JPS63112677A - Lignhin resin adhesive - Google Patents
Lignhin resin adhesiveInfo
- Publication number
- JPS63112677A JPS63112677A JP25585186A JP25585186A JPS63112677A JP S63112677 A JPS63112677 A JP S63112677A JP 25585186 A JP25585186 A JP 25585186A JP 25585186 A JP25585186 A JP 25585186A JP S63112677 A JPS63112677 A JP S63112677A
- Authority
- JP
- Japan
- Prior art keywords
- lignin
- resorcinol
- resin
- solution
- kraft
- 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.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 73
- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 32
- 239000000853 adhesive Substances 0.000 title claims abstract description 31
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229920005610 lignin Polymers 0.000 claims abstract description 51
- 239000002655 kraft paper Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 45
- 239000002699 waste material Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 5
- 238000004537 pulping Methods 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000022244 formylation Effects 0.000 abstract 1
- 238000006170 formylation reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229920005611 kraft lignin Polymers 0.000 description 13
- 239000011120 plywood Substances 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229930183217 Genin Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 241000315040 Omura Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 1
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 description 1
- 235000007746 carvacrol Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 description 1
- -1 methanol and water Chemical compound 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本光明はリグニン樹脂接着剤に関するものである。さら
に詳述すれば、本発明は、クラフトパルプ廃黛より分離
したクラフトリグニンまたは、クラフトパルプ廃液を樹
脂化したＪＡＳの特類ｊ＃コ用合板の規格を満足する接
着剤に間するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to lignin resin adhesives. More specifically, the present invention provides an adhesive that satisfies the JAS specification for plywood for special class J#, which is made by converting kraft lignin separated from kraft pulp waste or kraft pulp waste liquid into a resin. .
従来の技術
大村の主要成分中セルロースはパルプなどに使用されて
いるが残りの成分については、必ずしも有効に利用され
ているとはいえない、クラフトパルプ化法（ＫＰ法）は
、現存もっとも広く行なゎれている化学パルプ製造法で
あるが、その工程中で発生する蒸解廃液（クラフトパル
プ廃液）については単にこれを濃縮した後に燃焼してエ
ネルギーと薬品の回収を行っているのが大半であり、中
に含まれる成分が宥効に利用されているとはいいがたい
、クラフトパルプ廃液は、その固型分中ｉ、：約３約３
置
す、酩を加えて沈澱させることによって他の成分と分離
する事が出来る．このクラフトリグニンはフェノール性
水酸基などの活性基を多く含み１反応性に富んでいると
考えられるため、古くから接着剤の原料としての応用研
究が行なわれてきたが、実用化の域には達っしていない
．その主たる理由は，■廃液、あるいはリグニンに対し
て前処理が必要であること、■原料置換率（例：フェノ
ール等のリグニンによる代＃率）が低いため、経済的な
優位性がないこと、７か硬化時間が長く、熱圧温度が高
いなどの作業性の面での不利益があることなどの点であ
る。Conventional technology Cellulose, one of Omura's main components, is used in pulp, etc., but the remaining components cannot necessarily be used effectively.The kraft pulping method (KP method) is currently the most widely practiced method. Although the current chemical pulp manufacturing method is currently in use, most of the cooking waste liquid (kraft pulp waste liquid) generated during the process is simply concentrated and then burned to recover energy and chemicals. However, it is difficult to say that the components contained therein are used for soothing effects.The solid content of kraft pulp waste liquid is approximately 3.
It can be separated from other components by adding alcohol and precipitation. Since this kraft lignin contains many active groups such as phenolic hydroxyl groups and is thought to be highly reactive, research has long been conducted on its use as a raw material for adhesives, but it has not yet reached the level of practical application. I haven't. The main reasons for this are: ■ pretreatment is required for waste liquid or lignin; ■ raw material substitution rate (e.g., substitution rate of phenol, etc. with lignin) is low, so there is no economic advantage; 7) It has disadvantages in terms of workability, such as a long curing time and a high heat and pressure temperature.
