JP7450347B2 - Resin composition, resin molded article, and method for producing resin composition - Google Patents
Resin composition, resin molded article, and method for producing resin composition Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims description 64
- 239000011347 resin Substances 0.000 title claims description 64
- 239000011342 resin composition Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims description 125
- 239000000463 material Substances 0.000 claims description 98
- 238000004898 kneading Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000741 silica gel Substances 0.000 claims description 27
- 229910002027 silica gel Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 20
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 20
- 239000008188 pellet Substances 0.000 claims description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 239000010954 inorganic particle Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 239000006260 foam Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 15
- -1 polypropylene Polymers 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000011514 reflex Effects 0.000 description 8
- 230000005855 radiation Effects 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000010097 foam moulding Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 230000000191 radiation effect Effects 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Description
本発明は、特定の無機物粒子を混合した樹脂組成物、樹脂成形体、及び樹脂組成物の製造方法に関する。 The present invention relates to a resin composition mixed with specific inorganic particles, a resin molded article, and a method for producing the resin composition.
従来から、樹脂に無機物粒子を混合させた組成物は様々な方法が提案されている。近年、特に、保温効果や断熱効果の高い衣料、敷物などのプラスチック製品や繊維製品が広く用いられており、それらの機能を発現するために、赤外線（近赤外線や遠赤外線）が利用されている。また前記製品は、屋外の利用だけでなく、屋内利用にも使われるようになっている。例えば、特許文献１には、遠赤外線放射材料として０．１～１０ｍｍの比較的大きな粒径のＳｉＯ2，ＺｒＯ2などの無機物を使用することが提案されている。特許文献２～３には、遠赤外線放射材料として３μｍ以下の粒径のＳｉＯ2，ＺｒＯ2などの無機物を使用することが提案されている。特許文献４には、遠赤外線放射と近赤外吸収性マスターバッチ用樹脂組成物として、アンチモンドープ酸化スズ粒子を樹脂に混合することが提案されている。 Conventionally, various methods have been proposed for preparing compositions in which inorganic particles are mixed with resin. In recent years, plastic products and textile products such as clothing and rugs that have particularly high heat retention and insulation effects have been widely used, and infrared rays (near infrared and far infrared rays) are used to achieve these functions. . Moreover, the above-mentioned products are now being used not only for outdoor use but also for indoor use. For example, Patent Document 1 proposes the use of inorganic substances such as SiO 2 and ZrO 2 having relatively large particle sizes of 0.1 to 10 mm as far-infrared emitting materials. Patent Documents 2 and 3 propose the use of inorganic materials such as SiO 2 and ZrO 2 having a particle size of 3 μm or less as far-infrared emitting materials. Patent Document 4 proposes mixing antimony-doped tin oxide particles with a resin as a resin composition for a far-infrared radiation and near-infrared absorbing masterbatch.
しかし、従来の方法は、特許文献１～特許文献３では、遠赤外線放射材料だけなので使用する用途が制限される、使用環境により多量の遠赤外線放射材料を必要とするなど、制限されることがあった。また、特許文献４では、遠赤外線放射と近赤外吸収性とを有する粒子を混合しており、蓄熱性は高いが断熱性に劣る。さらに、無機物微粒子を樹脂にコンパウンド（混合）する場合、粒子径が小さくなるほど凝集等が起こりやすく、均一に微分散することは困難であった。分散させるには、例えば、特許文献１では元々の粒子径を大きくすることを試みているが、それでは粒子の持つ十分な効果を引き出すことができない。また特許文献４では特殊な分散剤を用いることを試みているが、コストが高くなるか、用途が制限されるなどの問題があった。よって、成形体、フィルム、繊維等に加工することが難しいという問題があった。 However, in Patent Documents 1 to 3, the conventional methods have limitations such as limited use of far-infrared emitting materials because they only use far-infrared rays, and depending on the usage environment, a large amount of far-infrared radiating materials are required. there were. Further, in Patent Document 4, particles having far-infrared radiation and near-infrared absorption are mixed, and the heat storage property is high, but the heat insulation property is poor. Furthermore, when compounding (mixing) inorganic fine particles with a resin, the smaller the particle size, the more likely they are to aggregate, making it difficult to achieve uniform fine dispersion. In order to disperse the particles, for example, Patent Document 1 attempts to increase the original particle diameter, but this method cannot bring out the sufficient effect of the particles. Further, in Patent Document 4, an attempt is made to use a special dispersant, but there are problems such as increased cost or limited use. Therefore, there was a problem in that it was difficult to process it into molded bodies, films, fibers, etc.
本発明は、前記従来の問題を解決するため、無機物微粒子を樹脂中に微分散して混合することができ、そのまま成形体とするか、あるいはマスターバッチとして他の樹脂を加えて樹脂成形体とするのに好適な樹脂組成物及び樹脂組成物の製造方法、並びにその樹脂組成物を用いて成形した樹脂成形体を提供する。さらに、温感効果を有する樹脂組成物及び樹脂成形体を提供する。 In order to solve the above-mentioned conventional problems, the present invention allows inorganic fine particles to be finely dispersed and mixed in a resin, and can be made into a molded body as it is, or can be made into a resin molded body by adding another resin as a masterbatch. Provided are a resin composition and a method for producing the resin composition, and a resin molded article molded using the resin composition. Furthermore, a resin composition and a resin molded article having a warming effect are provided.
本発明の樹脂組成物は、熱可塑性樹脂に、遠赤外線放射物質粒子及び近赤外線反射物質粒子を含有した樹脂組成物であって、
前記近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多く、
前記近赤外線反射物質無機粒子はＢ型シリカゲルであり、
前記遠赤外線放射物質粒子は酸化ジルコニウムであり、
前記遠赤外線放射物質粒子は微分散していることを特徴とする。
The resin composition of the present invention is a resin composition containing far-infrared emitting material particles and near-infrared reflecting material particles in a thermoplastic resin,
The amount of the near-infrared reflecting material particles is greater than the amount of the far-infrared emitting material particles,
The near-infrared reflective material inorganic particles are B-type silica gel,
The far-infrared emitting material particles are zirconium oxide,
The far-infrared emitting material particles are characterized in that they are finely dispersed.
