JP7454827B2 - vacuum insulation - Google Patents
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- JP7454827B2 JP7454827B2 JP2019030294A JP2019030294A JP7454827B2 JP 7454827 B2 JP7454827 B2 JP 7454827B2 JP 2019030294 A JP2019030294 A JP 2019030294A JP 2019030294 A JP2019030294 A JP 2019030294A JP 7454827 B2 JP7454827 B2 JP 7454827B2
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- 238000009413 insulation Methods 0.000 title description 16
- 239000011162 core material Substances 0.000 claims description 96
- 239000003463 adsorbent Substances 0.000 claims description 66
- 239000012774 insulation material Substances 0.000 claims description 66
- 239000011230 binding agent Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 42
- 239000005011 phenolic resin Substances 0.000 claims description 33
- 229920001568 phenolic resin Polymers 0.000 claims description 30
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 22
- 239000012784 inorganic fiber Substances 0.000 claims description 22
- 230000004888 barrier function Effects 0.000 claims description 20
- 238000005452 bending Methods 0.000 claims description 16
- 239000011810 insulating material Substances 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- 238000013001 point bending Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 55
- 229920005989 resin Polymers 0.000 description 48
- 239000011347 resin Substances 0.000 description 48
- -1 polyethylene Polymers 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 238000007789 sealing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000010276 construction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000011491 glass wool Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000007666 vacuum forming Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 210000002268 wool Anatomy 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229920013716 polyethylene resin Polymers 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 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
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 208000016509 ear folding Diseases 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
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- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Description
本発明は、真空断熱材に関する。 The present invention relates to vacuum insulation materials.
近年、地球温暖化防止等の観点から省エネルギー化、省資源化が強く望まれている。特に、冷蔵庫、冷凍庫、断熱ボックス、ジャー炊飯器、給湯器、自動販売機等の家庭用、業務用電化製品、自動車、複写機、床暖房や、住宅等の分野では、熱エネルギーを効率的に利用するという観点から、真空断熱材が用いられるようになっている。 In recent years, there has been a strong desire to save energy and resources from the perspective of preventing global warming. In particular, thermal energy can be used efficiently in fields such as refrigerators, freezers, insulated boxes, jar rice cookers, water heaters, vending machines, and other household and commercial appliances, automobiles, copiers, floor heating, and housing. From the viewpoint of practical use, vacuum insulation materials have come into use.
従来の真空断熱材は平面形状を有するものが一般的であるが、施工部位に応じて立体形状とする場合には、平面形状の真空断熱材に折り曲げ加工やＲ加工を施すか、あるいは複数の真空断熱材を貼り合わせている。しかしながら、折り曲げ加工やＲ加工では、真空断熱材を複雑な起伏のある形状や深絞り形状にすることはできず、折り曲げ箇所やＲ加工箇所の損傷による断熱性能の低下を招きやすい。また、例えば、リチウムイオン電池などのバッテリーを断熱する目的でカバーに真空断熱材を使用する場合、真空断熱材の貼り合わせでは、継ぎ目部分から熱が漏れて熱橋の不具合が生じ、断熱性能が低下する。従って、貼り合わせや曲げ加工を施すことなく、種々の形状を有する施工箇所に隙間なく密着でき、熱橋の少ない真空断熱材が要求されている。 Conventional vacuum insulation materials generally have a planar shape, but when creating a three-dimensional shape depending on the construction site, the planar vacuum insulation material must be bent or rounded, or multiple Vacuum insulation material is attached. However, by bending or R processing, it is not possible to form the vacuum insulation material into a complicated undulating shape or a deep drawing shape, and the insulation performance is likely to deteriorate due to damage to the bending or R processing. For example, when vacuum insulation is used in a cover to insulate a battery such as a lithium-ion battery, when the vacuum insulation is pasted together, heat leaks from the seams, causing problems with thermal bridges and impairing insulation performance. descend. Therefore, there is a need for a vacuum heat insulating material that can be closely attached to construction sites having various shapes without any gaps without bonding or bending, and has fewer thermal bridges.
また、真空断熱材においては減圧密封により芯材が厚み方向に圧縮されているが、従来の真空断熱材は、経年劣化等により真空度が低下して内圧が高まると芯材の厚みが復元してしまうという問題があった。一般に、真空断熱材は狭い間隙に施工されることが多いので、真空度が低下して厚みが復元すると、他の部材を圧迫するうえ、製品としての外観も損なわれる。従って、真空度が低下しても形状変化が生じない真空断熱材に対する要望がある。 In addition, in vacuum insulation materials, the core material is compressed in the thickness direction by vacuum sealing, but in conventional vacuum insulation materials, when the degree of vacuum decreases due to aging etc. and the internal pressure increases, the core material restores its thickness. There was a problem with this. Generally, vacuum insulation materials are often installed in narrow gaps, so if the degree of vacuum decreases and the thickness is restored, it not only puts pressure on other members, but also impairs the appearance of the product. Therefore, there is a need for a vacuum insulation material that does not change shape even when the degree of vacuum decreases.
ここで、真空断熱材製造工程の減圧密封前に、あらかじめ芯材を成形する技術が知られている。
特許文献１は、ガラスウールマットをプレス成形したグラスウール成形体を芯材とする真空断熱材を開示している。しかしながら、特許文献１は、芯材に立体形状を付与することを開示していない。また、特許文献１では、芯材の成形にバインダーが用いられておらず、芯材の剛性が不足するため、仮に芯材を立体形状に成形したとしても、ガスバリア性の外被材での減圧密封時に形状が崩れてしまう。
Here, a technique is known in which a core material is formed in advance before vacuum sealing in the vacuum insulation manufacturing process.
Patent Document 1 discloses a vacuum insulation material whose core material is a glass wool molded body obtained by press-molding a glass wool mat. However, Patent Document 1 does not disclose imparting a three-dimensional shape to the core material. Furthermore, in Patent Document 1, a binder is not used to mold the core material, and the core material lacks rigidity. It loses its shape when sealed.
特許文献２は、無機バインダーで成形した芯材を含む真空断熱材を開示している。しかしながら、特許文献２は、芯材に立体形状を付与することを開示しておらず、有機バインダーや水分吸着剤及びガス吸着剤の使用についても開示していない。 Patent Document 2 discloses a vacuum insulation material that includes a core material formed with an inorganic binder. However, Patent Document 2 does not disclose imparting a three-dimensional shape to the core material, nor does it disclose the use of an organic binder, moisture adsorbent, or gas adsorbent.
特許文献３は、真空断熱材において、芯材が有機系バインダーで成形されていること、及び水分吸着剤やガス吸着剤を使用することを開示している。しかしながら、特許文献３は、芯材に立体形状を付与することを意図するものではなく、芯材を立体形状に成形するためにバインダー量や吸着剤の量を調節することについては全く言及していない。 Patent Document 3 discloses that in a vacuum heat insulating material, the core material is formed of an organic binder, and that a moisture adsorbent or a gas adsorbent is used. However, Patent Document 3 does not intend to impart a three-dimensional shape to the core material, and does not mention at all about adjusting the amount of binder or adsorbent in order to form the core material into a three-dimensional shape. do not have.
従来の立体形状付与技術では達成できない要求を満たしつつ、真空度低下時の形状変化が少ない立体形状を有する真空断熱材を提供することを目的として、本発明者は、種々のバインダーを用いて予め立体形状に成形した芯材を試験した。
しかしながら、無機バインダーを用いると、芯材が必要以上に固くなり、角部や稜線部において外被材が損傷する場合があることを見いだした。また無機バインダーは高価であるため、製造コストが増大するという問題もある。
前記無機バインダーの問題は有機バインダーの使用により回避できたが、有機バインダーには経年劣化によりアウトガスが発生して真空度が低下するという問題があることを見いだした。
With the aim of providing a vacuum heat insulating material having a three-dimensional shape that is less likely to change in shape when the degree of vacuum decreases while satisfying requirements that cannot be achieved using conventional three-dimensional shape imparting techniques, the present inventor has developed a three-dimensional shape using various binders in advance. A core material formed into a three-dimensional shape was tested.
However, it has been found that when an inorganic binder is used, the core material becomes harder than necessary, and the outer covering material may be damaged at corners and ridges. Furthermore, since inorganic binders are expensive, there is also the problem of increased manufacturing costs.
Although the problems of inorganic binders can be avoided by using organic binders, it has been found that organic binders have a problem in that outgas is generated due to aging and the degree of vacuum is reduced.
