Heat resistant composition, heat resistance improvement agent, and resin composition

Abstract

A purpose of the present invention is to provide a novel heat resistant composition that imparts heat resistance to various materials and therefore can be suitably used particularly for improving the heat resistance of resin materials. Another purpose of the present invention is to provide a heat resistance improvement agent and a resin composition which comprise the heat resistant composition. The present invention is a composition which is used for imparting heat resistance, said composition comprising a trehalose derivative. The trehalose derivative is preferably one or more substances selected from the group consisting of trehalose benzoate, trehalose octaacetate, trehalose naphthoate, and trehalose fatty acid esters.

Description

Heat-resistant composition, heat resistance improver, and resin composition

[0001] The present invention relates to a heat-resistant composition, a heat resistance improver, and a resin composition that are used to impart heat resistance.

[0002] Resin materials and inorganic materials can be molded into various shapes, and the molded products are widely used in various fields. These molded products may contain various additives to improve their properties, and depending on the properties of the additives, the functions of the molded products can be improved or new functions can be imparted to the molded products (e.g., Patent Document 1).

[0003] For example, depending on the application in which the resin molded article is used, high heat resistance may be required, and in this case, various heat resistance improvers are used as additives to improve the heat resistance.

[0004] JP 2011-207798 A

[0005] An object of the present invention is to provide a novel heat-resistant composition that can be suitably used to impart heat resistance to various materials, particularly to improve the heat resistance of resin materials. Another object of the present invention is to provide a heat resistance improver and a resin composition containing the heat-resistant composition.

[0006] As a result of extensive research into achieving the above object, the present inventors have discovered that the above object can be achieved by using a trehalose derivative as an essential component, and have thus completed the present invention.

[0007] That is, the present invention encompasses, for example, the subject matter described in the following items. Item 1: A heat-resistant composition used to impart heat resistance, the composition containing a trehalose derivative. Item 2: The heat-resistant composition according to Item 1, wherein the trehalose derivative is one or more selected from the group consisting of trehalose benzoate, trehalose octaacetate, trehalose naphthoate, and trehalose fatty acid esters. Item 3: A heat-resistance improver containing the heat-resistant composition according to Item 1 or 2. Item 4: A resin composition containing the heat-resistance improver according to Item 3 and a resin.

[0008] The heat-resistant composition of the present invention can be suitably used to impart heat resistance to various materials.

[0009]

[0023] In the present specification, the terms "contain" and "comprise" include the concepts of "contain," "comprise," "consist essentially of," and "consist only of."

[0010] The heat-resistant composition of the present invention is a composition used to impart heat resistance and contains a trehalose derivative. The heat-resistant composition of the present invention can be suitably used to impart heat resistance to various materials, and particularly to improve the heat resistance of resin materials.

[0011] The heat-resistant composition of the present invention contains a trehalose derivative as an essential component. A trehalose derivative is a compound in which the hydrogen atom of a hydroxyl group of trehalose is substituted with another group. For example, a trehalose derivative is a compound formed by an esterification reaction between trehalose and a carboxylic acid ester compound. Therefore, a trehalose derivative is a compound having a structure in which a hydroxyl group in a trehalose molecule is replaced with a moiety derived from a carboxylic acid compound.

[0012] The trehalose derivative is preferably one or more selected from the group consisting of trehalose benzoate, trehalose octaacetate, trehalose naphthoate, and trehalose fatty acid esters. In this case, the heat-resistant composition of the present invention can be imparted with higher heat resistance. The trehalose derivative is more preferably selected from the group consisting of trehalose benzoate, trehalose octaacetate, and trehalose naphthoate, and even more preferably trehalose benzoate or trehalose octaacetate.

[0013] In trehalose benzoate, benzoate moieties may be introduced into some or all of the multiple hydroxyl groups (up to eight) derived from the trehalose molecule. In other words, trehalose benzoate may exist as a monoester, diester, triester, etc. The trehalose benzoate contained in the heat-resistant composition of the present invention may be any of these ester forms, or may contain not only one but also two or more ester forms. The degree of esterification of trehalose benzoate is also not particularly limited. For example, the degree of esterification of trehalose benzoate is 1 or more, preferably 1.1 or more, and may also be 6 or more, or 7 or more. The degree of esterification of trehalose benzoate is particularly preferably 7 to 8.