本発明の第１番目の樹脂組成物の製造方法は、熱可塑性樹脂を準備し、
遠赤外線放射物質粒子及び近赤外線反射物質粒子を準備し、
前記近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多くなるように、熱可塑性樹脂中に混練させる工程を含み、
前記近赤外線反射物質無機粒子はＢ型シリカゲルであり、
前記遠赤外線放射物質粒子は酸化ジルコニウムであり、
前記遠赤外線放射物質粒子は微分散していることを特徴とする。
The first method for producing a resin composition of the present invention includes preparing a thermoplastic resin,
Prepare far-infrared emitting material particles and near-infrared reflecting material particles,
The method includes a step of kneading the near-infrared reflective material particles into the thermoplastic resin so that the amount of the near-infrared reflective material particles is greater than the amount of the far-infrared emitting material particles;
The near-infrared reflective substance inorganic particles are B-type silica gel ,
The far-infrared emitting material particles are zirconium oxide,
The far-infrared emitting material particles are characterized in that they are finely dispersed .
本発明の第２番目の樹脂組成物の製造方法は、熱可塑性樹脂を準備し、
遠赤外線放射物質粒子及び近赤外線反射物質粒子を準備し、
前記近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多くなるようにして、
樹脂溶融部と、減圧ラインを備えた混練分散部と、押し出し部を連続して接続し、
前記混練溶融部に、水分散液とした遠赤外線放射物質粒子と、加熱溶融させた樹脂とを供給し、
次に前記混練分散部に送り、溶融混練と同時に前記減圧ラインから水分を気体の状態で除去し、押し出し部から樹脂組成物を押し出して冷却し、ペレット化する一次混練工程と、
得られたペレットと近赤外線反射物質粒子をドライブレンドし、溶融混練し、押し出し部から樹脂組成物を押し出して冷却し、ペレット化する二次混練工程を含み、
前記近赤外線反射物質無機粒子はＢ型シリカゲルであり、
前記遠赤外線放射物質粒子は酸化ジルコニウムであり、
前記遠赤外線放射物質粒子は微分散していることを特徴とする。
The second method for producing a resin composition of the present invention includes preparing a thermoplastic resin,
Prepare far-infrared emitting material particles and near-infrared reflecting material particles,
The amount of the near-infrared reflecting material particles is greater than the amount of the far-infrared emitting material particles,
The resin melting section, the kneading dispersion section equipped with a vacuum line, and the extrusion section are connected continuously,
Supplying far-infrared emitting material particles made into an aqueous dispersion and a heated and melted resin to the kneading and melting section,
Next, a primary kneading step of sending the resin composition to the kneading and dispersing section, removing water in a gaseous state from the vacuum line at the same time as melting and kneading, extruding the resin composition from the extrusion section, cooling it, and pelletizing it;
A secondary kneading step of dry blending the obtained pellets and near-infrared reflective material particles, melt-kneading, extruding the resin composition from an extrusion section, cooling, and pelletizing,
The near-infrared reflective material inorganic particles are B-type silica gel ,
The far-infrared emitting material particles are zirconium oxide,
The far-infrared emitting material particles are characterized in that they are finely dispersed .
本発明は、熱可塑性樹脂に、遠赤外線放射物質粒子及び近赤外線反射物質粒子を含有した樹脂組成物であって、前記近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多く、前記遠赤外線放射物質粒子は微分散していることにより、そのまま成形体とするか、あるいはマスターバッチとして他の樹脂を加えて成形体とするのに好適である。
また、熱可塑性樹脂に、遠赤外線放射物質粒子及び近赤外線反射物質粒子を含有しているため、相乗効果により成形体の温感効果を高めることができる。
さらに、水分散液とした遠赤外線放射物質粒子と、加熱溶融させた樹脂とを供給し、溶融混練と同時に前記減圧ラインから水分を気体の状態で除去し、押し出し部から樹脂組成物を押し出して冷却し、ペレット化する一次混練工程と、得られたペレットと近赤外線反射物質粒子をドライブレンドし、溶融混練し、押し出し部から樹脂組成物を押し出して冷却し、ペレット化する二次混練工程を含むことにより、無機物微粒子を樹脂中に微分散して混合することができる。
The present invention provides a resin composition containing far-infrared emitting material particles and near-infrared reflecting material particles in a thermoplastic resin, wherein the amount of the near-infrared reflecting material particles is greater than the amount of the far-infrared emitting material particles. Since the far-infrared emitting material particles are often finely dispersed, they are suitable for forming into a molded object as is or by adding another resin as a masterbatch.
Further, since the thermoplastic resin contains far-infrared emitting material particles and near-infrared reflecting material particles, the thermal sensation effect of the molded article can be enhanced due to a synergistic effect.
Further, far-infrared emitting material particles in the form of an aqueous dispersion and a heated and melted resin are supplied, and at the same time as melting and kneading, water is removed in a gaseous state from the vacuum line, and the resin composition is extruded from the extrusion section. A primary kneading step of cooling and pelletizing, and a secondary kneading step of dry blending the obtained pellets and near-infrared reflective material particles, melt-kneading, extruding the resin composition from an extrusion section, cooling, and pelletizing. By including the inorganic fine particles, the inorganic fine particles can be finely dispersed and mixed into the resin.
本発明は、熱可塑性樹脂に、遠赤外線放射物質粒子及び近赤外線反射物質粒子を含有した樹脂組成物である。遠赤外線放射物質粒子及び近赤外線反射物質粒子を含有した樹脂組成物は、例えば、成形してフィルム、繊維シート、あるいは発泡体などにすると、人体やペットのシートとして温かく有用である。特にシートにしたとき、太陽光などが照射されると表面温度が高く、有用である。近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多く、遠赤外線放射物質粒子は微分散している。近赤外線反射物質粒子の平均粒子径は、遠赤外線放射物質粒子の平均粒子径より大きいほうが好ましい。 The present invention is a resin composition containing far-infrared emitting material particles and near-infrared reflecting material particles in a thermoplastic resin. A resin composition containing far-infrared emitting material particles and near-infrared reflecting material particles, when molded into a film, fiber sheet, or foam, is useful as a warm sheet for the human body or a pet. In particular, when made into a sheet, the surface temperature is high when exposed to sunlight, making it useful. The amount of the near-infrared reflecting material particles is greater than the amount of the far-infrared emitting material particles, and the far-infrared emitting material particles are finely dispersed. The average particle diameter of the near-infrared reflecting material particles is preferably larger than the average particle diameter of the far-infrared emitting material particles.
