JPH10237208A - Expandable phenolic resin composition - Google Patents
Expandable phenolic resin compositionInfo
- Publication number
- JPH10237208A JPH10237208A JP3814197A JP3814197A JPH10237208A JP H10237208 A JPH10237208 A JP H10237208A JP 3814197 A JP3814197 A JP 3814197A JP 3814197 A JP3814197 A JP 3814197A JP H10237208 A JPH10237208 A JP H10237208A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- lower alcohol
- phenolic resin
- ketone
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 14
- 229920003986 novolac Polymers 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 150000002576 ketones Chemical class 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004604 Blowing Agent Substances 0.000 abstract description 5
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 4
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 abstract description 3
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 3
- 239000004312 hexamethylene tetramine Substances 0.000 abstract description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 abstract description 3
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000005187 foaming Methods 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012790 confirmation Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000005453 ketone based solvent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- -1 alkylphenols Chemical compound 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、繊維等で強化され
た断熱材、緩衝材、パネル、ボード等に有用な発泡性フ
ェノール樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamable phenolic resin composition useful for heat insulating materials, cushioning materials, panels, boards and the like reinforced with fibers and the like.
【０００２】[0002]
【従来の技術】従来、断熱材、緩衝材、パネル等はガラ
スウール、ロックウール、フェノール、ウレタン発泡体
等が使用されている。しかしながら、ガラスウール、ロ
ックウール等は、加工性、可とう性に優れるが強度が劣
る。フェノール発泡体では強度はある程度向上するが、
脆さがある。脆さの改善、機械的強度の向上のため、補
強用繊維を用いることが考えられている。フェノール発
泡体中に各種補強用繊維を混在させる方法としては、特
公昭４７−８９４５号公報では粉末状発泡性樹脂組成物
を多数積層された綿状シート状間に散布された後これら
を熱ロールや熱プレス等で粉末状発泡樹脂が溶融しうる
温度で予備成形して各綿状シート内部に樹脂を含浸させ
た後、この積層成形体を加熱発泡硬化させる方法が提案
されている。しかしながら、この方法では発泡硬化が起
こらず、樹脂が溶融する低い温度で含浸させるが許容温
度範囲が狭く、また加熱温度が低いとは言え加熱により
部分的に発泡硬化が起こったり、粉末状樹脂を散布する
ため発泡ムラが起こる問題等がある。2. Description of the Related Art Conventionally, glass wool, rock wool, phenol, urethane foam and the like have been used for heat insulating materials, cushioning materials, panels and the like. However, glass wool, rock wool and the like are excellent in workability and flexibility, but inferior in strength. Although phenol foam improves strength to some extent,
There is brittleness. In order to improve brittleness and mechanical strength, use of reinforcing fibers has been considered. As a method of mixing various reinforcing fibers in a phenol foam, Japanese Patent Publication No. 47-8945 discloses a method in which a powdery foamable resin composition is sprayed between a plurality of laminated cotton-like sheets, and then heated rolls are formed. There has been proposed a method in which a preform is formed at a temperature at which the powdered foamed resin can be melted by hot pressing or the like, the resin is impregnated inside each cotton sheet, and the laminated molded body is foamed and cured by heating. However, in this method, foaming hardening does not occur, and impregnation is performed at a low temperature at which the resin melts, but the allowable temperature range is narrow.Also, although the heating temperature is low, foaming hardening occurs partially by heating, There is a problem of foaming unevenness due to spraying.
