Resin pellets, manufacturing method for resin pellets, molded products, automotive parts, electronic equipment parts, fibers

Abstract

The present invention provides: a resin pellet which enables the formation of a molded article that exhibits a tensile strength at break equivalent to the tensile strength at break of a resin contained in the resin pellet; a method for producing a resin pellet; a molded article; a component for automobiles; a component for electronic devices; and a fiber. This resin pellet comprises a microcapsule that internally contains a heat storage material, and a thermoplastic resin; the content of the heat storage material is 70% by mass or less relative to the total mass of the resin pellet; and the capsule wall of the microcapsule contains at least one resin that is selected from the group consisting of a polyurethane urea, a polyurethane and a polyurea.

Description

[Technical field]

[0001] The present invention relates to a resin pellet, a method for producing a resin pellet, a molded product, an automobile part, an electronic device part, and a fiber. [Background technology]

[0002] Microcapsules have the potential to provide new value to customers by encapsulating and protecting functional materials such as heat storage materials, fragrances, dyes, adhesive hardeners, and pharmaceutical ingredients. In particular, microcapsules that contain phase change materials (PCMs) and function as heat storage materials that store heat generated outside are attracting attention. In recent years, attempts have been made to produce resin pellets containing microcapsules encapsulating a heat storage material. Patent Document 1 specifically discloses pellets containing microcapsules encapsulating a heat storage material and having capsule walls made of melamine resin. Patent Document 2 discloses a granule obtained by using microcapsules encapsulating a heat storage material and polyvinyl alcohol. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-137723 A [Patent Document 2] JP 2007-284517 A Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, it is desired that the tensile breaking strength of a molded article obtained using a resin pellet containing a resin and microcapsules encapsulating a heat storage material is approximately the same as the tensile breaking strength of the resin contained in the resin pellet. In other words, it is desired to provide a resin pellet capable of molding a molded article having a tensile breaking strength approximately the same as that of a molded article formed using a resin contained in the resin pellet and not containing a microcapsule encapsulating a heat storage material. The present inventors have evaluated the above-mentioned properties using the pellets described in Patent Document 1 and the granules described in Patent Document 2, and have found that they do not fully satisfy the above-mentioned requirements.

[0005] In view of the above circumstances, an object of the present invention is to provide a resin pellet capable of being molded into a molded article exhibiting a tensile breaking strength approximately equal to the tensile breaking strength of the resin contained in the resin pellet. Another object of the present invention is to provide a method for producing resin pellets, a molded product, an automobile part, an electronic device part, and a fiber. [Means for solving the problem]

[0006] As a result of extensive research into the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0007] (1) A resin pellet containing a microcapsule containing a heat storage material and a thermoplastic resin, The content of the heat storage material is 70% by mass or less based on the total mass of the resin pellets, A resin pellet, the capsule wall of a microcapsule containing at least one resin selected from the group consisting of polyurethane urea, polyurethane, and polyurea. (2) The resin pellet according to (1), wherein the capsule wall of the microcapsule contains polyurethaneurea. (3) The resin pellet according to (1) or (2), wherein the total content of the microcapsules and the thermoplastic resin is more than 90% by mass based on the total mass of the resin pellet. (4) The resin pellet according to any one of (1) to (3), wherein the resin contained in the capsule wall of the microcapsule has a structure represented by formula (Y) described below. (5) The resin contained in the capsule wall of the microcapsule is an aromatic or alicyclic diisocyanate; A compound having three or more active hydrogen groups in one molecule, The resin pellet according to any one of (1) to (4), which is a resin obtained by reacting with polymethylene polyphenyl polyisocyanate. (6) The resin pellet according to (5), wherein the compound having three or more active hydrogen groups in one molecule is a polyol having a molecular weight of 500 or less. (7) The resin contained in the capsule wall of the microcapsule is A tri- or higher functional polyisocyanate A which is an adduct of an aromatic or alicyclic diisocyanate and a compound having three or more active hydrogen groups in one molecule, and The resin pellet according to any one of (1) to (6), which is formed using a polyisocyanate B selected from the group consisting of aromatic diisocyanates and polymethylene polyphenyl polyisocyanates. (8) The resin pellet according to any one of (1) to (7), wherein the capsule wall of the microcapsule has a thermal decomposition temperature of 200° C. or higher. (9) The resin pellet according to any one of (1) to (8), wherein the thickness of the capsule wall of the microcapsule is 0.10 to 5.0 μm. (10) The resin pellet according to any one of (1) to (9), wherein the average inner diameter of the microcapsules is 200 μm or less. (11) The resin pellet according to any one of (1) to (10), wherein the melting point of the thermoplastic resin is 110° C. or higher. (12) The resin pellet according to any one of (1) to (11), wherein the thermoplastic resin is a water-insoluble resin. (13) A method for producing a resin pellet according to any one of (1) to (12), comprising the steps of: A method for producing resin pellets, comprising melting and kneading a thermoplastic resin in an extruder, adding microcapsules to the molten thermoplastic resin in the extruder and further melt-kneading the mixture, and cutting the strands extruded from the extruder to produce resin pellets. (14) A molded product obtained by molding the resin pellets according to any one of (1) to (12). (15) An automobile part molded using the resin pellets according to any one of (1) to (12). (16) A part for an electronic device, molded using the resin pellet according to any one of (1) to (12). (17) A fiber molded using the resin pellets according to any one of (1) to (12). Effect of the Invention

[0008] According to the present invention, it is possible to provide resin pellets that can be molded into molded articles exhibiting a tensile breaking strength similar to the tensile breaking strength of the resin contained in the resin pellets. Furthermore, according to the present invention, it is possible to provide a method for producing resin pellets, a molded product, an automobile part, an electronic device part, and a fiber. [Brief description of the drawings]

[0009] [Figure 1] FIG. 2 is a partial schematic diagram of an SEM image of a cross section of a resin pellet. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in a certain numerical range. In addition, in the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. The various components described below may be used alone or in combination of two or more. For example, the polyisocyanates described below may be used alone or in combination of two or more.

[0011] The resin pellet of the present invention is characterized in that the capsule walls of the microcapsules contain a predetermined resin and the content of the heat storage material is a predetermined value or less. It has been found that the decrease in tensile breaking strength can be suppressed by selecting a specific resin as the material for the capsule wall of the microcapsule. It has also been found that if the content of the heat storage material is too high, the tensile breaking strength of the resulting molded product decreases, and that the decrease in tensile breaking strength can be suppressed by setting the content at a specific value or less.

[0012] The resin pellet of the present invention contains microcapsules encapsulating a heat storage material (hereinafter, also simply referred to as "microcapsules") and a thermoplastic resin. First, the components contained in the resin pellets will be described in detail below.

[0013] <Microcapsules> A microcapsule has a core portion and a capsule wall for encapsulating a core material (an entity to be encapsulated (also referred to as an encapsulated component)) that constitutes the core portion.

[0014] The microcapsules contain a heat storage material as a core material (encapsulated component). Because the heat storage material is encapsulated in the microcapsules, the heat storage material can exist stably in a phase state according to the temperature.

[0015] (Heat storage material) The type of heat storage material is not particularly limited, and a material that changes phase in response to temperature changes can be used. A material that can repeatedly change phase between solid and liquid phases, accompanied by changes in state between melting and solidification in response to temperature changes, is preferred. The phase change of the heat storage material is preferably based on the phase change temperature of the heat storage material itself, and in the case of a phase change between a solid phase and a liquid phase, it is preferably based on the melting point.