近赤外線反射物質粒子は、ＣｏＯ，ＣｒＯ，ＭｎＯ2，Ｂｉ2Ｏ3，ＭｏＯ3，ＮｉＯ，Ｖ2Ｏ5，ＢａＯ，ＳｉＯ2（シリカゲル等）などの粒子が使用できるが、好ましくはシリカゲルである。Ａ型シリカゲルは細孔容積が小さく（０．４６ｍＬ／ｇ）、Ｂ型シリカゲルは大きい（０．７５ｍＬ／ｇ）。シリカゲル自体に近赤外線反射性能があるので、近赤外線反射と細孔による空洞による断熱効果に期待ができる。このことからＢ型シリカゲルが好ましい。シリカゲルのタイプ（Ａ型、Ｂ型）はＪＩＳ Ｚ ０７０１によって規定されている。近赤外線反射物質粒子の平均粒子径は１μｍ以上が好ましく、上限は１００μｍ以下が好ましい。より好ましい平均粒子径は１０～９０μｍである。粒子径は、篩分け法による４００メッシュ通過粒子（目合いの大きさが３７μｍ）、あるいはＳＥＭ写真などで確認ができる。篩分け法により求められる粒子径は、４００メッシュ通過粒子（目合いの大きさが３７μｍ）である、すなわち３７μｍ以下であることが好ましい。熱可塑性樹脂１００質量部に対し、近赤外線反射物質粒子の配合量は０．１～１００質量部が好ましく、より好ましくは１～７０質量部であり、さらに好ましくは５～５０質量部である。近赤外線反射特性は、例えばレフランプ試験や近赤外線反射率測定により評価できる。 As the near-infrared reflective material particles, particles such as CoO, CrO, MnO 2 , Bi 2 O 3 , MoO 3 , NiO, V 2 O 5 , BaO, SiO 2 (silica gel, etc.) can be used, but silica gel is preferable. . Type A silica gel has a small pore volume (0.46 mL/g), and type B silica gel has a large pore volume (0.75 mL/g). Since silica gel itself has near-infrared reflective properties, it can be expected to have a heat insulating effect due to near-infrared reflection and cavities created by pores. For this reason, type B silica gel is preferred. The types of silica gel (type A, type B) are defined by JIS Z 0701. The average particle diameter of the near-infrared reflective material particles is preferably 1 μm or more, and the upper limit is preferably 100 μm or less. A more preferable average particle diameter is 10 to 90 μm. The particle size can be confirmed by using a 400 mesh sieving method (with a mesh size of 37 μm) or an SEM photograph. The particle diameter determined by the sieving method is preferably a particle that passes through 400 mesh (the mesh size is 37 μm), that is, it is 37 μm or less. The amount of near-infrared reflective material particles blended is preferably 0.1 to 100 parts by weight, more preferably 1 to 70 parts by weight, and even more preferably 5 to 50 parts by weight, based on 100 parts by weight of the thermoplastic resin. Near-infrared reflection characteristics can be evaluated by, for example, a reflex lamp test or near-infrared reflectance measurement.
遠赤外線放射物質粒子は、ＳｉＯ2，Ａｌ2Ｏ3，ＴｉＯ2，ＦｅＯ2，ＣｕＯ2，ＺｎＯ2，ＭｎＯ2，ＭｇＯなどの粒子が使用できるが、好ましくは酸化ジルコニウムである。酸化ジルコニウムは遠赤外線放射特性が比較的高く、微粒子化でき、水分散液として樹脂に溶融混練できることから好ましい。遠赤外線放射物質粒子の平均粒子径は１００ｎｍ以下が好ましく、下限は１ｎｍである。より好ましい平均粒子径は１～９０ｎｍである。平均粒子径は、ＤＬＳ（Dynamic light scattering：動的光散乱法）により測定できる。熱可塑性樹脂１００質量部に対し、遠赤外線放射物質粒子の配合量は０．１～１５質量部が好ましく、より好ましくは０．５～１０質量部であり、さらに好ましくは１～５質量部である。遠赤外線放射特性は、例えばフーリエ変換赤外分光（ＦＴ－ＩＲ）試験により評価できる。 As far-infrared emitting material particles, particles of SiO 2 , Al 2 O 3 , TiO 2 , FeO 2 , CuO 2 , ZnO 2 , MnO 2 , MgO, etc. can be used, but zirconium oxide is preferable. Zirconium oxide is preferred because it has relatively high far-infrared radiation properties, can be made into fine particles, and can be melted and kneaded into a resin as an aqueous dispersion. The average particle diameter of the far-infrared emitting material particles is preferably 100 nm or less, and the lower limit is 1 nm. A more preferable average particle diameter is 1 to 90 nm. The average particle diameter can be measured by DLS (Dynamic light scattering). With respect to 100 parts by mass of the thermoplastic resin, the amount of the far-infrared emitting material particles is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass. be. The far-infrared radiation characteristics can be evaluated by, for example, a Fourier transform infrared spectroscopy (FT-IR) test.
遠赤外線放射物質粒子は、そのままの状態でも使用できるが、スラリーの状態で添加することが好ましい。スラリーの濃度は１～６０質量％が好ましく、より好ましくは５～５０質量％である。スラリーの濃度が上記範囲内にあると、遠赤外線放射物質の粒子、特に平均粒子径は１００ｎｍ以下の微粒子を、樹脂中に略均一に分散することができる。後述する製造方法で、特には図１に示す押し出し機等を用いるとよい。 Although the far-infrared emitting material particles can be used as they are, it is preferable to add them in the form of a slurry. The concentration of the slurry is preferably 1 to 60% by weight, more preferably 5 to 50% by weight. When the concentration of the slurry is within the above range, particles of the far-infrared emitting substance, particularly fine particles having an average particle diameter of 100 nm or less, can be substantially uniformly dispersed in the resin. In the manufacturing method described below, it is particularly preferable to use an extruder shown in FIG. 1 or the like.
近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子１００質量部に対して、１～１０００質量部が好ましく、より好ましくは２～１４０質量部であり、さらに好ましくは５～５０質量部である。各々の配合量において上記範囲を満たすことで、遠赤外線放射効果を活かしつつ、近赤外線反射効果を最大限に発揮することができる。 The blending amount of the near-infrared reflective material particles is preferably 1 to 1000 parts by mass, more preferably 2 to 140 parts by mass, and still more preferably 5 to 50 parts by mass, per 100 parts by mass of the far-infrared emitting material particles. be. By satisfying the above-mentioned range in each blending amount, it is possible to maximize the near-infrared reflection effect while taking advantage of the far-infrared radiation effect.