[0014] Trehalose octaacetate refers to an ester compound of trehalose and eight acetic acids.

[0015] Trehalose naphthoate is a compound in which naphthoate moieties can be introduced into some or all of the multiple hydroxyl groups (up to eight) derived from the trehalose molecule. In other words, trehalose naphthoate can exist as a monoester, diester, triester, etc. The trehalose naphthoate contained in the heat-resistant composition of the present invention may be any of these esters, or may contain one or more esters. The degree of esterification of trehalose naphthoate is also not particularly limited. The naphthyl group of the naphthoate moiety may be either a 1-naphthyl group or a 2-naphthyl group. For example, the degree of esterification of trehalose naphthoate is 1 or more, preferably 1.1 or more, and may also be 6 or more, or even 7 or more. The degree of esterification of trehalose naphthoate is particularly preferably 7 to 8.

[0016] Trehalose fatty acid esters can have fatty acid moieties introduced into some or all of the multiple hydroxyl groups (up to eight) derived from the trehalose molecule. That is, trehalose fatty acid esters can exist as monoesters, diesters, triesters, etc. The trehalose fatty acid ester contained in the heat-resistant composition of the present invention can be any of these esters, or can contain not only one but also two or more esters. The degree of esterification of the trehalose fatty acid ester is also not particularly limited. For example, the degree of esterification of the trehalose fatty acid ester is 1 or more, preferably 1.1 or more, more preferably 2 or more, and even more preferably 4 or more. The degree of esterification of the trehalose fatty acid ester can be 6 or more, or even 7 or more.

[0017] The trehalose derivative is particularly preferably trehalose benzoate and / or trehalose octaacetate, which can impart even higher heat resistance to the heat-resistant composition of the present invention.

[0018] The method for producing trehalose derivatives is not particularly limited, and a wide variety of known production methods can be used. For example, trehalose derivatives can be synthesized by reacting trehalose with a carboxylic acid compound. Alternatively, trehalose derivatives can be synthesized by transesterification of trehalose with a carboxylic acid ester compound.

[0019] When the trehalose derivative is trehalose benzoate, the carboxylic acid compound may be benzoic acid, and the carboxylic acid ester compound may be an alkyl ester of benzoic acid. The alkyl group in the alkyl ester moiety may be, for example, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group.

[0020] Trehalose benzoate can also be synthesized by reacting trehalose with benzoyl chloride.

[0021] When the trehalose derivative is trehalose octaacetate, the carboxylic acid compound may be acetic acid, and the acetate compound may be an alkyl ester of acetic acid. The alkyl group in the alkyl ester moiety may be, for example, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group.

[0022] When the trehalose derivative is trehalose naphthoate, the carboxylic acid compound may be 1-naphthalenecarboxylic acid or 2-naphthalenecarboxylic acid, and the carboxylic acid ester compound may be, for example, an alkyl ester of 1-naphthalenecarboxylic acid or an alkyl ester of 2-naphthalenecarboxylic acid. The alkyl group in the alkyl ester moiety may be, for example, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group.

[0023] Trehalose naphthoate can also be synthesized by reacting trehalose with naphthoyl chloride, specifically 1-naphthoyl chloride or 2-naphthoyl chloride.

[0024] Trehalose used in the method for producing a trehalose derivative may be synthesized by a known method, or trehalose may be commercially available.

[0025] Trehalose derivatives can also be obtained commercially.

[0026] The heat-resistant composition of the present invention may contain one or more trehalose derivatives.

[0027] The heat-resistant composition of the present invention may contain other ingredients in addition to the trehalose derivative, as long as the effects of the present invention are not impaired. Examples of other ingredients include pH adjusters, light stabilizers, antioxidants, preservatives, surfactants, fillers such as inorganic particles, flame retardants, pigments, colorants, mildew inhibitors, lubricants, etc. One or more of these additives may be contained in the heat-resistant composition of the present invention.

[0028] The heat-resistant composition of the present invention may be in either a solid or liquid form. When the heat-resistant composition of the present invention is in a solid form, its shape is not particularly limited, and examples thereof include powder, granules, flakes, blocks, pellets, etc. When the heat-resistant composition of the present invention is in a liquid form, it may be, for example, a solution or a dispersion such as a slurry. The liquid heat-resistant composition can be formed, for example, using a solvent.