[0016] The heat storage material may be, for example, any of a material capable of storing heat generated outside a molded product manufactured using resin pellets as sensible heat, a material capable of storing heat generated outside a molded product manufactured using resin pellets as latent heat (hereinafter also referred to as a "latent heat storage material"), a material that undergoes a phase change associated with a reversible chemical change, etc. The heat storage material is preferably one that can release the stored heat. Among these, in terms of ease of control over the amount of heat that can be exchanged and the magnitude of the amount of heat, the latent heat storage material is preferred as the heat storage material.

[0017] A latent heat storage material is a material that stores heat generated outside a molded product manufactured using resin pellets as latent heat. For example, in the case of a phase change between solid and liquid phases, the material can exchange heat by repeating the change between melting and solidifying with the melting point determined by the material as the phase change temperature. In the case of a phase change between solid and liquid, the latent heat storage material utilizes the heat of fusion at the melting point and the heat of solidification at the freezing point, and can store and release heat accompanying the phase change between solid and liquid.

[0018] The type of latent heat storage material is not particularly limited, and can be selected from compounds that have a melting point and are capable of undergoing a phase change. Examples of latent heat storage materials include ice (water); inorganic salts; aliphatic hydrocarbons such as paraffin (e.g., isoparaffin, normal paraffin); fatty acid ester compounds such as tri(capryl / capric acid) glyceryl, methyl myristate (melting point 16-19°C), isopropyl myristate (melting point 167°C), and dibutyl phthalate (melting point -35°C); alkylnaphthalene compounds such as diisopropylnaphthalene (melting point 67-70°C), 1-phenyl-1-xylylethane (melting point less than -50°C), etc. aromatic hydrocarbons such as diarylalkane compounds, alkylbiphenyl compounds such as 4-isopropylbiphenyl (melting point 11°C), triarylmethane compounds, alkylbenzene compounds, benzylnaphthalene compounds, diarylalkylene compounds, and arylindane compounds; natural animal and vegetable oils such as camellia oil, soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, coconut oil, castor oil, and fish oil; mineral oils; diethyl ethers; aliphatic diols; sugars; sugar alcohols, etc.

[0019] The phase change temperature of the heat storage material is not particularly limited, and may be appropriately selected depending on the type of heat generating element, the heat generating temperature of the heat generating element, the temperature after cooling or the holding temperature, the cooling method, and the like. It is preferable to select a heat storage material that has a phase change temperature (preferably a melting point) in a target temperature range (for example, the operating temperature of a heating element; hereinafter, also referred to as a "thermal control range"). The phase change temperature of the heat storage material differs depending on the thermal control region, but is preferably 0 to 80°C, and more preferably 10 to 70°C.

[0020] In terms of superior heat storage properties of molded articles produced using the resin pellets, the latent heat storage material is preferably an aliphatic hydrocarbon, and more preferably paraffin. The melting point of the aliphatic hydrocarbon (preferably paraffin) is not particularly limited, but in terms of application to various uses, it is preferably 0° C. or higher, more preferably 15° C. or higher, and even more preferably 20° C. or higher. There is no particular upper limit, but it is preferably 80° C. or lower, more preferably 70° C. or lower, even more preferably 60° C. or lower, and particularly preferably 50° C. or lower. As the aliphatic hydrocarbon, a straight-chain aliphatic hydrocarbon is preferred in that the heat storage property of a molded article produced using the resin pellets is superior. The number of carbon atoms in the straight-chain aliphatic hydrocarbon is not particularly limited, but is preferably 14 or more, more preferably 16 or more, and even more preferably 17 or more. The upper limit is not particularly limited, but is preferably 30 or less, more preferably 28 or less, and even more preferably 26 or less. As the aliphatic hydrocarbon, a straight-chain aliphatic hydrocarbon having a melting point of 0° C. or higher is preferable, and a straight-chain aliphatic hydrocarbon having a melting point of 0° C. or higher and 14 or more carbon atoms is more preferable.

[0021] Examples of linear aliphatic hydrocarbons (linear paraffins) having a melting point of 0° C. or higher include n-tetradecane (melting point 6° C.), n-pentadecane (melting point 10° C.), n-hexadecane (melting point 18° C.), n-heptadecane (melting point 22° C.), n-octadecane (melting point 28° C.), n-nonadecane (melting point 32° C.), n-eicosane (melting point 37° C.), and n-henicosane (melting point 40° C.). ℃), n-docosane (melting point 44°C), n-tricosane (melting point 48-50°C), n-tetracosane (melting point 52°C), n-pentacosane (melting point 53-56°C), n-hexacosane (melting point 57°C), n-heptacosane (melting point 60°C), n-octacosane (melting point 62°C), n-nonacosane (melting point 63-66°C), and n-triacontane (melting point 66°C).

[0022] When linear aliphatic hydrocarbons are used as the heat storage material, the content of linear aliphatic hydrocarbons is preferably 80 mass% or more, more preferably 90 mass% or more, further preferably 95 mass% or more, particularly preferably 98 mass% or more, based on the content of the heat storage material. The upper limit is 100 mass%.

[0023] The inorganic salt is preferably an inorganic hydrate, and examples thereof include hydrates of alkali metal chlorides (e.g., sodium chloride dihydrate, etc.), hydrates of alkali metal acetates (e.g., sodium acetate hydrate, etc.), hydrates of alkali metal sulfates (e.g., sodium sulfate hydrate, etc.), hydrates of alkali metal thiosulfates (e.g., sodium thiosulfate hydrate, etc.), hydrates of alkaline earth metal sulfates (e.g., calcium sulfate hydrate, etc.), and hydrates of alkaline earth metal chlorides (e.g., calcium chloride hydrate, etc.). Aliphatic diols include 1,6-hexanediol and 1,8-octanediol. Sugars and sugar alcohols include xylitol, erythritol, galactitol, and dihydroxyacetone.

[0024] The heat storage material may be used alone or in combination of two or more kinds. By using one heat storage material alone or a plurality of heat storage materials with different melting points, the temperature range in which the heat storage property is exhibited and the amount of heat storage can be adjusted according to the application. The temperature range in which heat can be stored can be expanded by mixing a heat storage material with a melting point at the central temperature where the heat storage effect of the heat storage material is desired with other heat storage materials with melting points before and after it. To explain this in detail using an example of using paraffin as the heat storage material, by using paraffin a, which has a melting point at the central temperature where the heat storage effect of the heat storage material is desired, as the central material and mixing paraffin a with other paraffins having the same carbon number before and after paraffin a, the molded product manufactured using the resin pellets can be designed to have a wide temperature range (thermal control range). The content of paraffin having a melting point at the core temperature where the heat storage effect is desired is not particularly limited, but is preferably 80 mass% or more, more preferably 90 mass% or more, even more preferably 95 mass% or more, and particularly preferably 98 mass% or more, based on the total mass of the heat storage material. The upper limit is 100 mass%.

[0025] When paraffin is used as the heat storage material, one type of paraffin may be used alone, or two or more types may be mixed and used. When multiple paraffins with different melting points are used, the temperature range in which the heat storage property is exhibited can be expanded.