また。近赤外線反射物質粒子の平均粒子径は、遠赤外線放射物質粒子の平均粒子径よりも大きいことが好ましい。近赤外線反射物質粒子の平均粒子径は、遠赤外線放射物質粒子の平均粒子径の１０倍以上がより好ましい。各々の平均粒子径において上記範囲を満たすことで、遠赤外線放射効果を活かしつつ、近赤外線反射効果を最大限に発揮することができる。 Also. The average particle diameter of the near-infrared reflecting material particles is preferably larger than the average particle diameter of the far-infrared emitting material particles. The average particle size of the near-infrared reflecting material particles is more preferably 10 times or more the average particle size of the far-infrared emitting material particles. By satisfying the above range for each average particle diameter, it is possible to maximize the near-infrared reflection effect while taking advantage of the far-infrared radiation effect.
樹脂組成物はそのまま成形体とするか、あるいはマスターバッチとして他の樹脂を加えて樹脂成形体とすることもできる。樹脂組成物としては、好ましくはペレット化等を行い、マスターバッチ用樹脂組成物とするのがよい。 The resin composition can be made into a molded article as it is, or can be made into a resin molded article by adding another resin as a masterbatch. The resin composition is preferably pelletized to obtain a masterbatch resin composition.
本発明の樹脂組成物の製造方法は、前記第１番目の方法と第２番目の方法があるが、遠赤外線放射物質粒子と近赤外線反射物質粒子の分散性が良いことから第２番目の方法が好ましい。理由としては、スラリーを添加した際、吸湿性を有する材料などスラリー化（水分散化）が困難な粒子（例えば、近赤外線反射物質粒子としてシリカゲルを用いた場合）を同時に練り込むと、スラリーの水分を含有したり、凝集したり、粒子の分散性が低下するため、一次混練工程でスラリーを溶融混練してペレットにし、二次混練工程で、得られたペレットと近赤外線反射物質粒子をドライブレンドするのがよい。 The method for producing the resin composition of the present invention includes the first method and the second method, but the second method is preferred because of the good dispersibility of far-infrared emitting material particles and near-infrared reflecting material particles. is preferred. The reason is that when adding slurry, if particles that are difficult to slurry (disperse in water) such as hygroscopic materials are mixed in at the same time (for example, when silica gel is used as near-infrared reflective material particles), the slurry becomes If the slurry contains water, aggregates, or the dispersibility of the particles decreases, the slurry is melt-kneaded into pellets in the primary kneading process, and the resulting pellets and near-infrared reflective material particles are dried in the secondary kneading process. Better to blend.
熱可塑性樹脂としては、例えばポリプロピレン、ポリエチレンなどのポリオレフィン、ポリオキシメチレン、ナイロンなどのポリアミド、ポリカーボネート、ポリ塩化ビニル、アクリロニトリル－ブタジエン－スチレン（ＡＢＳ）樹脂、アクリロニトリル－スチレン（ＡＳ）樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステル、それらの共重合体、及び熱可塑性エラストマー等があり、これら樹脂を単独でまたは二種以上組み合わせて用いることができる。この中でもポリプロピレン、ポリエチレンなどのポリオレフィンが好ましい。 Examples of thermoplastic resins include polyolefins such as polypropylene and polyethylene, polyamides such as polyoxymethylene and nylon, polycarbonate, polyvinyl chloride, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polyethylene terephthalate, Examples include polyesters such as polybutylene terephthalate, copolymers thereof, and thermoplastic elastomers, and these resins can be used alone or in combination of two or more. Among these, polyolefins such as polypropylene and polyethylene are preferred.
本発明の樹脂組成物は、成形加工した樹脂成形体とすることができる。樹脂成形体は前記の押し出し機を使用してそのまま押し出し成形しても良いし、一旦ペレット状にして、圧縮成形、真空成形、射出成形、トランスファ成形、押し出し成形、カレンダ成形等、あるいはこれらの成形法の組み合わせにより成形しても良い。樹脂成形体としては、繊維、フィラメント、不織布、シート、発泡体、フィルム、ブロック体、その他適宜形状に成形すると良い。 The resin composition of the present invention can be made into a molded resin article. The resin molded product may be extruded as is using the extruder described above, or it may be made into pellets and then subjected to compression molding, vacuum molding, injection molding, transfer molding, extrusion molding, calender molding, etc., or any of these molding methods. Molding may be performed by a combination of methods. The resin molded product may be molded into fibers, filaments, nonwoven fabrics, sheets, foams, films, blocks, or other appropriate shapes.
以下、図面を用いて説明する。図１は本発明の一実施態様で使用する押し出し機の模式的説明図である。この押し出し機１は、原料供給口２と、樹脂溶融部３と、混練分散部４と、減圧ライン５と、押し出し部６と、取り出し部７で構成されている。まず、樹脂溶融部３の原料供給口２からポリマーと、水に分散させた遠赤外線放射物質粒子を供給する。供給前に両者を混合しておいても良い。次に混練分散部４に送り、混練分散部４では複数枚の混練プレートが回転しており、ここでポリマーと水に分散させた遠赤外線放射物質粒子は均一に溶融混練される。次いで減圧ライン５から水分が水蒸気の状態で除去される。次いで押し出し部６から樹脂組成物が押し出され、冷却して取り出し部７から取り出される。冷却後カットすればペレット状の樹脂組成物となる。これが一次混練工程である。次に、一次混練工程で得られたペレット（場合によってはペレットを所望の大きさに粉砕してパウダー化して）と近赤外線反射物質粒子をドライブレンドし、溶融混練し、押し出し部から樹脂組成物を押し出して冷却し、ペレット化する。これが二次混練工程である。 This will be explained below using the drawings. FIG. 1 is a schematic illustration of an extruder used in one embodiment of the present invention. The extruder 1 includes a raw material supply port 2, a resin melting section 3, a kneading and dispersing section 4, a vacuum line 5, an extrusion section 6, and a take-out section 7. First, a polymer and far-infrared emitting material particles dispersed in water are supplied from the raw material supply port 2 of the resin melting section 3. Both may be mixed before supply. Next, it is sent to the kneading and dispersing section 4, where a plurality of kneading plates are rotating, and the far infrared emitting material particles dispersed in the polymer and water are uniformly melted and kneaded here. Moisture is then removed from the vacuum line 5 in the form of water vapor. Next, the resin composition is extruded from the extrusion section 6, cooled, and taken out from the extraction section 7. If it is cut after cooling, it becomes a pellet-shaped resin composition. This is the primary kneading step. Next, the pellets obtained in the primary kneading process (in some cases, the pellets are crushed into a desired size and powdered) and near-infrared reflective material particles are dry blended, melted and kneaded, and the resin composition is produced from the extrusion section. Extrude, cool, and pelletize. This is the secondary kneading step.
