JP2018172636A - Resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in heat storage, and capable of suppressing shape change caused by the phase change of a heat storage material and forming a molding allowing the maintenance of an initial shape.SOLUTION: The resin composition comprises (a) long chain fatty acid ester, (b) hydroxyl group containing polyolefin, (c) a polyol compound and (d) an isocyanate compound. The (b) hydroxyl group containing polyolefin and the (c) polyol compound are included at a specific ratio to the (a) long chain fatty acid ester of 100 pts.wt.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition capable of forming a molded article having excellent heat storage properties and excellent shape retention, and a molded article.

  In recent years, a technique for storing thermal energy, that is, a thermal storage technique, has attracted attention as one of the techniques for solving the recent energy problems. Thermal storage technology is a technology that makes effective use of natural energy such as solar heat and geothermal heat, and residual heat from air-conditioning equipment. For example, in a house, heat is stored using thermal energy generated by a high-efficiency heat source such as a heat pump. It is used as a technology for reducing energy consumption, as a multipurpose heat source.

  Examples of heat storage materials used in such heat storage technologies include sensible heat storage materials and latent heat storage materials. Especially, heat is stored when a substance changes phase from solid to liquid (heat storage), and phase change from liquid to solid. Organic latent heat storage materials utilizing the property of releasing (dissipating heat) when being used are widely adopted. As a material using such an organic latent heat storage material, Patent Document 1 describes a material in which paraffin is taken in and fixed in a thermoplastic elastomer.

JP, 2015-10777, A

  However, the material described in Patent Document 1 may change in shape with the phase change of the heat storage material. Further, deformation is likely to occur due to repeated phase change of the heat storage material, and it is difficult to maintain the original shape.

  This invention is made | formed in view of such a subject, and while obtaining the outstanding heat storage property, suppresses the shape change resulting from the phase change of a heat storage material, and obtains the molded object which can hold | maintain an initial shape. It is for the purpose.

  The present invention, as a result of intensive studies to solve the above problems, includes a long-chain fatty acid ester as a heat storage material, and further includes a hydroxyl group-containing polyolefin, a polyol compound, and an isocyanate compound under specific conditions. The present inventors have found that a molded article excellent in shape retention and the like as well as heat storage can be formed, and the present invention has been completed.

That is, the present invention has the following characteristics.
1. (A) long chain fatty acid ester,
(B) a hydroxyl group-containing polyolefin,
(C) including a polyol compound (excluding the (b) hydroxyl group-containing polyolefin), and (d) an isocyanate compound,
For (a) 100 parts by weight of the long-chain fatty acid ester,
The total amount of the (b) hydroxyl group-containing polyolefin and the (c) polyol compound is 5 to 200 parts by weight,
The resin composition, wherein the weight ratio [(b) :( c)] of the (b) hydroxyl group-containing polyolefin and the (c) polyol compound is 1:99 to 50:50.
2. 1 above. A molded body formed of the resin composition described in 1.

  INDUSTRIAL APPLICABILITY The present invention is useful because it can provide a resin composition and a molded body that have excellent heat storage properties and can form a molded body that is excellent in shape retainability and the like.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The resin composition of the present invention comprises a long-chain fatty acid ester (hereinafter also referred to as “(a) component”), a hydroxyl group-containing polyolefin (hereinafter also referred to as “(b) component”), a polyol compound (provided that ( b) excluding a hydroxyl group-containing polyolefin (hereinafter also referred to as “component (c)”) and an isocyanate compound (hereinafter also referred to as “component (d)”) under specific conditions. . In particular, the resin composition of the present invention exhibits excellent shape retention and the like while maintaining heat storage properties by containing the component (b) and the component (c) at a specific ratio together with the component (a). Can do. The resin composition of the present invention is suitable for a heat storage molded article.

<(A) component>
The resin composition of the present invention comprises (a) a long-chain fatty acid ester. By containing (a) component, the molded object which has the outstanding heat storage property can be obtained, and it is useful.

  As the component (a), it is preferable to use a long chain fatty acid ester having 8 to 36 carbon atoms (synonymous with 8 to 36 carbon atoms; the same shall apply hereinafter), and a long chain fatty acid ester having 10 to 30 carbon atoms is more preferable. It is preferable to use a long-chain fatty acid ester having 15 to 22 carbon atoms. Such a long-chain fatty acid ester has a high latent heat and has a phase change temperature (melting point) in a practical temperature range, and thus is easy to use for various applications.

