Heat accumulating composition

Abstract

A heat-accumulating composition comprising a substance A and a polymer 2, the heat-accumulating composition having a melting peak temperature between 10 and 60°C and a melting enthalpy between 10 and 60°C of 30 J / g or more, the heat-accumulating composition not having an island-in-sea structure, or the heat-accumulating composition having an island-in-sea structure, the volume average equivalent circle particle diameter of the islands (dispersed phase) being 1.5 μm or less or the area ratio of the islands (dispersed phase) being 15% or less.

Description

Technical Field

[0001] This invention relates to heat storage compositions. Background Technology

[0002] With the increasing desire for comfort, fiber products and building materials using various thermally functional raw materials have been developed.

[0003] Patent document 1 describes a heat storage material made by mixing a phase change material obtained by reacting an ethylene-methyl acrylate copolymer with n-eicosanol with polypropylene.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-188752 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, improvements in heat storage materials are required from the perspectives of heat storage properties, spinnability, tensile strength, and fiber hand feel. Therefore, the purpose of this application is to provide novel compositions and fibers with excellent heat storage properties.

[0009] Methods for solving problems

[0010] This invention relates to the following, but is not limited thereto.

[0011] [Invention 1]

[0012] A heat storage composition comprising substance A and polymer 2,

[0013] The above-mentioned heat storage composition has a melting peak temperature between 10 and 60°C, and has a melting enthalpy of 30 J / g or higher between 10 and 60°C.

[0014] The above-mentioned heat storage composition does not have an island structure, or the above-mentioned heat storage composition has an island structure, wherein the volume average equivalent spherical particle size of the island (dispersed phase) is less than 1.5 μm or the area fraction of the island (dispersed phase) is less than 15%.

[0015] [Invention 2]

[0016] The heat storage composition according to invention 1 has a plurality of melting peak temperatures, at least one of which is in the range of 60 to 120°C.

[0017] [Invention 3]

[0018] The heat storage composition according to any one of inventions 1 or 2 has a gel fraction of less than 15% by weight.

[0019] [Invention 4]

[0020] The heat storage composition according to any one of inventions 1 to 3, wherein substance A has a molecular weight of more than 2000.

[0021] [Invention 5]

[0022] A fiber comprising the heat-storing composition described in any one of inventions 1 to 4.

[0023] [Invention 6]

[0024] A heat-storing fiber comprising a heat-storing composition containing substance A and polymer 2.

[0025] The aforementioned fibers have a melting peak temperature between 10 and 60°C, and a melting enthalpy of 5 J / g or higher between 10 and 60°C.

[0026] The heat storage composition of the above-mentioned fibers does not have an island structure, or the heat storage composition of the above-mentioned fibers has an island structure, wherein the equivalent spherical particle size of the island (dispersed phase) is less than 0.1 μm or the area fraction of the island (dispersed phase) is less than 15%.

[0027] [Invention 7]

[0028] The heat-storing fiber according to invention 6 has multiple melting peak temperatures, at least one of which is in the range of 60 to 120°C.

[0029] [Invention 8]

[0030] According to invention 6 or 7, the heat-storing fiber has a gel fraction of less than 15% by weight in the heat-storing composition within the fiber.

[0031] [Invention 9]

[0032] The heat-storing fiber according to any one of inventions 6 to 8, wherein substance A has a molecular weight of more than 2000.

[0033] Invention Effects

[0034] The compositions of the present invention exhibit excellent heat retention. In one embodiment, the compositions of the present invention exhibit excellent shape retention. In another embodiment, the compositions of the present invention exhibit excellent formability and processability. In yet another embodiment, the fibers of the present invention exhibit excellent spinnability, stretchability, and a pleasant hand feel. Detailed Implementation

[0035] definition

[0036] All figures disclosed in this specification are approximate values, whether or not they are used in conjunction with the words “about” or “approximately”. They can vary between 1%, 2%, 5%, or sometimes 10% to 20%. Whenever a lower limit R is disclosed...L and upper limit R U When considering a numerical range, any numbers within that range are specifically disclosed. In particular, the following numbers within that range are specifically disclosed: R = R L +k ＊ (R U -R L (In the formula, k is a variable ranging from 1% to 100% in increments of 1%, that is, k is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99%, or 100%). Furthermore, arbitrary numerical ranges defined by the two R numbers described above are specifically disclosed.

[0037] The notation "lower limit ~ upper limit" indicates "above the lower limit and below the upper limit," while the notation "upper limit ~ lower limit" indicates "below the upper limit and above the lower limit." In other words, these notations represent a numerical range that includes both the lower and upper limits.

[0038] gel fraction

[0039] The gel fraction (wt%) was obtained through the following steps.

[0040] Weigh approximately 500 mg of the test sample (a cross-linked polymer or a composition containing it) and an empty wire mesh cage (mesh size: 400 mesh). Seal the wire mesh cage containing the test sample and 50 mL of xylene (in the examples, Kanto Chemical Co., Ltd.'s premium grade xylene (a mixture of o-xylene, m-xylene, p-xylene, and ethylbenzene, with a total weight of o-xylene, m-xylene, and p-xylene of 85% by weight or more) into a 100 mL test tube and perform heat extraction at 110°C for 6 hours.

[0041] After extraction, the mesh cage containing the extraction residue was removed from the test tube and dried under reduced pressure at 80°C for 3 hours using a vacuum dryer. The dried mesh cage containing the extraction residue was then weighed. The gel weight was calculated based on the weight difference between the dried mesh cage containing the extraction residue and the empty mesh cage. The gel fraction (wt%) was calculated based on the following formula.

[0042] Gel fraction = (gel weight / sample weight) × 100

[0043] Melting peak temperature

[0044] The melting peak temperature Tm (°C) is obtained through the following steps.

[0045] Using a differential scanning calorimeter (TA Instruments, DSC Q100 used in this example), measurements were performed on an aluminum disk containing the sample under a nitrogen atmosphere and any of the following measurement conditions.

[0046] Measurement conditions 1:

[0047] An aluminum disk containing approximately 10 mg of sample (1) was kept at 200°C for 5 minutes. Then (2) it was cooled from 200°C to -80°C at a rate of 5°C / minute. Then (3) it was kept at -80°C for 10 minutes. Then (4) it was heated from -80°C to approximately 200°C at a rate of 5°C / minute.

[0048] Measurement condition 2:

[0049] An aluminum disk containing approximately 5 mg of sample (1) was kept at 200°C for 5 minutes. Then (2) it was cooled from 200°C to -80°C at a rate of 5°C / minute. Then (3) it was kept at -80°C for 10 minutes. Then (4) it was heated from -80°C to approximately 200°C at a rate of 5°C / minute.

[0050] Measurement condition 3:

[0051] An aluminum disk containing approximately 10 mg of sample (1) was kept at 150°C for 5 minutes, then (2) cooled from 150°C to -80°C at a rate of 5°C / minute, then (3) kept at -80°C for 10 minutes, and then (4) heated from -80°C to approximately 150°C at a rate of 5°C / minute.

[0052] Measurement condition 4:

[0053] An aluminum disk containing approximately 5 mg of sample (1) was kept at 150°C for 5 minutes. Then (2) it was cooled from 150°C to -80°C at a rate of 5°C / minute. Then (3) it was kept at -80°C for 10 minutes. Then (4) it was heated from -80°C to approximately 150°C at a rate of 5°C / minute.

[0054] Measurement condition 5:

[0055] An aluminum disk containing approximately 5 mg of sample (1) was kept at 150°C for 5 minutes. Then (2) it was cooled from 150°C to -50°C at a rate of 5°C / minute. Then (3) it was kept at -50°C for 5 minutes. Then (4) it was heated from -50°C to approximately 150°C at a rate of 5°C / minute.

[0056] The differential scanning calorimetry curve obtained by heat measurement in process (4) is used as the melting curve. The melting curve is analyzed according to the method of JIS K7121-1987 to obtain the melting peak temperature at which the melting heat absorption reaches its maximum.

[0057] The glass transition temperature (midpoint glass transition temperature) was obtained by analyzing the melting curve measured according to the differential scanning calorimetry method described above, based on the method of JIS K7121-1987.

[0058] enthalpy of fusion

[0059] The enthalpy of fusion ΔH (J / g) was obtained by analyzing a portion of the above melting curve within the temperature range of 10–60 °C or 60–120 °C according to the method in JIS K7122-1987.

[0060] It should be noted that, regarding the multilayer heat storage composition in the examples, the composition after being mixed using a mixer (DSM Xplore) or a 20mmφ single screw extruder at 200°C will be used as the sample.

[0061] Number of melting peaks between 60 and 120°C

[0062] The number of melting peaks between 60 and 120 °C is obtained by analyzing the number of temperatures exhibiting maximum values ​​in the 60–120 °C range of the differential scanning calorimetry curve with the endothermic direction as positive. However, the intensity of the first peak observed between 10 and 60 °C, which is less than 1% of the area, is considered noise and not a peak.

[0063] Equivalent spherical diameter and volume average equivalent spherical diameter of the dispersed phase

[0064] The equivalent spherical particle size Di (μm) and volume-average equivalent spherical particle size Dv (μm) of the dispersed phase (islands in the island structure) contained in the compositions and fibers of the present invention are obtained by the following steps.

[0065] The heat storage compositions of the embodiments or comparative examples of the present invention were cut using a slicer at -70°C. After staining with ruthenium tetroxide vapor at room temperature for about 3 days, ultrathin sections with a thickness of about 1300 angstroms were prepared using a diamond scalpel at -70°C. It should be noted that, for the multilayer heat storage compositions in the embodiments (Examples A1 to A3 and Comparative Examples C1 to C2), the compositions after being mixed using a mixer (DSM Xplore) at 200°C for 5 minutes were used as samples.

[0066] Using a transmission electron microscope (JEM-2100F manufactured by Nippon Electron Ltd. in these examples), the ultrathin sections of Examples A1-A6 and Comparative Examples C1-C4 were observed at a magnification of 15,000x, while those of Examples B1-B4 and Comparative Example D1 were observed at a magnification of 60,000x. It should be noted that, regarding the heat-storing compositions in the examples (Examples A1-A6 and Comparative Examples C1-C4), any surface of the compound was observed. Regarding the fibers (Examples B1-B4 and Comparative Example D1), the radial cross-section of the fibers was observed. Using a transmission electron microscope, the diameter (equivalent spherical diameter) and volume-average equivalent spherical diameter of the dispersed phase were determined by performing the image analysis processing shown below on the digital images taken by a CCD camera at magnifications of 15,000x or 60,000x.

[0067] Image analysis and processing

[0068] Digital images (8-bit) obtained from a transmission electron microscope were read into a computer. Using image analysis software (Asahi Engineering Co., Ltd.'s A-Image Software was used in this example), island phases were identified visually based on the intensity of staining. The resolving area of ​​one field of view at 15,000x magnification was approximately 58–73 μm. 2 The range is approximately 4–5 μm at a magnification of 60,000. 2 The range is calculated using the average value of two or three fields of view. The shape of the dispersed phase is amorphous, so the diameter of the circle (equivalent spherical diameter Di (μm)) is determined, and the volume average equivalent spherical diameter Dv (μm) is calculated according to the following formula.

[0069] [Mathematical Expression 1]

[0070]

[0071] In the formula, i is an integer from 1 to n, and Di is the equivalent spherical particle size of each particle (each dispersed phase).

[0072] Area ratio of dispersed phase

[0073] The area fraction (%) of the dispersed phase is calculated based on the following formula.

[0074] Area ratio (%) = (Total area of ​​dispersed phase / Area of ​​analysis) × 100

[0075] It should be noted that dispersed phases with different staining concentrations are analyzed as different components.

[0076] Melt flow (g / 10 min)

[0077] Melt flow rate (MFR) shall be determined according to the method specified in JIS-K-7210. Unless otherwise specified, the determination shall be performed at a test temperature of 230°C and a load of 2.16 kg.

[0078] Shear viscosity (Pa·sec)

[0079] Using the heat storage composition of the embodiments or comparative examples of the present invention, a capillary tube with a diameter of 1 mm, a length of 40 mm, and an inflow angle of 90° was installed on a CAPILOGRAPH 1B (in the examples, a product manufactured by Toyo Seiki Co., Ltd. was used (cylinder diameter: 9.55 mm)). The measurement was conducted at a temperature of 270°C and a shear rate of 1.216 × 10⁻⁶. 3 sec -1 The shear viscosity was measured.

[0080] Elongation at break (%)

[0081] According to JIS L1013:2010, tensile tests were performed on unstretched or stretched yarns under the following conditions, and the elongation at break was measured three times in total, and the average value was taken. The higher the value of the elongation at break, the better the tensile properties (stretchability).

[0082] Measurement temperature: room temperature 23℃

[0083] Stretching speed: 10mm / minute

[0084] Clamping interval: 10mm

[0085] Spinning properties

[0086] Three testers evaluated the spinnability of the sample by spinning it with a spinning device to reach a consensus (good or broken yarn).

[0087] Softness

[0088] The following method was used to evaluate the softness (softness or hardness) of the sample by 5 testers to determine a consensus (soft or hard).

[0089] Method: Place your hand into 500g of the prepared short fibers, and the tester gently holds it to determine the softness.

[0090] The following describes several embodiments of the present invention in detail. However, the present invention is not limited to the following embodiments.

[0091] Heat storage composition E

[0092] The heat storage composition of the present invention (hereinafter, sometimes also referred to as "heat storage composition E") comprises substance A (sometimes also referred to as "phase change substance A") described later and polymer 2 (sometimes also referred to as "base resin") described later.

[0093] The heat storage composition E has a melting peak temperature between 10 and 60 °C and a melting enthalpy of more than 30 J / g between 10 and 60 °C.

[0094] The heat storage composition E does not have an island structure, or has an island structure, wherein the volume average equivalent spherical particle size of the islands (dispersed phase) is less than 1.5 μm or the area fraction of the islands (dispersed phase) is less than 15%.

[0095] The heat storage composition E has a melting peak temperature in the range of 10 to 60°C, more preferably in the range of 10 to 50°C, and even more preferably in the range of 10 to 40°C.

[0096] The preferred heat storage composition E has multiple melting peak temperatures, at least one of which is in the range of 60 to 120°C.

[0097] The heat storage composition E of the present invention has a melting enthalpy (ΔH) of 30 J / g or more between 10 and 60°C, preferably 40 J / g or more, and more preferably 50 J / g or more.

[0098] The heat storage composition E does not have an island structure, or has an island structure, wherein the volume average equivalent spherical diameter Dv of the islands (dispersed phase) is 1.5 μm or less, or the area fraction of the islands (dispersed phase) is 15% or less. Preferably, the volume average equivalent spherical diameter Dv of the islands (dispersed phase) is 1.5 μm or less and the area fraction of the islands (dispersed phase) is 15% or less. In the case where the heat storage composition E has an island structure, the content of polymer 2 in the islands (dispersed phase) is higher than the content of polymer 2 in the sea (continuous phase). Dv is preferably 1.3 μm or less, more preferably 1.0 μm or less. It should be noted that when multiple dispersed phases are present, Dv calculated without distinguishing all dispersed phases satisfies the above range.

[0099] When the heat storage composition E has an island structure, the area fraction of the islands (dispersed phase) in the cross-section of the heat storage composition E is preferably 15% or less, more preferably 13% or less, and even more preferably 10% or less. It should be noted that when multiple dispersed phases are present, the total area calculated without distinguishing all dispersed phases satisfies the above range.

[0100] The number of melting peaks at 60–120°C of the heat storage composition E is preferably 3 or less, more preferably 2 or less, and even more preferably 1.

[0101] Regarding the content of substance A and polymer 2 in the heat storage composition E, the total amount of substance A and polymer 2 is set to 100% by weight. Preferably, the content of substance A is 30-99% by weight and the content of polymer 2 is 70-1% by weight. More preferably, the content of substance A is 50-90% by weight and the content of polymer 2 is 50-10% by weight. Even more preferably, the content of substance A is 60-90% by weight and the content of polymer 2 is 40-10% by weight. When the heat storage composition E is mainly composed of polymers, it is sometimes referred to as a "resin composition". In addition, the heat storage composition E is sometimes referred to as a "heat storage material" or "heat storage material".

[0102] Heat storage fiber F

[0103] The heat storage composition E contained in the heat storage fiber (hereinafter, sometimes also referred to as "heat storage fiber F") of the present invention comprises substance A (sometimes also referred to as "phase change substance A") and polymer 2 (sometimes also referred to as "base resin") described later.

[0104] The heat storage fiber F has a melting peak temperature between 10 and 60°C, and a melting enthalpy of more than 5 J / g between 10 and 60°C.

[0105] The heat storage composition E contained in the heat storage fiber F does not have an island structure, or has an island structure, wherein the equivalent spherical particle size of the island (dispersed phase) is less than 0.1 μm or the area fraction of the island (dispersed phase) is less than 15%.

[0106] The heat storage fiber F has a melting peak temperature in the range of 10 to 60°C, more preferably in the range of 10 to 50°C, and even more preferably in the range of 10 to 40°C.

[0107] The preferred heat storage fiber F has multiple melting peak temperatures, at least one of which is in the range of 60 to 120°C.

[0108] The heat storage fiber F of the present invention has a melting enthalpy (ΔH) of 5 J / g or more between 10 and 60°C, preferably 10 J / g or more, and more preferably 15 J / g or more. Alternatively, the heat storage fiber F has a melting peak temperature between 10 and 60°C and a melting enthalpy of 20 J / g or more between 10 and 60°C.

[0109] The heat storage composition E of the heat storage fiber F does not have an island structure, or has an island structure, wherein the equivalent spherical particle size Di of the islands (dispersed phase) is less than 0.1 μm, or the area fraction of the islands (dispersed phase) is 15% or less. Preferably, the equivalent spherical particle size Di of the islands (dispersed phase) is less than 0.1 μm, and the area fraction of the islands (dispersed phase) is 15% or less. In the case where the above heat storage composition E has an island structure, the content of polymer 2 in the islands (dispersed phase) is higher than the content of polymer 2 in the sea (continuous phase). Di is preferably less than 0.1 μm, more preferably less than 0.09 μm. It should be noted that when multiple dispersed phases exist, Di calculated without distinguishing all dispersed phases satisfies the above range.

[0110] When the heat storage composition E of the heat storage fiber F has an island structure, the area fraction of the islands (dispersed phase) in the cross-section of the heat storage composition E is preferably 15% or less, more preferably 13% or less, and even more preferably 10% or less. It should be noted that when multiple dispersed phases are present, the total area calculated without distinguishing all dispersed phases satisfies the above range.

[0111] The preferred heat storage fiber F has multiple melting peak temperatures, at least one of which is in the range of 60 to 120°C.

[0112] The number of melting peaks of the heat storage fiber F at 60–120°C is preferably 3 or less, more preferably 2 or less, and even more preferably 1.

[0113] Substance A

[0114] The heat storage composition E contains a substance (sometimes also referred to as "substance A" or "phase change substance A") having a melting peak temperature between 10 and 60 °C and a melting enthalpy of 30 J / g or higher between 10 and 60 °C. In this specification, a phase change substance refers to a material that acquires heat storage properties through a phase change.

[0115] Substance A has a melting peak temperature in the range of 10 to 60°C, preferably in the range of 10 to 50°C, and more preferably in the range of 10 to 40°C.

[0116] In one embodiment, the enthalpy of fusion ΔH observed in substance A within a temperature range of 10–60 °C is 30 J / g or more, preferably 40 J / g or more, more preferably 50 J / g or more, and even more preferably 60 J / g or more. Furthermore, the aforementioned ΔH is typically 200 J / g or less.

[0117] From the viewpoint of shape retention, the gel fraction of the heat storage composition E and the heat storage fiber F is preferably 15% by weight or more, more preferably 20% by weight or more, further preferably 40% by weight or more, and even more preferably 60% by weight or more. It should be noted that the above gel fraction refers to the total weight of the heat storage composition E as 100% by weight. The gel fraction represents the degree of cross-linking of the cross-linked polymer. A high gel fraction means that the polymer contained in the composition or fiber has more cross-linked structures, forming a more robust network structure. If the gel fraction is high, the composition or fiber has high shape retention and is less prone to deformation.

[0118] On the other hand, from the viewpoint of spinnability, the gel fraction of the heat storage composition E is preferably 15% by weight or less, more preferably 12% by weight or less, and even more preferably 10% by weight or less. If the gel fraction is low, there is a tendency for the composition or fiber to have high spinnability.

[0119] Examples of substances A include high molecular weight substances (sometimes referred to as polymer 1) and low molecular weight substances (sometimes referred to as compound L). The heat storage composition E may contain two or more substances A. In this case, it may contain only two or more polymers 1, or only two or more compounds L, or both polymer 1 and compound L.

[0120] Polymer 1

[0121] Polymer 1 meets the requirements of substance A and has a molecular weight of over 2000.

[0122] The polymer 1 described above has a melting peak temperature in the range of 10 to 60°C, preferably in the range of 10 to 50°C, and more preferably in the range of 10 to 40°C.

[0123] For example, by adjusting the number of structural units B (described later) in polymer 1 and the L in equation (1) of structural unit B... 6 The number of carbon atoms can be adjusted to control the melting peak temperature of polymer 1. As a result, the heat storage performance of compositions containing polymer 1 can be adjusted.

[0124] The enthalpy of melting of polymer 1, ΔH, between 10 and 60°C is 30 J / g or more, preferably 40 J / g or more, more preferably 50 J / g or more, and even more preferably 60 J / g or more. Alternatively, ΔH is typically 200 J / g or less.

[0125] For example, by adjusting the number of structural units B (described later) in polymer 1 and L in the following formula (1) of structural unit B. 6 The number of carbon atoms can be adjusted to make ΔH fall within the aforementioned range. As a result, the heat storage performance of the composition containing polymer 1 can be adjusted.

[0126] From the viewpoint of further reducing the extrusion load during molding, the activation energy E of the flow of the aforementioned polymer 1 is... a Preferably, the concentration is 40 kJ / mol or higher, more preferably 50 kJ / mol or higher, and even more preferably 60 kJ / mol or higher. Furthermore, to ensure a good appearance of the extruded article, the concentration is preferably 100 kJ / mol or lower, more preferably 90 kJ / mol or lower, and even more preferably 80 kJ / mol or lower. a The size of E depends primarily on the number of long-chain branches in the polymer. Polymers containing more long-chain branches have higher E values. a higher.