本発明者は鋭意検討を進めたところ、特定種類の有機バインダー（フェノール樹脂製バインダー）と無機繊維とを特定の質量比で用いて立体形状に成形した特定の密度を有する芯材を用い、更にガス吸着剤と水分吸着剤を特定の質量比で用いると、種々の形状を有する施工箇所に隙間なく密着でき熱橋の少ない立体形状を有しつつ、アウトガス発生による真空度低下が少ない真空断熱材が得られることを見いだした。本発明は、この知見に基づいてなされたものである。
すなわち、本発明は、下記〔１〕～〔６〕に関するものである。
After conducting extensive studies, the present inventor found that a core material having a specific density formed into a three-dimensional shape using a specific type of organic binder (phenolic resin binder) and inorganic fibers in a specific mass ratio, and When a gas adsorbent and a moisture adsorbent are used in a specific mass ratio, the vacuum insulation material can adhere to construction sites with various shapes without gaps, and has a three-dimensional shape with few thermal bridges, while reducing the vacuum level drop due to outgassing. I found that it was possible to obtain The present invention has been made based on this knowledge.
That is, the present invention relates to the following [1] to [6].
〔１〕芯材と、ガス吸着剤と、水分吸着剤と、ガスバリア性の外被材とを含む、立体形状を有する真空断熱材であって、
前記芯材が、無機繊維及びフェノール樹脂製バインダーを含み、
前記芯材の密度が、２００～３９０ｋｇ／ｍ3であり、
前記芯材が、前記フェノール樹脂製バインダーにより立体形状に成形されており、
前記フェノール樹脂製バインダーの質量（ａ）が、前記無機繊維の質量に基づいて７～１５％であり、
前記ガス吸着剤の質量（ｂ）に対する前記フェノール樹脂製バインダーの質量（ａ）の比（ａ／ｂ）が、５．０～２５．０であり、
前記水分吸着剤の質量（ｃ）に対する前記ガス吸着剤の質量（ｂ）の比（ｂ／ｃ）が、０．１～１．０であり、
前記芯材、前記ガス吸着剤及び前記水分吸着剤が、前記外被材内に減圧密封されている、真空断熱材。
〔２〕前記ガス吸着剤が、銅イオン交換ＺＳＭ－５型ゼオライトである、前記〔１〕に記載の真空断熱材。
〔３〕前記無機繊維が、１～８μｍの平均繊維径を有する、前記〔１〕又は〔２〕に記載の真空断熱材。
〔４〕前記芯材が、長さ１５０ｍｍ及び幅５０ｍｍの寸法を有する試料を用いてスパン１００ｍｍ及びひずみ速度５０ｍｍ／分で３点曲げをして測定した場合に、１．０ｋＮ以上の曲げ最大荷重を有する、前記〔１〕～〔３〕のいずれか１項に記載の真空断熱材。
〔５〕前記芯材が、長さ１５０ｍｍ及び幅５０ｍｍの寸法を有する試料を用いてスパン１００ｍｍ及びひずみ速度５０ｍｍ／分で３点曲げをして測定した場合に、２０Ｎ／ｃｍ以上の曲げ弾性勾配を有する、前記〔１〕～〔４〕のいずれか１項に記載の真空断熱材。
〔６〕前記芯材の厚み方向に１０％圧縮したときの応力が７０ｋＰａ以上である、前記〔１〕～〔５〕のいずれか１項に記載の真空断熱材。
[1] A vacuum insulation material having a three-dimensional shape, including a core material, a gas adsorbent, a moisture adsorbent, and a gas barrier outer covering material,
The core material includes inorganic fibers and a phenolic resin binder,
The core material has a density of 200 to 390 kg/m 3 ,
The core material is formed into a three-dimensional shape by the phenolic resin binder,
The mass (a) of the phenolic resin binder is 7 to 15% based on the mass of the inorganic fiber,
The ratio (a/b) of the mass (a) of the phenolic resin binder to the mass (b) of the gas adsorbent is 5.0 to 25.0,
The ratio (b/c) of the mass (b) of the gas adsorbent to the mass (c) of the moisture adsorbent is 0.1 to 1.0,
A vacuum insulation material, wherein the core material, the gas adsorbent, and the moisture adsorbent are vacuum-sealed within the jacket material.
[2] The vacuum insulation material according to [1] above, wherein the gas adsorbent is a copper ion exchange ZSM-5 type zeolite.
[3] The vacuum insulation material according to [1] or [2] above, wherein the inorganic fiber has an average fiber diameter of 1 to 8 μm.
[4] Maximum bending load of 1.0 kN or more when the core material is measured by 3-point bending at a span of 100 mm and a strain rate of 50 mm/min using a sample having dimensions of 150 mm in length and 50 mm in width. The vacuum heat insulating material according to any one of [1] to [3] above.
[5] The core material has a bending elastic gradient of 20 N/cm or more when measured by three-point bending at a span of 100 mm and a strain rate of 50 mm/min using a sample having dimensions of 150 mm in length and 50 mm in width. The vacuum insulation material according to any one of [1] to [4] above.
[6] The vacuum insulation material according to any one of [1] to [5], wherein the core material has a stress of 70 kPa or more when compressed by 10% in the thickness direction.
本発明により、施工箇所の形状に隙間なく密着でき熱橋が少ない立体形状を有しつつ、アウトガス発生による真空度低下が少なく、安価に製造できる真空断熱材を提供することができる。 ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a vacuum heat insulating material that has a three-dimensional shape that can closely fit the shape of the construction site without any gaps and has few thermal bridges, has less decrease in the degree of vacuum due to outgas generation, and can be manufactured at low cost.
本発明は、立体形状を有する真空断熱材であって、
芯材と、ガス吸着剤と、水分吸着剤と、ガスバリア性の外被材とを含み、
前記芯材が、無機繊維及びフェノール樹脂製バインダーを含み、
前記芯材の密度が、２００～３９０ｋｇ／ｍ3であり、
前記芯材が、前記フェノール樹脂製バインダーにより立体形状に成形されており、
前記フェノール樹脂製バインダーの質量（ａ）が、前記無機繊維の質量に基づいて７～１５％であり、
前記ガス吸着剤の質量（ｂ）に対する前記フェノール樹脂製バインダーの質量（ａ）の比（ａ／ｂ）が、５．０～２５．０であり、
前記水分吸着剤の質量（ｃ）に対する前記ガス吸着剤の質量（ｂ）の比（ｂ／ｃ）が、０．１～１．０であり、
前記芯材、前記ガス吸着剤及び前記水分吸着剤が、前記外被材内に減圧密封されている、ことを特徴とする真空断熱材である。
The present invention is a vacuum insulation material having a three-dimensional shape,
Including a core material, a gas adsorbent, a moisture adsorbent, and a gas barrier outer covering material,
The core material includes inorganic fibers and a phenolic resin binder,
The core material has a density of 200 to 390 kg/m 3 ,
The core material is formed into a three-dimensional shape by the phenolic resin binder,
The mass (a) of the phenolic resin binder is 7 to 15% based on the mass of the inorganic fiber,
The ratio (a/b) of the mass (a) of the phenolic resin binder to the mass (b) of the gas adsorbent is 5.0 to 25.0,
The ratio (b/c) of the mass (b) of the gas adsorbent to the mass (c) of the moisture adsorbent is 0.1 to 1.0,
The vacuum insulation material is characterized in that the core material, the gas adsorbent, and the moisture adsorbent are vacuum-sealed within the jacket material.
本発明に用いられる芯材は、無機繊維を含む。無機繊維としては、真空断熱材分野で用いられているものを特に制限なく用いることができ、例えば、グラスウール、グラスファイバー、セラミックウール（シリカウール）、ロックウール、アルミナウール、炭素繊維等を使用することができる。 The core material used in the present invention contains inorganic fibers. As the inorganic fibers, those used in the field of vacuum insulation materials can be used without particular restriction, such as glass wool, glass fiber, ceramic wool (silica wool), rock wool, alumina wool, carbon fiber, etc. be able to.
