JP2018059574A - Composite heat insulation material - Google Patents
Composite heat insulation material Download PDFInfo
- Publication number
- JP2018059574A JP2018059574A JP2016197356A JP2016197356A JP2018059574A JP 2018059574 A JP2018059574 A JP 2018059574A JP 2016197356 A JP2016197356 A JP 2016197356A JP 2016197356 A JP2016197356 A JP 2016197356A JP 2018059574 A JP2018059574 A JP 2018059574A
- Authority
- JP
- Japan
- Prior art keywords
- heat insulating
- insulating material
- composite heat
- bonding
- heat insulation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000012774 insulation material Substances 0.000 title abstract 5
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 239000011810 insulating material Substances 0.000 claims description 97
- 238000009413 insulation Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000006260 foam Substances 0.000 description 28
- 239000005011 phenolic resin Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000004745 nonwoven fabric Substances 0.000 description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000004078 cryogenic material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Thermal Insulation (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、複合断熱材に関する。より詳細には、極低温物質の保冷に適した断熱材等に関するものである。 The present invention relates to a composite heat insulating material. More specifically, the present invention relates to a heat insulating material suitable for keeping a cryogenic substance cold.
液化ガス貯蔵用のタンク等、極低温物質の断熱には高い断熱性能が要求される。そのため、高い断熱性能を持つ発泡樹脂断熱材や、真空断熱材を、重ね合わせ、複合化して用いることがある。
複合化した断熱材の一例として特許文献１においては、断熱パネル同士を重ねる際に、断熱パネル同士が接する空間にウレタンフォームを注入する事により断熱パネルを接着した事例が開示されている。
High heat insulation performance is required for heat insulation of cryogenic substances such as tanks for storing liquefied gas. For this reason, a foamed resin heat insulating material having a high heat insulating performance or a vacuum heat insulating material may be overlapped and combined for use.
As an example of a composite heat insulating material, Patent Document 1 discloses an example in which a heat insulating panel is bonded by injecting urethane foam into a space where the heat insulating panels are in contact with each other when the heat insulating panels are overlapped.
しかしながら、特許文献１に記載の発明の様に、断熱材を複合化して厚みを厚くして極低温タンクに用いる場合、外気との大きな温度差により変形応力が生じる。特に断熱材の接着に用いた接合材と断熱材との線膨張係数の違いにより接合界面で大きな応力が生じ、亀裂が発生して複合断熱材が破壊されるおそれがあった。
また、複数の複合断熱材同士を接合する部分からの熱の流入を少なくする目的で、複合断熱材の面積を大きくした場合には、応力による変位がより大きくなり、亀裂が発生する懸念がいっそう高まる。
However, as in the invention described in Patent Document 1, when a heat insulating material is combined and thickened to be used for a cryogenic tank, a deformation stress is generated due to a large temperature difference from the outside air. In particular, due to the difference in coefficient of linear expansion between the bonding material used for bonding the heat insulating material and the heat insulating material, a large stress is generated at the bonding interface, and there is a possibility that the composite heat insulating material may be broken due to cracks.
In addition, if the area of the composite heat insulating material is increased for the purpose of reducing the inflow of heat from the part where a plurality of composite heat insulating materials are joined together, there is a further concern that displacement due to stress will increase and cracks will occur. Rise.
従って、本発明は、断熱性能が高く、かつ、液化ガスタンク等の極低温物質に用いても亀裂が発生しにくい複合断熱材を提供する事を目的とする。 Accordingly, an object of the present invention is to provide a composite heat insulating material that has high heat insulating performance and is less likely to crack even when used for a cryogenic material such as a liquefied gas tank.
本発明者らは、上記課題を解決するため鋭意検討を行った結果、断熱材を接合して使用する際に、断熱材間の接合部を繊維と接合材とで構成し、かつ、繊維と接合材のバランスを図ることにより本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention, when joining and using a heat insulating material, constituted a joint between the heat insulating materials with fibers and a bonding material, and The present invention has been completed by balancing the bonding materials.
すなわち、本発明は以下の［１］〜［３］を提供する。
［１］
２個の断熱材が接合部を介して接合された構造を有する複合断熱材であって、接合部が繊維と接合材とを含み、該接合部垂直断面の単位面積に占める前記接合材の面積割合が、１０％以上９０％以下である、複合断熱材。
That is, the present invention provides the following [1] to [3].
[1]
A composite heat insulating material having a structure in which two heat insulating materials are bonded via a bonding portion, the bonding portion including fibers and the bonding material, and the area of the bonding material occupying a unit area of the bonding portion vertical cross section The composite heat insulating material whose ratio is 10% or more and 90% or less.
［２］
前記接合部垂直断面において、前記接合材と前記断熱材とが接触する部分を有する［１］記載の複合断熱材。
[2]
The composite heat insulating material according to [1], wherein the bonding member has a portion in which the bonding material and the heat insulating material are in contact with each other in a vertical cross section.
［３］
少なくとも１個の前記断熱材の熱伝導率が０．００１Ｗ／ｍＫ以上０．０３５Ｗ／ｍＫ以下である［１］又は［２］記載の複合断熱材。
[3]
The composite heat insulating material according to [1] or [2], wherein the thermal conductivity of at least one of the heat insulating materials is 0.001 W / mK or more and 0.035 W / mK or less.
