Composition set, cured product and molded product

Abstract

To provide a novel composition set capable of giving a composition containing a magnetic powder.SOLUTION: There is provided a composition set. The composition set comprises a main agent containing a urethane prepolymer having an isocyanate group as a terminal group and a curing agent containing a polyol. At least one of the main agent and the curing agent contains a magnetic powder.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a composition set, a cured product, and a molded product. [Background technology]

[0002] Resin compositions containing magnetic powder are easy to mold, and thus molded products thereof are used as magnetic parts in a variety of fields. As a resin composition containing magnetic powder, for example, a thermoplastic elastomer composition containing a thermoplastic elastomer and magnetic powder has been disclosed (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2022 / 255218 Summary of the Invention [Problem to be solved by the invention]

[0004] The main object of the present disclosure is to provide a novel set of compositions capable of providing compositions containing magnetic powders. [Means for solving the problem]

[0005] The present disclosure provides a composition set according to [1], a cured product according to [2], and a molded product according to [3]. [1] A base agent containing polyisocyanate; a curing agent comprising a polyol; Equipped with At least one of the base agent and the curing agent contains magnetic powder. Composition set. [2] A cured product of a composition comprising the base agent and the curing agent in the composition set described in [1]. [3] A molded article comprising the cured product according to [2]. [Effects of the Invention]

[0006] According to the present disclosure, a novel composition set capable of providing a composition containing a magnetic powder is provided. Also according to the present disclosure, a cured product of the composition obtained by using such a composition set is provided. Furthermore, according to the present disclosure, a molded product including such a cured product is provided. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, embodiments of the present disclosure will be described. However, the present disclosure is not limited to the following embodiments. In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In addition, in numerical ranges described in stages in this specification, the upper or lower limit of a numerical range of a certain stage may be replaced with the upper or lower limit of a numerical range of another stage. In addition, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in an example.

[0008] As used herein, the term "polyol" refers to a compound having an average of more than one (for example, two or more) hydroxyl groups in the molecule.

[0009] As used herein, the term "polyisocyanate" refers to a compound having an average of more than one (for example, two or more) isocyanate group in the molecule.

[0010] Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. When the base agent or curing agent contains multiple substances corresponding to each component, the content of each component in the base agent or curing agent means the total amount of the multiple substances present in the base agent or curing agent, unless otherwise specified.

[0011] [Composition set] The composition set of one embodiment includes a base agent and a curing agent. The base agent includes a polyisocyanate (hereinafter, sometimes referred to as "component (a)"). The curing agent includes a polyol (hereinafter, sometimes referred to as "component (b)"). At least one of the base agent and the curing agent includes a magnetic powder (hereinafter, sometimes referred to as "component (c)").

[0012] (a) Component: Polyisocyanate There are no particular restrictions on the component (a), so long as it is a compound having an average of more than one (for example, two or more) isocyanate group in the molecule.

[0013] Examples of component (a) include aromatic polyisocyanates in which an isocyanate group is bonded to an aromatic hydrocarbon, aliphatic polyisocyanates in which an isocyanate group is bonded to an aliphatic hydrocarbon, and alicyclic polyisocyanates in which an isocyanate group is bonded to an alicyclic hydrocarbon. Component (a) may be a polymer of aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, or the like.

[0014] Examples of aromatic polyisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, m- or p-xylylene diisocyanate, and α,α,α',α'-tetramethylxylylene diisocyanate.

[0015] Examples of aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0016] Examples of alicyclic polyisocyanates include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0017] Component (a) may be, for example, a urethane prepolymer (hereinafter simply referred to as "urethane prepolymer") having an isocyanate group as a terminal group. The urethane prepolymer may be a reaction product of a polyol (hereinafter sometimes referred to as "component (a1)") and a polyisocyanate (hereinafter sometimes referred to as "component (a2)"). That is, the urethane prepolymer may have a polymer chain containing a structural unit derived from component (a1) and a structural unit derived from component (a2), and an isocyanate group bonded to the end of the polymer chain. Because the urethane prepolymer has an isocyanate group as a terminal group, it can undergo polymerization or crosslinking by reacting with component (b) contained in the curing agent, moisture (in the air or on the surface of the adherend), etc., resulting in the formation of a cured product of a composition containing a base agent and a curing agent.

[0018] Examples of the component (a1) include polyester polyols, polyether polyols, polyether ester polyols, polyurethane polyols, polycarbonate polyols, polyolefin polyols, etc. The component (a1) may be either a crystalline polyol or an amorphous polyol.

[0019] The component (a1) may contain, for example, a polyether polyol. The polyether polyol is not particularly limited, but examples thereof include polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyols.

