JP3855023B2 - Wood decomposition product, and method for bonding an object, method for curing an uncured epoxy compound, method for producing an epoxy resin, and method for producing a urethane resin using the wood decomposition product - Google Patents

Description

【００２６】
実施例１〜５を示した表１からわかるように、分解試薬のヒドロキシカルボン酸であるＬ−乳酸を用いて、木材を分解させることができた。この場合、反応温度を高くすることは必ずしも分解率の向上につながらず、むしろ高くなるにつれて分解率の低下を招いている。
【００２７】
（実施例６）
杉間伐材粉砕物１．００ｇにＬ−乳酸２０．００ｇを加え、２２０℃で１時間分解させた。分解率は５２．８％であった。
【００２８】
（実施例７）
３時間反応させたこと以外は、実施例６と同じ条件で分解生成物を得た。分解率は４７．７％であった。
【００２９】
（実施例８）
５時間反応させたこと以外は、実施例６と同じ条件で分解生成物を得た。分解率は３５．７％であった。
【００３０】
上記した実施例６〜８における実験条件および結果を以下の表２に示す。
【００３１】
【表２】

【００３２】
実施例６〜８を示した表２から明らかなように、反応時間を長くしても分解率の増大につながっていない。すなわち、上述した反応温度以外に、個々の反応系毎に最適な反応温度および反応時間が存在するものと考えられる。
【００３３】
（実施例９）
杉間伐材粉砕物１．００ｇにＬ−乳酸２０．００ｇを加え、２６０℃で７時間分解させた。分解率は６２．６％であった。
【００３４】
（実施例１０）
２９０℃で分解させたこと以外は、実施例９と同じ条件で分解生成物を得た。分解率は３．２％であった。
上記した実施例９，１０における実験条件および結果を以下の表３に示す。
【００３５】
【表３】

【００３６】
実施例９，１０を示した表３によれば、表１の実施例１〜５と同様、分解率が反応温度に依存していない。むしろ実施例１０のように、高温では分解率が極端に低くなった。この結果より、２９０℃の高温ではリグニンなどの不溶化が起こると思われる。
【００３７】
尚、実施例９における分解残さを赤外吸収スペクトル分析に供した。得られた分解残さの赤外吸収スペクトルより、１７４６ｃｍ−１ にエステル基の吸収があり、２９２４、１４５６ｃｍ−１にメチレン、１０３０、１０５８、１１０７ｃｍ−１に一級ＯＨ基、二級ＯＨ基、エーテル結合の吸収が有り、エステル基の吸収以外はセルロースの吸収スペクトルと同じであった。従って、分解残さはＬ−乳酸がエステル化したセルロースである。
【００３８】
（実施例１１）
米ツガ木粉１．００ｇにＬ−乳酸２０．００ｇを加え、２００℃で２時間分解させた。分解率は７．０％であった。
このとき得た分解生成物を上記のゲル浸透クロマトグラフで分析した。ゲル浸透クロマトグラフの分析結果より、米ツガ木粉の分解生成物のピーク１は数平均分子量＝１５４、重量平均分子量＝１５７、重量平均分子量／数平均分子量＝１．０２であった。分解生成物のピーク２は数平均分子量＝２３９、重量平均分子量＝２４０、重量平均分子量／数平均分子量＝１．０１であった。分解生成物のピーク３は数平均分子量＝３１４、重量平均分子量＝３１５、重量平均分子量／数平均分子量＝１．００であった。分解生成物のピーク４は数平均分子量＝６７４、重量平均分子量＝９２３、重量平均分子量／数平均分子量＝１．３７であった。分解生成物の全体ピークは数平均分子量＝２３２、重量平均分子量＝４２４、重量平均分子量／数平均分子量＝１．８３であった。
【００３９】
（実施例１２）
この実施例は「グリコール酸」による分解例を示している。
杉間伐材粉砕物１．００ｇにグリコール酸２０．００ｇを加え、２２０℃で２時間分解させた。分解率は４３．０％であった。
【００４０】
（実施例１３）
下記の実施例１３〜１５は「Ｌ−乳酸と木材膨潤剤系」による分解例を示している。
杉間伐材粉砕物１．００ｇにＬ−乳酸２０．００ｇ、更に木材膨潤剤としてエチレンカーボネート５．００ｇを加え、２６０℃で３時間分解させた。分解率は５０．２％であった。
【００４１】
（実施例１４）
エチレンカーボネート５．００ｇに代えてアニソール１０．００ｇを用い、７時間反応させたこと以外は、実施例１３と同じ条件で分解生成物を得た。分解率は５３．８％であった。
【００４２】
（実施例１５）
ラクチトール１．００ｇと水１．００ｇを加えた以外は、実施例１４と同じ条件で分解生成物を得た。分解率は６３．７％であった。
【００４３】
上記した実施例１２〜１５における実験条件および結果を以下の表４に示す。
【００４４】
【表４】

【００４５】
実施例１２〜１５を示した表４によれば、グリコール酸（ヒドロキシカルボン酸）によっても木材を良好に分解することができた。また、Ｌ−乳酸（ヒドロキシカルボン酸）に、木材膨潤剤（エチレンカーボネート（実施例１３）、アニソール（実施例１４，１５）、ラクチトール−水（実施例１５））を加えたものは、同様な実験条件である実施例４や実施例９と比べて分解率が高くなっている。
【００４６】
（比較例１）
下記の比較例１〜３は杉間伐材粉砕物に「木材膨潤剤だけ」を加えて観察したものである。
杉間伐材粉砕物１．００ｇに、木材膨潤剤としてアニソール２０．００ｇを加え、２６０℃で７時間反応させた。分解率は１６．４％であった。
【００４７】
（比較例２）
アニソール２０．００ｇに代えて、ラクチトール２．００ｇを水１０．００ｇ に溶かした水溶液を用いた以外は比較例１と同じ条件で反応させた。分解率は−２２．７８％と、残存固形分が増加した。
【００４８】
（比較例３）
アニソール２０．００ｇに代えて無水酢酸２０．００ｇを用い、反応時間を２時間にした以外は比較例１と同じ条件で反応させた。分解率は−３６．７２％と、残存固形分が増加した。
【００４９】
上記した比較例１〜３における実験条件および結果を以下の表５に示す。
【００５０】
【表５】