無機繊維は、好ましくは１～８μｍ、より好ましくは１．５～６μｍ、更に好ましくは２～４μｍの平均繊維径を有する。平均繊維径が上記範囲内であれば、芯材をプレス成形する際のマットの千切れや、成形品の偏肉や、無機繊維による皮膚刺激を低減しつつ、真空断熱材の経年劣化低減を可能にする適切な芯材強度や優れた断熱性が得られる。平均繊維径は、通気抵抗法または光学顕微鏡によって測定することができる。 The inorganic fibers preferably have an average fiber diameter of 1 to 8 μm, more preferably 1.5 to 6 μm, and even more preferably 2 to 4 μm. If the average fiber diameter is within the above range, it will reduce tearing of the mat when press-molding the core material, uneven thickness of the molded product, and skin irritation caused by inorganic fibers, while also reducing aging deterioration of the vacuum insulation material. Appropriate core material strength and excellent insulation properties can be obtained. The average fiber diameter can be measured by the airflow resistance method or by optical microscopy.
無機繊維としては、成形のしやすさやコストの面で、溶融延伸法で作られたグラスウール（短繊維）が最も好ましいが、長繊維グラスファイバー、ロックウール、シリカウール、アルミナウール、炭素繊維およびこれらの混合品を使用しても構わない。また、熱伝導率の悪化や芯材の剛性を損なわない範囲であれば、化学繊維や天然繊維などを混ぜても良い。 As the inorganic fiber, glass wool (short fiber) made by melt-drawing method is most preferable in terms of ease of molding and cost, but long fiber glass fiber, rock wool, silica wool, alumina wool, carbon fiber and these You may use a mixture of these. Further, chemical fibers, natural fibers, etc. may be mixed as long as they do not deteriorate thermal conductivity or impair the rigidity of the core material.
使用できる化学繊維の例として、ナイロン繊維、レーヨン繊維、アセテート繊維、アラミド繊維、ビニロン繊維、ポリエステル繊維、アクリル繊維、ポリウレタン繊維、ポリ塩化ビニル繊維、ポリエチレン繊維、ポリプロピレン繊維、セルロース繊維（例えばキュプラ）が挙げられる。天然繊維の例としては綿、麻、毛、絹などが挙げられる。 Examples of chemical fibers that can be used include nylon fibers, rayon fibers, acetate fibers, aramid fibers, vinylon fibers, polyester fibers, acrylic fibers, polyurethane fibers, polyvinyl chloride fibers, polyethylene fibers, polypropylene fibers, and cellulose fibers (e.g. cupro). Can be mentioned. Examples of natural fibers include cotton, linen, wool, and silk.
無機繊維は公知であり、市場で容易に入手できるか、又は調製可能である。
本発明の真空断熱材に用いる無機繊維は、例えば、溶融ガラスを繊維化してグラスウール等の無機繊維を紡出させて製造できる。繊維化の方法としては、従来公知の遠心法や、火焔法、吹き飛ばし法等が例示でき、特にこれらの方法に限定されない。遠心法による繊維化装置の例としては、スピナー等が挙げられる。グラスウール以外の他の無機繊維についても同様に製造することができる。
Inorganic fibers are known and readily available commercially or can be prepared.
The inorganic fibers used in the vacuum insulation material of the present invention can be produced, for example, by turning molten glass into fibers and spinning out inorganic fibers such as glass wool. Examples of the fiberization method include the conventionally known centrifugation method, flame method, blowing method, etc., but are not particularly limited to these methods. An example of a fiberizing device using a centrifugal method is a spinner. Inorganic fibers other than glass wool can also be produced in the same manner.
芯材の密度は、２００～３９０ｋｇ／ｍ3であり、好ましくは２２０～３５０ｋｇ／ｍ3、より好ましくは２４０～３００ｋｇ／ｍ3である。密度が上記範囲内であれば、芯材の立体形状への成形がより容易になり、真空成形時の急激な圧力降下に伴い外被材が芯材を圧縮したときの芯材形状の十分な保持が可能であり、更に真空断熱材の初期熱伝導率を適切な範囲としつつ断熱性の経年劣化を低減できる。 The density of the core material is 200 to 390 kg/m 3 , preferably 220 to 350 kg/m 3 , more preferably 240 to 300 kg/m 3 . If the density is within the above range, it will be easier to form the core material into a three-dimensional shape, and the core material will have a sufficient shape when the outer covering material compresses the core material due to the sudden pressure drop during vacuum forming. In addition, it is possible to maintain the initial thermal conductivity of the vacuum heat insulating material within an appropriate range while reducing aging deterioration of the heat insulating property.
芯材は、フェノール樹脂製バインダーを用いて立体形状に成形されている。フェノール樹脂製バインダーは無機バインダーよりも安価であるので製造コストを低減できる。またフェノール樹脂製バインダーを用いて得られた芯材は優れた剛性を有しつつも、無機バインダーを用いて得られた芯材よりも硬度が低いため、芯材による外被材損傷を防ぐことができる。
フェノール樹脂は大きくレゾール型とノボラック型とに分類されるが、アウトガス発生抑制、得られる芯材の硬度、芯材成形に必要なコスト、取扱性（硬化速度が速く、粘度が低い）等の観点から、揮発分（具体的には一酸化炭素、二酸化炭素、ホルムアルデヒド、低分子量アミン類、未反応フェノールなど）の発生が少ないレゾール型フェノール樹脂が好ましい。フェノール：ホルムアルデヒドのモル比が１：３のレゾール型フェノール樹脂がより好ましい。
本発明に適したフェノール樹脂としては、例えば、水溶性レゾール型やエマルジョン型のレゾール型のものが挙げられる。
フェノール樹脂製バインダーは公知であり、市場において容易に入手することができるか、又は調製可能である。
The core material is molded into a three-dimensional shape using a phenolic resin binder. Phenol resin binders are cheaper than inorganic binders, so manufacturing costs can be reduced. In addition, although the core material obtained using a phenolic resin binder has excellent rigidity, it has lower hardness than the core material obtained using an inorganic binder, so it is difficult to prevent damage to the outer covering material due to the core material. I can do it.
Phenolic resins are broadly classified into resol type and novolac type, but they are different from the viewpoints of outgassing suppression, hardness of the resulting core material, cost required for core material molding, ease of handling (fast curing speed, low viscosity), etc. Therefore, resol-type phenolic resins that generate less volatile components (specifically, carbon monoxide, carbon dioxide, formaldehyde, low molecular weight amines, unreacted phenol, etc.) are preferred. A resol type phenol resin with a phenol:formaldehyde molar ratio of 1:3 is more preferred.
Examples of phenolic resins suitable for the present invention include water-soluble resol type resins and emulsion type resol type resins.
Phenolic resin binders are known and can be readily obtained or prepared on the market.
フェノール樹脂製バインダーの質量（ａ）は、芯材に含まれる無機繊維の質量に基づいて、７～１５％、好ましくは７～１４％、より好ましくは７～１３％である。フェノール樹脂製バインダーの量が上記範囲内であれば、アウトガスの発生を抑制しつつ芯材に適度な剛性を付与することができる。 The mass (a) of the phenolic resin binder is 7 to 15%, preferably 7 to 14%, more preferably 7 to 13%, based on the mass of the inorganic fibers contained in the core material. If the amount of the phenolic resin binder is within the above range, appropriate rigidity can be imparted to the core material while suppressing the generation of outgas.
芯材は、厚み方向に１０％圧縮したときに、好ましくは７０ｋＰａ以上、より好ましくは７０～１２００ｋＰａ、更に好ましくは８０～６００ｋＰａ、更により好ましくは９０～２００ｋＰａの応力を有する。芯材の圧縮強度が上記範囲内であれば、真空成形時の急激な圧力降下に伴い外被材が芯材を圧縮したときの芯材形状の十分な保持が可能となる。厚み方向に１０％圧縮したときの応力は、例えば、万能試験機を用いてサンプルを２０ｍｍ／分で１０％圧縮した場合の応力として測定することができる。 The core material, when compressed by 10% in the thickness direction, preferably has a stress of 70 kPa or more, more preferably 70 to 1200 kPa, still more preferably 80 to 600 kPa, and even more preferably 90 to 200 kPa. If the compressive strength of the core material is within the above range, the shape of the core material can be sufficiently maintained when the core material is compressed by the outer covering material due to a sudden pressure drop during vacuum forming. The stress when the sample is compressed by 10% in the thickness direction can be measured, for example, as the stress when the sample is compressed by 10% at 20 mm/min using a universal testing machine.
