JP6681273B2 - Composition and non-combustible material - Google Patents
Composition and non-combustible material Download PDFInfo
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- JP6681273B2 JP6681273B2 JP2016102267A JP2016102267A JP6681273B2 JP 6681273 B2 JP6681273 B2 JP 6681273B2 JP 2016102267 A JP2016102267 A JP 2016102267A JP 2016102267 A JP2016102267 A JP 2016102267A JP 6681273 B2 JP6681273 B2 JP 6681273B2
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- 239000000463 material Substances 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title claims description 39
- 229920005989 resin Polymers 0.000 claims description 72
- 239000011347 resin Substances 0.000 claims description 72
- 239000002002 slurry Substances 0.000 claims description 61
- 239000000843 powder Substances 0.000 claims description 60
- 239000006260 foam Substances 0.000 claims description 53
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 49
- 239000000920 calcium hydroxide Substances 0.000 claims description 49
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 49
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 37
- 239000011810 insulating material Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000011521 glass Substances 0.000 claims description 31
- 239000002699 waste material Substances 0.000 claims description 30
- 238000011049 filling Methods 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 230000003405 preventing effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920005749 polyurethane resin Polymers 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 5
- 229920006248 expandable polystyrene Polymers 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 48
- 238000000034 method Methods 0.000 description 41
- 239000000047 product Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910001653 ettringite Inorganic materials 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 235000012216 bentonite Nutrition 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- -1 oxides Chemical class 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 229920006327 polystyrene foam Polymers 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 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 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
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000007931 coated granule Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 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
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 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
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- VIAVRLZATFJYHI-UHFFFAOYSA-L dialuminum oxygen(2-) sulfate Chemical compound [O-2].[Al+3].S(=O)(=O)([O-])[O-].[Al+3] VIAVRLZATFJYHI-UHFFFAOYSA-L 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 238000009422 external insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 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
- 229910052744 lithium Inorganic materials 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
- 238000002156 mixing Methods 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
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 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
- 229920002223 polystyrene 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
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Images
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- 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)
Description
本発明は、不燃材に関する。 The present invention relates to a noncombustible 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 condensation prevention and energy saving, in which the airtightness of a building is improved and dew condensation may occur due to the difference with the outside temperature. Above all, polyurethane foam and polystyrene foam are widely used because they are excellent in lightness, adhesiveness and cost. Since polyurethane foam and polystyrene foam are organic materials, they are inferior in incombustibility and often cause the spread of damage due to fire, and it is desired to take measures against them. As a solution, it is possible to use an inorganic heat insulating material such as glass wool or rock wool. However, the thermal conductivity of the inorganic heat insulating material tends to be higher than that of the organic material foam, and the heat insulating property may be inferior. Since glass wool, rock wool and the like are fibrous, there is a problem in that they have 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。 A material obtained by imparting nonflammability to a foam of an organic material is already on the market. For example, a non-combustible heat insulating board having a structure in which one or both sides of a phenol resin foam board is laminated with a non-combustible material such as aluminum foil, aluminum hydroxide paper, and gypsum-based board material can be used. However, when heat is applied due to a fire or the like, the surface facing the flame does not burn, but the heat melts the phenol resin inside, causing a problem that the board itself falls off and the fire spreads. As a technique for improving the combustion resistance of the urethane resin foam, a technique relating to a heat insulating material that forms a foam with an alkali metal carbonate, isocyanates, water and a reaction catalyst (Patent Document 1), lithium, sodium, potassium, boron , And one or more selected from the group consisting of hydroxides, oxides, carbonates, sulfates, nitrates, aluminates, borates, and phosphates of a metal selected from the group consisting of, and aluminum. There is a technique (Patent Document 2) relating to an injection material for improving the ground of a tunnel, which is a curable composition consisting of the above inorganic compound, water and isocyanates. These inventions do not describe heat insulation. In particular, 30% or more aqueous solution of alkali metal carbonate is reacted with isocyanates, and since a large amount of water is used, a large amount of unreacted water remains. Therefore, it is necessary to dry in order to use it as a heat insulating material. 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 coating a synthetic resin foam to improve combustion resistance, synthetic resin foam particles obtained by forming a coating of sepiolite and an aqueous organic binder containing a water-soluble resin as a main component and subjecting it to a surface treatment (Patent Document 3), a technique relating to a heat-insulating coated granule in which an inorganic powder and an aqueous inorganic binder containing water glass containing alkali metal silicate as a main component are further coated and dried and cured. An inorganic substance in which a silica-based inorganic substance composed of one or a mixture of two or more of calcium silicate, magnesium silicate, aluminum silicate, and aluminosilicate is filled in the cell foam structure of at least a part of the surface of the resin foam. A technique (Patent Document 4) related to a contained synthetic resin foam is disclosed. The technique using these silicates has a problem that the resin foam is melted by combustion, the binding force of the filled silicate itself is lost, and it is difficult to maintain the shape by pulverization.