【０００３】また、特開昭６１−２３３５２６号公報、
特開昭６１−２３３５２７号公報では綿状物質に予め粉
末状樹脂が相溶し得る液状物質を含浸させた方法が採ら
れ、粉末状樹脂の部分発泡硬化が起こることは改良され
たが、整泡剤や可塑剤等の添加が困難であり、更に発泡
ムラが起こる等の問題がある。発泡ムラ等の問題を解決
するため特開平２−１７３１３１公報では、ノボラック
型フェノール樹脂、硬化剤、整泡剤等をノボラックが可
溶な溶剤に溶解した組成物をシート状の不織布に含浸さ
せ用いる方法、特公平５−７５７７９公報ではノボラッ
ク型フェノール樹脂及びレゾール型フェノール樹脂の混
合フェノール樹脂、発泡剤、整泡剤を混合樹脂が可溶な
溶剤に溶解した組成物をシート状の不織布に含浸する方
法が提案されている。しかしながら、シート状の不織布
に含浸する際、樹脂分を調製し含浸場合、単一溶剤使用
では発泡剤、硬化剤及び混合フェノール樹脂のレゾール
型フェノール樹脂の溶解性が悪くなり沈殿物が発生し懸
濁液となり発泡ムラの問題が考えられる。また、混合フ
ェノール樹脂の場合、レゾール型フェノール樹脂のみが
硬化剤として働き、成形体の強度に問題が考えられる。[0003] Also, Japanese Patent Application Laid-Open No. 61-233526,
JP-A-61-233527 adopts a method in which a cotton-like substance is previously impregnated with a liquid substance in which a powdery resin is compatible, and it is improved that partial foaming hardening of the powdery resin occurs. It is difficult to add a foaming agent, a plasticizer, and the like, and there are problems such as uneven foaming. In order to solve the problems such as uneven foaming, JP-A-2-173131 discloses a sheet-shaped nonwoven fabric which is impregnated with a composition obtained by dissolving a novolak-type phenol resin, a curing agent, a foam stabilizer and the like in a solvent in which novolak is soluble. In Japanese Patent Publication No. 5-75779, a sheet-shaped nonwoven fabric is impregnated with a composition in which a mixed phenolic resin of a novolak type phenol resin and a resol type phenol resin, a foaming agent, and a foam stabilizer are dissolved in a solvent in which the mixed resin is soluble. A method has been proposed. However, when impregnating a sheet-shaped nonwoven fabric with a resin component and impregnating the resin, if a single solvent is used, the solubility of the foaming agent, the curing agent, and the resol-type phenolic resin of the mixed phenolic resin becomes poor, and precipitates are generated. It becomes a turbid liquid and the problem of uneven foaming is considered. In the case of a mixed phenolic resin, only the resole type phenolic resin acts as a curing agent, which may cause a problem in the strength of the molded article.
【０００４】[0004]
【発明が解決しようとする課題】本発明者の目的とする
ところは、発泡ムラが起こらず均一な成形体が得られ、
繊維等への含浸性が良く、溶剤にて樹脂分調製が容易に
出来、混合溶液の組成物の沈殿が無く安定である発泡性
フェノール樹脂組成物を提供するにある。SUMMARY OF THE INVENTION An object of the present inventors is to obtain a uniform molded article without uneven foaming.
An object of the present invention is to provide a foamable phenol resin composition which has good impregnation into fibers and the like, can easily prepare a resin component with a solvent, does not precipitate the composition of the mixed solution and is stable.
【０００５】[0005]
【問題を解決するための手段】本発明は、上記のような
課題をを解決するために鋭意研究した結果、ノボラック
型フェノール樹脂、硬化剤、有機分解型発泡剤及び整泡
剤を低級アルコール類及びケトン系溶剤の混合溶媒に溶
解させることにより、発泡ムラが起こらず均一な成形体
が得られ、繊維等への含浸性が良く、溶剤にて樹脂分調
製が容易に出来、混合溶液の組成物の沈殿が無く安定で
ある発泡性フェノール樹脂組成物が得られることを見出
した。Means for Solving the Problems The present invention has been intensively studied to solve the above-mentioned problems, and as a result, a novolak type phenol resin, a curing agent, an organic decomposition type foaming agent and a foam stabilizer have been added to lower alcohols. And a mixed solvent of a ketone-based solvent and a uniform molded body without foaming unevenness, good impregnation into fibers, etc., easy preparation of the resin component in the solvent, and composition of the mixed solution. It has been found that a foamable phenolic resin composition which is stable without any precipitates can be obtained.
