JP5013739B2 - Lightweight thermal insulation transparent film - Google Patents
Lightweight thermal insulation transparent film Download PDFInfo
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- JP5013739B2 JP5013739B2 JP2006124637A JP2006124637A JP5013739B2 JP 5013739 B2 JP5013739 B2 JP 5013739B2 JP 2006124637 A JP2006124637 A JP 2006124637A JP 2006124637 A JP2006124637 A JP 2006124637A JP 5013739 B2 JP5013739 B2 JP 5013739B2
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- 238000009413 insulation Methods 0.000 title description 7
- 239000011521 glass Substances 0.000 claims description 75
- -1 silane compound Chemical class 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 14
- 239000012756 surface treatment agent Substances 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 description 58
- 229920005989 resin Polymers 0.000 description 58
- 239000004594 Masterbatch (MB) Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 229920001684 low density polyethylene Polymers 0.000 description 13
- 239000004702 low-density polyethylene Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000005001 laminate film Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 206010037660 Pyrexia Diseases 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- DRNPGEPMHMPIQU-UHFFFAOYSA-N O.[Ti].[Ti].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO.CCCCO Chemical compound O.[Ti].[Ti].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO.CCCCO DRNPGEPMHMPIQU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CHHVJOKDGAOHMJ-UHFFFAOYSA-N methoxy(propyl)silane Chemical compound CCC[SiH2]OC CHHVJOKDGAOHMJ-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229940075065 polyvinyl acetate Drugs 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Description
本発明は、断熱性樹脂組成物、それを用いた軽量断熱性透明フィルム及びその断熱性樹脂組成物の製造方法に関する。 The present invention relates to a heat insulating resin composition, a lightweight heat insulating transparent film using the same, and a method for producing the heat insulating resin composition.
樹脂を軽量化し、断熱性を付与するため、樹脂を発泡させたり中空粒子を混合したりすることは良く知られている。発泡させる場合は、炭酸ガス等の気体を細かな泡として溶融した樹脂に均一に混合し成形しなければならない。発泡剤を用いる場合は、樹脂中に発泡剤を均一に分散し、加熱してガスを発生させて発泡させる。樹脂を溶融したとき均一に気体の泡を樹脂中に閉じ込めなければならないため、用いる樹脂の溶融張力が適当な範囲にあること、発泡剤の気体発生温度と樹脂の溶融温度を調整しなければならないなど、発泡させる樹脂の種類には制限があった。 It is well known to foam a resin or mix hollow particles in order to reduce the weight of the resin and to provide heat insulation. In the case of foaming, a gas such as carbon dioxide must be uniformly mixed with molten resin as fine bubbles and molded. When a foaming agent is used, the foaming agent is uniformly dispersed in the resin and heated to generate gas and foam. Since the gas bubbles must be confined in the resin even when the resin is melted, the melt tension of the resin used must be in an appropriate range, and the gas generation temperature of the blowing agent and the melting temperature of the resin must be adjusted. There were restrictions on the type of resin to be foamed.
中空粒子を用いる場合は、このような制限はないが、樹脂との接触面での剥離による強度低下の問題があった。また、発泡させる場合も、中空粒子を使用する場合も透明性を犠牲にしなければならなかった。 When hollow particles are used, there is no such limitation, but there is a problem of strength reduction due to peeling at the contact surface with the resin. In addition, transparency must be sacrificed when foaming and when using hollow particles.
中空粒子の一つであるガラスバルーンは、化学的に不活性で耐熱性が高いため多種の熱可塑性樹脂に用いることができるが、軽く壊れやすいため、溶融した樹脂中に均一に混合分散させて、成形するには困難が伴う。 Glass balloons, which are one of the hollow particles, are chemically inert and have high heat resistance, so they can be used for a variety of thermoplastic resins, but they are light and fragile, so they can be mixed and dispersed uniformly in the molten resin. It is difficult to mold.