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 coating a synthetic resin foam to improve combustion resistance, synthetic resin foam particles obtained by forming a coating of sepiolite and an aqueous organic binder containing a water-soluble resin as a main component and subjecting it to a surface treatment (Patent Document 3), a technique relating to a heat-insulating coated granule in which an inorganic powder and an aqueous inorganic binder containing water glass containing alkali metal silicate as a main component are further coated and dried and cured. An inorganic substance in which a silica-based inorganic substance composed of one or a mixture of two or more of calcium silicate, magnesium silicate, aluminum silicate, and aluminosilicate is filled in the cell foam structure of at least a part of the surface of the resin foam. A technique (Patent Document 4) related to a contained synthetic resin foam is disclosed. The technique using these silicates has a problem that the resin foam is melted by combustion, the binding force of the filled silicate itself is lost, and it is difficult to maintain the shape by pulverization.
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 fireproof coating material containing calcium aluminate, gypsum, and a set retarder is known (Patent Document 6). This technique is a material used for the purpose of coating the surface of a steel frame and protecting it from fire, and is different from the purpose of the present invention. Patent Document 6 does not describe an inorganic powder having a hollow structure and a waste glass foam powder.
また、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。 Further, a technology relating to a non-fired refractory heat insulating material composed of heat-resistant aggregate, lightweight aggregate, alumina-based binder, silicon carbide, and reinforcing fiber is disclosed. Shirasu balloon as the lightweight aggregate and calcium aluminum as the alumina-based binder are disclosed. Gate is described (Patent Document 7). This technology is premised on being used as a refractory heat insulating material in a high temperature range used in steelmaking and steelmaking, and is not intended for heat insulation in a normal environment.
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、硫酸アルミニウム、や水酸化カルシウムについて記載がない。
A technology relating to a non-fired refractory heat insulating material composed of heat-resistant aggregate, lightweight aggregate, alumina-based binder, silicon carbide, and reinforcing fiber is disclosed. Shirasu balloon as the lightweight aggregate and calcium aluminate as the alumina-based binder are disclosed. It is described (Patent Document 7). This technology is premised on being used as a refractory heat insulating material in a high temperature range used in steelmaking and steelmaking, and is not intended for heat insulation in a normal environment.
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 specific dry shrinkage reducing agent are contained, and the rapid hardening material is calcium aluminate alone or calcium aluminate and gypsum, and calcium aluminate 1 to 100 parts of cement A mortar composition is disclosed in which the amount is 20 parts, the gypsum is 30 to 300 parts with respect to 100 parts of calcium aluminate, and the drying shrinkage reducing agent is 0.1 to 10 parts with respect to 100 parts of cement. As the aggregate, there is described a lightweight aggregate produced by firing ceramic balloons, shirasu balloons, and waste glass as raw materials (Patent Document 8). However, there is no description about the use of specific amounts of the inorganic powder having a hollow structure and the waste glass foam powder, and the use as a non-combustible material.
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、更に、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 a substance containing hain, CaO raw material, CaSO 4 raw material, and at least one raw material selected from the group consisting of Al 2 O 3 raw material, Fe 2 O 3 raw material, and SiO 2 raw material. Was obtained by heat-treating a mixture of, and in a total of 100 parts of free lime, hydraulic compound and anhydrous gypsum, free lime 10-70 parts, hydraulic compound 10-50 parts, anhydrous gypsum 10-60 parts A technique relating to an early demolding material containing a heat-treated product contained in a proportion is disclosed, and there is a description of using awin as a hydraulic compound (Patent Document 9). However, there is no description about the use of specific amounts of the inorganic powder having a hollow structure and the waste glass foam powder, and the use as a non-combustible material.
更に、エトリンガイトを生成させる方法としては、硫酸アルミニウムと水酸化カルシウムからエトリンガイトを合成する方法（特許文献１０）、カルシウムアルミネートやアウイン含有物質の水和反応以外の技術を用いる各種合成方法（特許文献１１、特許文献１２）が提案されている。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、連続気泡を有する樹脂発泡体の不燃材として使用することについて記載はない。 Furthermore, as a method for producing ettringite, a method for synthesizing ettringite from aluminum sulfate and calcium hydroxide (Patent Document 10), various synthetic methods using techniques other than hydration reaction of calcium aluminate and a hain-containing substance (Patent Document 10) 11, Patent Document 12) have been proposed. However, there is no description about the use of a specific amount of the inorganic powder having a hollow structure and the waste glass foam powder, and the use as an incombustible material of the resin foam having open cells.
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 nonflammability without impairing heat insulation.
