JP2017210378A - Composition and non-flammable material - Google Patents
Composition and non-flammable material Download PDFInfo
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- JP2017210378A JP2017210378A JP2016102266A JP2016102266A JP2017210378A JP 2017210378 A JP2017210378 A JP 2017210378A JP 2016102266 A JP2016102266 A JP 2016102266A JP 2016102266 A JP2016102266 A JP 2016102266A JP 2017210378 A JP2017210378 A JP 2017210378A
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims description 84
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000006260 foam Substances 0.000 claims abstract description 42
- 239000004568 cement Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000011521 glass Substances 0.000 claims abstract description 26
- 239000002699 waste material Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 17
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000011049 filling Methods 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 13
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- 239000010881 fly ash Substances 0.000 claims description 6
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- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 229910052666 hauyne Inorganic materials 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 34
- 238000000034 method Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 238000009413 insulation Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 11
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- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 5
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- 239000011368 organic material Substances 0.000 description 5
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- 230000014759 maintenance of location Effects 0.000 description 4
- -1 oxides Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 238000010298 pulverizing process Methods 0.000 description 3
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- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
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- 238000001723 curing Methods 0.000 description 2
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- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
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- 238000005192 partition Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 101000718497 Homo sapiens Protein AF-10 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100026286 Protein AF-10 Human genes 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007931 coated granule Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005332 obsidian Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
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- 239000011819 refractory material Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Images
Landscapes
- Building Environments (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、不燃材に関する。 The present invention relates to a non-combustible material.
建築物は気密性が向上し、外気温度との差異により結露が生じる場合があった、結露防止や省エネの観点から、様々な断熱材や結露防止材が開発されてきた。中でもポリウレタンフォームやポリスチレンフォームは、軽量性、接着性、コスト等にも優れているため多用されている。ポリウレタンフォームやポリスチレンフォームは有機系素材であることから不燃性が劣り、しばしば火災による被害拡大の原因となり、その対策を施すことが望まれている。解決策として、グラスウールやロックウール等の無機系の断熱材を使用することが挙げられる。しかし、無機系の断熱材の熱伝導率は有機系素材のフォームよりも高い傾向があり、断熱性の点で劣る場合がある。グラスウールやロックウール等は繊維状であるため、作業性の点で穿痛感を有するといった課題がある。 Various heat insulating materials and anti-condensation materials have been developed from the viewpoint of preventing condensation and saving energy, where the building has improved airtightness and condensation may occur due to the difference from the outside air temperature. Among them, polyurethane foam and polystyrene foam are frequently used because they are excellent in lightness, adhesiveness, cost and the like. Since polyurethane foam and polystyrene foam are organic materials, they are incombustible and often cause damage due to fire, and countermeasures are desired. One solution is to use an inorganic heat insulating material such as glass wool or rock wool. However, the thermal conductivity of an inorganic heat insulating material tends to be higher than that of an organic material foam, and may be inferior in heat insulation. Since glass wool, rock wool, and the like are fibrous, there is a problem of having a feeling of pain in terms of workability.
有機系素材のフォームに不燃性を付与した素材は既に市販されている。例えば、フェノール樹脂フォームのボードの片面又は両面を不燃材であるアルミニウム箔、水酸化アルミニウム紙、セッコウ系板材等で積層した構造の不燃断熱ボードが挙げられる。しかし、火災等で熱が加わると、火炎に面した表面は燃えないが、熱で内部のフェノール樹脂が溶け、空洞となりボード自体が脱落し延焼するという課題がある。ウレタン樹脂発泡体の耐燃焼性を向上する技術としては、アルカリ金属炭酸塩、イソシアネート類、水及び反応触媒で発泡体を形成する断熱材料に関する技術（特許文献１）、リチウム、ナトリウム、カリウム、ホウ素、及びアルミニウムからなる群より選ばれる金属の、水酸化物、酸化物、炭酸塩類、硫酸塩、硝酸塩、アルミン酸塩、ホウ酸塩、及びリン酸塩類からなる群より選ばれる一種又は二種以上の無機化合物と水とイソシアネート類とからなる硬化性組成物で、主にトンネルの地盤改良用の注入材に関する技術（特許文献２）がある。これらの発明は、断熱性について記載されていない。特に、アルカリ金属炭酸塩３０％以上の水溶液とイソシアネート類を反応させ、多量の水を使用するため未反応の水が多量に残ることから断熱材として使用するためには乾燥する必要があり、作業工程が多い。 The material which gave the nonflammability to the foam of an organic material is already marketed. For example, a non-combustible heat insulating board having a structure in which one side or both sides of a phenol resin foam board is laminated with a non-combustible aluminum foil, aluminum hydroxide paper, gypsum-based board material, or the like. However, when heat is applied in a fire or the like, the surface facing the flame does not burn, but there is a problem that the phenol resin inside melts due to the heat and becomes a cavity and the board itself falls off and spreads. Technologies for improving the combustion resistance of urethane resin foams include technologies relating to heat insulating materials that form foams with alkali metal carbonates, isocyanates, water and reaction catalysts (Patent Document 1), lithium, sodium, potassium, boron , And a metal selected from the group consisting of aluminum, one or more selected from the group consisting of hydroxides, oxides, carbonates, sulfates, nitrates, aluminates, borates, and phosphates There is a technique (Patent Document 2) relating to an injection material for ground improvement of a tunnel, which is a curable composition comprising an inorganic compound of the above, water and isocyanates. These inventions are not described for heat insulation. In particular, an aqueous solution of 30% or more alkali metal carbonate and isocyanates are reacted, and since a large amount of water is used, a large amount of unreacted water remains. There are many processes.
合成樹脂発泡体を被覆して耐燃焼性を向上する技術としては、セピオライトと水溶性樹脂を主成分とする水性有機バインダーとからなる被覆を形成して表面処理を施した合成樹脂の発泡体粒子に、無機粉体とアルカリ金属ケイ酸塩を主成分とする水ガラスを含む水性無機バインダーとからなるコーティング材を更に被覆し、乾燥硬化させる断熱性被覆粒体に関する技術（特許文献３）、合成樹脂発泡体の少なくとも一部の表面の気泡構造内に、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ酸アルミニウム、アルミノケイ酸塩のうちの１種又は２種以上の混合物からなるシリカ系無機物が充填した無機物含有合成樹脂発泡体に関する技術（特許文献４）が開示されている。これらケイ酸塩類を用いる技術は、燃焼により、樹脂発泡体が溶け、充填されたケイ酸塩自体の結合力も失われ粉化し形状を保つことが難しいという課題がある。 As a technique for improving the combustion resistance by coating a synthetic resin foam, a synthetic resin foam particle is formed by forming a coating composed of sepiolite and an aqueous organic binder mainly composed of a water-soluble resin and performing surface treatment. In addition, a technology (Patent Document 3), synthesis relating to heat-insulating coated granules that are further coated with a coating material comprising an inorganic powder and a water-based inorganic binder containing water glass containing alkali metal silicate as a main component, followed by drying and curing. An inorganic substance in which a cellular structure of at least a part of the surface of a resin foam is filled with a silica-based inorganic substance made of one or a mixture of two or more of calcium silicate, magnesium silicate, aluminum silicate, and aluminosilicate The technique (patent document 4) regarding the containing synthetic resin foam is disclosed. The technique using these silicates has a problem that the resin foam is melted by combustion, and the bonding strength of the filled silicate itself is lost, and it is difficult to maintain the shape by pulverization.
更に、ビーズ法ポリスチレンフォームで形成された発泡樹脂において、発泡ビーズ間に形成された連続気泡に、酸素指数が２１より大きい有機系物質からなる充填材料を充填した発泡樹脂複合構造体に関する技術が開示されている（特許文献５）。これらの技術は、充填材料が有機系物質であり不燃レベルの耐燃焼性の向上は期待できない。これらの技術は実験例より、発泡体の空隙率が３体積％であり、本発明に比べて非常に密実な空隙を持つ発泡ポリスチレンフォームを対象にしている。 Furthermore, a technology related to a foamed resin composite structure in which, in a foamed resin formed of a polystyrene foam bead method, open cells formed between the foamed beads are filled with a filling material made of an organic material having an oxygen index greater than 21 is disclosed. (Patent Document 5). In these techniques, the filling material is an organic substance, and an improvement in incombustibility at a non-combustible level cannot be expected. From these experimental examples, these techniques are directed to a foamed polystyrene foam having a void volume of 3% by volume and a very dense void compared to the present invention.