そこで、特許文献１には、特定の範囲のメルトフローレイトを有する樹脂を用い、かつ成形方法として圧縮成形を用いることにより、射出成形に比べガラスバルーンの破壊率を低減した圧縮成形用樹脂組成物が開示されている。 Therefore, Patent Document 1 discloses a resin composition for compression molding that uses a resin having a melt flow rate in a specific range and uses a compression molding as a molding method to reduce the breaking rate of a glass balloon as compared with injection molding. Is disclosed.
また、特許文献２には、ガラスバルーンに表面処理を施すことによって樹脂との滑り性を良くし、それにより樹脂の粘度に拘らず樹脂中に均一にガラスバルーンを分散させ、ガラスバルーンの破壊を少なくして成形することができる樹脂組成物が開示されている。 Patent Document 2 discloses that the glass balloon is surface-treated to improve the slipperiness with the resin, thereby uniformly dispersing the glass balloon in the resin regardless of the viscosity of the resin, thereby destroying the glass balloon. A resin composition that can be molded with a small amount is disclosed.
前記特許文献の方法は、射出成形、押出し成形等樹脂に力がかかる場合、樹脂の溶融粘度が高い場合などでは、成形時にガラスバルーンが破壊されやすいため、使用できる樹脂の種類に制限があった。また、これまでガラスバルーンをフィルム成形用の樹脂に適用した例はなく、もちろんガラスバルーンを樹脂に分散することによって軽量で、断熱性がありかつ透明なフィルムを製造した例も見られない。 In the method of the above-mentioned patent document, when a force is applied to the resin, such as injection molding, extrusion molding, or the like, when the melt viscosity of the resin is high, the glass balloon is easily broken at the time of molding. . In addition, there has been no example of applying a glass balloon to a resin for film formation so far, and of course, no example of producing a light, heat-insulating and transparent film by dispersing a glass balloon in a resin.
本発明は、上記課題を解決することを鑑みてなされたものであり、フィルムから厚みのある成形体まで、成形物の厚さに関係なく成形可能なガラスバルーン含有熱可塑性樹脂組成物、該樹脂組成物を用いた軽量断熱性フィルム及び該樹脂組成物の製造方法を提供することを目的としている。 The present invention has been made in view of solving the above-mentioned problems, and includes a glass balloon-containing thermoplastic resin composition that can be molded from a film to a thick molded article regardless of the thickness of the molded article, and the resin. An object of the present invention is to provide a lightweight heat-insulating film using the composition and a method for producing the resin composition.
上記課題を解決するため、請求項１に係る発明は、ポリオレフィンを含む熱可塑性樹脂に、平均粒径が１０〜７０μｍで、表面処理剤で被覆された耐圧強度が７０ＭＰａ以上のガラスバルーンをその含有率が２〜５重量％になるように配合してなることを特徴とする軽量断熱性透明フィルムである。
In order to solve the above problems, the invention according to claim 1 includes a glass balloon having a mean particle size of 10 to 70 μm and a pressure strength of 70 MPa or more coated with a surface treatment agent on a thermoplastic resin containing polyolefin. It is a lightweight heat-insulating transparent film characterized by being blended so that the rate is 2 to 5% by weight .
また、請求項２に係る発明は、前記表面処理剤が有機シラン化合物、有機チタネート化合物または有機アルミネート化合物から選ばれた一種以上であることを特徴とする請求項１記載の軽量断熱性透明フィルムである。
The invention according to claim 2 is characterized in that the surface treatment agent is at least one selected from an organic silane compound, an organic titanate compound or an organic aluminate compound. It is.
また、請求項３に係る発明は、請求項１または２に記載の軽量断熱性透明フィルムに、透明性フィルムをラミネートするかまたは貼り合わせたことを特徴とする軽量断熱性透明フィルムである。
The invention according to claim 3 is a lightweight heat insulating transparent film characterized in that a transparent film is laminated or bonded to the light heat insulating transparent film according to claim 1 or 2 .
