containing the polyester polyurethane (X) according to [1] or [2]. [4] A sheet or film made from the resin composition according to [3]. [5] A coating agent containing the polyester polyurethane (X) according to [1] or [2] and a solvent. [6] The coating agent according to [5] used as an adhesive.[7] A polyester polyol (AB) containing a polyester polyol (AB) resin composition, wherein the polyester polyol (AB) is a reaction product (AB) obtained by reacting a glycol (A) from any of the glycols represented by the following formulas (1-1) to (1-3) with a dicarboxylic acid (B) represented by the following formula (2), the polyester polyol (AB) does not contain a polymerization component derived from lactide, and the polyester polyol (AB) is (i) a glycol in formulas (1-1) to (1-3) having 4 or fewer carbon atoms, that is, a glycol in formula (1-1) where m is 4 or less, or in formula (1-2) where p+q is 3 or less, or in formula (1-3) where r+s is 4 or less, or a reaction product with a dicarboxylic acid in formula (2) having 5 or more carbon atoms, that is, a dicarboxylic acid in formula (2) where n is 5 or more, or (ii) A polyester polyol (AB)-containing resin composition in which, in formulas (1-1) to (1-3), the glycol has 5 or more carbon atoms, that is, in formula (1-1), m is 5 or more, or in formula (1-2), p+q is 4 or more, or in formula (1-3), r+s is 5 or more, and in formula (2), the glycol is a reaction product with a dicarboxylic acid having 4 or fewer carbon atoms, that is, in formula (2), n is 4 or less.

[0015] (In equation (1-1), m represents an integer greater than or equal to 1.)

[0016] (In formula (1-2), R １ (where represents an alkyl group having 1 to 4 carbon atoms, and p and q are each independently 0 or integers of 1 or greater, with p + q being 1 or greater.)

[0017] (In equation (1-3), r and s each represent an integer greater than or equal to 1, independently of each other.)

[0018] (In formula (2), n represents an integer of 1 or more.) [8] The polyester polyol (AB) is a polyester polyol (AB) containing resin composition according to [7], wherein the polyester polyol (AB) is a reaction product of any glycol selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and diethylene glycol and any dicarboxylic acid selected from the group consisting of heptanediol, suberic acid, azelaic acid, and sebacic acid, or (ii) a reaction product of any glycol consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol and any dicarboxylic acid consisting of glutaric acid and adipic acid. [9] A sheet or film comprising the polyester polyol (AB) containing resin composition according to [7] or [8].

[10] A polyester polyol (AB) containing a polyester polyol (AB) and a solvent, wherein the polyester polyol (AB) is a reaction product (AB) obtained by reacting a glycol (A) from any of the glycols represented by the following formulas (1-1) to (1-3) with a dicarboxylic acid (B) represented by the following formula (2), the polyester polyol (AB) does not contain a polymerization component derived from lactide, and the polyester polyol (AB) is (i) a glycol in formulas (1-1) to (1-3) having 4 or fewer carbon atoms, that is, a glycol in formula (1-1) where m is 4 or less, or in formula (1-2) where p+q is 3 or less, or in formula (1-3) where r+s is 4 or less, or a reaction product with a dicarboxylic acid in formula (2) having 5 or more carbon atoms, that is, a dicarboxylic acid in formula (2) where n is 5 or more, or (ii) A polyester polyol (AB) containing coating agent, in formulas (1-1) to (1-3), the glycol having 5 or more carbon atoms, that is, the glycol in formula (1-1) where m is 5 or more, or in formula (1-2) where p+q is 4 or more, or in formula (1-3) where r+s is 5 or more, and in formula (2), the reaction product with a dicarboxylic acid having 4 or fewer carbon atoms, that is, a dicarboxylic acid in formula (2) where n is 4 or less.

[0019] (In equation (1-1), m represents an integer greater than or equal to 1.)

[0020] (In formula (1-2), R １ (where represents an alkyl group having 1 to 4 carbon atoms, and p and q are each independently 0 or integers of 1 or greater, with p + q being 1 or greater.)

[0021] (In equation (1-3), r and s each represent an integer greater than or equal to 1, independently of each other.)

[0022] (In equation (2), n represents an integer greater than or equal to 1.)

[0023]

[11] The polyester polyol (AB) containing coating agent according to

[10] , wherein the polyester polyol (AB) is (i) a reaction product of any glycol selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and diethylene glycol and any dicarboxylic acid selected from the group consisting of heptanediol, suberic acid, azelaic acid, and sebacic acid, or (ii) a reaction product of any glycol consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol and any dicarboxylic acid consisting of glutaric acid and adipic acid.

[12] The polyester polyol (AB) containing coating agent according to

[10] or

[11] , to be used as an adhesive.

[0024] According to the present invention, a polyester polyol exhibiting excellent biodegradability can be obtained solely by reacting a glycol with a dicarboxylic acid, without using a polyester polyol containing lactide, and a highly biodegradable polyester polyurethane can be provided using this highly biodegradable polyester polyol. Furthermore, the present invention can provide resin compositions and coating agents containing these highly biodegradable polyester polyols and polyester polyurethanes.

[0025] The polyester polyurethane of the present invention will be described in detail below, but the description of the constituent elements described below is an example of one embodiment of the present invention and is not limited to these contents.

[0026] (Polyester Polyurethane) The polyester polyurethane of the present invention is a polyester polyurethane (X) which is a reaction product (X) of a polyester polyol (AB) and a polyisocyanate. In the present invention, although the above polyester polyol (AB) does not contain lactide, a polyester polyol with excellent biodegradability can be obtained by reacting a specific diol (glycol) with a specific dicarboxylic acid. The polyester polyurethane of the present invention produced using such an excellent biodegradability polyester polyol has excellent biodegradability, and is particularly excellent in compost decomposition.