カルシウムアルミネートを用いた耐火材料としては、例えば、カルシウムアルミネート、セッコウ、及び凝結遅延剤を含有する耐火被覆材が知られている（特許文献６）。この技術は、鉄骨表面を被覆し火災から保護する目的で使用する材料であり、本発明の目的とは異なる。特許文献６は、中空構造を有する無機粉末、廃ガラス発泡体粉末について記載はない。 As a refractory material using calcium aluminate, for example, a refractory coating material containing calcium aluminate, gypsum, and a setting retarder is known (Patent Document 6). This technique is a material used for the purpose of covering the steel surface and protecting it from fire, and is different from the object of the present invention. Patent Document 6 does not describe inorganic powder having a hollow structure and waste glass foam powder.
耐熱骨材、軽量骨材、アルミナ系結合材、炭化珪素、及び補強繊維からなる不焼成耐火断熱材に関する技術が開示されており、軽量骨材としてシラスバルーン、アルミナ系結合材としてカルシウムアルミネートが記述されている（特許文献７）。この技術は、製鉄や製鋼で使用する高温領域の耐火断熱材に使用することを前提としており、通常環境下の断熱を目的とした用途ではない。特許文献７は、セッコウについて記載はない。
A technology related to a non-fired fire-resistant heat insulating material composed of a heat-resistant aggregate, a lightweight aggregate, an alumina-based binder, silicon carbide, and reinforcing fibers is disclosed, and a shirasu balloon as a lightweight aggregate and calcium aluminate as an alumina-based binder. (Patent Document 7). This technology is based on the premise that it is used for high-temperature refractory heat insulating materials used in steelmaking and steelmaking, and is not intended for heat insulation under normal circumstances.
セメント、骨材、急硬材、及び特定の乾燥収縮低減剤を含有してなり、急硬材がカルシウムアルミネート単独又はカルシウムアルミネートとセッコウであり、セメント１００部に対してカルシウムアルミネート１〜２０部であり、カルシウムアルミネート１００部に対してセッコウが３０〜３００部であり、乾燥収縮低減剤がセメント１００部に対して０．１〜１０部である、モルタル組成物が開示されており、骨材として、セラミックバルーン、シラスバルーン、廃ガラスを原料とし焼成して製造した軽量骨材が記述されている（特許文献８）。しかし、中空構造を有する無機粉末と廃ガラス発泡体粉末を特定量使用すること、不燃材として使用することについて記載はない。
Cement, aggregate, rapid hardening material, and a specific drying shrinkage reducing agent are included, and the rapid hardening material is calcium aluminate alone or calcium aluminate and gypsum, and
アウインを含有する物質を用いた技術としては、ＣａＯ原料と、ＣａＳＯ４原料と、さらに、Ａｌ２Ｏ３原料、Ｆｅ２Ｏ３原料及びＳｉＯ２原料からなる群から選ばれる少なくとも１種の原料とを混合したものを熱処理して得られ、かつ、遊離石灰、水硬性化合物及び無水石膏の合計１００部中、遊離石灰１０〜７０部、水硬性化合物１０〜５０部、無水石膏１０〜６０部の割合で含有する熱処理物を含有してなる早期脱型材に関する技術が開示されており、水硬性化合物としてアウインを使用する記載がある（特許文献９）。しかし、中空構造を有する無機粉末と廃ガラス発泡体粉末を特定量使用すること、不燃材として使用することについて記載はない。 As a technique using an auin-containing substance, a CaO raw material, a CaSO 4 raw material, and at least one raw material selected from the group consisting of an Al 2 O 3 raw material, an Fe 2 O 3 raw material, and a SiO 2 raw material Of 100 to 70 parts of free lime, hydraulic compound and anhydrous gypsum, 10 to 70 parts of free lime, 10 to 50 parts of hydraulic compound, and 10 to 60 parts of anhydrous gypsum. The technique regarding the early mold release material formed by containing the heat processing material contained in a ratio is indicated, and there is a statement which uses Auin as a hydraulic compound (patent documents 9). However, there is no description about using a specific amount of inorganic powder having a hollow structure and waste glass foam powder and using it as a noncombustible material.
本発明は断熱性を損なうことなく、不燃性を付与する組成物を提供する。 The present invention provides a composition that imparts incombustibility without impairing the heat insulating properties.
即ち、本発明は、（１）セメント、（２）比表面積で４５００〜１２０００ｃｍ２／ｇの少なくとも遊離石灰、無水セッコウ、及びアウインを含有する物質、（３）平均粒子径が２０〜６０μｍの中空構造を有する無機粉末、（４）平均粒子径が２０〜１３０μｍの廃ガラス発泡体粉末を含有する組成物であり、（３）の使用量が（１）と（２）の合計１００質量部に対して２０〜１５０質量部であり、（４）の使用量が（１）と（２）の合計１００質量部に対して２０〜１００質量部である組成物であり、（３）が、シラスバルーン、フライアッシュバルーンからなる群の１種以上である該組成物であり、（５）材料分離防止剤を含有する該組成物であり、樹脂成形体に充填するために使用する該組成物であり、該組成物と水を含有するスラリーであり、水の使用量が、組成物１００質量部に対して１５０〜５００質量部である該スラリーであり、樹脂成形体に該スラリーを充填した樹脂成形充填体であり、樹脂成形体が、発泡ポリウレタン樹脂、発泡ポリスチレン樹脂、発泡ポリオレフィン樹脂、発泡フェノール樹脂からなる群の１種以上である該樹脂成形充填体であり、樹脂成形体が、連続気泡を有する該樹脂成形充填体であり、連続気泡率が２５〜７０体積％である該樹脂成形充填体であり、樹脂成形体に該スラリーを充填することにより得られる樹脂成形充填体の製造方法であり、該組成物からなる不燃材であり、該樹脂成形充填体からなる不燃断熱材である。 That is, the present invention includes (1) cement, (2) a substance containing at least free lime, anhydrous gypsum, and auin having a specific surface area of 4500 to 12000 cm 2 / g, and (3) a hollow having an average particle diameter of 20 to 60 μm. An inorganic powder having a structure, (4) a composition containing waste glass foam powder having an average particle size of 20 to 130 μm, and the amount of (3) used is 100 parts by mass in total of (1) and (2) The composition is 20 to 150 parts by mass, the amount of (4) used is 20 to 100 parts by mass with respect to the total of 100 parts by mass of (1) and (2), and (3) is shirasu. A composition comprising at least one member selected from the group consisting of a balloon and a fly ash balloon; and (5) the composition containing a material separation inhibitor, the composition used for filling a resin molded body. Yes, containing the composition and water The slurry is a slurry in which the amount of water used is 150 to 500 parts by mass with respect to 100 parts by mass of the composition, and is a resin molded filler in which the slurry is filled in the resin molded body. The resin molded filler is one or more of the group consisting of a polyurethane foam resin, a foamed polystyrene resin, a foamed polyolefin resin, and a foamed phenol resin, and the resin molded body is the resin molded filler having open cells, The resin molded filler having an open cell ratio of 25 to 70% by volume, a method for producing a resin molded filler obtained by filling the resin molded body with the slurry, and a noncombustible material comprising the composition. Yes, it is a non-combustible heat insulating material made of the resin molded filler.
本発明は断熱性を損なうことなく、不燃性を付与する。 The present invention imparts nonflammability without impairing the heat insulating properties.
以下、本発明の実施形態を説明する。単位は特記しない限り、質量単位をいう。 Embodiments of the present invention will be described below. The unit is a mass unit unless otherwise specified.
本発明の（１）セメントとは、普通、早強、超早強、低熱及び中庸熱等の各種ポルトランドセメントや、これらポルトランドセメントに、高炉スラグ、フライアッシュ又はシリカを混合した各種混合セメント、ブレーン比表面積で２０００ｃｍ２/ｇ以上の石灰石粉末や高炉徐冷スラグ微粉末等を混合したフィラーセメント、並びに、都市ゴミ焼却灰や下水汚泥焼却灰を原料として製造された環境調和型セメント（エコセメント）等のポルトランドセメント等が挙げられる。これらのうちの１種以上が使用可能である。これらの中では、ポルトランドセメントが好ましい。 The (1) cement of the present invention includes various portland cements such as ordinary, early strength, ultra-early strength, low heat and moderate heat, various mixed cements obtained by mixing blast furnace slag, fly ash or silica with these portland cements, and brains. Environmentally friendly cement (eco-cement) manufactured from filler cement mixed with limestone powder with a specific surface area of 2000 cm 2 / g or more, blast furnace slow-cooled slag fine powder, etc., and municipal waste incineration ash and sewage sludge incineration ash And portland cement. One or more of these can be used. Of these, Portland cement is preferred.