立体形状を有する芯材は下記手順により製造できる。
まず、繊維化装置から遠心力によって排出された無機繊維へフェノール樹脂性バインダーを噴霧しながら集綿して集綿物を得る。集綿物中の前記バインダーは硬化していない。
次に、前記集綿物を、加熱された金型（施工箇所の形状に対応する金型）へ投入し、オーブンで焼成して、前記バインダーを熱硬化させて立体形状の芯材を得る。焼成条件は、バインダーを熱硬化させるのに十分であれば特に制限は無く、焼成時の加熱温度は、例えば、２００～２５０℃であり、加熱時間は、単位面積当たりの無機繊維の質量をＡ（ｇ／ｍ2）、無機繊維の質量に基づくバインダー付着量をＢ（％）とした場合に、Ａ×Ｂ（秒）であることが好ましい。加熱時の圧力は、芯材の密度に合わせて適宜調節でき、例えば、１．５～３．５ｔ／ｍ2であってもよい。
A core material having a three-dimensional shape can be manufactured by the following procedure.
First, a phenol resin binder is sprayed onto inorganic fibers discharged from a fiberizing device by centrifugal force, and the fibers are collected to obtain a collected material. The binder in the cotton collection has not been cured.
Next, the collected cotton material is put into a heated mold (a mold corresponding to the shape of the construction site) and fired in an oven to thermoset the binder and obtain a three-dimensional core material. The firing conditions are not particularly limited as long as they are sufficient to thermoset the binder, and the heating temperature during firing is, for example, 200 to 250°C, and the heating time is set so that the mass of inorganic fibers per unit area is A. (g/m 2 ), and where B (%) is the amount of binder attached based on the mass of the inorganic fibers, it is preferably A×B (seconds). The pressure during heating can be adjusted as appropriate depending on the density of the core material, and may be, for example, 1.5 to 3.5 t/m 2 .
芯材の形状は、真空断熱材が施工箇所へ隙間なく密着することを可能にする立体形状である。芯材の形状は、熱橋抑制の観点で、継ぎ目部分が最小限（好ましくはゼロ）となるように設定することが好ましい。 The shape of the core material is a three-dimensional shape that allows the vacuum insulation material to adhere closely to the construction site without any gaps. From the viewpoint of suppressing thermal bridges, the shape of the core material is preferably set so that the number of seams is minimal (preferably zero).
芯材の厚み、目付及び密度は、芯材全体に亘って一様であってもよく、断熱性や剛性が必要となる部分の厚み、目付及び／又は密度を他の部分よりも大きくしてもよい。例えば、断熱性が必要な箇所の厚みを芯材の最小厚みの１～５倍の厚みに設計して、断熱性や剛性を高めてもよい。また、真空度が低下した場合の形状崩れ防止のため、Ｒ形状部の厚み、目付及び／又は密度を大きく設計することができる。例えば、Ｒ３～Ｒ５０ｍｍの部位について、Ｒ頂点からの距離５０ｍｍまでの範囲の製品密度を２５０ｋｇ／ｍ3以上としてもよい。 The thickness, area weight, and density of the core material may be uniform throughout the core material, and the thickness, area weight, and/or density of the part where insulation and rigidity are required are larger than other parts. Good too. For example, the thickness of the portion where heat insulation is required may be designed to be 1 to 5 times the minimum thickness of the core material to improve heat insulation and rigidity. Further, in order to prevent the shape from collapsing when the degree of vacuum decreases, the thickness, area weight, and/or density of the rounded portion can be designed to be large. For example, for the region R3 to R50 mm, the product density in the range up to a distance of 50 mm from the R apex may be set to 250 kg/m 3 or more.
芯材が施工箇所に応じた立体形状に成形されていることで、真空断熱材は施工箇所の形状に隙間なく密着でき、従来の施工方法である複数の真空断熱材の貼り合わせによって生じる継ぎ目部分の熱橋による断熱性能の低下を防ぐことができる。折れやすい形状を有する部位の周辺には、リブ形状やビード形状を付与して補強してもよい。 Because the core material is molded into a three-dimensional shape according to the construction location, the vacuum insulation material can adhere to the shape of the construction location without any gaps, making it possible to avoid seams caused by pasting multiple vacuum insulation materials together using conventional construction methods. It is possible to prevent the deterioration of insulation performance due to thermal bridges. A rib shape or a bead shape may be added to the periphery of a portion having a shape that is likely to break for reinforcement.
芯材は、長さ１５０ｍｍ及び幅５０ｍｍの寸法を有する試料を用いてスパン１００ｍｍ及びひずみ速度５０ｍｍ／分で３点曲げをして測定した場合に、１．０ｋＮ以上の曲げ最大荷重を有することが好ましく、１．２ｋＮ以上の曲げ最大荷重を有することがより好ましい。曲げ最大荷重が１．０ｋＮ以上であれば、真空成形前の芯材形状に対する、真空成形後の寸法の変化率を１％以下にできる。 The core material can have a maximum bending load of 1.0 kN or more when measured by three-point bending at a span of 100 mm and a strain rate of 50 mm/min using a sample having dimensions of 150 mm in length and 50 mm in width. Preferably, it is more preferable to have a maximum bending load of 1.2 kN or more. If the maximum bending load is 1.0 kN or more, the rate of change in dimensions after vacuum forming with respect to the core shape before vacuum forming can be 1% or less.
また、芯材は、長さ１５０ｍｍ及び幅５０ｍｍの寸法を有する試料を用いてスパン１００ｍｍ及びひずみ速度５０ｍｍ／分で３点曲げをして測定した場合に、２０Ｎ／ｃｍ以上の曲げ弾性勾配を有することが好ましく、２５Ｎ／ｃｍ以上の曲げ弾性勾配を有することがより好ましく、２８Ｎ／ｃｍ以上の曲げ弾性勾配を有することが更に好ましい。曲げ弾性勾配が２０Ｎ／ｃｍ以上であれば、真空成形前の芯材形状に対する、真空成形後の寸法の変化率を１％以下にできる。 In addition, the core material has a bending elastic gradient of 20 N/cm or more when measured by three-point bending at a span of 100 mm and a strain rate of 50 mm/min using a sample having dimensions of 150 mm in length and 50 mm in width. It is preferable to have a bending elastic gradient of 25 N/cm or more, more preferably to have a bending elastic gradient of 28 N/cm or more. If the bending elasticity gradient is 20 N/cm or more, the rate of change in dimensions after vacuum forming with respect to the shape of the core material before vacuum forming can be 1% or less.
本発明の真空断熱材は、ガス吸着剤及び水分吸着剤を含む。ガス吸着剤及び水分吸着剤を用いることにより、フェノール樹脂製バインダーから発生するアウトガス、外部から侵入するガス（窒素、酸素、二酸化炭素等）や水分を除去して、経年劣化による真空断熱材の断熱性能の低下を抑制することができる。 The vacuum insulation material of the present invention contains a gas adsorbent and a moisture adsorbent. By using a gas adsorbent and a moisture adsorbent, outgas generated from the phenolic resin binder, gases (nitrogen, oxygen, carbon dioxide, etc.) that enter from the outside, and moisture are removed, and insulation of vacuum insulation materials due to aging deterioration is removed. Deterioration in performance can be suppressed.
本発明に用いられるガス吸着剤は、前記のアウトガスや外部侵入ガスを吸着する物質であれば特に制限されない。フェノール樹脂製バインダーからは一酸化炭素、二酸化炭素、ホルムアルデヒドや、アミン類等の低分子量のアウトガスが発生するので、これらのアウトガスを吸着することができる吸着剤が好ましい。そのようなガス吸着剤としては、例えば、ゼオライト、コバルトやリチウム等からなる合金や、活性炭等が挙げられる。ガス吸着性能及び生産性の観点から、ゼオライトが好ましく、銅イオン交換ＺＳＭ－５型ゼオライトがより好ましい。
ガス吸着剤は公知であり、市場において容易に入手することができるか、又は調製可能である。
The gas adsorbent used in the present invention is not particularly limited as long as it is a material that adsorbs the above-mentioned outgas and externally invaded gas. Since a phenolic resin binder generates low molecular weight outgases such as carbon monoxide, carbon dioxide, formaldehyde, and amines, an adsorbent that can adsorb these outgasses is preferable. Examples of such gas adsorbents include zeolite, alloys made of cobalt, lithium, etc., and activated carbon. From the viewpoint of gas adsorption performance and productivity, zeolite is preferred, and copper ion exchange ZSM-5 type zeolite is more preferred.
Gas adsorbents are known and readily available on the market or can be prepared.