[0020] Examples of the component (a2) include the aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates exemplified for the component (a).

[0021] When the urethane prepolymer is obtained by reacting the components (a1) and (a2), a catalyst for forming the urethane prepolymer (hereinafter sometimes referred to as the "component (a3)") may be used as needed. The component (a3) ​​can be a known catalyst that promotes the urethanization reaction or the urea reaction.

[0022] The content of the (a3) ​​component can be adjusted appropriately depending on the types of the (a1) component and the (a2) component, etc. The content of the (a3) ​​component may be, for example, 0.001 to 5 mass%, 0.005 to 1 mass%, or 0.01 to 0.1 mass% based on the total amount of the (a1) component and the (a2) component.

[0023] The urethane prepolymer can be obtained by reacting the (a1) component with the (a2) component in the presence or absence of the (a3) ​​component. The temperature and time for reacting the (a1) component with the (a2) component are not particularly limited, but may be, for example, 70 to 130°C and 30 minutes to 48 hours.

[0024] The content of the (a) component (or the sum of the (a1), (a2), and (a3) ​​components) based on the total amount of the main ingredient may be 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, or 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less.

[0025] (b) Polyol Component (b) is not particularly limited as long as it is a compound having an average of more than one (e.g., two or more) hydroxyl group per molecule, and may contain, for example, a polyether polyol exemplified as component (a1) above. Component (b) may contain a compound having two hydroxyl groups and a compound having three or more hydroxyl groups, as crosslinking is more likely to proceed.

[0026] The content of component (b) based on the total amount of the curing agent may be 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, or may be 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less.

[0027] The total content of the (a) component and the (b) component may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, based on the total amount of the base agent and the curing agent, and may be 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less.

[0028] (c) Component: magnetic powder There are no particular restrictions on component (c) as long as it is a magnetic powder, and it may be either a soft magnetic powder or a hard magnetic powder. The metal of component (c) may be, for example, at least one metal selected from the group consisting of pure iron, Fe-Si alloys, Fe-Si-Al alloys (Sendust), Fe-Ni alloys (Permalloy), Fe-Cu-Ni alloys (Permalloy), Fe-Co alloys (Permendur), Fe-Cr alloys (stainless steel), Fe-Ni-Cr alloys (stainless steel), Fe-Cr-Si alloys (electromagnetic stainless steel), Fe-Ni-Mn-C alloys (Invar), Sm-Co alloys (rare earth magnets), Nd-Fe-B alloys (rare earth magnets), Sm-Fe-N alloys (rare earth magnets), Al-Ni-Co alloys (Alnico magnets), Ni-Zn alloys (ferrites), Ni-Zn-Cu alloys (ferrites), Mn-Zn alloys (ferrites), and salts containing iron oxides. The metal powder that is the soft magnetic powder may be amorphous. The soft magnetic metal powder may be an Fe amorphous alloy. The soft magnetic metal powder may be at least one of amorphous iron powder and carbonyl iron powder. Furthermore, component (c) may contain multiple metal elements. For example, the metal powder may further contain at least one element selected from the group consisting of base metal elements, noble metal elements, transition metal elements, and rare earth elements in addition to the above elements. The metal powder may further contain at least one element selected from the group consisting of copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), tin (Sn), chromium (Cr), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), oxygen (O), beryllium (Be), phosphorus (P), boron (B), and silicon (Si).

[0029] The average particle size of component (c) may be 1 μm or more or 3 μm or more, and may be 200 μm or less, 100 μm or less, 50 μm or less, or 30 μm or less. Here, the average particle size refers to the median diameter (D50) in the volume-based particle size distribution. The average particle size of component (c) can be measured, for example, by laser diffraction scattering.

[0030] The content of component (c) may be 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total amount of the base agent and curing agent, and may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less.

[0031] In one embodiment, the base agent may include component (c). In one embodiment, the curing agent may include component (c).

[0032] At least one of the base agent and the curing agent may optionally contain other components (hereinafter, sometimes referred to as "component (d)"). Examples of component (d) include curing catalysts (catalysts for promoting the reaction between component (a) and component (b), moisture, etc.), coupling agents, antifoaming agents, nucleating agents, plasticizers, surfactants, flame retardants, fillers, photocoloring agents, thermal color inhibitors, imaging agents, thermal crosslinking agents, UV absorbers, light stabilizers, dehydrating agents, antioxidants, antioxidants, antistatic agents, adhesion promoters, dispersants, solvents, pigments, dyes, fragrances, and carbon black. The content of these other components may be 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 1% by mass or more, or 5% by mass or more, based on the total amount of the base agent and curing agent, and may be 50% by mass or less, 35% by mass or less, 10% by mass or less, 5% by mass or less, or 0.5% by mass or less.