本発明の（２）ブレーン比表面積が４５００〜１２０００ｃｍ２／ｇの遊離石灰、無水セッコウ、及びアウインを含有してなる物質（以下、アウイン含有物質ということもある）とは、ＣａＯ原料、Ａｌ２Ｏ３原料、ＣａＳＯ４原料等（必要に応じてＦｅ２Ｏ３原料やＳｉＯ２原料）を所定量配合して、キルン等で熱処理して得られる。ＣａＯ原料としては石灰石や消石灰等が挙げられ、Ａｌ２Ｏ３原料としてはボ−キサイトやアルミ残灰等が挙げられ、Ｆｅ２Ｏ３原料としては銅スラグ（銅カラミ）、鉄粉及び市販の酸化鉄等が挙げられ、ＳｉＯ２原料としては市販の二酸化ケイ素や珪石等が挙げられ、ＣａＳＯ４原料としては二水石膏、半水石膏、無水石膏、廃セッコウボード等が挙げられる。アウインの組成は、一般的に、３ＣａＯ・３Ａｌ２Ｏ３・ＣａＳＯ４で表される。 (2) A substance containing free lime, anhydrous gypsum and auin having a specific surface area of 4500 to 12000 cm 2 / g (hereinafter also referred to as auin-containing substance) of the present invention is a CaO raw material, Al 2 A predetermined amount of O 3 raw material, CaSO 4 raw material or the like (Fe 2 O 3 raw material or SiO 2 raw material as required) is mixed and heat-treated with a kiln or the like. Examples of the CaO raw material include limestone and slaked lime, examples of the Al 2 O 3 raw material include bauxite and aluminum residual ash, and examples of the Fe 2 O 3 raw material include copper slag (copper calami), iron powder, and commercially available products. Examples of the SiO 2 raw material include commercially available silicon dioxide and silica stone, and examples of the CaSO 4 raw material include dihydrate gypsum, hemihydrate gypsum, anhydrous gypsum, and waste gypsum board. The composition of Auin is generally represented by 3CaO · 3Al 2 O 3 · CaSO 4 .
本発明は、アウインを必須とするものであり、他にＣ３ＳやＣ４ＡＦ等といった別成分が目的とする性能を損なわない限り含有してもよい。 In the present invention, Auin is essential, and other components such as C 3 S and C 4 AF may be contained as long as the intended performance is not impaired.
カルシウムシリケート（以下、Ｃ３Ｓという）とは、ＣａＯ−ＳｉＯ２系を総称するものであり、特に限定されるものではないが、一般的に、２ＣａＯ・ＳｉＯ２や３ＣａＯ・ＳｉＯ２がよく知られている。通常は、３ＣａＯ・ＳｉＯ２として存在していると考えられる。カルシウムアルミノフェライト（以下、Ｃ４ＡＦという）とは、ＣａＯ−Ａｌ２Ｏ３−Ｆｅ２Ｏ３系の化合物を総称するものであり、特に限定されるものではないが、一般的に、４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３や６ＣａＯ・Ａｌ２Ｏ３・２Ｆｅ２Ｏ３等の化合物がよく知られている。通常は、４ＣａＯ・Ａｌ２Ｏ３・Ｆｅ２Ｏ３として存在していると考えられる。
Calcium silicate (hereinafter referred to as C 3 S) is a generic term for CaO—SiO 2 system, and is not particularly limited, but generally 2CaO · SiO 2 and 3CaO · SiO 2 are well known. It has been. Usually, it is considered to exist as 3CaO · SiO 2 . Calcium aluminoferrite (hereinafter referred to as C 4 AF) is a generic term for CaO—Al 2 O 3 —Fe 2 O 3 -based compounds, and is not particularly limited, but generally 4CaO · compounds such as Al 2 O 3 · Fe 2 O 3 and 6CaO · Al 2 O 3 · 2Fe 2
本発明のアウイン含有物質の組成は、アウイン含有物質１００％中、遊離石灰３０〜７０％、無水セッコウ１０〜５０％、アウイン５〜２５％、Ｃ４ＡＦ５〜２５％が好ましく、遊離石灰４０〜６０％、無水セッコウ２０〜４０％、アウイン１０〜２０％、Ｃ４ＡＦ１０〜２０％がより好ましい。 The composition of the auin-containing material of the present invention is preferably 30 to 70% free lime, 10 to 50% anhydrous gypsum, 5 to 25% auin, and 5 to 25% C 4 AF in 100% auin-containing material. 60%, anhydrous gypsum 20-40%, Auin 10~20%, C 4 AF10~20% is more preferable.
本発明のアウイン含有物質の粒度は、反応活性の点で、ブレーン比表面積で４５００〜１２０００ｃｍ２／ｇが好ましく、５０００〜１００００ｃｍ２／ｇがより好ましい。４５００ｃｍ２／ｇ未満では早期にエトリンガイトを生成できず、不燃性や断熱性が小さい場合があり、１２０００ｃｍ２／ｇを超えるとエトリンガイトが効率的に生成できず、含浸時の充填性が得られない場合がある。 The particle size of Auin containing materials of the present invention, in terms of reactivity, preferably 4500~12000cm 2 / g in Blaine specific surface area, 5000~10000cm 2 / g is more preferable. If it is less than 4500 cm 2 / g, ettringite cannot be produced at an early stage, and incombustibility and heat insulation may be small. If it exceeds 12000 cm 2 / g, ettringite cannot be produced efficiently, and filling properties during impregnation cannot be obtained. There is a case.
本発明のアウイン含有物質の使用量は、セメント１００部に対して１００〜２０００部が好ましく、２００〜１０００部がより好ましい。１００部未満では効率的なエトリンガイトの生成に寄与しない場合があり、２０００部を超えると断熱効果が頭打ちとなる場合がある。 100-2000 parts is preferable with respect to 100 parts of cement, and, as for the usage-amount of the Auin containing substance of this invention, 200-1000 parts is more preferable. If it is less than 100 parts, it may not contribute to the efficient production of ettringite, and if it exceeds 2000 parts, the heat insulation effect may reach its peak.
本発明の（３）中空構造を有する無機粉末（以下、中空無機粉末ということもある）としては、シラスバルーンに代表される火山性堆積物を高温で加熱して作られる発泡体、火力発電所から発生するフライアッシュバルーン、黒曜石や真珠岩を焼成したバルーン構造の無機粉末等が挙げられる。これらの中では、密度が小さく、樹脂成形体の連続気泡に充填した際に断熱性を損ないにくい点で、シラスバルーン、フライアッシュバルーンからなる群の１種以上が好ましい。 As the inorganic powder (3) having a hollow structure of the present invention (hereinafter sometimes referred to as a hollow inorganic powder), a foam produced by heating a volcanic deposit represented by a shirasu balloon at a high temperature, a thermal power plant Fly ash balloons generated from the above, inorganic powders of balloon structure obtained by firing obsidian and pearlite. Among these, at least one member selected from the group consisting of a shirasu balloon and a fly ash balloon is preferable because it has a low density and hardly impairs heat insulation properties when filled into open cells of a resin molded body.
本発明の中空構造を有する無機粉末の平均粒子径は、２０〜６０μｍが好ましく、３０〜５０μｍがより好ましい。２０μｍ未満では粒子が細かすぎてスラリーにした時の粘度が高くなり、含浸時の充填性が低下する場合があり、６０μｍを超えると燃焼後の形状を保持することが難しい場合がある。 20-60 micrometers is preferable and, as for the average particle diameter of the inorganic powder which has a hollow structure of this invention, 30-50 micrometers is more preferable. If it is less than 20 μm, the particles are too fine and the viscosity becomes high when it is made into a slurry, and the filling property at the time of impregnation may be lowered, and if it exceeds 60 μm, it may be difficult to maintain the shape after combustion.