ガス吸着剤は、ガス吸着剤の質量（ｂ）に対するフェノール樹脂製バインダーの質量（ａ）の比（ａ／ｂ）が、５．０～２５．０、好ましくは６．０～２４．０、より好ましくは７．０～２２．０、更に好ましくは７．５～２０．０となる量で、真空断熱材に含まれる。ガス吸着剤の量が上記範囲内であれば、フェノール樹脂バインダーから生じるアウトガスを効率よく吸着しつつ、製造費用を抑えることができる。 The gas adsorbent has a ratio (a/b) of the mass (a) of the phenolic resin binder to the mass (b) of the gas adsorbent from 5.0 to 25.0, preferably from 6.0 to 24.0. The amount contained in the vacuum insulation material is more preferably 7.0 to 22.0, and even more preferably 7.5 to 20.0. If the amount of the gas adsorbent is within the above range, it is possible to efficiently adsorb outgas generated from the phenolic resin binder while reducing manufacturing costs.
水分吸着剤は、水分を吸着する物質であれば特に制限無く使用することができ、例えば、酸化カルシウム等のアルカリ土類金属酸化物、酸化ナトリウム等のアルカリ金属酸化物、ゼオライトや、シリカゲル等が挙げられる。
水分吸着剤は公知であり、市場において容易に入手することができるか、又は調製可能である。
The moisture adsorbent can be used without any particular restriction as long as it is a substance that adsorbs moisture.For example, alkaline earth metal oxides such as calcium oxide, alkali metal oxides such as sodium oxide, zeolite, silica gel, etc. Can be mentioned.
Moisture adsorbents are known and readily available on the market or can be prepared.
水分吸着剤は、水分吸着剤の質量（ｃ）に対するガス吸着剤の質量（ｂ）の比（ｂ／ｃ）が、０．１～１．０、好ましくは０．１５～０．９、より好ましくは０．２～０．８、更に好ましくは０．２５～０．７５となる量で、真空断熱材に含まれる。水分吸着剤の量が上記範囲内であれば、真空断熱材の経年劣化による断熱性能の低下を抑制しつつ、製造費用を抑えることができる。 The moisture adsorbent has a ratio (b/c) of the mass (b) of the gas adsorbent to the mass (c) of the moisture adsorbent from 0.1 to 1.0, preferably from 0.15 to 0.9. It is preferably contained in the vacuum insulation material in an amount of 0.2 to 0.8, more preferably 0.25 to 0.75. If the amount of the moisture adsorbent is within the above range, manufacturing costs can be suppressed while suppressing deterioration of insulation performance due to aging of the vacuum insulation material.
本発明に用いられる外被材は、ガスバリア性を有していれば特に制限はないが、シール層及びガスバリア層を予め積層した多層フィルムが好ましく、芯材に接する側から順にシール層、ガスバリア層及び樹脂フィルム層を積層したものがより好ましい。
外被材の厚さは、特に制限はないが、損傷や真空度の低下を防ぐため、従来用いられているものよりも厚い外被材、例えば厚さ５０～１５０μｍのものを使用するのが好ましい。
The outer covering material used in the present invention is not particularly limited as long as it has gas barrier properties, but a multilayer film in which a sealing layer and a gas barrier layer are laminated in advance is preferable, and the sealing layer and the gas barrier layer are sequentially layered from the side in contact with the core material. It is more preferable to have a laminated resin film layer.
There is no particular limit to the thickness of the outer sheathing material, but in order to prevent damage and a decrease in the degree of vacuum, it is recommended to use an outer sheathing material that is thicker than that conventionally used, for example, one with a thickness of 50 to 150 μm. preferable.
ガスバリア層は、ガスを透過しない層であり、真空断熱材の真空度の低下を防ぐ観点から用いられる。ガスバリア層としては、金属箔や、樹脂フィルム上に金属等を蒸着した積層フィルム（蒸着膜フィルム）等が挙げられる。
金属箔の金属としては、アルミニウム、銅、ステンレス、鉄等が挙げられる。好ましくは、アルミニウムが用いられる。
蒸着膜は、蒸着法、スパッタ法等により、アルミニウム、ステンレス、コバルト、ニッケル等の金属又はシリカ、アルミナ、若しくはこれらの組み合わせを蒸着させて形成する。蒸着膜フィルムの基材となる樹脂フィルムとしては、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂等の芳香族ポリエステル系樹脂；ポリエチレン樹脂、ポリプロピレン樹脂、オレフィン共重合体等のポリオレフィン系樹脂；ポリ塩化ビニル樹脂、塩化ビニル共重合体等の塩化ビニル系樹脂；ナイロン６、ナイロン６６、メタキシリレンジアミン・アジピン酸縮合体等のポリアミド樹脂；ポリビニルアルコール樹脂、アクリロニトリル・ブタジエン・スチレン共重合体、アクリロニトリル・スチレン共重合体等のスチレン系樹脂；ポリメチルメタクリレート樹脂、アクリル酸エステル樹脂とメチルメタクリル酸エステル共重合体等のアクリル系樹脂、エチレン-ビニルアルコール共重合体、ポリビニルアルコール樹脂及びこれを部分ケン化した物等の熱可塑性樹脂、フェノール樹脂、ユリア樹脂等の熱硬化性樹脂から製造されるフィルムが用いられる。
ガスバリア層は、好ましくはポリビニルアルコール樹脂上にアルミ蒸着を行った積層フィルム又はアルミ箔である。
ガスバリア層の厚さは特に制限はないが、蒸着膜フィルムの場合には、蒸着膜の厚さは８００～２４００Åであることが好ましく、金属箔の場合には、６～５０μｍであることが好ましい。
ガスバリア層に用いられる金属箔や蒸着膜フィルムは公知であり、市場において容易に入手することができるか、又は調製可能である。
The gas barrier layer is a layer that does not allow gas to pass through, and is used from the viewpoint of preventing the degree of vacuum of the vacuum insulation material from decreasing. Examples of the gas barrier layer include metal foil and a laminated film (deposited film) in which a metal or the like is deposited on a resin film.
Examples of the metal of the metal foil include aluminum, copper, stainless steel, and iron. Preferably aluminum is used.
The deposited film is formed by depositing a metal such as aluminum, stainless steel, cobalt, or nickel, or silica, alumina, or a combination thereof by a vapor deposition method, a sputtering method, or the like. The resin film that serves as the base material for the vapor-deposited film includes aromatic polyester resins such as polyethylene terephthalate (PET) resin and polybutylene terephthalate (PBT) resin; polyolefin resins such as polyethylene resin, polypropylene resin, and olefin copolymers. ; Vinyl chloride resins such as polyvinyl chloride resins and vinyl chloride copolymers; Polyamide resins such as nylon 6, nylon 66, metaxylylenediamine-adipic acid condensates; Polyvinyl alcohol resins, acrylonitrile-butadiene-styrene copolymers , styrene resins such as acrylonitrile-styrene copolymers; acrylic resins such as polymethyl methacrylate resins, acrylic ester resins and methyl methacrylic ester copolymers, ethylene-vinyl alcohol copolymers, polyvinyl alcohol resins, and A film manufactured from a thermosetting resin such as a partially saponified thermoplastic resin, a phenolic resin, or a urea resin is used.
The gas barrier layer is preferably a laminated film or aluminum foil in which aluminum is vapor-deposited on a polyvinyl alcohol resin.
The thickness of the gas barrier layer is not particularly limited, but in the case of a vapor-deposited film, the thickness of the vapor-deposited film is preferably 800 to 2400 Å, and in the case of metal foil, it is preferably 6 to 50 μm. .
Metal foils and vapor-deposited films used for gas barrier layers are well known and can be easily obtained or prepared on the market.
シール層は、加熱により融着可能な樹脂である。熱融着可能な樹脂であれば、特に制限はない。具体的には、ポリエチレン樹脂、ポリプロピレン樹脂等のポリオレフィン樹脂、ポリアクリロニトリル樹脂、ポリエステル樹脂、エチレン－ビニルアルコール共重合体、又はそれらの混合体からなるフィルム等を用いることができる。好ましくはポリエチレン樹脂、ポリプロピレン樹脂、エチレン-ビニルアルコール共重合体が用いられる。
ポリエチレン樹脂は、０．９０～０．９８ｇ／ｃｍ3の密度のものが好ましい。
ポリプロピレン樹脂は、０．８５～０．９５ｇ／ｃｍ3の密度のものが好ましい。
シール層の厚さは特に制限はないが、５０～２００μｍであることが好ましい。
シール層に用いられる樹脂は公知であり、市場において容易に入手することができるか、又は調製可能である。
The seal layer is a resin that can be fused by heating. There is no particular restriction as long as the resin can be heat-sealed. Specifically, films made of polyolefin resins such as polyethylene resins and polypropylene resins, polyacrylonitrile resins, polyester resins, ethylene-vinyl alcohol copolymers, or mixtures thereof can be used. Preferably, polyethylene resin, polypropylene resin, or ethylene-vinyl alcohol copolymer is used.