[0026] When multiple paraffins are used, the content of the main paraffin is not particularly limited in terms of the temperature range in which the heat storage property is exhibited and the amount of heat storage, but is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, and even more preferably 95 to 100 mass%, based on the total mass of the paraffins. The term "main paraffin" refers to the paraffin that is contained in the greatest amount among the multiple paraffins contained. The content of the main paraffin is preferably 50% by mass or more based on the total mass of paraffins. The content of paraffin is not particularly limited, but is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, further preferably 95 to 100 mass%, and particularly preferably 98 to 100 mass%, based on the total mass of the heat storage material (preferably the latent heat storage material). In addition, the paraffin is preferably linear paraffin and preferably does not substantially contain branched paraffin. By containing linear paraffin and substantially not containing branched paraffin, the heat storage property is further improved. The reason for this is presumably that the association between linear paraffin molecules can be prevented from being inhibited by branched paraffin.

[0027] The content of the heat storage material in the resin pellets is 70 mass % or less with respect to the total mass of the resin pellets. In particular, the content is preferably 50% by mass or less, and more preferably 40% by mass or less, in view of the superior tensile breaking strength of the molded article obtained using the resin pellets of the present invention (hereinafter, also simply referred to as "superior effects of the present invention"). Although there is no particular lower limit, the content is preferably 10% by mass or more, and more preferably 20% by mass or more, in view of the superior heat storage property of the molded article.

[0028] The content of the heat storage material in the microcapsules is not particularly limited, but from the viewpoints of heat storage property and heat resistance of the microcapsules, it is preferably 40 to 95 mass %, more preferably 60 to 85 mass %.

[0029] (Other ingredients) The core material of the microcapsule may contain other components besides the above-mentioned heat storage material. Examples of other components that can be contained as the core material in the microcapsule include additives such as solvents, ultraviolet absorbers, light stabilizers, antioxidants, waxes, odor suppressants, and flame retardants. The content of the heat storage material in the core material is not particularly limited, but in order to obtain a molded product produced using the resin pellets with better heat storage properties, the content is preferably 80 to 100 mass%, and more preferably 90 to 100 mass%, relative to the total mass of the core material.

[0030] The microcapsules may contain a solvent as a core material. In this case, the solvent may be the above-mentioned heat storage material whose melting point is outside the temperature range (thermal control range; for example, the operating temperature of a heating element) in which the molded product produced using the resin pellets is used. In other words, the solvent refers to a material that remains in a liquid state and does not change phase in the thermal control range, and is distinguished from the heat storage material that undergoes a phase transition within the thermal control range and causes a heat absorption / dissipation reaction.

[0031] The content of the solvent in the core material is not particularly limited, but is preferably less than 30% by mass, more preferably less than 10% by mass, and even more preferably 1% by mass or less, based on the total mass of the core material. The lower limit is not particularly limited, but may be 0% by mass.

[0032] (Capsule wall (wall part)) The microcapsules have a capsule wall that encapsulates a core material. The material forming the capsule wall of the microcapsules may be at least one resin selected from the group consisting of polyurethane urea, polyurethane, and polyurea. Among these, polyurethane urea is preferred in that it provides a more excellent effect of the present invention. Polyurethane is a polymer having a plurality of urethane bonds, and is preferably a reaction product of a polyol and a polyisocyanate. Polyurea is a polymer having a plurality of urea bonds, and is preferably a reaction product of polyamine and polyisocyanate. Moreover, polyurethane urea is a polymer having a urethane bond and a urea bond, and is preferably a reaction product of a polyol, a polyamine, and a polyisocyanate, or a reaction product of a polyol and a polyisocyanate. When a polyol and a polyisocyanate are reacted to obtain a polyurethane urea, a part of the polyisocyanate reacts with water to become a polyamine, thereby obtaining the polyurethane urea.

[0033] The capsule wall of the microcapsule preferably has a urethane bond. The capsule wall having a urethane bond can be obtained, for example, by using the above-mentioned polyurethane urea or polyurethane. The urethane bond is a highly mobile bond, which can impart thermoplasticity to the capsule wall. In addition, it is easy to adjust the flexibility of the capsule wall. Therefore, it is difficult to impair the resin properties of the resin pellets, and it is easy to suppress the decrease in tensile breaking strength.

[0034] The polyurethanes, polyureas, and polyurethaneureas are preferably formed using polyisocyanates.

[0035] A polyisocyanate is a compound having two or more isocyanate groups, and examples of the polyisocyanate include aromatic polyisocyanates and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 4,4'-diphenylhexafluoropropane diisocyanate.

[0036] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,4-bis(isocyanatemethyl)cyclohexane, 1,3-bis(isocyanatemethyl)cyclohexane, isophorone diisocyanate, lysine diisocyanate, and hydrogenated xylylene diisocyanate.

[0037] Although difunctional aromatic polyisocyanates and aliphatic polyisocyanates have been exemplified above, examples of polyisocyanates include trifunctional or higher polyisocyanates (for example, trifunctional triisocyanates and tetrafunctional tetraisocyanates). More specifically, examples of the polyisocyanate include biuret or isocyanurate, which are trimers of the above-mentioned difunctional polyisocyanates, adducts of polyols such as trimethylolpropane and difunctional polyisocyanates, formalin condensates of benzene isocyanate, polyisocyanates having a polymerizable group such as methacryloyloxyethyl isocyanate, and lysine triisocyanate. Polyisocyanates are described in "Polyurethane Resin Handbook" (edited by Iwata Keiji, published by Nikkan Kogyo Shimbun, 1987).

[0038] Among these, tri- or higher functional polyisocyanates are preferred as the polyisocyanate. Examples of tri- or higher functional polyisocyanates include tri- or higher functional aromatic polyisocyanates and tri- or higher functional aliphatic polyisocyanates. As the tri- or higher functional polyisocyanate, a tri- or higher functional polyisocyanate which is an adduct (addition product) between a bifunctional polyisocyanate and a compound having three or more active hydrogen groups in one molecule (for example, a tri- or higher functional polyol, polyamine, or polythiol, etc.) (an adduct-type tri- or higher functional polyisocyanate), and a trimer (biuret type or isocyanurate type) of a bifunctional polyisocyanate are also preferred.

[0039] Examples of the adduct type tri- or higher functional polyisocyanates include Takenate (registered trademark) D-102, D-103, D-103H, D-103M2, P49-75S, D-110N, D-120N, D-140N, D-160N (all manufactured by Mitsui Chemicals, Inc.), Desmodur (registered trademark) L75, UL57SP (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate (registered trademark) HL, HX, L (manufactured by Nippon Polyurethane Co., Ltd.), P301-75E (manufactured by Asahi Kasei Corporation), and Burnock (registered trademark) D-750 (manufactured by DIC Corporation). Among these, as the adduct type tri- or higher functional polyisocyanate, Takenate (registered trademark) D-110N, D-120N, D-140N, and D-160N manufactured by Mitsui Chemicals, Inc., or Burnock (registered trademark) D-750 manufactured by DIC Corporation are preferable. Examples of isocyanurate-type trifunctional or higher polyisocyanates include Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N, D-204, D-204EA-1, D-262, D-268, D-370N, and D-376N (manufactured by Mitsui Chemicals, Inc.), Sumidur N3300, Desmodur (registered trademark) N3600, N3900, and Z4470BA (Sumika Bayer Urethane), Coronate (registered trademark) HX and HK (manufactured by Nippon Polyurethane Co., Ltd.), and Duranate (registered trademark) TPA-100, TKA-100, TSA-100, TSS-100, TLA-100, and TSE-100 (manufactured by Asahi Kasei Corporation). Examples of biuret-type tri- or higher functional polyisocyanates include Takenate (registered trademark) D-165N and NP1100 (manufactured by Mitsui Chemicals, Inc.), Desmodur (registered trademark) N3200 (Sumika Bayer Urethane), and Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Corporation).