本発明によるとガラスバルーンが壊れないため、成形体の厚さや成形方法に関係なく成形できるガラスバルーン含有軽量断熱性樹脂組成物、該樹脂組成物から製造する軽量断熱性透明フィルム、及び該樹脂組成物の製造方法を提供できる。 According to the present invention, since the glass balloon is not broken, the glass balloon-containing lightweight heat-insulating resin composition that can be molded regardless of the thickness of the molded body and the molding method, the lightweight heat-insulating transparent film produced from the resin composition, and the resin composition A method for manufacturing a product can be provided.
また、本発明のフィルムは軽いうえに断熱性と透明性を兼ね備えていることから、農業用では昼間には植物の生育には必要な光を通し、夜間は断熱効果により温室内を保温するフィルムとして、また、食品用では中身の見える保温性の食品容器用フィルムとして有用である。さらに、遮音性もあるため、例えば、建材の表面に貼る透明遮音フィルムとしても有用である。 In addition, since the film of the present invention is light and has both heat insulation and transparency, it is a film that keeps the inside of the greenhouse warm by the heat insulation effect during the daytime through the light necessary for plant growth in agriculture. As a food film, it is useful as a film for heat-retaining food containers with visible contents. Furthermore, since it also has sound insulation, it is useful, for example, as a transparent sound insulation film to be applied to the surface of building materials.
本実施形態に係る軽量断熱性樹脂組成物、該樹脂組成物から製造する軽量断熱性透明フィルム、及び該樹脂組成物の製造方法について説明する。なお、本実施形態は、本発明を実施するための一形態に過ぎず、本発明は本実施形態によって限定されるものではない。 The lightweight heat-insulating resin composition according to this embodiment, the lightweight heat-insulating transparent film produced from the resin composition, and the method for producing the resin composition will be described. In addition, this embodiment is only one form for implementing this invention, and this invention is not limited by this embodiment.
本発明で用いられる熱可塑性樹脂としては、低密度ポリエチレン、直鎖状低密度ポリエチレンなどのポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エステル共重合体等のポリオレフィン系樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、ＡＳ樹脂、アクリル系樹脂、塩化ビニル樹脂、各種ポリアミド樹脂、ポリオキシメチレン樹脂、ポリカーボネート樹脂、変性ポリフェニレンエーテル樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリビニールアセテート樹脂、ポリ塩化ビニリデン樹脂、ポリサルホン樹脂、ポリエーテルサルホン樹脂、ポリフェニレンサルファイド樹脂、ポリアリレート樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリイミド樹脂、ポリエーテルエーテルケトン樹脂、各種液晶樹脂、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体樹脂、ポリクロロトリフルオロエチレン樹脂、ポリフッ化ビニリデン樹脂、ポリフッ化ビニル樹脂、エチレン−テトラフルオロエチレン共重合体、エチレン−クロロトリフルオロエチレン共重合体樹脂およびこれらの共重合体等である。また、熱又は光硬化性樹脂であっても硬化前で熱可塑性を保持している樹脂であれば使用できる。 Examples of the thermoplastic resin used in the present invention include polyethylene such as low density polyethylene and linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Polyolefin resin such as polystyrene resin, ABS resin, AS resin, acrylic resin, vinyl chloride resin, various polyamide resins, polyoxymethylene resin, polycarbonate resin, modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, poly Vinyl acetate resin, polyvinylidene chloride resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyarylate resin, polyamideimide resin, polyetherimide resin , Polyimide resin, polyether ether ketone resin, various liquid crystal resins, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, polyvinyl fluoride resin, ethylene-tetrafluoroethylene copolymer A polymer, an ethylene-chlorotrifluoroethylene copolymer resin, and a copolymer thereof. Moreover, even if it is a heat | fever or photocurable resin, if it is resin which is holding thermoplasticity before hardening, it can be used.