【０００６】すなわち、低級アルコールとケトン系溶剤
との混合溶媒を用いることで、低級アルコール類にノボ
ラック型フェノール樹脂、硬化剤が溶解し、また、ケト
ン系溶剤にフェノール樹脂及び有機分解型発泡剤が溶解
し、ノボラック型フェノール樹脂が相溶化剤的役割とな
り、混合溶媒中で沈殿物のない安定な組成物を形成する
事が確認され、本組成物を使用することにより発泡ムラ
のない均一な成形体が得られた。That is, by using a mixed solvent of a lower alcohol and a ketone-based solvent, the novolak-type phenol resin and the curing agent are dissolved in the lower alcohols, and the phenol resin and the organic decomposition-type blowing agent are dissolved in the ketone-based solvent. It is confirmed that the novolak-type phenol resin plays a role as a compatibilizer and forms a stable composition without precipitates in a mixed solvent. The body is obtained.
【０００７】本発明で使用される低級アルコール類とケ
トン系溶剤の混合割合は低級アルコール類：ケトン系溶
剤＝８０：２０〜９：９１であり、好ましくは７０：３
０〜２０：８０である。ケトン系溶剤が８０：２０より
少なくなると有機分解型発泡剤が析出し、９：９１より
多すぎると硬化剤が析出する。また、低級アルコール類
が８０：２０より多すぎると有機分解型発泡剤が析出
し、９：９１より少なすぎると硬化剤が析出する。The mixing ratio of the lower alcohol and the ketone solvent used in the present invention is lower alcohol: ketone solvent = 80: 20 to 9:91, preferably 70: 3.
0:20:80. When the amount of the ketone solvent is less than 80:20, the organic decomposition type foaming agent precipitates, and when the amount is more than 9:91, the curing agent precipitates. On the other hand, if the lower alcohol is more than 80:20, the organic decomposition type foaming agent precipitates, and if the lower alcohol is less than 9:91, the curing agent precipitates.
【０００８】本発明で使用される低級アルコール類は、
通常メタノール、エタノール等の炭素数４以下のアルコ
ールであり、単独又は二種以上併用し使用しても良い。
本発明で使用されるケトン系溶剤とは、アセトン、メチ
ルエチルケトン等であり、単独又は二種以上併用し使用
しても良い。また、溶解性を悪化させない程度にエーテ
ル類、エステル類、アミン類等の溶剤を添加しても良
い。[0008] The lower alcohols used in the present invention include:
Usually, it is an alcohol having 4 or less carbon atoms such as methanol and ethanol, and may be used alone or in combination of two or more.
The ketone solvents used in the present invention include acetone, methyl ethyl ketone, and the like, and may be used alone or in combination of two or more. Further, solvents such as ethers, esters, and amines may be added to such an extent that the solubility is not deteriorated.
【０００９】本発明で使用されるノボラック型フェノー
ル樹脂は、通常の方法に従って、フェノール類とホルム
アルデヒドとを酸性触媒により反応させたものである。
本発明で使用されるノボラック型フェノール樹脂のフェ
ノール類としてはフェノール、オルソクレゾール、メタ
クレゾール、パラクレゾール、キシレノール類、アルキ
ルフェノール類、レゾルシノール、カテコール、ビスフ
ェノールＡ、ビスフェノールＦ等があり、単独もしくは
二種以上併用し使用しても良い。アルデヒド類として
は、ホルムアルデヒド、パラホルムアルデヒド、アセト
アルデヒド、フルフラール等が使用でき、単独もしくは
二種以上併用し使用しても良い。ノボラック型フェノー
ル樹脂合成で使用される酸性触媒は、塩酸、硫酸、ギ
酸、酢酸、蓚酸等が使用できる。The novolak type phenolic resin used in the present invention is obtained by reacting phenols and formaldehyde with an acidic catalyst according to a conventional method.
The phenols of the novolak type phenolic resin used in the present invention include phenol, orthocresol, metacresol, paracresol, xylenols, alkylphenols, resorcinol, catechol, bisphenol A, bisphenol F, etc., alone or in combination of two or more. You may use together. As the aldehydes, formaldehyde, paraformaldehyde, acetaldehyde, furfural and the like can be used, and they may be used alone or in combination of two or more. As the acidic catalyst used in the synthesis of the novolak type phenol resin, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.