[0127] Activation energy E of the flow a The following method was used to determine the complex melt viscosity-angular frequency curves of polymer 1 at three or more temperatures, including 170°C: 90°C, 110°C, 130°C, 150°C, and 170°C. These complex melt viscosity-angular frequency curves are double logarithmic curves with the logarithm of the complex melt viscosity (Pa·s) on the vertical axis and the logarithm of the angular frequency (rad / s) on the horizontal axis. Next, for the complex melt viscosity-angular frequency curves measured at temperatures other than 170°C, the angular frequency was set to α, coinciding with the curve at 170°C. T The complex melt viscosity is set to 1 / a. T Times. T The value is appropriately determined by coinciding the complex viscosity-angular frequency curves of the melt at temperatures other than 170℃ with the complex viscosity-angular frequency curve of the melt at 170℃.

[0128] The above a T Often referred to as the displacement factor, it is a value that varies depending on the temperature at which the complex viscosity-angular frequency curve of the melt is measured.

[0129] Next, at various temperatures T, calculate [ln(a T [)] and [1 / (T+273.16)], will [ln(a T [1 / (T+273.16)] and [1 / (T+273.16)] are approximated by least squares using the following equation (ii), and the slope m of the line representing equation (ii) is obtained. Substituting the above m into the following equation (iii), E is obtained. a .

[0130] ln(a T )=m(1 / (T+273.16))+n (ii)

[0131] E a=|0.008314×m| (iii)

[0132] a T Displacement factor

[0133] E a Activation energy of flow (unit: kJ / mol)

[0134] T: Temperature (unit: °C)

[0135] The above calculations can be performed using commercially available calculation software, such as Ochestrator manufactured by TA Instruments.

[0136] The above method is based on the following principles.

[0137] It is known that the complex viscosity-angular frequency curves (double logarithmic curves) of melt measured at different temperatures can coincide with a parent curve (sometimes also called the master curve) by horizontally shifting the curves at each temperature by a specified amount. This is known as the "temperature-time coincidence principle". This horizontal shift amount is called the displacement factor, which is a temperature-dependent value. The temperature dependence of the displacement factor is known to be expressed by the above equations (II) and (III), which are called Arrhenius equations.

[0138] Will [ln(a T The correlation coefficients of [1 / (T+273.16)] when approximated by least squares using the above equation (II) are set to 0.9 or higher.

[0139] The above-mentioned melt complex viscosity-angular frequency curves were determined using a viscoelastic measuring apparatus (e.g., ARES manufactured by TA Instruments), typically under the following conditions: geometry: parallel plates; plate diameter: 25 mm; plate spacing: 1.2–2 mm; strain: 5%; angular frequency: 0.1–100 rad / s. The measurements were performed under a nitrogen atmosphere. Furthermore, it is preferable to pre-prepare an appropriate amount (e.g., 1000 ppm by weight) of antioxidant in the test sample.

[0140] Regarding the tensile viscosity nonlinear index k, which represents the strain-cured strength of the polymer 1, from the viewpoint of excellent formability such as small necking during T-mold film processing, small thickness unevenness of the resulting film, and less tendency for bubble breakage during foaming molding, it is preferably 0.85 or higher, more preferably 0.90 or higher, and even more preferably 0.95 or higher. Strain curing of a polymer refers to a rapid increase in tensile viscosity above a certain strain when strain is applied to the polymer. Furthermore, from the viewpoint of ease of molding the polymer 1 or the heat-storing composition of the present invention containing the polymer 1 into the desired shape, the index k is preferably 2.00 or lower, more preferably 1.50 or lower, even more preferably 1.40 or lower, even more preferably 1.30 or lower, and particularly preferably 1.20 or lower.

[0141] The nonlinear exponent k of the tensile viscosity is determined by the method shown below.

[0142] Find the temperature at 110℃ and the time in 1 second. -1 The viscosity η at elongation t when the polymer is uniaxially stretched at a strain rate E 1(t) and at a temperature of 110℃ and 0.1 seconds -1 The viscosity η at elongation t when the polymer is uniaxially stretched at a strain rate E 0.1(t). The above η at any given elongation time t. E 1(t) and the above η E Substitute 0.1(t) into the following formula to find α(t).

[0143] α(t)=η E 1(t) / η E 0.1(t)

[0144] Plot the logarithm of α(t) (ln(α(t))) against the stretching time t. For t ranging from 2.0 to 2.5 seconds, approximate ln(α(t)) and t using the least squares method according to the following formula. The slope of the straight line representing this formula is k.

[0145] ln(α(t))=kt

[0146] The value of k is adopted when the correlation function r2 used in the least squares approximation according to the above formula is 0.9 or higher.

[0147] The viscosity under uniaxial tension was measured using a viscoelasticity measuring apparatus (e.g., ARES manufactured by TA Instruments) under a nitrogen atmosphere.

[0148] In tensile viscosity determination, polymers with long-chain branches exhibit the property of shifting their tensile viscosity from the linear region and rising sharply in the high-strain region, a phenomenon known as strain curing. In the case of strain-curing polymers, it is known that the logarithm of α(t) (ln(α(t))) increases proportionally to ln(l / l0) (where l0 and l are the sample lengths at stretching times 0 and t, respectively) [Reference: Kiyoto Koyama, Osamu Ishizuka; Journal of the China Textile Society, 37, T-258 (1981)]. In the case of non-strain-curing polymers, for any stretching time, α(t) is 1, and the slope k of the straight line plotted with the logarithm of α(t) (ln(α(t))) relative to the stretching time is 0. In the case of strain-curing polymers, especially in the high-strain region, the slope k of this straight line plotting is not 0. In this invention, as a parameter representing the degree of strain curing, the slope of the straight line drawn with respect to the stretching time using the logarithm (ln(α(t))) of the nonlinear parameter α(t) is defined as k.

[0149] When determining the polystyrene equivalent weight-average molecular weight Mw of polymer 1 of the present invention by gel permeation chromatography (GPC), the mobile phase is usually o-dichlorobenzene, and the measurement temperature is 140°C.

[0150] For the purpose of making the polymer 1 well moldable and processable, the polymer 1 preferably contains structural unit A from ethylene.

[0151] Regarding polymer 1, the ratio A defined by the following formula (I) is preferably 0.95 or less, more preferably 0.90 or less, and even more preferably 0.80 or less.

[0152] A = α1 / α0 (I)

[0153] In equation (I), α1 is obtained by gel permeation chromatography with a light scattering detector and a viscosity detector, measuring the absolute molecular weight and intrinsic viscosity of the polymer, plotting the logarithm of the absolute molecular weight on the horizontal axis and the logarithm of the intrinsic viscosity on the vertical axis, and approximating the logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity on the horizontal axis using the least squares method according to equation (II), and obtaining the slope value α1 of the straight line shown in equation (II).

[0154] log[η1]=α1logM1+logK1 (II)

[0155] In formula (II), [η1] represents the intrinsic viscosity of the polymer (unit: dl / g), M1 represents the absolute molecular weight of the polymer, and K1 is a constant.

[0156] α0 is obtained by gel permeation chromatography using a device equipped with a light scattering detector and a viscosity detector. The absolute molecular weight and intrinsic viscosity of polyethylene standard 1475a (manufactured by the National Institute of Standards and Technology, USA) are determined. The logarithm of the absolute molecular weight is plotted on the horizontal axis and the logarithm of the intrinsic viscosity is plotted on the vertical axis. The logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity are approximated by least squares according to equation (I-II) within the range where the horizontal axis is above the logarithm of the weight-average molecular weight of the aforementioned polyethylene standard 1475a and below the logarithm of the z-average molecular weight. The slope α0 of the straight line shown in equation (I-II) is then calculated.

[0157] log[η0]=α0logM0+logK0 (I-II)

[0158] In formulas (I-II), [η0] represents the intrinsic viscosity (unit: dl / g) of polyethylene standard material 1475a, M0 represents the absolute molecular weight of polyethylene standard material 1475a, and K0 is a constant.

[0159] It should be noted that in the determination of the absolute molecular weight and intrinsic viscosity of polymer and polyethylene standard 1475a based on gel permeation chromatography, the mobile phase was o-dichlorobenzene, and the measurement temperature was 155℃.

[0160] When determining the absolute molecular weight using data obtained from a light scattering detector and the intrinsic viscosity ([η]) using a viscosity detector, calculations were performed using Malvern's data processing software OmniSEC (registered trademark) (version 4.7) based on the literature "Size Exclusion Chromatography, Springer (1999)".

[0161] The aforementioned polyethylene standard material 1475a (manufactured by the National Institute of Standards and Technology, USA) is a non-branched high-density polyethylene.

[0162] Formulas (II) and (I-II) above are known as Mark-Hauwink-Sakurada formulas representing the relationship between the intrinsic viscosity and molecular weight of polymers. The smaller α1 is, the greater the number of polymer chains intertwined due to branched structures. The aforementioned polyethylene standard 1475a does not form branched structures; therefore, no intertwining of polymer chains due to branched structures occurs. The smaller the ratio of α1 to α0 of the aforementioned polyethylene standard 1475a, i.e., A, the greater the amount of long-chain branched structures formed by the structural unit A (described later) in the polymer.

[0163] The weight-average molecular weight of the polymer 1, as determined by gel permeation chromatography using a device equipped with a light scattering detector, is preferably 10,000 to 1,000,000, more preferably 50,000 to 750,000, and even more preferably 100,000 to 500,000.

[0164] It should be noted that in the determination of the weight-average molecular weight of polymer 1 based on gel permeation chromatography, the mobile phase was o-dichlorobenzene, and the determination temperature was 155℃.

[0165] Polymer 1 can be exemplified by polymers having long-chain alkyl or long-chain ether groups in their side chains that can be branched or substituted with functional groups. There are no particular limitations on the polymer; examples include polymers primarily composed of (meth)acrylates having long-chain alkyl or long-chain ether groups in their side chains that can be branched or substituted with functional groups; polymers primarily composed of vinyl ester backbones having long-chain alkyl or long-chain ether groups in their side chains that can be branched or substituted with functional groups; polymers primarily composed of vinyl ether backbones having long-chain alkyl or long-chain ether groups in their side chains that can be branched or substituted with functional groups; and polymers primarily composed of polyolefin backbones having long-chain alkyl or long-chain ether groups in their side chains that can be branched or substituted with functional groups. As for the side chain, long-chain alkyl groups that can be branched or substituted with functional groups are preferred, and polymers primarily composed of (meth)acrylates or polyolefin backbones are preferred. Examples of polymer 1 include those described in Japanese Patent Application Publication No. 2015-091903, WO2016 / 098674, and WO2017 / 217419.

[0166] Two or more of the above-mentioned polymers 1 can be used in combination. The heat storage composition E and the composite of the present invention described later may contain a sensible heat storage material. Examples of sensible heat storage materials include concrete, gravel, iron, copper, steel, and polyethylene.

[0167] As one embodiment of the polymer 1 described above, it can be exemplified by comprising having C 14～30 Polymers of alkyl structural units.

[0168] The polymer 1 described above preferably has the structural unit shown in the following formula (1) (sometimes also referred to as structural unit B).

[0169] [Chemical Formula 1]

[0170]

[0171] In equation (1),

[0172] R 1 Indicates a hydrogen atom or a methyl group.

[0173] L 11Indicates a single bond, -CO-O-, -O-CO-, or -O-.

[0174] L 12 This indicates a single bond, -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH(OH)-CH2-, or -CH2-CH(CH2OH)-.

[0175] L 13 Represents a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH-, or -N(CH3)-,

[0176] L 16 Indicate C 14～30 Alkyl groups. It should be noted that L... 11 L 12 and L 13 The left side of each of the horizontally written chemical formulas corresponds to the upper side (main chain side of the polymer) of formula (1), and the right side corresponds to the lower side (end side of the side chain of the polymer) of formula (1).

[0177] R 1 Hydrogen atoms are preferred.

[0178] L 11 Preferably -CO-O-, -O-CO-, or -O-, more preferably -CO-O- or -O-CO-, and even more preferably -CO-O-.

[0179] L 12 Preferably, it is a single bond, -CH2-, -CH2-CH2-, or -CH2-CH2-CH2-, and more preferably a single bond.

[0180] L 13 Preferably, it is a single bond, -O-CO-, -O-, -NH-, or -N(CH3)-, and more preferably a single bond.

[0181] In order to ensure good processability of the composition containing polymer 1, L in formula (1) 16 C 14～30 Alkyl group. As C 14～30 Alkyl groups, C can be cited as examples. 14～30 straight-chain alkyl and C 14～30 Branched alkyl groups. L 6 C is preferred 14～30 Straight-chain alkyl, more preferably C 14～24 Straight-chain alkyl groups, more preferably C 16～22 Straight-chain alkyl groups.

[0182] As mentioned above, C14～30 Straight-chain alkyl groups, for example, include tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, icosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and triadecyl.

[0183] As mentioned above, C 14～30 Branched alkyl groups, for example, include isotetradecyl, isopentadecanyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecanyl, isoeicosyl, isotidecyl, isodidecyl, isotridecyl, isotetradecyl, isopentadecanyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecanyl, and isotrianecanyl.

[0184] R in equation (1) 1 L 11 L 12 L 13 Examples of possible combinations include the following.

[0185] [Chemical Formula 2]

[0186]

[0187] [Chemical Formula 3]

[0188]

[0189] [Chemical Formula 4]

[0190]

[0191] [Chemical Formula 5]

[0192]

[0193] [Chemical Formula 6]

[0194]

[0195] [Chemical Formula 7]

[0196]

[0197] [Chemical Formula 8]

[0198]

[0199] [Chemical Formula 9]

[0200]

[0201] [Chemical Formula 10]

[0202]

[0203] [Chemical Formula 11]

[0204]

[0205] R in equation (1) 1 L 11 L 12 L 13 The preferred combination is the following combination.

[0206] [Chemical Formula 12]

[0207]

[0208] [Chemical Formula 13]

[0209]

[0210] [Chemical Formula 14]

[0211]

[0212] As R in equation (1) 1 L 11 L 12 L 13 The following combinations are preferred:

[0213] R 1 For hydrogen atoms, L 11 L 12 and L 13 For single bond, L 16 C 14～30 Combinations of alkyl groups; and

[0214] R 1 Hydrogen atom or methyl, L 11 -CO-O-, L 2 and L 3 For single bond, L 16 C 14～30 Combinations of alkyl groups.

[0215] R in equation (1) 1 L 11 L 12 and L 13 The preferred combination is the following combination.

[0216] [Chemical Formula 15]

[0217]

[0218] R in equation (1) 1 L 11 L 12 and L 13 The combination of is further preferably the following combination.

[0219] [Chemical Formula 16]

[0220]

[0221] The aforementioned structural unit B is preferably derived from hexadecene, octadecene, icosene, dodecene, tetradecene, hexadecene, octadecene, triadecene, trididecene, tetradecene, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecanyl acrylate, octadecyl acrylate, nonadecyl acrylate, icosene, dodecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecanyl acrylate, octadecyl acrylate, nonadecyl acrylate, triadecyl acrylate, tetradecyl methacrylate, pentadecyl methacrylate, and hexadecyl methacrylate. Alkyl esters, including heptadecanyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, triadecyl methacrylate, vinyl tetradecanoate, vinyl hexadecanoate, vinyl octadecanoate, vinyl eicosanoate, vinyl docosanoate, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, eicosyl vinyl ether, or docosyl vinyl ether.

[0222] The polymer 1 described above may have two or more of the above-mentioned structural units B, for example, it may be a polymer having structural units from n-hexadecyl acrylate and structural units from n-octadecyl acrylate.

[0223] To ensure good shape retention of the molded article containing the composition containing the polymer 1 above its melting peak temperature and good processability of the composition containing the polymer 1, the polymer 1 is preferably a polymer having structural units derived from ethylene (sometimes also referred to as structural unit A). Structural unit A is a structural unit obtained by polymerizing ethylene, and structural unit A can form a branched structure in the polymer.

[0224] The polymer 1 described above is preferably a polymer having structural unit B as shown in formula (1) and structural unit A from ethylene.

[0225] The polymer 1 described above may have at least one structural unit (sometimes also referred to as structural unit C) selected from the structural units shown in formula (2) and formula (3) below.

[0226] [Chemical Formula 17]

[0227]

[0228] [Chemical Formula 18]

[0229]

[0230] In equation (2),

[0231] R 2 Indicates a hydrogen atom or a methyl group.

[0232] L 21 Indicates a single bond, -CO-O-, -O-CO-, or -O-.

[0233] L 24 Indicate C 1～8 alkylene,

[0234] L 25 Represents hydrogen atom, epoxy group, -CH(OH)-CH2OH, carboxyl group, hydroxyl group, amino group, or C. 1～4 Alkylamino groups. It should be noted that L... 1 The left side of each of the horizontally written chemical formulas in the description of the chemical structure corresponds to the upper side (main chain side of the polymer) of formula (2), and the right side corresponds to the lower side (end side of the side chain of the polymer) of formula (2).

[0235] In equation (2), R 2 Hydrogen atoms are preferred.

[0236] In equation (2), L 21 Preferably -CO-O-, -O-CO-, or -O-, more preferably -CO-O- or -O-CO-, and even more preferably -CO-O-.

[0237] In equation (2), regarding L 24 C 1～8 Alkylenes, for example, include methylene, ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, and 2-ethyln-hexylene.

[0238] In equation (2), L 24 Preferably, it is methylene, ethylene, or n-propylene, and more preferably methylene.

[0239] In equation (2), regarding L 25 C 1～4 Alkylamino groups, for example, include methylamino, ethylamino, propylamino, butylamino, dimethylamino and diethylamino.

[0240] In equation (2), L 25 Preferably, it is a hydrogen atom, an epoxy group, or CH(OH)-CH2OH, and more preferably a hydrogen atom.

[0241] R in equation (2) 2 L 21 L 24 L 25 Examples of possible combinations include the following.

[0242] [Chemical Formula 19]

[0243]

[0244] [Chemical Formula 20]

[0245]

[0246] [Chemical Formula 21]

[0247]

[0248] [Chemical Formula 22]

[0249]

[0250] R in equation (2) 2 L 21 L 24 L 25 The preferred combination is the following combination.

[0251] [Chemical Formula 23]

[0252]

[0253] [Chemical Formula 24]

[0254]

[0255] [Chemical Formula 25]

[0256]

[0257] R in equation (2) 2 L 21 L 24 L 25 The preferred combination is the following combination.

[0258] [Chemical Formula 26]

[0259]

[0260] R in equation (2) 2 L 21 L 24 L 25 The combination of is further preferably the following combination.

[0261] [Chemical Formula 27]

[0262]

[0263] The structural units shown in formula (2) are derived from, for example, propylene, butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, acrylic acid, methacrylic acid, vinyl alcohol, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate. Vinyl formate, vinyl acetate, vinyl propionate, vinyl (n-butyrate), vinyl (isobutyrate), methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, glycidyl acrylate, glycidyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 3-(dimethylamino)propyl acrylate, and 3-(dimethylamino)propyl methacrylate.

[0264] In the case where polymer 1 contains structural unit C and structural unit C is represented by formula (3), the structural unit can be derived from maleic anhydride. Alternatively, structural unit C can be formed by a condensation reaction of two structural units that can be repeatedly selected from structural unit B and structural unit C shown in formula 2.

[0265] The polymer 1 described above may have two or more of the above-mentioned structural units C, for example, it may be a polymer having structural units from methyl acrylate, structural units from ethyl acrylate and structural units from glycidyl methacrylate.

[0266] The polymer 1 described above is preferably a polymer having structural unit B as shown in formula (1).

[0267] As a polymer 1 having structural unit B as shown in formula (1), the following can be cited:

[0268] Polymer 1 containing structural unit B,

[0269] Polymer 1 having structural unit B and structural unit A;

[0270] Polymer 1 having structural unit B and structural unit C; and

[0271] Polymer 1 having structural unit B, structural unit A and the aforementioned structural unit C.

[0272] Examples of the aforementioned "polymer 1 containing structural unit B" include:

[0273] Includes L 11 L 12 and L 13 For single bond, L 16 C 14～30 Polymers of alkyl groups of the structural unit B shown in formula (1); and

[0274] Includes L 11 -CO-O-, L 12 and L 13 For single bond, L 16 C 14～30 The alkyl group of the polymer is represented by the structural unit B of formula (1).

[0275] Examples of the aforementioned "polymer 1 having structural unit B and structural unit A" include:

[0276] With R 1 For hydrogen atoms, L 11 L 12 and L 13 For single bond, L 16 C 14～30 A polymer in which the alkyl group of formula (1) represents structural unit B and structural unit A, and the total number of structural unit A and structural unit B is 90% or more relative to 100% of the total number of all structural units contained in the polymer; and

[0277] With R 1Hydrogen atom or methyl, L 1 -CO-O-, L 12 and L 13 For single bond, L 16 C 14～30 The alkyl group of the structural unit B and structural unit A shown in formula (1) may also be a polymer 1 having the above-mentioned structural unit C, and the polymer having a total of 90% or more of the above-mentioned structural unit A and the above-mentioned structural unit B relative to the total number of all structural units contained in the polymer being 100%.

[0278] From the viewpoint of increasing ΔH, polymer 1 is preferably a polymer in which the total number of the above-mentioned structural unit B and the above-mentioned structural unit A contained in the polymer is 100%, and the number of the above-mentioned structural unit B is 50 to 80%.

[0279] From the viewpoint of processability, polymer 1 is preferably a polymer in which the total number of the above-mentioned structural unit B and the above-mentioned structural unit A contained in the polymer is 100%, and the number of the above-mentioned structural unit B is 10 to 50%.

[0280] As an example of the aforementioned "polymer 1 having structural unit B and structural unit C", a polymer having R 1 Hydrogen atom or methyl, L 11 -CO-O-, L 12 and L 13 For single bond, L 16 C 14～30 The structural units B and R of alkyl groups represented by formula (1) 2 Hydrogen atom or methyl, L 21 -CO-O-, L 24 Methylene, L 25 The polymer is a polymer of structural unit C represented by formula (2) with hydrogen atoms. In this case, it is preferable that the number of structural unit B is 80% or more relative to the total number of structural units B and structural units C contained in the polymer, which is 100%.

[0281] In one embodiment of polymer 1, the number of structural unit A is typically 0–99% relative to the total number of structural units A, B, and C being 100%, the total number of structural units B and C is typically 1–100%, and the number of structural units C is typically 0–99% relative to the total number of structural units B and C being 100%.