本発明で用いられるガラスバルーンは、平均粒径が１０〜７０μｍである。平均粒径が７０μｍを超えるガラスバルーンはフィルムにしたときに壊れやすくフィルム表面が疎になるため好ましくない。平均粒径が１０μｍ未満のガラスバルーンは、壊れにくくはなるが、単位体積あたりのガラス部分が多くなるため軽量化の効果が不十分なばかりでなく、製造が難しいため汎用性に欠け、コストアップになる。 The glass balloon used in the present invention has an average particle size of 10 to 70 μm. Glass balloons having an average particle size exceeding 70 μm are not preferred because they are fragile when formed into a film and the film surface becomes sparse. Glass balloons with an average particle size of less than 10 μm are less likely to break, but the glass portion per unit volume increases, so not only is the effect of weight reduction insufficient, but it is difficult to manufacture and lacks versatility, increasing costs. become.
当該ガラスバルーンの耐圧強度は、７０ＭＰａ以上が好ましい。ここで耐圧強度は、タルクと混合したガラスバルーンを乾燥窒素ガスにより加圧したときのガラスバルーンの残存率が９０％以上である圧力であり、ガラスバルーンの真比重の変化率から計算できる。この耐圧強度未満では、樹脂の溶融粘度をコントロールしたり、混練方法を工夫したりしても、分散工程やフィルム等への成形工程においてガラスバルーンが破壊されるため、目的とする性能を達成できない。 The pressure resistance of the glass balloon is preferably 70 MPa or more. Here, the pressure strength is a pressure at which the residual rate of the glass balloon is 90% or more when the glass balloon mixed with talc is pressurized with dry nitrogen gas, and can be calculated from the rate of change of the true specific gravity of the glass balloon. Below this pressure strength, even if the melt viscosity of the resin is controlled or the kneading method is devised, the glass balloon is broken in the dispersion step or the molding step into a film, etc., so the target performance cannot be achieved. .
当該ガラスバルーンは、樹脂との密着性を良くする為、表面処理されていることが好ましい。表面処理剤としては、有機シラン化合物、有機チタネート化合物又は有機アルミネート化合物が用いられ、通常の方法により表面処理できる。即ち、ガラスバルーンは、これらの化合物を水又は各種有機溶媒に溶解し、ガラスバルーンを浸漬、乾燥することにより表面処理される。また、ヘンシェルミキサー等のミキサー中でガラスバルーンを加熱撹拌しながら、水又は有機溶媒に溶解した表面処理剤を少しずつ添加することによっても表面処理できる。 The glass balloon is preferably surface-treated in order to improve the adhesion with the resin. As the surface treatment agent, an organic silane compound, an organic titanate compound or an organic aluminate compound is used, and the surface treatment can be performed by a usual method. That is, the glass balloon is surface-treated by dissolving these compounds in water or various organic solvents and immersing and drying the glass balloon. The surface treatment can also be carried out by gradually adding a surface treatment agent dissolved in water or an organic solvent while heating and stirring the glass balloon in a mixer such as a Henschel mixer.
表面処理剤としては、有機シラン化合物、有機チタネート化合物または有機アルミネート化合物であり、有機シラン化合物としては、例えば、ビニルトリエトキシシラン、ビニル−トリス−（２−メトキシエトキシ）シラン、γ−メタアクリロキシプロピルメトキシシラン、γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、γ−グリシドキシプロピルメトキシシラン、γ−メルカプトプロピルトリメトキシシランが挙げられる。有機チタネート化合物としては、例えば、テトラ−ｉ−プロピルチタネート、テトラ−ｎ−ブチルチタネート、ブチルチタネートダイマー、テトラステアリルチタネート、トリエタノールアミンチタネート、チタニウムアセチルアセトネート、チタニウムラクチート、オクチレンブリコールチタネート、イソプロピル（Ｎ−アミノエチルアミノエチル）チタネートが挙げられる。有機アルミネート化合物としては、例えば、アセトアルコキシアルミニウムジイソプロピネート等を挙げることができ、これらは一種以上を用いることもできる。 The surface treatment agent is an organic silane compound, an organic titanate compound, or an organic aluminate compound. Examples of the organic silane compound include vinyltriethoxysilane, vinyl-tris- (2-methoxyethoxy) silane, and γ-methacrylic acid. Roxypropylmethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxy Examples thereof include propylmethoxysilane and γ-mercaptopropyltrimethoxysilane. Examples of organic titanate compounds include tetra-i-propyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetrastearyl titanate, triethanolamine titanate, titanium acetylacetonate, titanium lactate, octylene bricol titanate, isopropyl (N-aminoethylaminoethyl) titanate. Examples of the organic aluminate compound include acetoalkoxyaluminum diisopropinate and the like, and one or more of them can be used.
