JPH01152006A - Manufacture of flame retardant woody product - Google Patents
Manufacture of flame retardant woody productInfo
- Publication number
- JPH01152006A JPH01152006A JP31267987A JP31267987A JPH01152006A JP H01152006 A JPH01152006 A JP H01152006A JP 31267987 A JP31267987 A JP 31267987A JP 31267987 A JP31267987 A JP 31267987A JP H01152006 A JPH01152006 A JP H01152006A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- retardant
- flame retardant
- wood product
- wood
- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 113
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000001913 cellulose Substances 0.000 claims abstract description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000002023 wood Substances 0.000 claims description 92
- 229920001187 thermosetting polymer Polymers 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000004640 Melamine resin Substances 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000010985 leather Substances 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011230 binding agent Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013007 heat curing Methods 0.000 abstract 3
- 239000002341 toxic gas Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 235000010980 cellulose Nutrition 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 6
- 235000013312 flour Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical class [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000019814 powdered cellulose Nutrition 0.000 description 1
- 229920003124 powdered cellulose Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
Description
本発明は難燃性木質製品の製造方法に係るもので、更に
詳しくは予め微粉化したセルロースを主体とする物質に
難燃剤を含浸被覆させた後、熱硬化性樹脂を添加し、之
を均一に混合した後、加熱加圧成形する難燃性木質製品
の製造方法に関する。The present invention relates to a method for manufacturing flame-retardant wood products, and more specifically, a material mainly composed of cellulose that has been pulverized in advance is impregnated and coated with a flame retardant, then a thermosetting resin is added, and the material is uniformly coated. The present invention relates to a method for producing a flame-retardant wood product, which is formed by heating and pressurizing the mixture.
木材を難燃化する方法としては、木材中で水溶性の無機
物イオン同志の反応を行い、水に不溶性かつ不燃性の無
機物を木材中に生成させる方法が開発されている（特開
昭６２−２４８６０２ ） 、この方法の欠点は木材中
に水溶性の無機物イオンを圧入又は含浸するのに長時間
を要することであり、且表面と内部の難燃度に差違を生
ずる事である。実際に水を充分に吸はせた木材をバリウ
ムイオンの水溶液に漬け、次いでリン酸イオンの水溶液
に浸すと木の内部に順番に浸透してリン酸バリウム塩が
生成され木材は難燃化されるが、木材の厚さ３〜５−／
麟の板で約８時間を要する。更に水洗乾燥しなければな
らないのでその生産性は非常に忠い。また樹種・樹脂・
気温・湿度等により木材内部に生成される無機物にバラ
ツキを生ずる事は避けられない。
次にＪＩＳで準不燃材料として認められている木毛セメ
ント板があるが、之は木片５０重量％に対しセメントが
ｓｏｗｎ％と多（、板状に成形したものは難燃性は高い
が外観はセメント板に近く木材とは程遠い。また通常の
木材加工用工具で加工する事は不可能であり難燃木材と
しては使用しに（い。
また発明者は木粉に難燃剤を含浸し之を難燃剤を添加し
た塩化ビニール樹脂で固化して難燃木材を造ったが、之
は火焔があたった時その表面が炭化すると共に塩素ガス
を発生し、人畜に有害であるので実用できなかった経験
がある。As a method for making wood flame retardant, a method has been developed in which water-soluble inorganic ions react with each other in the wood to generate water-insoluble and non-flammable inorganic substances in the wood (Japanese Unexamined Patent Application Publication No. 1983-1999). 248602), the disadvantage of this method is that it takes a long time to inject or impregnate water-soluble inorganic ions into the wood, and there is a difference in flame retardancy between the surface and the interior. In fact, when wood that has sufficiently absorbed water is immersed in an aqueous solution of barium ions and then in an aqueous solution of phosphate ions, the barium phosphate salts are generated and penetrate into the interior of the wood, making the wood flame retardant. However, the thickness of the wood is 3 to 5-/
It takes about 8 hours on a lin board. Furthermore, since it must be washed with water and dried, its productivity is extremely high. Also, tree species, resin,
It is unavoidable that the inorganic substances generated inside the wood will vary due to temperature, humidity, etc. Next, there is wood wool cement board, which is recognized as a quasi-noncombustible material by JIS, but it has a high percentage of cement (50% by weight of wood) and 50% of cement (those formed into a board are highly flame retardant, but have a poor appearance). It is similar to cement board and far from wood. Also, it cannot be processed with ordinary wood processing tools, so it cannot be used as a flame retardant wood. A flame-retardant wood was made by solidifying it with vinyl chloride resin containing a flame retardant, but when exposed to flames, the surface carbonized and emitted chlorine gas, which was harmful to humans and animals, so it could not be put to practical use. have experience.