【００５１】
実施例１３〜１５と比べ、表５に示した比較例１〜３は、分解試薬を用いることなく木材膨潤剤だけを加えたものである。従って、杉間伐材粉砕物があまり分解されなかったり（比較例１）、逆に残存固形分が増えたもの（比較例２，３）もある。
【００５２】
（実施例１６）
下記の実施例１６〜２０は「別の木材膨潤剤」を加えた場合の分解例を示している。
杉間伐材粉砕物１．００ｇにＬ−乳酸２０．００ｇ、更に木材膨潤剤としてN，N―ジメチルアセトアミド１０．００ｇおよび塩化リチウム０．４５ｇを加え、２２０℃で２時間分解させた。分解率は３４．８％であった。
【００５３】
（実施例１７）
N，N―ジメチルアセトアミド１０．００ｇおよび塩化リチウム０．４５ｇの代わりに、４−メチルモルホリン−４−オキシド２．００ｇを用いた以外は実施例１６と同じ条件で反応させた。分解率は６５．３％であった。
【００５４】
（実施例１８）
N，N―ジメチルアセトアミド１０．００ｇおよび塩化リチウム０．４５ｇの代わりに、尿素２．００ｇを用いた以外は実施例１６と同じ条件で反応させた。分解率は４３．５％であった。
【００５５】
（実施例１９）
N，N―ジメチルアセトアミド１０．００ｇおよび塩化リチウム０．４５ｇの代わりに、ジメチルホルムアミド５．００ｇを用いた以外は実施例１６と同じ条件で反応させた。分解率は４２．４％であった。
【００５６】
（実施例２０）
N，N―ジメチルアセトアミド１０．００ｇおよび塩化リチウム０．４５ｇの代わりに、水１０．００ｇを用いた以外は実施例１６と同じ条件で反応させた。分解率は２８．８％であった。
【００５７】
上記した実施例１６〜２０における実験条件および結果を以下の表６に示す。
【００５８】
【表６】

【００５９】
実施例１６〜２０を示した表６のように、種々の木材膨潤剤（Ｎ，Ｎ−ジメチルアセトアミド−塩化リチウム系、４−メチルモルホリン−４−オキシド、尿素、ジメチルホルムアミド、水）をＬ−乳酸（分解試薬）と併用した結果、分解率は、あまり低下することなく一定以上のレベルに保たれていることがわかる。そして、実施例１７（４−メチルモルホリン−４−オキシド）では実施例２より分解率は大きくなった。
【００６０】
（比較例４）
この比較例は「エタノールアミン」による分解例を示している。
米ツカ゛木粉１．００ｇにエタノールアミン２０．００ｇを加え、２５０℃で２時間分解させた。分解率は１８．５％であった。
【００６１】
（比較例５）
この比較例は「ジエタノールアミン」による分解例を示している。
米ツカ゛木粉１．００ｇにジエタノールアミン２０．００ｇを加え、２５０℃で２時間分解させた。分解率は２０．０％であった。
【００６２】
（比較例６）
この比較例は「エタノールアミンと木材膨潤剤系」による分解例を示している。
杉間伐材粉砕物１．００ｇにエタノールアミン２０．００ｇ、ジメチルホルムアミド１．００ｇを加え、２５０℃で２時間分解させた。分解率は３９．７％であった。
【００６３】
（比較例７）
この比較例は「アジピン酸」による分解例を示している。
米ツガ木粉１．００ｇにアジピン酸２０．００ｇを加え、２６０℃で２時間分解させた。分解率は２８．１％であった。
【００６４】
（比較例８）
この比較例は「コハク酸」による分解例を示している。
米ツガ木粉１．００ｇにコハク酸２０．００ｇを加え、２２０℃で２時間分解させた。分解率は３０．０％であった。
【００６５】
（比較例９）
下記の比較例９，１０は「アジピン酸と木材膨潤剤系」による分解例を示している。
杉間伐材粉砕物１．００ｇにアジピン酸２．００ｇ、硝酸ナトリウム１．００ｇを水１７．００ｇに溶かした水溶液を加え、２６０℃で２時間分解させた。分解率は３４．３％であった。
【００６６】
（比較例１０）
硝酸ナトリウム１．００ｇおよび水１７．００ｇに代えて、水のみ１０ｇを加え、２２０℃で分解させたこと以外は、比較例９と同じ条件で分解生成物を得た。分解率は３４．３％であった。
【００６７】
上記した比較例４〜１０における実験条件および結果を以下の表７と表８に示す。
【００６８】
【表７】

【００６９】
【表８】

【００７０】
表７および表８に示した比較例４〜１０は、概ね分解率が低いが種々の分解試薬（エタノールアミン（比較例４，６）、ジエタノールアミン（比較例５）、アジピン酸（比較例７，９，１０）、コハク酸（比較例８））によって、木材を十分に分解できた。この場合も、木材膨潤剤（ジメチルホルムアミド、硝酸ナトリウム、水）を併用すると、分解率が高くなっている。尚、これらの比較例４〜１０においても、他の反応条件を最適に選定すれば、まずまずの分解率が得られるものと考えられる。
【００７１】
（実施例２１）
下記の実施例２１〜２４は分解触媒となるルイス酸として「硫酸アルミニウム」を用いた例を示している。
杉間伐材粉砕物１．００ｇにＬ−乳酸２０ｇ、硫酸アルミニウム０．２ｇを加え、２２０℃で２時間分解させた。分解率は９３．３％であった。
【００７２】
（実施例２２）
実施例２１に対し、更にジメチルホルムアミド１．００ｇを加え、反応時間を１時間にした以外は実施例２１と同じ条件で反応させた。分解率は４９．５％であった。
【００７３】
（実施例２３）
実施例２１に対し、更にジメチルスルホキシド１．００ｇを加え、反応時間を１時間にした以外は実施例２１と同じ条件で反応させた。分解率は５１．７％であった。
【００７４】
（実施例２４）
実施例２１に対し、更にジメチルスルホキシド５．００ｇを加えた以外は実施例２１と同じ条件で反応させた。分解率は４９．５％であった。
【００７５】
（比較例１１）
実施例２１に対し、Ｌ−乳酸２０ｇに代えて水２０ｇを用いた以外は実施例２１と同じ条件で反応させた。分解率は３０．０％であった。
【００７６】
（比較例１２）
実施例２１に対し、Ｌ−乳酸２０ｇに代えて水２０ｇを用い、更にジメチルスルホキシド１．００ｇを加えた以外は実施例２１と同じ条件で反応させた。分解率は２２．４％であった。
【００７７】
（実施例２５）
この実施例はルイス酸として「三フッ化ホウ素エチルエーテル」を用いた分解例を示している。
杉間伐材粉砕物１．００ｇにＬ−乳酸２０．００ｇ、三フッ化ホウ素エチルエーテル０．２ｇを加えて、２２０℃で、２．０時間分解させた。分解率は５９．５％であった。
【００７８】
上記した実施例２１〜２４における実験条件と結果を以下の表９に示し、比較例１１，１２および実施例２５における実験条件と結果を表１０に示す。
【００７９】
【表９】