発明が解決しようとする問題点
本発明者らは，この様な状況を踏えて、クラフトリグニ
ンあるいはクラフトリグニンを含有するクラフト廃液を
利用した高性能でしかも低価格のリグニン樹脂接着剤の
開発について検討をすすめた．前述の様にリグニンある
いは、パルプ廃液を木材用接着剤に利用する研究は多く
あるが，その大半はリグニンフェノール樹脂についてで
ある。Problems to be Solved by the Invention In view of the above circumstances, the present inventors have investigated the development of a high-performance and low-cost lignin resin adhesive using kraft lignin or kraft waste liquid containing kraft lignin. I recommended. As mentioned above, there are many studies on the use of lignin or pulp waste liquid in wood adhesives, but most of them are on lignin phenolic resins.
本発明者らは、クラフトリグニンあるいはクラフト廃液
とレゾルシノールあるいはレゾルシノール樹脂との共縮
合によるリグニン・レゾルシ／−ル樹＠接着剤の製造法
について研究し、前述の問題点を解消したすぐれた接着
剤を得、本発明を完成するに至った．クラフトリグニン
あるいはクラフト廃液とレゾルシノールとを共縮合させ
た例は全くないと思われ，フェノールより高価なレゾル
シノールをリグニンで代替出来ることで，経済的優位性
は非常に大きいと思われる。The present inventors have researched a method for producing lignin resorcinol resin@adhesive by co-condensation of kraft lignin or kraft waste liquid with resorcinol or resorcinol resin, and have developed an excellent adhesive that solves the above-mentioned problems. As a result, we have completed the present invention. There seems to be no example of co-condensation of kraft lignin or kraft waste liquid with resorcinol, and the ability to replace resorcinol, which is more expensive than phenol, with lignin seems to have a great economic advantage.
発明の構成
り本発明の構成は，クラフトパルプ廃液中より分離して
得たリグニン変性物を単独であるいは一価のフェノール
類と混合したものをアルカリ性水溶液またはアルカリ性
アルコール−水混合溶液に溶解し、次いでアルデヒド類
を加えてホルミル化したリグニン樹脂液に、レゾルシノ
ールまたはレゾルシノール樹脂と，硬化剤とを混合した
ことを特徴とするリグニン・レゾルシノール樹脂接着剤
、
２）濃縮したクラフトパルプ廃液と１価のフェノール類
とアルコールを混合したものにアルデヒド類を加えてホ
ルミル化した樹脂液に、レゾルシノールまたはレゾルシ
ノール樹脂液と，硬化剤とを混合したことを特徴とする
リグニン・レゾルシノール樹脂接ｔｒ 剤。Structure of the Invention The structure of the present invention is to dissolve a modified lignin obtained by separating it from kraft pulp waste liquid alone or in a mixture with monovalent phenols in an alkaline aqueous solution or an alkaline alcohol-water mixed solution, A lignin/resorcinol resin adhesive characterized by mixing resorcinol or resorcinol resin and a hardening agent with a lignin resin liquid that has been formylated by adding aldehydes, 2) Concentrated kraft pulp waste liquid and monovalent phenol. 1. A lignin-resorcinol resin adhesive, which is characterized in that a resin liquid obtained by adding aldehydes to a mixture of alcohols and alcohols to formylate it, is mixed with resorcinol or a resorcinol resin liquid, and a curing agent.
３） クラフトパルプ廃液中より分離して得たリグニン
変性物をアルカリ性水溶液またはアルカリ性アルコール
−水混合溶液に溶解し、その溶液にレゾルシノールまた
はレゾルシノール樹脂と、硬化剤とを混合した事を特徴
とするりゲニン・レゾルシノール樹脂接着剤である。3) A modified lignin product obtained by separating from kraft pulp waste liquid is dissolved in an alkaline aqueous solution or an alkaline alcohol-water mixed solution, and resorcinol or resorcinol resin and a curing agent are mixed in the solution. Genin resorcinol resin adhesive.
本発明の構成要素について以下に詳説する。Components of the present invention will be explained in detail below.
（リグニン変性物）
本発明で用いるリグニン変性物は、クラフトパルプ廃液
を酸を用いてｐＨ２〜１０に調整し、生じた沈９を 通
して得たクラフトリグニンである。(Lignin modified product) The lignin modified product used in the present invention is kraft lignin obtained by adjusting the pH of kraft pulp waste liquid to 2 to 10 using an acid and passing through the resulting precipitate 9.
（クラフト廃液）
本発明で用いるクラフトパルプ廃液は、工程より発生す
る廃液を固型分濃度４５〜５０重量％程度に濃縮した、
濃縮クラフトパルプ廃液であり。(Kraft waste liquid) The kraft pulp waste liquid used in the present invention is obtained by concentrating the waste liquid generated from the process to a solid content of about 45 to 50% by weight.