即ち、本発明は、（１）硫酸アルミニウム、（２）水酸化カルシウム、（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、（２）の使用量が（１）１００質量部に対して１００〜２００部であり、（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、（４）の軟化点が８００℃以下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８００〜３０００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) aluminum sulfate, (2) calcium hydroxide, (3) inorganic powder having a hollow structure having an average particle size of 20 to 60 μm, and (4) waste glass having an average particle size of 20 to 130 μm. A composition containing foam powder, wherein the amount of (2) used is 100 to 200 parts per 100 parts by weight of (1), and the amount of (3) used is the sum of (1) and (2). The composition is 20 to 150 parts by mass with respect to 100 parts by mass, and the amount of (4) used is 20 to 100 parts by mass with respect to 100 parts by mass of the total of (1) and (2), and (3 ) Is the composition which is at least one member of the group consisting of Shirasu balloon and fly ash balloon, and is the composition having a softening point of (4) of 800 ° C. or lower, and (5) a material separation inhibitor The composition containing the composition, which is used for filling a resin molded product. The composition is a slurry containing the composition and water, wherein the amount of water used is 800 to 3000 parts by mass relative to 100 parts by mass of the composition, and the slurry is applied to a resin molding. The resin molded body is a filled resin molded body, wherein the resin molded body is at least one member selected from the group consisting of foamed polyurethane resin, foamed polystyrene resin, foamed polyolefin resin, and foamed phenol resin. Of the resin-molded filler having open cells, the resin-molded filler having an open-cell rate of 25 to 70% by volume, the resin-molded filler obtained by filling the resin-molded body with the slurry. It is a manufacturing method, a nonflammable material made of the composition, and a nonflammable heat insulating material made of the resin molding 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 heat insulation.
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。 Hereinafter, embodiments of the present invention will be described. Units refer to mass units unless otherwise specified.
本発明の（１）硫酸アルミニウムとは、一般的に市販されているものが使用でき、粉末が使用でき、無水物及び結晶水を有する水和物が使用できる。液体硫酸アルミニウムとして市販されているものも使用できる。粉末状硫酸アルミニウムの粒度は、特に限定するものではないが反応性を考慮すると１０メッシュを１００％通過する粒度であればよい。 As (1) aluminum sulfate of the present invention, generally commercially available products can be used, powder can be used, and anhydrate and hydrate having water of crystallization can be used. What is marketed as liquid aluminum sulfate can also be used. The particle size of the powdery aluminum sulfate is not particularly limited, but in view of reactivity, it may be any particle size that allows 100% of the particles to pass through 10 mesh.
本発明の（２）水酸化カルシウムとは、特に限定されるものではないが、生石灰（主成分は酸化カルシウムＣａＯ）を消化させたものでよく、多少の不純物を含有していても使用できる。焼成ドロマイトや遊離石灰（ｆ−ＣａＯ）を含む市販の膨張材を消化させたものや、カルシウムカーバイドからアセチレンを発生する時に生成する副生消石灰も使用できる。 The (2) calcium hydroxide of the present invention is not particularly limited, but it may be one obtained by digesting quicklime (main component is calcium oxide CaO), and can be used even if it contains some impurities. A commercially available expansive material containing calcined dolomite or free lime (f-CaO), or by-product slaked lime produced when acetylene is generated from calcium carbide can also be used.
本発明の水酸化カルシウムの粉末度は、ブレーン比表面積で３０００ｃｍ２／ｇ以上でよいが、細かい方がより反応が促進するので、４０００ｃｍ２／ｇ以上がより好ましく、５０００ｃｍ２／ｇ以上が最も好ましい。 The powdery degree of the calcium hydroxide of the present invention may be 3000 cm 2 / g or more in terms of Blaine specific surface area, but finer particles promote the reaction more, so 4000 cm 2 / g or more is more preferable, and 5000 cm 2 / g or more is most preferable. preferable.
本発明の水酸化カルシウムの使用量は、硫酸アルミニウム（固形分）１００部に対して１００〜２００部が好ましく、１２０〜１５０部がより好ましい。１００部未満では不燃性付与に効率的な量のエトリンガイトの生成が期待できない場合があり、２００部を超えると未反応の水酸化カルシウム量が増え連続気泡に充填した成形体密度が増加し、断熱性が小さい場合がある。 The amount of calcium hydroxide used in the present invention is preferably 100 to 200 parts, and more preferably 120 to 150 parts, per 100 parts of aluminum sulfate (solid content). If it is less than 100 parts, it may not be possible to expect the formation of an effective amount of ettringite for imparting incombustibility, and if it exceeds 200 parts, the amount of unreacted calcium hydroxide increases and the density of the molded body filled in the open cells increases, resulting in heat insulation. There are cases where the sex is small.