[0027] In this invention, a substance is said to be "biodegradable" if, for example, when released into the natural environment, it is broken down into carbon dioxide and water by the action of microorganisms, etc. Examples of environments in which decomposition occurs include seawater environments, freshwater environments, soil environments, and compost. In particular, this invention shows good results in compost biodegradation, which can be achieved by utilizing the action of microorganisms.

[0028] The compost decomposition rate of polyester polyurethane under composting conditions is preferably 15% or more, more preferably 24% or more, even more preferably 40% or more, and particularly preferably 50% or more. In this specification, the compost decomposition rate of polyester polyurethane under composting conditions can be determined by a method in accordance with JIS K6953-1:2011. Culture temperature: 58°C Culture period: 28 days

[0029] The polyester polyurethane of the present invention has excellent biodegradability and can be polymerized and thermoformed at relatively high temperatures, comparable to those of general-purpose resins. In other words, the polyester polyurethane of the present invention has excellent thermoformability and biodegradability. Furthermore, sheets, films, and the like can be obtained using a resin composition containing this polyester polyurethane.

[0030] <Polyester polyol (AB)> The polyester polyol (AB) according to the present invention is a reaction product (AB) obtained by reacting any one of the glycols (A) represented by the following formulas (1-1) to (1-3) with the dicarboxylic acid (B) represented by the following formula (2).

[0031]

[0032] In formula (1-1), m represents an integer of 1 or more.

[0033]

[0034] In formula (1-2), R １ represents an alkyl group having 1 to 4 carbon atoms, p and q each independently represent 0 or an integer of 1 or more, and p + q represents 1 or more.

[0035]

[0036] In formula (1-3), r and s each independently represent an integer of 1 or more.

[0037]

[0038] In formula (2), n represents an integer of 1 or more.

[0039] The polyester polyol (AB) according to the present invention does not contain polymerization components derived from lactide. In the present invention, even without containing lactide, a polyester polyol exhibiting excellent biodegradability can be obtained using only the polyester polyol obtained by reacting glycol and dicarboxylic acid. This is because a specific glycol and a specific dicarboxylic acid are reacted in combination. Specifically, for short carbon chain glycols in formulas (1-1) to (1-3) above, where the number of carbon atoms between the hydroxyl groups at both ends is 4 or less, a long carbon chain dicarboxylic acid in formula (2) above, where the number of carbon atoms between the carboxyl groups at both ends is 5 or more, is combined with these glycols and dicarboxylic acids to obtain a polyester polyol. As a result, a polyester polyol with good biodegradability, particularly compostability, can be obtained. Alternatively, for long carbon chain glycols in formulas (1-1) to (1-3) above, where the number of carbon atoms between the hydroxyl groups at both ends is 5 or more, a polyester polyol can be obtained by combining these glycols with short carbon chain dicarboxylic acids in formula (2) above, where the number of carbon atoms between the carboxyl groups at both ends is 4 or less, and reacting these glycols with the dicarboxylic acids. This yields a polyester polyol with good biodegradability, particularly compostability.

[0040] More specifically, the polyester polyol (AB) according to the present invention is a reaction product (polyester polyol) obtained by reacting a glycol having 4 or fewer carbon atoms in formulas (1-1) to (1-3) above, that is, a glycol in formula (1-1) where m is 4 or less, or in formula (1-2) where p+q is 3 or less, or in formula (1-3) where r+s is 4 or less, with a dicarboxylic acid having 5 or more carbon atoms in formula (2), that is, a dicarboxylic acid in formula (2) where n is 5 or more, or (ii) In formulas (1-1) to (1-3) above, if the glycol has 5 or more carbon atoms, that is, if m is 5 or more in formula (1-1), or if p+q is 4 or more in formula (1-2), or if r+s is 5 or more in formula (1-3), then the reaction product (polyester polyol) obtained by reacting it with a dicarboxylic acid having 4 or fewer carbon atoms in formula (2), that is, a dicarboxylic acid in formula (2) where n is 4 or less.

[0041] Examples of glycols having 4 or fewer carbon atoms in formulas (1-1) to (1-3) above include, for example, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, or diethylene glycol. Examples of glycols having 5 or more carbon atoms in formulas (1-1) to (1-3) above include, for example, 1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, or 1,6-hexanediol.

[0042] In formula (2) above, examples of dicarboxylic acids having 4 or fewer carbon atoms include malonic acid, glutaric acid, or adipic acid. In formula (2) above, examples of dicarboxylic acids having 5 or more carbon atoms include heptaneoic acid, suberic acid, azelaic acid, or sebacic acid. Among these, azelaic acid is preferably used.

[0043] In the present invention, preferred embodiments of combinations of specific glycols and specific dicarboxylic acids for producing polyester polyols (AB) include: (i) a combination of any glycol selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and diethylene glycol, and any dicarboxylic acid selected from the group consisting of heptanediol, suberic acid, azelaic acid, and sebacic acid; or (ii) a combination of any glycol consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol, and any dicarboxylic acid consisting of glutaric acid and adipic acid.

[0044] In the above formula (1-2), R １ Examples of C1-C4 alkyl groups represented by include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methylcyclopropyl group, and 2-methylcyclopropyl group. Among these, the methyl group is preferred from the viewpoint of excellent reactivity.

[0045] The number-average molecular weight (Mn) of polyester polyol (AB), measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 300 or higher, more preferably 500 or higher, even more preferably 1000 or higher, and particularly preferably 1500 or higher, from the viewpoint of processability and handling. A low number-average molecular weight (Mn) may result in poor compostability. On the other hand, the same number-average molecular weight (Mn) is preferably 10000 or less, more preferably 7000 or less, even more preferably 5000 or less, and particularly preferably 3000 or less, from the viewpoint of extraction after synthesis. Any combination of these upper and lower limits can be used.