[0029] The type of solvent is not particularly limited, and an appropriate solvent can be selected depending on the purpose. For example, a solvent can be selected depending on the purpose of dissolving or dispersing the trehalose derivative. The solvent may be water or various organic solvents. When the heat-resistant composition of the present invention contains a solvent, the content thereof is not particularly limited.

[0030] When the heat-resistant composition of the present invention is in a solid state, it may be dissolved or dispersed in a solvent when used or stored.

[0031] The content of the trehalose derivative in the heat-resistant composition of the present invention is not particularly limited. For example, the content of the trehalose derivative relative to the total amount of the heat-resistant composition of the present invention excluding the solvent can be 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The heat-resistant composition of the present invention may consist solely of the trehalose derivative.

[0032] The method for preparing the heat-resistant composition of the present invention is not particularly limited, and it can be obtained by mixing a predetermined amount of a trehalose derivative with other components that are blended as needed. The mixing method is not particularly limited, and a wide variety of known mixing means can be used.

[0033] The heat-resistant composition of the present invention contains a trehalose derivative, and therefore has high heat resistance. For example, in thermogravimetry (TG), the heat-resistant composition of the present invention exhibits a higher temperature at which it loses 10% by weight than, for example, a sucrose derivative.

[0034] Therefore, the heat-resistant composition of the present invention is suitable as an additive for imparting heat resistance, i.e., can be suitably used as a heat resistance improver. The heat resistance improver may consist solely of the heat-resistant composition of the present invention, or may be combined with other additives. By including the heat-resistant composition of the present invention, the heat resistance improver can impart heat resistance to various materials.

[0035] The method for using the heat-resistant composition of the present invention is not particularly limited, and for example, it can be incorporated into various materials by an appropriate method. For example, the heat-resistant composition of the present invention (or the heat-resistance improver) can be added to a material at any stage in the production of the material, thereby incorporating the heat-resistant composition into the material. Alternatively, when molding a material into a molded body, a raw material can be prepared in advance by mixing the material with the heat-resistant composition of the present invention, and then molding the raw material, thereby incorporating the heat-resistant composition of the present invention (or the heat-resistance improver) into the molded body. By these methods, the heat-resistant composition of the present invention can be incorporated into a material or a molded body thereof, thereby improving the heat resistance of the material.

[0036] When the heat-resistant composition of the present invention is added to various materials, the materials may be in a solid state or in a liquid state such as a solution.

[0037] The material is not particularly limited, and examples thereof include resins, glass, and other inorganic materials, preferably resins. That is, the heat-resistant composition of the present invention is preferably used to impart heat resistance to a resin. The heat-resistant composition of the present invention can also be combined with a resin to form a resin composition. The resin composition may be a molded product or a raw material for obtaining a molded product.

[0038] The type of resin is not particularly limited, and examples thereof include known resins such as acrylic resin, styrene resin, hydrogenated polystyrene resin, polyester resin, polycarbonate resin, fluororesin, polyvinyl chloride, polyurethane resin, polyamide resin, and polyolefin resin.

[0039] The shape of the material to which the heat-resistant composition of the present invention is added is not particularly limited, and examples thereof include films, thin films, sheets, substrates, and various other molded products.

[0040] When the heat-resistant composition of the present invention is incorporated into a material (e.g., a resin), the content is not particularly limited. For example, the trehalose derivative is preferably contained in an amount of 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, and is preferably contained in an amount of 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less, based on the total mass of the material.

[0041] In specifying the inventions included in the present disclosure, the components (properties, structures, functions, etc.) described in each embodiment of the present disclosure may be combined in any manner. In other words, the present disclosure includes all subject matter consisting of all combinations of the components that can be combined as described in this specification.