ガラスバルーンの混合量は、フィルム用途では、用いる樹脂に対して０．５〜５％が好ましい。０．５％より少ないと、断熱効果が不十分となり、５％を越えるとフィルムにしたときに透明性が低下するだけでなく機械的強度も低下するためフィルムとしての性能を維持できなくなる。 The mixing amount of the glass balloon is preferably 0.5 to 5% with respect to the resin to be used in a film application. When the content is less than 0.5%, the heat insulating effect is insufficient. When the content exceeds 5%, not only the transparency is lowered but also the mechanical strength is lowered when the film is formed, so that the performance as a film cannot be maintained.
本発明の軽量断熱性透明フィルムは、溶融した熱可塑性樹脂にガラスバルーンを混合分散させた後、フィルム化することによって製造できるが、ガラスバルーンの破壊を抑制しながら均一に混合するためには、予め高濃度のガラスバルーンを混合分散したマスターバッチを製造し、該マスターバッチを他の熱可塑性樹脂で混合希釈してからフィルム化するのが好ましく、このとき、耐候性、光安定性等の向上のために酸化防止剤、紫外線吸収剤、帯電防止剤等を添加してもよい。なお、該マスターバッチは、二軸押出機を用いて、溶融した樹脂中にガラスバルーンを添加するサイドフィード方式にするとガラスバルーンの破壊を最小限に留めることができる。 The lightweight heat-insulating transparent film of the present invention can be produced by mixing and dispersing a glass balloon in a molten thermoplastic resin and then forming a film, but in order to mix uniformly while suppressing the destruction of the glass balloon, It is preferable to prepare a master batch in which glass balloons of high concentration are mixed and dispersed in advance, and mix and dilute the master batch with another thermoplastic resin before forming a film. At this time, improvement in weather resistance, light stability, etc. Therefore, an antioxidant, an ultraviolet absorber, an antistatic agent, or the like may be added. In addition, when this masterbatch is a side feed method in which a glass balloon is added to a molten resin using a twin-screw extruder, the glass balloon can be minimized.
フィルム成形方法は特に選ばないが、フィルム成形に一般的に用いられる方法、例えば、Ｔダイ法、インフレーション法、多層成形法、押出ラミネーション等で成形できる。本発明によると、いずれの方法においてもガラスバルーンを破壊することなくフィルムとすることができる。 A film forming method is not particularly selected, but it can be formed by a method generally used for film forming, for example, a T-die method, an inflation method, a multilayer forming method, an extrusion lamination, or the like. According to the present invention, any method can be used as a film without breaking the glass balloon.
なお、フィルム化したときその中に含まれるガラスバルーンの粒径が大きい場合、特に、フィルムの厚さがガラスバルーンの粒径より小さい場合には、フィルムの表面が疎となるため幾分透明性が損なわれるが、該フィルム表面を低密度ポリエチレン、直鎖状ポリエチレン、ナイロン及びポリエチレンテレフタレート等の透明性のある樹脂フィルムをラミネートする又は貼り合わせることによって透明性を改善することができる。 In addition, when the particle size of the glass balloon contained in the film is large, particularly when the film thickness is smaller than the particle size of the glass balloon, the surface of the film becomes sparse so that it is somewhat transparent. However, transparency can be improved by laminating or laminating a transparent resin film such as low density polyethylene, linear polyethylene, nylon and polyethylene terephthalate on the film surface.
本発明を実施例によりさらに詳しく説明するが、本発明はこれらに制限されるものではない。なお、実施例及び比較例において部と記載されているものは重量部を表す。 The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, what is described as a part in an Example and a comparative example represents a weight part.