[0046] The weight-average molecular weight (Mw) of polyester polyol (AB), measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 700 or higher, more preferably 1,000 or higher, even more preferably 2,000 or higher, and particularly preferably 3,000 or higher, from the viewpoint of processability and handling. On the other hand, from the viewpoint of extraction after synthesis, the same weight-average molecular weight (Mw) is preferably 20,000 or lower, more preferably 14,000 or lower, and even more preferably 10,000 or lower. Any combination of these upper and lower limits can be used.

[0047] The hydroxyl value of polyester polyol (AB) is not particularly limited, but is preferably in the range of 5 to 250 mg KOH / g, more preferably 5 to 100 mg KOH / g, and even more preferably 5 to 75 mg KOH / g. The hydroxyl value can be measured by the method described in JIS-K0070.

[0048] Furthermore, the polyester polyol (AB) is preferably acid-modified to exhibit superior biodegradability. Specifically, an acid-modified polyester polyol (AB) is a polyol having an acidic group in its polyol molecule, such as a carboxyl group. An acid-modified polyester polyol (AB) can be produced, for example, by adjusting the composition to have both a hydroxyl group and a carboxyl group. The acid value of the polyester polyol (AB) is not particularly limited, but is preferably 0.5 to 10 mg KOH / g, and more preferably 1 to 5 mg KOH / g. Biodegradability is further improved if the acid value is within this range. The acid value can be measured by the method described in JIS-K0070.

[0049] <<Characteristics of Polyester Polyol (AB)>> The polyester polyol (AB) according to the present invention does not contain polymerization components derived from lactide. Lactide is a cyclic compound having two ester bonds in a molecule formed by the dehydration condensation of the hydroxyl group and carboxyl group of two hydroxy acid molecules. Examples include glycolide, 3,6-dimethyl-1,4-dioxane-2,5-dione (derived from 2-hydroxypropionic acid (lactic acid)), and 1,6-dioxacyclodecane-2,7-dione (derived from 4-hydroxybutanoic acid). Among these, so-called lactide derived from lactic acid may be optically active substances, and include L-lactide, D-lactide, and meso-lactide. Furthermore, the polyester polyol (AB) according to the present invention does not contain polymerization components derived from cyclic monomers. Cyclic monomers refer to monomers such as cyclic lactones, cyclic lactams, and cyclic ethers. Examples of cyclic lactones include ε-caprolactone, δ-valerolactone, and γ-nonalactone. Examples of cyclic lactams include β-lactam, γ-lactam, and δ-lactam. Examples of cyclic ethers include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and dioxane.

[0050] <<Method for producing polyester polyol (AB)>> Polyester polyol (AB) can be produced by esterifying the above-mentioned specific glycol and the above-mentioned specific dicarboxylic acid using a known method.

[0051] The mixing ratio of glycol to dicarboxylic acid is not particularly limited, but a molar ratio (glycol:dicarboxylic acid) of 80:20 to 50:50 is preferred, and 60:40 to 50:50 is more preferred.

[0052] The reaction may be carried out without a catalyst or in the presence of a catalyst. Examples of catalysts used in the reaction include acid catalysts. Examples of acid catalysts include titanium-based catalysts such as titanium tetraisopropoxide and titanyl acetylacetonate, and zirconia-based catalysts such as tetrabutyl zirconate. It is preferable to use a titanium-based catalyst because it can increase the activity of the transesterification and esterification reactions. Examples of titanium-based catalysts include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, tetrakis(2-ethylhexyloxy)titanium, and tetrastearyloxytitanium, but titanium tetraisopropoxide is preferred in terms of handling stability and catalytic activity. The amount of catalyst used is usually in the range of 0.001 to 5.0% by mass relative to the total mass of glycol and dicarboxylic acid.

[0053] The reaction to synthesize polyester polyols (AB) produces by-products such as water and lower alcohols. Removing these by-products from the reaction system during the reaction process facilitates the condensation reaction.

[0054] The reaction temperature is not particularly limited, but is usually 50 to 300°C. The reaction atmosphere may be air, or an inert gas atmosphere such as nitrogen gas or argon gas. The reaction time is usually 1 to 48 hours, but it is preferable to continue the reaction until no glycol or dicarboxylic acid remains in the reaction system. The progress of the reaction can be tracked, for example, by measuring the decrease in dicarboxylic acid by acid value measurement.

[0055] <Production of Polyester Polyurethane (X)> Polyester polyurethane (X) is obtained by reacting the polyester polyol (AB) according to the present invention with a polyisocyanate. If necessary, polyols other than polyester polyol (AB), chain extenders, chain inhibitors, and crosslinking agents may be used in combination. Polyester polyurethane (X) is a reaction product (X) obtained by the reaction of polyester polyol (AB) and polyisocyanate, and has structural units derived from polyester polyol and structural units derived from polyisocyanate.

[0056] Examples of chain extenders include aliphatic polyol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, and neopentyl glycol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone. Aromatic polyol compounds such as water; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, isophoronediamine, and other amine compounds can be used. These chain extenders may be used alone or in combination of two or more. Among these, aliphatic polyol compounds are preferred, and neopentyl glycol is more preferred.