[0040] Moreover, the polyisocyanate is preferably polymethylene polyphenyl polyisocyanate. The polymethylene polyphenyl polyisocyanate is preferably a compound represented by the formula (X).

[0041] [ka]

[0042] In formula (X), n represents the number of repeating units. The number of repeating units represents an integer of 1 or more, and n is preferably an integer of 1 to 10, and more preferably an integer of 1 to 5, in that the effects of the present invention are more excellent.

[0043] Examples of polyisocyanates containing polymethylene polyphenyl polyisocyanate include Millionate MR-100, Millionate MR-200, Millionate MR-400 (manufactured by Tosoh Corporation), WANNATE PM-200, WANNATE PM-400 (manufactured by Wanka Japan Co., Ltd.), Cosmonate M-50, Cosmonate M-100, Cosmonate M-200, Cosmonate M-300 (manufactured by Mitsui Chemicals, Inc.), and Boranate M-595 (manufactured by The Dow Chemical Company).

[0044] A polyol is a compound having two or more hydroxyl groups, and examples thereof include low molecular weight polyols (e.g., aliphatic polyols, aromatic polyols), polyether-based polyols, polyester-based polyols, polylactone-based polyols, castor oil-based polyols, polyolefin-based polyols, and hydroxyl group-containing amine-based compounds. The low molecular weight polyol means a polyol having a molecular weight of 500 or less, and examples thereof include difunctional low molecular weight polyols such as ethylene glycol, diethylene glycol, and propylene glycol, as well as trifunctional or higher low molecular weight polyols such as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, and sorbitol. In terms of controlling the flexibility of the microcapsules, further suppressing the decrease in tensile breaking strength, and improving heat resistance, the above polyol is preferably a low molecular weight polyol, more preferably a low molecular weight polyol having three or more functionalities, and even more preferably a low molecular weight polyol having three functionalities.

[0045] Examples of hydroxyl group-containing amine compounds include amino alcohols, which are oxyalkylated derivatives of amino compounds, etc. Examples of amino alcohols include N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine and N,N,N',N'-tetrakis[2-hydroxyethyl]ethylenediamine, which are propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine.

[0046] Polyamines are compounds having two or more amino groups (primary amino groups or secondary amino groups), and examples of such polyamines include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, tetraethylenepentamine, and hexamethylenediamine; epoxy compound adducts of aliphatic polyamines; alicyclic polyamines such as piperazine; and heterocyclic diamines such as 3,9-bis-aminopropyl-2,4,8,10-tetraoxaspiro-(5,5)undecane. In terms of improving the heat resistance of the resin, the polyamine is preferably a low molecular weight polyamine, more preferably a tri- or higher functional low molecular weight polyamine, and even more preferably a tri- or tetrafunctional low molecular weight polyamine. The low molecular weight polyamine means a polyamine having a molecular weight of 500 or less.

[0047] In particular, the resin contained in the capsule wall preferably has a structure represented by formula (Y), since this reduces bleeding of the heat storage material even when a molded article made from the resin pellets is exposed to a high-temperature environment. The structure represented by formula (Y) corresponds to the structure contained in the resin obtained when the compound represented by formula (X) above is used as a raw material for polyisocyanate.

[0048] [ka]

[0049] In formula (Y), n represents the number of repeating units. The number of repeating units represents an integer of 1 or more, and n is preferably an integer of 1 to 10, and more preferably an integer of 1 to 5, in that the effects of the present invention are more excellent.

[0050] Among these, the resin contained in the capsule wall is preferably a resin obtained by reacting an aromatic or alicyclic diisocyanate, a compound having three or more active hydrogen groups in one molecule, and polymethylene polyphenyl polyisocyanate, since there is little bleeding of the heat storage material even when a molded article made from the resin pellets is exposed to a high temperature environment. In addition, the aromatic or aliphatic diisocyanate is preferably an aromatic diisocyanate from the viewpoint of heat resistance. In addition, the compound having three or more active hydrogen groups in one molecule is preferably a polyol, more preferably a low molecular weight polyol.

[0051] In particular, the resin contained in the capsule wall is preferably formed using a tri- or higher functional polyisocyanate A (hereinafter also simply referred to as "polyisocyanate A") which is an adduct of an aromatic or alicyclic diisocyanate and a compound having three or more active hydrogen groups in one molecule, and a polyisocyanate B (hereinafter also simply referred to as "polyisocyanate B") selected from the group consisting of aromatic diisocyanates and polymethylene polyphenyl polyisocyanates. That is, the capsule wall is preferably a capsule wall formed using the polyisocyanate A and polyisocyanate B and containing the above-mentioned resin (at least one resin selected from the group consisting of polyurea, polyurethane urea, and polyurethane). The present invention is more effective when the polyisocyanate A and polyisocyanate B are used. In addition, the use of the polyisocyanate A and polyisocyanate B suppresses the destruction of microcapsules under high temperature conditions. When an adduct of a polyol and a polyisocyanate is used as the polyisocyanate A and is reacted with the polyisocyanate B, a polyurethane urea is often obtained as a result, similar to the reaction product of the polyol and the polyisocyanate. As the polyisocyanate B, an aromatic diisocyanate may be used alone, a polymethylene polyphenyl polyisocyanate may be used alone, or both may be used in combination. Among these, a mixture of an aromatic diisocyanate and a polymethylene polyphenyl polyisocyanate is preferred as the polyisocyanate B. In the above mixture, the mass ratio of polymethylene polyphenyl polyisocyanate to aromatic diisocyanate (mass of polymethylene polyphenyl polyisocyanate / mass of aromatic diisocyanate) is not particularly limited, but is preferably 0.1 to 10, more preferably 0.5 to 2, and even more preferably 0.75 to 1.5.

[0052] The viscosity of the polyisocyanate B is not particularly limited, but is preferably 100 to 1000 mPa·s in terms of providing better effects of the present invention. The above viscosity is measured at 25°C.

[0053] When polyisocyanate A and polyisocyanate B are used in combination, the mass ratio of polyisocyanate A to polyisocyanate B (mass of polyisocyanate A / mass of polyisocyanate B) is not particularly limited, but is preferably 98 / 2 to 20 / 80, more preferably 90 / 10 to 30 / 70, and even more preferably 85 / 15 to 40 / 60. When the mass ratio is within the above range, the effects of the present invention are more excellent.

[0054] The mass of the capsule wall in the microcapsules is not particularly limited, but is preferably from 5 to 60% by mass, and more preferably from 15 to 40% by mass, based on the total mass of the microcapsules.