本発明の複合断熱材は、上記構成を有することにより、極低温物質の保冷目的で用いた場合に、破壊することなく、かつ、高い断熱性能を維持しつつ使用することができる。 When the composite heat insulating material of the present invention has the above configuration, it can be used without breaking and maintaining high heat insulating performance when used for the purpose of keeping a cryogenic substance cold.
本発明を実施するための形態（以下、「本実施形態」と称する場合がある。）について詳細に説明する。 A mode for carrying out the present invention (hereinafter sometimes referred to as “the present embodiment”) will be described in detail.
本実施形態における複合断熱材は、２個の断熱材が、繊維と接合材とを含む接合部を介して接合された構造を少なくとも有している。なお、複合断熱材は、３個以上の断熱材が接合部を介して接合されたものの一部を構成するものであってもよい。 The composite heat insulating material in this embodiment has at least a structure in which two heat insulating materials are bonded via a bonding portion including a fiber and a bonding material. In addition, a composite heat insulating material may comprise a part of what 3 or more heat insulating materials were joined via the junction part.
本実施形態で使用する断熱材としては、例えば、フェノール樹脂発泡板、ウレタン樹脂発泡板、スチレン樹脂発泡板等の樹脂系の発泡板断熱材、グラスウールやシリカエアロゲルを芯材として使用した真空断熱材等の断熱材を使用することが出来る。真空断熱材の場合、真空が破れるとたちまち熱伝導率が大きくなってしまうので、熱伝導率が安定して小さい樹脂発泡板が好ましく、中でもフェノール樹脂発泡板は樹脂発泡板としては最も熱伝導率が小さく、特に好ましい。本実施形態の断熱材の熱伝導率の好ましい範囲は、０．００１Ｗ／ｍＫ以上０．０３５Ｗ／ｍＫ以下であり、より好ましくは０．００１Ｗ／ｍＫ以上０．０２８Ｗ／ｍＫ以下、さらに好ましくは０．０１Ｗ／ｍＫ以上０．０２１Ｗ／ｍＫ以下である。本実施形態の複合断熱材において、少なくとも１個の断熱材の熱伝導率が上記範囲であることが好ましい。 As a heat insulating material used in the present embodiment, for example, a resin-based foam heat insulating material such as a phenol resin foam plate, a urethane resin foam plate, a styrene resin foam plate, a vacuum heat insulating material using glass wool or silica airgel as a core material. Etc. can be used. In the case of vacuum insulation, the thermal conductivity increases as soon as the vacuum breaks, so a resin foam plate with a stable and low thermal conductivity is preferable. Among them, the phenol resin foam plate is the most thermally conductive resin foam plate. Is particularly preferable. The preferable range of the thermal conductivity of the heat insulating material of the present embodiment is 0.001 W / mK or more and 0.035 W / mK or less, more preferably 0.001 W / mK or more and 0.028 W / mK or less, and still more preferably 0. It is 0.01 W / mK or more and 0.021 W / mK or less. In the composite heat insulating material of the present embodiment, it is preferable that the thermal conductivity of at least one heat insulating material is in the above range.
本実施形態の複合断熱材は、接合材により接合されており、接合部に接合材と繊維が存在する。接合部垂直断面の単位面積に占める接合材の好ましい面積割合は、単位面積に対して１０％以上９０％以下、より好ましくは３５％以上７０％以下である。接合材の面積割合が１０％未満の場合、接着強度が小さくなり断熱材が接合部から分離してしまう事が懸念され、接合材の面積割合が９０％よりも大きい場合は、外気との大きな温度差により生じる変形応力により、破壊する恐れがある。 The composite heat insulating material of the present embodiment is bonded by a bonding material, and the bonding material and fibers are present at the bonded portion. The preferable area ratio of the bonding material to the unit area of the vertical cross section of the bonding portion is 10% or more and 90% or less, more preferably 35% or more and 70% or less with respect to the unit area. When the area ratio of the bonding material is less than 10%, there is a concern that the adhesive strength is reduced and the heat insulating material is separated from the bonded portion. When the area ratio of the bonding material is larger than 90%, it is large with the outside air. There is a risk of destruction due to deformation stress caused by the temperature difference.
本実施形態の複合断熱材の接合部垂直断面における好ましい接合材の形態としては、接合材の一部が断熱材に接している図２、図３の形態があげられる。図２、図３のような形態の場合は、図１の形態と比較すると接合部が応力に対してより安定化し、接合部の厚みが維持されやすくなるため好ましい。 As a preferable form of the bonding material in the vertical cross section of the bonded portion of the composite heat insulating material of the present embodiment, there are the forms of FIGS. 2 and 3 in which a part of the bonding material is in contact with the heat insulating material. 2 and 3 is preferable because the joint is more stable against stress and the thickness of the joint is easily maintained as compared to the form of FIG.
本実施形態で使用する断熱材の厚みは、５ｍｍ以上５００ｍｍ以下が好ましく、より好ましくは１０ｍｍ以上４００ｍｍ以下、さらに好ましくは２０ｍｍ以上３００ｍｍ以下である。
断熱材の厚みが５ｍｍ以上であると断熱性能がより高まり、５００ｍｍ以下であると応力抵抗性が高まる。断熱材の厚みは、定規やノギス等で測定できる。
The thickness of the heat insulating material used in the present embodiment is preferably 5 mm or more and 500 mm or less, more preferably 10 mm or more and 400 mm or less, and further preferably 20 mm or more and 300 mm or less.