The polyethylene resin preferably has a density of 0.90 to 0.98 g/cm 3 .
The polypropylene resin preferably has a density of 0.85 to 0.95 g/cm 3 .
The thickness of the sealing layer is not particularly limited, but is preferably 50 to 200 μm.
The resins used in the sealing layer are known and can be easily obtained or prepared on the market.
樹脂フィルム層は、ガスバリア層を保護する目的で、ガスバリア層上に任意に設けられる層である。樹脂フィルム層としては、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂等の芳香族ポリエステル系樹脂；ポリエチレン樹脂、ポリプロピレン樹脂、オレフィン共重合体等のポリオレフィン系樹脂；ポリ塩化ビニル樹脂、塩化ビニル共重合体等の塩化ビニル系樹脂；ナイロン６、ナイロン６６、メタキシリレンジアミン・アジピン酸縮合体等のポリアミド樹脂；ポリビニルアルコール樹脂、アクリロニトリル・ブタジエン・スチレン共重合体、アクリロニトリル・スチレン共重合体等のスチレン系樹脂；ポリメチルメタクリレート樹脂、アクリル酸エステル樹脂とメチルメタクリル酸エステル共重合体等のアクリル系樹脂等の熱可塑性樹脂、フェノール樹脂、ユリア樹脂等の熱硬化性樹脂から製造されるフィルムが用いられる。好ましくは、ＰＥＴ樹脂、ナイロン６又はナイロン６６である。
これらの樹脂フィルムには、有機質、無機質のフィラーを添加することもできる。これらの樹脂は単独で又は２種以上を混合して用いることができる。
樹脂フィルム層には、ガスバリア性フィルムのガスバリア性能を更に向上させるために、塩化ビニリデン樹脂、アクリロニトリル樹脂、ビニルアルコール樹脂等のビニルモノマーを重合、共重合させて得られるガスバリア性樹脂を塗布したり、積層したり、それらの粒子を樹脂フィルム層中に混合分散させることもできる。
樹脂フィルム層の厚さは特に制限はないが、１２～３０μｍであることが好ましい。
樹脂フィルム層に用いられる樹脂は公知であり、市場において容易に入手することができるか、又は調製可能である。
The resin film layer is a layer that is optionally provided on the gas barrier layer for the purpose of protecting the gas barrier layer. For the resin film layer, aromatic polyester resins such as polyethylene terephthalate (PET) resins and polybutylene terephthalate (PBT) resins; polyolefin resins such as polyethylene resins, polypropylene resins, and olefin copolymers; polyvinyl chloride resins, chlorinated resins, etc. Vinyl chloride resins such as vinyl copolymers; polyamide resins such as nylon 6, nylon 66, metaxylylenediamine-adipic acid condensates; polyvinyl alcohol resins, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers Films manufactured from styrene resins such as polymethyl methacrylate resins, thermoplastic resins such as acrylic resins such as acrylic ester resins and methyl methacrylic ester copolymers, and thermosetting resins such as phenolic resins and urea resins. is used. Preferably, PET resin, nylon 6 or nylon 66 is used.
Organic or inorganic fillers can also be added to these resin films. These resins can be used alone or in combination of two or more.
In order to further improve the gas barrier performance of the gas barrier film, the resin film layer may be coated with a gas barrier resin obtained by polymerizing or copolymerizing vinyl monomers such as vinylidene chloride resin, acrylonitrile resin, or vinyl alcohol resin. It is also possible to laminate them or to mix and disperse these particles in a resin film layer.
The thickness of the resin film layer is not particularly limited, but is preferably 12 to 30 μm.
The resin used for the resin film layer is known and can be easily obtained or prepared on the market.
本発明の真空断熱材において、芯材、ガス吸着剤及び水分吸着剤を減圧密封した部位の周りには、通常、外被材を構成するガスバリア性フィルムのシール層同士が接着した「耳部」が形成される。耳部は、芯材に沿って耳部を折る「耳折り」によって折りたたまれてもよく、その際、真空断熱材の施工時に熱源に接しない側の面に折りたたむのが好ましい。 In the vacuum insulation material of the present invention, around the part where the core material, gas adsorbent, and moisture adsorbent are sealed under reduced pressure, there is usually an "edge part" where the sealing layers of the gas barrier film constituting the outer covering material are adhered to each other. is formed. The ear portion may be folded by “ear folding” in which the ear portion is folded along the core material, and in this case, it is preferable to fold the ear portion to the side that does not come into contact with the heat source during construction of the vacuum insulation material.
本発明の真空断熱材において、芯材、ガス吸着剤及び水分吸着剤は、ガスバリア性の外被材内に減圧密封されている。真空断熱材の内部圧力は、例えば、０．５～２０Ｐａ、好ましくは０．５～１０Ｐａである。内部圧力が上記範囲内であれば、真空断熱材内部のガスを介する熱伝導を抑制できるため、真空断熱材の断熱性を高めることができる。 In the vacuum heat insulating material of the present invention, the core material, the gas adsorbent, and the moisture adsorbent are sealed under reduced pressure within the outer cover material having gas barrier properties. The internal pressure of the vacuum insulation material is, for example, 0.5 to 20 Pa, preferably 0.5 to 10 Pa. If the internal pressure is within the above range, heat conduction through the gas inside the vacuum insulation material can be suppressed, so that the insulation properties of the vacuum insulation material can be improved.
熱や衝撃等による損傷対策として、真空断熱材の表面にグラスウールや発泡体などの断熱材を張り合わせて真空断熱材を保護してもよい。 As a measure against damage caused by heat, impact, etc., the vacuum insulation material may be protected by laminating a heat insulating material such as glass wool or foam on the surface of the vacuum insulation material.
本発明の真空断熱材は、袋状の外被材の内部に、立体形状に成形された芯材、ガス吸着剤及び水分吸着剤を配置し、外被材で芯材、ガス吸着剤及び水分吸着剤を減圧密封することにより製造することができる。減圧密封の方法は、当該技術分野において従来公知の方法を用いることができる。 In the vacuum insulation material of the present invention, a core material, a gas adsorbent, and a moisture adsorbent formed into a three-dimensional shape are arranged inside a bag-like outer covering material, and the core material, gas adsorbent, and moisture absorbent are arranged in the outer covering material. It can be manufactured by sealing the adsorbent under reduced pressure. As the vacuum sealing method, a method conventionally known in the technical field can be used.
減圧密封前に、好ましくは減圧密封装置に挿入する直前まで、芯材及び外被材を加熱乾燥しておくことで、得られる真空断熱材の熱伝導率を低減することができる。乾燥温度は、芯材については、例えば、１５０～２５０℃であり、外被材については、例えば、５０～８０℃である。
減圧密封時にガス吸着剤や水分吸着剤の位置がずれないよう、吸着剤の形状に応じた窪みや穴を予め芯材に設けておくことが好ましい。
The thermal conductivity of the resulting vacuum insulation material can be reduced by heating and drying the core material and the outer covering material before vacuum sealing, preferably just before inserting into the vacuum sealing device. The drying temperature is, for example, 150 to 250°C for the core material, and 50 to 80°C for the outer covering material.
In order to prevent the position of the gas adsorbent or moisture adsorbent from shifting during vacuum sealing, it is preferable to provide a depression or a hole in the core material in advance in accordance with the shape of the adsorbent.
外被材を芯材に沿ってシワなく密着させるために、減圧密封装置内に金型を設置しておき、装置内を真空にした後に真空断熱材を特定形状にプレスしてもよい。金型は、下型と上型の組み合わせでもよく、下型のみでもよい。下型は凸形状であることが好ましい。
外被材として２枚の多層フィルムで芯材を挟んで外縁のシール層を熱融着させる場合には、同じ大きさの多層フィルムを用いてもよく、減圧密封後の外被材のシワを減らすために、芯材の立体形状に応じて異なる大きさの多層フィルムを用いてもよい。
In order to tightly fit the outer cover material along the core material without wrinkles, a mold may be installed in a vacuum sealing device, and after the inside of the device is evacuated, the vacuum insulation material may be pressed into a specific shape. The mold may be a combination of a lower mold and an upper mold, or only the lower mold. It is preferable that the lower mold has a convex shape.