発明者はセルロースを主体とする物質を微粉化し之を熱
可塑性樹脂あるいは熱硬化性樹脂を結合剤として、セル
ロースを主体とする物質の含有率５０〜９８％の製品を
成形する技術を開発し之を実用化しているが、之を難燃
化するにあたり、第１段階として塩化ビニール樹脂を結
合剤として成形品を造ったところ、ｌｉｌ燃性は良好で
あったが火焔が成形品にあたった時その表面が炭化する
と同時に塩化ビニール樹脂が分解して塩素ガスを発生す
るため人畜に有害で実用化できない事が分った。
そこで第２段階として微粉化したセルロースを主体とす
る物質に特許第７８２９３６号に示される防湿防炎剤を
含浸して難燃化し、之を粉末状熱硬化性樹脂を結合剤と
して加熱成形したところ有害ガスを発生しない木質製品
を得た。その難燃度は建築物の内装材料及び工法の難燃
性試験方法（ＪＩＳ−Ａ １３２１ ）に於ける難燃１
級に合格したが、更に難燃度を高める為に熱硬化性樹脂
にも難燃剤を添加して加熱加圧成形し、かつその木質製
品表面に離燃性塗料を塗布したところＪＩＳの準不燃に
合格する難燃性木質製品を得て本発明を完成し、た。
また本発明品は昭５１建告１２３１による準不燃材料及
び難燃材料の指定に於いてその第４のガス有害性試験に
も合格し人畜に無毒であることが証明された。
以下本発明を更に詳述する。
先づセルロースを主体とする物質の微粉化度であるが、
之は微細な程良いが ４〜１００メツシユを使用する。
４メツシユはおが肩程度１θ０メツシュはメリケン粉程
度である。４メツシユ以下では難燃化にバラツキを生じ
るし、１００メツシユ 以上では微粉化のコストが高く
ついて採算上問題が生じる。
セルロースを主体とする物質の難燃剤は種々あり、リン
系、臭素系、アンチモン系其他があるが実験の結果最も
セルロース系に適合する難燃剤はリン系であり、その中
でも特許第７８２９３６号に示される（有機リン化合物
水溶液を高速回転撹拌しつつアルミナゾルの希釈液およ
びコロイダルシリカの希釈液を添加した）難燃剤が最も
使いやすく且効果的であった。
難燃剤は液状が効果的で粉末状セルロースを主体とする
物質（以下セルロース粉末という）に含浸する割合は、
セルロース粉末１００重量部に対し１重量部以下では全
く難燃効化は無（，３０重量部以上では原価が高くつく
のみならず木質感が疎外されるので適当でない。難燃剤
は必ずしも液状に限らないが液状の方が分散効果が良い
。
液状の、難燃剤はセルロース粉末への含浸速度が早いの
で粉末を高速撹拌しつつ難燃剤を添加する必要がある。
難燃剤の含浸度合いにバラツキがあると製品の難燃性に
バラツキを生ずるからである。
この様にして液状の難燃剤をセルロース粉末に含浸被覆
するのでその加工速度は非常に速＜、１００−のセルロ
ース粉末の難燃処理時間は僅かに３０分であるのに比し
て、３１１／Ｉ１１厚のブナ材の中道水溶性の無機物イ
オンを浸透させ難燃化するには１０時間を要し、その生
産性は本発明の比ではない。また本発明の難燃性木質製
品はその難燃性も均質で同所を切断してもその効力は同
じである。
次に結合剤であるが、熱可塑性樹脂は其特性からして耐
熱度は低くかつ難燃化が困難で最も難燃度の高い塩化ビ
ニール系樹脂は加熱時に塩素ガスを発生するので使用で
きない。熱硬化性樹脂はその特性からして耐熱度が高（
難燃性を有するので、熱硬化性樹脂２〜３０重量部を難
燃化したセルロース粉末と均一に分散混合した後加熱加
圧成形して難燃性木質製品を製造する。熱硬化性樹脂の
添加率はセルロース粉末１００重量部に対して最低２Ｍ
量部は必要で之以下では製品としての強度が得られない
。また３０重量部以上添加すると製品硬度が高（なり過
ぎて木質感が無くなるのみならず二次加工が困難となる
ので適当ではない。
熱硬化性樹脂は粉末状が望ましいが必ずしも粉末には限
らない。しかしながらセルロースを主体とする物質が粉
末状であるから熱硬化性樹脂も粉末状が望ましく更に望
ましくはフェノール樹脂、メラミン樹脂、ユリヤ樹脂の
１種もしくは２種以上の混合物が使用しやすい。
難燃化した熱硬化性樹脂を結合剤として使用すれば木質
製品の難燃度は一段と向上する。熱硬化性樹脂の難燃剤
としては臭素系の反応型難燃剤が良＜、ＴＢＡ （テト
ラブロムビスフェノールＡ）、ＨＢＢ （ヘキサブロム
ベンゼン）、ＴＢＰ（臭素化フェノール）等があり何れ
も熱硬化性樹脂と良（まざり良好な難燃性を得られる。
例えばフェノール樹脂１００重量部に対しＴＢＡを１０
重量部配合した時ＵＬ−９４による難燃性の判定は５Ｅ
−０を示した。
以上の様に難燃化したセルロース粉末と難燃化した粉末
状熱硬化性樹脂を良（混合し之を加熱加圧成形した難燃
性木質製品に更に難燃性塗料を表面に塗装して準不燃の
木質製品を得ることが出来た。
難燃性塗料は種々有るがルーフブルーフ（大日本インキ
化学工業株式会社製品の商品名）が最も効果的であった
。ルーフブルーフは有機含リン化合物系難燃剤（ルーフ
ブルーフＰ）とメラミン系樹脂固着剤（ルーフブルーフ
ＦＩＸ）を混合し更に硬化促進剤（カタリストＸ）を混
合して塗布する常温硬化型の難燃塗料で、本発明の難燃
性木質製品に塗装した結果米国では一般建材の不燃縁に
相当する Ｕ Ｌ−７２３防火試験の１級に合格した。
またＵＬ （ＵＮＤＥＲＷＲＩＴＥＲ８−ＬＡＢＯＲＡ
ＴＯＲＩＥＳ）で実施するＬ Ａ Ｆ Ｄ −Ｓ ｔｄ
５２による１０００時間の加速ウェザリング（実際の屋
外曝露３〜５年に相当）後の防火デストも合格し、ロサ