Concentrated kraft pulp waste liquid.
高濃度でクラフトリグニンを含有する。Contains kraft lignin in high concentrations.
（−価のフェノール類）
本発明に用いる一価のフェノール類は、フェノール、ク
レゾール、キシレノール、カルバクロール、チモール、
ナフトールなどであるが、フェノールが好ましい．−価
のフェノールの使用割合は任意であり特に限定されない
がリグニン変性物７０〜１００重量％に対し，０〜３０
重量％の使用で充分であり、すぐれたリグニン樹脂接着
剤を得る事が出来る。(-valent phenols) The monovalent phenols used in the present invention include phenol, cresol, xylenol, carvacrol, thymol,
Examples include naphthol, but phenol is preferred. The proportion of phenol used is arbitrary and not particularly limited, but it is 0 to 30% by weight for 70 to 100% by weight of the modified lignin.
The use of % by weight is sufficient and an excellent lignin resin adhesive can be obtained.
（アルデヒド類）
本発明に於けるアルデヒド類としてはレゾルシノール樹
脂の製造に用いられるアルデヒド類であればいずれも使
用できるが、ホルムアルデヒドが好ましい。(Aldehydes) As the aldehydes in the present invention, any aldehydes used in the production of resorcinol resins can be used, but formaldehyde is preferred.
（アルカリ性溶液）
本発明に用いるアルカリ性溶液は力性ソーダまたは力性
カリの水溶液あるいはメタノールなどの低級アルコール
と水の混合溶液であり、力性ソーダ水溶液が好ましい。(Alkaline Solution) The alkaline solution used in the present invention is an aqueous solution of aqueous sodium hydroxide or potassium hydroxide, or a mixed solution of a lower alcohol such as methanol and water, and an aqueous aqueous sodium hydroxide solution is preferable.
（レゾルシノール樹脂とレゾルシノール）は
レゾルシノール樹脂■、レゾルシノールとホルムアルデ
ヒドなどのアルデヒド類とからレゾルシノール樹脂接着
剤を製造する周知の方法に従って製造される。(Resorcinol resin and resorcinol) is produced according to a well-known method for producing resorcinol resin adhesives from resorcinol resin (1), resorcinol, and aldehydes such as formaldehyde.
レゾルシノール樹脂とレゾルシノールは併用してもよい
。Resorcinol resin and resorcinol may be used together.
これら成分の使用割合は任意であり特に限定されないが
、固型分比（ｆＥ量比）でリグニン樹脂１０に対し１〜
７の範囲で充分な接着効果を示す。The usage ratio of these components is arbitrary and not particularly limited, but the solid content ratio (fE amount ratio) is 1 to 1 to 10 parts of lignin resin.
A sufficient adhesion effect is exhibited within the range of 7.
（アルコール） メタノール、エタノールなどの低級７ルコールである。(alcohol) Lower 7 alcohols such as methanol and ethanol.
（硬化剤）
本発明に用いる硬化剤はパラホルムアルデヒドなどレゾ
ルシノール樹脂接着剤に於し）て通常使用されている硬
化剤である．ただし、ヘキサメチレンテトラミンは使用
できない。(Curing agent) The curing agent used in the present invention is a curing agent commonly used in resorcinol resin adhesives, such as paraformaldehyde. However, hexamethylenetetramine cannot be used.
（任意成分）
本発明は必要に応じて増量剤などのフィラーを添加して
もよい。(Optional Components) In the present invention, fillers such as extenders may be added as necessary.
実施例
本発明をいっそう理解しやすくするために以下に実施例
を示して具体的に説明するが、下記の実施例はこの発明
を何ら制限するもので６士な（Ｘ。EXAMPLES In order to make the present invention easier to understand, the present invention will be explained in detail below using examples, but the following examples do not limit the present invention in any way (X.
１） リグニンの製法
クラフトパルプ廃液に酸を加えｐＨ８．５〜９．０に調
整し、その除土じた沈澱を 過し、乾燥して粉砕したも
のをリグニン試料とした。1) Lignin production method Acid was added to the kraft pulp waste liquid to adjust the pH to 8.5 to 9.0, and the resulting precipitate was filtered, dried, and ground to obtain a lignin sample.