[0042] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0043] (Preparation Example 1: Trehalose Benzoate) Trehalose benzoate was prepared by a known method. Specifically, 34.2 parts of trehalose and 70 parts of water were charged and dissolved in a 1 L five-neck flask equipped with a stirring rod, thermometer, cooling condenser, dropping funnel, and pH electrode connected to a pH meter. Then, 100 parts of cyclohexanone containing 75.0 parts of benzoyl chloride was gradually added while cooling to below 10°C in a water bath. Subsequently, while maintaining the temperature below 20°C, 48.5 parts of a 48% aqueous solution of caustic soda was added via the dropping funnel at a rate that maintained the pH at 10-11. The water bath was removed, and the mixture was stirred at room temperature for 1 hour at 20-30°C for aging to complete the reaction. A small amount of sodium carbonate was then added and the mixture was heated to convert the traces of remaining benzoyl chloride into sodium benzoate. The mixture was then allowed to stand for approximately 30 minutes, after which the aqueous phase was separated and removed. 70 parts of water was added, and the mixture was heated to 40 to 50°C in a hot water bath. After stirring for 30 minutes, the mixture was allowed to stand for about 30 minutes to separate and remove the aqueous phase. After repeating the same procedure two more times (total number of water washes: 3), the mixture was heated to 120°C and the solvent was distilled off under reduced pressure to obtain the title trehalose benzoate having an esterification substitution degree of 7 to 8.

[0044] (Production Example 2: Trehalose Octaacetate) A 500 mL separable flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube was placed in a heating oil bath. Using this separable flask, 50 g (0.15 mol) of trehalose, 570 g (7.2 mol) of pyridine, and 120 g (1.18 mol) of acetic anhydride were mixed and reacted at 70°C for 2 hours while bubbling nitrogen gas at a flow rate of 10 mL / min. Pyridine, unreacted acetic anhydride, and by-product acetic acid were distilled off under reduced pressure. 220 g of methanol was added to the resulting residue, mixed, and allowed to stand at −5°C for 18 hours to precipitate crystals. The solution was filtered, and the precipitated crystals were collected, washed with 30 g of −5°C methanol, and further dried at 45°C under reduced pressure for 8 hours to obtain trehalose octaacetate with an esterification degree of 7 to 8.

[0045] (Production Example 3: Trehalose fatty acid ester) 15.4 g of trehalose, 19.5 g of methyl palmitate, and 45.5 g of methyl stearate were dissolved in 100 g of DMSO and reacted for 10 hours at 90 to 110° C. under reduced pressure. After distilling off the solvent, the resulting mixture was purified and dried to obtain the title trehalose fatty acid ester with an esterification degree of 5.

[0046] Example 1 Trehalose benzoate obtained in Production Example 1 was obtained as a heat-resistant composition.

[0047] Example 2 Trehalose octaacetate obtained in Production Example 2 was obtained as a heat-resistant composition.

[0048] Example 3 The trehalose fatty acid ester obtained in Production Example 3 was obtained as a heat-resistant composition.

[0049] Comparative Example 1 Sucrose benzoate (esterification degree of 7 to 8) produced by a known method was obtained as a heat-resistant composition.

[0050] Comparative Example 2 Sucrose acetate (esterification degree of 7 to 8) produced by a known method was obtained as a heat-resistant composition.

[0051] (Evaluation Method) [Heat Resistance Measurement] The heat resistance of the heat-resistant compositions obtained in each of the Examples and Comparative Examples was measured by thermogravimetry (TG). Thermogravimetry (TG) was performed using a "differential thermal and thermogravimetry simultaneous analyzer TG-DTA8122" manufactured by RIGAKU Corporation. The measurement was performed under conditions of heating from room temperature to 500°C at a rate of 10°C / min in a nitrogen gas flow. The heat-resistant composition used in the thermogravimetry was 10 mg, and alumina powder was used as a reference.

[0052] (Evaluation Results) Table 1 shows the results of the heat loss temperatures obtained by TG measurement of the heat-resistant compositions obtained in each of the Examples and Comparative Examples, showing the temperatures at which the weight was reduced by 5% and the temperatures at which the weight was reduced by 10%.

[0053] The results shown in Table 1 indicate that the trehalose derivatives (trehalose benzoate and trehalose octaacetate) have higher temperatures for both 5% and 10% weight loss than the corresponding sucrose derivatives, and are therefore superior in heat resistance.

[0054]

Claims

1. A heat-resistant composition used to impart heat resistance, the heat-resistant composition comprising a trehalose derivative.

2. The heat-resistant composition according to claim 1, wherein the trehalose derivative is at least one member selected from the group consisting of trehalose benzoate, trehalose octaacetate, trehalose naphthoate and trehalose fatty acid esters.

3. A heat resistance improver containing the heat resistant composition according to claim 1 or 2.

4. A resin composition comprising the heat resistance improver according to claim 3 and a resin.

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