本発明の中空構造を有する無機粉末の使用量は、混合セメント１００部に対して２０〜１５０部が好ましく、３０〜１２０部がより好ましい。混合セメントとは、（１）と（２）の混合物が好ましい。混合セメント１００部とは、（１）と（２）の合計１００部が好ましい。２０部未満では燃焼後の形状を保持することが難しい場合があり、１５０部を超えると不燃性が低下する場合がある。 20-150 parts is preferable with respect to 100 parts of mixed cement, and, as for the usage-amount of the inorganic powder which has the hollow structure of this invention, 30-120 parts is more preferable. The mixed cement is preferably a mixture of (1) and (2). 100 parts of the mixed cement is preferably 100 parts in total of (1) and (2). If it is less than 20 parts, it may be difficult to maintain the shape after combustion, and if it exceeds 150 parts, nonflammability may be reduced.
本発明の（４）廃ガラス発泡体粉末としては、ガラスビン等の廃棄物を粉砕後、焼成して製造し、粒度調整したものであれば使用できる。 The (4) waste glass foam powder of the present invention can be used as long as it is produced by pulverizing and firing waste such as glass bottles and adjusting the particle size.
本発明の廃ガラス発泡体粉末の平均粒子径は２０〜１３０μｍが好ましく、４０〜１００μｍがより好ましい。２０μｍ未満では粒子が細かすぎてスラリーにしたときの粘度が高くなり、燃焼後の形状を保持することが難しい場合があり、１３０μｍを超えると断熱性が低下する場合がある。 20-130 micrometers is preferable and, as for the average particle diameter of the waste glass foam powder of this invention, 40-100 micrometers is more preferable. If it is less than 20 μm, the particles are too fine to increase the viscosity when made into a slurry, and it may be difficult to maintain the shape after combustion, and if it exceeds 130 μm, the heat insulating property may be lowered.
廃ガラス発泡体の軟化点は、燃焼後の形状保持性が向上する点で、８００℃以下が好ましい。８００℃を超えると無機粉末や燃焼で分解した生成物に対する融着効果が十分に発揮できない場合がある。軟化点は、例えば、ＪＩＳ Ｒ ３１０３−１により求める。 The softening point of the waste glass foam is preferably 800 ° C. or lower in view of improving shape retention after combustion. If it exceeds 800 ° C., the fusion effect on the inorganic powder or the product decomposed by combustion may not be sufficiently exhibited. A softening point is calculated | required by JISR3103-1, for example.
本発明の廃ガラス発泡体粉末の使用量は、混合セメント１００部に対して２０〜１００部が好ましく、３０〜８０部がより好ましい。２０部未満では燃焼後の形状を十分に保持することが難しい場合があり、１００部を超えると不燃性が低下する場合がある。 20-100 parts is preferable with respect to 100 parts of mixed cement, and, as for the usage-amount of the waste glass foam powder of this invention, 30-80 parts is more preferable. If it is less than 20 parts, it may be difficult to maintain the shape after combustion sufficiently, and if it exceeds 100 parts, nonflammability may be reduced.
本発明は（５）材料分離防止剤を使用することが好ましい。 In the present invention, it is preferable to use (5) a material separation preventing agent.
本発明の材料分離防止剤とは、混合セメント、中空構造を有する無機粉末及び廃ガラス発泡体粉末に水を加えてスラリー状にした時の材料分離を防止し、充填性を向上する効果を発揮するものをいう。材料分離防止剤としては、有機系物質、ベントナイト類、コロイダルシリカ分散液等が挙げられる。有機系物質としては、メチルセルロース、メチルエチルセルロース等のセルロースエーテル類、カルボキシルメチルセルロース又はそのアルカリ金属塩、ポリアクリルアミド類、ポリビニルピロリドン、ポリビニルアルコール等が挙げられる。これらの中では、不燃性を阻害しにくい点で、ベントナイト類、コロイダルシリカ分散液からなる群の１種以上が好ましい。特に、コロイダルシリカ分散液は、適度なゲル化作用により粘性を与えて材料分離防止効果を付与すると共に、不燃性を高める効果も発揮する点で、好ましい。 The material separation preventive agent of the present invention is effective for preventing material separation and improving filling property when water is added to a mixed cement, inorganic powder having a hollow structure and waste glass foam powder to form a slurry. Say what you do. Examples of the material separation inhibitor include organic substances, bentonites, and colloidal silica dispersions. Examples of organic substances include cellulose ethers such as methyl cellulose and methyl ethyl cellulose, carboxymethyl cellulose or alkali metal salts thereof, polyacrylamides, polyvinyl pyrrolidone, and polyvinyl alcohol. Among these, one or more members selected from the group consisting of bentonites and colloidal silica dispersions are preferable in that nonflammability is hardly inhibited. In particular, the colloidal silica dispersion is preferable in that it imparts a viscosity by an appropriate gelling action to give an effect of preventing material separation and also exhibits an effect of enhancing nonflammability.
本発明の材料分離防止剤の使用量は、混合セメント１００部に対して、固形分換算で、０．０５〜１０部が好ましい。有機系物質の場合は、混合セメント１００部に対して、固形分換算で、０．０５〜０．５部が好ましい。ベントナイト類の場合は、混合セメント１００部に対して、固形分換算で、１〜１０部が好ましい。コロイダルシリカ分散液の場合は、混合セメント１００部に対して、固形分換算で、０．５〜５部が好ましい。 The amount of the material separation inhibitor of the present invention is preferably 0.05 to 10 parts in terms of solid content with respect to 100 parts of the mixed cement. In the case of an organic material, 0.05 to 0.5 part is preferable in terms of solid content with respect to 100 parts of the mixed cement. In the case of bentonites, 1 to 10 parts are preferable in terms of solid content with respect to 100 parts of the mixed cement. In the case of a colloidal silica dispersion, 0.5 to 5 parts are preferable in terms of solid content with respect to 100 parts of the mixed cement.
本発明は、水を混合してスラリーを調製する。スラリーを調製する時の水の量は、組成物１００部に対して１５０〜５００部が好ましく、２００〜４００部がより好ましい。１５０部未満では連続気泡への充填性が低下する場合があり、５００部を超えると連続気泡内で生成する水和物強度が低下し、連続気泡への充填性が低下する場合がある。組成物とは、（１）〜（４）を含有する組成物が好ましい。組成物１００部とは、（１）〜（４）の合計１００部が好ましい。（５）を含有する場合、組成物とは、（１）〜（５）を含有する組成物が好ましく、組成物１００部とは、（１）〜（５）の合計１００部が好ましい。 In the present invention, a slurry is prepared by mixing water. The amount of water when preparing the slurry is preferably 150 to 500 parts, more preferably 200 to 400 parts, relative to 100 parts of the composition. If it is less than 150 parts, the filling property to open cells may be reduced, and if it exceeds 500 parts, the strength of hydrate produced in the open cells may be reduced, and the filling property to open cells may be reduced. The composition is preferably a composition containing (1) to (4). 100 parts of the composition is preferably 100 parts in total of (1) to (4). In the case of containing (5), the composition is preferably a composition containing (1) to (5), and 100 parts of the composition is preferably 100 parts in total of (1) to (5).
本発明のスラリーの粘度は、材料分離しない粘度であれば特に限定しないが、充填後の樹脂成形体の密度のばらつきが小さい点で、１００〜７００ｍＰａ・sが好ましく、３００〜７００ｍＰａ・sがより好ましく、４００〜７００ｍＰａ・sが最も好ましい。 The viscosity of the slurry of the present invention is not particularly limited as long as the viscosity does not cause material separation, but is preferably 100 to 700 mPa · s, more preferably 300 to 700 mPa · s, in terms of small variation in density of the resin molded body after filling. 400 to 700 mPa · s is most preferable.