[0282] In one embodiment, the number of structural unit A in polymer 1 is 1 to 99% relative to the total number of structural units A, B, and C (100%). To ensure good shape retention of the molded article containing the heat-storing composition of the present invention, this is preferably 70 to 99%, more preferably 80 to 97.5%, and even more preferably 85 to 92.5%. To ensure good shape retention of the molded article containing the heat-storing composition of the present invention, the total number of structural units B and C in polymer 1 is preferably 1 to 30% relative to the total number of structural units A, B, and C (100%), more preferably 2.5 to 20%, and even more preferably 7.5 to 15%.

[0283] In one embodiment, the amount of structural unit B in polymer 1 is typically 1 to 100% relative to the total number of structural units B and structural units C, and preferably 60 to 100%, more preferably 80 to 100%, in order to improve the heat storage performance of the composition containing polymer 1.

[0284] In one embodiment, the amount of structural unit C in polymer 1 is typically 0 to 99% relative to the total number of structural units B and structural units C, and preferably 0 to 40%, more preferably 0 to 20%, in order to achieve good heat storage performance of the composition containing polymer 1.

[0285] The number of structural unit A, structural unit B, and structural unit C is determined using a known method. 13 C nuclear magnetic resonance spectrum (hereinafter referred to as C nuclear magnetic resonance spectrum) 13 C-NMR spectrum or 1 H nuclear magnetic resonance spectrum (hereinafter referred to as H nuclear magnetic resonance spectrum) 1 The integral values ​​of the signals attributable to each structural unit in the H-NMR spectrum are obtained.

[0286] In the case where polymer 1 is a polymer manufactured by reacting the precursor polymer P (described later) with the compound α (described later), the number of structural units A, B, and C can be determined, for example, by the following method.

[0287] <Number of structural units A1 from ethylene and structural units C1 from methyl acrylate when the precursor polymer P is an ethylene-methyl acrylate copolymer> (unit: %)

[0288] When the precursor polymer P contains structural unit A from ethylene, firstly, determine the number of structural units A1 and C1 contained in the precursor polymer P. 13Given the C-NMR spectra, for example, by calculating the integral values ​​of the ranges a1, b1, c1, d1, and e1, the number of binary units (AA, AC, CC) of structural unit A and structural unit C can be determined using the following formula. Substituting these values ​​into the following formula, the number of structural unit A and structural unit C can be calculated. It should be noted that AA represents structural unit A-structural unit A binary unit, AC represents structural unit A-structural unit C binary unit, and CC represents structural unit C-structural unit C binary unit.

[0289] a1: 28.1-30.5ppm

[0290] b1: 31.9-32.6 ppm

[0291] c1: 41.7ppm

[0292] d1: 43.1-44.2 ppm

[0293] e1: 45.0-46.5ppm

[0294] AA = a1 / 4 + b1 / 2

[0295] AC = e1

[0296] CC = c1 + d1

[0297] <Conversion rate X from structural unit C1 of methyl acrylate to structural unit B shown in formula (1) B > (Unit: %)

[0298] Structural unit C in precursor polymer P reacts with compound α (described later) to form structural unit B in polymer 1. Therefore, the conversion rate X of structural unit C1 to structural unit B based on the above reaction is determined by the following method. B .

[0299] The conversion rate is calculated by substituting the integral value (hereinafter referred to as integral value F1) of the signal (range f1) of the specific carbon contained in the side chain of the structural unit C belonging to the precursor polymer P and the integral value (hereinafter referred to as integral value G1) of the signal (range g1) of the specific carbon contained in the side chain of the structural unit B belonging to the polymer 1 into the following formula.

[0300] f1: 50.0-51.2ppm

[0301] g1: 55.0-56.8ppm

[0302] The number of structural units A from ethylene, structural unit B as shown in formula (1), and structural unit C from methyl acrylate contained in polymer 1 is greater than (unit: %).

[0303] In the reaction between precursor polymer P and compound α (described later), structural unit A in precursor polymer P remains unchanged. Therefore, the number of structural units A in polymer 1 is the same as the number of structural units A1 in precursor polymer P (number of structural units A = number of structural units A1). The number of structural units B in polymer 1 is related to the number of structural units C1 in precursor polymer P and the conversion rate X. B The product is calculated as follows: (Number of structural unit B = Number of structural unit C1 × Conversion rate X) B / 100). The number of structural units C contained in polymer 1 is calculated as the difference between the number of structural units C1 contained in the precursor polymer P and the number of structural units B contained in polymer 1 (number of structural units C = number of structural units C1 - number of structural units B).

[0304] The contents (by weight%) of structural unit A, structural unit B and structural unit C contained in polymer 1 of the present invention can be calculated by the following formula.

[0305] Weight % of structural unit A = (Number of structural units A × Molecular weight of structural unit A) / (Number of structural units A × Molecular weight of structural unit A + Number of structural units B × Molecular weight of structural unit B + Number of structural units C × Molecular weight of structural unit C)

[0306] Weight % of structural unit B = (Number of structural units B × Molecular weight of structural unit B) / (Number of structural units A × Molecular weight of structural unit A + Number of structural units B × Molecular weight of structural unit B + Number of structural units C × Molecular weight of structural unit C)

[0307] Weight % of structural unit C = (Number of structural units C × Molecular weight of structural unit C) / (Number of structural units A × Molecular weight of structural unit A + Number of structural units B × Molecular weight of structural unit B + Number of structural units C × Molecular weight of structural unit C)

[0308] In one example, the precursor polymer P can be a polymer having at least one structural unit C selected from the structural units shown in formula (2) and the structural units shown in formula (3) above (wherein, in formula (2), L 21 is -CO-O-, -O-CO-, or O-).

[0309] compound α

[0310] The compound used to form structural unit B by reacting with structural unit C in the precursor polymer P (sometimes also called compound α) is selected from at least one of the following compounds:

[0311] With C 14～30Alkyl alcohols,

[0312] With C 14～30 alkyl amines,

[0313] With C 14～30 alkyl alkyl halides,

[0314] With C 14～30 alkyl carboxylic acids,

[0315] With C 14～30 Alkyl carboxylic amides,

[0316] With C 14～30 The alkyl carboxylic acid halide (Japanese: カルボンハライド), with C 14～30 alkyl carbamic acid,

[0317] With C 14～30 alkyl alkyl ureas, and

[0318] With C 14～30 Alkyl isocyanates.

[0319] Examples of methods for manufacturing polymer 1 include reacting precursor polymer P with compound α, and polymerizing monomers corresponding to the structural units of polymer 1. The alkyl group of compound α may be a straight-chain alkyl group or a branched-chain alkyl group, preferably a straight-chain alkyl group.

[0320] The aforementioned precursor polymer P is a raw material used to manufacture polymer 1. Precursor polymer P does not substantially contain structural unit B shown in formula (1). The aforementioned precursor polymer P may contain structural units that do not belong to any of structural units A, B, and C.

[0321] The precursor polymer P is preferably a polymer in which the number of structural unit A is 0 to 99% and the number of structural unit C is 1 to 100% relative to the total number of structural unit A and structural unit C, and more preferably a polymer in which the number of structural unit A is 70 to 99% and the number of structural unit C is 1 to 30%.

[0322] Methods for forming structural unit B in polymer 1 include, for example, reacting structural unit C contained in precursor polymer P with compound α, polymerization of the monomer that will become the raw material for structural unit B, or copolymerizing ethylene with the monomer that will become the raw material for structural unit B. The alkyl group of compound α is preferably a straight-chain alkyl group. It should be noted that in the method of polymerization of the monomer, polymerization initiators such as azo compounds can be used. Examples of such azo compounds include azobisisobutyronitrile (AIBN).

[0323] Examples of precursor polymers P mentioned above include:

[0324] Acrylic polymers, methacrylic polymers, vinyl alcohol polymers, methyl acrylate polymers, ethyl acrylate polymers, n-propyl acrylate polymers, n-butyl acrylate polymers, methyl methacrylate polymers, ethyl methacrylate polymers, n-propyl methacrylate polymers, n-butyl methacrylate polymers, vinyl formate polymers, vinyl acetate polymers, vinyl propionate polymers, (n-butyric acid) vinyl ester polymers, methyl vinyl ether polymers, ethyl vinyl ether polymers, n-propyl vinyl ether polymers, n-butyl vinyl ether polymers, maleic anhydride polymers, glycidyl acrylate polymers, glycidyl methacrylate polymers, 3-(dimethylamino)propyl acrylate polymers, 3-(dimethylamino)propyl methacrylate polymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, ethylene-propylene copolymers ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-vinyl formate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-(n-butyric acid)vinyl ester copolymer, ethylene-methyl vinyl ether copolymer, ethylene-ethyl vinyl ether copolymer, ethylene-n-propyl vinyl ether copolymer, ethylene-n-butyl vinyl ether copolymer, ethylene-maleic anhydride copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-3-(dimethylamino)propyl acrylate copolymer, and ethylene-3-(dimethylamino)propyl methacrylate copolymer.

[0325] As mentioned above, having C 14～30 Straight-chain alkyl alcohols, for example, include n-tetradecanoic alcohol, n-pentadecanol, n-hexadecanoic alcohol, n-heptadecanoic alcohol, n-octadecanoic alcohol, n-nonadecanol, n-eicosyl alcohol, n-timodecanoic alcohol, n-timodecanoic alcohol, n-timodecanoic alcohol, n-nonadecanol and n-triadecanol.

[0326] As mentioned above, having C 14～30 Branched alkyl alcohols, for example, include isotetradecanool, isopentadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, isohexadecanol, and isohexadecanol.

[0327] As mentioned above, having C14～30 Straight-chain alkyl amines, for example, include tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine, octadecylamine, nonadecanylamine, eicosylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine, octadecylamine, nonadecanylamine, and triadecylamine.

[0328] As mentioned above, having C 14～30 Branched alkyl amines, for example, include isotetradecylamine, isopentadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, isohexadedecylamine, and isohexadedecylamine.

[0329] As mentioned above, having C 14～30 Alkyl halides of straight-chain alkyl groups, for example, include tetradecyl iodide, pentadecyl iodide, hexadecyl iodide, heptadecanyl iodide, octadecyl iodide, nonadecanyl iodide, eicosyl iodide, dodecyl iodide, tridecyl iodide, tetradecyl iodide, pentadecyl iodide, hexadecyl iodide, heptadecanyl iodide, nonadecanyl iodide, and triadecyl iodide.

[0330] As mentioned above, having C 14～30 Branched alkyl alkyl alkyl halides, for example, include isotetradecyl iodide, isopentadedecyl iodide, isohexadecyl iodide, isoheptadecyl iodide, isooctadecyl iodide, isononadedecyl iodide, isoeicosyl iodide, isododecyl iodide, isodidecyl iodide, isotridecyl iodide, isotetradecyl iodide, isopentadedecyl iodide, isohexadecyl iodide, isoheptadecyl iodide, isooctadecyl iodide, isononadedecyl iodide and isotrianedecyl iodide.

[0331] As mentioned above, having C 14～30 Examples of straight-chain alkyl carboxylic acids include tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, and triacontanoic acid.

[0332] As mentioned above, having C 14～30Branched alkyl carboxylic acids, for example, include isotetradecanoic acid, isopentadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, isohexadecanoic acid, and isohexadecanoic acid.

[0333] As mentioned above, having C 14～30 Examples of linear alkyl carboxylic acid amides include tetradecanoic acid amide, pentadecanoic acid amide, hexadecanoic acid amide, heptadecanoic acid amide, octadecanoic acid amide, nonadecanoic acid amide, eicosanoic acid amide, dodecanoic acid amide, tridecanoic acid amide, tetradecanoic acid amide, pentadecanoic acid amide, hexadecanoic acid amide, heptadecanoic acid amide, octadecanoic acid amide, nonadecanoic acid amide, and triacontanoic acid amide.

[0334] As mentioned above, having C 14～30 Branched alkyl carboxylic acid amides, for example, include isotetradecanoic acid amide, isopentadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, isohexadecanoic acid amide, and isohexadecanoic acid amide.

[0335] As mentioned above, having C 14～30 Carboxyl halides of straight-chain alkyl groups, for example, include n-tetradecanoyl chloride, n-pentadecanoyl chloride, n-hexadecanoyl chloride, n-octadecanoyl chloride, n-nonadecanoyl chloride, n-eicosanoyl chloride, n-docodecanoyl chloride, n-tridecanoyl chloride, n-tetradecanoyl chloride, n-pentadecanoyl chloride, n-hexadecanoyl chloride, n-heptadecanoyl chloride, n-octadecanoyl chloride, n-nonadecanoyl chloride, and n-triadecanoyl chloride.

[0336] As mentioned above, having C 14～30 Branched alkyl carboxyl halides, for example, include isotetradecanoyl chloride, isopentadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, isohexadecanoyl chloride, and isohexadecanoyl chloride.

[0337] As mentioned above, having C 14～30Examples of straight-chain alkyl carbamic acids include tetradecylcarbamic acid, pentadecylcarbamic acid, hexadecylcarbamic acid, heptadecanylcarbamic acid, octadecylcarbamic acid, nonadecanylcarbamic acid, eicosylcarbamic acid, dodecylcarbamic acid, tridecylcarbamic acid, tetradecylcarbamic acid, pentadecylcarbamic acid, hexadecylcarbamic acid, heptadecanylcarbamic acid, octadecylcarbamic acid, nonadecanylcarbamic acid, and triadecylcarbamic acid.

[0338] As mentioned above, having C 14～30 Branched alkyl carbamic acids, for example, include isotetradecylcarbamic acid, isopentadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, isohexadedecylcarbamic acid, and isohexadedecylcarbamic acid.

[0339] As mentioned above, having C 14～30 Alkyl ureas with straight-chain alkyl groups, for example, include tetradecylurea, pentadecylurea, hexadecylurea, heptadecanylurea, octadecylurea, nonadecanylurea, icosylurea, dodecylurea, tridecylurea, tetradecylurea, pentadecylurea, hexadecylurea, heptadecanylurea, octadecylurea, nonadecanylurea, and triadecylurea.

[0340] As mentioned above, having C 14～30 Branched alkyl alkyl ureas, for example, include isotetradecyl urea, isopentadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, isohexadedecyl urea, and isohexadedecyl urea.

[0341] As mentioned above, having C 14～30Straight-chain alkyl isocyanates, for example, include tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, heptadecanyl isocyanate, octadecyl isocyanate, nonadecanyl isocyanate, eicosyl isocyanate, dodecyl isocyanate, tridecyl isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, heptadecanyl isocyanate, octadecyl isocyanate, nonadecanyl isocyanate, and triadecyl isocyanate.

[0342] As mentioned above, having C 14～30 Branched alkyl isocyanates, for example, include isotetradecyl isocyanate, isopentadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, isohexadedecyl isocyanate, and isohexadedecyl isocyanate.

[0343] When the precursor polymer P contains a structural unit A derived from ethylene, in order to ensure good shape retention of the molded body of the polymer 1 containing the precursor polymer P, the product of the reactivity ratios r1×r2, where r1 is set as r1 and r2 is set as r2, is preferably 0.5 to 5.0, more preferably 0.5 to 3.0.

[0344] The reactivity ratio r1 of ethylene is a value defined by r1 = k11 / k12, where k11 is the reaction rate of ethylene bonded to the polymer terminally bound to structural unit A during the copolymerization of ethylene and the monomer forming structural unit C, and k12 is the reaction rate of the monomer forming structural unit C bonded to the polymer terminally bound to structural unit A. This reactivity ratio r1 indicates whether the polymer terminally bound to structural unit A reacts more readily with ethylene or with the monomer forming structural unit C during the copolymerization of ethylene. The larger r1 is, the more readily the polymer terminally bound to structural unit A reacts with ethylene, and therefore the more easily it forms chains of structural unit A.

[0345] The reactivity ratio r2 of the monomer forming structural unit C is defined as the reaction rate of ethylene bonded to the polymer terminally forming structural unit C during copolymerization of ethylene and the monomer forming structural unit C, where k21 is the reaction rate of the monomer forming structural unit C bonded to the polymer terminally forming structural unit C, and k22 is the reaction rate of the monomer forming structural unit C bonded to the polymer terminally forming structural unit C. This reactivity ratio r2 indicates whether the polymer terminally forming structural unit C reacts more readily with either ethylene or the monomer forming structural unit C during copolymerization of ethylene and the monomer forming structural unit C. The larger r2 is, the more readily the polymer terminally forming structural unit C reacts with the monomer forming structural unit C, thus facilitating the formation of structural unit C chains.

[0346] The product of reactivity ratios, r1×r2, was calculated using the method described in the literature "Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T. Macromolecules, 1982, 15, 1150". In this invention, the product of reactivity ratios, r1×r2, is calculated by using the precursor polymer P... 13 The fractions of each binary group AA, AC, CC of the above structural unit A and the above structural unit C calculated by nuclear magnetic resonance spectroscopy are substituted into the following formula to obtain the result.

[0347] r1×r2=AA[CC / (AC / 2) 2 ]

[0348] The product of reactivity ratios, r1×r2, is an indicator of the monomer chain distribution of a copolymer. The closer the product of reactivity ratios, r1×r2, is to 1, the higher the randomness of the monomer chain distribution of the copolymer; the closer the product of reactivity ratios, r1×r2, is to 0, the higher the alternating copolymerization of the monomer chain distribution of the copolymer; and the greater the product of reactivity ratios, r1×r2, is to 1, the higher the block copolymerization of the monomer chain distribution of the copolymer.

[0349] The melt flow rate (MFR) of the precursor polymer P, measured according to JIS K7210 at a temperature of 190°C and a load of 21N, is preferably 0.1 to 500 g / 10 min or less, more preferably 1 to 100 g / 10 min, and even more preferably 5 to 50 g / 10 min or less.

[0350] Methods for manufacturing the precursor polymer P include, for example, coordination polymerization, cationic polymerization, anionic polymerization, and free radical polymerization, with free radical polymerization being preferred, and free radical polymerization under high pressure being more preferred.

[0351] The temperature at which the precursor polymer P reacts with compound α is typically 40–250 °C. This reaction can be carried out in the presence of a solvent. Examples of solvents include hexane, heptane, octane, nonane, decane, toluene, and xylene. Furthermore, in cases where byproducts are generated during the reaction, to promote the reaction, the byproducts can be removed by vacuum distillation, or the byproducts can be azeotropically reacted with the solvent. The vaporized byproducts and solvent are then cooled, and the distillate containing both byproducts and solvent is separated into a byproduct layer and a solvent layer. The reaction is continued while only the recovered solvent layer is returned to the reaction system as reflux.

[0352] Furthermore, the reaction between precursor polymer P and compound α can be carried out simultaneously by melt-blending precursor polymer P and compound α. In cases where byproducts are generated during the reaction of precursor polymer P and compound α while melt-blending, the byproducts can be removed by vacuum distillation to promote the reaction. Examples of melt-blending apparatus used in melt-blending include single-screw extruders, twin-screw extruders, and Banbury mixers. The preferred temperature for the melt-blending apparatus is 100–250°C.

[0353] When reacting precursor polymer P with compound α, a catalyst may be added to promote the reaction. Examples of catalysts include alkali metal salts and group 4 metal complexes. Examples of alkali metal salts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkali metal alkoxides such as lithium methoxide and sodium methoxide. Examples of group 4 metal complexes include tetra(isopropyl) orthotitanate, tetra(n-butyl) orthotitanate, and tetra(octadecyl) orthotitanate. The amount of catalyst added is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 5 parts by weight, relative to 100 parts by weight of the total amount of precursor polymer P and compound α used in the reaction.

[0354] In order to ensure good shape retention of the molded article of the present invention above the melting peak temperature of the polymer 1 and good processability of the composition containing the polymer 1, the polymer 1 preferably has structural unit A derived from ethylene.

[0355] The polymer 1 described above can form a mixture with unreacted compound α, or with a catalyst added to promote the reaction. The content of unreacted compound α in the mixture is preferably less than 3 parts by weight relative to 100 parts by weight of the polymer 1.

[0356] The polymer 1 mentioned above can be a cross-linked polymer or an uncross-linked polymer.

[0357] In one embodiment, polymer 1 is an uncrosslinked polymer (hereinafter, sometimes also referred to as polymer α).

[0358] In one embodiment, the gel fraction of polymer α is less than 20% by weight.

[0359] Polymer α is a polymer containing 100% of all structural units in the polymer, and the total number of the above-mentioned structural units A, B and C is preferably 90% or more, more preferably 95% or more, and even more preferably 100%.

[0360] Crosslinking

[0361] In one embodiment, polymer 1 and / or polymer 2 described later are cross-linked. That is, at least a portion of the molecules of polymer 1 and polymer 2 are linked intermolecularly by covalent bonds. It should be noted that "polymer 1 is cross-linked" means one or both of the following: polymer 1 is linked to each other intermolecularly by covalent bonds, and polymer 1 is linked to a polymer different from polymer 1 (which may be polymer 2, or a polymer other than polymer 1 and 2) intermolecularly by covalent bonds.

[0362] Examples of methods for crosslinking polymers include crosslinking by irradiation with ionizing radiation and crosslinking by using organic peroxides.

[0363] In cases where a polymer is crosslinked by irradiation with ionizing radiation, the polymer α, pre-formed into the desired shape, is typically irradiated with ionizing radiation. Forming is performed using known methods, preferably extrusion molding, injection molding, or compression molding. The irradiated body can be a body containing only polymer 1 and polymer 2 as polymer components, or it can be a body containing a composition that includes polymers 1 and 2 but also polymers different from them. In the latter case, the base resin described later can be cited as a polymer different from polymer 1. When the body contains the uncrosslinked polymer and base resin of the present invention, the content of the uncrosslinked polymer of the present invention is preferably 1 to 99% by weight, as the total amount of the uncrosslinked polymer and base resin of the present invention is 100% by weight.

[0364] Examples of ionizing radiation include alpha rays, beta rays, gamma rays, electron beams, neutron rays, and X-rays, with gamma rays or electron beams from cobalt-60 being preferred. When the polymer-containing molded body is sheet-shaped, ionizing radiation can be irradiated from at least one side of the sheet-shaped molded body.

[0365] Irradiation with ionizing radiation is performed using an ionizing radiation irradiation device, with an irradiation dose typically ranging from 5 to 300 kGy, preferably from 10 to 150 kGy. The polymer 1 described above can be obtained as a polymer with a high degree of cross-linking at a lower irradiation dose than usual.

[0366] In cases where the crosslinked polymer 1 is obtained by irradiation with ionizing radiation, if the molded body irradiated with ionizing radiation contains a crosslinking aid, a crosslinked polymer 1 with a higher degree of crosslinking can be obtained. The crosslinking aid is used to increase the degree of crosslinking of polymer 1 and improve its mechanical properties; preferably, compounds having multiple double bonds within the molecule are used. Examples of crosslinking aids include N,N'-m-phenylene bismaleimide, toluene bismaleimide, triallyl isocyanurate, triallyl cyanurate, p-quinone dioxime, nitrobenzene, diphenylguanidine, divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and allyl methacrylate. Furthermore, multiple crosslinking aids can be used in combination.