【００１０】本発明で使用される有機分解型発泡剤は、
Ｎ,Ｎ’−ジニトロソペンタメチレンテトラミン、ベン
ゼンスルホニルヒドラジド、アゾビスイソブチロニトリ
ル等の有機系発泡剤が使用でき、単独又は二種以上併用
し使用しても良い。整泡剤としては、一般に使用される
シリコーン系、アルキルフェノール・エチルオキシド付
加物、高級アルコール硫酸エステル塩、高級脂肪酸塩等
の界面活性剤の単独もしくは二種以上を併用し使用して
も良い。[0010] The organic decomposition type blowing agent used in the present invention includes:
Organic blowing agents such as N, N'-dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, and azobisisobutyronitrile can be used, and they may be used alone or in combination of two or more. As the foam stabilizer, generally used surfactants such as silicones, alkylphenol / ethyl oxide adducts, higher alcohol sulfates and higher fatty acids may be used alone or in combination of two or more.
【００１１】本発明においてノボラックの硬化剤として
通常の硬化剤が使用できる、例えば、ヘキサメチレンテ
トラミン、パラホルムアルデヒド等が挙げられる。本発
明の発泡性フェノール樹脂組成物特性を悪化させない程
度に改質剤として無機及び有機フィラーを添加しても差
し支えない。また、繊維素グルコール酸ナトリウム、ポ
リビニルアルコール、ポリビニルブチラール、ポリアク
リル酸ソーダ、メチルセルロース、アルギン酸ソーダ、
カゼイン、デンプン、ポリエチレングリコール等の水溶
性高分子及びグリセリン、桐油、ゴム物質等の可塑剤、
リン酸アンモニウム、トリクロロエチルホスフェート等
の難燃剤等を添加しても良い。In the present invention, a conventional curing agent can be used as a novolak curing agent, for example, hexamethylenetetramine, paraformaldehyde and the like. Inorganic and organic fillers may be added as modifiers to such an extent that the properties of the foamable phenolic resin composition of the present invention are not deteriorated. Also, sodium cellulose glycolate, polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, methylcellulose, sodium alginate,
Casein, starch, water-soluble polymers such as polyethylene glycol and plasticizers such as glycerin, tung oil, rubber substances,
Flame retardants such as ammonium phosphate and trichloroethyl phosphate may be added.
【００１２】[0012]
【実施例】以下、本発明を実施例により説明する。しか
し、本発明は実施例によって限定されるものではない。
また、製造例、実施例、比較例で示される「部」及び
「％」はすべて「重量部」及び「重量％」である。The present invention will be described below with reference to examples. However, the present invention is not limited by the examples.
Further, “parts” and “%” shown in Production Examples, Examples, and Comparative Examples are “parts by weight” and “% by weight”.
【００１３】（実施例１）攪拌機及び冷却器付き反応釜
にフェノールとホルムアルデヒドを酸触媒により常法に
従って反応し得られたノボラック型フェノール樹脂Ａ１
００部、硬化剤Ａとしてヘキサメチレンテトラミン５
部、発泡剤ＡとしてＮ，Ｎ’−ジニトロソペンタメチレ
ンテトラミン１．５部、整泡剤Ａとしてオキシエチレン
ブロックポリマー０．５部に溶剤Ａとしてメチルアルコ
ール３５部、溶剤Ｂとしてアセトン１３６部を加え攪拌
混合し不揮発分３７％の混合液Ａを得た。得られた混合
液の沈殿物及び使用割合の溶媒で不揮発分２０％まで希
釈した場合と溶剤Ａにて不揮発分２０％まで希釈した場
合の沈殿物の確認を行った。また、得られた混合液Ａを
ガラス不織布に常法に従って含浸乾燥させ後、１５０℃
で１０分間発泡硬化させ、発泡ムラの評価を行った。(Example 1) A novolak-type phenolic resin A1 obtained by reacting phenol and formaldehyde in a reaction vessel equipped with a stirrer and a cooler using an acid catalyst according to a conventional method.