本発明の樹脂成形体とは、スラリー等の液状物質が浸透できる気泡を有する樹脂成形体である。連続気泡を有する樹脂成形体であれば特に限定するものではない。樹脂としては、発泡ポリビニルアルコール樹脂、発泡ポリウレタン樹脂、発泡ポリスチレン樹脂、ポリエチレンフォーム等の発泡ポリオレフィン樹脂、フェノール樹脂フォーム等の発泡フェノール樹脂等が挙げられる。これらの発泡樹脂は独立気泡により発泡体を形成するものであり、直径数ｍｍの樹脂発泡粒状体である。樹脂成形体としては、連続気泡が生じるように、これらの樹脂発泡粒状体を型枠に詰めて加圧し成形する。ポリスチレン樹脂についてはビーズ法ポリスチレンフォームの製造方法に準拠して、連続気泡を有する樹脂成形体を製造することが可能である。これらの中では、断熱材としてよく使われる点で、発泡ポリウレタン樹脂、発泡ポリスチレン樹脂、発泡ポリオレフィン樹脂、発泡フェノール樹脂からなる群の１種以上が好ましく、発泡ポリウレタン樹脂成形体、発泡ポリスチレン樹脂成形体からなる群の１種以上が好ましい。 The resin molded body of the present invention is a resin molded body having bubbles in which a liquid substance such as slurry can permeate. There is no particular limitation as long as it is a resin molded body having open cells. Examples of the resin include foamed polyvinyl alcohol resin, foamed polyurethane resin, foamed polystyrene resin, foamed polyolefin resin such as polyethylene foam, and foamed phenol resin such as phenol resin foam. These foamed resins form foams by closed cells, and are resin foam granules having a diameter of several mm. As the resin molded body, these resin foam granules are packed in a mold and molded so as to generate open cells. As for the polystyrene resin, it is possible to produce a resin molded body having open cells in accordance with a method for producing a beaded polystyrene foam. Among these, one or more members selected from the group consisting of foamed polyurethane resin, foamed polystyrene resin, foamed polyolefin resin, and foamed phenol resin are preferable because they are often used as heat insulating materials. One or more members of the group consisting of
本発明の樹脂成形体の連続気泡率は２５〜７０体積％が好ましい。２５体積％未満ではスラリーを均一に浸透することが難しい場合があり、７０体積％を超えると密度が大きくなり、断熱性が損なわれる場合がある。スラリーの浸透方法としては、以下の方法が挙げられる。連続気泡率が５０体積％未満の樹脂成形体の場合、圧搾空気による圧入や真空ポンプによる減圧による吸引によりスラリーを浸透する方法が好ましい。連続気泡率が５０体積％以上の樹脂成形体の場合、常圧下で、自然に或いは振動を加えながら気泡内に浸透させる方法が好ましい。 The open cell ratio of the resin molding of the present invention is preferably 25 to 70% by volume. If the amount is less than 25% by volume, it may be difficult to uniformly penetrate the slurry. If the amount exceeds 70% by volume, the density may increase and the heat insulating property may be impaired. Examples of the method for infiltrating the slurry include the following methods. In the case of a resin molded body having an open cell ratio of less than 50% by volume, a method of infiltrating the slurry by press-fitting with compressed air or suction by depressurization with a vacuum pump is preferable. In the case of a resin molded body having an open cell ratio of 50% by volume or more, a method of permeating into the bubbles naturally or while applying vibration is preferable under normal pressure.
本発明のスラリーの浸透量は、連続気泡率（体積％）に対して０．８〜１．５容量倍の容量のスラリーを浸透させることが好ましい。０．８容量倍未満では十分な不燃性を付与することができない場合があり、１．５容量倍を超えると樹脂成形充填体の密度が大きくなりすぎて断熱性が低下する場合がある。 The amount of penetration of the slurry of the present invention is preferably infiltrated with a slurry having a volume of 0.8 to 1.5 times the volume of the open cell rate (volume%). If it is less than 0.8 volume times, sufficient nonflammability may not be imparted, and if it exceeds 1.5 volume times, the density of the resin molded filler may become too high and the heat insulation may be lowered.
連続気泡に含浸したスラリーは、例えば、水和反応により水和生成物が生成し、水和生成物が連続気泡内で充填固化する。スラリーを乾燥すると、自由水が蒸発するので、樹脂成形充填体に細孔ができ、断熱性の向上に寄与する。水和生成物はエトリンガイト等である。エトリンガイトは分子内に多量の水を結晶水として有するので、加熱により１００℃程度から徐々に脱水し、消火作用を示し、樹脂成形充填体に不燃性を付与する。平均粒子径が２０〜６０μｍの中空構造を有する無機粉末、平均粒子径が２０〜１３０μｍの廃ガラス発泡体粉末を含有することにより、例えば、形状保持性が得られる。 In the slurry impregnated in the open cells, for example, a hydrated product is generated by a hydration reaction, and the hydrated product is filled and solidified in the open cells. Since the free water evaporates when the slurry is dried, pores are formed in the resin molded filler, which contributes to the improvement of heat insulation. Hydrated products are ettringite and the like. Since ettringite has a large amount of water as crystal water in the molecule, it gradually dehydrates from about 100 ° C. by heating, exhibits a fire extinguishing action, and imparts nonflammability to the resin molded filler. By containing an inorganic powder having a hollow structure with an average particle size of 20 to 60 μm and a waste glass foam powder with an average particle size of 20 to 130 μm, for example, shape retention can be obtained.
本発明のスラリーを連続気泡に充填した後の樹脂成形充填体の養生方法は、特に限定するものではないが、充填後、水分が蒸発しないように、常温で３日程度養生したり、更に養生時間を短縮するために５０℃以下の温度で加温養生したりしてもよい。 The curing method of the resin molded filler after filling the slurry of the present invention into open cells is not particularly limited, but after the filling, it is cured for about 3 days at room temperature or further cured so that the water does not evaporate. In order to shorten time, you may heat cure at the temperature of 50 degrees C or less.
本発明では、不織布、繊維シート等の補強材を不燃断熱材の片面或いは両面に配置することも可能である。 In the present invention, reinforcing materials such as non-woven fabrics and fiber sheets can be disposed on one side or both sides of the non-combustible heat insulating material.
本発明の不燃断熱材の形状は、特に限定するものではないが、一般的にはボード状にすることが好ましく、例えば、縦２００〜１０００ｍｍ、横２００〜２０００ｍｍ、厚さ１０〜１００ｍｍが好ましい。サイズが大きすぎると作業性が低下する場合がある。 The shape of the non-combustible heat insulating material of the present invention is not particularly limited, but in general, it is preferably a board shape, for example, 200 to 1000 mm in length, 200 to 2000 mm in width, and 10 to 100 mm in thickness. If the size is too large, workability may be reduced.
本発明の不燃断熱材の密度は、断熱性を損なわない範囲で調製する。不燃断熱材の密度は７０〜３００ｋｇ／ｍ３が好ましく、９０〜２３０ｋｇ／ｍ３がより好ましい。７０ｋｇ／ｍ３未満では十分な不燃性を確保することが難しい場合があり、３００ｋｇ／ｍ３を超えると十分な断熱性が得られない場合がある。 The density of the incombustible heat insulating material of the present invention is adjusted within a range not impairing the heat insulating property. Density of noncombustible insulation material is preferably 70~300kg / m 3, 90~230kg / m 3 and more preferably. If it is less than 70 kg / m 3 , it may be difficult to ensure sufficient incombustibility, and if it exceeds 300 kg / m 3 , sufficient heat insulation may not be obtained.
本発明の組成物は、不燃材として使用できる。本発明のスラリーは、不燃材スラリーとして使用できる。本発明のスラリーを連続気泡に充填した樹脂成形体は、不燃断熱材として使用できる。 The composition of the present invention can be used as a non-combustible material. The slurry of the present invention can be used as a noncombustible material slurry. The resin molding which filled the slurry of this invention in the open cell can be used as a nonflammable heat insulating material.
本発明の不燃断熱材を用いた断熱方法としては、一般的なボード状断熱材が設置されている方法と同じ方法が採用できる。例えば、外張り断熱を壁で実施する場合は、柱等にボード状の不燃断熱材を釘等で仮止めし、気密性を必要とする場合は、ボード状の不燃断熱材の継ぎ目に気密テープを貼る。そして透湿防水シートを表面に貼り付け、専用のビスで胴縁を施工する。充填断熱を壁で実施する場合は、ボード状の不燃断熱材を柱間のサイズに合わせてカットし、隙間ができないように不燃断熱材を柱間にはめ込んで施工する。 As a heat insulating method using the non-combustible heat insulating material of the present invention, the same method as a method in which a general board-shaped heat insulating material is installed can be adopted. For example, when carrying out heat insulation with a wall, temporarily fix a board-like non-combustible heat insulating material to the pillar with a nail or the like, and if air tightness is required, air-tight tape at the joint of the board-like non-combustible heat insulating material Paste. Then, a moisture-permeable waterproof sheet is attached to the surface, and the trunk edge is constructed with a special screw. When filling insulation is carried out with walls, board-like non-combustible heat insulating material is cut according to the size between the columns, and the non-combustible heat insulating material is fitted between the columns so that there is no gap.