[0367] The amount of crosslinking aid added is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 2.0 parts by weight, relative to 100 parts by weight of the total weight of the polymer contained in the molded body irradiated with ionizing radiation.

[0368] As a method for crosslinking using organic peroxides, an example is a method of crosslinking polymer α by means of a known molding method accompanied by heating, in which a composition comprising the above-mentioned polymer α, polymer 2 and organic peroxide are crosslinked. Known molding methods accompanied by heating include extrusion molding, injection molding, and compression molding.

[0369] When crosslinking is performed using an organic peroxide, it is suitable to use an organic peroxide having a decomposition temperature above the flow initiation temperature of the resin component contained in the heat storage composition E. Examples of preferred organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxide, 2,5-dimethyl-2,5-di-tert-butylperoxide, α,α-di-tert-butylperoxide, and tert-butylperoxide-2-ethylhexyl carbonate.

[0370] The heat storage composition E and the composite of the present invention described later may contain known additives as needed. Examples of such additives include inorganic fillers, organic fillers, flame retardants, antioxidants, weathering agents, ultraviolet absorbers, heat stabilizers, light stabilizers, lubricants, anti-blocking agents, anti-static agents, anti-fogging agents, anti-drip agents, crystal nucleating agents, pigments, dyes, adsorbents, metal chlorides, hydrotalcite, aluminates, organosilicon compounds, antibacterial agents, deodorizers, light-absorbing heating materials, moisture-absorbing heating materials, and far-infrared heating materials.

[0371] Compound L

[0372] Compound L meets the requirements of substance A and has a molecular weight of less than 2000.

[0373] Compound L has a melting peak temperature (maximum crystallization transition temperature) in the range of 10 to 60°C, more preferably in the range of 10 to 50°C, and even more preferably in the range of 10 to 40°C.

[0374] The melting enthalpy ΔH of compound L at 10–60 °C is 30 J / g or more, preferably 100 J / g or more, and more preferably 150 J / g or more.

[0375] The molecular weight of compound L is 2000 or less. Compound L, as long as its molecular weight is 2000 or less, can be a compound containing one or more structural units (repeating units) in its molecule. The molecular weight of compound L is preferably 150 to 500, more preferably 150 to 400, and even more preferably 150 to 300. Compound L can also be a "polymer," such as a dimer.

[0376] Alternatively, in one embodiment, the heat storage composition E may comprise both polymer 1 and compound L.

[0377] In this case, the temperature difference between the melting peak temperature of compound L contained in the composition and the melting peak temperature of polymer 1 is preferably 15°C or less, more preferably 10°C or less, and even more preferably 5°C or less.

[0378] The offset temperature of the melt curve (the intersection of the tangent at the inflection point of the melt curve on the melting end side and the baseline) is preferably 10–110°C, more preferably 20–50°C, and even more preferably 20–40°C. The greater the difference between the offset temperature of the melt curve and the melt peak temperature, the wider the temperature range over which the substance exhibits a heat storage effect.

[0379] Examples of compounds L include low molecular weight organic substances. Examples of low molecular weight organic substances include alkanes, long-chain fatty acids, long-chain alcohols, long-chain fatty acid esters, and sugar alcohols. They can be encapsulated in organic microcapsules, fixed with gelling agents, or sealed in containers such as plastics.

[0380] Compound L preferably has C 14～30 Alkyl group. As C 14～30 Alkyl groups, C can be cited as examples. 14～30 straight-chain alkyl and C 14～30 Branched alkyl groups. Preferably C14. 14～30 Straight-chain alkyl, more preferably C 14～24 Straight-chain alkyl groups, more preferably C 16～22 Straight-chain alkyl groups.

[0381] As mentioned above, C 14～30Straight-chain alkyl groups, for example, include tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, icosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and triadecyl.

[0382] As mentioned above, C 14～30 Branched alkyl groups, for example, include isotetradecyl, isopentadecanyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecanyl, isoeicosyl, isotidecyl, isodidecyl, isotridecyl, isotetradecyl, isopentadecanyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecanyl, and isotrianecanyl.

[0383] Compound L can be at least one heat-storing substance selected from hydrocarbons, fatty acids, fatty acid salts, fatty acid esters, aliphatic ethers, aliphatic ketones, aliphatic alcohols, and aliphatic amides. Furthermore, compound L can be a mixture of two or more compounds selected from the above-mentioned compounds (which can be of the same or different types).

[0384] The aforementioned hydrocarbons are preferably straight-chain saturated hydrocarbons, straight-chain unsaturated hydrocarbons, branched-chain saturated hydrocarbons, or branched-chain unsaturated hydrocarbons, with straight-chain saturated hydrocarbons being particularly preferred. Examples of straight-chain saturated hydrocarbons include n-tetradecane, n-pentadecanane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecanane, n-icosane, n-icosane, n-tricardecane, n-tetradecane, n-pentadecanane, n-hexadecane, n-octadecane, n-nonadecane, and n-triane. Furthermore, hydrocarbons include various alkane compounds.

[0385] The aforementioned fatty acids are preferably straight-chain saturated fatty acids, straight-chain unsaturated fatty acids, branched-chain saturated fatty acids, or branched-chain unsaturated fatty acids, with straight-chain saturated fatty acids being particularly preferred. Examples of straight-chain saturated fatty acids include, for instance, n-tetradecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, n-eicosanoic acid, n-docosanoic acid, n-tridecanoic acid, n-tetradecanoic acid, n-pentanoic acid, n-hexadecanoic acid, n-hexadecanoic acid, n-octadecanoic acid, n-nonadecanoic acid, and n-trianedecanoic acid.

[0386] Examples of the fatty acid salts mentioned above include sodium salts, potassium salts, and ammonium salts of the fatty acids mentioned above.

[0387] The aforementioned fatty acid esters are preferably straight-chain saturated fatty acid esters, straight-chain unsaturated fatty acid esters, branched-chain saturated fatty acid esters, or branched-chain unsaturated fatty acid esters, and particularly preferably straight-chain saturated fatty acid esters. Examples of straight-chain saturated fatty acid esters include:

[0388] Tetradecyl orthoformate, hexadecyl orthoformate, octadecyl orthoformate, eicosyl orthoformate, dodecyl orthoformate, tetradecyl orthoformate, hexadecyl orthoformate, octadecyl orthoformate, triadecyl orthoformate;

[0389] Tetradecyl orthoacetate, hexadecyl orthoacetate, octadecyl orthoacetate, eicosyl orthoacetate, dodecyl orthoacetate, tetradecyl orthoacetate, hexadecyl orthoacetate, octadecyl orthoacetate, triadecyl orthoacetate;

[0390] Tetradecyl n-propionate, hexadecyl n-propionate, octadecyl n-propionate, eicosyl n-propionate, dodecyl n-propionate, tetradecyl n-propionate, hexadecyl n-propionate, octadecyl n-propionate, triadecyl n-propionate.

[0391] Tetradecyl butyrate, hexadecyl butyrate, octadecyl butyrate, eicosyl butyrate, dodecyl butyrate, tetradecyl butyrate, hexadecyl butyrate, octadecyl butyrate, triadecyl butyrate;

[0392] Tetradecyl n-valerate, hexadecyl n-valerate, octadecyl n-valerate, eicosyl n-valerate, dodecyl n-valerate, tetradecyl n-valerate, hexadecyl n-valerate, octadecyl n-valerate, triadecyl n-valerate;

[0393] Tetradecyl hexanoate, hexadecyl hexanoate, octadecyl hexanoate, eicosyl hexanoate, dodecyl hexanoate, tetradecyl hexanoate, hexadecyl hexanoate, octadecyl hexanoate, triadecyl hexanoate;

[0394] Tetradecyl n-heptanoate, hexadecyl n-heptanoate, octadecyl n-heptanoate, eicosyl n-heptanoate, dodecyl n-heptanoate, tetradecyl n-heptanoate, hexadecyl n-heptanoate, octadecyl n-heptanoate, triadecyl n-heptanoate;

[0395] Tetradecyl octanoate, hexadecyl octanoate, octadecyl octanoate, eicosyl octanoate, dodecyl octanoate, tetradecyl octanoate, hexadecyl octanoate, octadecyl octanoate, triadecyl octanoate;

[0396] Tetradecyl nonanoate, hexadecyl nonanoate, octadecyl nonanoate, eicosyl nonanoate, dodecyl nonanoate, tetradecyl nonanoate, hexadecyl nonanoate, octadecyl nonanoate, triadecyl nonanoate;

[0397] Tetradecyl n-decanoate, hexadecyl n-decanoate, octadecyl n-decanoate, eicosyl n-decanoate, dodecyl n-decanoate, tetradecyl n-decanoate, hexadecyl n-decanoate, octadecyl n-decanoate, triadecyl n-decanoate;

[0398] Tetradecyl n-dodecanoate, hexadecyl n-dodecanoate, octadecyl n-dodecanoate, eicosyl n-dodecanoate, dodecyl n-dodecanoate, tetradecyl n-dodecanoate, hexadecyl n-dodecanoate, octadecyl n-dodecanoate, triadecyl n-dodecanoate;

[0399] Methyl n-tetradecanoate, ethyl n-tetradecanoate, propyl n-tetradecanoate, butyl n-tetradecanoate, pentyl n-tetradecanoate, hexyl n-tetradecanoate, heptyl n-tetradecanoate, octyl n-tetradecanoate, nonyl n-tetradecanoate, decyl n-tetradecanoate, dodecyl n-tetradecanoate, tetradecyl n-hexadecanoate, hexadecyl n-tetradecanoate, octadecyl n-tetradecanoate, eicosyl n-tetradecanoate, dodecyl n-tetradecanoate, hexadecyl n-tetradecanoate, hexadecyl n-tetradecanoate, triadecyl n-tetradecanoate;

[0400] Methyl hexadecanoate, ethyl hexadecanoate, propyl hexadecanoate, butyl hexadecanoate, pentyl hexadecanoate, hexyl hexadecanoate, heptyl hexadecanoate, octyl hexadecanoate, nonyl hexadecanoate, decyl hexadecanoate, dodecyl hexadecanoate, tetradecyl hexadecanoate, hexadecyl hexadecanoate, octadecyl hexadecanoate, eicosyl hexadecanoate, dodecyl hexadecanoate, tetradecyl hexadecanoate, octadecyl hexadecanoate, triadecyl hexadecanoate;

[0401] Methyl n-octadecanoate, ethyl n-octadecanoate, propyl n-octadecanoate, butyl n-octadecanoate, pentyl n-octadecanoate, hexyl n-octadecanoate, heptyl n-octadecanoate, octyl n-octadecanoate, nonyl n-octadecanoate, decyl n-octadecanoate, dodecyl n-octadecanoate, tetradecyl n-octadecanoate, hexadecyl n-octadecanoate, eicosyl n-octadecanoate, dodecyl n-octadecanoate, hexadecyl n-octadecanoate, hexadecyl n-octadecanoate, triadecyl n-octadecanoate;

[0402] Methyl eicosanoate, ethyl eicosanoate, propyl eicosanoate, butyl eicosanoate, pentyl eicosanoate, hexyl eicosanoate, heptyl eicosanoate, octyl eicosanoate, nonyl eicosanoate, decyl eicosanoate, dodecyl eicosanoate, tetradecyl eicosanoate, hexadecyl eicosanoate, octadecyl eicosanoate, icosanoate, didecyl eicosanoate, octadecyl eicosanoate, triadecyl eicosanoate;

[0403] Methyl n-dodecanoate, ethyl n-dodecanoate, propyl n-dodecanoate, butyl n-dodecanoate, pentyl n-dodecanoate, hexyl n-dodecanoate, heptyl n-dodecanoate, octyl n-dodecanoate, nonyl n-dodecanoate, decyl n-dodecanoate, dodecyl n-dodecanoate, tetradecyl n-dodecanoate, hexadecyl n-dodecanoate, octadecyl n-dodecanoate, eicosyl n-dodecanoate, tetradecyl n-dodecanoate, hexadecyl n-dodecanoate, octadecyl n-dodecanoate, triadecyl n-dodecanoate;

[0404] Methyl tetracosinate, ethyl tetracosinate, propyl tetracosinate, butyl tetracosinate, pentyl tetracosinate, hexyl tetracosinate, heptyl tetracosinate, octyl tetracosinate, nonyl tetracosinate, decyl tetracosinate, dodecyl tetracosinate, tetradecyl tetracosinate, hexadecyl tetracosinate, octadecyl tetracosinate, eicosyl tetracosinate, dodecyl tetracosinate, hexadecyl tetracosinate, octadecyl tetracosinate, triadecyl tetracosinate;

[0405] Methyl hexacosanoate, ethyl hexacosanoate, propyl hexacosanoate, butyl hexacosanoate, pentyl hexacosanoate, hexyl hexacosanoate, heptyl hexacosanoate, octyl hexacosanoate, nonyl hexacosanoate, decyl hexacosanoate, dodecyl hexacosanoate, tetradecyl hexacosanoate, hexadecyl hexacosanoate, octadecyl hexacosanoate, eicosanoate, dodecyl hexacosanoate, tetradecyl hexacosanoate, octadecyl hexacosanoate, triadecyl hexacosanoate;

[0406] Methyl octadecanoate, ethyl octadecanoate, propyl octadecanoate, butyl octadecanoate, pentyl octadecanoate, hexyl octadecanoate, heptyl octadecanoate, octyl octadecanoate, nonyl octadecanoate, decyl octadecanoate, dodecyl octadecanoate, tetradecyl octadecanoate, hexadecyl octadecanoate, octadecyl octadecanoate, eicosyl octadecanoate, dodecyl octadecanoate, tetradecyl octadecanoate, hexadecyl octadecanoate, octadecyl octadecanoate, triadecyl octadecanoate;

[0407] Methyl triaconate, ethyl triaconate, propyl triaconate, butyl triaconate, pentyl triaconate, hexyl triaconate, heptyl triaconate, octyl triaconate, nonyl triaconate, decyl triaconate, dodecyl triaconate, tetradecyl triaconate, hexadecyl triaconate, octadecyl triaconate, eicosyl triaconate, dodecyl triaconate, tetradecyl triaconate, hexadecyl triaconate, octadecyl triaconate.

[0408] Alternatively, it can be a compound composed of multiple fatty acid esters bonded together, such as triacylglycerol.

[0409] The aforementioned aliphatic ethers are preferably straight-chain saturated aliphatic ethers, straight-chain unsaturated aliphatic ethers, branched-chain saturated aliphatic ethers, or branched unsaturated aliphatic ethers, and particularly preferably straight-chain saturated aliphatic ethers. Examples of straight-chain saturated aliphatic ethers include:

[0410] Tetradecyl methyl ether, tetradecyl ethyl ether, tetradecyl propyl ether, tetradecyl butyl ether, tetradecyl pentyl ether, tetradecyl hexyl ether, tetradecyl heptayl ether, tetradecyl octyl ether, tetradecyl nonyl ether, tetradecyl decyl ether, tetradecyl dodecyl ether, ditetradecyl ether, tetradecyl hexadecyl ether, tetradecyl octadecyl ether, tetradecyl eicosyl ether, tetradecyl dodecyl ether, tetradecyl octadecyl ether, tetradecyl eicosyl ether, tetradecyl dodecyl ether, tetradecyl octadecyl ether, tetradecyl triadecyl ether;

[0411] Hexadecyl methyl ether, hexadecyl ethyl ether, hexadecyl propyl ether, hexadecyl butyl ether, hexadecyl pentyl ether, hexadecyl hexyl ether, hexadecyl heptadecyl ether, hexadecyl octyl ether, hexadecyl nonyl ether, hexadecyl decyl ether, hexadecyl dodecyl ether, dihexadecyl ether, hexadecyl octadecyl ether, hexadecyl eicosyl ether, hexadecyl dodecyl ether, hexadecyl tetradecyl ether, hexadecyl hexadecyl ether, hexadecyl octadecyl ether, hexadecyl triacontyl ether:

[0412] Octadecyl methyl ether, octadecyl ethyl ether, octadecyl propyl ether, octadecyl butyl ether, octadecyl pentyl ether, octadecyl hexyl ether, octadecyl heptyl ether, octadecyl octyl ether, octadecyl nonyl ether, octadecyl decyl ether, octadecyl dodecyl ether, dioctadecyl ether, octadecyl eicosyl ether, octadecyl dodecyl ether, octadecyl tetradecyl ether, octadecyl hexadecyl ether, octadecyl dioctadecyl ether, octadecyl triadecyl ether;

[0413] Eicosyl methyl ether, eicosyl ethyl ether, eicosyl propyl ether, eicosyl butyl ether, eicosyl pentyl ether, eicosyl hexyl ether, eicosyl heptyl ether, eicosyl octyl ether, eicosyl nonyl ether, eicosyl decyl ether, eicosyl dodecyl ether, dieicosyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether, eicosyl dodecyl ether;

[0414] 2-Dialkylmethyl ether, 2-Dialkylethyl ether, 2-Dialkylpropyl ether, 2-Dialkylbutyl ether, 2-Dialkylpentyl ether, 2-Dialkylhexyl ether, 2-Dialkylheptyl ether, 2-Dialkyloctadecyl ether, 2-Dialkyldodecyl ether, 2-Dialkyltetraalkyl ether, 2-Dialkylhexadecyl ether, 2-Dialkyloctadecyl ether, 2-Dialkyltrianealkyl ether;

[0415] Tetracosyl methyl ether, tetracosyl ethyl ether, tetracosyl propyl ether, tetracosyl butyl ether, tetracosyl pentyl ether, tetracosyl hexyl ether, tetracosyl heptyl ether, tetracosyl octyl ether, tetracosyl nonyl ether, tetracosyl decyl ether, tetracosyl dodecyl ether, ditetracosyl ether, tetracosyl hexadecyl ether, tetracosyl octadecyl ether, tetracosyl triacontyl ether;

[0416] Hexadecyl methyl ether, hexadecyl ethyl ether, hexadecyl propyl ether, hexadecyl butyl ether, hexadecyl pentyl ether, hexadecyl hexyl ether, hexadecyl heptyl ether, hexadecyl octyl ether, hexadecyl nonyl ether, hexadecyl decyl ether, hexadecyl dodecyl ether, dihexadecyl ether, hexadecyl octadecyl ether, hexadecyl triacontyl ether;

[0417] Octadecyl methyl ether, octadecyl ethyl ether, octadecyl propyl ether, octadecyl butyl ether, octadecyl pentyl ether, octadecyl hexyl ether, octadecyl heptyl ether, octadecyl octyl ether, octadecyl nonyl ether, octadecyl decyl ether, octadecyl dodecyl ether, dioctadecyl ether, octadecyl triacontyl ether;

[0418] Triacontylmethyl ether, triacontylethyl ether, triacontylpropyl ether, triacontylbutyl ether, triacontylpentyl ether, triacontylhexyl ether, triacontylheptyl ether, triacontyloctyl ether, triacontylnonyl ether, triacontyldecyl ether, triacontyldodecyl ether, ditrianetyl ether.

[0419] The aforementioned aliphatic ketones are preferably straight-chain saturated aliphatic ketones, straight-chain unsaturated aliphatic ketones, branched-chain saturated aliphatic ketones, or branched-chain unsaturated aliphatic ketones, and particularly preferably straight-chain saturated aliphatic ketones. Examples of straight-chain saturated aliphatic ketones include:

[0420] Tetradecyl methyl ketone, tetradecyl ethyl ketone, tetradecyl propyl ketone, tetradecyl butyl ketone, tetradecyl pentyl ketone, tetradecyl hexyl ketone, tetradecyl heptayl ketone, tetradecyl octyl ketone, tetradecyl nonyl ketone, tetradecyl decyl ketone, tetradecyl dodecyl ketone, ditetradecyl ketone, tetradecyl hexadecyl ketone, tetradecyl octadecyl ketone, tetradecyl eicosyl ketone, tetradecyl dodecyl ketone, tetradecyl octadecyl ketone, tetradecyl eicosyl ketone, tetradecyl dodecyl ketone, tetradecyl dodecyl ketone, tetradecyl dodecyl ketone, tetradecyl triadecyl ketone;

[0421] Hexadecyl methyl ketone, hexadecyl ethyl ketone, hexadecyl propyl ketone, hexadecyl butyl ketone, hexadecyl pentyl ketone, hexadecyl hexyl ketone, hexadecyl heptadecone, hexadecyl octyl ketone, hexadecyl nonyl ketone, hexadecyl decyl ketone, hexadecyl dodecyl ketone, dihexadecyl ketone, hexadecyl octadecyl ketone, hexadecyl eicosyl ketone, hexadecyl dodecyl ketone, hexadecyl tetradecyl ketone, hexadecyl hexadecyl ketone, hexadecyl octadecyl ketone, hexadecyl triadecyl ketone;

[0422] Octadecylmethyl ketone, octadecyl ethyl ketone, octadecyl propyl ketone, octadecyl butyl ketone, octadecyl pentyl ketone, octadecyl hexyl ketone, octadecyl heptyl ketone, octadecyl octyl ketone, octadecyl nonyl ketone, octadecyl decyl ketone, octadecyl dodecyl ketone, dioctadecyl ketone, octadecyl eicosyl ketone, octadecyl dodecyl ketone, octadecyl dodecyl ketone, octadecyl dodecyl ketone, octadecyl dodecyl ketone, octadecyl dodecyl ketone, octadecyl dodecyl tetradecyl ketone, octadecyl dodecyl ketone, octadecyl triacontyl ketone;

[0423] Eicosyl methyl ketone, eicosyl ethyl ketone, eicosyl propyl ketone, eicosyl butyl ketone, eicosyl pentyl ketone, eicosyl hexyl ketone, eicosyl heptyl ketone, eicosyl octyl ketone, eicosyl nonyl ketone, eicosyl decyl ketone, eicosyl dodecyl ketone, di-eicosyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone, eicosyl dodecyl ketone;

[0424] 2-Dialkylmethyl ketone, 2-Dialkylethyl ketone, 2-Dialkylpropyl ketone, 2-Dialkylbutyl ketone, 2-Dialkylpentyl ketone, 2-Dialkylhexyl ketone, 2-Dialkylheptyl ketone, 2-Dialkyloctadecyl ketone, 2-Dialkyltetraalkyl ketone, 2-Dialkylhexadecyl ketone, 2-Dialkyloctadecyl ketone, 2-Dialkyltrianealkyl ketone;

[0425] Tetramethyl ketone, tetraethyl ketone, tetrapropyl ketone, tetrabutyl ketone, tetrapentyl ketone, tetrahexyl ketone, tetrahedral heptamethyl ketone, tetraoctyl ketone, tetranonyl ketone, tetradecyl ketone, tetradodecyl ketone, ditetraalkyl ketone, tetrahexaalkyl ketone, tetraoctadecyl ketone, tetratetraalkyltrianealkyl ketone;

[0426] Hexadecyl methyl ketone, hexadecyl ethyl ketone, hexadecyl propyl ketone, hexadecyl butyl ketone, hexadecyl pentyl ketone, hexadecyl hexyl ketone, hexadecyl heptyl ketone, hexadecyl octyl ketone, hexadecyl nonyl ketone, hexadecyl decyl ketone, hexadecyl dodecyl ketone, bis(hexadecyl ketone), hexadecyl octadecyl ketone, hexadecyl triacontyl ketone;

[0427] Octadecylmethyl ketone, octadecylethyl ketone, octadecylpropyl ketone, octadecylbutyl ketone, octadecylpentyl ketone, octadecylhexyl ketone, octadecylheptyl ketone, octadecyloctyl ketone, octadecylnonyl ketone, octadecyldecyl ketone, octadecyldodecyl ketone, dioctadecyl ketone, octadecyltrianealkyl ketone;

[0428] Triacontylmethyl ketone, triacontylethyl ketone, triacontylpropyl ketone, triacontylbutyl ketone, triacontylpentyl ketone, triacontylhexyl ketone, triacontylheptyl ketone, triacontyloctyl ketone, triacontylnonyl ketone, triacontyldecyl ketone, triacontyldodecyl ketone, ditrianetyl ketone.