When the core material is sandwiched between two multilayer films and the sealing layer on the outer edge is heat-sealed as the outer covering material, multilayer films of the same size may be used to prevent wrinkles on the outer covering material after vacuum sealing. To reduce this, multilayer films of different sizes may be used depending on the three-dimensional shape of the core material.
真空断熱材は、バインダーからのアウトガス発生による真空度の低下に伴って熱伝導率が上昇する。従って、アウトガス発生による真空度の低下は、真空断熱材の熱伝導率の経時的変化を測定することによって、間接的に評価することができる。 The thermal conductivity of the vacuum insulation material increases as the degree of vacuum decreases due to outgas generation from the binder. Therefore, the decrease in the degree of vacuum due to the generation of outgas can be indirectly evaluated by measuring the change over time in the thermal conductivity of the vacuum insulation material.
本発明の真空断熱材は、従来の真空断熱材と同様の用途、例えば、冷蔵庫、自動販売機、蓄電池、建築、土木、断熱ボックス、貯塔タンク、冷凍コンテナ、冷凍倉庫等の断熱材が用いられる一般的な分野等に用いることができる。特に、立体形状を有するリチウムイオン電池などのバッテリー用断熱ケース、自動車の内装断熱材、電磁波遮蔽材などの自動車部品、風呂やエコ給湯、床暖房用断熱材など熱源設備の保温材、並びに医療用又は娯楽用のクーラーボックス用断熱材として適している。 The vacuum insulation material of the present invention can be used in the same applications as conventional vacuum insulation materials, such as refrigerators, vending machines, storage batteries, architecture, civil engineering, insulation boxes, storage tanks, refrigerated containers, and frozen warehouses. It can be used in general fields, etc. In particular, insulation cases for batteries such as three-dimensional lithium-ion batteries, automotive interior insulation materials, electromagnetic wave shielding materials and other automotive parts, heat insulating materials for heat source equipment such as baths, eco-hot water heaters, floor heating insulation materials, and medical applications. It is also suitable as an insulation material for recreational cooler boxes.
（芯材の製造）
溶融遠心法による繊維化装置を用いてガラス繊維（平均繊維径３μｍ）を製造した。装置から排出されたガラス繊維にフェノール樹脂製バインダーを噴霧しながら集綿して、集綿物を得た。集綿物を２１０℃に加熱した金型へ投入し、２．５ｔ／ｍ2（実施例１～５及び比較例１～３）又は４．０ｔ／ｍ2（比較例４）の圧力をかけながら１２分間焼成してバインダーを硬化させて、平板状（４５０ｍｍ×４５０ｍｍ×１５ｍｍ）の芯材（密度２５０ｋｇ／ｍ3（実施例１～５及び比較例１～３）又は４００ｋｇ／ｍ3（比較例４））を得た。
(Manufacture of core material)
Glass fibers (average fiber diameter 3 μm) were produced using a fiberizing device using a melt centrifugation method. Glass fibers discharged from the apparatus were collected while spraying a phenolic resin binder to obtain a collected material. The collected cotton material was put into a mold heated to 210°C, and a pressure of 2.5 t/m 2 (Examples 1 to 5 and Comparative Examples 1 to 3) or 4.0 t/m 2 (Comparative Example 4) was applied. The binder was cured by baking for 12 minutes while heating, and then the core material of a flat plate (450 mm x 450 mm x 15 mm) with a density of 250 kg/m 3 (Examples 1 to 5 and Comparative Examples 1 to 3) or 400 kg/m 3 (Comparative Example 4)) was obtained.
（外被材の製袋）
ポリエチレン（厚み５０μｍ）、アルミ箔（厚み６．５μｍ）、ポリエチレンテレフタレート（厚み１２μｍ）、ポリアミド（厚み２５μｍ）をこの順に積層して構成されたガスバリア性の多層フィルムを、互いのポリエチレン層が接するように２枚重ね、芯材の挿入のための開口部を残して外周部をヒートシールして袋状に形成した。
(Bag making of outer cover material)
A gas barrier multilayer film made by laminating polyethylene (thickness 50 μm), aluminum foil (thickness 6.5 μm), polyethylene terephthalate (thickness 12 μm), and polyamide (thickness 25 μm) in this order is placed so that the polyethylene layers are in contact with each other. Two sheets were stacked on top of each other, and the outer periphery was heat-sealed to form a bag shape, leaving an opening for inserting the core material.
（真空断熱材の製造）
芯材を２１０℃で１時間、袋状の外被材を８０℃で１時間それぞれ乾燥した後、袋状の外被材の内部に、芯材、ガス吸着剤（銅イオン交換ＺＳＭ－５型ゼオライト、表１に示す量）及び水分吸着剤（酸化カルシウム、１０ｇ）を配置した。外被材を真空チャンバー内に置き、真空チャンバー内を２Ｐａ以下に真空引きして５分保持し、ヒートシールして外被材の開口部を密封し、平板状（４５０ｍｍ×４５０ｍｍ×１５ｍｍ）の実施例１～５及び比較例１～３の真空断熱材（密度２５０ｋｇ／ｍ3）及び比較例４の真空断熱材（密度４００ｋｇ／ｍ3）を得た。各真空断熱材における、芯材中のガラス繊維の質量に基づくフェノール樹脂製バインダーの質量（強熱減量）、フェノール樹脂製バインダーの質量（樹脂量）、ガス吸着剤添加量、ガス吸着剤の質量（ｂ）に対するフェノール樹脂製バインダーの質量（ａ）の比（ａ／ｂ）、及び水分吸着剤の質量（ｃ）に対するガス吸着剤の質量（ｂ）の比（ｂ／ｃ）は、表１に示される通りであった。
(Manufacture of vacuum insulation materials)
After drying the core material at 210°C for 1 hour and the bag-shaped outer covering material for 1 hour at 80°C, the core material and gas adsorbent (copper ion exchange ZSM-5 type) were dried inside the bag-shaped outer covering material. Zeolite, the amount shown in Table 1) and a water adsorbent (calcium oxide, 10 g) were placed. Place the outer cover material in a vacuum chamber, evacuate the inside of the vacuum chamber to 2 Pa or less, hold for 5 minutes, heat seal to seal the opening of the outer cover material, and form a flat plate (450 mm x 450 mm x 15 mm). Vacuum insulation materials of Examples 1 to 5 and Comparative Examples 1 to 3 (
実施例１、実施例４及び比較例４の芯材について、長さ１５０ｍｍ及び幅５０ｍｍの寸法を有する試料を用いてスパン１００ｍｍ及びひずみ速度５０ｍｍ／分で３点曲げをして測定した場合の曲げ最大荷重及び曲げ弾性勾配、万能試験機を用いて試料を２０ｍｍ／分で１０％圧縮した場合の応力（圧縮強度）並びに真空成型時の変形率を測定した。結果を表２に示す。
（アウトガス発生による真空度低下の評価）
製造した各真空断熱材について、９０℃恒温槽でエージング試験を行ない、経過日数０、７、１４、２９及び５７日での熱伝導率を測定した。熱伝導率は、ＪＩＳ１４１２－２に準拠し、熱伝導率計（英弘精機製 ＨＣ－０７４／６００）を用いて熱流計法で測定した。結果を、表３に示す。
(Evaluation of decrease in vacuum level due to outgas generation)
For each manufactured vacuum insulation material, an aging test was conducted in a 90° C. constant temperature bath, and the thermal conductivity was measured at 0, 7, 14, 29, and 57 days. The thermal conductivity was measured in accordance with JIS1412-2 using a heat flow meter method using a thermal conductivity meter (HC-074/600 manufactured by Hideko Seiki). The results are shown in Table 3.
実施例１～３は、同じフェノールバインダー質量（強熱減量（％））を有する比較例１と比較して、試験期間中の熱伝導率変化量が小さく、アウトガス発生による真空度低下が少なかったことが示されている。同様に、実施例４及び５は、同じフェノールバインダー質量（強熱減量（％））を有する比較例２及び３と比較して、試験期間中の熱伝導率変化量が小さく、アウトガス発生による真空度低下が少なかったことが示されている。また、芯材密度が４００ｋｇ／ｍ3である比較例４では、製造直後の初期熱伝導率が、実施例１～５及び比較例１～３よりも大きく、５ｍＷ／ｍＫを超えていた。 In Examples 1 to 3, compared to Comparative Example 1 having the same phenol binder mass (ignition loss (%)), the amount of change in thermal conductivity during the test period was smaller, and the degree of vacuum decreased less due to outgassing. It has been shown that Similarly, in Examples 4 and 5, compared to Comparative Examples 2 and 3 having the same phenol binder mass (ignition loss (%)), the amount of change in thermal conductivity during the test period was small, and the vacuum due to outgas generation was It is shown that there was little decrease in the degree of Furthermore, in Comparative Example 4 in which the core material density was 400 kg/m 3 , the initial thermal conductivity immediately after production was higher than Examples 1 to 5 and Comparative Examples 1 to 3, exceeding 5 mW/mK.