実施例１
＜表面処理ガラスバルーンの製造＞
有機シラン化合物（信越ポリマー社製：ＫＢＥ−９０３）の１０％水溶液に、平均粒径２７μｍで耐圧強度１２４ＭＰａのガラスバルーン（住友３Ｍ社製：グラスバブルズＳ６０ＨＳ）を浸漬後、１２０℃で乾燥して、表面処理ガラスバルーンを製造した。
＜ガラスバルーンマスターバッチの製造＞
低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）８０部に、上記表面処理ガラスバルーン２０部を加え、二軸押出機を用いて混練押出してガラスバルーンマスターバッチを製造した。
＜ガラスバルーン含有樹脂フィルムの製造＞
上記ガラスバルーンマスターバッチ１０部及び低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）９０部を混合し、東洋精機製作所製ラボプラストミル付属Ｔダイによりフィルム成形して、厚さ８０μｍのガラスバルーン含有樹脂フィルムを製造した。また、Ｔダイでのフィルム成形時に５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムでラミネートすることによりＰＥＴラミネートフィルムを製造した。
Example 1
<Manufacture of surface-treated glass balloons>
A glass balloon (Sumitomo 3M Co., Ltd .: Glass Bubbles S60HS) having an average particle size of 27 μm and a pressure strength of 124 MPa is immersed in a 10% aqueous solution of an organosilane compound (Shin-Etsu Polymer Co., Ltd .: KBE-903) and dried at 120 ° C. Thus, a surface-treated glass balloon was manufactured.
<Manufacture of glass balloon masterbatch>
20 parts of the surface-treated glass balloon was added to 80 parts of low density polyethylene (Nihon Unicar Co., Ltd .: NUC8160), and kneaded and extruded using a twin screw extruder to produce a glass balloon master batch.
<Manufacture of glass balloon-containing resin film>
10 parts of the above glass balloon masterbatch and 90 parts of low density polyethylene (Nihon Unicar Co., Ltd .: NUC8160) are mixed, formed into a film using a T-die attached to a lab plast mill manufactured by Toyo Seiki Seisakusho, and a glass balloon-containing resin film having a thickness of 80 μm. Manufactured. Also, a PET laminate film was produced by laminating with a 50 μm polyethylene terephthalate (PET) film during film formation with a T-die.
実施例２
実施例１のガラスバルーンマスターバッチ２５部及び低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）７５部から、実施例１と同様にしてガラスバルーン含有樹脂フィルム及びそのＰＥＴラミネートフィルムを製造した。
Example 2
A glass balloon-containing resin film and its PET laminate film were produced in the same manner as in Example 1 from 25 parts of the glass balloon masterbatch of Example 1 and 75 parts of low-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC8160).
実施例３
実施例１のガラスバルーンマスターバッチ２５部、低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）７２部及び接着性樹脂であるアドマーＬＦ１２８（三井化学社製）３部から、実施例１と同様にしてガラスバルーン含有樹脂フィルム及びそのＰＥＴラミネートフィルムを製造した。
Example 3
Glass in the same manner as in Example 1 from 25 parts of the glass balloon masterbatch of Example 1, 72 parts of low-density polyethylene (manufactured by Nippon Unicar Company: NUC8160) and 3 parts of Admer LF128 (manufactured by Mitsui Chemicals), which is an adhesive resin. A balloon-containing resin film and its PET laminate film were produced.
実施例４
＜ガラスバルーンマスターバッチの製造＞
ポリプロピレン（プライムポリマー社製：プライムポリプロＦ３２７Ｄ）８０部に、実施例１の表面処理ガラスバルーン２０部を加え、二軸押出機を用いて混練押出してガラスバルーンマスターバッチを製造した。
＜ガラスバルーン含有樹脂フィルムの製造＞
上記ガラスバルーンマスターバッチ２５部及びポリプロピレン（プライムポリマー社製：プライムポリプロＦ３２７Ｄ）７５部から、実施例１と同様にしてガラスバルーン含有樹脂フィルム及びそのＰＥＴラミネートフィルムを製造した。
Example 4
<Manufacture of glass balloon masterbatch>
20 parts of the surface-treated glass balloon of Example 1 was added to 80 parts of polypropylene (manufactured by Prime Polymer Co., Ltd .: Prime Polypro F327D), and kneaded and extruded using a twin screw extruder to produce a glass balloon master batch.