【００８０】
【表１０】

【００８１】
実施例２１〜２４を示した表９のように、分解触媒として硫酸アルミニウムを併用した場合は、低濃度で短時間の反応であっても良好な分解率が得られることがわかる。また、比較例１１，１２は比較的分解率が低い。
【００８２】
（実施例２６）
下記の実施例２６，２７はポリ塩化ビニル皮膜で被われた「ポリ塩化ビニル張り合板」を原料木材とした例を示している。
ポリ塩化ビニル張り合板の粉砕物（ふるいの目の開きが０．８４〜１．６８ｍｍのふるいを通過した分）１．００ｇに、Ｌ−乳酸２０．０ｇ、硫酸アルミニウム０．２ｇを加え、２２０℃で２時間分解させた。分解率は３１．９％であった。ポリ塩化ビニルは塊となり、木材分解生成物から容易に分離できた。
【００８３】
（実施例２７）
ポリ塩化ビニル張り合板の小片（縦２０ｍｍ、横２０ｍｍ、厚さ２．５ｍｍ）１．００ｇに、Ｌ−乳酸２０．０ｇを加え、２２０℃で１０分間分解させた。分解率は１２．０％であった。ポリ塩化ビニルは合板木材から剥がれ容易に分離できた。
【００８４】
（実施例２８）
この実施例は「防虫機能ないし防腐機能を有する防腐剤が塗布されたＣＣＡ木材」を原料木材とした例を示している。
ＣＣＡ木材の粉砕物（ふるいの目の開きが０．８４〜１．６８ｍｍのふるいを通過した分）１．００ｇに、Ｌ−乳酸２０．０ｇを加え、撹拌機および冷却器付き三口フラスコを用いた開放系で、２２０℃で１時間分解させた。分解率は３２．６％であった。分解生成液にはクロム、銅、砒素などの重金属が含まれており、これら重金属の回収が可能となった。従って、防腐剤処理木材の廃棄処理が容易になった。
【００８５】
（実施例２９）
下記の実施例２９〜３１は分解生成物を「接着剤」に利用した例を示している。
杉間伐材粉砕物１．００ｇに、L−乳酸２０．００ｇ、硫酸アルミニウム０．２０ｇを加え、２２０℃で２時間分解させた。分解率は９３．３％であった。得られた分解生成物１１ｇを杉間伐材粉砕物８９ｇと混合し、ホットプレスにて、１８０℃で、２ＭＰａ、１０分間圧縮した。そして、インストロン材料試験機５５６９型により、ヘッドスピード５ｍｍ／分、スパン４５ｍｍの条件で曲げ強度を測定した。
【００８６】
（実施例３０）
ホットプレスによる圧縮時間を２０分間にした以外は、実施例２９と同じ条件で行った。
【００８７】
（実施例３１）
杉間伐材粉砕物１．００ｇに、L−乳酸２０．００ｇを加え、２２０℃で２時間分解させた。分解率は５４．５％であった。得られた分解生成物１１ｇを杉間伐材粉砕物８９ｇと混合し、ホットプレスにて、１８０℃で、６ＭＰａ、２０分間圧縮した。そして、インストロン材料試験機１１２２型により、ヘッドスピード１０ｍｍ／分、スパン４５ｍｍの条件で曲げ強度を測定した。
これらの実施例２９〜３１の結果は以下の表１１に示す。
【００８８】
【表１１】