以下、実施例により本発明をさらに具体的に説明する。本発明は、下記の実施例に限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples. The present invention is not limited to the following examples.
（測定方法）
＜近赤外線反射特性試験(1) 温度センサーによるレフランプ試験＞
試験は人工気象室内（20℃、65％RH）で行った。試料（発泡体）をタテ15 cm、ヨコ15 cmに切り出して試料台の上に設置した。試料と試料台の間に温度センサー端子（4CH温度データロガー、TM-947SDJ；佐藤商事）を付けて固定した。試料の50cm上方にレフランプ（アイランプPRF500W；岩崎電気）を用意し、照射10分・消灯10分での温度変化を計測した。
＜近赤外線反射特性試験(2) サーモカメラによるレフランプ試験＞
試料(発泡体)を加熱プレス機で（150℃、10 MPa、1分）でフィルム状にし、5cm×5cmに切り、試料台の上に設置した。試料の50 cm上方にレフランプ（アイランプPRF500W ; 岩崎電気）を用意し、10分間照射した。照射後９分、照射後９分５５秒での温度変化をサーモカメラ（FLIR C3 ; FLIR）で撮影した。
＜近赤外線反射特性試験(3) 分光光度計による近赤外線反射率測定＞
試料の測定は分光光度計（U-4100形分光光度計；日立）に60φ積分球付属装置（紫外可視近赤外域用；日立）を取り付けて行った。試料を4 cm×4 cmに切り、酸化アルミニウムの板と積分球の間に固定した後、1000 nm～1600 nmの近赤外線を照射して反射率を測定した。
＜遠赤外線放射特性試験＞
FT-IR法により、測定温度：40℃、試験装置：パーキンエルマー社製 FT-IR SpectrumOne Fronier Tを使用し、遠赤外線分光放射特性を測定した。
(Measuring method)
<Near infrared reflection characteristics test (1) Ref lamp test using temperature sensor>
The test was conducted in an artificial climate room (20°C, 65% RH). A sample (foam) was cut out to a length of 15 cm and width of 15 cm and placed on a sample stand. A temperature sensor terminal (4CH temperature data logger, TM-947SDJ; Sato Corporation) was attached and fixed between the sample and the sample stage. A reflex lamp (eye lamp PRF500W; Iwasaki Electric) was prepared 50 cm above the sample, and temperature changes were measured after 10 minutes of irradiation and 10 minutes of extinguishment.
<Near infrared reflection characteristics test (2) Ref lamp test using thermo camera>
The sample (foam) was formed into a film using a hot press (150°C, 10 MPa, 1 minute), cut into 5 cm x 5 cm, and placed on a sample stand. A reflex lamp (eye lamp PRF500W; Iwasaki Electric) was prepared 50 cm above the sample and irradiated for 10 minutes. The temperature change at 9 minutes and 9 minutes and 55 seconds after irradiation was photographed with a thermo camera (FLIR C3; FLIR).
<Near-infrared reflection characteristics test (3) Near-infrared reflectance measurement using a spectrophotometer>
The samples were measured using a spectrophotometer (U-4100 type spectrophotometer; Hitachi) equipped with a 60φ integrating sphere attachment (for ultraviolet-visible and near-infrared regions; Hitachi). The sample was cut to 4 cm x 4 cm, fixed between an aluminum oxide plate and an integrating sphere, and the reflectance was measured by irradiating it with near-infrared rays of 1000 nm to 1600 nm.
<Far-infrared radiation characteristics test>
The far-infrared spectral radiation characteristics were measured by the FT-IR method using a measurement temperature of 40° C. and a test device: FT-IR SpectrumOne Fronier T manufactured by PerkinElmer.
（実施例１）
ポリエチレン（ＬＤＰＥ）の約半分から全量を１ｍｍ以下に粉砕し、残りのペレットは（直径２ｍｍ、高さ２ｍｍの円柱状）のままにする。その樹脂１００質量部に対し、酸化ジルコニウムスラリー（製品名ＳＺＲ－Ｗ、堺化学工業社製、酸化ジルコニウム濃度３０質量％、粒子径Ｄ50：３ｎｍ，Ｄmax：３０ｎｍ（Measured by Dynamic light scattering,メーカー値））１０質量部（乾燥質量で３質量部）をブレンドした。ブレンドした樹脂と酸化ジルコニウムスラリーを押し出し機に投入した。樹脂溶融部、混練分散部で混錬を行い、押し出し部から吐出された樹脂組成物を冷却し、ペレタイザーを通してペレット化した。得られた樹脂組成物を再粉砕し、樹脂組成物１００質量部に対し、粉体Ｂ型シリカゲル（製品名：トヨタシリカゲルＢ白４００下、豊田化工社製、粉体、篩分け法による４００メッシュ通過粒子：３７μｍ以下，メーカー値）１０質量部とドライブレンドし、同工程にて酸化ジルコニウムとＢ型シリカゲルを含有した樹脂組成物ペレットを得た。押し出し機内における加工温度は、１５０～１６０℃とした。
(Example 1)
Approximately half to the entire amount of polyethylene (LDPE) is ground to less than 1 mm, leaving the remaining pellets (cylindrical shape with a diameter of 2 mm and a height of 2 mm). For 100 parts by mass of the resin, zirconium oxide slurry (product name SZR-W, manufactured by Sakai Chemical Industry Co., Ltd., zirconium oxide concentration 30% by mass, particle size D 50 : 3 nm, D max : 30 nm (Measured by Dynamic light scattering, manufacturer) value)) 10 parts by weight (3 parts by weight dry weight) were blended. The blended resin and zirconium oxide slurry were charged into an extruder. Kneading was performed in a resin melting section and a kneading and dispersing section, and the resin composition discharged from an extrusion section was cooled and pelletized through a pelletizer. The obtained resin composition was re-pulverized, and 100 parts by mass of the resin composition was mixed with powder type B silica gel (product name: Toyota Silica Gel B White 400 Lower, manufactured by Toyota Kako Co., Ltd., powder, 400 mesh by sieving method). Passing particles: 37 μm or less, manufacturer's value) were dry blended with 10 parts by mass, and in the same process, resin composition pellets containing zirconium oxide and B-type silica gel were obtained. The processing temperature in the extruder was 150 to 160°C.