<Manufacture of glass balloon-containing resin film>
A glass balloon-containing resin film and its PET laminate film were produced in the same manner as in Example 1 from 25 parts of the glass balloon master batch and 75 parts of polypropylene (manufactured by Prime Polymer Co., Ltd .: Prime Polypro F327D).
比較例１
＜ガラスバルーンマスターバッチの製造＞
低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）８０部に、平均粒径２７μｍで耐圧強度１２４ＭＰａのガラスバルーン（住友３Ｍ社製：グラスバブルズＳ６０ＨＳ）２０部を加え、二軸押出機を用いて混練押出してガラスバルーンマスターバッチを製造した。
＜ガラスバルーン含有樹脂フィルムの製造＞
上記ガラスバルーンマスターバッチ２５部及び低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）７５部から、実施例１と同様にしてガラスバルーン含有樹脂フィルム及びそのＰＥＴラミネートフィルムを製造した。
Comparative Example 1
<Manufacture of glass balloon masterbatch>
20 parts of a glass balloon (Sumitomo 3M: Glass Bubbles S60HS) having an average particle diameter of 27 μm and a compressive strength of 124 MPa are added to 80 parts of low density polyethylene (Nihon Unicar Co., Ltd .: NUC8160) and kneaded using a twin screw extruder. Extruded to produce a glass balloon masterbatch.
<Manufacture of glass balloon-containing resin film>
A glass balloon-containing resin film and its PET laminate film were produced in the same manner as in Example 1 from 25 parts of the glass balloon masterbatch and 75 parts of low-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC8160).
比較例２
＜ガラスバルーンマスターバッチの製造＞
低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）８０部に、平均粒径４０μｍで耐圧強度２８ＭＰａのガラスバルーン（住友３Ｍ社製：グラスバブルズＳ３８）２０部を加え、二軸押出機を用いて混練押出してガラスバルーンマスターバッチを製造した。
＜ガラスバルーン含有樹脂フィルムの製造＞
上記ガラスバルーンマスターバッチ２５部及び低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）７５部から、実施例１と同様にしてガラスバルーン含有樹脂フィルム及びそのＰＥＴラミネートフィルムを製造した。
Comparative Example 2
<Manufacture of glass balloon masterbatch>
20 parts of a glass balloon (Sumitomo 3M Co., Ltd .: Glass Bubbles S38) having an average particle diameter of 40 μm and a compressive strength of 28 MPa are added to 80 parts of low density polyethylene (Nihon Unicar Co., Ltd .: NUC8160) and kneaded using a twin screw extruder. Extruded to produce a glass balloon masterbatch.
<Manufacture of glass balloon-containing resin film>
A glass balloon-containing resin film and its PET laminate film were produced in the same manner as in Example 1 from 25 parts of the glass balloon masterbatch and 75 parts of low-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC8160).
比較例３
実施例１で製造したガラスバルーンマスターバッチ２部及び低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）９８部から、実施例１と同様にしてガラスバルーン含有樹脂フィルム及びそのＰＥＴラミネートフィルムを製造した。
Comparative Example 3
A glass balloon-containing resin film and its PET laminate film were produced in the same manner as in Example 1 from 2 parts of the glass balloon masterbatch produced in Example 1 and 98 parts of low-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC8160).
比較例４
実施例１で製造したガラスバルーンマスターバッチ５０部及び低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）５０部から、実施例１と同様にしてガラスバルーン含有樹脂フィルム及びそのＰＥＴラミネートフィルムを製造した。
Comparative Example 4
A glass balloon-containing resin film and its PET laminate film were produced in the same manner as in Example 1 from 50 parts of the glass balloon masterbatch produced in Example 1 and 50 parts of low-density polyethylene (manufactured by Nippon Unicar Co., Ltd .: NUC8160).