[0057] <<Polyisocyanates>> Examples of polyisocyanates include 1,3- and 1,4-phenylenediisocyanate, 1-methyl-2,4-phenylenediisocyanate, 1-methyl-2,6-phenylenediisocyanate, 1-methyl-2,5-phenylenediisocyanate, 1-methyl-3,5-phenylenediisocyanate, 1-ethyl-2,4-phenylenediisocyanate, 1-isopropyl-2,4-phenylenediisocyanate, and 1,3-dimethyl-2 ,4-phenylenediisocyanate, 1,3-dimethyl-4,6-phenylenediisocyanate, 1,4-dimethyl-2,5-phenylenediisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphtha Naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methylnaphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenyl Aromatic polyisocyanates such as ylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate, and toluene diisocyanate; linear aliphatic polyisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate;Alicyclic polyisocyanates such as 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di(isocyanate methyl)cyclohexane, 1,4-di(isocyanate methyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These may be used individually or in combination of two or more. Among these, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diphenylmethane diisocyanate, and toluene diisocyanate are more preferred.

[0058] As mentioned in the above examples, the present invention preferably uses 1,6-hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), which were also used in the examples. Adducts of these, such as trimethylolpropane (TMP) (TMP-adduct of HDI or TMP-adduct of IPDI), can also be suitably used. In the present invention, the polyisocyanate is particularly preferably a linear aliphatic polyisocyanate.

[0059] To control the molecular weight of the resulting polyester polyurethane (in this specification, polyester polyurethane is also abbreviated as polyurethane), a chain arrestor having one active hydrogen group may be used as needed. Examples of these chain arrestors include aliphatic monohydroxy compounds having a hydroxyl group, such as methanol, ethanol, propanol, butanol, and hexanol, and aliphatic monoamines having an amino group, such as morpholine, diethylamine, dibutylamine, monoethanolamine, and diethanolamine. These may be used individually or in combination of two or more.

[0060] To improve the heat resistance and strength of the resulting polyurethane, crosslinking agents having three or more active hydrogen groups or isocyanate groups can be used as needed.

[0061] Polyester polyurethane (X) can be obtained by known methods for producing polyurethane. Specifically, for example, it can be produced by charging polyester polyol (AB), polyisocyanate, and various additives (such as the chain extender mentioned above) and reacting them. These reactions are preferably carried out at a temperature of 40 to 200°C for 1 to 40 hours. The reaction may also be carried out in an organic solvent.

[0062] Examples of organic solvents that can be used include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketone solvents such as methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; and ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, and hydroxybutyl acetate. These organic solvents may be used individually or in combination of two or more.

[0063] When producing polyester polyurethane (X), it is preferable to use a titanium-based catalyst. Examples of titanium-based catalysts include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, tetrakis(2-ethylhexyloxy)titanium, and tetrastearyloxytitanium. However, titanium tetraisopropoxide is preferred in terms of handling stability and catalytic activity. The amount of catalyst used is usually in the range of 0.001 to 5.0% by mass relative to the total mass of polyester polyol (AB) and polyisocyanate.

[0064] The content of structural units derived from polyester polyol (AB) in 100% by mass of polyester polyurethane (X) is preferably 10 to 98% by mass, more preferably 20 to 98% by mass. This tends to result in a more favorable effect. In this specification, the content of each structural unit in the polyurethane is measured by NMR.

[0065] The number-average molecular weight (Mn) of polyester polyurethane (X) can be 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, or 10,000 or more at the lower limit, and 1,000,000 or less, 500,000 or less, 100,000 or less, 500,000 or less, or 15,000 or less at the upper limit. Any combination of these upper and lower limits can be used. Within the above ranges, the effect tends to be more favorably obtained. The number-average molecular weight (Mn) of polyester polyurethane (X) can be measured by GPC.

[0066] (Resin composition) Examples of the resin composition in this embodiment include a thermoplastic resin composition containing the polyester polyol (AB) or polyester polyurethane (X) according to the present invention described above, or a thermosetting resin composition.

[0067] <Thermoplastic Resin Composition> If the resin composition of this embodiment is a thermoplastic resin composition, it may further contain, for example, other resins, crystallization nucleating agents, heat stabilizers, hydrolysis inhibitors, and other additives as needed.

[0068] <<Crystallization Nucleating Agent>> The crystallization nucleating agent used in the thermoplastic resin composition according to this embodiment may be any crystallization nucleating agent used for thermoplastic resins derived from biomass resources such as polybutylene succinate. For example, talc-based nucleating agents, nucleating agents made of metal salt materials having a phenyl group, and nucleating agents made of benzoyl compounds are preferably used. Other known crystallization nucleating agents, such as benzoates, silica, and phosphate ester salts, may also be used.

[0069] <<Heat Stabilizers and Hydrolysis Inhibitors>> The thermoplastic resin composition of this embodiment preferably contains a phenolic antioxidant and a phosphite antioxidant as heat stabilizers for the resin composition, and a carbodiimide compound-based hydrolysis inhibitor, such as polycarbodiimide resin (product name: Carbodilite, manufactured by Nisshinbo Chemical Co., Ltd.), as a hydrolysis inhibitor. The heat stabilizers and hydrolysis inhibitors to be added may be selected from the above three types of additives, but the above two types of heat stabilizers and hydrolysis inhibitors have different functions, and it is preferable to add both additives. The amount of heat stabilizers and hydrolysis inhibitors to be added varies depending on the type, but generally, it is preferable to add about 0.1 to 5 parts by mass of each per 100 parts by mass of the thermoplastic resin composition.

[0070] <<Other Additives>> It is preferable to further add silicone-based flame retardants, organometallic salt-based flame retardants, organophosphorus-based flame retardants, metal oxide-based flame retardants, metal hydroxide-based flame retardants, etc., to the thermoplastic resin composition of this embodiment. This improves flame retardancy and suppresses the spread of fire, and also improves the fluidity of the biodegradable resin composition, thereby ensuring better moldability.