When the thickness of the heat insulating material is 5 mm or more, the heat insulating performance is further increased, and when it is 500 mm or less, the stress resistance is increased. The thickness of the heat insulating material can be measured with a ruler or a caliper.
本実施形態で使用する繊維としては、高分子繊維が好ましく、高分子繊維としては、例えば、樹脂繊維、ガラス繊維、セルロース繊維などが利用できる。好ましい繊維の形態としては、糸を織った布帛や、繊維を接着剤や熱融着により接着、あるいは機械的作用でからませて布状にした不織布やフェルト、また繊維を抄造法によりシート状に成形したもの等が使用できる。特に好ましい繊維の形態としては、ポリプロピレン繊維、ポリエチレンテレフタレート繊維、ナイロン繊維等の樹脂繊維からなる不織布があげられる。本実施形態で用いる不織布の好ましい破断伸度は、１％以上５００％以下であり、より好ましくは５％以上１００％以下である。破断伸度はＪＩＳ−Ｌ−１９０６−１９９４により測定する事ができる。 As the fiber used in the present embodiment, a polymer fiber is preferable. As the polymer fiber, for example, a resin fiber, a glass fiber, a cellulose fiber, or the like can be used. Preferable fiber forms include fabrics woven from yarn, non-woven fabrics or felts that are made by bonding fibers with adhesives or heat-sealing, or entangled by mechanical action, and fibers made into a sheet by papermaking. Molded ones can be used. Particularly preferred fiber forms include nonwoven fabrics made of resin fibers such as polypropylene fibers, polyethylene terephthalate fibers, and nylon fibers. The preferable breaking elongation of the nonwoven fabric used in the present embodiment is 1% or more and 500% or less, more preferably 5% or more and 100% or less. The breaking elongation can be measured according to JIS-L-1906-1994.
本実施形態で使用する接合材としては、例えば、ウレタン系接着剤、ＳＢＲ系接着剤、ニトリルゴム系接着剤、エポキシ系接着剤、でんぷん糊、ニカワ等が挙げられる。中でも、低温で亀裂が発生しにくいという観点から、ウレタン系接着剤が好ましい。 Examples of the bonding material used in the present embodiment include urethane adhesives, SBR adhesives, nitrile rubber adhesives, epoxy adhesives, starch pastes, glues, and the like. Among these, urethane adhesives are preferable from the viewpoint that cracks hardly occur at low temperatures.
本実施形態における好ましい接合部の厚みは、１μｍ以上５０００μｍ以下であり、より好ましくは１０μｍ以上４０００μｍ以下であり、更に好ましくは１００μｍ以上３０００μｍ以下である。接合部分の厚みは、デジタル顕微鏡やＳＥＭ等で確認することが出来る。 In the present embodiment, a preferable thickness of the bonding portion is 1 μm or more and 5000 μm or less, more preferably 10 μm or more and 4000 μm or less, and further preferably 100 μm or more and 3000 μm or less. The thickness of the joined portion can be confirmed with a digital microscope, SEM, or the like.
本実施形態の複合断熱材は、例えば、極低温物質を貯蔵又は輸送する際の極低温タンクの保冷に利用でき、この場合、タンク表面温度と外気との温度差が１５０℃以上の貯蔵又は輸送用極低温タンクに、特に有意な効果を発現することができる。 The composite heat insulating material of the present embodiment can be used, for example, for cold storage of a cryogenic tank when storing or transporting a cryogenic substance. In this case, the temperature difference between the tank surface temperature and the outside air is 150 ° C. or more. A particularly significant effect can be exhibited in the cryogenic tank.
本実施形態の複合断熱材の製造方法としては、例えば、（１）接合材を塗布した不織布等の繊維に断熱材を貼り合わせて接合する方法；（２）不織布等の繊維上に樹脂発泡体等の断熱材を形成した、繊維／断熱材／繊維が一体となった部材の繊維に接合材を塗布し、接合材を塗布した繊維に断熱材を貼り合わせて接合する方法；（３）繊維／断熱材／繊維が一体となった部材の繊維に接合材を塗布し、同様の他の部材と貼り合わせて接合する方法；等が挙げられる。
ここで注意すべきは、繊維を接合材で埋め尽くさないことである。このようにすると複合断熱材を外気との大きな温度差のある環境下で使用すると、これにより生じる変形応力により、破壊する恐れがある。
Examples of the method for producing the composite heat insulating material of the present embodiment include: (1) a method of bonding a heat insulating material to a fiber such as a nonwoven fabric coated with a bonding material; and (2) a resin foam on a fiber such as a non-woven fabric. A method of applying a bonding material to a fiber / heat insulating material / fiber integrated member formed with a heat insulating material such as, and bonding the heat insulating material to the fiber coated with the bonding material; (3) Fiber A method in which a bonding material is applied to a fiber of a member in which / a heat insulating material / fiber is integrated, and bonded to another similar member is bonded.
It should be noted here that the fibers are not filled with the bonding material. In this case, when the composite heat insulating material is used in an environment having a large temperature difference from the outside air, the composite heat insulating material may be broken due to the deformation stress generated thereby.
複合断熱材の特性は以下の方法によって求めた。 The characteristics of the composite heat insulating material were determined by the following method.