（実施例２）
ポリエチレン（ＬＤＰＥ）の約半分から全量を１ｍｍ以下に粉砕し、残りのペレットは（直径２ｍｍ、高さ２ｍｍの円柱状）のままにする。その樹脂１００質量部に対し、酸化ジルコニウムスラリー（製品名ＳＺＲ－Ｗ、堺化学工業社製、酸化ジルコニウム濃度３０質量％、粒子径Ｄ50：３ｎｍ，Ｄmax：３０ｎｍ（Measured by Dynamic light scattering,メーカー値））１０質量部（乾燥質量で３質量部）をブレンドした。ブレンドした樹脂と酸化ジルコニウムスラリーを押し出し機に投入した。樹脂溶融部、混練分散部で混錬を行い、押し出し部から吐出された樹脂組成物を冷却し、ペレタイザーを通してペレット化した。得られた樹脂組成物を再粉砕し、樹脂組成物１００質量部に対し、粉体Ｂ型シリカゲル（製品名：トヨタシリカゲルＢ白４００下、豊田化工社製、粉体、篩分け法による４００メッシュ通過粒子：３７μｍ以下，メーカー値）３０質量部とドライブレンドし、同工程にて酸化ジルコニウムとＢ型シリカゲルを含有した樹脂組成物ペレットを得た。押し出し機内における加工温度は、１５０～１６０℃とした。
(Example 2)
Approximately half to the entire amount of polyethylene (LDPE) is ground to less than 1 mm, leaving the remaining pellets (cylindrical shape with a diameter of 2 mm and a height of 2 mm). For 100 parts by mass of the resin, zirconium oxide slurry (product name SZR-W, manufactured by Sakai Chemical Industry Co., Ltd., zirconium oxide concentration 30% by mass, particle size D 50 : 3 nm, D max : 30 nm (Measured by Dynamic light scattering, manufacturer) value)) 10 parts by weight (3 parts by weight dry weight) were blended. The blended resin and zirconium oxide slurry were charged into an extruder. Kneading was performed in a resin melting section and a kneading and dispersing section, and the resin composition discharged from an extrusion section was cooled and pelletized through a pelletizer. The obtained resin composition was re-pulverized, and 100 parts by mass of the resin composition was mixed with powder type B silica gel (product name: Toyota Silica Gel B White 400 Lower, manufactured by Toyota Kako Co., Ltd., powder, 400 mesh by sieving method). Passing particles: 37 μm or less, manufacturer's value) was dry blended with 30 parts by mass, and in the same process, resin composition pellets containing zirconium oxide and B-type silica gel were obtained. The processing temperature in the extruder was 150 to 160°C.
（実施例３）
実施例１で得られたマスターバッチ樹脂組成物ペレット１０質量部と、ＬＤＰＥ樹脂１００質量部を用いて、公知の方法でシート発泡成形して樹脂発泡シート（樹脂成形体）を得た。この樹脂発泡シートは厚さ約２ｍｍ（定規で目視して測定）、単位面積当たりの質量は８０ｇ／ｍ2、みかけ密度は約０．０４ｇ／ｃｍ3であった。また、シリカゲル含量は０．９１質量％、酸化ジルコニウム含量は０．２７質量％であった。
図４Ａは本発明の実施例１の発泡体樹脂のＳＥＭ観察１００倍の写真及び図４Ｂは同１０００倍の観察写真である。いずれも無機物の分散状態は良好である。
(Example 3)
Using 10 parts by mass of the masterbatch resin composition pellets obtained in Example 1 and 100 parts by mass of LDPE resin, sheet foam molding was performed by a known method to obtain a resin foam sheet (resin molded body). This resin foam sheet had a thickness of about 2 mm (measured visually with a ruler), a mass per unit area of 80 g/m 2 , and an apparent density of about 0.04 g/cm 3 . Further, the silica gel content was 0.91% by mass, and the zirconium oxide content was 0.27% by mass.
FIG. 4A is a 100x SEM photograph of the foam resin of Example 1 of the present invention, and FIG. 4B is a 1000x photograph. In both cases, the inorganic substances were well dispersed.
（実施例４）
実施例１で得られたマスターバッチ樹脂組成物ペレット３０質量部と、ＬＤＰＥ樹脂１００質量部を用いて、公知の方法でシート発泡成形して樹脂発泡シート（樹脂成形体）を得た。得られた樹脂発泡シートは厚さ約２ｍｍ、単位面積当たりの質量は８０ｇ／ｍ2、みかけ密度は約０．０４ｇ／ｃｍ3であった。また、シリカゲル含量は２．３質量％、酸化ジルコニウム含量は０．６９質量％であった。
図５Ａは本発明の実施例１の発泡体樹脂のＳＥＭ観察１００倍の写真及び図５Ｂは同１０００倍の観察写真である。いずれも無機物の分散状態は良好である。
(Example 4)
Using 30 parts by mass of the masterbatch resin composition pellets obtained in Example 1 and 100 parts by mass of LDPE resin, sheet foam molding was performed by a known method to obtain a resin foam sheet (resin molded body). The resulting resin foam sheet had a thickness of about 2 mm, a mass per unit area of 80 g/m 2 , and an apparent density of about 0.04 g/cm 3 . Further, the silica gel content was 2.3% by mass, and the zirconium oxide content was 0.69% by mass.
FIG. 5A is a 100x SEM photograph of the foam resin of Example 1 of the present invention, and FIG. 5B is a 1000x photograph. In both cases, the inorganic substances were well dispersed.
（実施例５）
実施例２で得られたマスターバッチ樹脂組成物ペレット２０質量部と、ＬＤＰＥ樹脂１００質量部を用いて、公知の方法でシート発泡成形して樹脂発泡シート（樹脂成形体）を得た。この樹脂発泡シートは厚さ約２ｍｍ、単位面積当たりの質量は１１０ｇ／ｍ2、みかけ密度は約０．０５５ｇ／ｃｍ3であった。また、シリカゲル含量は５．０質量％、酸化ジルコニウム含量は０．５質量％であった。
図６Ａは本発明の実施例１の発泡体樹脂のＳＥＭ観察１００倍の写真及び図６Ｂは同１０００倍の観察写真である。いずれも無機物の分散状態は良好である。
(Example 5)
Using 20 parts by mass of the masterbatch resin composition pellets obtained in Example 2 and 100 parts by mass of LDPE resin, sheet foam molding was performed by a known method to obtain a resin foam sheet (resin molded body). This resin foam sheet had a thickness of about 2 mm, a mass per unit area of 110 g/m 2 , and an apparent density of about 0.055 g/cm 3 . Further, the silica gel content was 5.0% by mass, and the zirconium oxide content was 0.5% by mass.