00 parts, as a curing agent A, hexamethylenetetramine 5
Parts, 1.5 parts of N, N'-dinitrosopentamethylenetetramine as foaming agent A, 0.5 parts of oxyethylene block polymer as foam stabilizer A, 35 parts of methyl alcohol as solvent A, and 136 parts of acetone as solvent B The mixture was stirred and mixed to obtain a mixed solution A having a nonvolatile content of 37%. The sediment of the obtained mixed liquid and the sediment of the case where it was diluted to 20% of the non-volatile content with the solvent of the usage ratio and the case where it was diluted to 20% of the non-volatile content with the solvent A were confirmed. Further, the obtained mixed solution A was impregnated and dried on a glass nonwoven fabric according to a conventional method, and then dried at 150 ° C.
For 10 minutes, and evaluated for uneven foaming.
【００１４】（実施例２）ノボラック型フェノール樹脂
Ａ１００部、発泡剤Ｂとしてベンゼンスルホニルヒドラ
ジド１．６部、整泡剤Ｂとしてシリコンオイル１部、溶
剤Ａを５０部、溶剤Ｂを５０部とした以外は実施例１と
同様の方法で不揮発分５０％の混合液Ｂを得た。以下、
実施例１と同様な方法で確認・評価を行った。Example 2 100 parts of novolak type phenolic resin A, 1.6 parts of benzenesulfonyl hydrazide as foaming agent B, 1 part of silicone oil as foam stabilizer B, 50 parts of solvent A, and 50 parts of solvent B A mixed solution B having a nonvolatile content of 50% was obtained in the same manner as in Example 1 except for the above. Less than,
Confirmation and evaluation were performed in the same manner as in Example 1.
【００１５】（実施例３）ノボラック型フェノール樹脂
Ａ１００部、発泡剤Ｂ１．５部、整泡剤Ａ０．７部、溶
剤Ｃとしてエチルアルコール１０２部、溶剤Ｄとしてメ
チルエチルケトン６９部とした以外は実施例１と同様の
方法で不揮発分３８％の混合液Ｃを得た。以下、実施例
１と同様に確認・評価を行った。(Example 3) [0015] Except that 100 parts of novolak type phenol resin A, 1.5 parts of foaming agent B, 0.7 parts of foam stabilizer A, 102 parts of ethyl alcohol as solvent C, and 69 parts of methyl ethyl ketone as solvent D were used. In the same manner as in Example 1, mixed liquid C having a nonvolatile content of 38% was obtained. Hereinafter, confirmation and evaluation were performed in the same manner as in Example 1.
【００１６】（比較例１）ノボラック型フェノール樹脂
Ａ１００部、発泡剤Ｂとしてベンゼンスルホニルヒドラ
ジド１．６部、整泡剤Ｂとしてシリコンオイル１部を加
熱ロールにて混練後、粉砕し粉末樹脂Ａを得た。得られ
た粉末樹脂Ａをガラス不織布に散布し熱ロールにて溶融
含浸させた後、１５０℃で１０分間発泡硬化させ、発泡
ムラの確認・評価を行った。(Comparative Example 1) 100 parts of novolak-type phenolic resin A, 1.6 parts of benzenesulfonylhydrazide as a foaming agent B, and 1 part of silicone oil as a foam stabilizer B were kneaded with a heating roll, and then pulverized to powder resin A. Obtained. The obtained powdered resin A was sprinkled on a glass nonwoven fabric, melt-impregnated with a hot roll, foamed and cured at 150 ° C. for 10 minutes, and the unevenness of foaming was confirmed and evaluated.
【００１７】（比較例２）溶媒を溶剤Ａ４０６部にした
た以外は、実施例１と同法で不揮発分２０％の混合液Ｄ
を得た。以下、実施例１と同様の方法で確認・評価を行
った。Comparative Example 2 A mixed solution D having a nonvolatile content of 20% was prepared in the same manner as in Example 1 except that the solvent was changed to 406 parts of the solvent A.