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 hollow inorganic powder), a foam made by heating a volcanic deposit represented by Shirasu balloon at a high temperature, a thermal power plant And fly ash balloons generated from the above, and inorganic powder having a balloon structure obtained by firing obsidian and pearlite. Among these, at least one member selected from the group consisting of Shirasu balloon and fly ash balloon is preferable because it has a low density and does not easily impair the heat insulating property when filled in the open cells of the 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 become too fine and the viscosity when made into a slurry becomes high, and the filling property at the time of impregnation may be reduced. 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、硫酸アルミニウム（固形分）と水酸化カルシウムの合計１００部に対して２０〜１５０部が好ましく、３０〜１２０部がより好ましい。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。 The use amount of the inorganic powder having a hollow structure of the present invention is preferably 20 to 150 parts, and more preferably 30 to 120 parts, based on 100 parts of the total amount of aluminum sulfate (solid content) and calcium hydroxide. If it is less than 20 parts, it may be difficult to maintain the shape after burning, and if it exceeds 150 parts, the incombustibility may decrease.
本発明の（４）廃ガラス発泡体粉末とは、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 crushing waste such as a glass bottle and then firing it to adjust 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 become too fine and the viscosity when made into a slurry becomes high, and it may be difficult to maintain the shape after combustion. If it exceeds 130 μm, the heat insulating property may deteriorate.
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 that the shape retention after combustion is improved. If the temperature exceeds 800 ° C, the fusion effect to the inorganic powder or the product decomposed by combustion may not be sufficiently exhibited. The softening point is obtained, for example, according to JIS R3103-1.
本発明の廃ガラス発泡体粉末の使用量は、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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。 The used amount of the waste glass foam powder of the present invention is preferably 20 to 100 parts, and more preferably 30 to 80 parts, based on 100 parts of the total amount of aluminum sulfate (solid content) and calcium hydroxide. If it is less than 20 parts, it may be difficult to sufficiently maintain the shape after burning, and if it exceeds 100 parts, the nonflammability may decrease.
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、硫酸アルミニウム、水酸化カルシウム、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 preventing agent of the present invention prevents material separation when aluminum sulfate, calcium hydroxide, inorganic powder having a hollow structure and waste glass foam powder is added with water to form a slurry, thereby improving filling property. The one that exerts the effect of Examples of the material separation preventing agent include organic substances, bentonites, colloidal silica dispersions and the like. Examples of the organic substance include cellulose ethers such as methyl cellulose and methyl ethyl cellulose, carboxymethyl cellulose or alkali metal salts thereof, polyacrylamides, polyvinylpyrrolidone and polyvinyl alcohol. Among these, at least one selected from the group consisting of bentonites and colloidal silica dispersions is preferable because it is difficult to inhibit nonflammability. In particular, the colloidal silica dispersion liquid is preferable because it imparts viscosity by an appropriate gelling action to impart a material separation preventing effect and also exhibits an effect of increasing nonflammability.
本発明の材料分離防止剤の使用量は、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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、硫酸アルミニウム（固形分）と水酸化カルシウムの合計１００部に対して、固形分換算で、０．５〜５部が好ましい。 The material separation preventing agent of the present invention is preferably used in an amount of 0.05 to 10 parts in terms of solid content based on 100 parts of aluminum sulfate (solid content) and calcium hydroxide in total. In the case of an organic substance, 0.05 to 0.5 parts in terms of solid content is preferable with respect to a total of 100 parts of aluminum sulfate (solid content) and calcium hydroxide. In the case of bentonites, it is preferably 1 to 10 parts in terms of solid content with respect to a total of 100 parts of aluminum sulfate (solid content) and calcium hydroxide. In the case of colloidal silica dispersion, 0.5 to 5 parts in terms of solid content is preferable with respect to a total of 100 parts of aluminum sulfate (solid content) and calcium hydroxide.
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８００〜３０００部が好ましく、１０００〜２０００部がより好ましい。８００部未満では連続気泡への充填性が低下する場合があり、３０００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, water is mixed to prepare a slurry. When preparing the slurry, the amount of water is preferably 800 to 3000 parts, more preferably 1000 to 2000 parts, relative to 100 parts of the composition. If it is less than 800 parts, the filling property into the open cells may be lowered, and if it exceeds 3000 parts, the strength of the hydrate formed in the open cells may be lowered, and the filling property into the open cells may be lowered. 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). When (5) is contained, 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).