＜接合部垂直断面の単位面積に占める接合材の面積割合＞
接合部垂直断面の単位面積に占める接合材の面積割合は、次のようにして測定した。
複合断熱材から、接合部が概略水平になる向きに見て任意の面を定め、幅約８ｍｍ×奥行約３０ｍｍ×厚み約８ｍｍの試験片を、接合部が厚みの中央に位置するように幅方向１０ｃｍおきに３個切り出した。更に、互いに異なる他の２つの面を定め、同様にして各面から３個ずつ試験片を採取し、合計９個の試験片を用意した。その後、上記試験片を、幅×厚み面から奥行き方向約１ｍｍの位置でフェザー剃刀により切削し、観察試料とした。次に、観察試料をサンプル台にカーボンテープで貼りつけ、金をスパッタリング（放電電流値２０ｍＡ、スパッタ時間２４０秒）し、走査型電子顕微鏡（日本電子株式会社製、ＪＳＭ−６０６０ＬＶ）で接合している２個の断熱材が視野に収まり、かつ接合部の写真における面積割合が３０％以上となるように倍率を調整しながら観察試料の任意の場所における接合部垂直断面の写真を撮影した。次に、各写真を紙に印刷して、接合部断面を、繊維状の形態が認められる繊維部分（図１〜３の４）と繊維状の形態が認められない固体の接合材部分（図１〜４の５）とに切り分け、切り分けた各部分の紙の重さを測り、以下の式から各写真における面積割合を算出した。なお、底の見えない空洞は接合部垂直断面積には含めるが、繊維部分と接合材部分には含めない。
接合材の面積割合（％）＝（（接合材部分の重さ）／（接合部垂直断面部分の重さ））×１００
また、接合材が断熱材と接触している構造の有無は、上記のいずれの写真においても、接合部垂直断面において接合材と断熱材とが接触する部分が確認できなかった場合を「無」、いずれかの写真で確認できた場合を「有」と評価した。
<The ratio of the area of the bonding material to the unit area of the vertical section of the bonding part>
The area ratio of the bonding material to the unit area of the vertical cross section of the bonding portion was measured as follows.
An arbitrary surface is defined from the composite heat insulating material when the joint portion is substantially horizontal, and a test piece having a width of about 8 mm, a depth of about 30 mm, and a thickness of about 8 mm is placed so that the joint portion is positioned at the center of the thickness. Three pieces were cut every 10 cm in the direction. Further, two other surfaces different from each other were determined, and three test pieces were sampled from each surface in the same manner to prepare a total of nine test pieces. Then, the said test piece was cut with the feather razor in the position of about 1 mm in the depth direction from the width x thickness surface, and it was set as the observation sample. Next, the observation sample is attached to the sample table with carbon tape, gold is sputtered (discharge current value 20 mA, sputtering time 240 seconds), and bonded with a scanning electron microscope (JSM-6060LV, manufactured by JEOL Ltd.). A photograph of a vertical cross section of the joint at an arbitrary position of the observation sample was taken while adjusting the magnification so that the two heat insulating materials contained in the field of view and the area ratio in the photograph of the joint became 30% or more. Next, each photograph is printed on paper, and the cross section of the joint portion is a fiber portion (4 in FIGS. 1 to 3) in which a fibrous form is recognized and a solid joint material portion (FIG. 1) in which the fibrous form is not recognized. 1 to 4) and the weight of each cut paper was measured, and the area ratio in each photograph was calculated from the following formula. In addition, although the cavity where the bottom cannot be seen is included in the joint vertical sectional area, it is not included in the fiber portion and the joint material portion.
Area ratio (%) of bonding material = ((weight of bonding material portion) / (weight of bonding portion vertical cross-section portion)) × 100
In addition, the presence or absence of a structure in which the bonding material is in contact with the heat insulating material is “no” in any of the above photographs when the portion where the bonding material and the heat insulating material are in contact with each other in the vertical cross section of the bonding portion cannot be confirmed. The case where it was confirmed by any of the photos was evaluated as “Yes”.
＜断熱材の熱伝導率＞
複合断熱材を構成する断熱材の熱伝導率は、６００ｍｍ角に切り出した板状断熱材を、低温板５℃、高温板３５℃の条件で、平板熱流計法に従い、ＪＩＳ Ａ１４１２に準拠して測定した。
<Thermal conductivity of thermal insulation>
The thermal conductivity of the heat insulating material constituting the composite heat insulating material is a plate heat insulating material cut into a 600 mm square, according to JIS A1412 in accordance with a plate heat flow meter method under conditions of a low temperature plate of 5 ° C. and a high temperature plate of 35 ° C. It was measured.
以下に、実施例に基づいて本実施形態の複合断熱材をより詳細に説明する。
フェノール樹脂発泡板を以下の要領で製造し、さらに接合材で接合して複合断熱材を作製し、液体窒素に浸漬して亀裂の発生等を評価した。
Below, based on an Example, the composite heat insulating material of this embodiment is demonstrated in detail.
A phenolic resin foam board was produced in the following manner, further joined with a joining material to produce a composite heat insulating material, and immersed in liquid nitrogen to evaluate the occurrence of cracks and the like.