I got Hereinafter, confirmation and evaluation were performed in the same manner as in Example 1.
【００１８】（比較例３）溶媒を溶剤Ｂ９９部にした以
外は実施例２と同法で不揮発分４９％の混合液Ｅを得
た。以下、実施例１と同様の方法で確認・評価を行っ
た。Comparative Example 3 A mixed solution E having a nonvolatile content of 49% was obtained in the same manner as in Example 2 except that the solvent was changed to 99 parts of the solvent B. Hereinafter, confirmation and evaluation were performed in the same manner as in Example 1.
【００１９】実施例１〜３及び比較例１〜３の確認・評
価の結果を表１に示す。Table 1 shows the results of confirmation and evaluation of Examples 1 to 3 and Comparative Examples 1 to 3.
【表１】 [Table 1]
【００２０】表１から明らかなように、ノボラック型フ
ェノール樹脂、硬化剤、有機分解型発泡剤及び整泡剤を
低級アルコール類及びケトン系溶剤の混合溶媒に溶解さ
せた発泡フェノール樹脂組成物は発泡性粉末状フェノー
ル樹脂樹脂及び単一溶媒の発泡性フェノール樹脂組成物
と比べて、混合液の状態及び希釈時の状態が良く、発泡
ムラがなく均一であることを示している。As is clear from Table 1, the foamed phenolic resin composition obtained by dissolving a novolak type phenolic resin, a curing agent, an organic decomposition type foaming agent and a foam stabilizer in a mixed solvent of a lower alcohol and a ketone solvent is used. Compared to the powdery phenolic resin resin and the foamable phenolic resin composition of a single solvent, the state of the mixed solution and the state at the time of dilution are good, indicating that there is no foaming unevenness and uniformity.
【００２１】[0021]
【発明の効果】以上の説明で明らかなように、本発明の
発泡性フェノール樹脂組成物は発泡ムラが起こらず均一
な成形体が得られ、溶剤にて樹脂割合の調製が容易に出
来、樹脂組成物の沈殿が無く安定な樹脂組成物が得ら
れ、断熱材、緩衝材、パネル、ボード等の発泡性フェノ
ール樹脂組成物に好適である。As is clear from the above description, the foamable phenolic resin composition of the present invention can provide a uniform molded article without uneven foaming, and can easily adjust the resin ratio with a solvent. A stable resin composition is obtained without precipitation of the composition, and is suitable for a foamable phenol resin composition such as a heat insulating material, a buffer material, a panel, and a board.
Claims (2)
有機分解型発泡剤及び整泡剤を低級アルコール類及びケ
トン系溶剤の混合溶媒に溶解させた発泡性フェノール樹
脂組成物。1. A novolak type phenol resin, a curing agent,
A foamable phenol resin composition in which an organic decomposition type foaming agent and a foam stabilizer are dissolved in a mixed solvent of a lower alcohol and a ketone solvent.
類：ケトン系溶剤＝８０：２０〜９：９１である請求項
１記載の発泡性フェノール樹脂組成物。2. The foamable phenolic resin composition according to claim 1, wherein the mixing ratio of the mixed solvent is lower alcohol: ketone solvent = 80: 20 to 9:91.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3814197A JPH10237208A (en) | 1997-02-21 | 1997-02-21 | Expandable phenolic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3814197A JPH10237208A (en) | 1997-02-21 | 1997-02-21 | Expandable phenolic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10237208A true JPH10237208A (en) | 1998-09-08 |
Family
ID=12517149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3814197A Pending JPH10237208A (en) | 1997-02-21 | 1997-02-21 | Expandable phenolic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10237208A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8436061B2 (en) | 2000-04-06 | 2013-05-07 | American Aerogel Corporation | Organic, open cell foam materials, their carbonized derivatives, and methods for producing same |
-
1997
- 1997-02-21 JP JP3814197A patent/JPH10237208A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8436061B2 (en) | 2000-04-06 | 2013-05-07 | American Aerogel Corporation | Organic, open cell foam materials, their carbonized derivatives, and methods for producing same |
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