以下、実施例に基づき詳細に説明する。特記しない限り、常温（２３℃）で実施した。 Hereinafter, it demonstrates in detail based on an Example. Unless otherwise stated, it was carried out at room temperature (23 ° C.).
（不燃材スラリーの調製）
表１に示すセメント１００部、表１に示す量のアウイン含有物質、セメントとアウイン含有物質の合計１００部に対して表１に示す量の中空無機粉末（以下無機粉末をいうこともある）、セメントとアウイン含有物質の合計１００部に対して表１に示す量の廃ガラス発泡体粉末を混合することにより不燃材を調製した。水を不燃材１００部に対して２５０部となるように、攪拌しながら少量ずつ加えた。全ての水を加えてから５分間攪拌し、不燃材スラリーを調製した。
(Preparation of non-combustible material slurry)
100 parts of cement shown in Table 1, the amount of Auin-containing material shown in Table 1, hollow inorganic powder in the amount shown in Table 1 with respect to a total of 100 parts of cement and Auin-containing material (hereinafter sometimes referred to as inorganic powder), A nonflammable material was prepared by mixing the amount of waste glass foam powder shown in Table 1 with a total of 100 parts of cement and auin-containing material. Water was added little by little with stirring so that the amount was 250 parts with respect to 100 parts of the noncombustible material. After adding all the water, the mixture was stirred for 5 minutes to prepare a noncombustible material slurry.
（不燃断熱材の調製）
連続気泡を有する発泡樹脂成形体Ａ１（サイズ：縦２０ｃｍ×横２０ｃｍ×厚み５ｃｍ）を、図１に示す減圧含浸装置にセットした。発泡樹脂成形体上面に不燃材スラリー９５０ｃｍ３（連続気泡率に対して１．３６容量倍、単位は容量）を発泡樹脂成形体の上面に流し込んだ。セットした発泡樹脂成形体下面側から、開閉コックを徐々に開けることにより、減圧室を減圧し、連続気泡内に不燃材スラリーを浸透させ、不燃断熱材を製造した。浸透後、減圧含浸装置から不燃断熱材を取り外し、３日間常温で乾燥させ、不燃性、均一性、密度、形状保持性及び熱伝導率を評価した。結果を表１に示す。
(Preparation of non-combustible insulation)
A foamed resin molding A1 having open cells (size: 20 cm long × 20 cm wide × 5 cm thick) was set in the vacuum impregnation apparatus shown in FIG. 950 cm 3 of non-combustible material slurry (1.36 times the volume of the open cell ratio, the unit is the volume) was poured into the upper surface of the foamed resin molded body. By gradually opening the open / close cock from the lower surface side of the set foamed resin molded body, the decompression chamber was decompressed, and the incombustible material slurry was infiltrated into the open cells to produce an incombustible heat insulating material. After infiltration, the non-combustible heat insulating material was removed from the vacuum impregnation apparatus and dried at room temperature for 3 days to evaluate non-combustibility, uniformity, density, shape retention and thermal conductivity. The results are shown in Table 1.
（減圧含浸装置）
減圧含浸装置を図１に示す。減圧含浸装置（容器本体）１は、減圧室２，減圧室と発泡樹脂成形体をセットする部分の仕切り板３，不織布４，発泡樹脂成形体５，不燃材スラリー６，トラップ容器７，真空ポンプ８、開閉コック９から構成される。
(Low pressure impregnation equipment)
A vacuum impregnation apparatus is shown in FIG. The decompression impregnation apparatus (container body) 1 includes a
（使用材料）
発泡樹脂成形体Ａ１：市販されているポリスチレン発泡ビーズ（直径２〜５ｍｍ）にＥＶＡエマルジョンを１％加え、ビーズ表面に均一に塗布されるように混合し、金型に詰めて加圧することにより成形体を作製した。連続気泡率３５体積％、熱伝導率０．０３４Ｗ／ｍ・Ｋ
セメントａ：デンカ社製 普通ポルトランドセメント ブレーン比表面積３３００ｃｍ２／ｇ
セメントｂ：デンカ社製 早強ポルトランドセメント、ブレーン比表面積４５００ｃｍ２／ｇ
セメントｃ：デンカ社製 Ｂ種高炉セメント、ブレーン比表面積３４００ｃｍ２／ｇ
アウインを含有する物質（１）：遊離石灰５０％ 無水セッコウ３０％ アウイン１５％ Ｃ４ＡＦ１５％ ブレーン比表面積４５００ｃｍ２／ｇ
アウインを含有する物質（２）：遊離石灰５０％ 無水セッコウ３０％ アウイン１５％ Ｃ４ＡＦ１５％ ブレーン比表面積６２００ｃｍ２／ｇ
アウインを含有する物質（３）：遊離石灰５０％ 無水セッコウ３０％ アウイン１５％ Ｃ４ＡＦ１５％ ブレーン比表面積１２０００ｃｍ２／ｇ
アウインを含有する物質（４）：遊離石灰５０％ 無水セッコウ３０％ アウイン１５％ Ｃ４ＡＦ１５％ ブレーン比表面積４２００ｃｍ２／ｇ
アウインを含有する物質（５）：遊離石灰５０％ 無水セッコウ３０％ アウイン１５％ Ｃ４ＡＦ１５％ ブレーン比表面積１３０００ｃｍ２／ｇ
中空無機粉末ア：アクシーズケミカル社製シラスバルーン、商品名：ＭＳＢ−３０１、平均粒子径５０μｍ
中空無機粉末イ：アクシーズケミカル社製シラスバルーン、商品名：ＩＳＭ−Ｆ０１５、平均粒子径１０μｍ
中空無機粉末ウ：アクシーズケミカル社製シラスバルーン、商品名：ＭＳＢ−５０１１、平均粒子径７０μｍ
廃ガラス発泡体粉末α：ＤＥＮＮＥＲＴ ＰＯＲＡＶＥＲ ＧＭＢＨ社製廃ガラス発泡体粉末、商品名：Ｐｏｒａｖｅｒ（０．０４−０．１２５ｍｍ粒度品）、軟化点７００−７５０℃、平均粒子径９０μｍ
廃ガラス発泡体粉末β：廃ガラス発泡体粉末αを粉砕した粒度調整品、軟化点７００−７５０℃、平均粒子径１５μｍ
廃ガラス発泡体粉末γ：ＤＥＮＮＥＲＴ ＰＯＲＡＶＥＲ ＧＭＢＨ社製廃ガラス発泡体粉末、商品名：Ｐｏｒａｖｅｒ（０．１−０．３ｍｍ粒度品）の粒度調整品、軟化点７００−７５０℃、平均粒子径１４０μｍ
ガラス粉末θ：旭ガラス社製、商品名：ＡＦＳ１７１７、平均粒子径２．５μｍ、軟化点８０８℃
水：水道水
(Materials used)
Foamed resin molded product A1: Molded by adding 1% EVA emulsion to commercially available polystyrene foam beads (2-5 mm in diameter), mixing them so that they are evenly applied to the surface of the beads, filling them in a mold and pressing them. The body was made. Open cell rate 35% by volume, thermal conductivity 0.034 W / m · K
Cement a: DENKA normal portland cement Blaine specific surface area 3300 cm 2 / g
Cement b: Denka's early strength Portland cement, Blaine specific surface area 4500 cm 2 / g
Cement c: Class B blast furnace cement manufactured by Denka Co., Blaine specific surface area 3400 cm 2 / g
Material containing Auin (1): Free lime 50% Anhydrous gypsum 30% Auin 15% C 4 AF 15% Blaine specific surface area 4500 cm 2 / g
Material containing Auin (2): free lime 50% anhydrous gypsum 30% Auin 15% C 4 AF 15% Blaine specific surface area 6200 cm 2 / g
Substance containing Auin (3): Free lime 50% Anhydrous gypsum 30% Auin 15% C 4 AF 15% Blaine specific surface area 12000 cm 2 / g
Material containing Auin (4): Free lime 50% Anhydrous gypsum 30% Auin 15% C 4 AF 15% Blaine specific surface area 4200 cm 2 / g
Material containing Auin (5): Free lime 50% Anhydrous gypsum 30% Auin 15% C 4 AF 15% Blaine specific surface area 13000 cm 2 / g
Hollow inorganic powder A: Shirasu balloon made by Axes Chemical Co., Ltd., trade name: MSB-301, average particle size 50 μm
Hollow inorganic powder A: Shirasu balloon manufactured by Axes Chemical Co., Ltd., trade name: ISM-F015, average particle size 10 μm
Hollow inorganic powder C: Shirasu balloon made by Axes Chemical Co., Ltd., trade name: MSB-5011, average particle size 70 μm
Waste glass foam powder α: Waste glass foam powder manufactured by DENNERT PORVER GMBH, trade name: Poraver (0.04-0.125 mm particle size product), softening point 700-750 ° C., average particle diameter 90 μm
Waste glass foam powder β: Particle size adjusted product obtained by pulverizing waste glass foam powder α, softening point 700-750 ° C., average particle diameter 15 μm
Waste glass foam powder γ: Waste glass foam powder manufactured by DENNERT POREVER GMBH, trade name: Poraver (0.1-0.3 mm particle size) particle size adjusted product, softening point 700-750 ° C., average particle size 140 μm
Glass powder θ: manufactured by Asahi Glass Co., Ltd., trade name: AFS1717, average particle size 2.5 μm, softening point 808 ° C.