ンゼルス消防局より仮免許証を得た。
以上の様にして不燃縁の木質製品を得ることができ本発
明は完成したが、本発明による木質製品は木材同様の二
次加工性を有し更に成形加工性に於いて種々の特徴を有
する。
その第１点はセルロース粉末から直接難燃性木質製品を
成形できる事である。従来の難燃性木質製品は原木から
板材または角材を取り之を難燃化するか、あるいは更に
製品化してから難燃化するか、何れにしても原木材を必
要とし且高価な加工費を必要とするが、本発明はセルロ
ースを主体とする物質なら何でも良く例えばハードボー
ドの打抜ｍ・ベニヤ板工場のサンダー粉・製材工場のお
が屑あるいは有効利用法が無（て困っている全国の森林
間伐材等いづれも之を微粉化すれば使用できるので材料
原価は安く、且つ成形は金型を所望の形状に作れば粉末
から直接所望の難燃性木質製品が得られるので加工度の
高い木質製品はどその価格は安価にできる。例へば彫刻
を施した高価な玄関ドアー・欄間・格天井・ルーバー扉
等は木質製品の数分の１の価格で生産が可能である。
その第す点は成形に際し発泡剤を混入し押出引抜成型あ
るいは圧縮成形を実施すれば木材と同程度の軽い難燃性
木質製品を生産することができる事である。
その第３点は押出引抜成形・多列ロールによる連続加熱
加圧成形により天然木では得られない長尺の木管や薄板
其他異形断面の難燃性長尺木質製品を安価に製造する事
ができる事である。その実用例としては障子やふすまの
框及び桟・手すり・敷居・鴨居・回り縁・破風板・はな
かくし板・つけ胴差し・ぬれ縁・床板・天井板・外壁材
等である。
その第４点は表面を天然木にする為、予め難燃剤を含浸
した天然木単板を成形後に製品表面に貼着するか、或は
成形金型内に上記難燃単板を固定してインサート成形す
れば表面が天然木単板の難燃性木質製品を容易にかつ安
価に製造することができる事である。その実用例として
は玄関扉・間仕切板・キッチン扉・其他家風用扉等であ
る。
その第５点は成形品の強度が不足する場合原料の混合に
際しガラス繊維炭素繊維等不燃繊維の短いチョップを混
入分散させれば強度を増した難燃性木質製品が得られる
事である。
その第６点は高強度が要求される場合、補強材として金
属パイプ・金属板・金網等を成形金型内にインサートし
て成形すれば木材以上の信頼性のある高強度の難燃性木
質製品が得られる事である。その実用例として玄関扉に
は金網を、窓枠や窓には金属アングルを、柱には角パイ
プをインサートすれば建築用材として充分の強度を得ら
れる。
その第７点は圧縮成形金型によるエンボス成形法である
。即ち金型に木目・皮シボ・布目等を彫刻して圧縮成形
を行えば、製品の表面には所望の凹凸模様が造られ之に
難燃塗料による目止め着色塗装を行えば表面に木目模様
や皮シボ模様等の滓出た難燃性木質製品を安価に求める
事ができる。The inventor has developed a technology for molding a product containing 50 to 98% of a cellulose-based material by pulverizing a cellulose-based material and using a thermoplastic resin or thermosetting resin as a binder. However, in making it flame retardant, as a first step, we made molded products using vinyl chloride resin as a binder, and although the flammability was good, when flames hit the molded products, At the same time as the surface carbonizes, the vinyl chloride resin decomposes and generates chlorine gas, which is harmful to humans and animals and has been found to be unsuitable for practical use. Therefore, in the second step, a material mainly composed of pulverized cellulose was impregnated with the moisture-proofing and flame-retardant agent shown in Patent No. 782936 to make it flame retardant, and then heated and molded using a powdered thermosetting resin as a binder. A wood product that does not emit harmful gases was obtained. Its flame retardancy is flame retardant 1 in the flame retardant test method for building interior materials and construction methods (JIS-A 1321).