[0055] (Physical properties of microcapsules) The average particle size of the microcapsules is not particularly limited, but is preferably 1 to 500 μm, more preferably 1 to 200 μm, further preferably 1 to 100 μm, and particularly preferably 2 to 50 μm. The smaller the particle size of the microcapsules, the better the appearance of the molded product. The average inner diameter of the microcapsules is not particularly limited, and from the viewpoint of obtaining the effects of the present invention, it is preferably 200 μm or less, more preferably 1 to 100 μm, and even more preferably 2 to 50 μm. The inner diameter of the microcapsules refers to the diameter of the core portion. The average particle size and average inner diameter of the microcapsules can be controlled by changing the dispersion conditions in the emulsification step of the method for producing microcapsules described below. The average particle size and average inner diameter of the microcapsules are measured by the following method. First, a cross-sectional slice of the resin pellet or a molded product produced using the resin pellet is prepared, and the cross-section is observed at 1000 times with a scanning electron microscope (SEM). FIG. 1 shows a schematic diagram of a part of an SEM image of a cross-section of a resin pellet 13. From the SEM image of the cross-section, the inside of the microcapsule 10 (inclusion 10b), the capsule wall 10a, and the thermoplastic resin 12 are observed separately. Among the microcapsules 10 present in the observed field of view, the particle size and inner diameter of 20 microcapsules are measured in order from the largest microcapsule 10, and the average value is calculated by arithmetically averaging these. This operation is performed in five fields of view, and the average value obtained at each point is calculated, and the obtained value is the average particle size and average inner diameter of the microcapsule. The inner diameter measured above is the longest inner diameter when the microcapsule is observed.

[0056] The thickness of the capsule wall of the microcapsule (wall thickness) is not particularly limited, but is preferably 10.00 μm or less, more preferably 5.00 μm or less, and even more preferably 2.00 μm or less, in terms of the superior effect of the present invention. On the other hand, since the strength of the capsule wall can be maintained by having a certain degree of thickness, the wall thickness is preferably 0.01 μm or more, and more preferably 0.10 μm or more, and even more preferably 0.2 μm or more, in terms of less bleeding of the heat storage material even when a molded product molded using the resin pellets is exposed to a high temperature environment. The wall thickness refers to the average value obtained by measuring the individual wall thicknesses (μm) of any 20 microcapsules using a scanning electron microscope (SEM). Specifically, a cross-sectional slice of the resin pellet or a molded article produced using the resin pellet is prepared, the cross-section is observed using an SEM, and 20 microcapsules having a size of ±10% of the average particle size calculated by the above-mentioned measurement method are selected. The cross-section of each of the selected microcapsules is observed to measure the wall thickness, and the average value of the 20 microcapsules is calculated to determine the wall thickness of the microcapsule.

[0057] If the average particle size of the microcapsules is Dm (unit: μm) and the thickness of the capsule wall of the microcapsules is δ (unit: μm), the ratio of the capsule wall thickness of the microcapsules to the average particle size of the microcapsules (δ / Dm) is preferably 0.300 or less, more preferably 0.200 or less, and even more preferably 0.100 or less. The lower limit of δ / Dm is preferably 0.001 or more, more preferably 0.005 or more, and even more preferably 0.010 or more, in terms of maintaining the strength of the microcapsules.

[0058] The glass transition temperature of the capsule wall of the microcapsule is not particularly limited, but it is preferably 150° C. or higher, or the capsule wall does not exhibit a glass transition temperature. In other words, it is preferable that the glass transition temperature of the material constituting the capsule wall of the microcapsule is 150° C. or higher, or the material constituting the capsule wall of the microcapsule does not exhibit a glass transition temperature. When the capsule wall of the microcapsule exhibits a glass transition temperature, the temperature is preferably 160° C. or higher, more preferably 180° C. or higher, and even more preferably 200° C. or higher, in terms of better heat resistance. When the capsule wall of the microcapsule exhibits a glass transition temperature, the upper limit of the temperature is not particularly limited, but is often equal to or lower than the thermal decomposition temperature of the capsule wall of the microcapsule, and is generally equal to or lower than 250° C. In particular, it is preferable that the capsule wall of the microcapsule does not exhibit a glass transition temperature, in terms of superior heat resistance.

[0059] In addition, the capsule wall of the microcapsule does not exhibit a glass transition temperature means that the capsule wall of the microcapsule (the material constituting the capsule wall of the microcapsule) does not exhibit a glass transition temperature between 25°C and a temperature obtained by subtracting 5°C from the thermal decomposition temperature of the capsule wall described below (thermal decomposition temperature - 5°C). In other words, it means that the glass transition temperature is not exhibited in the range from "25°C" to "(thermal decomposition temperature (°C) - 5°C)". The glass transition temperature of the capsule wall of the microcapsule is 150° C. or higher, or the method for making the capsule wall not show a glass transition temperature is not particularly limited, and can be adjusted by appropriately selecting the raw materials when manufacturing the microcapsule. For example, since polyurea has a property of showing a high glass transition temperature, a method of forming the capsule wall from polyurea can be exemplified. Another method is to increase the crosslink density in the material forming the capsule wall. Another method is to introduce an aromatic ring group (e.g., a benzene ring group) into the material forming the capsule wall.

[0060] The glass transition temperature of the capsule wall of the microcapsule can be measured by the following method. Ethyl acetate is added to the microcapsules and stirred at 25°C for 24 hours. The resulting solution is then filtered, and the resulting residue is vacuum-dried at 60°C for 48 hours to obtain microcapsules that contain nothing inside (hereinafter simply referred to as "measurement material"). In other words, the capsule wall material of the microcapsules, which is the subject of glass transition temperature measurement, is obtained. Next, the thermal decomposition temperature of the obtained measurement material is measured using a thermogravimetric differential thermal analyzer TG-DTA (apparatus name: DTG-60, Shimadzu Corporation). Note that the thermal decomposition temperature is the temperature (°C) at which the measurement material is heated from room temperature at a constant heating rate (10°C / min) in a thermogravimetric analysis (TGA) in an air atmosphere, and the mass of the measurement material before heating is reduced by 5% by mass. Next, the glass transition temperature of the measurement material is measured using a differential scanning calorimeter DSC (apparatus name: DSC-60a Plus, Shimadzu Corporation) in a sealed pan at a heating rate of 5°C / min in the range of 25°C to (thermal decomposition temperature (°C) - 5°C). The glass transition temperature of the capsule wall of the microcapsule is the value at the second heating cycle.

[0061] The thermal decomposition temperature of the capsule wall of the microcapsule is not particularly limited, but is preferably 200° C. or higher, more preferably 220° C. or higher, and even more preferably 230° C. or higher, in terms of superior heat resistance. The thermal decomposition temperature of the capsule wall means the temperature at which the capsule wall loses 5% by mass. The measurement method may be a method using a thermogravimetric differential thermal analyzer TG-DTA (apparatus name: DTG-60, Shimadzu Corporation) used when measuring the above-mentioned glass transition temperature.

[0062] The content of the microcapsules in the resin pellets is not particularly limited, and is adjusted so that the content of the heat storage material falls within the above-mentioned range. More specifically, the content of the microcapsules is preferably 10 to 85 mass% relative to the total mass of the resin pellets, more preferably 20 to 80 mass%, further preferably 25 to 75 mass%, and particularly preferably 35 to 65 mass%, in terms of better effects of the present invention and better heat storage properties of the resin pellets. The greater the amount of microcapsules in the resin pellets, the better the heat storage capacity, and the smaller the amount of microcapsules, the better the tensile breaking strength of the molded article obtained using the resin pellets.