【００８９】
表１１中でカッコ内の値は分解生成物を用いずに、杉間伐材粉砕物だけを圧縮して固めたものの曲げ強度を示している。
実施例２９〜３１のように、分解生成物を併存させて杉間伐材粉砕物をプレスすると、分解生成物を用いることなくプレスしたもの（かっこ内数値）と比べ、７〜１９倍程度に曲げ強度が向上した。すなわち、分解生成物が杉間伐材粉砕物に対し優れた接着性を有していることがわかる。
【００９０】
尚、実施例２９〜３１により得た分解生成物はいずれも、プレスの際に樹脂が熱で流動してフィルムになった。そのフィルムの赤外吸収スペクトルから、１７３６ｃｍ−１ にエステル基の吸収、１６０４、１５０９、１４５９ｃｍ−１ にフェニル基の吸収、１２６６ｃｍ−１ にフェニル−Ｏ−Ｃのエーテル結合の吸収、他の吸収はヘミセルロース、セルロースの吸収とほぼ一致した。すなわち、２９３７、２８５０、１４５９ｃｍ−１ にメチレン結合の吸収、１１１２、１０５７、１０００ｃｍ−１ に二級ＯＨ、一級ＯＨ、Ｃ−Ｏ−Ｃエーテル結合の吸収があった。従って、これはリグニン成分、Ｌ−乳酸でエステル化したヘミセルロース成分、セルロース成分を示しており、これらの成分が接着に寄与しているものと考えられる。
【００９１】
（実施例３２）
この実施例は分解生成物を「エポキシ化合物の硬化剤」に利用した例を示している。
実施例２で得た分解生成物２０ｇに、ビスフェノールＡタイプのエポキシ化合物（未硬化のプレポリマーであり、油化シェルエポキシ（株）製で商品名エピコート８２８を使用）を５０ｇ、硬化促進剤としての三フッ化ホウ素アニリン錯体を２．５ｇ加え、１００℃で２時間、その後１５０℃で２時間加熱し、硬化エポキシ樹脂を得た。
尚、フェノール性ＯＨ基やカルボキシル基の多い分解生成物の場合は、促進剤としてベンジルジメチルアミンなどの芳香族第三級アミンを用いると良い。
【００９２】
（実施例３３）
この実施例は分解生成物を「エポキシ樹脂原料」に利用した例を示している。
実施例２で得た分解生成物５０ｇに、４０％水酸化ナトリウム水溶液２０ｇを加え、５０℃で１０分間撹拌する。そして、エピクロルヒドリン５０ｇを加え、１００℃で１時間反応させる。その後、水洗し、エバポレータで過剰のエピクロルヒドリンを留去して、粘ちょう液状のエポキシ樹脂を得た。
一方、実施例２で得た分解生成物２０ｇに、三フッ化ホウ素アニリン錯体１．０ｇを加え、１００℃で２時間、その後１５０℃で２時間加熱することにより、硬化エポキシ樹脂が得られる。
【００９３】
（実施例３４）
この実施例は分解生成物を「ウレタン樹脂原料」に利用した例を示している。
実施例２で得た分解生成物５０ｇに、ウレタン化触媒としてトリエチレンジアミン０．０５ｇ、オクテン酸スズ（II）０．１８ｇを加え、次いでトルイレンジイソシアネート２５ｇを加えて撹拌する。その後、１００℃で２時間放置すると、発泡状のウレタン樹脂が得られた。この場合、ウレタン化触媒無しでも、加熱するだけでウレタン樹脂が得られる。
【００９４】
【発明の効果】
以上詳述したように、本発明によれば、木材を分解処分することができ、工業的に有用な分解生成物が得られた。この木材分解生成物は原材料として接着剤や樹脂原料となり得、色も淡い褐色程度なので種々の用途に用いられる。また、分解生成物を得る分解反応は比較的低い温度で、比較的短時間に、かつ比較的簡単な操作により実現可能であるので、簡易な設備をもって木材の処分および有効利用を図ることができる。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to the decomposition of wood and the use of the decomposition products. In particular, the present invention intends to recycle wood by chemically treating wood scraps to obtain industrially valuable raw materials. It is.
[0002]
[Prior art]
  Conventionally, used wood has been crushed into chips and transported to a paper mill for paper making, transported to a board manufacturing factory for particle board, or subjected to incineration. Such wood chips have a low bulk specific gravity and many paper mills are located in remote areas, which increases transportation costs. In addition, the Dioxin Measures Special Measures Law (enforced on January 15, 2000) established air emission standard values for dioxins from waste incinerators, making incineration in small incinerators difficult. Yes. In particular, some of the wood scraps produced during the manufacture of furniture and joinery are covered with polyvinyl chloride, making papermaking, boarding and incineration difficult.
[0003]
  On the other hand, wood that has been coated or impregnated with antiseptic or antiseptic preservatives, such as wooden sleepers, wooden utility poles, wooden bases and large drawers in houses (preservative treated wood such as chromium, copper, arsenic, etc.) The so-called CCA timber coated with a preservative containing harmful heavy metals such as CCA timber cannot be disposed of and is currently piled up.
  Therefore, a method for decomposing wood with a phenol-sulfuric acid-based decomposing reagent and using the decomposition product as a raw material for phenol resin is disclosed in, for example, Japanese Patent Application Laid-Open No. 6-263880. Alternatively, a method is known in which wood is decomposed with a glycol-sulfuric acid-based decomposition reagent and the decomposition product is used as a raw material for urethane resin.
[0004]
[Problems to be solved by the invention]
  However, like the above-mentioned phenol resin raw material and urethane resin raw material, such decomposition using a sulfuric acid catalyst has a defect that the decomposition product becomes black due to carbonization, and its use is remarkably limited. In addition, the former is difficult to distill off phenol, and the fluidity during molding is poor.
  On the other hand, adhesives used for plywood, etc., are mainly composed of urea resin that releases formaldehyde (methylol urea), trimethylol melamine, etc., but there is a problem with house sick syndrome due to formaldehyde released from such adhesives. Therefore, the development of an adhesive that does not cause Housesick syndrome is eagerly desired.
[0005]
[Means for Solving the Problems]
  In order to solve the above problems, the present inventors have devised an invention in which, for example, pulverized wood is decomposed at a relatively low temperature of about 100 to 300 ° C. to obtain a wood decomposition product. Has been devised for use as an adhesive, an epoxy resin raw material and a curing agent, or a urethane resin raw material.
  That is, the invention created by the present inventors is that the woodAcidIt is a wood decomposition product obtained by further decomposition. In decomposing wood with the above compound, a wood swelling agent may be used in combination.
[0006]
  In addition, the wood degradation product of the present invention is obtained by converting wood into hydroxycarboxylic acid in the presence of Lewis acid.AcidIt can also be obtained by further decomposition.
[0007]
  As the raw wood from which the wood decomposition product of the present invention is obtained, wood treated with a preservative or wood covered with a polyvinyl chloride film is also applied.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
  In the present invention, the wood scrap can be used as a raw material as it is, but it is preferable to perform a pretreatment by pulverizing the raw material (if necessary, separating polyvinyl chloride or the like) and sieving the pulverized product. Examples of the crushing include impact crushers (hammer type, chain type), shear crushers, cutting crushers, compression crushers (roll type, conveyor type, screw type), stamp mills, ball mills, rod mills. It can be performed by a pulverizer or the like. The smaller the pulverized product, the larger the surface area involved in the reaction, which is desirable, but a pulverized product that passes through a sieve with an opening of 10 mm is preferable. A pulverized material passing through a sieve having an opening of 3 mm, more preferably 1 mm, is preferable.
[0009]
  The tree species used as the raw material wood of the present invention is not particularly limited. For example, coniferous trees such as pine, fir, spruce, larch, togasawara, tsuka, hinoki, hiba, nezuko, cedar, and boxwood, maple, beech, alder tree. , Cherry, persimmon, cypress, birch, birch, red oak, onigurumi, chestnut, shii, oak, oak, geese, yellowfin, haruni, zelkova, honoki, camphor, taboo, cypress, wig, asada, dronoki, linden , Hardwoods such as bark, drill, tammo, Inuenju, and Yamaguchi.
[0010]
  Wood decomposition test used in the present inventionWith medicineSome hydroxycarboxylic acids include saturated hydroxycarboxylic acids and unsaturated hydroxycarboxylic acids.
  Examples of the saturated hydroxycarboxylic acid include glycolic acid, lactic acid, 2-hydroxybutyric acid, 2-hydroxy-2-methylpropanoic acid, 2-hydroxy-4-methylpentanoic acid, 2-ethyl-2-hydroxybutyric acid, 3-hydroxypropionic acid, 10-hydroxystearic acid, 3,3,3-trichloro-2-hydroxypropionic acid, 2- (lactoyloxy) propionic acid, hydroxybenzoic acid, salicylic acid, 5-chlorosalicylic acid, 3,5 -Dichlorosalicylic acid, 3-nitrosalicylic acid, 3,5-dinitrosalicylic acid, methylsalicylic acid, thymotic acid, vanillic acid, isovanillic acid, hydroxyphenylacetic acid, 3- (o-hydroxyphenyl) propionic acid, mandelic acid, phenyllactic acid, 3 -Hydroxyphenylpropionic acid, 2 Such as hydroxy-2,2-diphenylethane acid.
  Examples of the unsaturated hydroxycarboxylic acid include hydroxycinnamic acid, 4-hydroxy-3-methoxycinnamic acid, 3-hydroxy-4-methoxy cinnamic acid, and 2-hydroxy-4-phenyl-3. -Butenoic acid, 4-allyl-2-hydroxy-6-methoxybenzoic acid, 2-hydroxy-6- (8,11-pentadecadienyl) benzoic acid, 12-hydroxy-9-octadecenoic acid, etc..
[0011]
  The weight ratio between the wood chips and the compound used as the decomposition reagent is 1: 0.2 to 35, preferably 1: 0.5 to 5. By changing this ratio, the molecular weight of the resulting decomposition product can be adjusted. Incidentally, when the decomposition reagent is small, the molecular weight of the decomposition product increases, and when the decomposition reagent is large, the molecular weight of the decomposition product decreases.