[0429] The aforementioned aliphatic alcohols are preferably straight-chain saturated aliphatic alcohols, straight-chain unsaturated aliphatic alcohols, branched-chain saturated aliphatic alcohols, or branched-chain unsaturated aliphatic alcohols, with straight-chain saturated aliphatic alcohols being particularly preferred. Examples of straight-chain saturated aliphatic alcohols include n-tetradecanoyl alcohol, n-pentadecanol, n-hexadecanoyl alcohol, n-heptadecanoyl alcohol, n-octadecanoyl alcohol, n-nonadecanol, n-eicosyl alcohol, n-timodecanoyl alcohol, n-timodecanoyl alcohol, n-tetradecanoyl alcohol, n-pentadecanol, n-hexadecanoyl alcohol, n-timodecanoyl alcohol, n-nonadecanol, and n-triadecanol.

[0430] The aforementioned aliphatic amides are preferably straight-chain saturated aliphatic amides, straight-chain unsaturated aliphatic amides, branched-chain saturated aliphatic amides, or branched-chain unsaturated aliphatic amides, and particularly preferably straight-chain saturated aliphatic amides. Examples of straight-chain saturated aliphatic amides include, for example, n-tetradecylamine, n-pentadecanylamine, n-heptadecylamine, n-octadecylamine, n-nonadecanylamine, n-eicosylamine, n-monodecylamine, n-dorylamine, n-tridecylamine, n-tetradecylamine, n-pentadecanylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecanylamine, and n-triadecylamine.

[0431] In one embodiment, to further suppress the exudation of compound L, compound L may be contained in the heat storage composition E in the form of being encapsulated in microcapsules or in the form of being filled in porous microparticles.

[0432] In one embodiment, microcapsules containing compound L encapsulate compound L and have a resin-containing membrane as a shell. Examples of materials forming this membrane include thermoplastic resins and thermosetting resins. Specifically, examples of resins forming the membrane include melamine resins, acrylic resins, urethane resins, nylon resins, and olefin resins. The material forming the membrane is preferably a resin that is not damaged during the manufacture of a heat-storing composition E containing microcapsules containing compound L and polymer 1, or during the manufacture of a molded article containing the heat-storing composition E. In one embodiment, the average primary particle size of the microcapsules containing compound L (hereinafter sometimes referred to as primary particles) is preferably 0.2 to about 1000 μm, more preferably 0.2 to 500 μm. In another embodiment, the aforementioned microcapsules with an average primary particle size of 0.2 to 50 μm, more preferably 0.2 to 10 μm, aggregate to form secondary particles, the average particle size of which (average secondary particle size) is preferably 10 to about 1000 μm, more preferably 50 to 500 μm. Examples of microcapsules containing alkanes as compound L include Micronal 5001X (manufactured by BASF) and RIKEN RESIN PMCD-25SP (manufactured by Riken Kogyo Co., Ltd.).

[0433] In this specification, "porous microparticles" refers to microparticles containing inorganic or organic matter with pores extending from their surface to their interior. Porous microparticles can be hollow microparticles with internal cavities or microparticles without cavities. Examples of porous microparticles containing inorganic matter include metal oxides such as silica and alumina, silicates such as calcium silicate and magnesium silicate, carbonates such as calcium carbonate and magnesium carbonate, phosphates such as magnesium phosphate and apatite. Examples of porous microparticles containing organic matter include foams containing various resins such as polyethylene and polyurethane, and expanded graphite. From the viewpoint of mechanical strength and chemical stability, porous microparticles containing inorganic matter are preferred. Furthermore, from the perspective of the availability and easy acquisition of commercially available microparticles with uniform particle size, porous silica is more preferred. The particle size of the porous microparticles is preferably 0.2 μm to 500 μm, more preferably 0.2 μm to 300 μm.

[0434] When the porous particles are porous particles containing inorganic substances, the surface of the porous particles can be coated with a resin layer. Examples of resins used as the resin layer include various reactive resins such as melamine resin, acrylic resin, and urethane resin, as well as thermoplastic resins such as nylon resin and polyolefin resin.

[0435] Porous microparticles filled with compound L can be microparticles formed by introducing a component that is a trapping substance of compound L into porous microparticles, and by trapping compound L by the trapping substance. For example, when compound L is an alkane and the porous microparticles are silica, examples of trapping substances include reactive silyl groups that have an affinity for alkane, such as oligomers or polymers like polyisobutylene, polyoxypropylene, polyacrylate, polyether polyol, and polymethacrylate, and are bonded to each other as reactive groups that have an affinity for silica.

[0436] Polymer 2

[0437] The heat storage composition E contains substance A and a base resin (sometimes also called polymer 2) having a melting peak temperature or glass transition temperature between 60 and 120°C.

[0438] In one embodiment, the melting peak temperature or glass transition temperature of polymer 2 is preferably 60–120°C, more preferably 70–110°C.

[0439] The heat storage composition E may contain two or more polymers 2.

[0440] Examples of polymers 2 with melting peak temperatures in the range of 60 to 120°C include low-density polyethylene (LDPE), ethylene-α-olefin copolymers, and ethylene-vinyl acetate copolymers (EVA).

[0441] Examples of polymers 2 with glass transition temperatures in the range of 60–120°C include cyclic olefin polymers (COP), cyclic olefin copolymers (COC), polystyrene (PS), polyvinyl chloride (PVC), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyamide 6 (PA6), polyamide 66 (PA66), polycarbonate (PC), polyphenylene sulfide (PPS), and polyetheretherketone (PEEK).

[0442] The ethylene-α-olefin copolymer described above, as polymer 2, is a copolymer having structural units derived from ethylene and structural units derived from α-olefins. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 4-methyl-1-hexene; these can be used individually or in combination. The α-olefin is preferably C10. 4～8 The α-olefin is more preferably 1-butene, 1-hexene, or 1-octene.

[0443] The density of polymer 2, the high-pressure low-density polyethylene (LDPE) and ethylene-α-olefin copolymer, is 860–960 kg / m³. 3 .

[0444] In one embodiment, polymer 2 has structural unit A and structural unit C, which are described as in polymer 1. Polymer 2 is preferably a polymer in which the number of structural unit A is 0 to 99% and the total number of structural unit C is 1 to 100% relative to the total number of structural unit A and structural unit C, more preferably a polymer in which the number of structural unit A is 70 to 99% and the total number of structural unit C is 1 to 30%.

[0445] As polymer 2, examples include the following:

[0446] Acrylic polymers, methacrylic polymers, vinyl alcohol polymers, methyl acrylate polymers, ethyl acrylate polymers, n-propyl acrylate polymers, n-butyl acrylate polymers, methyl methacrylate polymers, ethyl methacrylate polymers, n-propyl methacrylate polymers, n-butyl methacrylate polymers, vinyl formate polymers, vinyl acetate polymers, vinyl propionate polymers, (n-butyric acid) vinyl ester polymers, methyl vinyl ether polymers, ethyl vinyl ether polymers, n-propyl vinyl ether polymers, n-butyl vinyl ether polymers, maleic anhydride polymers, glycidyl acrylate polymers, glycidyl methacrylate polymers, 3-(dimethylamino)propyl acrylate polymers, 3-(dimethylamino)propyl methacrylate polymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, ethylene-propylene copolymers ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-vinyl formate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-(n-butyric acid)vinyl ester copolymer, ethylene-methyl vinyl ether copolymer, ethylene-ethyl vinyl ether copolymer, ethylene-n-propyl vinyl ether copolymer, ethylene-n-butyl vinyl ether copolymer, ethylene-maleic anhydride copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-3-(dimethylamino)propyl acrylate copolymer, and ethylene-3-(dimethylamino)propyl methacrylate copolymer.

[0447] Polymer 2 is preferably an ethylene-based copolymer. Examples of ethylene-based copolymers include ethylene-unsaturated carboxylic acid copolymers, ethylene-vinyl alcohol copolymers, ethylene-unsaturated carboxylic acid ester copolymers, ethylene-vinyl carboxylic acid ester copolymers, and ethylene-alkyl vinyl ether copolymers.

[0448] Examples of ethylene-unsaturated carboxylic acid copolymers include ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and ethylene-maleic anhydride copolymers.

[0449] Examples of ethylene-unsaturated carboxylic acid ester copolymers include ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-n-propyl acrylate copolymers, ethylene-n-butyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-n-propyl methacrylate copolymers, ethylene-n-butyl methacrylate copolymers, ethylene-glycidyl acrylate copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-3-(dimethylamino)propyl acrylate copolymers, and ethylene-3-(dimethylamino)propyl methacrylate copolymers.

[0450] Examples of ethylene-carboxylic acid vinyl ester copolymers include ethylene-formate vinyl ester copolymers, ethylene-vinyl acetate copolymers, ethylene-propionic acid vinyl ester copolymers, and ethylene-(n-butyric acid) vinyl ester copolymers.

[0451] Polymer 2 is more preferably an ethylene-unsaturated carboxylic acid copolymer or an ethylene-unsaturated carboxylic acid ester copolymer, and even more preferably an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-n-propyl acrylate copolymer, an ethylene-n-butyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl methacrylate copolymer, an ethylene-n-propyl methacrylate copolymer, and an ethylene-n-butyl methacrylate copolymer.

[0452] From the viewpoint of processability, polymer 2 preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 min, as measured according to JIS K7210 at a temperature of 190°C and a load of 21 N. More preferably, it has a MFR of 0.1 to 30 g / 10 min.

[0453] The amount of ethylene structural units in the above-mentioned ethylene-based copolymer resin is preferably 50 to 99% by weight.

[0454] The heat storage composition E can be formed into any shape. When the heat storage composition E is extruded, injected, vacuum formed, blow molded or calendered, from the viewpoint of processability, the melt flow rate (MFR) of the heat storage composition E, as measured according to JIS K7210 at 230°C and 2.16 kgf load, is preferably 0.1 to 30 g / 10 min.

[0455] When the heat storage composition E is spun into fibers as described later, the melt flow rate (MFR) of the heat storage composition E, measured according to JIS K7210 at 230°C and a load of 2.16 kgf, is preferably 0.1 to 1000 g / 10 min. More preferably, it is 10 to 500 g / 10 min, and even more preferably, it is 20 to 100 g / 10 min.

[0456] When the heat storage composition E is spun into fibers as described later, the temperature of 270°C and the shear rate of 1.216 × 10⁻⁶ were obtained using a capillary rheometer. 3 sec -1 The shear viscosity η is preferably 3 to 100 Pa·s. More preferably, it is 4 to 80 Pa·s, and even more preferably, it is 5 to 60 Pa·s.

[0457] When the heat storage composition E contains an additive, the additive may be pre-mixed in one or more raw materials used in the manufacturing process of the heat storage composition E, or it may be mixed after the heat storage composition E is manufactured.

[0458] In the case of the above-described manufacturing process involving crosslinking of polymers, the additives can be incorporated into the polymer before crosslinking or after crosslinking.

[0459] When manufacturing the heat storage composition E, if additives are added to the heat storage composition E, the additives can be added while the heat storage composition E is melt-mixed.

[0460] The amount of these additives relative to 100 parts by weight of the heat storage composition E is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, and even more preferably 0.01 to 1 part by weight.

[0461] Examples of inorganic fillers include talc, calcium carbonate, and calcined kaolin.

[0462] Examples of organic fillers include fibers, wood flour, and cellulose powder.

[0463] Examples of antioxidants include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, lactone-based antioxidants, and vitamin-based antioxidants.

[0464] Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, toluene diamine (Toluene diamine)-based ultraviolet absorbers, aniline-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers.

[0465] Examples of light stabilizers include hindered amine light stabilizers and benzoate light stabilizers.

[0466] Examples of pigments include titanium dioxide and carbon black.

[0467] Examples of adsorbents include metal oxides such as zinc oxide and magnesium oxide.

[0468] Examples of metal chlorides include ferric chloride and calcium chloride.

[0469] Examples of lubricants include fatty acids, higher alcohols, aliphatic amides, and aliphatic esters.

[0470] The heat storage composition E can be manufactured by first melt-blending phase change material A and polymer 2, as well as other additives as needed, to prepare a high-concentration masterbatch, and then further adding phase change material A and / or polymer 2 for melt-blending.

[0471] The heat storage composition E can be manufactured by simply mixing phase change material A and polymer 2 with other additives as needed, or by dissolving phase change material A in a solvent and then mixing polymer 2 with other additives as needed, or by dissolving polymer 2 in a solvent and then mixing phase change material A with other additives as needed, or by mixing phase change material A and polymer 2 with a solvent or a solution obtained by dissolving other additives as needed in a solvent, or by mixing a solution obtained by dissolving phase change material A in a solvent with a solution obtained by dissolving polymer 2 and other additives as needed in a solvent.

[0472] The heat storage composition E can be manufactured by first mixing phase change material A and polymer 2, as well as other additives as needed, either by simply mixing or dissolving them in a solvent to prepare a high-concentration masterbatch, and then further adding phase change material A or polymer 2 directly or dissolving them in a solvent as needed, and mixing them together.

[0473] The heat storage composition E can be manufactured by mixing monomers or prepolymers of polymer 1, monomers or prepolymers of polymer 2, and other additives as needed, or by further polymerization. Examples of polymerization methods include bulk polymerization, casting polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

[0474] The heat storage composition E obtained by the above method can be used as a raw material to manufacture polymers and molded articles.

[0475] Formed body

[0476] By molding the heat storage composition E, it is possible to manufacture a molded body containing the composition.

[0477] There are no particular limitations on the method of forming the heat storage composition E. Examples include injection molding, extrusion molding, vacuum forming, air compression molding, compression molding, transfer molding, injection molding, compression molding, lamination molding, blow molding, calendering, blow molding, hollow molding, two-color molding, foaming molding, insert molding, in-mold coating molding, rotational molding, hand lay-up molding, spray molding, matching mold molding, vacuum injection molding, filament winding molding, centrifugal molding, pultrusion molding, and other forming methods.

[0478] Examples of molded bodies according to the present invention include injection molded bodies, extruded molded bodies, vacuum molded bodies, compressed air molded bodies, press molded bodies, transfer molded bodies, injection molded bodies, compression molded bodies, laminated molded bodies, blow molded bodies, calendered molded bodies, blow molded bodies, hollow molded bodies, two-color molded bodies, foam molded bodies, insert molded bodies, in-mold coated bodies, rotational molded bodies, hand lay-up molded bodies, spray molded bodies, mating molded bodies, vacuum injection molded bodies, filament winding molded bodies, centrifugal molded bodies, pultruded bodies, sheets, films, etc. The molded body can be a single-layer structure or a multi-layer structure.

[0479] The molded body of the present invention can be a multilayer structure consisting of layers that are part of the composition of the present invention and layers different from those layers. Examples of materials constituting layers different from those of the composition of the present invention include resins, metals, paper, leather, etc., which are different from those of the composition of the present invention. The multilayer structure can be manufactured by bonding layers that are part of the composition of the present invention and layers different from those layers.

[0480] Due to its excellent formability and shape retention, the heat storage composition E can be any shape, such as spherical, cube shape, bead shape, cylindrical shape, powder, stick shape, needle shape, fiber shape, strand shape, filament shape, strip shape, rope shape, mesh shape, plate shape, sheet shape, film shape, woven fabric shape, non-woven fabric shape, capsule shape, foam shape, and any three-dimensional shape. The shape can be selected according to the intended use.

[0481] Furthermore, when the heat storage composition E is in the form of spheres, cubes, beads, pellets, or powder, a core-shell structure can be formed in which the heat storage composition E is covered by a material different from the heat storage composition E (hereinafter sometimes referred to as "material D"), or a core-shell structure in which material D is covered by the heat storage composition E. It should be noted that material D can be, for example, an organic compound, a polymer, a metal, or an inorganic compound other than a metal. Material D can be a thermal functional raw material described later.

[0482] In addition, when the heat storage composition E is in the form of a stick, needle, fiber, strand, filament, strip, rope, or mesh, a core-sheath structure in which the heat storage composition E is covered by material D, or a core-sheath structure in which material D is covered by heat storage composition E, can be formed.

[0483] In addition, when the heat storage composition E is in the form of a plate, sheet, film, woven fabric, non-woven fabric, box, or capsule, a laminated structure in which the heat storage composition E is covered by material D on one or both sides, or a laminated structure in which material D is covered by heat storage composition E on one or both sides, can be formed.

[0484] Foam-like molded bodies and molded bodies of different shapes from foam-like bodies, or material D can form core-shell structures, core-sheath structures, or laminated structures.

[0485] The heat storage composition E can be spun. The heat storage composition E can be formed, for example, into a part of a fiber, a fiber, a filament, silk, fabric, nonwoven fabric, filling material, or building material.

[0486] In one embodiment, the heat storage composition E is a heat storage material (fiber, building material, etc.). The cross-sectional shape of the heat storage material (fiber, building material, etc.) can be a circular cross-section, a polygonal or multi-leaf-shaped cross-section, or a hollow cross-section.

[0487] In one embodiment, the heat storage composition E is fibrous, and the fineness of the single filament is not particularly limited. From the viewpoint of ease of fiberization, it is preferably 1 dtex or more, and from the viewpoint of fiber softness, it is preferably 20 dtex or less.

[0488] Examples of methods for manufacturing this fiber include dry spinning, wet spinning, and melt spinning, with melt spinning being the preferred method. Furthermore, general spinning methods use fragments containing a heat-storing composition as raw material and mainly include two steps: spinning and drawing. Examples of suitable spinning methods for manufacturing fibers containing a heat-storing composition E include continuous polymerization spinning, which involves spinning continuously from the heat-storing composition manufacturing step without fragmenting the heat-storing composition E; direct spinning and drawing methods (spinning and drawing) that perform both spinning and drawing steps in one step; high-speed spinning methods that do not require a drawing step; the POY-DTY method, which obtains drawn yarn (DTY) through a false twisting process from semi-drawn yarn (POY); and spunbond spinning. These methods are more rational than the general spinning methods described above.

[0489] In one embodiment, the fiber containing the heat storage composition E can be a composite fiber. A composite fiber is a fiber formed by bonding two or more fibers with different components within a single filament. Examples of composite fibers include core-sheath type composite fibers, laminated type composite fibers, split type composite fibers, and island type composite fibers.

[0490] The fineness of the monofilament of the composite fiber containing the heat storage composition E is not particularly limited, but from the viewpoint of ease of fiberization, it is preferably 1 dtex or more, and from the viewpoint of fiber softness, it is preferably 20 dtex or less.

[0491] Examples of core-sheath type composite fiber structures include a core-sheath structure where the heat storage composition E is covered by material D, or a core-sheath structure where material D is covered by the heat storage composition E. A core-sheath structure where the heat storage composition E is covered by material D is preferred. Material D is preferably the aforementioned polymer 2, and more preferably polypropylene (PP), polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), or polyamide 66 (PA66).

[0492] As a core-sheath composite fiber in which the heat storage composition E is covered by material D, a composite fiber with a core area ratio of 10% to 90% in the radial cross-section of the fiber is preferred. From the viewpoint of temperature regulation function, the core area ratio is preferably 10% or more, and from the viewpoint of fiber strength, the core area ratio is preferably 90% or less. When the core contains polypropylene, from the viewpoint of the overall dyeability of the fiber, the core area ratio is preferably 20% to 60%.

[0493] To control the composite morphology of the core and sheath, the ratio of the melt viscosity of the sheath component to the core component is preferably in the range of 0.3 or higher and 4.0 or lower.

[0494] Adhesive composite fibers are generally curled according to differences in shrinkage rates, but when the composite fiber is curled into a spiral shape, the heat storage composition E can be on the inside of the spiral, and the material D can also be on the inside of the spiral. Preferably, the heat storage composition E is an adhesive composite fiber on the inside of the spiral. As material D, polymer 2 mentioned above is preferred, and polypropylene (PP), polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), and polyamide 66 (PA66) are more preferred.

[0495] As a structure of segmented composite fiber, when the segmented composite fiber is composed of radial fibers at the center and multiple wedge-shaped fibers around it, it can be a radial fiber centered on the heat storage composition E, or a radial fiber centered on the material D, preferably a segmented composite fiber with radial fibers centered on the heat storage composition E. As material D, polymer 2 is preferred, and more preferably polypropylene (PP), polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), or polyamide 66 (PA66). The segmented composite fiber can be segmented and opened by chemical treatment to obtain extremely fine fibers.

[0496] As a structure of island-type composite fiber, the heat storage composition E can be a marine fiber, and material D can be a marine fiber, preferably an island-type composite fiber in which material D is a marine fiber. Material D is preferably polymer 2, more preferably polypropylene (PP), polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), or polyamide 66 (PA66). In island-type composite fibers, the marine fibers can be removed by chemical treatment to obtain ultrafine fibers composed of multiple island fibers.