[0063] (Method of manufacturing microcapsules) The method for producing the microcapsules is not particularly limited, and any known method can be used. For example, there is an interfacial polymerization method including a step of dispersing an oil phase containing a heat storage material and a capsule wall material in an aqueous phase containing an emulsifier to prepare an emulsion (emulsification step), and a step of polymerizing the capsule wall material at the interface between the oil phase and the aqueous phase to form a capsule wall and thus form a microcapsule (encapsulation step). The capsule wall material means a material capable of forming a capsule wall. Each step of the interfacial polymerization method will be described in detail below.

[0064] In the emulsification step of the interfacial polymerization method, an oil phase containing a heat storage material and a capsule wall material is dispersed in an aqueous phase containing an emulsifier to prepare an emulsion. The capsule wall material contains at least a polyisocyanate and at least one compound selected from a polyol and a polyamine. The emulsion is formed by dispersing an oil phase containing the heat storage material and the capsule wall material in an aqueous phase containing an emulsifier. The oil phase contains at least a heat storage material and a capsule wall material, and may further contain other components such as a solvent and / or an additive, if necessary. As the solvent that may be contained in the oil phase, a water-insoluble organic solvent is preferable from the viewpoint of excellent dispersion stability, and ethyl acetate, methyl ethyl ketone, or toluene is more preferable. The aqueous phase can include at least an aqueous medium and an emulsifier. Examples of the aqueous medium include water and a mixed solvent of water and a water-soluble organic solvent, and water is preferred. "Water-soluble" means that the amount of the target substance dissolved in 100% by mass of water at 25°C is 5% by mass or more. The content of the aqueous medium is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass, based on the total mass of the emulsion which is a mixture of the oil phase and the aqueous phase.

[0065] Emulsifiers include dispersants, surfactants, and combinations thereof. As the dispersant, any known dispersant can be used, and polyvinyl alcohol is preferred. The surfactant may be a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant. The surfactant may be used alone or in combination of two or more kinds. The content of the emulsifier is preferably more than 0% by mass and not more than 20% by mass, more preferably 0.005 to 10% by mass, even more preferably 0.01 to 10% by mass, and particularly preferably 1 to 5% by mass, relative to the total mass of the emulsion which is a mixture of the oil phase and the aqueous phase. The aqueous phase may contain other ingredients, such as UV absorbers, antioxidants, and preservatives, as necessary.

[0066] Dispersion refers to dispersing an oil phase as oil droplets in an aqueous phase (emulsification). Dispersion can be performed using a means commonly used for dispersing an oil phase and an aqueous phase (e.g., a homogenizer, a Manton Gauley, an ultrasonic disperser, a dissolver, a Keddy Mill, and other known dispersing devices).

[0067] The mixing ratio of the oil phase to the aqueous phase (oil phase mass / aqueous phase mass) is preferably from 0.1 to 1.5, more preferably from 0.2 to 1.2, and even more preferably from 0.4 to 1.0.

[0068] In the encapsulation process, the capsule wall material is polymerized at the interface between the oil phase and the aqueous phase to form the capsule wall, forming the microcapsules.

[0069] The polymerization is preferably carried out under heating. The reaction temperature in the polymerization is preferably 40 to 100° C., more preferably 50 to 80° C. The reaction time in the polymerization is preferably about 0.5 to 10 hours, more preferably about 1 to 5 hours.

[0070] In order to prevent aggregation of the microcapsules during polymerization, it is preferable to further add an aqueous solution (for example, water, an aqueous acetic acid solution, etc.) to reduce the probability of collision between the microcapsules. It is also preferable to carry out sufficient stirring. Furthermore, a dispersant for preventing aggregation may be added to the reaction system during polymerization. Furthermore, if necessary, a charge control agent such as nigrosine or any other auxiliary agent may be added to the reaction system during polymerization.

[0071] <Thermoplastic resin> The resin contained in the resin pellets is not particularly limited, and examples thereof include known thermoplastic resins. Examples of thermoplastic resins include AS (acrylonitrile styrene) resin, ABS (acrylonitrile butadiene styrene) resin, polyethylene resin, polyester resin (polyether ester elastomer, etc.), polypropylene resin, ethylene-propylene copolymer, polyvinylidene chloride, polyamide, acetal resin, polycarbonate resin, polyphenylene sulfide resin, polyetherimide resin, aromatic polyether ketone resin, polysulfone resin, fluororesin (polyvinylidene fluoride, etc.), polyamideimide resin, and acrylic resin. Among them, polypropylene resin, polyethylene resin, ABS (acrylonitrile butadiene styrene) resin, or polyester resin is preferred.

[0072] The melting point of the thermoplastic resin is not particularly limited, but is preferably 110° C. or higher, more preferably 130° C. or higher, in order to provide a molded article with better heat resistance. The upper limit is not particularly limited, but is preferably 300° C. or lower, more preferably 250° C. or lower, in order to provide a molded article with better moldability. The melting point of a thermoplastic resin can be measured by a differential scanning calorimeter (DSC) or the like.

[0073] As the thermoplastic resin, a water-insoluble resin is preferred in terms of achieving the effects of the present invention. The term "water-insoluble" in the context of a water-insoluble resin means that the amount of the target substance dissolved in 100% by mass of water at 25°C is less than 5% by mass.

[0074] The content of the thermoplastic resin in the resin pellets is not particularly limited, and is adjusted so that the content of the heat storage material falls within the above-mentioned range. More specifically, the content of the thermoplastic resin is preferably 15 to 85 mass% relative to the total mass of the resin pellets, more preferably 20 to 80 mass%, further preferably 20 to 75 mass%, and particularly preferably 35 to 65 mass%, in terms of better effects of the present invention and better heat storage properties of the resin pellets. The higher the content of the thermoplastic resin in the resin pellets, the better the tensile breaking strength of the molded product obtained using the resin pellets, and the lower the content, the better the heat storage capacity.

[0075] <Other ingredients> The resin pellets may contain components other than the above-mentioned microcapsules and thermoplastic resin. Examples of other components include fillers, stabilizers, oxidation / reduction agents, molding aids, decomposition inhibitors, lubricants, release agents, colorants such as pigments, dispersants, and plasticizers. The filler is not particularly limited, and examples thereof include inorganic fillers composed of glass, silica, wollastonite, aluminum hydroxide, kaolin, titanium oxide, alumina, mica, talc, carbon, potassium titanate, etc., and metal fillers composed of copper, etc. The filler may be in the form of particles, fibers, or whiskers.

[0076] <Resin pellets> The resin pellets contain the above-mentioned microcapsules and a thermoplastic resin. The shape of the resin pellets is not particularly limited, and the size thereof is also not particularly limited. The resin pellets are preferably in the form of a cylinder or prism, more preferably a cylinder, and more preferably have a cylindrical shape, for example, a height of 0.01 to 100 mm (preferably 0.05 to 10 mm) and a diameter of 0.01 to 50 mm (preferably 0.05 to 30 mm). The heat storage capacity of the resin pellets is preferably high, more preferably 40 J / g or more, more preferably 50 J / g or more, and even more preferably 70 J / g or more. There is no particular upper limit, but it is often 300 J / g or less. The amount of heat storage can be measured by differential scanning calorimetry (DSC). The tensile breaking strength of the resin pellets preferably exhibits a value close to the inherent tensile breaking strength of the thermoplastic resin, and the difference between the tensile breaking strength of the resin pellets and the tensile breaking strength of the thermoplastic resin contained in the resin pellets is preferably 0 to 20 MPa or less, more preferably 0 to less than 10 MPa, and even more preferably 0 to less than 5 MPa.