２）クラフトパルプ廃液
工程中で発生する蒸解廃液をクラフトリグニンを主成分
とする固型分が約４８重量％濃度になるように濃縮した
ものを試料とした。2) A sample was prepared by concentrating the cooking waste liquid generated during the kraft pulp waste liquid process so that the solid content mainly composed of kraft lignin was about 48% by weight.
３）樹脂の製造
イ）前記リグニンをホルマリンとメタノールにけん濁し
、次いでフェノールを加えた後、力性ソーダの４０重量
％水溶液を加えて溶かし、加熱しながら反応させて、リ
グニン樹脂液を調製した．この樹脂液にレゾルシノール
またはレゾルシノール樹脂液を加え，さらに触媒として
パラホルムアルデヒドを加えて接着剤とした。3) Production of resin a) The lignin was suspended in formalin and methanol, then phenol was added, and a 40% by weight aqueous solution of sodium hydroxide was added and dissolved, and the mixture was reacted with heating to prepare a lignin resin liquid. ．． Resorcinol or resorcinol resin liquid was added to this resin liquid, and paraformaldehyde was further added as a catalyst to form an adhesive.
口）濃縮したクラフト廃液にフェノールとメタノールを
加えて加熱しながら反応させリグニン樹脂を調製した．
この樹脂液にレゾルシノール又はレゾルシノール樹脂液
ヲ加え、さらにパラホルムアルデヒドを加えて接着剤と
した。A) Lignin resin was prepared by adding phenol and methanol to concentrated kraft waste liquid and reacting while heating.
Resorcinol or a resorcinol resin liquid was added to this resin liquid, and paraformaldehyde was further added to prepare an adhesive.
ハ）前記リグニンを少量の力性ソーダの４０重量％水溶
液に溶解し、この溶液にレゾルシノールまたはレゾルシ
ノール樹脂液を加え、これにパラホルムアルデヒドを加
えて接着剤とした。c) The above lignin was dissolved in a small amount of 40% by weight aqueous solution of sodium hydroxide, resorcinol or resorcinol resin liquid was added to this solution, and paraformaldehyde was added to this to prepare an adhesive.
０ 合板の作成と接着力試験
前記の樹脂液にｐ−増量剤（大阪合同株式会社製の商品
名）を１０重量％添加した後、樹脂液７ｇ／１５Ｘ１５
ｃｍ’をラワン単板（２７ｍｍ厚）の表裏に塗布し、１
０ Ｋｇ／ｃｍ″の冷圧で３０分間，次いで７０〜１
２０℃， ｌ Ｏ ｋｇ／ｃｒｒｒ’、１５〜４０分
間の条件で加熱圧締し、３プライ合板を作成した。0 Preparation of plywood and adhesive strength test After adding 10% by weight of p-extending agent (trade name manufactured by Osaka Godo Co., Ltd.) to the above resin solution, 7g of resin solution/15X15
cm' on the front and back sides of lauan veneer (27 mm thick),
0 Kg/cm'' cold pressure for 30 minutes, then 70~1
A 3-ply plywood was produced by heat-pressing at 20°C, lOkg/crrr' for 15 to 40 minutes.
１週間の熟成後ＪＡＳ Ｂタイプの試験片を作り、Ｊ
ＡＳの構造用合板の特類の規格に準じて常態および連続
煮沸試験を行った。After aging for one week, JAS B type specimens were made and JAS
Normal and continuous boiling tests were conducted in accordance with AS's special standards for structural plywood.
実施例１
クラフトリグニン４５ｇ、フェノール５ｇ、３７ｉｉ％
ホルマリン５０ｍＪＬ、メタノール５０ｍｌ、４０重量
％カセイソーダ水溶液ｌＯ ＩＩｉをフラスコにはかり
とり混合した．これをかくはんしながら５０℃で１時間
反応させて、リグニンフェノール樹脂液を調製した．ま
た、これとは別にレゾルシノールをアルカリ性水溶液に
溶かし３７重１％ホルマリン溶液を加えて樹脂化し、レ
ゾルシノール樹脂液を調製した。Example 1 Kraft lignin 45g, phenol 5g, 37ii%
50 mJL of formalin, 50 ml of methanol, and a 40% by weight aqueous solution of caustic soda lO IIi were weighed into a flask and mixed. This was stirred and reacted at 50°C for 1 hour to prepare a lignin phenol resin solution. Separately, resorcinol was dissolved in an alkaline aqueous solution and a 37% by weight 1% formalin solution was added to form a resin, thereby preparing a resorcinol resin solution.