However, in order to further increase the degree of flame retardancy, we added a flame retardant to the thermosetting resin and molded it under heat and pressure, and then applied a flame retardant paint to the surface of the wood product. The present invention was completed by obtaining a flame-retardant wood product that passed the test. Furthermore, the product of the present invention passed the fourth gas toxicity test under the designation of quasi-nonflammable materials and flame-retardant materials according to Notification No. 1231 of 1972, and was proved to be non-toxic to humans and animals. The present invention will be explained in more detail below. First, the degree of fineness of substances mainly composed of cellulose,
The finer the finer the better, but use 4 to 100 pieces. 4 mesh is about the same as a saw's shoulder, and 1θ0 mesh is about the same as powdered flour. If the number of meshes is less than 4, the flame retardancy will vary, and if the number of meshes is more than 100 meshes, the cost of pulverization will be high, causing problems in terms of profitability. There are various flame retardants based on cellulose, including phosphorus-based, bromine-based, antimony-based, and others, but as a result of experiments, the flame retardant that is most compatible with cellulose is the phosphorus-based flame retardant. The flame retardant prepared by adding a dilute solution of alumina sol and a dilute solution of colloidal silica to an aqueous solution of an organic phosphorus compound while stirring at high speed was the easiest to use and most effective. The flame retardant is effective in liquid form, and the rate at which it is impregnated into a substance mainly composed of powdered cellulose (hereinafter referred to as cellulose powder) is:
If it is less than 1 part by weight per 100 parts by weight of cellulose powder, there will be no flame retardant effect at all (but if it is more than 30 parts by weight, it is not suitable as it will not only increase the cost but also remove the wood texture. Flame retardants are not necessarily in liquid form. The dispersion effect is better when it is in liquid form. Liquid flame retardants impregnate cellulose powder quickly, so it is necessary to add the flame retardant while stirring the powder at high speed. This is because it causes variations in the flame retardancy of the product.Since the liquid flame retardant is impregnated and coated on the cellulose powder in this way, the processing speed is very fast. In contrast, it takes 10 hours to infiltrate 311/I11 thick beech wood with water-soluble inorganic ions to make it flame retardant, and the productivity is lower than that of the present invention. In addition, the flame retardant property of the flame retardant wood product of the present invention is homogeneous, and its effectiveness remains the same even when cut in the same place.Next, regarding the binder, thermoplastic resin is difficult to use due to its properties. PVC resin, which has low heat resistance and is difficult to make flame retardant, cannot be used because it generates chlorine gas when heated.Thermosetting resins have high heat resistance due to their characteristics (
Since it has flame retardancy, a flame retardant wood product is produced by uniformly dispersing and mixing 2 to 30 parts by weight of the thermosetting resin with flame retardant cellulose powder and then heating and press molding. The addition rate of thermosetting resin is at least 2M per 100 parts by weight of cellulose powder.
A certain amount is necessary, and if it is less than this, the strength of the product cannot be obtained. Also, if more than 30 parts by weight is added, the hardness of the product will be too high (too much, resulting in a loss of wood texture and making secondary processing difficult), which is not appropriate. The thermosetting resin is preferably in powder form, but is not necessarily in powder form. However, since the substance mainly composed of cellulose is in powder form, the thermosetting resin is also preferably in powder form, and more preferably one or a mixture of two or more of phenol resin, melamine resin, and urea resin is easily used.Flame retardant. The flame retardance of wood products can be further improved by using a thermosetting resin as a binder. Bromine-based reactive flame retardants are good flame retardants for thermosetting resins, such as TBA (tetrabromobisphenol A ), HBB (hexabromobenzene), TBP (brominated phenol), etc., all of which have good flame retardancy with thermosetting resins.
Flame retardant rating according to UL-94 when combined in parts by weight is 5E
-0 was shown. As mentioned above, flame-retardant cellulose powder and flame-retardant powder thermosetting resin are mixed together and then heated and pressed to form a flame-retardant wood product, and then a flame-retardant paint is further applied to the surface. We were able to obtain a semi-incombustible wood product. There are various flame retardant paints, but Roof Blue (trade name of Dainippon Ink & Chemicals Co., Ltd.) was the most effective. Roof Blue is an organic phosphorus-containing compound. This is a room temperature-curing flame retardant paint that is applied by mixing a flame retardant (Roof Blue P) and a melamine resin fixing agent (Roof Blue FIX) and a curing accelerator (Catalyst X). As a result of coating it on a non-combustible wood product, it passed the first grade of the UL-723 fire protection test, which corresponds to noncombustible edges for general building materials in the United States.