  Specific examples of the component (a) include, for example, methyl laurate (melting point 5 ° C.), methyl myristate (melting point 19 ° C.), methyl palmitate (melting point 30 ° C.), methyl stearate (melting point 38 ° C.), stearic acid. Examples include butyl (melting point: 25 ° C.) and methyl arachidate (melting point: 45 ° C.). These can be used alone or in combination of two or more.

<(B) component>
The resin composition of the present invention contains a hydroxyl group-containing polyolefin (component (b)). Component (b) is a substance having at least a hydroxyl group (preferably having two or more hydroxyl groups) in a substance having a polyolefin structure (polydiene structure), and has good compatibility with both component (a) and component (c). Also, it has reactivity with an isocyanate compound (component (d)) described later. In the present invention, by using the component (b) having such characteristics, it is possible to obtain advantageous effects in shape retention and the like.

  Examples of the component (b) include polybutadiene polyol, polyisoprene polyol, and hydrogenated products thereof. As the component (b), one or more selected from hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol are particularly preferable.

The hydroxyl value of the component (b) is not particularly limited, but is 5 mg / KOH to 150 mg / KOH (preferably 10 mg / KOH to 100 mg / KOH, more preferably 20 mg / KOH to 80 mg / KOH). Is preferred.
(B) The molecular weight (number average molecular weight) of a component becomes like this. Preferably it is 500-20000, More preferably, it is 800-15000, More preferably, it is 1000-10000. Such component (b) is more suitable in terms of shape retention, and is also suitable in terms of flexibility and the like.

<(C) component>
The resin composition of the present invention contains (c) a polyol compound. The component (c) is a component that forms a molded product by reacting with an isocyanate compound (component (d)) described later, and plays a role of supporting and holding the component (a).

  (C) As a component, for example, polyester polyol, acrylic polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, polytetramethylene polyol, polyoxypropylene polyol, polyoxypropylene ethylene polyol, epoxy polyol, alkyd polyol, fluorine-containing Examples include polyols, silicon-containing polyols, cellulose and / or derivatives thereof, polysaccharides such as amylose, plant oil polyols such as castor oil, palm oil, and soybean oil. These can be used alone or in combination of two or more. Of these, polyether polyol is preferably used in the present invention.

Examples of the polyester polyol include aromatic polyester polyols, aliphatic polyester polyols, and aromatic / aliphatic polyester polyols, and one or more of these can be used. Specifically, as the aromatic polyester polyol, for example, a condensed polyester polyol obtained by reacting an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride with a polyhydric alcohol, polyethylene terephthalate, etc. And phthalic acid polyester polyols obtained by decomposing the phthalic acid polyester moldings. Examples of the aliphatic polyester polyol include aliphatic polybases such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, oleic acid, linoleic acid, linolenic acid, palmitic acid, stearic acid, and castor oil fatty acid. Examples include condensed polyester polyols obtained by reacting an acid with a polyhydric alcohol.
Examples of polyether polyols include aromatic polyether polyols, glycerin polyether polyols, amino group-containing polyether polyols, and the like. Specifically, as the aromatic polyether polyol, for example, bisphenol A obtained by adding bisphenol A as an initiator and adding alkylene oxide (for example, at least one of ethylene oxide, propylene oxide, and the like). -Type polyether polyol, aromatic amine (for example, toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensation product, etc.) Examples include aromatic amine polyether polyols obtained by adding alkylene oxide as an agent.
Examples of the glycerin-based polyether polyol include polyether polyols obtained by adding alkylene oxide using glycerin as an initiator.
Examples of the amino group-containing polyether polyol include those obtained by adding an alkylene oxide using a low molecular weight amine (for example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) as an initiator.
In the present invention, it is particularly preferable to use an aliphatic polyester polyol, a polyether polyol (glycerin-based polyether polyol) using glycerin as an initiator, or the like.

The hydroxyl value of the component (c) is not particularly limited, but it is 10 mg / KOH to 350 mg / KOH (preferably 20 mg / KOH to 300 mg / KOH, more preferably 80 mg / KOH to 250 mg / KOH). Is preferred.
The molecular weight (number average molecular weight) of the component (c) is preferably 500 to 50000, more preferably 600 to 30000, and still more preferably 700 to 20000. Such a component (c) is more preferable in terms of shape retention, and is also preferable in terms of flexibility.