[0497] Examples of fiber forms containing the heat-storing composition E include long fibers (multifilaments, monofilaments) and short fibers (man-made short fibers). Long fibers (multifilaments, monofilaments) can be used directly, or processed into false-twist yarns, or blended yarns through air blending. Short fibers (man-made short fibers) can be used directly, or spun into spun yarns, or blended into blended yarns. They can be core-spun yarns formed by combining short fibers with long fibers, or they can be processed into twisted yarns, cross-twisted yarns, or core-spun yarns through twisting.

[0498] Fibers containing heat-storing composition E may contain antioxidants, pigments, dyes, antibacterial agents, deodorizers, antistatic agents, flame retardants, inactive microparticles, light-absorbing heat-generating agents, moisture-absorbing heat-generating agents, far-infrared heat-generating agents, ultraviolet absorbers, ultraviolet scattering agents, infrared shielding agents, lubricants, oils, slubbers, and other additives. These additives may be added during or after spinning.

[0499] There are no particular restrictions on the types of antioxidants that can be added; they can be selected appropriately depending on the purpose. Examples include phenolic compounds, phosphorus compounds, and hindered amine compounds. Only one type of antioxidant can be used, or two or more can be used in combination.

[0500] The antioxidants of phenolic compounds are inhibitors of free radical chain reactions with phenolic structures. One type can be used alone, or two or more can be used in combination. Examples include pentaerythritol-tetra(3-(3,5-di-tert-butyl-4-hydroxyphenol)propionate (e.g., Irganox 1010 manufactured by BASF), 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene (e.g., ADKSTAB AO-330 manufactured by ADEKA), and 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxellaspiro[5,5]-undecane (e.g., Sumitomo Chemical's Sumilizer GA-80, ADKSTAB manufactured by ADEKA). AO-80 and 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (e.g., THANOX1790 manufactured by Tokyo Chemical Industry and CYANOX1790 manufactured by CYTEC) have high oxidative decomposition inhibition effects and are therefore suitable for use. Among them, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5,5]-undecane (e.g., Sumilizer GA-80 manufactured by Sumitomo Chemical and ADKSTAB AO-80 manufactured by ADEKA) and 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (e.g., THANOX1790 manufactured by Tokyo Chemical Industry and CYANOX1790 manufactured by CYTEC) are particularly suitable because, when exposed to nitrogen oxide gas, the phenolic compounds themselves do not easily transform into quinone compounds, which are the cause of yellowing.

[0501] Phosphorus-based antioxidants are those that reduce peroxides without generating free radicals and are themselves oxidized. Only one type can be used, or two or more can be used in combination. Among them, tris(2,4-di-tert-butylphenyl) phosphite (e.g., BASF's Irgafos 168) and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5,5]undecane (e.g., ADEKA's ADKSTAB PEP-36) exhibit high oxidative decomposition inhibition effects and are therefore suitable for use.

[0502] In addition, 2,4,8,10-tetratert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphatane (Sumilizer GP, manufactured by Sumitomo Chemicals), an antioxidant with a phenolic and phosphorus-based skeleton, exhibits excellent oxidative decomposition inhibition effects, especially in high-temperature processing above 230°C, and is therefore suitable for use.

[0503] The hindered amine compound antioxidant is an antioxidant that captures free radicals generated by ultraviolet light and heat, and regenerates phenolic antioxidants that have lost their antioxidant function. Only one type can be used, or two or more can be used in combination. Among them, amino ether-type hindered amine compounds or high molecular weight hindered amine compounds with a molecular weight of 1000 or higher are suitable. Among hindered amine compounds, amino ether-type hindered amine compounds have low basicity. The inventors conducted in-depth research on the yellowing of polyolefin compositions caused by nitrogen oxide gases and phenolic compounds, and found that the lower the basicity of the hindered amine compound, the more it inhibits the transformation of phenolic compounds (as antioxidants) and phenolic compounds contained in the packaging agent into quinone compounds, which are the causative agents of yellowing. That is, amino ether-type hindered amine compounds can inhibit the yellowing of polyolefin compositions caused by nitrogen oxide gases and phenolic compounds during long-term storage, and are therefore preferred. Specific examples of hindered amine compounds of the amino ether type include bis(1-undecoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonates (e.g., ADKSTAB LA-81 manufactured by ADEKA) and sebacic acid bis[2,2,6,6-tetramethyl-1-(octoxy)piperidin-4-yl] (e.g., Tinuvin PA123 manufactured by BASF), but are not limited to these. In addition to hindered amine compounds of the amino ether type, specific examples of hindered amine compounds with low basicity include esters of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol and 3,5,5-trimethylhexanoic acid (e.g., Tinuvin 249 manufactured by BASF), but are not limited to these. High molecular weight hindered amine compounds with a molecular weight of 1000 or higher are preferred because they can suppress dissolution from the interior of the polyolefin composition caused by washing or cleaning with organic solvents, and exhibit excellent durability of the oxidative decomposition inhibition effect. Specific examples of high molecular weight hindered amine compounds with a molecular weight of 1000 or more include N-N'-N”-N”'-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine (e.g., SABO-produced SABOSTAB). UV119), poly((6-((1,1,3,3-tetramethylbutyl)amino)-1,3,5-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)imino)-1,6-hexamethylenediamine (2,2,6,6-tetramethyl-4-piperidinyl)imino) (e.g., BASF-manufactured CHIMASORB 944), dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine (e.g., BASF-manufactured CHIMASORB 2020), etc., but not limited to these.

[0504] The fabric or grey fabric containing fibers with heat-retaining composition E can be any of the following: woven fabric, knitted fabric, or nonwoven fabric. Examples of woven structures include plain weave, twill weave, satin weave and their variations, dobby weave, and jacquard weave. Examples of knitted structures include weft knitting, warp knitting, and their variations.

[0505] The weight per unit area and needle number of the fabric or nonwoven fabric containing fibers containing heat-retaining composition E are not particularly limited.

[0506] Fabrics and nonwovens containing fibers containing heat-retaining composition E may contain only fibers containing heat-retaining composition E, or they may be used after being interwoven or cross-knitted with other fibers. Other fibers include inorganic fibers such as carbon fiber, inorganic fibers, and metal fibers; refined fibers such as Lyocell; rayon, cupro fiber, and regenerated fibers such as Polynosic; semi-synthetic fibers such as acetate, triacetate, and Promix; acrylic acid and acrylic fibers; vinylon, Vinylidene chloride, polyvinyl chloride, polyethylene, Polyclerium, aramid, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), and urethane; synthetic fibers such as cotton and cellulose fibers; plant fibers such as hemp (flax, ramie, hemp, jute); natural fibers such as wool, wool, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.), and silk; and feathers such as down and feathers. The proportion of fiber containing heat storage composition E is not particularly specified, but is preferably 20 to 100% by weight.

[0507] Nonwoven fabrics containing fibers with heat storage composition E may contain fibers with thermally bonded adhesive.

[0508] The heat-fusion bonding fiber preferably comprises a core-sheath type or a bonded type composite fiber containing the heat storage composition E and a material with a melting point different from that of the heat storage composition E. The material with a melting point different from that of the heat storage composition E is preferably the aforementioned polymer 2, and more preferably polypropylene (PP), polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), or polyamide 66 (PA66).

[0509] When using this hot-melt adhesive fiber, its content is preferably 5 to 20% by weight in the total fiber content of the nonwoven fabric.

[0510] Methods for manufacturing nonwoven fabrics containing fibers with a heat-storing composition E typically include a web-forming process and a web-bonding process. Examples of web-forming processes include dry bonding, wet bonding, spunbonding, meltblowing, and air-laid web formation. Examples of web-bonding processes include chemical bonding, thermal bonding, needle punching, and water jet weaving.

[0511] Fabrics containing fibers with heat-retaining composition E have temperature-regulating properties, thus reducing the weight per unit area and thickness of the fabric, resulting in a soft feel against the skin without compromising the fashionability of the garment. In one embodiment, fabrics containing fibers of the present invention containing polymer 1 (a high molecular weight phase change substance) exhibit superior hand feel and wash durability compared to fabrics containing fibers containing compound L (a low molecular weight phase change substance) encapsulated in microcapsules.

[0512] Thermal functional raw materials

[0513] Examples of thermally functional raw materials include materials that provide a cooling sensation upon contact, materials that absorb moisture and generate heat, materials that absorb light and generate heat, materials that emit far-infrared radiation, materials that provide insulation, materials that provide heat resistance, and materials that absorb water and dry quickly. Thermally functional raw materials can also be components of fibers, fibers, filaments, silk, fabrics (cloths / grey fabrics), nonwoven fabrics, fillings, and building materials.

[0514] Examples of materials that provide a cooling sensation upon contact include materials containing inorganic fillers, fibers with high thermal conductivity, and materials that rapidly absorb and diffuse moisture to capture heat of vaporization. There are no particular limitations on the types of fibers that indicate a cold sensation upon contact. Examples include refined fibers such as lyocell, rayon, cupro, regenerated fibers such as polynitrocellulose, acetate, triacetate, prometheus, acrylic acid, acrylic fibers, vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, polyacrylamide, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), and other synthetic fibers such as urethane; cotton, cellulose fibers; plant fibers such as hemp (flax, ramie, hemp, jute); natural fibers such as down, wool, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.), and silk; and feathers such as down and feathers. Preferably, the cold sensation evaluation value Qmax = 0.2 W / cm² is used when making the fabric. 2 The above are materials that provide a cooling sensation upon contact.

[0515] The Qmax mentioned above was measured using a Thermo Lab KES-F7-11 testing machine manufactured by KATO TECH Co., Ltd. The hot plate of the testing machine, heated to ambient temperature +10°C (or 20°C), was placed on the fabric, and the maximum amount of heat transfer from the hot plate to the fabric was measured.

[0516] The inorganic fillers mentioned above are not particularly limited, and examples include light calcium carbonate, heavy calcium carbonate, etc.; barium carbonate, basic magnesium carbonate, etc.; calcium sulfate, barium sulfate; titanium dioxide, iron oxide, tin oxide, titanium oxide, zinc oxide, magnesium oxide, ferrite powder, zinc sulfide, zinc carbonate, aluminum nitride, silicon nitride, boron nitride, satin white, calcined diatomaceous earth, etc.; calcium silicate, aluminum silicate, magnesium silicate, amorphous silica, amorphous synthetic silica, colloidal silica, etc.; colloidal alumina, boehmite, aluminum hydroxide, magnesium hydroxide, alumina, alumina hydrate, zinc barium white, zeolite, hydrated halloysite, clay, hydrotalcite, aluminosilicate, talc, pyrophyllite, soapstone, lithium. Montmorillonite, zinc montmorillonite, magnesium-rich montmorillonite, montmorillonite, bedesite, naphthalene, etc.; mica, vermiculite, phlogopite, biotite, lithium mica, muscovite, sodium mica, chlorite, glauconite, etc.; clinoptilolite, oolitic chlorite, nickel chlorite, chlorophyllite, aluminum chlorite, diaspore, emarginate, pearl mica, manganese zoisite, serpentine, limonite, fibrous serpentine, neutral rock, beniolite, magnetite, iron serpentine, magnesium nickel silicate, kaolinite, dickite, pearl clay, halloysite, etc.; kaolinite, delaminated kaolinite, calcined kaolinite, sepiolite, palygorskite, ibex, diaspore, ferrosilicon, manganese silicate, activated clay, bentonite, sericite, graphite, carbon fiber, etc. These can be used individually or in combination of two or more.

[0517] The shape of the aforementioned inorganic filler is not particularly limited; for example, shaped or non-shaped materials such as spheres, needles, and plates can be included.

[0518] Examples of fibers with high thermal conductivity include highly oriented polyethylene fibers and highly oriented polybenzoxazole fibers, which improve thermal conductivity based on tension and orientation.

[0519] The aforementioned moisture-absorbing and heat-generating raw materials utilize a heat-generating reaction (condensation heat) that converts kinetic energy into thermal energy. These materials generate adsorption heat during moisture absorption and release moisture in low-humidity environments, thus controlling temperature and humidity. There are no particular limitations on the types of fibers that exhibit moisture absorption and heat generation. Examples include refined fibers such as Lyocell, rayon, cupro fiber, regenerated fibers such as Polynosic fiber, acetate, triacetate, Prometheus, acrylic acid, acrylic fibers, vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, Polyacrylamide, aramid, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), urethane and other synthetic fibers, cotton, cellulose fibers, plant fibers such as hemp (flax, ramie, hemp, jute), down, wool, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.), silk and other animal fibers, down, feathers and other feathers, etc.

[0520] The aforementioned light-absorbing and heat-generating raw materials are materials that absorb sunlight and convert it into heat energy. Light-absorbing and heat-generating fibers that include light-absorbing and heat-generating materials can be exemplified by fibers with highly efficient light-absorbing and heat-generating materials such as zirconium carbide and organic pigments that are fixed inside and on the surface of the fiber to absorb specific wavelengths of sunlight and convert them into heat energy. There are no particular limitations. More specifically, examples include refined fibers such as Lyocell, rayon, cupro fiber, regenerated fibers such as Polynosic fiber, acetate, triacetate, Prometheus and other semi-synthetic fibers, acrylic acid, acrylic fibers, vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, Polyacrylamide, aramid, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), urethane and other synthetic fibers, cotton, cellulose fibers, plant fibers such as hemp (flax, ramie, hemp, jute), natural fibers such as wool, wool, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.), silk and other animal fibers, down, feathers and other feathers, etc.

[0521] The aforementioned far-infrared emitting raw materials are those that emit far-infrared rays when heated. As far-infrared processed fibers containing far-infrared radiating raw materials, examples include fibers with ceramics that have high far-infrared radiating properties fixed inside and on the surface of the fiber, without particular limitation. More specifically, examples include refined fibers such as Lyocell, rayon, cupro fiber, regenerated fibers such as Polynosic fiber, acetate, triacetate, Prometheus semi-synthetic fibers, acrylic acid, acrylic fibers, vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, Polyacrylamide, aramid, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), urethane and other synthetic fibers, cotton, cellulose fibers, plant fibers such as hemp (flax, ramie, hemp, jute), natural fibers such as wool, wool, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.), silk and other animal fibers, down, feathers and other feathers, etc.

[0522] The aforementioned insulating raw materials are those that trap a large amount of low thermal conductivity air within the fabric, preventing heated air from escaping. There are no particular limitations on the types of fibers exhibiting insulating properties; examples include hollow fibers and feathers. More specifically, examples include refined fibers such as Lyocell, rayon, cupro fiber, regenerated fibers such as Polynosic, acetate, triacetate, Prometheus, acrylic acid, acrylic fibers, vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, Polyacrylamide, aramid, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), urethane, and other synthetic fibers; cotton, cellulose fibers, plant fibers such as hemp (flax, ramie, hemp, jute), down, wool, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.), silk, and other natural animal fibers, down, feathers, etc. Feathers such as down and feathers are preferred.

[0523] The aforementioned heat insulation materials are materials used to block sunlight. There are no particular limitations on the types of fibers that demonstrate heat insulation properties. Examples include fibers incorporating inorganic microparticles, and fibers and woven fabrics that reflect and scatter sunlight by creating a layered, hollow structure. More specifically, examples include refined fibers such as Lyocell, rayon, cupro fiber, regenerated fibers such as Polynosic fiber, acetate, triacetate, Prometheus, acrylic acid, acrylic fibers, vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, Polyacrylamide, aramid, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), and other synthetic fibers such as urethane, cotton, cellulose fibers, plant fibers such as hemp (flax, ramie, hemp, jute), natural fibers such as wool, cashmere, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.), silk, down, feathers, and other feathers.

[0524] The aforementioned quick-drying and moisture-wicking raw materials are those that rapidly absorb sweat and dry it, keeping the inside of clothing dry and comfortable. There are no particular limitations on the types of fibers exhibiting quick-drying and moisture-wicking properties; examples include ultrafine fibers utilizing capillary action, fibers with improved shapes to increase surface area, fibers combining hydrophilic and hydrophobic properties, and fabrics utilizing changes in fiber crimp caused by humidity. More specifically, examples include refined fibers such as lyocell, rayon, cupro, regenerated fibers such as Polynosic, acetate, triacetate, semi-synthetic fibers such as Promix, acrylic, and acrylic-based fibers. Synthetic fibers such as vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, Polecler, aromatic polyamide, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), and urethane; cotton, cellulose fibers; plant fibers such as hemp (flax, ramie, hemp, jute); natural fibers such as wool, cashmere, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.); and silk; down, feathers, etc.

[0525] The cross-sectional shape of the fiber containing thermal functional raw materials can be circular, polygonal, multi-leaf, or hollow.

[0526] The fineness of the monofilament of the fiber containing thermal functional raw materials is not particularly limited, but from the viewpoint of ease of fiberization, it is preferably 1 dtex or more, and from the viewpoint of fiber softness, it is preferably 20 dtex or less.

[0527] Fibers containing thermally functional raw materials can be composite fibers. Composite fibers refer to fibers composed of two or more fibers with different components bonded together within a single filament. Examples of composite fibers include core-sheath type composite fibers, laminated type composite fibers, split type composite fibers, and island type composite fibers.

[0528] The fineness of the monofilament of the fiber containing thermal functional raw materials is not particularly limited, but from the viewpoint of ease of fiberization, it is preferably 1 dtex or more, and from the viewpoint of fiber softness, it is preferably 20 dtex or less.

[0529] As forms of fibers containing thermally functional raw materials, examples include long fibers (multifilaments, monofilaments) and short fibers (man-made short fibers). Long fibers (multifilaments, monofilaments) can be used directly, or processed into false-twisted yarns through false twisting, or into blended yarns through air blending, etc. Short fibers (man-made short fibers) can be used directly, or spun into spun yarns, or blended into blended yarns. They can be core-spun yarns made by combining short fibers with long fibers, or they can be processed into twisted yarns, cross-twisted yarns, or core-spun yarns through twisting.

[0530] Fibers containing thermally functional raw materials may contain antioxidants, pigments, dyes, antibacterial agents, deodorizers, antistatic agents, flame retardants, non-reactive microparticles, light-absorbing heating materials, moisture-absorbing heating materials, far-infrared heating materials, ultraviolet absorbers, lubricants, ultraviolet scattering agents, infrared shielding agents, oils, slubs, and other additives. These additives may be added during or after spinning.

[0531] Complex

[0532] The composite of the present invention comprises a heat-storing composition E. It may also contain the aforementioned thermally functional raw materials. The composite can be shaped in any manner, for example, it can be composite fibers, filaments, silk, fabrics, nonwovens, or fillings.

[0533] The composite of the present invention can be a composite fiber. The aforementioned composite fiber refers to a fiber formed by bonding two or more fibers with different components within a single filament. Examples of composite fibers include core-sheath type composite fibers, laminated type composite fibers, split type composite fibers, and island type composite fibers.

[0534] The fineness of the monofilaments of the above-mentioned composite fibers is not particularly limited. From the viewpoint of ease of fiberization, it is preferred to be 1 dtex or more, and from the viewpoint of fiber softness, it is preferred to be 20 dtex or less.

[0535] Examples of core-sheath type composite fiber structures include a core-sheath structure in which the heat storage composition E is covered by a heat-functional raw material, or a core-sheath structure in which the heat-functional raw material is covered by the heat storage composition E. The preferred structure is a core-sheath structure in which the heat storage composition E is covered by a heat-functional raw material.

[0536] As a core-sheath structure composite fiber in which the heat storage composition E is covered by a thermally functional raw material, it is preferable that the area ratio of the core portion in the radial cross section of the fiber is 10% to 90% of the composite fiber. From the viewpoint of the sustainability of the thermal function, the area ratio of the core portion is preferably 10% or more, and from the viewpoint of fiber strength, the area ratio of the core portion is preferably 90% or less.

[0537] Adhesive composite fibers are generally curled according to the difference in shrinkage rate, but when the composite fiber is curled into a spiral shape, the heat storage composition E can be on the inside of the spiral, and the heat-functional raw material can also be on the inside of the spiral. Preferably, the heat storage composition E is an adhesive composite fiber on the inside of the spiral.

[0538] As a structure of segmented composite fiber, when the segmented composite fiber consists of radial fibers at the center and multiple wedge-shaped fibers around it, it can be a radial fiber centered on the heat storage composition E, or a radial fiber centered on the thermal functional raw material, preferably a segmented composite fiber with radial fibers centered on the heat storage composition E. The segmented composite fiber can be segmented and opened by chemical treatment to obtain ultrafine fibers.

[0539] As a structure of island-type composite fiber, the heat storage composition E can be a marine fiber, and the thermal functional raw material can be a marine fiber.

[0540] Examples of composite fibers incorporating the present invention include long fibers (multifilaments, monofilaments) and short fibers (man-made short fibers). Long fibers (multifilaments, monofilaments) can be used directly, or they can be processed into false-twisted yarns through false twisting, or into blended yarns through air blending, etc. Short fibers (man-made short fibers) can be used directly, or they can be spun into spun yarns, or into blended yarns through blending. They can be core-spun yarns formed by combining short fibers with long fibers, or they can be produced into twisted yarns, cross-twisted yarns, or core-spun yarns through twisting processes.

[0541] The composite of the present invention may contain antioxidants, pigments, dyes, antibacterial agents, deodorizers, antistatic agents, flame retardants, inactive microparticles, light-absorbing heating materials, moisture-absorbing heating materials, far-infrared heating materials, ultraviolet absorbers, ultraviolet scattering agents, infrared shielding agents, lubricants, oils, slubbers, and other additives. These additives may be added during or after spinning.

[0542] Fabrics and nonwovens spun from composite fibers containing the composite of the present invention can be any of woven fabrics, knitted fabrics, or nonwoven fabrics. Examples of woven structures include plain weave, twill weave, satin weave and variations thereof, dobby weave, and jacquard weave. Examples of knitted structures include weft knitting, warp knitting, and variations thereof.

[0543] Fabrics or nonwovens containing the composite of the present invention can be used by blending, interweaving, cross-knitting, or twisting the fibers of the heat storage composition E and the fibers of the thermal functional raw materials. Alternatively, they can be used by interweaving or cross-knitting with other fibers. Other fibers include inorganic fibers such as carbon fiber, inorganic fibers, and metal fibers; refined fibers such as lyocell; rayon, cupro fiber, and regenerated fibers such as Polinosic; semi-synthetic fibers such as acetate, triacetate, and Prometheus; acrylic acid and acrylic fibers; vinylon, vinylidene chloride, polyvinyl chloride, polyethylene, Policocellulosic, aramid, polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyamide 66 (PA66), and urethane; synthetic fibers such as cotton and cellulose fibers; plant fibers such as hemp (flax, ramie, hemp, jute); natural fibers such as down, wool, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.); and feathers such as down and feathers.