本発明におけるスラリーは、硫酸アルミニウム、水酸化カルシウム、平均粒子径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からなる混合物を所定量の水でスラリー状にすればよい。急激な増粘による攪拌時の負荷を抑制し、急激な反応を抑制する点で、＜１＞予め、硫酸アルミニウム、平均粒子径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からなる混合物をスラリー状に調製し、そのスラリーに粉状の水酸化カルシウムを徐々に加える方法や、＜２＞水に、１０〜５０％の水酸化カルシウムを分散させた水酸化カルシウムスラリーを、徐々に加えて調製する方法を使用できる。効率的にエトリンガイトを生成する点で、＜３＞５０〜８０℃に加温されたスラリーに、粉状の水酸化カルシウムを徐々に加える方法や、＜４＞水に１０〜５０％の水酸化カルシウムを分散させた水酸化カルシウムスラリーを、徐々に加え、加え終わってから１５〜６０分間攪拌して調製する方法を使用できる。 The slurry in the present invention is a slurry of a mixture of aluminum sulfate, calcium hydroxide, 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 in a predetermined amount of water. Just make a shape. <1> Aluminum sulfate, an inorganic powder having a hollow structure with an average particle diameter of 20 to 60 μm, and an average particle diameter of 20 to 20 in advance in order to suppress the load at the time of stirring due to sudden thickening and suppress the rapid reaction. A method of preparing a mixture of 130 μm waste glass foam powder into a slurry and gradually adding powdery calcium hydroxide to the slurry, or <2> dispersing 10 to 50% of calcium hydroxide in water It is possible to use a method of gradually adding the calcium hydroxide slurry. From the viewpoint of efficiently producing ettringite, <3> a method of gradually adding powdery calcium hydroxide to a slurry heated to 50 to 80 ° C., or <4> water to 10 to 50% of hydroxide A method of gradually adding a calcium hydroxide slurry in which calcium is dispersed and stirring for 15 to 60 minutes after completion of the addition can be used.
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 100 to 700 mPa · s is preferable, and 300 to 700 mPa · s is more preferable, in that the variation in the density of the resin molded body after filling is small. 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 product of the present invention is a resin molded product having bubbles capable of penetrating a liquid substance such as a slurry. There is no particular limitation as long as it is a resin molded product having open cells. Examples of the resin include expanded polyvinyl alcohol resin, expanded polyurethane resin, expanded polystyrene resin, expanded polyolefin resin such as polyethylene foam, and expanded phenol resin such as phenol resin foam. These foamed resins form foams with closed cells and are resin foamed granules having a diameter of several mm. As the resin molded body, these resin foam granules are packed in a mold and pressed so that open cells are generated. Regarding the polystyrene resin, it is possible to manufacture a resin molded product having open cells in accordance with the method for manufacturing a polystyrene foam using the bead method. Among these, at least one selected from the group consisting of foamed polyurethane resin, foamed polystyrene resin, foamed polyolefin resin, and foamed phenol resin is preferable because it is often used as a heat insulating material. One or more of the group consisting of is preferred.
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 molded product of the present invention is preferably 25 to 70% by volume. If it is less than 25% by volume, it may be difficult to uniformly permeate the slurry, and if it exceeds 70% by volume, the density may increase and the heat insulating property may be impaired. The following methods may be mentioned as a method of infiltrating the slurry. In the case of a resin molded body having an open cell rate of less than 50% by volume, a method of infiltrating the slurry by a press-fitting with compressed air or a suction by depressurizing with a vacuum pump is preferable. In the case of a resin molded product having an open cell ratio of 50% by volume or more, a method of allowing the resin molded article to permeate into the cells under normal pressure naturally or while applying vibration is preferable.
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 the slurry of the present invention that penetrates is preferably 0.8 to 1.5 times the volume of the open cell ratio (volume%). If it is less than 0.8 times by volume, sufficient incombustibility may not be imparted, and if it exceeds 1.5 times by volume, the density of the resin molding filler may become too large and the heat insulating property may be deteriorated.
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 into the open cells, for example, a hydration product is generated by a hydration reaction, and the hydration product is filled and solidified in the open cells. When the slurry is dried, free water evaporates, so that pores are formed in the resin molding filling, which contributes to the improvement of heat insulation. Hydration products are ettringite and the like. Since ettringite has a large amount of water as crystallization water in the molecule, it gradually dehydrates from about 100 ° C. by heating, exhibits a fire extinguishing action, and imparts nonflammability to the resin molding filler. By containing an inorganic powder having a hollow structure having an average particle diameter of 20 to 60 μm and a waste glass foam powder having an average particle diameter of 20 to 130 μm, shape retention can be obtained, for example.
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 method for curing the resin-molded filling body after filling the slurry of the present invention into continuous cells is not particularly limited, but after filling, it is cured at room temperature for about 3 days or further so as not to evaporate water. In order to shorten the time, heating and curing may be performed at a temperature of 50 ° C. or lower.
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, it is also possible to dispose a reinforcing material such as a nonwoven fabric or a fiber sheet on one side or both sides of the noncombustible 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 noncombustible heat insulating material of the present invention is not particularly limited, but it is generally preferable to make it into 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 decrease.