＜フェノール樹脂の合成＞
反応器に５２質量％ホルムアルデヒド水溶液３５００ｋｇと９９質量％フェノール２５１０ｋｇを仕込み、プロペラ回転式の攪拌機により攪拌し、温調機により反応器内部液温度を４０℃に調整した。次いで５０質量％水酸化ナトリウム水溶液を加えながら昇温して、反応を進行させた。オストワルド粘度が６０センチストークス（２５℃における測定値）に到達した段階で、反応液を冷却し、尿素を５７０ｋｇ（ホルムアルデヒド仕込み量の１５モル％に相当）添加した。その後、反応液を３０℃まで冷却し、パラトルエンスルホン酸一水和物の５０質量％水溶液でｐＨを６．４に中和した。６０℃で脱水処理して、得られた反応液（熱硬化型樹脂組成物）の粘度を測定したところ、４０℃における粘度は５，８００ｍＰａ・ｓであった。
<Synthesis of phenolic resin>
The reactor was charged with 3500 kg of a 52% by weight aqueous formaldehyde solution and 2510 kg of 99% by weight phenol, stirred with a propeller rotating stirrer, and the temperature inside the reactor was adjusted to 40 ° C. with a temperature controller. Next, the temperature was raised while adding a 50 mass% aqueous sodium hydroxide solution to advance the reaction. When the Ostwald viscosity reached 60 centistokes (measured value at 25 ° C.), the reaction solution was cooled, and 570 kg of urea (corresponding to 15 mol% of the charged amount of formaldehyde) was added. Thereafter, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.4 with a 50 mass% aqueous solution of paratoluenesulfonic acid monohydrate. When the viscosity of the resulting reaction solution (thermosetting resin composition) was measured after dehydration at 60 ° C., the viscosity at 40 ° C. was 5,800 mPa · s.
＜フェノール樹脂組成物の調製＞
フェノール樹脂を主成分とする脱水をした上記反応液９６．５質量部に対して、界面活性剤としてエチレンオキサイド−プロピレンオキサイドのブロック共重合体（ＢＡＳＦ製、製品名「プルロニック（登録商標）Ｆ−１２７」）を３．５質量部の割合で混合した。
得られた界面活性剤含有フェノール樹脂組成物１００質量部に対して、発泡剤としてイソペンタン５０質量％とイソブタン５０質量％との混合物７質量部、硬化触媒としてキシレンスルホン酸８０質量％とジエチレングリコール２０質量％との混合物１１質量部を、２５℃に温調したミキシングヘッドに供給し、フェノール樹脂組成物を得た。
ここで、使用する混合機は、上部側面に界面活性剤含有フェノール樹脂組成物、及び発泡剤の導入口があり、回転子が攪拌する攪拌部の中央付近の側面に硬化触媒の導入口を備え、攪拌部以降はフォームを吐出するためのノズルを有する分配部に繋がっているピンミキサーを使用した。
<Preparation of phenol resin composition>
A block copolymer of ethylene oxide-propylene oxide (product of BASF, product name “Pluronic® F— 127 ") was mixed in a proportion of 3.5 parts by weight.
7 parts by mass of a mixture of 50% by mass of isopentane and 50% by mass of isobutane as a blowing agent, 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as a curing catalyst with respect to 100 parts by mass of the obtained phenol resin composition containing a surfactant. 11 parts by mass of a mixture with% was supplied to a mixing head whose temperature was adjusted to 25 ° C. to obtain a phenol resin composition.
Here, the mixer to be used has a surfactant-containing phenol resin composition and a foaming agent inlet on the upper side surface, and a curing catalyst inlet on the side surface near the center of the stirring unit where the rotor stirs. After the stirring unit, a pin mixer connected to a distribution unit having a nozzle for discharging foam was used.
＜フェノール樹脂発泡板１の製造＞
不織布（旭化成株式会社製、「旭化成エルタス ＰＣ８１００」、坪量１００ｇ／ｍ２、厚み０．８０ｍｍ、破断伸度９０％）を移動させながら、その上に上記フェノール樹脂組成物を供給した。不織布上に供給されたフェノール樹脂組成物は、さらにその上から同種の不織布で被覆して上下の不織布で挟み込んで、８５℃のスラット型ダブルコンベアへ送り、３０分の滞留時間で硬化させた後、１１０℃のオーブンで２時間キュアして厚み８０ｍｍのフェノール樹脂発泡板１を得た。
<Manufacture of phenolic resin foam board 1>
While moving the non-woven fabric (Asahi Kasei Elutus PC8100, manufactured by Asahi Kasei Co., Ltd., basis weight 100 g / m 2 , thickness 0.80 mm, elongation at break 90%), the above phenol resin composition was supplied thereon. The phenol resin composition supplied on the nonwoven fabric is further coated with the same kind of nonwoven fabric from above, sandwiched between upper and lower nonwoven fabrics, sent to a 85 ° C. slat type double conveyor, and cured after a residence time of 30 minutes. And curing in an oven at 110 ° C. for 2 hours to obtain a phenolic resin foam board 1 having a thickness of 80 mm.