  The weight ratio of the component (b) and the component (c) is 10 to 200 parts by weight in total (preferably 12 to 150 parts by weight, more preferably 15 to 100 parts by weight, based on 100 parts by weight of the component (a). Preferably, the weight ratio [(b) :( c)] of the component (b) to the component (c) is 1:99 to 50:50 (preferably 5:95 to 45: 55). In the present invention, by including the component (b) and the component (c) at such a ratio, it is possible to form a molded body having excellent heat storage properties and excellent shape retention. (B) When there are too few components than the said ratio, there exists a possibility that the retention of (a) component may be impaired, and it becomes disadvantageous for thermal storage property and its sustainability. It is also disadvantageous in terms of flexibility. (B) When there are too many components than the said ratio, there exists a possibility that a shape change may arise with the phase change of a thermal storage material, and it is easy to produce a deformation | transformation by repetition of the phase change of a thermal storage material, and keeps an original shape. Difficult to do. In addition, the strength of the molded body becomes weak, and the handleability of the molded body (particularly in the case of a sheet) tends to be insufficient.

<(D) component)>
The resin composition of the present invention contains (d) an isocyanate compound. The component (d) used in the present invention is not limited as long as it has two or more isocyanate groups in one molecule. For example, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, araliphatic diisocyanate. Etc., and those derivatized by allohanation, biuretization, dimerization (uretidione), trimerization (isocyanurate), adduct formation, carbodiimide reaction, etc., and mixtures thereof, and can be copolymerized therewith Examples include copolymers with monomers. These can be used alone or in combination of two or more.

  Examples of the aliphatic diisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI). 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-penta Methylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, Njiisoshiane - DOO, dimer acid diisocyanate, norbornene diisocyanate.

  Examples of the alicyclic diisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4 ′. -Methylene bis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate ( IPDI), norbornane diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate Over doors and the like.

  Examples of the aromatic diisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and naphthylene- 1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate, polymeric MDI, carbodiimide-modified MDI, polyol-modified MDI, castor oil-modified MDI, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenyl group Pan-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, 3,3′-dimethoxydiphenyl-4,4′-diisocyanate, dianisidine Examples thereof include diisocyanate and tetramethylene xylylene diisocyanate.

  Examples of the araliphatic diisocyanate include 1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3. -Bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, etc. .

  In the present invention, it is particularly preferable to use aliphatic diisocyanates such as HMDI and derivatives thereof, and aromatic diisocyanates such as MDI and derivatives thereof. Such an isocyanate compound is preferable because it is easy to adjust the pot life and the curing rate.

  In the resin composition of the present invention, the component (c) and the component (d) react to form an appropriate three-dimensional crosslinked structure, and the component (b) includes both the component (a) and the component (c). While being compatible with each other, it reacts with the component (d) and contributes to the formation of a three-dimensional crosslinked structure. A molded body obtained by such a resin composition is greatly different from a molded body made of a thermoplastic resin in the prior art. The molded body obtained by the present invention can hold and retain a large amount of the component (a) in the crosslinked structure, suppress the shape change caused by the phase change of the heat storage material, and maintain the initial shape. Can do. In addition, it is possible to obtain a molded body having strength, flexibility, and the like, and the handleability of the molded body (particularly in the case of a sheet) is improved. Furthermore, it is excellent in terms of suppressing leakage of component (a) and processability of the molded body.

  In the present invention, the mixing amount of the component (a) is preferably 30% by weight or more, more preferably 35 to 95% by weight, and further preferably 40 to 90% by weight with respect to the total amount of the resin composition. By using 30% by weight or more of component (a), excellent heat storage properties can be obtained.

  The component (d) has a molar ratio (NCO / OH molar ratio) between the isocyanate group contained in the component (d) and the hydroxyl group contained in the component (b) and the component (c) (0.5 to 8.0). More preferably, mixing is performed within a range of 0.7 to 7.0, and more preferably 0.8 to 5.0. In the present invention, the component (d) is contained so as to satisfy such an NCO / OH molar ratio, so that it is more preferable in terms of shape retention, and (a) component retention, heat storage performance and its It is also suitable in terms of sustainability.

  In addition to the above components, the resin composition of the present invention includes, for example, a layered clay mineral, a surfactant, a heat conductive material, a compatibilizer, a reaction accelerator, a flame retardant, a pigment, an aggregate, a viscosity modifier, a plasticizer, Buffering agent, dispersing agent, cross-linking agent, pH adjusting agent, antiseptic, antifungal agent, antibacterial agent, algae inhibitor, wetting agent, antifoaming agent, leveling agent, lubricant, dehydrating agent, UV absorber, antioxidant, Additives such as light stabilizers, fibers, fragrances, chemical adsorbents, photocatalysts, hygroscopic powders and the like can also be contained.