  In terms of processing costs, it is better to add less material. However, there are cases where it cannot be reduced from the viewpoint of wettability. Further, since the pulverized wood is bulky, it may not be sufficiently immersed in the decomposition reagent, and the surface of the pulverized wood may not be wetted. However, when it does not wet sufficiently, the pulverized wood can be wetted and decomposed by adding a liquid (decomposition product) generated by the decomposition to a new decomposition reagent of the same type as that used for the decomposition. Moreover, it is also possible to efficiently use the pulverized wood efficiently by separating the excessive decomposition reagent from the decomposition product.
[0012]
  Examples of the wood swelling agent used in the present invention include sodium nitrate-water (sodium nitrate aqueous solution), ethylene carbonate, lactitol-water (lactitol aqueous solution), dimethyl sulfoxide, dimethylformamide, N-methylmorpholine-N-oxide, N , N-dimethylacetamide-lithium chloride system (mixture of N, N-dimethylacetamide and lithium chloride), anisole, urea, water and the like. These wood swelling agents act as solubilizers and swelling agents for lignin, hemicellulose, and cellulose, which are wood components, and accelerate the decomposition of the wood components. For example, anisole is believed to prevent insolubilization due to condensation of lignin at high temperatures.
[0013]
  Examples of the Lewis acid used in the present invention include aluminum sulfate, boron trifluoride, aluminum trichloride, titanium tetrachloride, tin trichloride (a trace amount of water is required as a cocatalyst), diethyl etherate, and the like. . These Lewis acids act as a catalyst for the wood decomposition reaction and increase the decomposition rate of the wood components.
[0014]
  The decomposition temperature of the wood in the present invention is about 100 to 300 ° C., which is a relatively low temperature. Preferably, a decomposition temperature of 200 ° C. to 300 ° C. is desirable because the decomposition rate is increased. And it is desirable to decompose in a nitrogen atmosphere in order to prevent coloring due to oxidation reaction. Furthermore, when an antioxidant such as 2,6-di-t-butyl-4-methylphenol is added and decomposed, coloring can be further prevented. It is also possible to perform decomposition under atmospheric pressure or under pressure. Incidentally, when using a low boiling point hydroxycarboxylic acid or the like, it is desirable to perform decomposition under pressure at a temperature higher than the boiling point.
[0015]
  The constituent components of wood are mainly lignin, hemicellulose, and cellulose. These compounds (R—O—R ′) have an ether bond and are easily opened by an acid (HX) as shown in the following formula.
        R—O—R ′ + HX → R—X + R′—OH
  The glycoxy bond of hemicellulose and cellulose is generally weak against acids and stable to bases, but the C-2 (α-position) hydrogen is attacked by the bases by the aldehyde group at the reducing end. In this case, sugar residues are removed one by one from the reducing end. Therefore, the base is easily decomposed in the order of (1 → 3) bond> (1 → 4) bond = (1 → 6) bond> (1 → 2) bond.
  Hydroxycarvone as described aboveAcidSince it has a bifunctional group, a functional group also exists at the terminal of the decomposition product obtained by solvolysis. Incidentally, the solvolysis products of wood with hydroxycarboxylic acids are partly polysaccharide hydroxycarboxylic acid esters. These decomposition products can be used for adhesives, epoxy resin raw materials, and urethane resin raw materials without purification. This method of using the decomposition product does not require a purification step and can be carried out without any problem even if there is some moisture.
[0016]
  Further, the preservative-treated wood can be used as raw material wood. In that case, heavy metals such as chromium, copper, and arsenic contained in the preservative can be recovered and processed. In addition, polyvinyl chloride-clad plywood covered with a polyvinyl chloride film (for example, wood ends of furniture and fittings) is decomposed into a liquid state only by the wood part. It can be easily separated.
[0017]
  Since OH groups and COOH groups contained in a large amount in the wood decomposition product of the present invention tend to cause ionic bonds and hydrogen bonds, the wood decomposition product of the present invention is used as an adhesive between objects. Since the adhesive made of this wood decomposition product contains a large amount of natural components such as lignin, it is considered human-friendly and contributes to the elimination of Housesick syndrome.
  Moreover, since the active hydrogen of OH group and NH2 group contained in the wood decomposition product of the present invention is added to the oxygen atom of the uncured epoxy compound to cause intermolecular crosslinking, the wood decomposition product is not uncured epoxy. Used as a curing agent for compounds.
  And since the wood decomposition product of this invention exists in a cellulose, hemicellulose, and lignin and contains the polyhydroxy compound which has many OH groups, it can become a part of the raw material of the epoxy resin which reacts with epichlorohydrin. Or it can become a part of the raw material of the urethane resin which reacts with an isocyanate compound. In this case, examples of the isocyanate compound used in the present invention include diisocyanates, polyisocyanates, isocyanate regenerated products, and non-yellowing isocyanates.
[0018]
【Example】
  The present invention will be specifically described with reference to examples.
  In the following examples, wood powder obtained by pulverizing rice tsuga (scientific name: Tsuga heterophylla Sarg.) With a Willet-type pulverizer as a timber (passage with a sieve opening of 0.25 mm, bulk specific gravity of 0.45), or Wakayama prefecture cedar (scientific name: Cryptomeria japonica D.Don) crushed thinned timber is classified by sieve machine (product name “Ugran” manufactured by Morishita Kikai Co., Ltd., 0.25-2 mm sieve opening) Used (bulk specific gravity 0.17). Therefore, pulverized wood, decomposition reagent, etc. are charged into a sealed reaction vessel (type name TVS-N2 type (cap bolt type), 200 ml capacity with a portable reactor manufactured by Pressure Glass Industry Co., Ltd.) at a predetermined temperature. Decompose for a predetermined time. After completion of the decomposition, the solid content is filtered off, and the solid content on the glass filter is washed successively with a solvent such as methanol, tetrahydrofuran, acetone, and water, and the insoluble content remaining on the glass filter is weighed after drying under reduced pressure. The decomposition rate was calculated by dividing this weighed value by the weight of the crushed wood of the raw material. The molecular weight of the liquid decomposition product that passed through the glass filter was measured at 40 ° C. using a tetrahydrofuran solvent by gel permeation chromatography.
[0019]
(Example 1)
  The following Examples 1-10 show the decomposition example by "L-lactic acid".
  20.00 g of L-lactic acid was added to 1.00 g of the crushed cedar thinned material and decomposed at 200 ° C. for 2 hours. The decomposition rate was 27.4%.
[0020]
(Example 2)
  A decomposition product was obtained under the same conditions as in Example 1 except that decomposition was performed at 220 ° C. The decomposition rate was 54.5%.
[0021]
(Example 3)
  A decomposition product was obtained under the same conditions as in Example 1 except that decomposition was performed at 240 ° C. The decomposition rate was 48.6%.
[0022]
(Example 4)
  A decomposition product was obtained under the same conditions as in Example 1 except that decomposition was performed at 260 ° C. The decomposition rate was 43.5%.
[0023]
(Example 5)
  A decomposition product was obtained under the same conditions as in Example 1 except that decomposition was performed at 280 ° C. The decomposition rate was 42.2%.
[0024]
  Table 1 below shows the experimental conditions and results in Examples 1 to 5 described above.
[0025]
[Table 1]