[0033] [Cured product] The cured product of one embodiment is a cured product of a composition (curable composition) containing a main agent and a curing agent in the composition set. The composition containing a main agent and a curing agent can be prepared by mixing the main agent and the curing agent. The main agent and the curing agent may be mixed at 10 to 35°C for 1 to 60 minutes, for example.

[0034] The method for mixing the base agent and the curing agent is not particularly limited, and may be, for example, a method in which they are mixed by hand application using a normal caulking gun, or a method in which they are mixed using a mechanical rotary mixer, static mixer, or the like in combination with a metering pump (e.g., a gear pump, a plunger pump, a mono pump, or the like) and a throttle valve for feeding the raw materials.

[0035] When the base agent and curing agent are mixed, the equivalent ratio (molar ratio) of isocyanate groups (NCO) in the base agent to hydroxyl groups (OH) in the curing agent (NCO groups / OH groups) may be, for example, 1.0 to 5.0. The isocyanate groups in the base agent are mainly derived from component (a), and the hydroxyl groups in the curing agent are mainly derived from component (b).

[0036] The prepared composition can be cured, for example, by curing the composition, since the isocyanate groups of component (a) react with component (b) and moisture (water in the air or on the surface of the adherend). The conditions for curing the composition (curing conditions) may be, for example, 10 to 35°C and 30 to 60% RH (relative humidity) for 0.5 to 7 days. In this way, a cured product of the composition can be obtained. The prepared composition has the advantage that a cured product can be obtained at such a low temperature and in a short period of time, and further, no heating device or light irradiation device is required for curing.

[0037] The cured product of the composition contains a urethane polymer having urethane bonds formed by polymerizing or crosslinking components (a) and (b). The cured product of the composition containing such a urethane polymer has excellent properties such as flexibility, stretchability, and bending properties, and can be molded into any shape.

[0038] [Molded product] The molded product of one embodiment is obtained by curing the composition and includes a cured product of the composition. The shape of the molded product including the cured product is not particularly limited and may include, for example, a film (membrane), a plate, a powder, or a granule, and may be any shape depending on the application. The shape of the molded product including the cured product may be, for example, a continuous shape or a discontinuous shape. Here, a continuous shape means a shape that is continuous in at least one direction. Examples of continuous shapes include a linear shape, a curved shape, and a planar shape. A discontinuous shape means a shape that is not continuous in one direction and is interrupted. Examples of discontinuous shapes include a dot shape, a spot shape, and a dashed line shape.

[0039] Examples of methods for obtaining a molded product from a composition include a method including a step of forming a composition (composition film, composition layer, etc.) in a desired shape by applying the composition, and a step of curing the composition (composition film, composition layer, etc.) in a desired shape to obtain a cured product (cured product film, cured product layer, etc.) in a desired shape.

[0040] The application method is not particularly limited, and examples thereof include a method using an application device such as a dispenser connected to the mixer exemplified in the above mixing method. The application pattern of the composition can be arbitrarily set according to the desired shape.

[0041] The method for curing a composition (composition film, composition layer, etc.) to obtain a cured product (cured product film, cured product layer, etc.) may be the same as the conditions (curing conditions) for curing the above-mentioned composition.

[0042] A cured product of the composition tends to have excellent flexibility, stretchability, bending properties, etc., and can therefore be molded into a three-dimensional shape by bending the cured product of the composition, etc. Therefore, the molded product can also be obtained by a method including, for example, a step of obtaining a first molded product in the shape of a film (membrane), a plate, or the like, and a step of further molding the first molded product to obtain a second molded product.

[0043] The molded article can be suitably used as a magnetic part. If necessary, the molded article may be magnetized by applying an external magnetic field. [Example]

[0044] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0045] Example 1 [Preparation of Composition Set and Evaluation of Cured Films] <Preparing the main agent> A mixer equipped with a stirrer, a nitrogen inlet tube, a vacuum pump, and a heating / cooling device was charged with 62.5 parts by mass of Preminol 3012 (a polyether polyol (a polymer of propylene glycol using glycerin as an initiator), manufactured by AGC Inc., number average molecular weight: 12,000, number of hydroxyl groups: 3) as component (a1), and 31.3 parts by mass of DINP (diisononyl phthalate) as component (d1) (plasticizer), and the mixture was stirred at room temperature (25°C) for 5 minutes. The mixer was then heated to 120°C, and the pressure inside the mixer was reduced to 2.7 kPa (20 mmHg) using a vacuum pump, and the mixture was stirred for 1 hour. The contents were then cooled to a temperature of 80°C, and 6.3 parts by mass of Millionate MT (4,4'-diphenylmethane diisocyanate, manufactured by Tosoh Corporation, NCO content: 33.6%) was added as component (a2) to the kneading vessel. Nitrogen was then introduced, and the contents were stirred for 30 minutes. The contents were then cooled to a temperature of 40°C. The viscous material obtained through the above process was designated as Main Component A. Table 1 shows the formulation (parts by mass) of Main Component A.