FIG. 6A is a 100x SEM photograph of the foam resin of Example 1 of the present invention, and FIG. 6B is a 1000x photograph. In both cases, the inorganic substances were well dispersed.
（実施例６）
実施例１で得られたシート発泡成形体を、加熱プレス機で１分間（１６０℃、１０ＭＰａ）プレスしてフィルム（樹脂成形体）を得た。このフィルムの厚みは７０μｍ、単位面積当たりの質量は６０ｇ／ｍ2であった。
(Example 6)
The sheet foam molded product obtained in Example 1 was pressed for 1 minute (160° C., 10 MPa) using a heating press to obtain a film (resin molded product). The thickness of this film was 70 μm, and the mass per unit area was 60 g/m 2 .
（実施例７）
実施例２で得られたシート発泡成形体を、加熱プレス機で１分間（１６０℃、１０ＭＰａ）プレスしてフィルム（樹脂成形体）を得た。このフィルムの厚みは７０μｍ、単位面積当たりの質量は６０ｇ／ｍ2であった。
(Example 7)
The sheet foam molded product obtained in Example 2 was pressed for 1 minute (160° C., 10 MPa) using a heating press to obtain a film (resin molded product). The thickness of this film was 70 μm, and the mass per unit area was 60 g/m 2 .
（実施例８）
実施例３で得られたシート発泡成形体を、加熱プレス機で１分間（１６０℃、１０ＭＰａ）プレスしてフィルム（樹脂成形体）を得た。このフィルムの厚みは７０μｍ、単位面積当たりの質量は６０ｇ／ｍ2であった。
(Example 8)
The sheet foam molded product obtained in Example 3 was pressed for 1 minute (160° C., 10 MPa) using a hot press machine to obtain a film (resin molded product). The thickness of this film was 70 μm, and the mass per unit area was 60 g/m 2 .
（比較例１）
マスターバッチ樹脂組成物ペレットは加えず、ＬＤＰＥ樹脂１００質量部を用いて、公知の方法でシート発泡成形して樹脂発泡シートを得た。この樹脂発泡シートは厚さ約２ｍｍ、単位面積当たりの質量は８０ｇ／ｍ2、みかけ密度は約０．０４ｇ／ｃｍ3であった。
図７Ａは比較例１の発泡体樹脂のＳＥＭ観察１００倍の写真及び図７Ｂは、同１０００倍の観察写真である。
以上の実施例３～５及び比較例１の近赤外線反射特性(1) 温度センサーによるレフランプ試験で測定した温度を表１と図２にレフランプ照射時のその温度変化グラフを示す。
(Comparative example 1)
A resin foam sheet was obtained by sheet foam molding by a known method using 100 parts by mass of LDPE resin without adding masterbatch resin composition pellets. This resin foam sheet had a thickness of about 2 mm, a mass per unit area of 80 g/m 2 , and an apparent density of about 0.04 g/cm 3 .
FIG. 7A is a 100x SEM photograph of the foam resin of Comparative Example 1, and FIG. 7B is a 1000x photograph.
Near-infrared reflection characteristics of Examples 3 to 5 and Comparative Example 1 (1) The temperatures measured in a reflex lamp test using a temperature sensor are shown in Table 1 and a graph of temperature changes during reflex lamp irradiation is shown in FIG.
表１及び図２の結果から、温度の高い順に、比較例１、実施例３、実施例４、実施例５となっており、シリカゲルの濃度に比例して、試料と試料台の間に設置した温度センサーの温度が低くなっていた。この結果からレフランプにより照射された赤外線がシリカゲルにより透過及び／又は吸収されにくくなったものと推定される。 From the results in Table 1 and Figure 2, the order of temperature is Comparative Example 1, Example 3, Example 4, and Example 5. The temperature of the temperature sensor was getting low. From this result, it is presumed that the infrared rays irradiated by the reflex lamp were less likely to be transmitted and/or absorbed by the silica gel.
次に、近赤外線反射特性試験(2)のサーモカメラによるレフランプ試験結果を示す。レフランプ照射時の温度変化より、レフランプ照射後９分、照射後９分５５秒において、温度の高い順に、実施例５、実施例４、実施例３、比較例１となっており、シリカゲルの濃度に比例して、試料の表面温度が高くなっていた。サーモカメラは、物質表面から放射されている赤外線エネルギーの強度を温度情報として検出・可視化して、温度分布などの画像表示を行う装置であり、この結果からレフランプによる照射された近赤外線がシリカゲルにより反射しているものと推定される。 Next, the near-infrared reflection characteristic test (2) reflex lamp test results using a thermo camera are shown. According to the temperature change during Ref lamp irradiation, 9 minutes after Ref lamp irradiation and 9 minutes 55 seconds after irradiation, in order of highest temperature, Example 5, Example 4, Example 3, and Comparative Example 1, and the concentration of silica gel The surface temperature of the sample increased in proportion to A thermo camera is a device that detects and visualizes the intensity of infrared energy emitted from the surface of a material as temperature information, and displays images such as temperature distribution.From this result, the near infrared rays irradiated by the reflex lamp are detected by silica gel. It is presumed that it is a reflection.
実施例６～８及び比較例１の近赤外線の反射率（近赤外線反射特性試験(3) 分光光度計による近赤外線反射率測定）を表２と図３に示す。 The near-infrared reflectance (near-infrared reflection characteristic test (3) near-infrared reflectance measurement using a spectrophotometer) of Examples 6 to 8 and Comparative Example 1 are shown in Table 2 and FIG.
表２と図３の結果の結果から、近赤外線反射性が確認できた。よって、近赤外線反射特性試験(1)～(3)の結果を総合すると、シリカゲルの濃度に比例して近赤外線反射性による断熱性が高く、試料表面の温度上昇と試料裏面の温度上昇抑制が確認できた。次に、遠赤外線分光放射特性を表３に示す。 From the results shown in Table 2 and FIG. 3, near-infrared reflectivity was confirmed. Therefore, combining the results of the near-infrared reflection characteristics tests (1) to (3), it can be seen that the near-infrared reflection property has high insulation properties in proportion to the concentration of silica gel, and the temperature rise on the surface of the sample and the temperature rise on the back side of the sample can be suppressed. It could be confirmed. Next, Table 3 shows far-infrared spectral radiation characteristics.