[0026]
  As can be seen from Table 1 showing Examples 1 to 5, wood could be decomposed using L-lactic acid which is a hydroxycarboxylic acid as a decomposition reagent. In this case, increasing the reaction temperature does not necessarily lead to an improvement in the decomposition rate, but rather causes a decrease in the decomposition rate as the reaction temperature increases.
[0027]
(Example 6)
  20.00 g of L-lactic acid was added to 1.00 g of cedar thinned timber, and the mixture was decomposed at 220 ° C. for 1 hour. The decomposition rate was 52.8%.
[0028]
(Example 7)
  A decomposition product was obtained under the same conditions as in Example 6 except that the reaction was performed for 3 hours. The decomposition rate was 47.7%.
[0029]
(Example 8)
  A decomposition product was obtained under the same conditions as in Example 6 except that the reaction was performed for 5 hours. The decomposition rate was 35.7%.
[0030]
  The experimental conditions and results in Examples 6 to 8 described above are shown in Table 2 below.
[0031]
[Table 2]

[0032]
  As is apparent from Table 2 showing Examples 6 to 8, even if the reaction time was increased, the decomposition rate was not increased. That is, it is considered that there is an optimum reaction temperature and reaction time for each individual reaction system in addition to the reaction temperature described above.
[0033]
Example 9
  20.00 g of L-lactic acid was added to 1.00 g of cedar thinned timber, and the mixture was decomposed at 260 ° C. for 7 hours. The decomposition rate was 62.6%.
[0034]
(Example 10)
  A decomposition product was obtained under the same conditions as in Example 9 except that decomposition was performed at 290 ° C. The decomposition rate was 3.2%.
  The experimental conditions and results in Examples 9 and 10 described above are shown in Table 3 below.
[0035]
[Table 3]

[0036]
  According to Table 3 showing Examples 9 and 10, as in Examples 1 to 5 in Table 1, the decomposition rate does not depend on the reaction temperature. Rather, as in Example 10, the decomposition rate was extremely low at high temperatures. From this result, it seems that insolubilization such as lignin occurs at a high temperature of 290 ° C.
[0037]
  The decomposition residue in Example 9 was subjected to infrared absorption spectrum analysis. From the infrared absorption spectrum of the obtained decomposition residue, there was absorption of an ester group at 1746 cm −1, methylene at 2924, 1456 cm −1, primary OH group, secondary OH group, ether bond at 1030, 1058, 1107 cm −1. The absorption spectrum of cellulose was the same as that of cellulose except for the ester group. Therefore, the decomposition residue is cellulose esterified with L-lactic acid.
[0038]
(Example 11)
  20.00 g of L-lactic acid was added to 1.00 g of rice tsuga wood flour, and decomposed at 200 ° C. for 2 hours. The decomposition rate was 7.0%.
  The decomposition product obtained at this time was analyzed by the gel permeation chromatograph. From the analysis results of the gel permeation chromatograph, the peak 1 of the decomposition product of rice tsuga wood flour was number average molecular weight = 154, weight average molecular weight = 157, weight average molecular weight / number average molecular weight = 1.02. Peak 2 of the decomposition product was number average molecular weight = 239, weight average molecular weight = 240, and weight average molecular weight / number average molecular weight = 1.01. Peak 3 of the decomposition product was number average molecular weight = 314, weight average molecular weight = 315, and weight average molecular weight / number average molecular weight = 1.00. Peak 4 of the decomposition product was number average molecular weight = 674, weight average molecular weight = 923, weight average molecular weight / number average molecular weight = 1.37. The overall peaks of the decomposition products were number average molecular weight = 232, weight average molecular weight = 424, weight average molecular weight / number average molecular weight = 1.83.
[0039]
(Example 12)
  This example shows an example of decomposition by “glycolic acid”.
  20.00 g of glycolic acid was added to 1.00 g of cedar thinned wood, and decomposed at 220 ° C. for 2 hours. The decomposition rate was 43.0%.
[0040]
(Example 13)
  Examples 13 to 15 below show examples of decomposition by “L-lactic acid and wood swelling agent system”.
  20.00 g of L-lactic acid and 5.00 g of ethylene carbonate as a wood swelling agent were added to 1.00 g of cedar thinned timber and further decomposed at 260 ° C. for 3 hours. The decomposition rate was 50.2%.
[0041]
(Example 14)
  A decomposition product was obtained under the same conditions as in Example 13 except that 10.00 g of anisole was used instead of 5.00 g of ethylene carbonate and the reaction was performed for 7 hours. The decomposition rate was 53.8%.
[0042]
(Example 15)
  A decomposition product was obtained under the same conditions as in Example 14 except that 1.00 g of lactitol and 1.00 g of water were added. The decomposition rate was 63.7%.
[0043]
  Table 4 below shows the experimental conditions and results in Examples 12 to 15 described above.
[0044]
[Table 4]

[0045]
  According to Table 4 showing Examples 12 to 15, wood could be satisfactorily decomposed with glycolic acid (hydroxycarboxylic acid). Moreover, what added the wood swelling agent (ethylene carbonate (Example 13), anisole (Examples 14 and 15), lactitol-water (Example 15)) to L-lactic acid (hydroxycarboxylic acid) is the same. Compared with Example 4 and Example 9 which are experimental conditions, the decomposition rate is high.
[0046]
(Comparative Example 1)
  The following Comparative Examples 1 to 3 are observed by adding “only wood swelling agent” to the crushed cedar thinned material.
  20.00 g of anisole as a wood swelling agent was added to 1.00 g of cedar thinned timber and reacted at 260 ° C. for 7 hours. The decomposition rate was 16.4%.
[0047]
(Comparative Example 2)
  The reaction was carried out under the same conditions as in Comparative Example 1 except that an aqueous solution in which 2.00 g of lactitol was dissolved in 10.00 g of water was used instead of 20.00 g of anisole. The decomposition rate was -22.78%, and the residual solid content increased.
[0048]
(Comparative Example 3)
  The reaction was conducted under the same conditions as in Comparative Example 1 except that 20.00 g of acetic anhydride was used instead of 20.00 g of anisole and the reaction time was 2 hours. The decomposition rate was -36.72%, and the residual solid content increased.
[0049]
  The experimental conditions and results in Comparative Examples 1 to 3 described above are shown in Table 5 below.
[0050]
[Table 5]

[0051]
  Compared with Examples 13-15, Comparative Examples 1-3 shown in Table 5 add only a wood swelling agent, without using a decomposition reagent. Therefore, the cedar thinned timber is not decomposed much (Comparative Example 1), or conversely, the residual solid content is increased (Comparative Examples 2 and 3).
[0052]
(Example 16)
  Examples 16 to 20 below show examples of decomposition when “another wood swelling agent” is added.
  20.00 g of L-lactic acid, 10.00 g of N, N-dimethylacetamide and 0.45 g of lithium chloride as a wood swelling agent were added to 1.00 g of cedar thinned wood, and decomposed at 220 ° C. for 2 hours. The decomposition rate was 34.8%.
[0053]
(Example 17)
  The reaction was conducted under the same conditions as in Example 16 except that 2.00 g of 4-methylmorpholine-4-oxide was used instead of 10.00 g of N, N-dimethylacetamide and 0.45 g of lithium chloride. The decomposition rate was 65.3%.
[0054]
(Example 18)
  The reaction was conducted under the same conditions as in Example 16 except that 2.00 g of urea was used instead of 10.00 g of N, N-dimethylacetamide and 0.45 g of lithium chloride. The decomposition rate was 43.5%.
[0055]
(Example 19)
  The reaction was conducted under the same conditions as in Example 16 except that 5.00 g of dimethylformamide was used instead of 10.00 g of N, N-dimethylacetamide and 0.45 g of lithium chloride. The decomposition rate was 42.4%.
[0056]
(Example 20)
  The reaction was conducted under the same conditions as in Example 16 except that 10.00 g of water was used instead of 10.00 g of N, N-dimethylacetamide and 0.45 g of lithium chloride. The decomposition rate was 28.8%.
[0057]
  The experimental conditions and results in Examples 16 to 20 described above are shown in Table 6 below.
[0058]
[Table 6]