L A F D -S td carried out at TORIES)
After 1,000 hours of accelerated weathering (equivalent to 3-5 years of actual outdoor exposure) under the 52, he passed the fire protection test and received a provisional license from the Los Angeles Fire Department. The present invention has been completed by being able to obtain a wood product with a non-combustible edge as described above, but the wood product according to the present invention has secondary processability similar to that of wood, and furthermore has various characteristics in terms of moldability. . The first point is that flame-retardant wood products can be molded directly from cellulose powder. Conventional flame-retardant wood products require the use of raw wood and expensive processing costs. However, the present invention can be applied to any material that is mainly composed of cellulose, such as punching m from hardboard, sanding powder from plywood factories, sawdust from sawmills, or even forest thinning across the country where there is no effective way to use it. All materials can be used if they are pulverized, so the material cost is low, and the desired flame-retardant wood product can be obtained directly from the powder by molding the mold into the desired shape, making it a highly processed wood product. For example, expensive carved entrance doors, transoms, coffered ceilings, louvered doors, etc. can be produced at a fraction of the price of wooden products. By mixing a foaming agent and performing extrusion pultrusion molding or compression molding, it is possible to produce a flame-retardant wood product that is as light as wood. By heating and pressure forming, it is possible to inexpensively produce long wood pipes, thin plates, and other flame-retardant long wood products with irregular cross-sections that cannot be obtained with natural wood.Practical examples include shoji and sliding frames. and crosspieces, handrails, sills, lintels, wraparound edges, gable boards, sill boards, sashes, wet edges, floorboards, ceiling boards, exterior wall materials, etc.The fourth point is to use natural wood for the surface. If a natural wood veneer pre-impregnated with a flame retardant is attached to the product surface after molding, or if the flame retardant veneer is fixed in a mold and insert molded, the surface becomes flame retardant than a natural wood veneer. It is possible to easily and inexpensively manufacture synthetic wood products.Practical examples include entrance doors, partition boards, kitchen doors, and other doors for other homes.The fifth point is the strength of the molded product. If there is a shortage of wood, a flame-retardant wood product with increased strength can be obtained by mixing and dispersing short chopped non-combustible fibers such as glass fibers and carbon fibers when mixing raw materials.The sixth point is that high strength is required. In cases where metal pipes, metal plates, wire mesh, etc. are inserted as reinforcing materials into the mold and molded, a high-strength, flame-retardant wood product that is more reliable than wood can be obtained. For example, inserting wire mesh into the entrance door, metal angles into the window frames and windows, and square pipes into the columns will provide sufficient strength as building materials.The seventh point is embossing molding using a compression molding mold. In other words, if you carve wood grain, leather grain, cloth grain, etc. into a mold and perform compression molding, the desired uneven pattern will be created on the surface of the product, and if you apply a sealing color with flame retardant paint, it will be finished. Flame-retardant wood products with wood grain patterns, leather grain patterns, etc. on the surface can be obtained at low prices.