比較例５
低密度ポリエチレン（日本ユニカー社製：ＮＵＣ８１６０）から、実施例１と同様にしてガラスバルーンを含まないポリエチレンフィルム及びそのＰＥＴラミネートフィルムを製造した。
Comparative Example 5
In the same manner as in Example 1, a polyethylene film containing no glass balloon and a PET laminate film thereof were produced from low-density polyethylene (manufactured by Nippon Unicar Company Limited: NUC8160).
比較例６
ポリプロピレン（プライムポリマー社製：プライムポリプロＦ３２７Ｄ）から、実施例１と同様にしてガラスバルーンを含まないポリプロピレンフィルム及びそのＰＥＴラミネートフィルムを製造した。
Comparative Example 6
A polypropylene film not containing a glass balloon and its PET laminate film were produced from polypropylene (manufactured by Prime Polymer Co., Ltd .: Prime Polypro F327D) in the same manner as in Example 1.
上記の実施例、比較例で製造したフィルムについて以下の評価方法により評価した。 The films produced in the above Examples and Comparative Examples were evaluated by the following evaluation methods.
＜断熱効果＞
実施例及び比較例で製造したフィルムを用いて、長さ２００ｍｍ、幅１５０ｍｍの袋を作成し、純水１００ｍｌを入れ密封し、６０℃のオーブンに１２時間放置した。純水の温度が６０℃であることを確認後、これを温度２３℃、湿度５０％の恒温室中に放置し、２０分後の純水の温度を測定した。その結果、無添加フィルムに比べ２℃以上の保温効果のあるものを◎、０．５〜２℃未満の保温効果のあるものを○、０．５℃未満のものを保温効果なし×、として評価した。
<Insulation effect>
A bag having a length of 200 mm and a width of 150 mm was prepared using the films produced in Examples and Comparative Examples, sealed with 100 ml of pure water, and left in an oven at 60 ° C. for 12 hours. After confirming that the temperature of pure water was 60 ° C., this was left in a constant temperature room at a temperature of 23 ° C. and a humidity of 50%, and the temperature of pure water after 20 minutes was measured. As a result, the film having a heat retention effect of 2 ° C. or higher compared to the additive-free film is indicated as “A”, the film having a heat retention effect of less than 0.5 to 2 ° C. evaluated.
＜ヘーズ＞
東洋精機製ヘーズメーターにより測定し、その値が２０以下を透明性大◎、２０〜５０を透明性あり○、５０以上を透明性なし×、として評価した。
<Haze>
The value was measured with a haze meter manufactured by Toyo Seiki, and the value was evaluated as 20 or less when the transparency was large ◎, 20 to 50 was transparency ○, and 50 or more was not transparency ×.
＜フィルム伸び率＞
インテスコ製万能試験機２０１型を用い、ＪＩＳ Ｋ ７１２７に準じて測定し、無添加フィルムに比べ保持率が８０％以上をフィルム強度大◎、６０〜８０％をフィルム強度あり○、６０％以下をフィルム強度なし×、として評価した。
<Film elongation>
Measured in accordance with JIS K 7127 using an Intesco Universal Testing Machine Model 201, the retention rate is 80% or higher compared to the additive-free film, the film strength is large ◎, 60-80% is film strength ◯, 60% or less No film strength was evaluated as x.
実施例及び比較例の評価結果を表１に示した。 The evaluation results of Examples and Comparative Examples are shown in Table 1.
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| US20100280164A1 (en) | 2009-04-29 | 2010-11-04 | Tundra Composites, LLC. | Inorganic Composite |
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| JP3393618B2 (en) * | 1994-03-18 | 2003-04-07 | 出光石油化学株式会社 | Polycarbonate resin composition |
| JP2004189867A (en) * | 2002-12-11 | 2004-07-08 | Sumitomo Chem Co Ltd | Aromatic liquid crystal polyester solution composition |
| WO2005066262A1 (en) * | 2003-12-30 | 2005-07-21 | 3M Innovative Properties Company | Filled composite |
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