[0059]
  As shown in Table 6 showing Examples 16 to 20, various wood swelling agents (N, N-dimethylacetamide-lithium chloride system, 4-methylmorpholine-4-oxide, urea, dimethylformamide, water) were added to L- As a result of the combined use with lactic acid (decomposition reagent), it can be seen that the decomposition rate is maintained at a certain level or more without much decrease. In Example 17 (4-methylmorpholine-4-oxide), the decomposition rate was higher than in Example 2.
[0060]
(ComparisonExample4)
  thisComparisonThe example shows an example of decomposition with “ethanolamine”.
  Ethanolamine (20.00 g) was added to 1.00 g of rice bran wood flour, and decomposed at 250 ° C. for 2 hours. The decomposition rate was 18.5%.
[0061]
(ComparisonExample5)
  thisComparisonThe example shows an example of decomposition with “diethanolamine”.
  20.00 g of diethanolamine was added to 1.00 g of rice vine wood powder and decomposed at 250 ° C. for 2 hours. The decomposition rate was 20.0%.
[0062]
(ComparisonExample6)
  thisComparisonThe example shows an example of decomposition by “ethanolamine and wood swelling agent system”.
  Ethanolamine (20.00 g) and dimethylformamide (1.00 g) were added to 1.00 g of cedar thinned timber, and decomposed at 250 ° C. for 2 hours. The decomposition rate was 39.7%.
[0063]
(ComparisonExample7)
  thisComparisonThe example shows an example of decomposition by “adipic acid”.
  20.00 g of adipic acid was added to 1.00 g of rice tsuga wood flour and decomposed at 260 ° C. for 2 hours. The decomposition rate was 28.1%.
[0064]
(ComparisonExample8)
  thisComparisonThe example shows an example of decomposition with “succinic acid”.
  20.00 g of succinic acid was added to 1.00 g of rice tsuga wood flour and decomposed at 220 ° C. for 2 hours. The decomposition rate was 30.0%.
[0065]
(ComparisonExample9)
  belowComparisonExample9,10Shows an example of decomposition by “adipic acid and wood swelling agent system”.
  An aqueous solution obtained by dissolving 2.00 g of adipic acid and 1.00 g of sodium nitrate in 17.00 g of water was added to 1.00 g of cedar thinned timber, and the mixture was decomposed at 260 ° C. for 2 hours. The decomposition rate was 34.3%.
[0066]
(ComparisonExample10)
  In place of 1.00 g of sodium nitrate and 17.00 g of water, 10 g of water alone was added and decomposed at 220 ° C.ComparisonExample9The decomposition product was obtained under the same conditions. The decomposition rate was 34.3%.
[0067]
  AboveComparisonExample4~10The experimental conditions and results are shown in Tables 7 and 8 below.
[0068]
[Table 7]

[0069]
[Table 8]

[0070]
  Shown in Table 7 and Table 8ComparisonExample4~10Has a low degradation rate, but various degradation reagents (ethanolamine (ComparisonExample4,6), Diethanolamine (ComparisonExample5), Adipic acid (ComparisonExample7,9,10), Succinic acid (ComparisonExample8)), The wood was fully decomposed. Also in this case, when a wood swelling agent (dimethylformamide, sodium nitrate, water) is used in combination, the decomposition rate is high. In addition, theseComparisonExample4~10However, it is considered that a reasonable decomposition rate can be obtained if other reaction conditions are optimally selected.
[0071]
(Example21)
  Examples below21~24Shows an example in which “aluminum sulfate” is used as a Lewis acid as a decomposition catalyst.
  20 g of L-lactic acid and 0.2 g of aluminum sulfate were added to 1.00 g of cedar thinned timber and decomposed at 220 ° C. for 2 hours. The decomposition rate was 93.3%.
[0072]
(Example22)
  Example21Dimethylformamide was further added in an amount of 1.00 g, and the reaction time was 1 hour.21It was made to react on the same conditions. The decomposition rate was 49.5%.
[0073]
(Example23)
  Example21In addition to 1.00 g of dimethyl sulfoxide, the reaction time was 1 hour.21It was made to react on the same conditions. The decomposition rate was 51.7%.
[0074]
(Example24)
  Example21In Example, except that 5.00 g of dimethyl sulfoxide was further added.21It was made to react on the same conditions. The decomposition rate was 49.5%.
[0075]
(ComparisonExample11)
  Example21On the other hand, Example was used except that 20 g of water was used instead of 20 g of L-lactic acid.21It was made to react on the same conditions. The decomposition rate was 30.0%.
[0076]
(ComparisonExample12)
  Example21On the other hand, Example was used except that 20 g of water was used instead of 20 g of L-lactic acid and 1.00 g of dimethyl sulfoxide was further added.21It was made to react on the same conditions. The decomposition rate was 22.4%.
[0077]
(Example25)
  This example shows a decomposition example using “boron trifluoride ethyl ether” as a Lewis acid.
  20.00 g of L-lactic acid and 0.2 g of boron trifluoride ethyl ether were added to 1.00 g of cedar thinned timber, and the mixture was decomposed at 220 ° C. for 2.0 hours. The decomposition rate was 59.5%.
[0078]
  Example above21~24Table 9 shows the experimental conditions and results inExperimental conditions and results in Comparative Examples 11 and 12 and Example 25Table 10 shows.
[0079]
[Table 9]

[0080]
[Table 10]