[0544] Examples of woven fabrics include plain weave, twill weave, satin weave and their variations, dobby weave, and jacquard weave. Examples of knitted fabrics include weft knitting, warp knitting and their variations. For both woven and knitted fabrics, to improve heat storage efficiency, the heat-storing material can be biased to one side.

[0545] The unit area weight, needle number, etc. of the fabric or nonwoven fabric that includes the composite of the present invention are not particularly limited.

[0546] Fabrics or nonwovens containing the composite of the present invention can be laminated. One type of fabric or nonwoven containing the heat-retaining composition E can be laminated, or two or more types of the same fabric or nonwoven can be laminated, or the fabric or nonwoven can be laminated together with fabrics or nonwovens containing thermally functional raw materials. The method of lamination and the number of layers are not particularly limited. When laminated with a cooling material, the cooling material is preferably skin-side. When laminated with a heat-insulating material, the heat-retaining composition E is preferably an intermediate layer or skin-side.

[0547] Nonwoven fabrics containing the composite of the present invention may contain thermally bonded adhesive fibers.

[0548] The heat-fusion bonding fiber is preferably a core-sheath type or laminated type composite fiber composed of a heat storage composition E and a material with a melting point different from that of the heat storage composition E. As the material with a melting point different from that of the heat storage composition E, the aforementioned polymer 2 is preferred, and more preferably polypropylene (PP), polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), or polyamide 66 (PA66).

[0549] When using this heat-fused adhesive fiber, its content is preferably 5 to 20% by weight in the total fiber content of the nonwoven fabric.

[0550] The manufacturing method of a nonwoven fabric incorporating the composite of the present invention generally includes a web forming process and a web bonding process. Examples of web forming processes include dry bonding, wet bonding, spunbonding, meltblowing, and air-blowing web forming. Examples of web bonding processes include chemical bonding, thermal bonding, needle punching, and water jet weaving.

[0551] In the manufacture of fillers comprising the composite of the present invention, fibers containing the heat-storing composition E and fibers containing thermally functional raw materials may be mixed. Other fibers may also be mixed. Examples of other fibers include inorganic fibers such as carbon fiber, inorganic fibers, and metal fibers; refined fibers such as lyocell; rayon, cupro fiber, and regenerated fibers such as polyoxocrystalline fiber; semi-synthetic fibers such as acetate, triacetate, and prometheus; acrylic acid; acrylic fibers; vinylon; vinylidene chloride; polyvinyl chloride; polyethylene; polyacrylamide; aramid; polybutylene terephthalate (PBT); polypropylene terephthalate (PTT); polyamide 66 (PA66); synthetic fibers such as urethane; cotton; cellulose fibers; plant fibers such as hemp (flax, ramie, hemp, jute); natural fibers such as wool, cashmere, animal hair (Angora rabbit hair, cashmere, mohair, alpaca hair, camel hair, etc.); and silk; feathers such as down and feathers. Alternatively, a fabric or nonwoven fabric containing the heat-retaining composition E can be laminated on a filler containing thermally functional raw materials. A filler containing the composite of the present invention refers to an article in which the composite is filled inside a bag-shaped outer casing.

[0552] Fabrics or greige fabrics incorporating the composite of the present invention have temperature-regulating functions, thus reducing the weight per unit area and thickness of the fabric or greige fabric, resulting in a soft feel against the skin without compromising the fashionability of the garment. Furthermore, fabrics or greige fabrics incorporating the composite of the present invention containing polymer 1 (a high molecular weight phase change substance) exhibit superior wash durability compared to fabrics or greige fabrics containing composite raw materials containing compound L (a low molecular weight phase change substance) encapsulated in microcapsules.

[0553] In one embodiment, the heat-storing composition E, due to its excellent heat storage properties, processability, shape retention, and moisture permeability, is suitable for use, for example, as articles or components for which heat insulation or cold retention is required directly or indirectly. It should be noted that the composition of the present invention, with its excellent heat storage properties, can also be used in articles where heat storage properties are not required.

[0554] Products or components that require thermal insulation or cold insulation properties, whether directly or indirectly, include building materials, furniture, interior decorations, bedding, bathroom materials, vehicles, air conditioning equipment, electrochemical products, insulated containers, clothing, daily necessities, agricultural materials, fermentation systems, thermoelectric conversion systems, and heat transport media.

[0555] Examples of building materials include flooring materials, wall materials, wallpaper, ceiling materials, roofing materials, geothermal systems, tatami mats, doors, partitions, sliding windows, sliding doors, windows, and window frames.

[0556] When used as flooring, wall, ceiling, or roofing material, in order to maintain a more constant indoor space temperature relative to changes in external ambient temperature, it is suitable to use, for example, a heat-storing composition E in the form of a plate, sheet, or foam, and a laminate containing material D of insulation and / or material D of thermal insulation.

[0557] Examples of the aforementioned insulation materials include polystyrene foam, polyurethane foam, acrylic resin foam, phenolic resin foam, polyethylene resin foam, foamed rubber, glass wool, asbestos, foamed ceramics, vacuum insulation materials, and composites thereof.

[0558] Examples of the aforementioned thermal insulation materials include aluminum plates, aluminum foils, aluminum powder coatings, ceramic powder coatings, and composites thereof.

[0559] When used as a wall material, ceiling material or roof material, in order to impart fire resistance, for example, a laminate of heat-storing composition E and a fire-retardant, quasi-non-combustible or non-combustible fire-resistant material containing material D in the form of a plate, sheet or foam may be used.

[0560] Examples of fire-resistant materials mentioned above include concrete, gypsum, wood-based cement, calcium silicate, glass, metal, foamed fire-resistant materials, materials containing flame retardants, and their composites.

[0561] When used as a component of a geothermal system, in order to efficiently use the heat generated by heating elements such as heating cables, surface heaters, and hot water pipes for maintaining room temperature, it is appropriate to use, for example, a heat storage composition E in the form of a plate, sheet, or foam, an insulation material containing material D, and a laminate containing sensible heat storage material D.

[0562] Examples of sensible heat storage materials include concrete, mortar, concrete slabs, and composites thereof.

[0563] When used as a component of tatami mats, in order to maintain a more constant indoor temperature relative to changes in the external ambient temperature, it is suitable to use, for example, a heat-storing composition E in the form of a board, sheet, or foam, an insulation material containing material D, a tatami board containing material D, and a laminate containing a tatami surface of material D. Furthermore, when used as tatami mat boards, heat-storing tatami boards containing a mixture of heat-storing composition E and wood fibers are suitable; and when used as tatami surface materials, heat-storing tatami surfaces containing heat-storing fibers forming a core-sheath structure are suitable, wherein the core-sheath structure is a core-sheath structure of fibrous (fiber-like) or strand-like heat-storing composition E and tatami surface material containing material D.

[0564] When used as a component of a door, partition, or sliding window, in order to maintain a more constant room temperature separated by the door, partition, or sliding window, a heat-storing composition E in the form of a plate, sheet, or foam, an insulation material containing material D, and a laminate containing a surface material of material D may be used, for example.

[0565] When used as a component of a sliding door, in order to maintain a more constant room temperature in the room separated by the sliding door and to provide a certain degree of light transmission, a heat-storing composition E in the form of foam or non-woven fabric, or a laminate having a heat-storing composition E in the form of foam or non-woven fabric and a sliding door paper containing material D, may be used.

[0566] When used as a window component, in order to maintain a more constant indoor temperature relative to changes in the external ambient temperature, or to provide a certain degree of light transmittance, for example, a heat-storing composition E in the form of foam or non-woven fabric, as well as a laminate containing glass, polycarbonate or polymethyl methacrylate, may be suitable.

[0567] When used as a component of a window frame, in order to maintain the indoor space temperature more consistently relative to changes in the external ambient temperature, or to prevent condensation by reducing the temperature difference between the window frame and the room temperature, a laminate of a heat-storing composition E in the form of a plate, sheet, or foam and a metal window frame or a polymer window frame different from polymer 1 can be used, for example.

[0568] As furniture, interior decorations, and bedding, examples include partitions, blinds, curtains, carpets, quilts, and mattresses.

[0569] When used as a component of a partition, in order to maintain a more constant room temperature in the room separated by the partition, for example, a heat storage composition E in the form of a plate, sheet or foam, an insulation material containing material D, and a laminate containing a surface material of material D may be used.

[0570] When used as a component of louvers, in order to maintain a more constant indoor temperature relative to changes in the external ambient temperature, or to provide shading performance, a laminate containing a plate-like or sheet-like heat-storing composition E and a heat-insulating material D can be appropriately used. For example, if the louver blade material is composed of an insulating surface and a heat-storing surface as described above, the insulating surface can be used as the outer side in summer, and the heat-storing surface can be used as the outer side during the day and flipped to the inner side at night in winter. This allows for control of the amount of solar heat flowing into the building according to the season and time of day, thereby reducing the power consumption of the air conditioning equipment.

[0571] When used as curtains, carpets, or bedding, in order to provide any feel or texture, heat-storing woven fabrics or heat-storing nonwoven fabrics containing heat-storing fibers can be used, wherein the heat-storing fibers form a core-sheath structure with a fiber material containing a fibrous (fiber-like) or strand-like heat-storing composition E and material D.

[0572] When used as a carpet, in order to impart any feel or texture, a laminate of woven or nonwoven fabric containing a heat-retaining composition E in the form of a board, sheet or foam and fibers containing material D can be used.

[0573] When used as a mattress, to impart softness, a heat-retaining composition E in the form of foam can be used, for example.

[0574] Examples of bathroom materials include bath tub materials, bathtub cover materials, bathroom flooring materials, bathroom wall materials, and bathroom ceiling materials.

[0575] When used as bath tub material or bathtub cover material, in order to maintain a more constant hot water temperature in the bath tub relative to temperature fluctuations in the bathroom, it is suitable to use, for example, a heat storage composition E in the form of a plate, sheet or foam, an insulation material containing material D, and a laminate containing a surface material of material D.

[0576] When used as bathroom flooring, bathroom wall material, and bathroom ceiling material, in order to maintain a more constant bathroom temperature relative to changes in the external ambient temperature, it is suitable to use, for example, a heat-storing composition E in the form of a plate, sheet, or foam, an insulation material containing material D, and a laminate containing material D.

[0577] Examples of vehicle components include engine warm-up systems, fuel evaporation loss prevention devices (canisters), vehicle air conditioning, interior materials, components of the body of refrigerated vehicles, and components of the body of insulated vehicles.

[0578] As components of air conditioning equipment, examples include heat storage materials for main heat storage air conditioning systems, components of heat storage tanks for water-based heat storage air conditioning systems, components of heat storage tanks for ice-based heat storage air conditioning systems, heat medium piping materials or their insulation materials, refrigerant piping materials or their insulation materials, and air duct materials for heat exchange ventilation systems.

[0579] Examples of electrochemical products include:

[0580] Televisions, Blu-ray recorders, DVD recorders, monitors, displays, projectors, rear-projection televisions, stereo systems, radios and cassette recorders, digital cameras, digital camcorders, mobile phones, smartphones, laptops, desktop computers, tablet PCs, PDAs, printers, 3D printers, scanners, home game consoles, portable game consoles, batteries for electronic devices, and transformers for electronic devices, etc.

[0581] Electric heaters, fan heaters, dehumidifiers, humidifiers, electric blankets, kotatsu, electric blankets, electric knee pads, electric foot warmers, heated toilet seats, hot water toilet seats, irons, trouser seam heat presses, bedding dryers, clothing dryers, hair dryers, hair curlers, warm massagers, thermotherapy devices, dishwashing machines, dish dryers, and dry-type water-containing waste disposal machines, etc.

[0582] IH cooking heaters, hot plates, microwave ovens, ovens, rice cookers, cookie makers, bread makers, toasters, electric fermenters, electric kettles, electric water kettles, coffee makers, and other heating cooking appliances;

[0583] Cooking appliances that generate frictional heat, such as blenders, food processors, and rice milling machines; and

[0584] Refrigerated and frozen storage, constant temperature and humidity cold storage, milk cold storage, brown rice cold storage, vegetable cold storage, refrigerated rice cabinets, frozen and refrigerated display cases, prefabricated cold storage, prefabricated refrigerated display cases, temperature and humidity food preparation carts, wine cellars, food vending machines, lunchboxes, etc.

[0585] When used as a component of electronic devices, in order to protect electronic components from the heat generated by the electronic components constituting the electronic device, a plate-shaped or sheet-shaped heat storage composition E may be suitable, for example. Especially in cases where highly integrated electronic components or other devices generate a large amount of local heat, in order to effectively absorb the heat emitted by the heat-generating element by the plate-shaped or sheet-shaped heat storage composition E, a laminate having a plate-shaped or sheet-shaped heat storage composition E and a highly thermally conductive material containing material D may be suitable, for example.

[0586] Examples of high thermal conductivity materials include carbon nanotubes, boron nitride nanotubes, graphite, copper, aluminum, boron nitride, aluminum nitride, aluminum oxide, magnesium oxide, and their composites.

[0587] When used as a component of an electronic device that is in contact with the human body, in order to suppress the heat generated by the electronic components constituting the electronic device from being conducted to the human body through the housing constituting the electronic device, a laminate having a plate-shaped or sheet-shaped heat storage composition E and the aforementioned housing material may be used, for example.

[0588] When used as a component of a heated household appliance, in order to protect other components constituting the heated household appliance from the heat generated by the heating device constituting the heated household appliance, a plate-shaped or sheet-shaped heat storage composition E may be suitable, for example. In addition, in order to improve heat preservation performance and suppress power consumption, a laminate having a plate-shaped, sheet-shaped, or foam-shaped heat storage composition E and an insulating material containing material D may be suitable, for example.

[0589] When used as a component of a heating cooking appliance, in order to protect other components constituting the heating appliance from the heat generated by the heating device constituting the heating appliance, a plate-shaped or sheet-shaped heat storage composition E may be suitable, for example. In addition, in order to improve heat retention performance and suppress power consumption, a laminate of a plate-shaped, sheet-shaped, or foam-shaped heat storage composition E and an insulating material containing material D may be suitable, for example.

[0590] When used as a component of a cooking appliance that generates frictional heat, in order to protect food from the effects of frictional heat, for example, a laminate having a plate-shaped or sheet-shaped heat storage composition E and a high thermal conductivity material containing material D can be used.

[0591] When used as a component of a powered, insulated, cold-proof storage facility, in order to maintain the internal temperature more consistently relative to changes in the external ambient temperature, for example, a heat storage composition E in the form of a plate, sheet, or foam, and a laminate containing a heat insulation material D and / or a heat insulation material containing material D may be used.

[0592] As a heat-insulating and cold-insulating container, it can be used for the transportation and storage of specimens and organs, the transportation and storage of pharmaceuticals and chemicals, and the transportation and storage of food.

[0593] In addition, when used in components for heat-insulating and cold-insulating containers, in order to maintain the internal temperature more consistently relative to changes in the external ambient temperature, for example, a laminate of a heat-storing composition E in the form of a plate, sheet, or foam and an insulating material containing material D and / or a heat-insulating material containing material D may be used.

[0594] Examples of clothing include pajamas, winter clothing, gloves, socks, sportswear, wetsuits, drysuits, heat-resistant protective clothing, and fire-resistant protective clothing. Furthermore, when used in clothing, to maintain a constant body temperature and provide a suitable tactile feel, heat-retaining woven fabrics or nonwoven fabrics containing heat-retaining fibers can be appropriately used, for example, to form a core-sheath structure with a fibrous material comprising a fibrous (fiber-like) or strand-like heat-retaining composition E and a material D.

[0595] When used in wet or dry diving suits, in order to maintain a more constant body temperature relative to cold water, for example, a laminate of the above-mentioned heat-storing composition E in the form of a plate or sheet, the above-mentioned heat-storing woven fabric or the above-mentioned heat-storing nonwoven fabric, and an insulating material containing material D can be used.

[0596] When used in heat-resistant protective clothing or fire-resistant protective clothing, in order to maintain body temperature more consistently relative to the heat source or flame, for example, the above-mentioned heat-storing composition E in the form of a plate or sheet, the above-mentioned heat-storing woven fabric or the above-mentioned heat-storing nonwoven fabric, the heat-insulating material containing material D, and the laminate containing the heat-insulating material D can be used.

[0597] Examples of everyday consumer goods include tableware, lunch boxes, water bottles, thermos flasks, hand warmers, hot water bottles, cold insulation materials, and microwave-safe insulation materials.

[0598] When used as a component of tableware or lunch boxes, in order to maintain the food temperature more consistently relative to the external ambient temperature, it can be used, for example, in the form of a laminate of a heat-storing composition E in the form of a plate, sheet, or foam and an insulating material containing material D.

[0599] Fermentation systems that ferment water-containing waste, sludge, livestock manure, or other organic waste such as animal and aquatic product residues, as well as vegetation, discharged from businesses or households to produce compost or biogas include, for example, biological water-containing waste treatment machines, composting fermentation tanks, and biogas fermentation tanks.

[0600] When used as the above-mentioned fermentation system, in order to maintain the temperature inside the tank at a more constant level suitable for fermentation relative to changes in the external ambient temperature, for example, a laminate of a heat storage composition E in the form of a plate, sheet or foam and an insulating material containing material D can be used.

[0601] Examples of agricultural materials include plastic greenhouse films, agricultural insulation sheets, flexible and rigid irrigation hoses, and agricultural electrical pads for seedling cultivation. When used as agricultural materials, in order to maintain a more constant temperature around crops at a level suitable for crop growth relative to changes in the external ambient temperature, a laminate of a heat-storing composition E in the form of a plate, sheet, or foam and an insulating material containing material D can be used, for example.

[0602] Example

[0603] The present invention will now be described in more detail through examples and comparative examples, but the present invention is not limited to the examples.

[0604] I. The number of structural units A from ethylene and structural units C from methyl acrylate contained in the precursor polymer (ethylene-methyl acrylate copolymer) (unit: %)

[0605] Nuclear magnetic resonance spectra (hereinafter referred to as NMR spectra) were measured using a nuclear magnetic resonance spectrometer (NMR) under the measurement conditions shown below. Next, the quantities (number [mol%] and weight [wt%]) of structural unit A, structural unit B, and structural unit C were determined according to the method described above.

[0606] <Carbon nuclear magnetic resonance (CNMR) 13 C-NMR measurement conditions >

[0607] Device: AVANCE III 600HD manufactured by Bruker Bio Spin Co., Ltd.

[0608] Measurement probe: 10mm CryoProbe

[0609] Determination solvent: a mixture of 1,2-dichlorobenzene and 1,1,2,2-tetrachloroethane with a d2 ratio of 85 / 15 (volume ratio).

[0610] Sample concentration: 100 mg / mL

[0611] Measurement temperature: 135℃

[0612] Measurement method: Proton decoupling method

[0613] Points earned: 256 times

[0614] Pulse width: 45 degrees

[0615] Pulse repetition time: 4 seconds

[0616] Measurement standard: Tetramethylsilane

[0617] II. Unreacted with C 14～30 Content of alkyl compounds (by weight %)

[0618] In the “manufacturing of substance A” of each embodiment, the product obtained is substance A reacting with unreacted C. 14～30 A mixture of alkyl compounds. The product contains unreacted compounds with C... 14～30 The content of alkyl compounds was determined using gas chromatography (GC) and by the following method. The content of unreacted compounds was the value when the total weight of substance A and unreacted compounds was set to 100% by weight.

[0619] [GC Measurement Conditions]

[0620] GC device: Shimadzu GC2014

[0621] Column: DB-5MS (60m, 0.25mmφ, 1.0μm)

[0622] Column temperature: The column, which was kept at 40°C, was heated to 300°C at a rate of 10°C / min, and then held at 300°C for 40 minutes.

[0623] Vaporization chamber / detector temperature: 300℃ / 300℃ (FID)

[0624] Carrier gas: Helium

[0625] Pressure: 220 kPa

[0626] Total flow rate: 17.0 mL / min

[0627] Column flow rate: 1.99 mL / min

[0628] Flushing flow rate: 3.0 mL / min

[0629] Linear velocity: 31.8 cm / s

[0630] Injection method / shunt ratio: shunt injection / 6:1

[0631] Injection volume: 1μL

[0632] Sample preparation method: 8 mg / mL (o-dichlorobenzene solution)

[0633] (1) Calibration curve preparation

[0634] [Solution Preparation]

[0635] Weigh 5 mg of the standard into a 9 mL vial, then weigh 100 mg of n-tetane (internal standard) into the vial. Add 6 mL of o-dichlorobenzene (solvent) to completely dissolve the sample, obtaining a standard solution for calibration curve preparation. Prepare two more standard solutions using the same procedure as above, except that the amounts of the standard are changed to 25 mg and 50 mg.

[0636] [GC Measurement]

[0637] Under the GC determination conditions described above, determine the standard solution used to prepare the calibration curve, prepare a calibration curve with the vertical axis set as the GC area ratio of the standard to the internal standard and the horizontal axis set as the weight ratio of the standard to the internal standard, and calculate the slope 'a' of the calibration curve.

[0638] (2) The analyte in the sample (product) (unreacted material with C) 14～30 Determination of the content of alkyl compounds

[0639] [Solution Preparation]

[0640] Weigh 50 mg of the sample and 100 mg of n-tetane into a 9 mL vial, add 6 mL of o-dichlorobenzene, and dissolve the sample completely at 80 °C to obtain the sample solution.

[0641] [GC Measurement]

[0642] Under the aforementioned GC determination conditions, the sample solution is measured, and the content P of the analyte in the sample is calculated according to the following formula. S .

[0643] P S Content (wt%) of the analyte in the sample.

[0644] W S : Sample weight (mg)

[0645] W IS Weight (mg) of internal standard (IS)

[0646] A S Peak area counting of the object being measured

[0647] A IS Peak area count of internal standard (IS)

[0648] a: The slope of the calibration curve for the object being measured.

[0649] [Mathematical Expression 2]

[0650]

[0651] III. Raw Materials

[0652] Reference Example 1

[0653] <Preparation of Precursor Polymers>

[0654] cf1: Ethylene-methyl acrylate copolymer

[0655] The ethylene-methyl acrylate copolymer (cf1) is manufactured as follows.

[0656] In a high-pressure autoclave reactor, at a reaction temperature of 195℃ and a reaction pressure of 160MPa, tert-butyl peroxypentanoate was used as a free radical polymerization initiator to copolymerize ethylene and methyl acrylate to obtain ethylene-methyl acrylate copolymer cf1. The composition and MFR of the obtained copolymer cf1 are as follows.