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 non-combustible heat insulating material of the present invention is adjusted within a range that does not impair 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。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。 The composition of the present invention can be used as a noncombustible material. The slurry of the present invention can be used as a noncombustible material slurry. The resin molded product obtained by filling the open cell with the slurry of the present invention can be used as a noncombustible heat insulating material. 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 external insulation is performed on a wall, a board-shaped non-combustible heat insulating material is temporarily fixed to a pillar with nails, etc., and when airtightness is required, air-tight tape is applied to the joint of the board-shaped non-combustible heat insulating material. Paste. Then, a moisture-permeable waterproof sheet is attached to the surface, and the furring is constructed with special screws. When the wall is used for the filling insulation, the board-shaped non-combustible heat insulating material is cut according to the size between the pillars, and the non-combustible heat insulating material is fitted between the pillars 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, detailed description will be given based on examples. Unless otherwise specified, it was carried out at room temperature (23 ° C).
（不燃材スラリーの調製）
硫酸アルミニウム１００部、表１に示す量の水酸化カルシウム、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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）、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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１２００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３０分間攪拌し、不燃材スラリーを調製した。
(Preparation of noncombustible material slurry)
100 parts of aluminum sulfate, the amount of calcium hydroxide shown in Table 1, and the amount of hollow inorganic powder shown in Table 1 with respect to a total of 100 parts of aluminum sulfate (solid content) and calcium hydroxide (hereinafter sometimes referred to as inorganic powder. ), Aluminum sulfate (solid content) and 100 parts of calcium hydroxide in total, and the amount of waste glass foam powder shown in Table 1 was mixed to prepare a noncombustible material. Water was added little by little with stirring so that the amount was 1200 parts with respect to 100 parts of the non-combustible material. After all the water was added, the mixture was stirred for 30 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 heat insulating material)
The foamed resin molding A1 having open cells (size: length 20 cm × width 20 cm × thickness 5 cm) was set in the vacuum impregnation apparatus shown in FIG. On the upper surface of the foamed resin molded body, 950 cm 3 of non-combustible material slurry (1.36 times the volume of the open cell ratio, the unit is volume) was poured on the upper surface of the foamed resin molded body. The decompression chamber was decompressed by gradually opening the open / close cock from the lower surface side of the foamed resin molded body that was set, and the incombustible material slurry was permeated into the open cells to produce an incombustible heat insulating material. After the infiltration, the non-combustible heat insulating material was removed from the vacuum impregnating apparatus and dried at room temperature for 3 days, and the non-combustibility, uniformity, density, shape retention and thermal conductivity were evaluated. 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。
(Reduced pressure impregnation device)
The vacuum impregnation device is shown in FIG. The reduced pressure impregnation device (container body) 1 includes a reduced
（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
硫酸アルミニウム：大明化学工業社製、粉末状硫酸アルミニウム 酸化アルミニウム含有量１７．５％、１０メッシュを１００％通過
水酸化カルシウム：上田石灰製造社製、消石灰、ブレーン比表面積５０００ｃｍ２／ｇ以上
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
(Material used)
Foamed resin molded product A1: 1% of EVA emulsion is added to commercially available polystyrene foamed beads (diameter: 2 to 5 mm), mixed so as to be evenly coated on the bead surface, packed in a mold and pressed. The body was made. Open cell rate 35% by volume, thermal conductivity 0.034 W / mK
Aluminum sulphate: Daimei Chemical Industry Co., Ltd., powdered aluminum sulphate Aluminum oxide content 17.5%, 100% through 10 mesh Calcium hydroxide: Ueda lime manufacturing, slaked lime, Blaine specific surface area 5000 cm 2 / g or more Hollow inorganic Powder a: Silas balloon manufactured by Axis Chemicals, trade name: MSB-301, average particle size 50 μm
Hollow inorganic powder B: Silas balloon manufactured by Axis Chemicals, trade name: ISM-F015,
Hollow inorganic powder C: Silas balloon manufactured by Axis Chemicals, trade name: MSB-5011, average particle size 70 μm
Waste glass foam powder α: DENNERT POROVER GMBH waste glass foam powder, trade name: Poraver (0.04-0.125 mm particle size product), softening point 700-750 ° C., average particle size 90 μm
Waste glass foam powder β: A particle size-adjusted product obtained by crushing 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 POROVER GMBH, trade name: Poraver (0.1-0.3 mm particle size product) particle size adjusted product, softening point 700-750 ° C., average particle size 140 μm
Glass powder θ: Asahi Glass Co., Ltd., trade name: AFS1717, average particle diameter 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 type particle size distribution meter. The model used was LA-920 (Horiba Seisakusho).