このリグニンフェノール樹脂液と、レゾルシノール樹脂
液を固型分比で８：２および７：３でそれぞれ混合し、
これに増量剤とｐ−ホルムアルデヒドを硬化剤として加
え、接着剤とした。この接着剤を使用して、前記の様な
方法でラワンの３プライ合板を作成した。熱圧条件は、
７０℃１５分間とした。レゾルシノール樹脂は室温硬化
型接着剤であるがこの場合は７０℃の中温を使用した。This lignin phenol resin liquid and resorcinol resin liquid are mixed at a solid content ratio of 8:2 and 7:3, respectively,
A filler and p-formaldehyde were added as a hardening agent to form an adhesive. Using this adhesive, 3-ply lauan plywood was made in the manner described above. The heat and pressure conditions are
The temperature was 70°C for 15 minutes. Although resorcinol resin is a room temperature curing adhesive, in this case, a medium temperature of 70° C. was used.
それは室温での２４〜４８時間という操作時間の短縮を
はかるためである。結果は、７２時間の連続煮沸後の強
度がリグニン樹脂対レゾルシノール樹脂が８：２のもの
テ１４．５にｇ／ｃｒｎ’、７：３のも（７） テ１８
．８Ｋｇ／ｃｒｔｆ テあり、いずれもＪＡＳの構造用
合板の特類の規格７０ Ｋｇ／ｃｍ″を大きく上回って
いた。This is to shorten the operation time to 24 to 48 hours at room temperature. The results showed that the strength after 72 hours of continuous boiling was 14.5 g/crn' for the lignin resin to resorcinol resin of 8:2, and 7:3 for the case of lignin resin to resorcinol resin (7).
．． 8Kg/crtf, both of which far exceeded the JAS special standard for structural plywood of 70Kg/cm''.
第１表
実施例２
実施例１のリグニン・フェノール樹脂と同様の薬品配合
で、反応条件を５０℃１時間から、５０℃２時間に延長
して樹脂を調製した０反応条件を延長した分レゾルシノ
ール樹脂の混合量を減じて、リグニン樹脂対レゾルシノ
ール樹脂ｌＯ：１．１０：２および１０：３の混合比（
固型分比）で混合し、増量剤と硬化剤を加えてそれぞれ
接着剤を調製した。硬化条件は、実施例１と同じ７０℃
１５分とした。結果は、ｌｏ：Ｌのものは、ＪＡＳ規格
をわずかに上回る程度であるが、１０：２，１０：３の
ものは、それぞれ１２．４Ｋｇ／ａｍ’、１８．５Ｋｇ
／ｃｒｎ’と大きく上回っていた。Table 1 Example 2 Resorcinol was prepared by extending the reaction conditions from 50°C for 1 hour to 50°C for 2 hours using the same chemical formulation as the lignin/phenol resin in Example 1. By reducing the amount of resin mixed, the mixing ratio of lignin resin to resorcinol resin lO: 1.10:2 and 10:3 (
A filler and a hardening agent were added to prepare adhesives. Curing conditions were 70°C, the same as in Example 1.
It was set to 15 minutes. The results show that lo:L slightly exceeds the JAS standard, but 10:2 and 10:3 have 12.4Kg/am' and 18.5Kg, respectively.
/crn', which was significantly higher.
第２表
実施例３
実施例２と同様の方法で調製したリグニン・フェノール
樹脂とレゾルシノール樹脂をｌＯ：２の割合で混合し、
増量剤と硬化剤を加えて接着剤とした０合板の硬化時間
を１０．２０．３０゜４０分間とそれぞれ変動させて強
度試験を行った。その結果、硬化時間を２０分間に延長
すると煮慕後の強度は１９．０Ｋｇ／ｃばと向上したが
、それ以上延長しても強度の増加はなかった。また、１
０分間の硬化時間でも１１ ｋｇ／ｃｍ’強度があった
。Table 2 Example 3 A lignin phenolic resin prepared in the same manner as in Example 2 and a resorcinol resin were mixed at a ratio of 1O:2,
A strength test was conducted by varying the curing time of 0 plywood, which was made into an adhesive by adding an extender and a hardening agent, to 10, 20, and 30 degrees for 40 minutes. As a result, when the curing time was extended to 20 minutes, the strength after boiling improved to 19.0 kg/c, but no increase in strength occurred when the curing time was extended beyond that. Also, 1
Even with a curing time of 0 minutes, the strength was 11 kg/cm'.