  Among these, as the layered clay mineral, it is preferable to use an organically treated layered clay mineral. Examples of the layered clay mineral include smectite, vermiculite, kaolinite, allophane, mica, talc, halloysite, and sepiolite. Further, swellable fluorine mica, swellable synthetic mica, and the like can be used. Examples of the organic treatment include ion exchange (intercalation) of a cation existing between layers of a layered clay mineral with a long-chain alkylammonium ion or the like. In the present invention, smectite and vermiculite are particularly preferably used because they are easily organically treated. Furthermore, among the smectites, montmorillonite, hectorite, and the like are particularly preferably used. In the present invention, particularly, organically treated montmorillonite, organically treated hectorite, and the like can be preferably used.

  The mixing amount of the layered clay mineral is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, and further preferably 3 to 30 parts by weight with respect to 100 parts by weight of the component (a).

  Examples of the surfactant include a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more. However, the resin composition of the present invention may be an embodiment that does not contain such a surfactant.

  In the present invention, in addition to the above components, a heat storage material other than the component (a) can be mixed as long as the effect is not significantly inhibited. Examples of the heat storage material other than the component (a) include aliphatic hydrocarbons, long chain alcohols, long chain fatty acids, polyether compounds, fatty acid triglycerides, and the like, and one or more of these are used. Can do.

  The resin composition of the present invention is a resin composition containing the component (a), the component (b), the component (c), the component (d), and the like. For example, as a production method, the component (a), (b ) Component, (c) component, and (d) component are mixed, and a molded body can be obtained by a method of reacting (b) component and (c) component with (d) component.

  Although the reaction temperature at the time of manufacturing a molded object is not specifically limited, It is preferable to set it as more than the phase change temperature of (a) component. Although specific reaction temperature changes with kinds of (a) component to be used, Preferably it should just be 20-80 degreeC. The reaction time is preferably 0.2 to 5 hours. Moreover, in order to accelerate | stimulate reaction, the said reaction accelerator can be mixed or energy, such as a heat | fever and light, can also be given.

  The shape of the molded body may be a sheet shape, a rod shape, a needle shape, a spherical shape, a square shape, a powder shape, and the like, and the shape is not particularly limited. In the present invention, it is particularly preferable to use it as a sheet. In the sheet-like molded body, for example, various base materials can be laminated on one or both sides of the molded body, and various base materials can be laminated in advance at the time of sheet molding to obtain a molded body. At this time, the forming method of the molded body is not particularly limited, and may be a known method such as extrusion molding, mold molding, or spray coating, roller coating, brush coating, trowel coating, pouring, etc. on various substrates. The method of applying can be adopted. Although the thickness of a sheet-like molded object is not specifically limited, Preferably what is necessary is just to be about 1-100 mm.

  The resin composition of the present invention can be suitably used mainly as a material for interior / exterior materials such as wall materials, ceiling materials, floor materials, etc. of buildings such as houses. In addition, floor heating systems, air conditioning systems, interior materials for vehicles, industrial products such as machinery and equipment, thermoelectric conversion systems, heat transfer media, refrigeration / freezers, bathtubs / bathrooms, cooler boxes, heat insulation sheets, anti-condensation sheets, cooling It can also be applied as a material used for sheets, electrical products, OA equipment, plants, tanks, clothing, curtains, carpets, bedding, daily miscellaneous goods, and the like.

  The resin composition of this invention can set a heat storage material suitably according to a use. For example, when used as an interior / exterior material for a building, a heat storage material having a melting point of about 15 ° C. to 40 ° C. may be used. When used for floor heating, the heat storage material has a melting point of 25 ° C. to 40 ° C. Use a nearby one.

  Moreover, a heat insulating body can also be laminated | stacked on the molded object obtained from the resin composition of this invention. As a result, in order to show excellent heat storage and heat insulation, it is possible to keep the temperature in the space at the optimum temperature against changes in the external temperature by applying it to wall materials, ceiling materials, floor materials, etc. of buildings. This can save energy. Examples of such a heat insulator include polystyrene foam, polyurethane foam, acrylic resin foam, phenol resin foam, polyethylene resin foam, foam rubber, glass wool, rock wool, foam ceramic, etc., or a composite thereof. Etc. Moreover, you may use a commercially available heat insulator. The thermal conductivity of the heat insulator is preferably less than 0.1 W / (m · K), more preferably 0.08 W / (m · K) or less, and even more preferably 0.05 W / (m · K) or less. .