＜フェノール樹脂発泡板２の製造＞
上下の不織布として、不織布（旭化成株式会社製、「旭化成エルタス Ｅ０５０３０」、坪量３０ｇ／ｍ２、厚み０．１５ｍｍ、破断伸度２０％）を用いたこと以外は、フェノール樹脂発泡板１と同様にして厚み８０ｍｍのフェノール樹脂発泡板２を得た。
<Manufacture of phenolic
As the upper and lower nonwoven fabrics, the same as the phenolic resin foam board 1 except that non-woven fabrics (Asahi Kasei Elutus E05030, basis weight 30 g / m 2 , thickness 0.15 mm, elongation at break 20%) were used. Thus, a phenol
ウレタン系接着剤ＬＯＣＴＩＴＥ ＵＫ ５４００（ヘンケル社製）１ｋｇとＬＯＣＴＩＴＥ ＵＫ ８２０２（ヘンケル社製）４ｋｇをペール缶に計量し、均一に混合し接合材とした。
幅１５００ｍｍ×長さ１２００ｍｍ×厚み０．２ｍｍのＰＰシートに、幅１０００ｍｍ×長さ１０００ｍｍの枠を書き、枠の中に上記接合材を均一に塗布した。重量を測定した、幅１０００ｍｍ×長さ１０００ｍｍに切り出したフェノール樹脂発泡板１（断熱材Ａ）を、不織布が下になるように、接合材が塗布されたＰＰシートの枠に合わせて伏せ、ＰＰシートとフェノール樹脂発泡板１とがずれない様に裏返し、ＰＰシートを押して、接合材をフェノール樹脂発泡板１の不織布に転写した。ＰＰシートをフェノール樹脂発泡板１から剥がし、小口に付着した接合材を拭き取った。接合材を転写した後のフェノール樹脂発泡板１の重量を測定し、転写前のフェノール樹脂発泡板１の重量から計算した、転写した接合材量は１６０ｇ／ｍ２であった。接合材を転写させた不織布上に、別途幅１０００ｍｍ×長さ１０００ｍｍに切り出したフェノール樹脂発泡板１（断熱材Ｂ）を、不織布が断熱材Ａ側に向くように、ずれない様に合わせ、上に２０ｋｇの錘１０個をのせ、２４時間以上経過後に錘を外し、複合断熱材を得た。
1 kg of urethane adhesive LOCTITE UK 5400 (manufactured by Henkel) and 4 kg of LOCTITE UK 8202 (manufactured by Henkel) were weighed into a pail can and mixed uniformly to obtain a bonding material.
A PP sheet having a width of 1500 mm, a length of 1200 mm, and a thickness of 0.2 mm was written on a frame having a width of 1000 mm and a length of 1000 mm, and the bonding material was uniformly applied in the frame. The phenolic resin foam board 1 (heat insulating material A) cut out to a width of 1000 mm and a length of 1000 mm was weighed in accordance with the frame of the PP sheet on which the bonding material was applied so that the nonwoven fabric was on the bottom, and PP The sheet and the phenolic resin foam board 1 were turned over so that they did not shift, and the PP sheet was pressed to transfer the bonding material to the nonwoven fabric of the phenolic resin foam board 1. The PP sheet was peeled off from the phenolic resin foam plate 1, and the bonding material adhering to the fore edge was wiped off. The weight of the phenolic resin foam plate 1 after transferring the bonding material was measured, and the amount of the transferred bonding material calculated from the weight of the phenolic resin foam plate 1 before transfer was 160 g / m 2 . On the nonwoven fabric to which the bonding material has been transferred, the phenolic resin foam board 1 (heat insulating material B) separately cut into a width of 1000 mm × length of 1000 mm is aligned so that the nonwoven fabric faces the heat insulating material A side, 10 weights of 20 kg were put on the plate, and after 24 hours or more, the weight was removed to obtain a composite heat insulating material.
断熱材Ｂをフェノール樹脂発泡板２に変更し、接合材量が２１０ｇ／ｍ２で有った以外は、実施例１と同様にして複合断熱材を得た。
A composite heat insulating material was obtained in the same manner as in Example 1 except that the heat insulating material B was changed to the phenol
接合材量が５０３ｇ／ｍ２で有った以外は、実施例１と同様にして複合断熱材を得た。 A composite heat insulating material was obtained in the same manner as in Example 1 except that the amount of the bonding material was 503 g / m 2 .
断熱材Ａと断熱材Ｂをフェノール樹脂発泡板２に変更し、接合材量が６２ｇ／ｍ２で有った以外は、実施例１と同様にして複合断熱材を得た。
The heat insulating material A and the heat insulating material B were changed to the phenol
接合材量が８８ｇ／ｍ２で有った以外は、実施例１と同様にして複合断熱材を得た。 A composite heat insulating material was obtained in the same manner as in Example 1 except that the amount of the bonding material was 88 g / m 2 .
断熱材Ａと断熱材Ｂをフェノール樹脂発泡板２に変更し、接合材量が３１０ｇ／ｍ２で有った以外は、実施例１と同様にして複合断熱材を得た。
A heat insulating material A and a heat insulating material B were changed to the phenol resin foamed
接合材量が１０２１ｇ／ｍ２で有った以外は、実施例１と同様にして複合断熱材を得た。 A composite heat insulating material was obtained in the same manner as in Example 1 except that the amount of the bonding material was 1021 g / m 2 .