[0071] The thermoplastic resin composition of this embodiment may contain fillers. Examples of fillers include talc, mica, montmorillonite, and kaolin. These fillers act as crystal nuclei, promoting the crystallization of the copolyester and improving the impact strength and heat resistance of the molded article. The rigidity of the molded article can also be increased.

[0072] The thermoplastic resin composition of this embodiment may also contain various additives as appropriate, such as antioxidants, antiblocking agents, colorants, flame retardants, mold release agents, antifogging agents, surface wetting improvers, incineration aids, lubricants, dispersion aids, various surfactants, plasticizers, compatibilizers, weather resistance improvers, ultraviolet absorbers, processing aids, antistatic agents, colorants, lubricants, and mold release agents. As plasticizers, known plasticizers generally used for polymers can be used without particular limitations, such as polyester plasticizers, glycerin-based plasticizers, polycarboxylic acid ester-based plasticizers, polyalkylene glycol-based plasticizers, and epoxy-based plasticizers. As compatibilizers, there are no particular limitations as long as they function as compatibilizers for copolymer A and copolymer B. Examples of compatibilizers include inorganic fillers, glycidyl compounds, polymer compounds obtained by grafting or copolymerizing acid anhydrides, and organometallic compounds, and one or more of these may be used. These compounding processes improve heat resistance, flexural strength, impact strength, and flame retardancy, further promoting their application to molded parts such as casings for electronic devices like laptops and mobile phones.

[0073] Furthermore, various conventionally known fillers can be incorporated as packing agents. Functional additives such as chemical fertilizers, soil conditioners, and plant activators can also be added. These fillers are broadly classified into inorganic fillers and organic fillers. These can be used individually or as a mixture of two or more types.

[0074] Examples of inorganic fillers include anhydrous silica, mica, talc, titanium dioxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, wolastenate, calcined perlite, silicates such as calcium silicate and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate, and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, and barium sulfate. The inorganic filler content is usually 1 to 80% by weight of the total composition, preferably 3 to 70% by weight, and more preferably 5 to 60% by weight. Examples of organic fillers include raw starch, modified starch, pulp, chitin / chitosan, coconut shell powder, wood powder, bamboo powder, bark powder, and powders such as kenaf and straw. These can be used individually or as a mixture of two or more. The amount of organic filler added is typically 0.01 to 70% by weight of the total composition.

[0075] All conventionally known mixing / kneading techniques can be applied to the preparation of the composition. Mixers such as horizontal cylindrical, V-shaped, and double-cone mixers, ribbon blenders, super mixers, and various continuous mixers can be used. Kneaders such as roll and internal mixers (batch type), single-stage and double-stage continuous kneaders, twin-screw extruders, and single-screw extruders can be used. Kneading methods include adding various additives, fillers, and thermoplastic resins to a heated and melted mixture. Blending oils can also be used to uniformly disperse the aforementioned additives.

[0076] <Thermosetting Resin Composition> When the resin composition of this embodiment is a thermosetting resin composition, it mainly contains, for example, a polyester polyol (AB) or polyester polyurethane (X) according to the present invention having reactive groups such as hydroxyl groups, carboxyl groups, and isocyanate groups, and further contains a curing agent such as an isocyanate curing agent or a polyamine curing agent that can react with the reactive groups through heat.

[0077] Examples of curing agents according to this embodiment include polyisocyanates having aromatic structures in their molecular structure, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and xylylene diisocyanate; compounds obtained by modifying some of the isocyanate groups of these polyisocyanates with carbodiimide; allophanate compounds derived from these polyisocyanates; polyisocyanates having alicyclic structures in their molecular structure, such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-(isocyanate methyl)cyclohexane; linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate; and this allophanate Examples include polyisocyanates; isocyanurates of these polyisocyanates; allophanates derived from these polyisocyanates; billets derived from these polyisocyanates; trimethylolpropane-modified adducts; polyfunctional isocyanates such as polyisocyanates which are reaction products of the aforementioned polyisocyanates with polyol components; polyethylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, piperazine, or N-aminoalkylpiperazine having an alkyl chain with 2 to 6 carbon atoms; and amine compounds such as 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine, or IPDA).

[0078] <Cured product of resin composition> The cured product of the resin composition in this embodiment is the cured product of the resin composition as a thermoplastic resin composition as described above, or the cured product of the resin composition as a thermosetting resin composition as described above.

[0079] The polyester polyol (AB) and polyester polyurethane (X) according to the present invention can be used in a wide range of applications. Specifically, they can be used in a broad range of applications such as artificial leather, synthetic leather, shoes, thermoplastic resins, foamed resins, thermosetting resins, paints, laminate adhesives, elastic fibers, urethane raw materials, automobile parts, sporting goods, vibration damping materials, vibration-damping materials, fiber treatment agents, and binders.

[0080] (Coating agent) The coating agent contains the polyester polyol (AB) and the polyester polyurethane (X) according to the present invention, and further contains other components including other resins and various solvents such as water and organic solvents, as needed.

[0081] Coating agents can be applied to various substrates. An example of a coating agent's application is described below. For example, coating agents are used as surface coatings for food packaging containers. Examples of substrates include plastic films such as styrene resin films, polyolefin resin films, polyester resin films, and nylon resin films, or laminates thereof. Other examples of substrates include paper, metal vapor-deposited films, and aluminum foil. Coating agents are suitably used on biodegradable substrates. Examples of biodegradable substrates include paper, polyester films, polyolefin films, and starch films. Coating agents can also be used as inks or adhesives.

[0082] (Ink) The ink contains the polyester polyol (AB) or polyester polyurethane (X) according to the present invention, and a colorant, and further contains, as necessary, other components including extender pigments such as calcium carbonate and talc, pigment dispersants, and various solvents such as aqueous solvents such as water and organic solvents. The ink is, for example, a printing ink. The ink may be, for example, a water-based ink or a water-free ink (solvent-based ink).