Water: tap water
（測定方法）
ブレーン比表面積：ＪＩＳ Ｒ５２０１に従い、測定した。
平均粒子径：レーザ回折式粒度分布計で測定した。機種は、ＬＡ−９２０（堀場製作所）を使用した。
均一性：装置から取り出した不燃断熱材を縦方向及び横方向で４分割し、更に、分割した不燃断熱材ブロックを厚さ方向に２分割し、合計８個の分割成形体としてそれぞれの密度を求めた。求めた密度の最小値と最大値の差を求めた。差か小さいほど均一に含浸していると評価した。
密度：均一性を求めるために算出した８点の密度の平均値を算出した。
不燃性：ＩＳＯ−５６６０−１：２００２に示されたコーンカロリーメータによる発熱試験に準拠して評価した。縦１０ｃｍ×横１０ｃｍ×厚さ５ｃｍの不燃断熱材を試験体とした。例えば、この試験体を用いて加熱時間が２０分間のときの総発熱量が８ＭＪ／ｍ２以下であれば不燃性の効果が大きい。
熱伝導率：縦１０ｃｍ×横５ｃｍ×厚み５ｃｍの試験体を用いて迅速熱伝導率計（ボックス式プローブ法）で測定した。
形状保持性：不燃性試験後の試験体を観察し、亀裂、崩壊、収縮がない場合を○、亀裂、崩壊、収縮の何れかがある場合を×とした。
(Measuring method)
Blaine specific surface area: measured according to JIS R5201.
Average particle diameter: Measured with a laser diffraction particle size distribution meter. The model used was LA-920 (Horiba Seisakusho).
Uniformity: The non-combustible heat insulating material taken out from the apparatus is divided into four parts in the vertical direction and the horizontal direction, and further, the divided non-combustible heat insulating material block is divided into two parts in the thickness direction, and the respective densities are obtained as a total of eight divided molded bodies. Asked. The difference between the minimum value and the maximum value obtained was determined. It was evaluated that the smaller the difference, the more uniformly impregnated.
Density: The average value of the density of 8 points calculated for obtaining uniformity was calculated.
Nonflammability: Evaluated according to a heat generation test using a cone calorimeter shown in ISO-5660-1: 2002. A non-combustible heat insulating material having a length of 10 cm, a width of 10 cm, and a thickness of 5 cm was used as a test specimen. For example, if the total calorific value when the heating time is 20 minutes using this test body is 8 MJ / m 2 or less, the effect of nonflammability is great.
Thermal conductivity: It measured with the rapid thermal conductivity meter (box type probe method) using the test body of length 10cm x width 5cm x thickness 5cm.
Shape retention: The specimen after the nonflammability test was observed, and the case where there was no crack, collapse, or shrinkage was rated as “◯”, and the case where there was any crack, decay or shrinkage was marked as “X”.
セメントａ１００部、アウイン含有物質（２）５００部、セメントとアウイン含有物質の合計１００部に対して廃ガラス発泡体粉末α６０部、セメントとアウイン含有物質の合計１００部に対して表２に示す量の中空無機粉末エを混合して不燃材スラリーを調製したこと以外は、実施例１と同様に行った。結果を表２に示す。 100 parts of cement a, 500 parts of auin-containing material (2), 100 parts of waste glass foam powder for a total of 100 parts of cement and auin-containing material, and the amount shown in Table 2 for a total of 100 parts of cement and auin-containing substance The same procedure as in Example 1 was conducted, except that a non-combustible material slurry was prepared by mixing the hollow inorganic powders. The results are shown in Table 2.
（使用材料）
無機粉末エ：東海工業社製フライアッシュバルーン分級品、平均粒子径４５μｍ
(Materials used)
Inorganic powder D: Fly ash balloon classification product manufactured by Tokai Kogyo Co., Ltd., average particle size 45 μm
セメントa１００部、アウイン含有物質（２）５００部、セメントとアウイン含有物質の合計１００部に対して廃ガラス発泡体粉末α６０部、セメントとアウイン含有物質の合計１００部に対して中空無機粉末ア６０部、セメントとアウイン含有物質の合計１００部に対して固形分換算で表３に示す量の材料分離防止剤を混合して不燃材スラリーを調製したこと以外は、実施例１と同様に行った。スラリー粘度も測定した。結果を表３に示す。
（使用材料）
材料分離防止剤（１）：信越化学工業社製メチルセルロース、商品名：ＳＭ４０００
材料分離防止剤（２）：クニミネ工業社製ベントナイト、商品名：クニゲルＧＳ
材料分離防止剤（３）：日産化学工業社製コロイダルシリカ分散液、商品名：スノーテックス５０
100 parts of cement a, 500 parts of Auin-containing material (2), 60 parts of waste glass foam powder α for a total of 100 parts of cement and Auin-containing material, and 60% of hollow inorganic powder for 60 parts of cement and Auin-containing material The same procedure as in Example 1 was conducted except that a non-combustible material slurry was prepared by mixing the amount of the material separation inhibitor shown in Table 3 in terms of solid content with respect to a total of 100 parts of the cement and auin-containing substance. . The slurry viscosity was also measured. The results are shown in Table 3.
(Materials used)
Material separation inhibitor (1): methyl cellulose manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SM4000
Material separation inhibitor (2): Benitonite manufactured by Kunimine Kogyo Co., Ltd., Trade name: Kunigel GS
Material separation inhibitor (3): Colloidal silica dispersion manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex 50
（測定方法）
スラリー粘度（粘度）：不燃材スラリーの粘度をＢ型粘度計で測定した。
(Measuring method)
Slurry viscosity (viscosity): The viscosity of the noncombustible material slurry was measured with a B-type viscometer.
セメントa１００部、アウイン含有物質（２）５００部、セメントとアウイン含有物質の合計１００部に対して廃ガラス発泡体粉末α６０部、セメントとアウイン含有物質の合計１００部に対して中空無機粉末ア６０部を混合して不燃材を調製し、不燃材１００部に対して表４に示す量の水を混合して不燃材スラリーを調製したこと以外は、実施例１と同様に行った。スラリー粘度も測定した。結果を表４に示す。 100 parts of cement a, 500 parts of Auin-containing material (2), 60 parts of waste glass foam powder α for a total of 100 parts of cement and Auin-containing material, and 60% of hollow inorganic powder for 60 parts of cement and Auin-containing material Parts were mixed to prepare a noncombustible material, and the same procedure as in Example 1 was performed except that 100 parts of noncombustible material was mixed with water in the amount shown in Table 4 to prepare a noncombustible material slurry. The slurry viscosity was also measured. The results are shown in Table 4.