第３表
実施例４
実施例２と同様の方法でＷ製したリグニン・フェノール
樹脂とレゾルシノール［１４を１０：１の割合で混合し
、増量剤と硬化剤を加えて接着剤とした。レゾルシノー
ル樹脂の配合割合を減らした分合板の硬化温度を８５．
１００．１２０℃と上昇させて、接着力試験を行った。Table 3 Example 4 A lignin/phenol resin produced by W in the same manner as in Example 2 and resorcinol [14] were mixed at a ratio of 10:1, and an extender and a curing agent were added to prepare an adhesive. By reducing the blending ratio of resorcinol resin, the curing temperature of the plywood was increased to 85.
Adhesion tests were conducted at elevated temperatures of 100.120°C.
硬化時間はいずれも１５分間とした。その結果８５℃１
５分間の硬化条件でも規格を充分上回ることが出来た。The curing time was 15 minutes in all cases. The result was 85℃1
Even under the curing conditions of 5 minutes, it was possible to sufficiently exceed the specifications.
第４表
実施例５
実施例２と同様の方法でｍ製したりゲニン・フェノール
樹脂に、レゾルシノールを１０：１の比率で混合し、硬
化剤（Ｐ−ホルムアルデヒド）と増量剤を加えて接着剤
とした。これは単体のレゾルシノールを使用することで
、レゾルシノール樹脂製造の工程を省略しようとしたも
のである。Table 4 Example 5 An adhesive was prepared by mixing resorcinol with genin phenol resin at a ratio of 10:1 in the same manner as in Example 2, and adding a hardening agent (P-formaldehyde) and an extender. And so. This is an attempt to omit the resorcinol resin production process by using single resorcinol.
硬化条件は、実施例４と同様に８５，１００゜１２０℃
と温度条件を変化させ、硬化時間は１５分とした。煮沸
試験の結果は、８５℃では、７．０Ｋｇ／ｃｒｎ’と規
格をかろうじて、満足する程度であるが、１００℃では
１２．３Ｋｇ、１２０℃では１５．８Ｋｇ／ｃゴと大き
く上回った。The curing conditions were 85,100° and 120°C as in Example 4.
The temperature conditions were changed and the curing time was 15 minutes. The results of the boiling test were 7.0 Kg/crn' at 85°C, which was just barely satisfying the standard, but at 100°C, it was 12.3 Kg/crn', and at 120°C, it was 15.8 Kg/crn', which far exceeded the standard.
第５表
実施例６
次にリグニンのホルミル化物とレゾルシノール樹脂の共
縮合物について試験した。クラフトリグニン２５ｇ、３
７重量％のホルマリン２５１立、メタノール２５＋ａｉ
および４０重量％力性ソーダ５Ｉｌｉを混合し、かくは
んしながら５０℃で１時間反応させて樹脂化した。この
樹脂液とレゾルシノール樹脂を９：１．８：２および７
：３の割合（固型分比）でそれぞれ混合し、増量剤と硬
化剤（Ｐ−ホルムアルデヒド）をそれぞれ加えて接着剤
とした０合板の硬化条件は、７０℃１５分間とした。そ
の煮沸試験の結果は９：１のものは。Table 5 Example 6 Next, a co-condensate of a formylated lignin and a resorcinol resin was tested. Kraft lignin 25g, 3
7% by weight formalin 251, methanol 25+ai
and 40% by weight of sodium hydroxide 5Ili were mixed and reacted at 50° C. for 1 hour with stirring to form a resin. This resin liquid and resorcinol resin were mixed at 9:1.8:2 and 7.
The curing conditions for the 0 plywood were 70° C. for 15 minutes. The boiling test result was 9:1.
７．８ Ｋｇ／ｃｒｎ’とやや低いが、８：２．７：３
のものはそれぞれ１１．５．１３．０Ｋｇ／ｃゴと大き
く規格を上回った。7.8 Kg/crn', which is a little low, but 8:2.7:3
The weights were 11.5 and 13.0 kg/c, respectively, which greatly exceeded the standards.