[0081]
  Example21~24Table showing9Thus, it can be seen that when aluminum sulfate is used in combination as a decomposition catalyst, a good decomposition rate can be obtained even in a short time reaction at a low concentration. Also,ComparisonExample11,12Has a relatively low decomposition rateYes.
[0082]
(Example26)
  Examples below26,27Shows an example in which “polyvinyl chloride laminated plywood” covered with a polyvinyl chloride film is used as a raw material wood.
  Pulverized polyvinyl chloride plywood (sieveofL-lactic acid (20.0 g) and aluminum sulfate (0.2 g) were added to 1.00 g), which was passed through a sieve having an opening of 0.84 to 1.68 mm, and decomposed at 220 ° C. for 2 hours. The decomposition rate was 31.9%. The polyvinyl chloride was agglomerated and could be easily separated from the wood degradation products.
[0083]
(Example27)
  20.0 g of L-lactic acid was added to 1.00 g of a piece of polyvinyl chloride-clad plywood (length 20 mm, width 20 mm, thickness 2.5 mm), and decomposed at 220 ° C. for 10 minutes. The decomposition rate was 12.0%. Polyvinyl chloride peeled off the plywood wood and could be easily separated.
[0084]
(Example28)
  This example shows an example in which “CCA wood coated with an antiseptic or antiseptic preservative” is used as the raw material wood.
  CCA pulverized material (sieveof20.0 g of L-lactic acid was added to 1.00 g), and the open system using a three-neck flask with a stirrer and a condenser was used at 220 ° C. Decompose for 1 hour. The decomposition rate was 32.6%. The decomposition product liquid contains heavy metals such as chromium, copper, and arsenic, and these heavy metals can be recovered. Therefore, disposal processing of the preservative-treated wood is facilitated.
[0085]
(Example29)
  Examples below29~31Shows an example in which the decomposition product is used as an “adhesive”.
  L-lactic acid (20.00 g) and aluminum sulfate (0.20 g) were added to 1.00 g of cedar thinned wood, and the mixture was decomposed at 220 ° C. for 2 hours. The decomposition rate was 93.3%. 11 g of the obtained decomposition product was mixed with 89 g of cedar thinned timber and compressed with a hot press at 180 ° C. for 2 MPa for 10 minutes. Then, the bending strength was measured with an Instron material testing machine 5569 under the conditions of a head speed of 5 mm / min and a span of 45 mm.
[0086]
(Example30)
  Example except that the compression time by hot pressing was 20 minutes29Performed under the same conditions.
[0087]
(Example31)
  20.00 g of L-lactic acid was added to 1.00 g of cedar thinned timber and decomposed at 220 ° C. for 2 hours. The decomposition rate was 54.5%. 11 g of the obtained decomposition product was mixed with 89 g of cedar thinned timber and compressed with a hot press at 180 ° C. and 6 MPa for 20 minutes. Then, the bending strength was measured with an Instron material testing machine type 1122 under the conditions of a head speed of 10 mm / min and a span of 45 mm.
  These examples29~31The results are shown in Table 11 below.
[0088]
[Table 11]

[0089]
  In Table 11, the value in parentheses indicates the bending strength of a product obtained by compressing and hardening only a cedar thinned timber product without using a decomposition product.
  Example29~31Thus, when the pulverized cedar thinned material was pressed with the decomposition product coexisting, the bending strength was improved by about 7 to 19 times compared to the pressed product without using the decomposition product (value in parentheses). That is, it can be seen that the decomposition product has excellent adhesiveness to the cedar thinned material.
[0090]
  Examples29~31In any of the decomposition products obtained by the above, the resin flowed with heat during pressing to form a film. From the infrared absorption spectrum of the film, the absorption of the ester group at 1736 cm −1, the absorption of the phenyl group at 1604, 1509, 1459 cm −1, the absorption of the ether bond of phenyl-O—C at 1266 cm −1, and other absorptions It almost coincided with the absorption of hemicellulose and cellulose. That is, absorption of methylene bonds was observed at 2937, 2850, and 1459 cm −1, and absorption of secondary OH, primary OH, and C—O—C ether bonds were observed at 1112, 1057, and 1000 cm −1. Therefore, this shows a lignin component, a hemicellulose component esterified with L-lactic acid, and a cellulose component, and these components are considered to contribute to adhesion.
[0091]
(Example32)
  In this example, the decomposition product is used as an “epoxy compound curing agent”.
  20 g of the decomposition product obtained in Example 2 was added to 50 g of a bisphenol A type epoxy compound (uncured prepolymer, manufactured by Yuka Shell Epoxy Co., Ltd., using the product name Epicoat 828) as a curing accelerator. 2.5 g of the boron trifluoride aniline complex was added and heated at 100 ° C. for 2 hours and then at 150 ° C. for 2 hours to obtain a cured epoxy resin.
  In the case of a decomposition product having many phenolic OH groups and carboxyl groups, an aromatic tertiary amine such as benzyldimethylamine may be used as an accelerator.
[0092]
(Example33)
  This example shows an example in which a decomposition product is used as an “epoxy resin raw material”.
  To 50 g of the decomposition product obtained in Example 2, 20 g of 40% aqueous sodium hydroxide solution is added and stirred at 50 ° C. for 10 minutes. Then, 50 g of epichlorohydrin is added and reacted at 100 ° C. for 1 hour. Thereafter, the mixture was washed with water, and excess epichlorohydrin was distilled off with an evaporator to obtain a viscous liquid epoxy resin.
  On the other hand, 1.0 g of boron trifluoride aniline complex is added to 20 g of the decomposition product obtained in Example 2, and the cured epoxy resin is obtained by heating at 100 ° C. for 2 hours and then at 150 ° C. for 2 hours.
[0093]
(Example34)
  This example shows an example in which a decomposition product is used as a “urethane resin raw material”.
  To 50 g of the decomposition product obtained in Example 2, 0.05 g of triethylenediamine and 0.18 g of tin (II) octenoate are added as a urethanization catalyst, and then 25 g of toluylene diisocyanate is added and stirred. Then, when it was allowed to stand at 100 ° C. for 2 hours, a foamed urethane resin was obtained. In this case, even without a urethanization catalyst, a urethane resin can be obtained by simply heating.
[0094]
【The invention's effect】
  As described above in detail, according to the present invention, wood can be disposed of by decomposition, and industrially useful decomposition products are obtained. This wood decomposition product can be used as a raw material for an adhesive or a resin material, and has a light brown color, so that it can be used for various purposes. In addition, since the decomposition reaction for obtaining the decomposition product can be realized at a relatively low temperature, in a relatively short time, and by a relatively simple operation, it is possible to dispose and effectively use wood with simple equipment. .

Claims (8)

Wood, wood degradation product obtained by more decomposed hydroxycarboxylic acids. Wood, in the presence of wood swelling agent, wood degradation product obtained by more decomposed hydroxycarboxylic acids. Wood, in the presence of a Lewis acid, wood degradation product obtained by more decomposed hydroxycarboxylic acids.   The wood decomposition product according to any one of claims 1 to 3, wherein the raw material wood is wood treated with a preservative or wood covered with a polyvinyl chloride film.   A method for adhering an object, comprising adhering an object through the wood decomposition product according to any one of claims 1 to 4.   A method for curing an uncured epoxy compound, comprising: reacting the wood decomposition product according to any one of claims 1 to 4 with an uncured epoxy compound to cure.   The manufacturing method of the epoxy resin characterized by making the wood decomposition product of any one of Claim 1 thru | or 4 react with epichlorohydrin, and obtaining an epoxy resin.   A method for producing a urethane resin, comprising: reacting the wood decomposition product according to any one of claims 1 to 4 with an isocyanate compound to obtain a urethane resin.