Uniformity: The non-combustible heat insulating material taken out from the device is divided into four parts in the vertical direction and the horizontal direction, and the divided non-combustible heat insulating material block is further divided into two parts in the thickness direction. I asked. The difference between the minimum value and the maximum value of the obtained density was obtained. The smaller the difference, the more the impregnation was evaluated.
Density: The average value of the densities of 8 points calculated to obtain the uniformity was calculated.
Nonflammability: Evaluated in accordance with a heat generation test by 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 body. For example, when the total calorific value when the heating time is 20 minutes using this test body is 8 MJ / m 2 or less, the nonflammable effect is large.
Thermal conductivity: Measured by a rapid thermal conductivity meter (box type probe method) using a test body of 10 cm in length × 5 cm in width × 5 cm in thickness.
Shape retention: The specimen after the nonflammability test was observed, and when there was no crack, collapse, or shrinkage, it was marked with ◯, and when there was any crack, collapse, or shrinkage, it was marked with x.
硫酸アルミニウム１００部、水酸化カルシウム１３０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計１００部に対して廃ガラス発泡体粉末α６０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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。 Aluminum sulfate 100 parts, calcium hydroxide 130 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts, waste glass foam powder α 60 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts On the other hand, the same procedure as in Example 1 was performed except that the amount of the hollow inorganic powder D shown in Table 2 was mixed to prepare a noncombustible material slurry. 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
(Material used)
Inorganic powder d: Tokai Kogyo Co., Ltd. fly ash balloon classified product, average particle diameter 45 μm
硫酸アルミニウム１００部、水酸化カルシウム１３０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計１００部に対して廃ガラス発泡体粉末α６０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計１００部に対して中空無機粉末ア６０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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。 Aluminum sulfate 100 parts, calcium hydroxide 130 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts, waste glass foam powder α 60 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts On the other hand, the non-combustible slurry was prepared by mixing 60 parts of the hollow inorganic powder a, aluminum sulfate (solid content) and 100 parts of total calcium hydroxide with the material separation inhibitor in an amount shown in Table 3 in terms of solid content. The same procedure as in Example 1 was carried out except the above. The slurry viscosity was also measured. Table 3 shows the results.
（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
(Material used)
Material separation preventing agent (1): methyl cellulose manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SM4000
Material separation inhibitor (2): bentonite manufactured by Kunimine Industry 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.
硫酸アルミニウム１００部、水酸化カルシウム１３０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計１００部に対して廃ガラス発泡体粉末α６０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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。 Aluminum sulfate 100 parts, calcium hydroxide 130 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts, waste glass foam powder α 60 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts Example 1 except that 60 parts of the hollow inorganic powder were mixed to prepare an incombustible material, and 100 parts of the incombustible material was mixed with the amount of water shown in Table 4 to prepare an incombustible material slurry. I went the same way. The slurry viscosity was also measured. The results are shown in Table 4.
硫酸アルミニウム１００部、硫酸アルミニウム（固形分）と後添加する水酸化カルシウムの合計１００部に対して廃ガラス発泡体粉末α６０部、硫酸アルミニウム（固形分）と後添加する水酸化カルシウムの合計１００部に対して中空無機粉末ア６０部を含有した混合物を調製した。硫酸アルミニウム、廃ガラス発泡体粉末、中空無機粉末、後添加する水酸化カルシウムの合計１００部に対して１２００部となる水に、その混合物を徐々に加えてスラリーを調製した。そのスラリーを攪拌しながら、硫酸アルミニウム１００部に対して水酸化カルシウムが１３０部となるように添加し、不燃材スラリーを調製した。連続気泡を有する発泡樹脂成形体を作製した。水酸化カルシウムの添加条件を表５に示した。上記以外は、実施例１と同様に行った。結果を表５に示す。 100 parts of aluminum sulfate 100 parts, aluminum sulfate (solid content) and 100 parts of post-added calcium hydroxide to 100 parts of waste glass foam powder α, aluminum sulfate (solid content) and 100 parts of post-added calcium hydroxide On the other hand, a mixture containing 60 parts of hollow inorganic powder A was prepared. A slurry was prepared by gradually adding the mixture to water, which was 1200 parts with respect to 100 parts in total of aluminum sulfate, waste glass foam powder, hollow inorganic powder, and calcium hydroxide to be added later. While stirring the slurry, calcium hydroxide was added to 130 parts with respect to 100 parts of aluminum sulfate to prepare a noncombustible material slurry. A foamed resin molding having open cells was produced. The conditions for adding calcium hydroxide are shown in Table 5. Except for the above, the same procedure as in Example 1 was carried out. Table 5 shows the results.