第６表
実施例７
固型分４８重量％に濃縮したＫＰ（クラフトパルプ）廃
液９４ｇに少量の硫酸を加えた後、フェノール１５ｇ、
バラホルムアルデヒド４０ｇおよびメタノール５０１文
を続けて加えて混合した後、７０℃で４時間反応させて
樹脂化した。このリクニンーフェノール樹脂とレゾルシ
ノールを６：４の割合で混合し、硬化剤（Ｐ−ホルムア
ルデヒド）と増量剤をそれぞれ加えて接着剤とした０合
板の硬化条件は１００℃５分、１５分、１２０℃５分、
１５分の４種類である。結果は、１２０℃５分のものは
やや弱いが、他はいずれもＪＡＳ構造用合板の規格を満
足するもので、特に１２０”０１５分で硬化させたもの
は１４．７Ｋｇ／＋：ＩＴ！’と良結果を示した。Table 6 Example 7 After adding a small amount of sulfuric acid to 94 g of KP (kraft pulp) waste liquid concentrated to a solid content of 48% by weight, 15 g of phenol,
40 g of rose formaldehyde and 501 g of methanol were successively added and mixed, and then reacted at 70° C. for 4 hours to form a resin. This Likunin-phenolic resin and resorcinol were mixed in a ratio of 6:4, and a curing agent (P-formaldehyde) and an extender were added to make an adhesive.The curing conditions for the zero plywood were: 100℃ for 5 minutes, 15 minutes, 120℃ 5 minutes,
There are 4 types of 15 minutes. The results are a little weak for the one cured at 120℃ for 5 minutes, but all the others meet the JAS structural plywood standards, especially the one cured at 120℃ for 15 minutes at 14.7Kg/+:IT!' showed good results.
第７表
発明の効果
本発明は、リグニンの有効な利用法の一環としてクラフ
トパルプ廃液中のリグニンを分離するか、あるいはクラ
フトバルブ廃液を濃縮して、レゾルシノール樹脂接着剤
の基質に利用する事を可能とした。Table 7 Effects of the Invention The present invention provides a method for effectively utilizing lignin by separating lignin from kraft pulp waste liquid or by concentrating kraft valve waste liquid and using it as a substrate for resorcinol resin adhesive. made possible.
クラフトリグニンに０〜３０重量％のフェノールを加え
た混合物にホルムアルデヒドを添加し、樹脂化して得ら
れるリグニン樹脂、あるいは濃縮したクラフト廃液にｌ
Ｏ〜３０ｆｉｉ％のフェノールを加えた混合物にホルム
アルデヒドを添加し、樹脂化して得られるリグニン樹脂
、あるいはクラフトリグニンを少量のアルカリ性水溶液
に溶解して得たリグニン溶液などに、レゾルシノール樹
脂、又はレゾルシノールを混合してリグニン・レゾルシ
ノール樹脂を製造する事が出来た。高価なレゾルシノー
ルの代わりに、リグニンあるいはクラフト廃液が利用可
能との研究報告は皆無と思われ、この成果は、リグニン
の新しい高度利用の道を押し開くものと考えられる。Formaldehyde is added to a mixture of kraft lignin and 0 to 30% by weight of phenol, and lignin resin obtained by resinizing it or concentrated kraft waste liquid is used.
Mix resorcinol resin or resorcinol with a lignin resin obtained by adding formaldehyde to a mixture of O~30fii% phenol and making it into a resin, or a lignin solution obtained by dissolving kraft lignin in a small amount of alkaline aqueous solution. We were able to produce lignin resorcinol resin. There seems to be no research report on the possibility of using lignin or kraft waste liquid in place of the expensive resorcinol, and this result is thought to open up new avenues for advanced utilization of lignin.
本発明は、リグニンを利用した低価格のレゾルシノール
樹脂系接着剤の提供を可能にするものでもあり、林産資
源の高度利用の道を切り開くものである。The present invention also makes it possible to provide a low-cost resorcinol resin adhesive that uses lignin, and opens the way to advanced utilization of forest resources.