【実施例及び効果］
以下その実施の１例を述べるが本発明はこれら実施例に
のみ限定されるものではない。
実施例１゜
４０メツシユに微粉砕した木粉１００ｋｇをヘンシェル
ミキサーに投入し、ミキサー外壁のジャケットに通じる
過熱蒸気により１００℃に加熱しつつ撹拌すると、約１
０分で木粉は水分含有率５％以下に乾燥された。之に特
許第７８２９３６号による防湿性防炎剤１ＯｋＪｒを投
入し更に１０分間加熱撹拌すると防炎剤が均一に含浸被
覆された難燃化木粉が得られた。
之に更にユリア樹脂初期縮合物１０ｋｇをメタノール１
０艙に溶解した液を投入し１０分間加熱撹拌するとメタ
ノールは揮散し、難燃化木粉に尿素樹脂が均一に添着し
た粉末が得られた。この粉末（所要ｆｆ１）を金型に投
入し１８０℃に加熱しつつ１００ｋｇ／ｃｉの圧力で圧
縮成形する七、５分間で尿素樹脂は硬化し尿素樹脂を結
合剤とした木粉８７％の難燃性木質製品を得た。この難
燃性木質製品の難燃性試験をＪ Ｉ Ｓ Ａ−１３２１
１：：より行った結果ＪＩＳ難燃１級に合格した。圧縮
成形金型を必要に応じて所望の形状に造れば如何なる形
状の難燃性木質製品も簡単にかつ安価に製造することが
できる。
実施例２゜
１００メツシユに微粉砕した木粉１００ｋｇをヘンシェ
ルミキサーに投入し、ミキサー外壁部のジャケットに通
じる過熱蒸気により１０（ｌ に加熱しつつ撹拌すると
、約１０分で木粉は水分含有率５％以下に乾燥された。
之に特許第７８２９３６号による防湿性防炎剤１５−を
投入し更に１０分間加熱撹拌すると防炎剤が均一に含浸
被覆された難燃化木粉が得られた。
フェノール樹脂（レゾール） １０−をメタノール４０
艙に溶解した液を上記の難燃化木粉に投入して良く混合
拡散した後２をガラス繊維テープに塗布含浸させ加熱乾
燥してフェノール樹脂をＢ −ｓｔａｇｅでプリプレグ
したテープを造り、之を特開昭５１−５８４６７号に見
る様に芯金に捲付けて、予熱機を通過した後芯金と共に
硬化成形用ホットダイを通過引抜くと中空パイプが出来
る。この様にして長尺の難燃性木管を得た。この木管の
難燃性試験をＪ Ｉ Ｓ Ａ−１３２１により行った結
果ＪＩＳ難燃１級に合格した。以上の様にプレプレグの
形状ならびに引抜ダイの形状を所望の断面形状にすれば
所望形状の長尺な難燃性木質製品を安価に且大量に製造
することができる。
実施例３゜
８０メツシユに微粉化したハードボードの打抜屑１００
ｋｇ をヘンシェルミキサーに投入しミキサー外壁部の
ジャケットに通じる過熱蒸気により １００℃に加熱し
つつ３分間撹拌し水分を除去した後、之に特許第７８２
９３６号による防湿性防炎剤１２−を投入し更に１０分
間加熱撹拌すると防炎剤が均一に含浸被覆された難燃化
ハードボード粉が得られた。
別途にフェノール樹脂（レゾール）１０ｂおよび難燃性
可塑剤クレジルジフェノールフォスフェート１−をメタ
ノール２０−に溶解した液をつ（す、之に上記の難燃化
ハードボード粉を投入し均一に撹拌混合させた後２をガ
ラス繊維布に塗布含浸し加熱乾燥してフェノール樹脂が
Ｂ −ｓｔａｇｅの状態でブリブレツブしたシートを
造る。このシートを予備加熱室を通過させステンレス板
に挟みながら特開昭６２−２２５３３１−４項第３図に
示される様に水平多列のロールにより加熱加圧しつつ送
り出して難燃性ハードボードを得た。之に更に全面にル
ーフプルーフを塗装し常温硬化させて不燃級のハードボ
ードを得た。このハードボードはＵ Ｌ −７９３防火
試験１級に合格し米国に於ける一般建材の不燃級に相当
する事が証明されたので自動車の内装削具他用途は多々
あると推定され、材料はスクラップで良く安価かつ有用
な新素材である。
実施例４、
ベニヤ板工場で発生するサンダー粉は若干の接着剤とペ
ーパーの石粉が混入しているが９５％以上は木粉である
。然し夾雑物が混入している為通常の木粉としては利用
されず燃料として使用される程度であるが、このサンダ
ー粉を利用する難燃性雨戸の製造方法を述べる。サンダ
ー粉１００ｂをヘンシェルミキサーに投入しミキサー外
壁部のジャゲットに通じる過熱蒸気により１００℃で
５分間加熱撹拌して水分を除去した後、之に特許第７８
２９３６号による防湿性防炎剤１３−を投入し更に１０
分間加熱撹拌すると防炎剤は均一にサンダー粉に含浸被
覆され難燃性サンダー粉を得た。メラミン樹脂（初期縮
合物） １０−をメタノール１０ｋｇに溶解した液を上
記難燃性サンダー粉に投入し更に１０分間加熱撹拌する
とメタノールは揮散しメラミン樹脂が均一に添着した難
燃サンダー粉を得られた。この粉末（所要量）を雨戸の
金型に投入して１８０℃に加熱しつつ１００ｋｇ／−の
圧力で５分間加熱圧縮する。雨戸の金型は表面部に天然
木から転写した木目のエツチングを施し裏面部には周囲
の補強桟と横桟を設けておく。プレス成形品の表面部の
木目状凹凸には難燃塗料で目止め着色塗装を行い、その
色合い及び凹凸の感触は天然水量等に仕上げた後、全面
にルーフ・プルーフを塗装し常温硬化させる。この様に
して出来た雨戸は ＵＬ−７２３の防火試験１級に合格
し米国に於ける一般建材の不燃級に相当するので、従来
木造建築であるにもかかわらず防火の理由から雨戸に止
むを得ず金属サツシュを使用した為周囲の木造と調和せ
ず違和感があったが、本発明により周囲と調和した色合
いに仕上げる事が可能で防火性もあり尚且大量生産も可
能で金属サツシュに比して安価となる。
【発明の効果】[Examples and Effects] An example of the implementation will be described below, but the present invention is not limited only to these examples. Example 1: 100 kg of wood flour finely ground to 40 mesh was put into a Henschel mixer, heated to 100°C by superheated steam connected to the jacket on the outer wall of the mixer, and stirred.
The wood flour was dried to a moisture content of 5% or less in 0 minutes. 1 OkJr of a moisture-proof flame retardant according to Japanese Patent No. 782,936 was added thereto, and the mixture was further heated and stirred for 10 minutes to obtain flame-retardant wood powder uniformly impregnated with the flame retardant. In addition, add 10 kg of urea resin initial condensate to 1 part of methanol.
When the dissolved liquid was poured into a tank and heated and stirred for 10 minutes, the methanol was evaporated and a powder in which the urea resin was uniformly attached to the flame-retardant wood powder was obtained. This powder (required ff1) is put into a mold and heated to 180°C and compression molded at a pressure of 100 kg/ci. The urea resin hardens in 7.5 minutes, making it difficult to use 87% wood powder using urea resin as a binder. A flammable wood product was obtained. The flame retardant test of this flame retardant wood product was conducted according to JIS A-1321.