[0083] (Adhesive) The adhesive contains the polyester polyol (AB) or polyester polyurethane (X) according to the present invention, and further contains other components including other resins, curing agents, and various solvents such as water-based solvents and organic solvents, as needed. The adhesive can also be used as a laminating adhesive composition used when laminating to the above-mentioned various substrates to manufacture composite films mainly used for packaging materials for food, pharmaceuticals, detergents, etc. Such adhesives can be, for example, a two-component curing adhesive containing the polyester polyol (AB) or polyester polyurethane (X) according to the present invention, a polymer polyol other than polyester polyol (AB) or a chain extender, and a polyisocyanate, or a one-component adhesive made of acrylic resin, urethane resin, or ethylene-vinyl acetate copolymer. These adhesives can be solvent-type, solvent-free, aqueous, or alcohol-type adhesives as needed.

[0084] (Sheet) The sheet is made using a resin composition containing the polyester polyol (AB) or polyester polyurethane (X) according to the present invention. In addition to the polyester polyol (AB) or polyester polyurethane (X) according to the present invention, the resin composition may also contain other resins and various additives. Examples of various additives include plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, and heat stabilizers. Examples of sheets include unstretched sheets, biaxially oriented sheets, and foamed sheets. The sheet is not particularly limited in its use, but can be used in a wide range of applications, such as food packaging containers, construction materials, household electrical appliances, and general merchandise.

[0085] (Film) The film is made using a resin composition containing the polyester polyol (AB) or polyester polyurethane (X) according to the present invention. In addition to the polyester polyol (AB) or polyester polyurethane (X) according to the present invention, the resin composition may also contain other resins and various additives. Examples of various additives include plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, and heat stabilizers. Examples of films include unoriented films, biaxially oriented films, and uniaxially oriented films, which can be produced, for example, by melting film raw material pellets in an extruder and then forming a film using a T-die or inflation method. In the case of the T-die method, a biaxially oriented film can be obtained by performing longitudinal stretching using a difference in roll speed and transverse stretching using a tenter.

[0086] (Laminate) The laminate has at least one selected from the sheets and films of this embodiment, and further has other components such as a printed layer and a resin film as needed. The laminate can be obtained, for example, by laminating a film or sheet to one or both sides of at least one selected from the sheets and films of this embodiment to improve mechanical strength or chemical resistance. Specifically, it can be obtained by thermal laminating a polystyrene-based inflation film to at least one of the front and back sides of the sheet or film, or by laminating an olefin-based film (CPP) using an adhesive. The adhesive used is not particularly limited, but may be, for example, the adhesive of this embodiment or a known adhesive.

[0087] (Molded body) The molded body is obtained by molding at least one selected from the sheet, film, and laminate of this embodiment. The molded body is obtained, for example, by thermoforming the sheet, film, and laminate of this embodiment. Examples of thermoforming methods include hot plate contact heating molding, vacuum forming, vacuum pressure forming, and plug-assisted forming, and indirect heating molding using an infrared heater as the heat source is particularly preferred.

[0088] The present invention will be further described below with reference to examples, but the scope of the present invention is not limited to these examples.

[0089] <Evaluation of Molecular Weight> In the examples and comparative examples, the molecular weight of the resin was measured using gel permeation chromatography (GPC) under the following conditions. Measurement equipment: System Agilent 1260 Infinity II Liquid transfer pump G7110B 1260 Infinity II RI (differential refractometer) detector G7162B 1260 Infinity II Autosampler G7129C Infinity II Data processing: OpenLab CDS2 Measurement conditions: Column temperature 40°C Eluent chloroform (HCl ３ Flow rate 0.3 ml / min Standard: Polystyrene column: Shodex GPC HK-G 1 tube, Shodex GPC HK-404L 4 tubes Sample: 0.5% by mass chloroform solution (based on resin solids content) filtered through a microfilter (100 μl)

[0090] <Evaluation of Acid Value> The acid value of the resins in the examples and comparative examples was calculated using the following procedure. Approximately 1 g of the sample was weighed into a stoppered Erlenmeyer flask, dissolved in 20 mL of acetone, and phenolphthalein reagent was added as an indicator. The solution was held for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned pale pink, and the acid value was determined by the following formula: Acid value (mg KOH / g) = (5.611 × a × F) / S S: Amount of sample taken (g) a: Amount of 0.1 N alcoholic potassium hydroxide solution consumed (mL) F: Factor of 0.1 N alcoholic potassium hydroxide solution

[0091] <Melting Point Measurement> Measurement device: Mettler DSC822 Measurement conditions: Under nitrogen atmosphere, temperature rise / fall rate of 5°C / min, measurement temperature range -60°C to 200°C

[0092] <Evaluation of Biodegradability> In the examples and comparative examples, the degree of biodegradation was calculated using the following procedure, and the biodegradability was evaluated from the value of the degree of biodegradation.

[0093] <<Evaluation of Compost Decomposition>> The compost decomposition rate was measured according to the method in accordance with JIS K6953-1:2011. Culture temperature: 58°C Culture period: 28 days Evaluation criteria: A (Best): Compost decomposition rate of 50% or more B (Good): Compost decomposition rate of 40% or more and less than 50% C (Good): Compost decomposition rate of 24% or more and less than 40% D (Acceptable): Compost decomposition rate of 15% or more and less than 24% (lower limit for practical use) E (Unacceptable): Compost decomposition rate of less than 15% (not suitable for practical use)

[0094] (Synthesis Example 1) <Synthesis of Poly(1,3-propanediol / azelaic acid)> In a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, rectification tube, and water separator, 160 parts by mass of 1,3-propanediol, 340 parts by mass of azelaic acid, and 0.1 parts by mass of titanium tetraisopropoxide (TIPT) were charged. The esterification reaction was carried out under a nitrogen stream, maintaining a reaction solution temperature of 200°C and a vapor temperature of 98°C. The reaction was terminated when the acid value of the reaction solution became 2 mg KOH / g or less, yielding polyester polyol (1) (also denoted as PE-1).