断熱材Ｂをフェノール樹脂発泡板２に変更し、接合材量が８０７ｇ／ｍ２で有った以外は、実施例１と同様にして複合断熱材を得た。
複合断熱材の製造に用いた断熱材の熱伝導率は、上記フェノール樹脂発泡板１は０．０２０Ｗ／ｍＫ、上記フェノール樹脂発泡板２は０．０２０Ｗ／ｍＫであった。
A composite heat insulating material was obtained in the same manner as in Example 1 except that the heat insulating material B was changed to the phenol
The heat conductivity of the heat insulating material used for the production of the composite heat insulating material was 0.020 W / mK for the phenol resin foam plate 1 and 0.020 W / mK for the phenol
＜複合断熱材の接合部の変位＞
幅１０００ｍｍ×長さ１０００ｍｍの複合断熱材の４辺中央部で接合部厚みをノギスで測定し、その平均値を液体窒素浸漬前の接合部厚みとする。次に幅１２００ｍｍ×長さ１２００ｍｍ×深さ５００ｍｍのＳＵＳ３０４製の浴槽に液体窒素を深さ１００ｍｍ程度まで入れて、断熱材Ａが下側となるようにして複合断熱材を浮かべ、上から押さえつけて、断熱材Ａと接合部との界面の１０ｍｍ下まで液体窒素に浸漬した。６０分間経過後、複合断熱材を取り出し、２４時間以上経過後、液体窒素浸漬前と同様にして接合部厚みを測定し、液体窒素浸漬後の接合部厚みとする。厚みの測定はデジタルノギスにより測定した。液体窒素浸漬後の接合部厚みを液体窒素浸漬前の接合部厚みで割って小数点２位を四捨五入し、接合部の変位とした。
最後に、複合断熱材周縁部に水性インクをしみこませて亀裂の有無を目視で確認した。
なお、上記実験での外気温は２３℃であった。
<Displacement of joint part of composite heat insulating material>
The joint thickness is measured with calipers at the center of the four sides of the composite heat insulating material having a width of 1000 mm and a length of 1000 mm, and the average value is defined as the joint thickness before immersion in liquid nitrogen. Next, liquid nitrogen is put in a SUS304 bathtub of width 1200 mm × length 1200 mm × depth 500 mm to a depth of about 100 mm, the composite heat insulating material is floated so that the heat insulating material A is on the lower side, and pressed from above. Then, it was immersed in liquid nitrogen up to 10 mm below the interface between the heat insulating material A and the joint. After the elapse of 60 minutes, the composite heat insulating material is taken out, and after the elapse of 24 hours or more, the junction thickness is measured in the same manner as before immersion in liquid nitrogen to obtain the junction thickness after immersion in liquid nitrogen. The thickness was measured with a digital caliper. The junction thickness after immersion in liquid nitrogen was divided by the junction thickness before immersion in liquid nitrogen, and rounded off to the second decimal place to obtain the displacement of the junction.
Finally, water-based ink was soaked into the peripheral edge portion of the composite heat insulating material to visually check for cracks.
In addition, the external temperature in the said experiment was 23 degreeC.
実施例と比較例の結果を表１にまとめた。 The results of Examples and Comparative Examples are summarized in Table 1.
本発明は、液化石油ガス（ＬＰＧ）、液化天然ガス（ＬＮＧ）、液化水素（ＬＨ２）、液化窒素（ＬＮ２）、液化酸素（ＬＯ２）、液化ヘリウム（ＬＨｅ）等の極低温物質を貯蔵又は輸送する際の極低温タンクに適した複合断熱材である。 The present invention relates to cryogenic substances such as liquefied petroleum gas (LPG), liquefied natural gas (LNG), liquefied hydrogen (LH 2 ), liquefied nitrogen (LN 2 ), liquefied oxygen (LO 2 ), and liquefied helium (LHe). It is a composite insulation suitable for cryogenic tanks for storage or transportation.
１ 複合断熱材
２ 断熱材
３ 接合部
４ 繊維部分
５ 接合材部分
DESCRIPTION OF SYMBOLS 1 Composite
Claims (3)
接合部が繊維と接合材とを含み、該接合部垂直断面の単位面積に占める、前記接合材の面積割合が、１０％以上９０％以下である、複合断熱材。 A composite heat insulating material having a structure in which two heat insulating materials are joined via a joint,
A composite heat insulating material, wherein a bonding portion includes fibers and a bonding material, and an area ratio of the bonding material in a unit area of the vertical cross section of the bonding portion is 10% or more and 90% or less.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016197356A JP6993080B2 (en) | 2016-10-05 | 2016-10-05 | Composite insulation |
| JP2021150642A JP2022001793A (en) | 2016-10-05 | 2021-09-15 | Composite heat insulating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016197356A JP6993080B2 (en) | 2016-10-05 | 2016-10-05 | Composite insulation |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021150642A Division JP2022001793A (en) | 2016-10-05 | 2021-09-15 | Composite heat insulating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018059574A true JP2018059574A (en) | 2018-04-12 |
| JP6993080B2 JP6993080B2 (en) | 2022-01-13 |
Family
ID=61909969
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016197356A Active JP6993080B2 (en) | 2016-10-05 | 2016-10-05 | Composite insulation |
| JP2021150642A Pending JP2022001793A (en) | 2016-10-05 | 2021-09-15 | Composite heat insulating material |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021150642A Pending JP2022001793A (en) | 2016-10-05 | 2021-09-15 | Composite heat insulating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP6993080B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6993080B2 (en) * | 2016-10-05 | 2022-01-13 | 旭化成建材株式会社 | Composite insulation |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51105657A (en) * | 1974-09-20 | 1976-09-18 | Nippon Sofuran Kako Kk | |
| JPH03121398A (en) * | 1989-03-23 | 1991-05-23 | Osaka Gas Co Ltd | Heat insulating material |
| JPH0761493A (en) * | 1993-08-20 | 1995-03-07 | Dow Kakoh Kk | Panel for heat insulation of extremely low temperature tank |