1:: As a result, it passed JIS flame retardant grade 1. Flame-retardant wood products of any shape can be manufactured easily and at low cost by making a compression molding mold into a desired shape as needed. Example 2: 100 kg of wood flour finely ground into 100 meshes was put into a Henschel mixer, and stirred while being heated to 10 (liters) by superheated steam passing through the jacket on the outer wall of the mixer. The moisture content of the wood flour decreased in about 10 minutes. When the moisture-proof flame retardant 15- according to Patent No. 782936 was added to the wood and the mixture was heated and stirred for an additional 10 minutes, a flame retardant wood powder uniformly impregnated with the flame retardant was obtained. Phenol resin (resol) 10- to methanol 40-
The solution dissolved in the tank was poured into the above flame-retardant wood powder, mixed and diffused well, and then applied to a glass fiber tape to impregnate it, heated and dried to make a tape prepregned with phenol resin at the B-stage. As shown in Japanese Patent Application Laid-Open No. 51-58467, a hollow pipe is produced by wrapping it around a core metal, passing through a preheater, and then pulling it out through a hardening molding hot die together with the core metal. In this way, a long flame-retardant wood pipe was obtained. A flame retardant test of this woodwind was conducted according to JIS A-1321, and as a result, it passed JIS flame retardant class 1. As described above, by making the shape of the prepreg and the shape of the drawing die into the desired cross-sectional shape, long flame-retardant wood products of the desired shape can be produced in large quantities at low cost. Example 3 100 pieces of hardboard punching waste pulverized into 80 mesh
kg was put into a Henschel mixer, heated to 100°C by superheated steam passing through the jacket on the outer wall of the mixer, and stirred for 3 minutes to remove moisture.
Moisture-proof flame retardant 12- according to No. 936 was added and heated and stirred for an additional 10 minutes to obtain flame retardant hardboard powder uniformly impregnated with the flame retardant. Separately, add a solution in which phenol resin (resol) 10b and flame retardant plasticizer cresyl diphenol phosphate 1- are dissolved in methanol 20-.Pour the above flame-retardant hardboard powder into it and stir evenly. After mixing, 2 is coated on a glass fiber cloth to impregnate it and heated and dried to make a sheet in which the phenol resin is bubbling in the B-stage state.This sheet is passed through a preheating chamber and sandwiched between stainless steel plates while being heated in JP-A-62. -225331-4 As shown in Figure 3, a flame-retardant hardboard was obtained by heating and pressurizing it with a horizontal multi-row roll and sending it out.Furthermore, the entire surface was coated with roof proof and cured at room temperature to obtain a flame-retardant hardboard. This hardboard has passed the UL-793 fire protection test grade 1 and has been proven to be equivalent to the noncombustible grade of general building materials in the United States, so it has many uses such as car interior trimming tools. It is estimated that the material is scrap, which is a cheap and useful new material.Example 4: Sanding powder generated at a plywood factory contains some adhesive and paper stone powder, but more than 95% is wood powder. However, due to the contaminants mixed in, it cannot be used as normal wood flour and is only used as fuel. However, we will describe a method for manufacturing flame-retardant shutters using this sander powder. Sander Powder 100b was put into a Henschel mixer and heated to 100℃ by superheated steam passing through the jacket on the outer wall of the mixer.
After heating and stirring for 5 minutes to remove moisture, the patent No. 78
13- of the moisture-proof flame retardant according to No. 2936 was added and further 10
When heated and stirred for a minute, the flame retardant was uniformly impregnated into the sander powder to obtain flame-retardant sander powder. Melamine resin (initial condensate) 10- dissolved in 10 kg of methanol is added to the above flame-retardant sander powder and heated and stirred for an additional 10 minutes, the methanol evaporates and flame-retardant sander powder to which the melamine resin is uniformly adhered is obtained. Ta. This powder (required amount) is put into a shutter mold, heated to 180°C, and heated and compressed at a pressure of 100 kg/- for 5 minutes. The mold for the shutter is etched with the wood grain transferred from natural wood on the front surface, and surrounding reinforcing bars and horizontal bars are provided on the back surface. The wood grain-like irregularities on the surface of the press-formed product are painted with flame-retardant paint to fill them in, and after the color and texture of the irregularities are finished to match natural water content, Roof Proof is applied to the entire surface and cured at room temperature. The shutters made in this way have passed the UL-723 fire protection test class 1 and are equivalent to the non-combustible class of general building materials in the United States, so even though buildings are traditionally made of wood, shutters have been used for fire prevention reasons. Unfortunately, the use of metal sashes did not blend in with the surrounding wooden structures, giving a sense of incongruity, but with the present invention, it is possible to finish in a color that harmonizes with the surroundings, is fireproof, and can be mass-produced, compared to metal sashes. This makes it cheaper. 【Effect of the invention】
Claims (10)
０重量部に対して難燃剤１〜３０重量部を均一に被覆合
浸させた後、熱硬化性樹脂２〜３０重量部を添加し、之
を均一に混合した後、加熱加圧成形する事を特徴とする
難燃性木質製品の製造方法。(1) Substance 10 mainly composed of pre-pulverized cellulose
After uniformly coating and co-immersing 1 to 30 parts by weight of a flame retardant to 0 parts by weight, 2 to 30 parts by weight of a thermosetting resin is added, and after uniformly mixing, the mixture is heated and pressure molded. A method for producing a flame-retardant wood product characterized by:
範囲第（１）項記載の難燃性木質製品の製造方法。(2) The method for producing a flame-retardant wood product according to claim (1), wherein a flame retardant is blended in advance with the thermosetting resin.