[0095] The number-average molecular weight Mn of polyester polyol (1) was 2100, its hydroxyl value was 49, its acid value was 2.1, its glass transition temperature (Tg) was below -60°C, and its melting point (Tm) was 45°C.

[0096] (Synthesis Examples 2 to 12) Polyester polyols (2) to (12) (also referred to as PE-2 to PE12) were synthesized in the same manner as in Synthesis Example 1, except that the types and amounts of glycol and dicarboxylic acid used were changed to those listed in Tables 1-1 to 1-2, respectively. In this specification, Tables 1-1 to 1-3 are collectively referred to as Table 1. For each of polyester polyols (2) to (12), the number average molecular weight Mn, hydroxyl value, acid value, glass transition temperature (Tg), and melting point (Tm) were measured. The obtained results are shown in Tables 1-1 to 1-2. In Table 1, if the melting point peak could not be detected due to the amorphous resin, it is indicated as '-' in the Tm column (e.g., Synthesis Example 2).

[0097] (Synthesis Examples 13 to 17) Polyester polyols (13) to (17) (also denoted as PE-13 to PE17) were synthesized in the same manner as in Synthesis Example 1, except that the types and amounts of glycol and dicarboxylic acid used were changed to those listed in Table 1-3. Polyester polyols (13) to (17) are polyester polyols corresponding to comparative examples, and Synthesis Examples 13 to 15 are examples of polyester polyols synthesized by combining short carbon chain glycols with four or fewer carbon atoms between the hydroxyl groups at both ends in formulas (1-1) to (1-3) above, and short carbon chain dicarboxylic acids with four or fewer carbon atoms between the carboxyl groups at both ends in formula (2) above. Furthermore, synthesis examples 16-17 are examples of polyester polyols synthesized by combining a long carbon chain glycol with 5 or more carbon atoms between the hydroxyl groups at both ends in formulas (1-1) to (1-3) above, and a long carbon chain dicarboxylic acid with 5 or more carbon atoms between the carboxyl groups at both ends in formula (2) above. For each of the polyester polyols (13) to (17), the number-average molecular weight Mn, hydroxyl value, acid value, glass transition temperature (Tg), and melting point (Tm) were measured. The results obtained are shown in Table 1-3.

[0098] (Example 1) 100 parts by mass of polyester polyol (1) (PE-1) obtained in Synthesis Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, nitrogen gas inlet, and reflux condenser, and dissolved in 350 parts by mass of ethyl acetate to obtain an ethyl acetate solution of polyester polyol. 0.1 parts by mass of titanium tetraisopropoxide (TIPT) and 5.7 parts by mass of hexamethylene diisocyanate (HDI) were charged into the solution, and the reaction was carried out under a nitrogen atmosphere at 70-80°C. The reaction was terminated when the weight percentage of isocyanate fell to less than 0.05% by mass to obtain a polyester urethane polyol solution. The results of the biodegradability evaluation are shown in Table 2-1 below. Hereinafter, Tables 2-1 to 2-3 will be collectively referred to as Table 2.

[0099] (Examples 2-16) The same procedure as in Example 1 was followed, except that the types and amounts of polyester polyol and isocyanate were changed to the values ​​shown in Table 2, to obtain a polyester urethane polyol solution.

[0100] (Comparative Examples 1-5) The procedure was carried out in the same manner as in Example 1, except that the types and amounts of polyester polyol and isocyanate were changed to the values ​​shown in Table 2, to obtain a polyester urethane polyol solution.

[0101] Table 2 summarizes the evaluation results of the compost decomposition properties of Examples 1 to 16 and Comparative Examples 1 to 5.

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] In Table 2, the abbreviations are as follows: HDI-TMP is Sumijoule HT (trimethylolpropane (TMP) adduct of hexamethylene diisocyanate (HDI)) manufactured by Covestro; IPDI-TMP is Takenate D-140N (trimethylolpropane (TMP) adduct of isophorone diisocyanate (IPDI)) manufactured by Mitsui Chemicals.

[0109] From the above examples, it was confirmed that the polyester polyurethane (X) obtained from the polyester polyol (AB) according to the present invention has excellent biodegradability, particularly in compost biodegradability.

Claims

1. A polyester polyurethane (X) which is a reaction product (X) of a polyester polyol (AB) and a polyisocyanate, wherein the polyester polyol (AB) is a reaction product (AB) obtained by reacting a glycol (A) from any of the glycols represented by the following formulas (1-1) to (1-3) with a dicarboxylic acid (B) represented by the following formula (2), the polyester polyol (AB) does not contain a polymerization component derived from lactide, and the polyester polyol (AB) is (i) a glycol in formulas (1-1) to (1-3) with a carbon number of 4 or less, that is, a glycol in formula (1-1) with m being 4 or less, or in formula (1-2) with p+q being 3 or less, or in formula (1-3) with r+s being 4 or less, or a reaction product with a dicarboxylic acid in formula (2) with a carbon number of 5 or more, that is, a dicarboxylic acid in formula (2) with n being 5 or more, or (ii) Polyester polyurethane (X) is a reaction product of a glycol having 5 or more carbon atoms in formulas (1-1) to (1-3), that is, a glycol in formula (1-1) where m is 5 or more, or in formula (1-2) where p+q is 4 or more, or in formula (1-3) where r+s is 5 or more, in formula (2) where n is 4 or less, in formula (2). (In equation (1-1), m represents an integer greater than or equal to 1.) (In formula (1-2), R １ (where represents an alkyl group having 1 to 4 carbon atoms, and p and q are each independently 0 or integers of 1 or greater, with p + q being 1 or greater.) (In equation (1-3), r and s each represent an integer greater than or equal to 1, independently of each other.) (In equation (2), n represents an integer greater than or equal to 1.) 2. The polyester polyurethane (X) according to claim 1, wherein the polyester polyol (AB) is (i) a reaction product of any glycol selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and diethylene glycol and any dicarboxylic acid selected from the group consisting of heptanediol, suberic acid, azelaic acid, and sebacic acid, or (ii) a reaction product of any glycol consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol and any dicarboxylic acid consisting of glutaric acid and adipic acid.