Claims (1)
性物を単独であるいは１価のフェ ノール類と混合したものをアルカリ性水溶液またはアル
カリ性アルコール−水混合溶液に溶解し、次いでアルデ
ヒド類を加えてホルミル化したリグニン樹脂液に、レゾ
ルシノールおよび／またはレゾルシノール樹脂液と、硬
化剤とを混合したことを特徴とするリグニン・レゾルシ
ノール樹脂接着剤。 ２）濃縮したクラフトパルプ廃液と１価のフェノール類
とアルコールを混合したものにアルデヒド類を加えてホ
ルミル化した樹脂液に、レゾルシノールおよび／または
、レゾルシ ノール樹脂液と、硬化剤とを混合したことを特徴とする
、リグニン・レゾルシノール樹脂接着剤。 ３）クラフトパルプ廃液中より分離して得たリグニン変
性物をアルカリ性水溶液またはアルカリ性アルコール−
水混合溶液に溶解し、その溶液にレゾルシノールおよび
／またはレゾルシノール樹脂と、硬化剤とを混合したこ
とを特徴とするリグニン・レゾルシノール樹脂接着剤。[Claims] 1) A modified lignin obtained by separating from kraft pulp waste liquid, alone or mixed with monovalent phenols, is dissolved in an alkaline aqueous solution or an alkaline alcohol-water mixed solution, and then aldehyde A lignin/resorcinol resin adhesive, characterized in that a lignin resin liquid which has been formylated by adding a compound of the same type as above, is mixed with resorcinol and/or a resorcinol resin liquid, and a curing agent. 2) Resorcinol and/or resorcinol resin liquid and a curing agent are mixed with a resin liquid that is formylated by adding aldehydes to a mixture of concentrated kraft pulp waste liquid, monohydric phenols, and alcohol. A lignin/resorcinol resin adhesive. 3) The lignin-denatured product separated from kraft pulp waste liquid is treated with an alkaline aqueous solution or alkaline alcohol.
A lignin-resorcinol resin adhesive characterized in that it is dissolved in an aqueous mixed solution and that resorcinol and/or resorcinol resin and a curing agent are mixed in the solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25585186A JPH0753858B2 (en) | 1986-10-29 | 1986-10-29 | Lignin resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25585186A JPH0753858B2 (en) | 1986-10-29 | 1986-10-29 | Lignin resin adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63112677A true JPS63112677A (en) | 1988-05-17 |
| JPH0753858B2 JPH0753858B2 (en) | 1995-06-07 |
Family
ID=17284469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25585186A Expired - Lifetime JPH0753858B2 (en) | 1986-10-29 | 1986-10-29 | Lignin resin adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753858B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004210816A (en) * | 2002-12-26 | 2004-07-29 | Araco Corp | Adhesive material and its manufacturing method |
| JP2017052895A (en) * | 2015-09-10 | 2017-03-16 | 島根県 | Adhesive containing phenolic resin and lignophenol, and wood product using the same |
| WO2017163163A1 (en) * | 2016-03-21 | 2017-09-28 | Stora Enso Oyj | Liquid lignin composition, ugnin-based resin, and method of increasing the solubility of lignin |
| CN115975561A (en) * | 2022-10-20 | 2023-04-18 | 中国林业科学研究院林产化学工业研究所 | E NF Preparation method of graded lignin-based wood adhesive |
-
1986
- 1986-10-29 JP JP25585186A patent/JPH0753858B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004210816A (en) * | 2002-12-26 | 2004-07-29 | Araco Corp | Adhesive material and its manufacturing method |
| JP2017052895A (en) * | 2015-09-10 | 2017-03-16 | 島根県 | Adhesive containing phenolic resin and lignophenol, and wood product using the same |
| WO2017163163A1 (en) * | 2016-03-21 | 2017-09-28 | Stora Enso Oyj | Liquid lignin composition, ugnin-based resin, and method of increasing the solubility of lignin |
| CN108884374A (en) * | 2016-03-21 | 2018-11-23 | 斯道拉恩索公司 | The method of the solubility of the wooden promotor composition of liquid, the resin based on lignin and raising lignin |
| US10717873B2 (en) | 2016-03-21 | 2020-07-21 | Stora Enso Oyj | Liquid lignin composition, lignin-based resin, and method of increasing the solubility of lignin |
| CN115975561A (en) * | 2022-10-20 | 2023-04-18 | 中国林业科学研究院林产化学工业研究所 | E NF Preparation method of graded lignin-based wood adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0753858B2 (en) | 1995-06-07 |
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