（熱橋の評価）
本願発明では、三次元形状にすることで、継ぎ目をなくして（又は減らして）熱橋を低減できる。立体形状の真空断熱材では熱伝導率の直接の測定ができないため、平板形状の真空断熱材を用いて、継ぎ目をなくすことによる熱橋の低減を評価した。継ぎ目からの熱橋は、立体形状の場合でも平板形状の場合と同等に発生する。
(Evaluation of thermal bridge)
In the present invention, by creating a three-dimensional shape, it is possible to eliminate (or reduce) seams and reduce thermal bridges. Since it is not possible to directly measure the thermal conductivity of three-dimensional vacuum insulation materials, we evaluated the reduction of thermal bridges by using flat plate-shaped vacuum insulation materials and eliminating seams. Thermal bridges from seams occur equally in the case of a three-dimensional shape as in the case of a flat plate shape.
図１に示すように、継ぎ目を有さない真空断熱材（縦５００ｍｍ×横５００ｍｍ×厚さ１５ｍｍを1枚、配置例1）と、継ぎ目を有する真空断熱材（縦２５０ｍｍ×横２５０ｍｍ×厚さ１５ｍｍを4枚、配置例2）を用いて、熱伝導率を測定した。熱伝導率は、ＪＩＳ１４１２－２に準拠し、熱伝導率計（英弘精機製 ＨＣ－０７４／６００）を用いて熱流計法で測定した。熱伝導率の測定値は、配置例１では０．００３００９Ｗ／ｍＫ、配置例２では０．００９２３５Ｗ／ｍＫであった。配置例１と配置例２の熱伝導率の差は、継ぎ目からの熱橋の有無によることが確認される。 As shown in Figure 1, vacuum insulation material without seams (one sheet of 500 mm length x 500 mm width x 15 mm thickness, arrangement example 1) and vacuum insulation material with seams (250 mm length x 250 mm width x thickness) Thermal conductivity was measured using four 15 mm pieces according to arrangement example 2). The thermal conductivity was measured in accordance with JIS1412-2 using a heat flow meter method using a thermal conductivity meter (HC-074/600 manufactured by Hideko Seiki). The measured value of thermal conductivity was 0.003009 W/mK for Arrangement Example 1 and 0.009235 W/mK for Arrangement Example 2. It is confirmed that the difference in thermal conductivity between Arrangement Example 1 and Arrangement Example 2 is due to the presence or absence of a thermal bridge from the seam.
（立体形状を有する真空断熱材の製造）
（１）立体形状を有する芯材の製造
溶融遠心法による繊維化装置を用いてガラス繊維（平均繊維径３μｍ）を製造した。装置から排出されたガラス繊維にフェノールバインダーを、噴霧しながら集綿して、集綿物を得た。集綿物を２１０℃に加熱した立体形状を有する金型へ投入し、２．５ｔ／ｍ2の圧力をかけながら１２分間焼成してバインダーを硬化させて、図２に示す立体形状を有する芯材（密度２５０ｋｇ／ｍ3）を得た。
(Manufacture of vacuum insulation material with three-dimensional shape)
(1) Production of core material having a three-dimensional shape Glass fibers (average fiber diameter 3 μm) were produced using a fiberizing device using a melt centrifugation method. A phenol binder was sprayed onto the glass fibers discharged from the apparatus, and the fibers were collected to obtain a collected material. The collected cotton material was put into a mold having a three-dimensional shape heated to 210°C, and baked for 12 minutes while applying a pressure of 2.5 t/m 2 to harden the binder, resulting in a core having a three-dimensional shape as shown in Figure 2. A material (
（２）外被材の製袋
ポリエチレン（厚み５０μｍ）、アルミ箔（厚み６．５μｍ）、ポリエチレンテレフタレート（厚み１２μｍ）、ポリアミド（厚み２５μｍ）をこの順に積層して構成されたガスバリア性の多層フィルムを、互いのポリエチレン層が接するように２枚重ね、芯材の挿入のための開口部を残して外周部をヒートシールして袋状に形成した。
(2) Bag making of outer covering material A gas barrier multilayer film made by laminating polyethylene (thickness 50 μm), aluminum foil (thickness 6.5 μm), polyethylene terephthalate (thickness 12 μm), and polyamide (thickness 25 μm) in this order. Two polyethylene layers were stacked one on top of the other so that the polyethylene layers were in contact with each other, and the outer periphery was heat-sealed to form a bag shape, leaving an opening for inserting the core material.
（３）立体形状を有する真空断熱材の製造
芯材を２１０℃で１時間、袋状の外被材を８０℃で１時間それぞれ乾燥した後、袋状の外被材の内部に、芯材、ガス吸着剤（銅イオン交換ＺＳＭ－５型ゼオライト）及び水分吸着剤（酸化カルシウム）を配置した。外被材を真空チャンバー内に置き、真空チャンバー内を２Ｐａ以下に真空引きして５分保持し、ヒートシールして外被材の開口部を密封し、密度２５０ｋｇ／ｍ3の、芯材の形状と同様の立体形状を有する真空断熱材を得た。
(3) Production of vacuum insulation material with three-dimensional shape After drying the core material at 210°C for 1 hour and the bag-shaped outer covering material for 1 hour at 80°C, the core material is dried inside the bag-shaped outer covering material. , a gas adsorbent (copper ion exchange ZSM-5 type zeolite) and a water adsorbent (calcium oxide) were arranged. Place the outer cover material in a vacuum chamber, evacuate the vacuum chamber to 2 Pa or less, hold for 5 minutes, heat seal the opening of the outer cover material, and remove the core material with a density of 250 kg/ m3 . A vacuum insulation material having a three-dimensional shape similar to the shape was obtained.
本発明の真空断熱材は、立体形状を有する部材に施工する断熱材として特に有用である。 The vacuum heat insulating material of the present invention is particularly useful as a heat insulating material applied to a member having a three-dimensional shape.
Claims (5)
前記芯材が、無機繊維及びフェノール樹脂製バインダーを含み、
前記芯材の密度が、２００～３９０ｋｇ／ｍ3であり、
前記芯材が、前記フェノール樹脂製バインダーにより平板形状ではない立体形状に成形されており、
前記フェノール樹脂製バインダーの質量（ａ）が、前記無機繊維の質量に基づいて７～１５％であり、
前記ガス吸着剤の質量（ｂ）に対する前記フェノール樹脂製バインダーの質量（ａ）の比（ａ／ｂ）が、５．０～２５．０であり、
前記水分吸着剤の質量（ｃ）に対する前記ガス吸着剤の質量（ｂ）の比（ｂ／ｃ）が、０．１～１．０であり、
前記芯材、前記ガス吸着剤及び前記水分吸着剤が、前記外被材内に減圧密封されており、
前記ガス吸着剤が、銅イオン交換ＺＳＭ－５型ゼオライトである、真空断熱材。 A vacuum insulation material having a three-dimensional shape other than a flat plate shape, including a core material, a gas adsorbent, a moisture adsorbent, and a gas barrier outer covering material,
The core material includes inorganic fibers and a phenolic resin binder,
The core material has a density of 200 to 390 kg/m 3 ,
The core material is formed into a three-dimensional shape other than a flat plate shape by the phenolic resin binder,
The mass (a) of the phenolic resin binder is 7 to 15% based on the mass of the inorganic fiber,
The ratio (a/b) of the mass (a) of the phenolic resin binder to the mass (b) of the gas adsorbent is 5.0 to 25.0,
The ratio (b/c) of the mass (b) of the gas adsorbent to the mass (c) of the moisture adsorbent is 0.1 to 1.0,
The core material, the gas adsorbent, and the moisture adsorbent are vacuum-sealed within the jacket material,
A vacuum insulation material, wherein the gas adsorbent is a copper ion exchange ZSM-5 type zeolite .
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