3. A resin composition containing the polyester polyurethane (X) described in claim 1 or 2.

4. A sheet or film comprising the resin composition described in claim 3.

5. A coating agent comprising the polyester polyurethane (X) described in claim 1 or 2, and a solvent.

6. The coating agent according to claim 5, to be used as an adhesive.

7. A polyester polyol (AB) containing a polyester polyol (AB) resin composition, wherein the polyester polyol (AB) is a reaction product (AB) obtained by reacting a glycol (A) from any of the glycols represented by the following formulas (1-1) to (1-3) with a dicarboxylic acid (B) represented by the following formula (2), the polyester polyol (AB) does not contain a polymerization component derived from lactide, and the polyester polyol (AB) is (i) a glycol in formulas (1-1) to (1-3) having 4 or fewer carbon atoms, that is, a glycol in formula (1-1) where m is 4 or less, or in formula (1-2) where p+q is 3 or less, or in formula (1-3) where r+s is 4 or less, or a reaction product with a dicarboxylic acid in formula (2) having 5 or more carbon atoms, that is, a dicarboxylic acid in formula (2) where n is 5 or more, or (ii) A polyester polyol (AB)-containing resin composition in which, in formulas (1-1) to (1-3), the glycol has 5 or more carbon atoms, that is, in formula (1-1), m is 5 or more, or in formula (1-2), p+q is 4 or more, or in formula (1-3), r+s is 5 or more, and in formula (2), the glycol is a reaction product with a dicarboxylic acid having 4 or fewer carbon atoms, that is, in formula (2), n is 4 or less. (In equation (1-1), m represents an integer greater than or equal to 1.) (In formula (1-2), R １ (where represents an alkyl group having 1 to 4 carbon atoms, and p and q are each independently 0 or integers of 1 or greater, with p + q being 1 or greater.) (In equation (1-3), r and s each represent an integer greater than or equal to 1, independently of each other.) (In equation (2), n represents an integer greater than or equal to 1.) 8. The polyester polyol (AB)-containing resin composition according to claim 7, wherein the polyester polyol (AB) is (i) a reaction product of any glycol selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and diethylene glycol and any dicarboxylic acid selected from the group consisting of heptanediol, suberic acid, azelaic acid, and sebacic acid, or (ii) a reaction product of any glycol consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol and any dicarboxylic acid consisting of glutaric acid and adipic acid.

9. A sheet or film comprising the polyester polyol (AB)-containing resin composition according to claim 7 or claim 8.

10. A polyester polyol (AB)-containing coating agent comprising a polyester polyol (AB) and a solvent, wherein the polyester polyol (AB) is a reaction product (AB) obtained by reacting a glycol (A) from any of the glycols represented by the following formulas (1-1) to (1-3) with a dicarboxylic acid (B) represented by the following formula (2), the polyester polyol (AB) does not contain a polymerization component derived from lactide, and the polyester polyol (AB) is (i) a glycol in formulas (1-1) to (1-3) having 4 or fewer carbon atoms, that is, a glycol in formula (1-1) where m is 4 or less, or in formula (1-2) where p+q is 3 or less, or in formula (1-3) where r+s is 4 or less, or a reaction product with a dicarboxylic acid in formula (2) having 5 or more carbon atoms, that is, a dicarboxylic acid in formula (2) where n is 5 or more, or (ii) A polyester polyol (AB) containing coating agent, in formulas (1-1) to (1-3), the glycol having 5 or more carbon atoms, that is, the glycol in formula (1-1) where m is 5 or more, or in formula (1-2) where p+q is 4 or more, or in formula (1-3) where r+s is 5 or more, and in formula (2), the reaction product with a dicarboxylic acid having 4 or fewer carbon atoms, that is, a dicarboxylic acid in formula (2) where n is 4 or less. (In equation (1-1), m represents an integer greater than or equal to 1.) (In formula (1-2), R １ (where represents an alkyl group having 1 to 4 carbon atoms, and p and q are each independently 0 or integers of 1 or greater, with p + q being 1 or greater.) (In equation (1-3), r and s each represent an integer greater than or equal to 1, independently of each other.) (In equation (2), n represents an integer greater than or equal to 1.) 11. The polyester polyol (AB) containing coating agent according to claim 10, wherein the polyester polyol (AB) is (i) a reaction product of any glycol selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and diethylene glycol and any dicarboxylic acid selected from the group consisting of heptanediol, suberic acid, azelaic acid, and sebacic acid, or (ii) a reaction product of any glycol consisting of 3-methyl-1,5-pentanediol and 1,6-hexanediol and any dicarboxylic acid consisting of glutaric acid and adipic acid.

12. A polyester polyol (AB)-containing coating agent according to claim 10 or claim 11, to be used as an adhesive.

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