[0077] <Method of manufacturing resin pellets> The method for producing the resin pellets is not particularly limited, and known methods can be used. For example, there is a method in which the microcapsules and the resin are melt-kneaded in an extruder, and the strands extruded from the extruder are cut to form pellets. It is preferable to handle the microcapsules as powder. For example, the method of obtaining the microcapsule powder includes removing the solvent from the dispersion of the microcapsules obtained by the above-mentioned interfacial polymerization method to obtain the microcapsule powder. For example, the method of removing the solvent includes using a spray dryer to obtain the microcapsule powder from the dispersion of the microcapsules.

[0078] Among these, a method in which a thermoplastic resin is melt-kneaded in an extruder, microcapsules are added to the molten thermoplastic resin in the extruder and further melt-kneaded, and the strands extruded from the extruder are cut to produce resin pellets is preferred, since this method can further suppress the destruction of microcapsules during melt-kneading. The above-mentioned method can be carried out by using an extruder equipped with a plurality of raw material supply ports. For example, a thermoplastic resin is supplied to an extruder equipped with a plurality of raw material supply ports, melt-kneaded, and a microcapsule is supplied to the extruder from a raw material supply port located downstream of the raw material supply port that supplied the thermoplastic resin, and further melt-kneaded, and the strand extruded from the extruder is cut to produce resin pellets. The above method corresponds to a method of side-feeding the microcapsules into an extrusion molding machine and mixing them with a softened thermoplastic resin. Side-feeding is a method in which a feeder for supplying the microcapsules is installed separately from a feeder for supplying the thermoplastic resin, and the microcapsules are added to the thermoplastic resin that has been kneaded in advance in the extruder.

[0079] As the extruder, a known device can be used, and examples thereof include a known extruder (for example, a twin-screw extruder).

[0080] <Molded products> A molded article can be obtained by molding the resin pellets of the present invention. The molded article contains microcapsules and a thermoplastic resin.

[0081] The molding method using the resin pellets is not particularly limited, and any known molding method can be used, such as extrusion molding, injection molding, blow molding, compression molding, press molding, and molding with a 3D printer.

[0082] Examples of molded articles that can be produced using the resin pellets of the present invention include automobile parts, electronic device parts, and fibers (clothing). Examples of automotive parts include engine covers, battery cases, heat exchangers, interior parts, and vehicle intake system piping. Examples of electronic device parts include housings and battery cases. EXAMPLES

[0083] The features of the present invention will be described in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below.

[0084] <Example 1> As a heat storage material, 100 parts by mass of eicosane (manufactured by Sasol) was dissolved in 120 parts by mass of ethyl acetate to obtain solution A. Furthermore, 25 parts by mass of trimethylolpropane adduct of tolylene diisocyanate (Burnoc D-750, containing 25% ethyl acetate, manufactured by DIC) was added to the stirred solution A to obtain solution B. Then, 170 parts by mass of a 3% by mass aqueous solution of polyvinyl alcohol (Kuraray Poval KL-318, manufactured by Kuraray) was added to the above solution B to emulsify and disperse. 300 parts by mass of water was added to the emulsion after emulsification and dispersion, and the mixture was heated to 70°C while stirring, stirred for 1 hour, and then cooled. Furthermore, water was added to the obtained solution to adjust the concentration, and a heat storage material-encapsulated microcapsule liquid with a solid content concentration of 20% was obtained. The capsule walls of the microcapsules comprised polyurethaneurea. The average particle size of the obtained microcapsules was 5 μm. As shown in the structural formula below, the above-mentioned Burnock D-750 corresponds to a trifunctional polyisocyanate that is an adduct of an aromatic diisocyanate and trimethylolpropane.

[0085] [ka]

[0086] Next, the liquid of the heat storage material-encapsulating microcapsules prepared above was powdered using a spray dryer (Mini Spray Dryer B-290, manufactured by Buchi) to obtain a powder of the heat storage material-encapsulating microcapsules.

[0087] Using a twin-screw extruder (2D25S) equipped with a first raw material supply port arranged on the upstream side and a second raw material supply port arranged on the downstream side, 100 parts by mass of polypropylene resin (Novatec PP MA-3, manufactured by Japan Polypropylene Corporation) was fed into the twin-screw extruder as a thermoplastic resin from the first raw material supply port under a melting temperature condition of 200°C, and the polypropylene resin was melted. At that time, 100 parts by mass of the powder of the heat storage material-containing microcapsules was fed into the twin-screw extruder from the second raw material supply port, and the powder of the heat storage material-containing microcapsules was fed into the melt of the thermoplastic resin. The melt obtained in the twin-screw extruder was extruded from a die to form strands, and the strands were cut to form pellets, producing cylindrical resin pellets (diameter 3 mm x height 3 mm). The resin pellets were used to produce a molded plate material having dimensions of 150 mm length x 50 mm width x 1 mm thickness by injection molding.

[0088] <Examples 2 to 25> As shown in Table 1 below, the resin pellets and plate materials were produced according to the same procedure as in Example 1, except that the types and amounts of polyisocyanate A, polyisocyanate B, heat storage material, and resin used, as well as the properties of the microcapsules (particle size, wall thickness, δ / D, glass transition temperature, and thermal decomposition temperature) were changed. In Examples 2 to 25, polyisocyanate A and polyisocyanate B were used in a predetermined mass ratio instead of Burnock D-750 used in Example 1. The total mass of polyisocyanate A and polyisocyanate B was the same as the amount of Burnock D750 used in Example 1.

[0089] <Comparative Example 1> Resin pellets were produced according to the procedure of Example 1 of Patent Document 1. Using the produced resin pellets, a plate material was produced according to the same procedure as in Example 1. The capsule walls of the microcapsules used in Comparative Example 1 were made of melamine resin.

[0090] <Comparative Example 2> Resin pellets were produced according to the procedure of Example 6 of JP 2019-218518 A. Using the produced resin pellets, a plate material was produced according to the same procedure as in Example 1. In Comparative Example 2, a porous body (silica) was used as the heat storage material particles.

[0091] <Comparative Example 3> Except for changing the heat storage material used to paraffin (eicosane), resin pellets were produced according to the procedure of Example 10 of Patent Document 2. Using the produced resin pellets, a plate material was produced according to the same procedure as in Example 1. In Comparative Example 3, the content of the heat storage material was 74 mass % with respect to the total mass of the resin pellets.

[0092] In Table 1, "D-120N" represents Takenate D-120N. Takenate D-120N corresponds to a trifunctional polyisocyanate that is an adduct of an alicyclic diisocyanate and trimethylolpropane, as shown in the following structural formula.