ユリヤ樹脂の１種もしくは２種以上の混合物である特許
請求の範囲第（１）項または第（２）項記載の難燃性木
質製品の製造方法。(3) Thermosetting resin is phenol resin, melamine resin,
The method for producing a flame-retardant wood product according to claim (1) or (2), which is one or a mixture of two or more urea resins.
範囲第（１）項または第（２）項または第（３）頁記載
の難燃性木質製品の製造方法。(4) A method for producing a flame-retardant wood product according to claim 1, 2, or page 3, wherein a foaming agent is mixed during hot-pressure molding.
加熱加圧成形する特許請求の範囲第（１）項〜第（４）
項の何れかに記載の難燃性木質製品の製造方法。(5) Claims (1) to (4) in which 1 to 20 parts by weight of chopped flame-retardant fibers are added and molded under heat and pressure.
A method for producing a flame-retardant wood product according to any of the above.
をインサートする特許請求の範囲第（１）項〜第（４）
項の何れかに記載の難燃性木質製品の製造方法。(6) Claims (1) to (4) in which net-like or cloth-like flame-retardant fibers are inserted during hot-pressure molding.
A method for producing a flame-retardant wood product according to any of the above.
許請求の範囲第（１）項〜第（６）項の何れかに記載の
難燃性木製品の製造方法。(7) A method for producing a flame-retardant wood product according to any one of claims (1) to (6), wherein metal parts are inserted during hot-pressure molding.
熱加圧成形する特許請求の範囲第（１）項〜第（７）項
の何れかに記載の難燃性木質製品の製造方法。(8) A flame-retardant wood product according to any one of claims (1) to (7), in which a piece of wood processed into a desired shape is fixed in a mold and molded under heat and pressure. Production method.
成形品の表面に木目、皮目、布目等のシボを形成する特
許請求の範囲第（１）項〜第（８）項の何れかに記載の
難燃性木質製品の製造方 法。(9) Claims (1) to (8) above, in which a compression molding mold is engraved during hot-pressure molding to form grains such as wood grain, leather grain, cloth grain, etc. on the surface of the molded product. A method for producing a flame-retardant wood product according to any one of the above.
難燃塗料を塗布した特許請求の範囲第（１）項〜第（９
）項の何れかに記載の難燃性木質製品の製造方法。(10) Claims (1) to (9) further apply a flame-retardant paint to a flame-retardant wood product made by heat-pressing molding.
) A method for producing a flame-retardant wood product as described in any of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31267987A JPH01152006A (en) | 1987-12-10 | 1987-12-10 | Manufacture of flame retardant woody product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31267987A JPH01152006A (en) | 1987-12-10 | 1987-12-10 | Manufacture of flame retardant woody product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01152006A true JPH01152006A (en) | 1989-06-14 |
Family
ID=18032122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31267987A Pending JPH01152006A (en) | 1987-12-10 | 1987-12-10 | Manufacture of flame retardant woody product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01152006A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01145103A (en) * | 1987-11-30 | 1989-06-07 | Sangyo Gijutsu Kenkyusho:Kk | Manufacture of fire-retardant woody product |
| JPH03258535A (en) * | 1990-03-09 | 1991-11-18 | Tomiyasu Honda | Composite and its manufacture |
| JPH03258538A (en) * | 1990-03-09 | 1991-11-18 | Tomiyasu Honda | Composite and its manufacture |
| JP2006015677A (en) * | 2004-07-05 | 2006-01-19 | Achilles Corp | Fire-retardant woody board |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56144907A (en) * | 1980-04-14 | 1981-11-11 | Bitou Hitoshi | Manufacture of incombustible molding |
-
1987
- 1987-12-10 JP JP31267987A patent/JPH01152006A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56144907A (en) * | 1980-04-14 | 1981-11-11 | Bitou Hitoshi | Manufacture of incombustible molding |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01145103A (en) * | 1987-11-30 | 1989-06-07 | Sangyo Gijutsu Kenkyusho:Kk | Manufacture of fire-retardant woody product |
| JPH03258535A (en) * | 1990-03-09 | 1991-11-18 | Tomiyasu Honda | Composite and its manufacture |
| JPH03258538A (en) * | 1990-03-09 | 1991-11-18 | Tomiyasu Honda | Composite and its manufacture |
| JP2006015677A (en) * | 2004-07-05 | 2006-01-19 | Achilles Corp | Fire-retardant woody board |
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