セメントa１００部、アウイン含有物質（２）５００部、セメントとアウイン含有物質の合計１００部に対して廃ガラス発泡体粉末α６０部、セメントとアウイン含有物質の合計１００部に対して中空無機粉末ア６０部を混合して不燃材を調製し、表５に示す量の連続気泡率を有する発泡樹脂成形体を使用して不燃断熱材を製造したこと以外は実施例１と同様に行った。不燃材スラリーの浸透量は連続気泡率の１．３６容量倍（単位は容量）とした。結果を表５に示す。 100 parts of cement a, 500 parts of Auin-containing material (2), 60 parts of waste glass foam powder α for a total of 100 parts of cement and Auin-containing material, and 60% of hollow inorganic powder for 60 parts of cement and Auin-containing material The incombustible material was prepared by mixing the parts, and the same procedure as in Example 1 was performed except that the incombustible heat insulating material was produced using a foamed resin molded article having an open cell ratio in the amount shown in Table 5. The infiltration amount of the non-combustible material slurry was 1.36 times the open cell ratio (unit: volume). The results are shown in Table 5.
（使用材料）
発泡樹脂成形体Ａ（Ａ１〜Ａ４）：市販されている発泡ポリスチレン樹脂ビーズ（粒径２〜５ｍｍ）に市販のＥＶＡエマルジョンを１％加え混合し、金型に詰め加圧し、連続気泡を有する発泡ポリスチレン樹脂成形体とした。連続気泡率は加圧度合いを調整することにより制御した。不燃材スラリー未充填の発泡樹脂成形体の熱伝導率は０．０３４Ｗ／ｍ・Ｋ
発泡樹脂成形体Ｂ（Ｂ１〜Ｂ４）：市販されている発泡硬質ポリウレタン樹脂成形体を砕き、粒径２〜５ｍｍの粒状物に調整した。市販のＥＶＡエマルジョンを１％加え混合し、金型に詰め加圧し、連続気泡を有する発泡ポリウレタン樹脂成形体とした。連続気泡率は加圧度合いを調整することにより制御した。不燃材スラリー未充填の発泡樹脂成形体の熱伝導率は０．０２７Ｗ／ｍ・Ｋ
発泡樹脂成形体Ｃ（Ｃ１〜Ｃ４）：市販されているポリエチレンフォームを使い、発泡樹脂成形体Ｂと同様に行い、発泡樹脂成形体を得た。不燃材スラリー未充填の発泡樹脂成形体の熱伝導率は０．０３０Ｗ／ｍ・Ｋ
発泡樹脂成形体Ｄ（Ｄ１〜Ｄ４）：市販されているフェノール樹脂フォームを使い、発泡樹脂成形体Ｂと同様に行い、発泡樹脂成形体を得た。不燃材スラリー未充填の発泡樹脂成形体の熱伝導率は０．０２２Ｗ／ｍ・Ｋ
(Materials used)
Foamed resin molded product A (A1 to A4): 1% of commercially available EVA emulsion is added to and mixed with commercially available expanded polystyrene resin beads (
Foamed resin molded body B (B1 to B4): A commercially available foamed hard polyurethane resin molded body was crushed and adjusted to a granular material having a particle diameter of 2 to 5 mm. 1% of a commercially available EVA emulsion was added and mixed, filled in a mold and pressed to obtain a foamed polyurethane resin molded article having open cells. The open cell ratio was controlled by adjusting the degree of pressurization. The thermal conductivity of the foamed resin molding not filled with the non-combustible material slurry is 0.027 W / m · K.
Foamed resin molded body C (C1 to C4): Using a commercially available polyethylene foam, the same procedure as for foamed resin molded body B was carried out to obtain a foamed resin molded body. The thermal conductivity of the foamed resin molding not filled with non-combustible material slurry is 0.030 W / m · K
Foamed resin molded product D (D1 to D4): Using a commercially available phenol resin foam, the same procedure as for foamed resin molded product B was performed to obtain a foamed resin molded product. The thermal conductivity of the foamed resin molding not filled with non-combustible material slurry is 0.022 W / m · K.
（測定方法）
連続気泡率：作製した発泡樹脂成形体の上面以外にエポキシ樹脂を塗装し遮水膜を形成させた。上面より、振動を加えながら溢れるまで水を流し込み、溢れた水をふき取り、充填された水の量を測定することにより連続気泡率を算出した。
連続気泡率（体積％）＝〔（水を充填した後の樹脂成形体質量−水を充填する前の樹脂成形体質量）／樹脂成形体の体積〕×１００、但し、水を充填した後の樹脂成形体質量は、塗装に使用したエポキシ樹脂の質量を除いた質量である。
(Measuring method)
Open cell ratio: An epoxy resin was applied to the top of the produced foamed resin molded body to form a water shielding film. From the upper surface, water was poured until it overflowed while applying vibration, the excess water was wiped off, and the amount of the filled water was measured to calculate the open cell ratio.
Open cell ratio (% by volume) = [(Mass of resin molded product after filling with water−Mass of resin molded product before filling with water) / Volume of resin molded product] × 100, but after filling with water The resin molded body mass is a mass excluding the mass of the epoxy resin used for coating.
実験Ｎｏ．１−１３の不燃断熱材を、厚さ１ｃｍ×０．５ｍ角のセッコウボードに敷き詰めた断熱壁を６枚作製した。断熱壁６枚からなる箱体を作製した。箱体内部の温度を３０℃に調整し、外気温度を１０℃に低下させて箱体内部の温度変化を確認した。比較のために、不燃材スラリーを充填する前の断熱材（発泡樹脂成形体Ａ１）を敷き詰めた断熱壁からなる箱体、セッコウボードのみからなる箱体を作製し、温度変化を確認した。
その結果、実験Ｎｏ．１−１３の不燃断熱材を用いた箱体は１時間後に１２℃温度が低下した。不燃材スラリーを充填する前の断熱材の場合は１時間後に１０℃低下した。不燃材スラリーを充填しても、断熱性は低下しないことが判った。このことは、不燃材スラリーを充填しても、温度低下が不燃材スラリーを充填しない場合と同等であることから、裏付けられる。セッコウボードのみの場合は１時間後に１８℃低下し、外気温とほぼ同じ温度になり、断熱性を示さなかった。
Experiment No. Six heat-insulating walls were prepared by spreading 1-13 incombustible heat insulating material on a gypsum board having a thickness of 1 cm × 0.5 m square. A box made of six heat insulating walls was produced. The temperature inside the box was adjusted to 30 ° C., and the outside air temperature was lowered to 10 ° C. to confirm the temperature change inside the box. For comparison, a box made of a heat insulating wall and a box made of only a gypsum board were filled with a heat insulating material (foamed resin molded body A1) before filling with the noncombustible material slurry, and the temperature change was confirmed.
As a result, Experiment No. The box using the incombustible heat insulating material 1-13 had a 12 ° C. temperature drop after 1 hour. In the case of the heat insulating material before filling with the non-combustible material slurry, the temperature decreased by 10 ° C. after 1 hour. It was found that the heat insulating property does not decrease even when the nonflammable material slurry is filled. This is supported by the fact that even if the nonflammable material slurry is filled, the temperature drop is equivalent to the case where the nonflammable material slurry is not filled. In the case of the gypsum board alone, the temperature dropped by 18 ° C. after 1 hour, almost the same as the outside air temperature, and did not show heat insulation.
本発明は、良好な断熱性を維持しながら不燃性を付与でき、燃焼後も断熱材の形状を維持できるので、火災時の延焼を阻止する効果が大きくなり、防火安全性の高い建築物、車両、航空機、船舶、冷凍、冷蔵設備の建造等に寄与できる。本発明は、連続気泡を有する樹脂系断熱材に不燃性を付与し、燃焼後も崩壊や変形がなく、形状を保持できる断熱材を提供できる。 The present invention can impart incombustibility while maintaining good heat insulation, and since the shape of the heat insulating material can be maintained even after combustion, the effect of preventing the spread of fire at the time of fire is increased, and a fireproof safety building, It can contribute to the construction of vehicles, aircraft, ships, refrigeration and refrigeration equipment. INDUSTRIAL APPLICABILITY The present invention can provide a heat insulating material that imparts nonflammability to a resin-based heat insulating material having open cells and can maintain its shape without being collapsed or deformed even after combustion.
１ 減圧含浸装置（容器本体）
２ 減圧室
３ 減圧室と連続気泡を有する発泡樹脂成形体をセットする部分の仕切り板
４ 不織布
５ 発泡樹脂成形体
６ 不燃材スラリー
７ トラップ容器
８ 真空ポンプ
９ 開閉コック
1 Vacuum impregnation equipment (container body)
2
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