（水酸化カルシウムの添加条件）
条件１：実施例１と同様に添加した。
条件２：粉末状の水酸化カルシウムを徐々にスラリーへ添加えた。
条件３：濃度２０％の水酸化カルシウムスラリーを調製し、スラリーへ添加した（水酸化カルシウムスラリー調製で使用した水の量は、硫酸アルミニウム、廃ガラス発泡体粉末、中空無機粉末からなる混合物に加えた水量１２００部から差し引く）
(Calcium hydroxide addition conditions)
Condition 1: The same as in Example 1 was added.
Condition 2: Powdered calcium hydroxide was gradually added to the slurry.
Condition 3: A calcium hydroxide slurry having a concentration of 20% was prepared and added to the slurry (the amount of water used in the calcium hydroxide slurry preparation was added to a mixture of aluminum sulfate, waste glass foam powder and hollow inorganic powder). Deducted from 1,200 parts of water)
使用する水の温度（水温）を６５℃にしたこと以外は、実施例５と同様に行った。結果を表６に示す。 The same procedure as in Example 5 was performed except that the temperature of water used (water temperature) was set to 65 ° C. Table 6 shows the results.
硫酸アルミニウム１００部、水酸化カルシウム１３０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計１００部に対して廃ガラス発泡体粉末α６０部、硫酸アルミニウム（固形分）と水酸化カルシウムの合計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７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７に示す。 Aluminum sulfate 100 parts, calcium hydroxide 130 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts, waste glass foam powder α 60 parts, aluminum sulfate (solid content) and calcium hydroxide total 100 parts Example 1 except that 60 parts of the hollow inorganic powder were mixed to prepare an incombustible material, and the incombustible heat insulating material was produced using the foamed resin molding having the amount of open cells shown in Table 7. I went the same way. The permeation amount of the non-combustible material slurry was 1.36 times the open cell ratio (unit: volume). The results are shown in Table 7.
（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
(Material used)
Foamed resin molded product A (A1 to A4): 1% of commercially available EVA emulsion is added to commercially available foamed polystyrene resin beads (
Foamed resin molded product B (B1 to B4): A commercially available foamed rigid polyurethane resin molded product 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, mixed, filled in a mold and pressurized to obtain a foamed polyurethane resin molding having open cells. The open cell rate was controlled by adjusting the degree of pressurization. The thermal conductivity of the foamed resin molding not filled with non-combustible material slurry is 0.027 W / mK
Foamed resin molded product C (C1 to C4): A commercially available polyethylene foam was used, and the same procedure as the 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 the non-combustible material slurry is 0.030 W / mK
Foamed resin molded body D (D1 to D4): A commercially available phenol resin foam was used, and the same procedure as the foamed resin molded body B was performed to obtain a foamed resin molded body. The thermal conductivity of the foamed resin molding not filled with the non-combustible material slurry is 0.022 W / mK
（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 rate: An epoxy resin was applied on the surface other than the top surface of the produced foamed resin molded article to form a water-blocking film. The open cell ratio was calculated by pouring water from the top surface while applying vibration until it overflowed, wiping off the overflowed water, and measuring the amount of filled water.
Open cell rate (volume%) = [(mass of resin molded body after filling water-mass of resin molded body before filling water) / volume of resin molded body] × 100, but after filling with water The mass of the resin molded body is the 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１０．５℃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 the non-combustible heat insulating material 1-13 on a gypsum board of 1 cm × 0.5 m square. A box consisting of 6 heat insulating walls was produced. The temperature inside the box was checked by adjusting the temperature inside the box to 30 ° C and lowering the outside air temperature to 10 ° C. For comparison, a box made of a heat insulating wall filled with a heat insulating material (foamed resin molded article A1) before being filled with the non-combustible material slurry and a box made of only gypsum board were prepared and the temperature change was confirmed.
As a result, the experiment No. The box body using the non-combustible heat insulating material of 1-13 had a temperature drop of 10.5 ° C. after 1 hour. In the case of the heat insulating material before being filled with the noncombustible material slurry, the temperature dropped by 10 ° C. after 1 hour. It was found that the heat insulating property does not decrease even if the non-combustible material slurry is filled. This is supported by the fact that even if the noncombustible material slurry is filled, the temperature drop is equivalent to the case where the noncombustible material slurry is not filled. In the case of only the gypsum board, the temperature decreased by 18 ° C. after 1 hour, the temperature became almost the same as the outside temperature, and the heat insulating property was not exhibited.
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 non-combustibility while maintaining good heat insulation, and can maintain the shape of the heat insulating material even after combustion, so that the effect of preventing the spread of fire at the time of the fire becomes large, and a building with high fire safety, It can contribute to the construction of vehicles, aircraft, ships, refrigeration, and refrigeration facilities. INDUSTRIAL APPLICABILITY The present invention can provide a heat insulating material that imparts incombustibility to a resin-based heat insulating material having open cells, is not collapsed or deformed even after burning, and can retain its shape.
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 device (container body)
2
Claims (13)
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