[0093] [ka]

[0094] In Table 1, "MR-100" represents Millionate MR-100, "MR-200" represents Millionate MR-200, and "MR-400" represents Millionate MR-400. Millionate MR-100, Millionate MR-200, and Millionate M-400 are all mixtures of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate (corresponding to the compound represented by formula (X)). In Table 1, the column "mass ratio (A / B)" indicates the ratio of the mass of polyisocyanate A to the mass of polyisocyanate B. In Table 1, the column "Amount (relative to capsule) [mass %]" in the "Heat storage material" column indicates the content (mass %) of the heat storage material relative to the total mass of the microcapsule. In Table 1, the column "Particle size (μm)" indicates the average particle size (μm) of the microcapsules. In Table 1, the "Wall Thickness" column indicates the wall thickness of the microcapsules. In Table 1, the column "Inner diameter (μm)" indicates the average inner diameter (μm) of the microcapsules. In Table 1, the column "δ / D" indicates the ratio of δ, which is the number average wall thickness (μm) of the microcapsules, to D, which is the average particle size (μm) of the microcapsules. In Table 1, the column "Thermal decomposition temperature [°C]" indicates the thermal decomposition temperature (°C) of the capsule wall of the microcapsule. In Table 1, the "Type" column in the "Resin" column indicates the type of thermoplastic resin. In Table 1, the "Amount [mass %]" column in the "Resin" column indicates the content (mass %) of the thermoplastic resin relative to the total mass of the resin pellet. In Table 1, the column "Amount of heat storage material (relative to resin pellets) [mass %]" indicates the content (mass %) of the heat storage material relative to the total mass of the resin pellets. In Table 1, "PP" in the "Resin" column stands for Novatec PP MA-3 (manufactured by Japan Polypropylene, melting point 170°C, polypropylene resin), "PE" stands for Novatec HD HJ360 (melting point 132°C, polyethylene resin), "ABS" stands for Toyolac 600-309 (manufactured by Toray Industries, melting point 130-150°C, ABS resin), "Elastomer" stands for Hytrel 3046 (manufactured by DuPont, melting point 160°C, polyether ester resin), and "PVA" stands for polyvinyl alcohol. In addition, polypropylene, polyethylene, ABS resin, and polyether ester resin are classified as water-insoluble resins.

[0095] <Evaluation> (heat storage amount) The resin pellets produced in the examples and comparative examples were subjected to heat storage measurement using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Corporation).

[0096] (Heat resistance (bleed out)) The plate materials produced in the examples and comparative examples were treated at 80° C. for 4 hours, and then visually inspected for bleeding (leaking) and rated according to the following criteria. A: No bleeding was observed. B: Slight bleeding was observed. C: Bleeding was clearly observed.

[0097] (Tensile breaking strength) The tensile breaking strength of each of the plate materials produced in the examples and comparative examples was measured in accordance with JIS K7161. In addition, comparative plates, which were molded products having dimensions of 150 mm length x 50 mm width x 1 mm thickness, were produced by injection molding using the resins used in each of the examples and comparative examples. The tensile breaking strength of each comparative plate was measured according to JIS K7161. The tensile breaking strength of the plate materials produced in each Example and Comparative Example was compared with the tensile breaking strength of the comparative plate materials corresponding to each Example and Comparative Example, and the difference between the two was determined and evaluated according to the following criteria. A: Less than 5MPa B: 5MPa or more, less than 10MPa C: 10MPa or more

[0098] [Table 1]

[0099] As shown in Table 1, it was confirmed that the resin pellets of the present invention exhibited the desired effects. By comparing Example 1 with the other Examples, it was confirmed that the effect was superior when the resin had a polymethylene polyphenyl structure. From a comparison of Examples 2 to 6, it was confirmed that a more excellent effect was obtained when the mass ratio A / B was 90 / 10 to 30 / 70 (preferably 85 / 15 to 40 / 60). A comparison between Example 4 and Example 7 confirmed that the effect was superior when an aromatic diisocyanate was used. A comparison of Examples 16 to 19 confirmed that a more excellent effect was achieved when the capsule wall thickness of the microcapsules was 0.10 to 5.0 μm. From the results of Example 15, it was confirmed that when δ / D is 0.100 or less, the effect is more excellent. From the results of Example 23, it was confirmed that when the content of the thermoplastic resin relative to the total mass of the resin pellets was 35 mass % or more, the tensile elastic strength was superior. From the results of Example 25, it was confirmed that when the content of the heat storage material relative to the total mass of the resin pellets is 20 mass % or more, excellent heat storage properties are obtained. [Explanation of symbols]

[0100] 10 Microcapsules 10a Capsule wall 10b Inclusions 12 Thermoplastic resin 13 Resin pellets

Claims

1. A resin pellet including a microcapsule containing a heat storage material and a thermoplastic resin, The content of the heat storage material is 70% by mass or less with respect to the total mass of the resin pellets, a capsule wall of the microcapsule contains at least one resin selected from the group consisting of polyurethane urea, polyurethane, and polyurea, which is obtained by reacting an aromatic or alicyclic diisocyanate, a compound having three or more active hydrogen groups in one molecule, and polymethylene polyphenyl polyisocyanate; The resin pellets, wherein the capsule wall of the microcapsules has a thickness of 0.10 to 5.0 μm.

2. The resin pellet according to claim 1 , wherein the capsule wall of the microcapsule comprises the polyurethaneurea.

3. The resin pellet according to claim 1 or 2, wherein a total content of the microcapsules and the thermoplastic resin is more than 90 mass% with respect to a total mass of the resin pellet.

4. The resin pellet according to any one of claims 1 to 3, wherein the resin contained in the capsule wall of the microcapsule has a structure represented by formula (Y). 【Chemistry 1】 n represents an integer of 1 or more.

5. The resin pellet according to any one of claims 1 to 4, wherein the compound having three or more active hydrogen groups in one molecule is a polyol having a molecular weight of 500 or less.

6. The resin contained in the capsule wall of the microcapsule is The polyisocyanate is formed using a polyisocyanate A having three or more functional groups, which is an adduct of the aromatic or alicyclic diisocyanate and the compound having three or more active hydrogen groups in one molecule, and a polyisocyanate B, The resin pellet according to any one of claims 1 to 4, wherein the polyisocyanate B is a polymethylene polyphenyl polyisocyanate or a mixture of an aromatic diisocyanate and the polymethylene polyphenyl polyisocyanate.

7. The resin pellet according to any one of claims 1 to 6, wherein the thermal decomposition temperature of the capsule wall of the microcapsule is 200°C or higher.

8. The resin pellet according to any one of claims 1 to 7, wherein the average inner diameter of the microcapsules is 200 µm or less.

9. The resin pellet according to any one of claims 1 to 8, wherein the melting point of the thermoplastic resin is 110°C or higher.

10. The resin pellet according to any one of claims 1 to 9, wherein the thermoplastic resin is a water-insoluble resin.

11. A method for producing resin pellets according to any one of claims 1 to 10, A method for producing resin pellets, comprising melting and kneading the thermoplastic resin in an extruder, adding the microcapsules to the molten thermoplastic resin in the extruder and further melt-kneading the mixture, and cutting the strands extruded from the extruder to produce resin pellets.

12. A molded product obtained by molding the resin pellets according to any one of claims 1 to 10.

13. An automobile part molded using the resin pellet according to any one of claims 1 to 10.

14. A part for electronic equipment molded using the resin pellet according to any one of claims 1 to 10.

15. A fiber formed using the resin pellet according to any one of claims 1 to 10.

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