[0657] Number of structural units derived from ethylene: 64.5% by weight

[0658] Number of structural units derived from methyl acrylate: 35.5% by weight

[0659] MFR (determined according to JIS K7210, at 190°C and 21N load): 30g / 10min

[0660] cf2: Ethylene-methyl acrylate copolymer

[0661] The following is a method for manufacturing ethylene-methyl acrylate copolymer (cf2).

[0662] In a high-pressure autoclave reactor, at a reaction temperature of 195℃ and a reaction pressure of 160MPa, tert-butyl peroxypentanoate was used as a free radical polymerization initiator to copolymerize ethylene and methyl acrylate to obtain ethylene-methyl acrylate copolymer cf2. The composition and MFR of the obtained copolymer cf2 are as follows.

[0663] Number of structural units derived from ethylene: 68.8% by weight

[0664] Number of structural units derived from methyl acrylate: 31.2% by weight

[0665] MFR (measured according to JIS K7210 at 190°C and 21N load): 40.5g / 10min

[0666] <with C 14～30 Alkyl compounds >

[0667] B-1: GINOL-16 (1-Hexadecanool) [Gold Rej preparation]

[0668] B-2: GINOL-18 (1-Octadecanool) [GODREJ preparation]

[0669] B-3: KALCOL 220-80 (1-docosanol) [manufactured by Kao Corporation]

[0670] <Catalyst>

[0671] C-1: Tetraisopropyl titanate [manufactured by Nippon Soda Co., Ltd.]

[0672] See Example 2

[0673] <The manufacture of substance A>

[0674] A-1: Ethylene-hexadecyl acrylate-octadecyl acrylate-methyl acrylate copolymer

[0675] After nitrogen purging of the reactor equipped with a stirrer, B-1: 30 parts by weight, B-2: 62 parts by weight, and C-1: 0.60 parts by weight were added relative to cf1: 100 parts by weight. The jacket temperature was set to 140℃, and the reactor was heated and stirred for 5 hours under reduced pressure of 0.4 kPa to obtain polymer A-1 (ethylene-hexadecyl acrylate-octadecyl acrylate-methyl acrylate copolymer). The obtained polymer A-1 has a melting peak temperature Tm (℃) and a melting enthalpy ΔH between 10 and 60℃, as well as unreacted C... 14～30 The contents (wt%) of the alkyl compounds are as follows.

[0676] Structural unit (A): 84.5 mol%

[0677] Structural unit (B): 12.9 mol%

[0678] Structural unit (C): 2.6 mol%

[0679] Melting peak temperature Tm: 32℃ (Measurement condition 3)

[0680] Enthalpy of fusion ΔH between 10 and 60 °C: 76 J / g (determination condition 3)

[0681] Unreacted with C 14～30 Content of alkyl compounds: 0.9% by weight

[0682] A-2: Ethylene-hexadecyl acrylate-methyl acrylate copolymer

[0683] After nitrogen purging of the reactor equipped with a stirrer, B-1: 86 parts by weight and C-1: 0.60 parts by weight were added relative to cf1: 100 parts by weight. The jacket temperature was set to 140℃, and the mixture was heated and stirred for 3 hours under reduced pressure of 0.4 kPa to obtain polymer A-2 (ethylene-hexadecyl acrylate-methyl acrylate copolymer). The obtained polymer A-2 has a melting peak temperature Tm (℃) and a melting enthalpy ΔH between 10 and 60℃, and the unreacted C... 14～30 The contents (wt%) of the alkyl compounds are as follows.

[0684] Structural unit (A): 84.1 mol%

[0685] Structural unit (B): 13.3 mol%

[0686] Structural unit (C): 2.6 mol%

[0687] Melting peak temperature Tm: 23℃ (Measurement condition 3)

[0688] Enthalpy of fusion ΔH between 10 and 60 °C: 65 J / g (determination condition 3)

[0689] Unreacted with C 14～30 Content of alkyl compounds: 0.9% by weight

[0690] A-3: Ethylene-α-olefin copolymer

[0691] After vacuum drying, 1.4 L of a toluene solution containing 706 g of α-olefin C2024 (a mixture of olefins with carbon numbers of 18, 20, 22, 24, and 26, manufactured by INEOS) was added to a 5 L autoclave equipped with a stirrer and internally purged with nitrogen. Next, toluene was added in 3 L increments. The autoclave was heated to 60 °C, and ethylene was added to stabilize the system at a partial pressure of 0.1 MPa. A hexane solution of triisobutylaluminum (0.34 mol / L, 14.7 mL) was then added. Next, a toluene solution of dimethylphenylammonium tetra(pentafluorophenyl)borate (1.0 mmol / 13.4 mL) and a toluene solution of diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconia (0.2 mmol / L, 7.5 mL) were added to initiate polymerization, with ethylene gas supplied to maintain a constant total pressure.

[0692] After 3 hours, 2 ml of ethanol was added to stop the polymerization. After polymerization stopped, a toluene solution containing the polymer was added to acetone, thereby precipitating the ethylene-α-olefin copolymer. The filtered polymer was then washed twice more with acetone.

[0693] The obtained polymer was vacuum dried at 80°C, yielding 369 g of polymer. The melting peak temperature Tm (°C) of the obtained polymer A-3 and the unreacted polymer with C... 14～30 The contents (wt%) of the alkyl compounds are as follows.

[0694] Structural unit (A): 84.6 mol%

[0695] Structural unit (B): 15.4 mol%

[0696] Melting peak temperature Tm: 34℃ (Measurement condition 5)

[0697] Enthalpy of fusion ΔH between 10 and 60 °C: 83 J / g (determination condition 5)

[0698] A-4: Ethylene-docoyl acrylate-methyl acrylate copolymer

[0699] After nitrogen purging of the reactor equipped with a stirrer, B-3: 120 parts by weight and C-1: 0.60 parts by weight were added relative to cf2: 100 parts by weight. The jacket temperature was set to 140℃, and the reactor was heated and stirred for 5 hours under reduced pressure of 0.4 kPa to obtain polymer A-4 (ethylene-docoyl acrylate-methyl acrylate copolymer). The obtained polymer A-4 has a melting peak temperature Tm (℃) and a melting enthalpy ΔH between 10 and 60℃, and the unreacted C... 14～30 The contents (wt%) of the alkyl compounds are as follows.

[0700] Structural unit (A): 87.1 mol%

[0701] Structural unit (B): 10.9 mol%

[0702] Structural unit (C): 2.0 mol%

[0703] Melting peak temperature Tm: 51℃ (Measurement condition 3)

[0704] Enthalpy of fusion ΔH between 10 and 60 °C: 92 J / g (determination condition 3)

[0705] Unreacted with C 14～30 Content of alkyl compounds: 1.2% by weight

[0706] <Polymer 2>

[0707] D-1: ACRYFT WH206-F (Ethylene-methyl methacrylate copolymer, melting point temperature 86°C) [Manufactured by Sumitomo Chemical Co., Ltd.]

[0708] D-2: Sumitomo Nobrene (propylene homopolymer, melting point 163°C) [Manufactured by Sumitomo Chemical Co., Ltd.]

[0709] D-3: ENGAGE8100 (ethylene-octene copolymer, melting point 57°C) [Manufactured by The Dow Chemical Company]

[0710] D-4: Sumitomo Nobrene (propylene random copolymer, melting point 132°C) [Manufactured by Sumitomo Chemical Co., Ltd.]

[0711] D-5: HI-ZEX 3300F (High-density polyethylene, melt peak temperature 132°C) [Manufactured by Prime Polymer Co., Ltd.]

[0712] D-6: ACRYFT WD106 (Ethylene-methyl methacrylate copolymer, melting point 101°C) [Manufactured by Sumitomo Chemical Co., Ltd.]

[0713] <Organic peroxides>

[0714] E-1: CH-12 (a mixture containing 8 wt% 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane and 92 wt% polypropylene) (1-minute half-life temperature: 180°C) [Made by Nippon Oil Co., Ltd.]

[0715] E-2: A mixture containing 50 wt% 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, calcium carbonate, and amorphous silica (1-minute half-life temperature: 180°C) [Manufactured by KAYAKUAKZO Co., Ltd.]

[0716] <Crosslinking aids>

[0717] F-1: Hi-Cross MS50 (a mixture of 50 wt% trimethylolpropane trimethacrylate and 50 wt% amorphous silica) [Manufactured by Seiko Chemical Co., Ltd.]

[0718] F-2: Hi-Cross M (Trimethylolpropane Trimethacrylate) [Manufactured by Seiko Chemical Co., Ltd.]

[0719] <Antioxidants>

[0720] G-1: IRGANOX 1010 (Pentaerythritol = tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]) [Manufactured by BASF]

[0721] <Processing Heat Stabilizer>

[0722] H-1: IRGAFOS168 (tris(2,4-di-tert-butylphenyl) phosphite) [manufactured by BASF]

[0723] <Lubricant>

[0724] I-1: ALFLOW AD-281F (Ethylene dioleoamide) [Manufactured by Nippon Oil Company]

[0725] Packaging Materials

[0726] J-1: EXCELLEN VL VL700 (linear low-density polyethylene, melt peak temperature 90°C) [Manufactured by Sumitomo Chemical Co., Ltd.]

[0727] J-2: Sumitomo Nobrene (propylene homopolymer, melting point 163°C) [Manufactured by Sumitomo Chemical Co., Ltd.]

[0728] <Extruder>

[0729] Twin-screw extruder (1)

[0730] Screw diameter D = 75mm

[0731] • Effective screw length L / screw diameter D = 40

[0732] Single-screw extruder (2)

[0733] • Screw diameter D = 20mm

[0734] Spinning apparatus (3)

[0735] • Screw diameter D = 20mm

[0736] Composite spinning device (4)

[0737] • Screw diameter D = 25mm

[0738] Twin-screw extruder (5)

[0739] • Screw diameter D = 15mm

[0740] • Effective screw length L / screw diameter D = 45

[0741] IV. Preparation and Evaluation of Heat Storage Compositions

[0742] Example A1:

[0743] Preparation of resin compositions comprising ethylene-hexadecyl acrylate-octadecyl acrylate-methyl acrylate copolymer and ethylene-methyl methacrylate copolymer

[0744] The polymers A-1 (73.4 parts by weight), D-1 (23.8 parts by weight), E-1 (2.5 parts by weight), G-1 (0.1 parts by weight), H-1 (0.1 parts by weight), and I-1 (0.1 parts by weight) obtained in Reference Example 2 were fed into a twin-screw extruder (1) and melt-blended at a screw speed of 350 rpm, a discharge rate of 150 kg / hr, and a maximum barrel temperature of 220°C to produce resin composition A1'. Furthermore, J-1 was fed into a single-screw extruder (2) and melt-blended at a discharge rate of 9 kg / hr and a maximum barrel temperature of 240°C to produce sheet-like J-1. Next, using a multi-layer sheet forming machine equipped with a multi-layer die, the resin composition A1' and J-1 are extruded in multiple layers at a die temperature of 230°C, with the outer layer / inner layer / outer layer being J-1 / resin composition A1' / J-1 and the weight ratio of the outer layer / inner layer / outer layer being 4.5 / 150 / 4.5, to produce packaged granules of the heat-storing composition A1.

[0745] The prepared heat storage composition A1 was spun using a spinning device (3) at a maximum barrel temperature of 190°C, a die diameter of 0.8 mmφ, and a traction speed of 48.5 m / min to produce unstretched yarn, and a tensile test was performed on the unstretched yarn. DSC determination was carried out under test conditions 1.

[0746] Example A2:

[0747] Preparation of resin compositions comprising ethylene-hexadecyl acrylate-octadecyl acrylate-methyl acrylate copolymer and ethylene-methyl methacrylate copolymer

[0748] Using polymers A-1 (62.9 parts by weight), D-1 (34.3 parts by weight), E-1 (2.5 parts by weight), G-1 (0.1 parts by weight), H-1 (0.1 parts by weight), and I-1 (0.1 parts by weight) obtained in Reference Example 2, except that, granules and undrawn filaments of resin composition A2 were prepared in the same manner as in Example A1, and tensile tests were performed on the undrawn filaments. DSC determination was performed under test conditions 1.

[0749] Example A3:

[0750] Preparation of resin compositions comprising ethylene-hexadecyl acrylate-methyl acrylate copolymer and ethylene-methyl methacrylate copolymer

[0751] Using polymers A-2 (73.4 parts by weight), D-1 (23.8 parts by weight), E-1 (2.5 parts by weight), G-1 (0.1 parts by weight), H-1 (0.1 parts by weight), and I-1 (0.1 parts by weight) obtained in Reference Example 2, granules and undrawn filaments of resin composition A3 were prepared in the same manner as in Example A1, and tensile tests were performed on the undrawn filaments. DSC measurements were performed under test conditions 1.

[0752] Example A4:

[0753] Preparation of resin compositions comprising ethylene-α-olefin copolymers and ethylene-octene copolymers

[0754] Polymers A-3 (69.9 parts by weight), D-3 (29.9 parts by weight), G-1 (0.1 parts by weight), and H-1 (0.1 parts by weight) obtained in Reference Example 2 were fed into a twin-screw extruder (5) and melt-blended at a maximum barrel temperature of 220°C to produce granules and undrawn filaments of resin composition A4. Tensile tests were performed on the undrawn filaments. DSC determination was performed under test conditions 1.

[0755] Comparative example C1:

[0756] Preparation of resin compositions comprising ethylene-hexadecyl acrylate-octadecyl acrylate-methyl acrylate copolymer and propylene homopolymer

[0757] Using polymers A-1 (73.4 parts by weight), D-2 (23.8 parts by weight), E-1 (2.5 parts by weight), G-1 (0.1 parts by weight), H-1 (0.1 parts by weight), and I-1 (0.1 parts by weight) obtained in Reference Example 2, resin composition C1' was prepared in the same manner as in Example A1. Next, the discharge rate of J-2 was set to 8 kg / hr, the outer layer / inner layer / outer layer ratio was set to J-2 / resin composition C1' / J-2, and the outer layer / inner layer / outer layer weight ratio was set to 4 / 150 / 4. Particles and undrawn filaments of composition C1 were prepared in the same manner as in Example A1, and tensile tests were performed on the undrawn filaments. DSC measurements were performed under test conditions 1.

[0758] Comparative example C2:

[0759] Preparation of resin compositions comprising ethylene-hexadecyl acrylate-octadecyl acrylate-methyl acrylate copolymer and ethylene-methyl methacrylate copolymer

[0760] Using polymers A-1 (73.4 parts by weight), D-6 (23.8 parts by weight), E-1 (2.5 parts by weight), G-1 (0.1 parts by weight), H-1 (0.1 parts by weight), and I-1 (0.1 parts by weight) obtained in Reference Example 2, except that, granules and undrawn filaments of resin composition C2 were prepared in the same manner as in Example A1, and tensile tests were performed on the undrawn filaments. DSC determination was performed under test conditions 1.

[0761] Comparative example C3:

[0762] Preparation of resin compositions comprising ethylene-docosyl acrylate-methyl acrylate copolymer and propylene random copolymer

[0763] The polymers A-4 (78.2 parts by weight), D-4 (19.6 parts by weight), E-2 (1.0 parts by weight), F-1 (1.0 parts by weight), G-1 (0.1 parts by weight), and H-1 (0.1 parts by weight) obtained in Reference Example 2 were fed into a twin-screw extruder (5) and melt-blended at a maximum barrel temperature of 220°C to produce granules of resin composition C3. Then, attempts were made to produce undrawn filaments, but yarn breakage occurred, making it difficult to obtain samples. DSC determination was performed under determination conditions 1.

[0764] Comparative example C4:

[0765] Preparation of resin compositions comprising ethylene-docosyl acrylate-methyl acrylate copolymer and high-density polyethylene

[0766] The polymers A-4 (78.2 parts by weight), D-5 (19.6 parts by weight), E-2 (1.0 parts by weight), F-1 (1.0 parts by weight), G-1 (0.1 parts by weight), and H-1 (0.1 parts by weight) obtained in Reference Example 2 were fed into a twin-screw extruder (5) and melt-blended at a maximum barrel temperature of 220°C to produce granules of resin composition C4. Then, attempts were made to produce undrawn filaments, but yarn breakage occurred, making it difficult to obtain samples. DSC determination was performed under determination conditions 1.

[0767] V. Production and Evaluation of Fibers Containing Heat Storage Compositions

[0768] Example B1

[0769] Using a composite spinning apparatus (4), and with 40 parts by weight of the heat storage composition A1 and 60 parts by weight of polyester obtained in Example A1, an undrawn filament of a core-sheath type composite fiber with sheath: polyester and core: heat storage composition A1 was obtained. The undrawn filament of the obtained core-sheath type composite fiber was drawn in a bath at 80°C at a draw ratio of 3 to 4 times to obtain a drawn filament. Fineness was studied, and a drawn filament with a fineness of 3.1 dtex was obtained. In addition, the melting peak temperature Tm (°C) of the obtained drawn filament is as follows. DSC measurement was performed under measurement conditions 2.

[0770] Melting peak temperature Tm: 32℃

[0771] The enthalpy of fusion ΔH observed by differential scanning calorimetry in the temperature range of 10–60 °C was 24 J / g.

[0772] Example B2

[0773] Using a composite spinning apparatus (4), and with 40 parts by weight of the heat storage composition A1 and 60 parts by weight of polyester obtained in Example A1, an undrawn filament of a core-sheath type composite fiber with sheath of polyester and core of the heat storage composition A1 was obtained. The undrawn filament of the obtained core-sheath type composite fiber was drawn in a bath at 80°C at a draw ratio of 3 to 4 times to obtain a drawn filament with a fineness of 4.3 dtex. The melting peak temperature Tm (°C) of the obtained drawn filament is as follows. DSC measurement was performed under measurement conditions 2.

[0774] Melting peak temperature Tm: 32℃

[0775] The enthalpy of fusion ΔH observed by differential scanning calorimetry in the temperature range of 10–60 °C was 25 J / g.

[0776] Example B3

[0777] Using a composite spinning apparatus (4), and with 50 parts by weight of the heat storage composition A2 and 50 parts by weight of polyester obtained in Example A2, an undrawn filament of a core-sheath type composite fiber with sheath of polyester and core of heat storage composition A2 was obtained. The undrawn filament of the obtained core-sheath type composite fiber was drawn in a bath at 80°C at a draw ratio of 3 to 4 times to obtain a drawn filament with a fineness of 3.2 dtex. The melting peak temperature Tm (°C) of the obtained drawn filament is as follows. DSC measurement was performed under measurement conditions 2.

[0778] Melting peak temperature Tm: 32℃

[0779] The enthalpy of fusion ΔH observed by differential scanning calorimetry in the temperature range of 10–60 °C was 31 J / g.

[0780] Example B4

[0781] Using a composite spinning apparatus (4), and with 50 parts by weight of the heat storage composition A3 and 50 parts by weight of polyester obtained in Example A3, an undrawn filament of a core-sheath type composite fiber with sheath of polyester and core of heat storage composition A3 was obtained. The undrawn filament of the obtained core-sheath type composite fiber was drawn in a bath at 80°C at a draw ratio of 3 to 4 times to obtain a drawn filament with a fineness of 3.0 dtex. The melting peak temperature Tm (°C) of the obtained drawn filament is as follows. DSC measurement was performed under measurement conditions 2.

[0782] Melting peak temperature Tm: 23℃

[0783] The enthalpy of fusion ΔH observed by differential scanning calorimetry in the temperature range of 10–60 °C was 23 J / g.

[0784] Comparative Example D1

[0785] Using a composite spinning apparatus (4), and with 40 parts by weight of the heat storage composition C1 obtained in Comparative Example C1 and 60 parts by weight of polyester, an undrawn core-sheath type composite fiber with sheath: polyester and core: heat storage composition C1 was obtained. The undrawn core-sheath type composite fiber was drawn in a bath at 80°C at a draw ratio of 3 to 4 times to obtain a drawn fiber. Fineness was studied, and a drawn fiber with a fineness of 4.8 dtex was obtained. In addition, the melting peak temperature Tm (°C) of the obtained drawn fiber is as follows.

[0786] Melting peak temperature Tm: 30℃

[0787] The enthalpy of fusion ΔH observed by differential scanning calorimetry in the temperature range of 10–60 °C was 22 J / g.

[0788] [Table 1]

[0789]

[0790] [Table 2]

[0791]

Claims

1. A heat storage composition comprising substance A and polymer 2, The heat storage composition has a melting peak temperature between 10°C and 60°C, and a melting enthalpy of 30 J / g or higher between 10°C and 60°C. The melting peak temperature of polymer 2 is 60℃~86℃. The polymer 2 is an ethylene-unsaturated carboxylic acid ester copolymer. The heat storage composition has an island structure, wherein the volume average equivalent spherical particle size of the islands (i.e., the dispersed phase) is less than 1.5 μm or the area fraction of the islands (i.e., the dispersed phase) is less than 15%. The heat storage composition has multiple melting peak temperatures, at least one of which is in the range of 60°C to 120°C.

2. The heat storage composition according to claim 1, wherein the polymer 2 is an ethylene-methyl methacrylate copolymer.

3. The heat storage composition according to claim 1, wherein the gel fraction is less than 15% by weight.

4. The heat storage composition according to claim 1, wherein, Substance A has a molecular weight of over 2000.

5. A fiber comprising the heat-storing composition according to any one of claims 1 to 4.

6. A heat-storing fiber comprising a heat-storing composition containing substance A and polymer 2, The fiber has a melting peak temperature between 10°C and 60°C, and a melting enthalpy of 5 J / g or higher between 10°C and 60°C. The melting peak temperature of polymer 2 is 60℃~86℃. The polymer 2 is an ethylene-unsaturated carboxylic acid ester copolymer. The heat storage composition of the fiber has an island structure, wherein the equivalent spherical particle size of the island, i.e., the dispersed phase, is less than 0.1 μm or the area fraction of the island, i.e., the dispersed phase, is less than 15%. The heat-storing fiber has multiple melting peak temperatures, at least one of which is in the range of 60°C to 120°C.

7. The heat-storing fiber according to claim 6, wherein the polymer 2 is an ethylene-methyl methacrylate copolymer.

8. The heat-storing fiber according to claim 6, wherein, The gel fraction of the heat storage composition within the fiber is less than 15% by weight.

9. The heat-storing fiber according to claim 7 or 8, wherein, Substance A has a molecular weight of over 2000.

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