[0046] [Table 1]

[0047] <Preparation of intermediate hardener> A mixing vessel equipped with a stirrer, nitrogen inlet tube, vacuum pump, and heating / cooling device was charged with 98.6 parts by mass of Preminol 5005 (polypropylene glycol, manufactured by AGC Corporation, number average molecular weight: 5000, number of hydroxyl groups: 2, hydroxyl value: 28 mgKOH / g, glass transition temperature: approximately -50°C) as component (b). The mixing vessel was heated to 120°C, and the pressure inside the mixing vessel was reduced to 2.7 kPa (20 mmHg) using a vacuum pump. The contents were stirred for 1 hour. The contents were cooled to 40°C, and 1.0 part by mass of molecular sieve 4A as component (d2) (dehydrating agent) and 0.4 part by mass of Kao Raiser No. 120 (imidazole (amine catalyst), manufactured by Kao Corporation) as component (d3) (curing catalyst) were added and stirred for 15 minutes. The viscous material obtained through the above process was used as a curing agent intermediate. Table 2 shows the compounding composition (parts by mass) of the intermediate curing agent.

[0048] [Table 2]

[0049] <Preparing the hardener> To 10.0 parts by mass of the above-mentioned curing agent intermediate, 67.2 parts by mass of MQFP14-12 (Nd-Fe-B alloy, manufactured by Magnequench, D50: 25 μm) was added as component (c), and the mixture was stirred for 5 minutes using a stirrer to obtain curing agent B.

[0050] <Preparing the composition set> The above-mentioned base agent A and the above-mentioned curing agent B were used as the composition set of Example 1.

[0051] <Preparation of Composition and Fabrication of Cured Film> To 77.2 parts by mass of curing agent B, 18.8 parts by mass of base agent A was added, and the mixture was stirred for 2 minutes. The stirred mixture was degassed for 20 minutes using a vacuum degassing device, yielding a composition containing base agent A and curing agent B. The resulting composition was applied to a release sheet (size: 250 mm x 150 mm, thickness: 0.05 mm, material: polyethylene terephthalate), and then formed into a film with a thickness of 1 mm using an applicator. The resulting laminated sheet of the release sheet and composition was aged at 23°C for 72 hours, yielding a cured film of Example 1 containing a cured product of the composition.

[0052] <Evaluation of cured film> (glass transition temperature) Measurements were performed using a differential scanning calorimeter (Shimadzu Corporation, product name: DSC-60A Plus). Approximately 10 mg of the cured film was cut out and placed in an aluminum cell, which was then capped with an aluminum lid. Measurements were performed by scanning the temperature range from -125°C to 120°C at a rate of 5°C / min, and the temperature at which the baseline shifted was taken as the glass transition temperature. The results are shown in Table 3.

[0053] (tensile modulus, breaking strength, and breaking elongation) The cured film was cut into a rectangular shape (length: 60 mm, width: 5 mm), and the release sheet was peeled off to obtain a test specimen. The tensile modulus (MPa), breaking strength (MPa), and breaking elongation (%) of the test specimen were measured using an autograph (Shimadzu Corporation, product name: AGS-1kNX, load cell: 50 N) at a chuck distance of 40 mm and a pulling rate of 200 mm / min. The results are shown in Table 3.

[0054] (90° bending test) A 90° bending test was performed on cured film at 23°C. In the 90° bending test, a rectangular piece of cured film (length: 60 mm, width: 5 mm) was cut and fixed near the center, and one end of the longitudinal direction was lifted perpendicular to the center fixed part. After 60 seconds of standing, the lifted end was returned to its original position, and the condition of the folded center fixed part was observed. If no change in the state of the center fixed part after bending was observed compared to before bending, the test piece was deemed to have bending resistance and rated as "A." On the other hand, if a change in state was observed in the center fixed part after bending, such as breakage or cracking, compared to before bending, the test piece was rated as "B." The results are shown in Table 3.

[0055] [Table 3]

Claims

1. a base agent containing polyisocyanate; a curing agent comprising a polyol; Equipped with At least one of the base agent and the curing agent contains magnetic powder. Composition set.

2. A cured product of a composition comprising the base agent and the curing agent in the composition set according to claim 1.

3. A molded article comprising the cured product according to claim 2.

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