  A heat conductor having a thermal conductivity of 0.1 W / (m · K) or more can be laminated on the molded body obtained in the present invention. Examples of the heat conductor include a resin board and a resin sheet such as a glass plate, acrylic resin, and vinyl resin, a metal plate such as copper, aluminum, iron, brass, zinc, magnesium, and nickel, or a resin board containing a metal material. Or a resin sheet, a slate board, a gypsum board, a calcium silicate board, an ALC board, a wood wool cement board, a plywood etc. are mentioned.

  In order to show excellent heat storage and heat dissipation by laminating a heat conductor on the molded body obtained in the present invention, it can be stored in the molded body by applying it to wall materials, ceiling materials, floor materials, etc. of buildings. The generated cold heat and heat can be efficiently transferred into the space, the temperature in the space can be maintained at an optimum temperature, and energy saving can be achieved. It is also possible to obtain the effect of preventing condensation that is likely to occur in the heat conductor.

  A fire-retardant material such as a flame-retardant material, a semi-incombustible material, and a non-combustible material can be laminated on the molded product obtained in the present invention. Thereby, in addition to the outstanding heat storage property, fireproofness can be improved and it can apply also to the site | parts (for example, interior material etc. of a building) which require fireproofness. Examples of such fireproof materials include concrete plates, glass plates, metal plates, wooden wool cement plates, plaster boards, flat plates such as calcium silicate plates, metal film, film molded products such as glass fibers, and foamable fireproof materials. And flame retardant-containing materials.

  The following examples illustrate the features of the present invention more clearly, but the present invention is not limited to these examples.

(Examples 1-18 and Comparative Examples 1-4)
After preparing the main ingredient component at a temperature of 50 ° C. with the raw materials shown in Table 1 and the blending amounts shown in Table 2, and mixing the isocyanate compound so that the NCO / OH molar ratio is 1.1 / 1, 250 × 170 × The test was obtained by enclosing in a 5 mm polyethylene terephthalate film (100 μm) and curing at 50 ° C. for 30 minutes. The following evaluation was performed about the obtained test body. The results are shown in Table 2. Examples 1 to 18 were good results in any test.

(1) Heat storage property The amount of latent heat of the test specimen was calculated from the amount of latent heat of the heat storage component and the content thereof.
○: Latent heat amount is 300 kJ / m ² or more.
X: Latent heat amount is less than 300 kJ / m ² .

(2) Handling (handling)
The state of the test specimen was evaluated when the edge of the specimen left in the horizontal direction in an atmosphere of 40 ° C. was grasped with one hand and lifted up as it was.
A: The test specimen is lifted while maintaining the level.
○: The specimen is lifted up while maintaining almost horizontal.
X: The specimen cannot be kept horizontal.

(3) Shape retention The appearance of the test specimen after the hot / cold cycle test (50 cycles of 10 ° C. for 3 hours and 40 ° C. for 3 hours) was visually observed.
A: No change in appearance of the specimen.
○: Almost no change in appearance on the specimen.
Δ: Some warping and deformation are observed in the test specimen.
X: Warping or deformation is observed in the test specimen.

(4) Workability About the test body cut | disconnected with the cutter, after implementing a heating / cooling cycle test (same as the above), the presence or absence of the heat storage material from the cross section of the test body was observed.
A: No seepage of the heat storage material is observed.
○: There is almost no seepage of the heat storage material.
Δ: Some exudation of heat storage material is seen.
×: Exudation of heat storage material is observed.

Claims (2)

(A) long chain fatty acid ester,
(B) a hydroxyl group-containing polyolefin,
(C) including a polyol compound (excluding the (b) hydroxyl group-containing polyolefin), and (d) an isocyanate compound,
For (a) 100 parts by weight of the long-chain fatty acid ester,
10 to 200 parts by weight in total of the (b) hydroxyl group-containing polyolefin and the (c) polyol compound,
The resin composition, wherein the weight ratio [(b) :( c)] of the (b) hydroxyl group-containing polyolefin and the (c) polyol compound is 1:99 to 50:50. The molded object formed with the resin composition described in Claim 1.