表３から、酸化ジルコニウムの濃度にほぼ比例して赤外線分光放射率が高くなることが確認できた。
以上の実施例、比較例から、熱可塑性樹脂に遠赤外線放射物質粒子及び近赤外線反射物質粒子を含有させると、相乗効果により樹脂成形体の温感効果を高めることができる。
From Table 3, it was confirmed that the infrared spectral emissivity increased almost in proportion to the concentration of zirconium oxide.
From the above Examples and Comparative Examples, when the thermoplastic resin contains far-infrared emitting material particles and near-infrared reflective material particles, the thermal sensation effect of the resin molded article can be enhanced due to a synergistic effect.
本発明の樹脂組成物は、マスターバッチ用樹脂組成物として有用である。本発明の樹脂組成物は、繊維、フィラメント、不織布、シート、発泡体、フィルム、ブロック体、その他適宜形状に成形した成形体に用いることができる。得られた樹脂成形体は、衣類、寝具、敷物、カーテン、ブラインド、屋外部材、日よけ用シートなどに用いることができる。 The resin composition of the present invention is useful as a resin composition for masterbatches. The resin composition of the present invention can be used for fibers, filaments, nonwoven fabrics, sheets, foams, films, blocks, and other molded bodies shaped into appropriate shapes. The obtained resin molded product can be used for clothing, bedding, rugs, curtains, blinds, outdoor members, sunshade sheets, and the like.
１ 押し出し機
２ 原料供給口
３ 樹脂溶融部
４ 混練分散部
５ 減圧ライン
６ 押し出し部
７ 取り出し部
1 Extruder 2 Raw material supply port 3 Resin melting section 4 Kneading and dispersing section 5 Decompression line 6 Extrusion section 7 Removal section
Claims (8)
前記近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多く、
前記近赤外線反射物質無機粒子はＢ型シリカゲルであり、
前記遠赤外線放射物質粒子は酸化ジルコニウムであり、
前記遠赤外線放射物質粒子は微分散していることを特徴とする樹脂組成物。 A resin composition containing far-infrared emitting material particles and near-infrared reflecting material particles in a thermoplastic resin,
The amount of the near-infrared reflecting material particles is greater than the amount of the far-infrared emitting material particles,
The near-infrared reflective material inorganic particles are B-type silica gel,
The far-infrared emitting material particles are zirconium oxide,
A resin composition characterized in that the far-infrared emitting substance particles are finely dispersed.
遠赤外線放射物質粒子及び近赤外線反射物質粒子を準備し、
前記近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多くなるように、熱可塑性樹脂中に混練させる工程を含み、
前記近赤外線反射物質無機粒子はＢ型シリカゲルであり、
前記遠赤外線放射物質粒子は酸化ジルコニウムであり、
前記遠赤外線放射物質粒子は微分散していることを特徴とする樹脂組成物の製造方法。 Prepare thermoplastic resin,
Prepare far-infrared emitting material particles and near-infrared reflecting material particles,
The method includes a step of kneading the near-infrared reflective material particles into the thermoplastic resin so that the amount of the near-infrared reflective material particles is greater than the amount of the far-infrared emitting material particles,
The near-infrared reflective material inorganic particles are B-type silica gel ,
The far-infrared emitting material particles are zirconium oxide,
A method for producing a resin composition , wherein the far-infrared emitting material particles are finely dispersed .
遠赤外線放射物質粒子及び近赤外線反射物質粒子を準備し、
前記近赤外線反射物質粒子の配合量は、遠赤外線放射物質粒子の配合量より多くなるようにして、
樹脂溶融部と、減圧ラインを備えた混練分散部と、押し出し部を連続して接続し、
前記混練溶融部に、水分散液とした遠赤外線放射物質粒子と、加熱溶融させた樹脂とを供給し、
次に前記混練分散部に送り、溶融混練と同時に前記減圧ラインから水分を気体の状態で除去し、押し出し部から樹脂組成物を押し出して冷却し、ペレット化する一次混練工程と、
得られたペレットと近赤外線反射物質粒子をドライブレンドし、溶融混練し、押し出し部から樹脂組成物を押し出して冷却し、ペレット化する二次混練工程を含み、
前記近赤外線反射物質無機粒子はＢ型シリカゲルであり、
前記遠赤外線放射物質粒子は酸化ジルコニウムであり、
前記遠赤外線放射物質粒子は微分散していることを特徴とする樹脂組成物の製造方法。 Prepare thermoplastic resin,
Prepare far-infrared emitting material particles and near-infrared reflecting material particles,
The amount of the near-infrared reflecting material particles is greater than the amount of the far-infrared emitting material particles,
The resin melting section, the kneading dispersion section equipped with a vacuum line, and the extrusion section are connected continuously,
Supplying far-infrared emitting material particles made into an aqueous dispersion and a heated and melted resin to the kneading and melting section,
Next, a primary kneading step of sending the resin composition to the kneading and dispersing section, removing water in a gaseous state from the vacuum line at the same time as melting and kneading, extruding the resin composition from the extrusion section, cooling it, and pelletizing it;
A secondary kneading step of dry blending the obtained pellets and near-infrared reflective material particles, melt-kneading, extruding the resin composition from an extrusion section, cooling, and pelletizing,
The near-infrared reflective material inorganic particles are B-type silica gel ,
The far-infrared emitting material particles are zirconium oxide,
A method for producing a resin composition , wherein the far-infrared emitting material particles are finely dispersed .
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| JP2012051113A (en) | 2010-08-31 | 2012-03-15 | Hiraoka & Co Ltd | Heat controllable sheet |
| CN104177685A (en) | 2014-08-19 | 2014-12-03 | 东莞市普凯塑料科技有限公司 | Infrared reflection/emission thermal-insulating plastic functional master batch and preparation method thereof |
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| JP2012051113A (en) | 2010-08-31 | 2012-03-15 | Hiraoka & Co Ltd | Heat controllable sheet |
| CN104177685A (en) | 2014-08-19 | 2014-12-03 | 东莞市普凯塑料科技有限公司 | Infrared reflection/emission thermal-insulating plastic functional master batch and preparation method thereof |
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