| JP2004339018A (en) * | 2003-05-16 | 2004-12-02 | Matsushita Electric Ind Co Ltd | Porous structure and composite material provided with the same |
| JP2008542651A (en) * | 2005-05-30 | 2008-11-27 | ティーアイ マリン コントラクティング エイエス | Method and system for thermal insulation of cryogenic containers and tanks |
| JP2014092328A (en) * | 2012-11-05 | 2014-05-19 | Kobe Steel Ltd | Heat insulation member |
| WO2014141418A1 (en) * | 2013-03-14 | 2014-09-18 | 名古屋油化株式会社 | Heat-insulating sound-absorbing material and heat-insulating sound-absorbing material molded article |
| JP2015190484A (en) * | 2014-03-27 | 2015-11-02 | 株式会社フォームテック | Heat insulation panel for covering spherical curved surface of liquefied gas tank |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6993080B2 (en) * | 2016-10-05 | 2022-01-13 | 旭化成建材株式会社 | Composite insulation |
-
2016
- 2016-10-05 JP JP2016197356A patent/JP6993080B2/en active Active
-
2021
- 2021-09-15 JP JP2021150642A patent/JP2022001793A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51105657A (en) * | 1974-09-20 | 1976-09-18 | Nippon Sofuran Kako Kk | |
| JPH03121398A (en) * | 1989-03-23 | 1991-05-23 | Osaka Gas Co Ltd | Heat insulating material |
| JPH0761493A (en) * | 1993-08-20 | 1995-03-07 | Dow Kakoh Kk | Panel for heat insulation of extremely low temperature tank |
| JP2004339018A (en) * | 2003-05-16 | 2004-12-02 | Matsushita Electric Ind Co Ltd | Porous structure and composite material provided with the same |
| JP2008542651A (en) * | 2005-05-30 | 2008-11-27 | ティーアイ マリン コントラクティング エイエス | Method and system for thermal insulation of cryogenic containers and tanks |
| JP2014092328A (en) * | 2012-11-05 | 2014-05-19 | Kobe Steel Ltd | Heat insulation member |
| WO2014141418A1 (en) * | 2013-03-14 | 2014-09-18 | 名古屋油化株式会社 | Heat-insulating sound-absorbing material and heat-insulating sound-absorbing material molded article |
| JP2015190484A (en) * | 2014-03-27 | 2015-11-02 | 株式会社フォームテック | Heat insulation panel for covering spherical curved surface of liquefied gas tank |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6993080B2 (en) | 2022-01-13 |
| JP2022001793A (en) | 2022-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2793827C (en) | Phenolic resin foam laminated sheet and method for manufacturing the same | |
| CN102964772B (en) | Chopped fiber reinforced phenolic resin foam material and preparation method thereof | |
| JP6550415B2 (en) | Phenolic resin foam laminate and method for producing the same | |
| US9701803B2 (en) | Closed-cell tannin-based foams | |
| TW201334972A (en) | Phenol board having honeycomb structure | |
| Zhou et al. | Thermomechanical analyses of phenolic foam reinforced with glass fiber mat | |
| JP6627756B2 (en) | Resin supply material, preform, and method for producing fiber reinforced resin | |
| Yu et al. | Cryogenic characteristics of chopped glass fiber reinforced polyurethane foam | |
| WO2004009681A2 (en) | Composite foam made from polymer microspheres reinforced with long fibers | |
| WO2016136791A1 (en) | Resin supply material, preform, and method for producing fiber-reinforced resin | |
| JP2022001793A (en) | Composite heat insulating material | |
| JP6126761B1 (en) | Fiber reinforced sheet and structure | |
| JP6081188B2 (en) | Phenol resin foam laminate and method for producing the same | |
| TW201714722A (en) | Resin supply material, preform, and method for producing fiber-reinforced resin | |
| KR101801560B1 (en) | Composite panel and method for manufacturing thereof | |
| US20190329512A1 (en) | Core member made of a composite plastic material, and method for the production thereof | |
| JP2019018512A (en) | Resin foam composite body | |
| JP2002339472A (en) | Heat insulating incombustible panel | |
| JP2014092194A (en) | Heat insulating panel for membrane-type tank of liquefied natural gas carrier | |
| JP6568445B2 (en) | Manufacturing method of fiber reinforced sheet and manufacturing method of structure | |
| JP2007131803A (en) | Method for producing phenolic resin foam | |
| Li et al. | Preparation and characterization of phenolic foam modified by nitrile butadiene rubber powder | |
| CN202299221U (en) | Phenolic foam composite plate | |
| CN204570954U (en) | A kind of composite cement foam plate exterior wall heat-preserving system | |
| CN208948066U (en) | A kind of enhancing container |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190905 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201201 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210201 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20210615 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210915 |
|
| C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20210915 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20210927 |
|
| C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20210928 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20211130 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20211209 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6993080 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |