JP5314942B2 - Adhesive for wood material, wood board and method for producing wood board - Google Patents
Adhesive for wood material, wood board and method for producing wood board Download PDFInfo
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本発明は、従来の高アルカリレゾール型フェノール樹脂と同様の生産性で、接着力が強く、アルカリ汚染の少ない単板積層材、合板を製造することができる木質材料用接着剤、該接着剤を用いて木質単板を接着し積層した木質板とその製造方法に関する。 The present invention has the same productivity as a conventional high alkali resol type phenolic resin, a strong adhesive force, and a single plate laminated material with little alkali contamination, an adhesive for a wood material capable of producing a plywood, and the adhesive The present invention relates to a wooden board obtained by bonding and laminating wood veneers and a manufacturing method thereof.
従来、建材用合板などの木質板の製造には、ユリア樹脂、ユリアメラミン樹脂に代表されるアミノ系樹脂が接着剤として用いられてきた。
しかしながら、近年の健康志向の高まりと木質板の構造用への用途拡大の為に、ホルムアルデヒド放散量が少なく、耐久性が高いレゾール型フェノール樹脂を木質板用接着剤として用いることが多くなってきている。
ところが、例えばレゾール型フェノール樹脂は、その製造時にアミノ樹脂と比べて多量のアルカリ触媒を用いる。そのため、レゾール型フェノール樹脂を木質板用接着剤として用いると、成板後の木質板が水や湿気に晒された場合に、硬化した接着剤のアルカリ分が木材成分と反応しながら表面層に染み出し、アルカリ汚染と呼ばれる変色を引き起こす問題がある。
また、従来の接着剤は、必要に応じてレゾール型フェノール樹脂の硬化性を促進する為に、アルカリ触媒やアルカリ性の塩を添加することがある。この場合にも、成板後の木質板が水や湿気に晒された場合に、硬化した接着剤のアルカリ分が木材成分と反応しながら表面層に染み出し、アルカリ汚染による変色を引き起こす問題がある。
Conventionally, amino resins typified by urea resins and urea melamine resins have been used as adhesives in the production of wood boards such as plywood for building materials.
However, due to the recent increase in health-consciousness and the expansion of applications to the construction of wooden boards, resol-type phenolic resins with low formaldehyde emissions and high durability are increasingly used as adhesives for wooden boards. Yes.
However, for example, a resol-type phenol resin uses a larger amount of an alkali catalyst than that of an amino resin during its production. Therefore, when resol-type phenolic resin is used as an adhesive for wood boards, when the wood board after lamination is exposed to water or moisture, the alkali content of the cured adhesive reacts with the wood components in the surface layer. There is a problem of bleeding and causing discoloration called alkali contamination.
Moreover, the conventional adhesive agent may add an alkali catalyst or an alkaline salt as needed to promote the curability of the resol type phenol resin. In this case as well, there is a problem that when the wood board after the lamination is exposed to water or moisture, the alkali content of the cured adhesive exudes to the surface layer while reacting with the wood components, causing discoloration due to alkali contamination. is there.
従来、このアルカリ汚染を防ぐための方法としては、接着剤に酸性物質や酸性塩を添加し、接着剤中のアルカリ成分を中和する方法が提案されている（例えば、特許文献１参照。）。
しかしながら、木材接着用の高アルカリレゾール型フェノール樹脂が硬化する際のｐＨは、アルカリ側が最適であり、中和してしまうと硬化速度が著しく劣化する。その為、この接着剤を木質単板に接着し、木質板を得ようとしても、硬化に非常に時間がかかり、生産性が良好でない問題がある。
Conventionally, as a method for preventing this alkaline contamination, a method has been proposed in which an acidic substance or an acidic salt is added to an adhesive to neutralize an alkali component in the adhesive (for example, see Patent Document 1). .
However, the pH at which the highly alkaline resol type phenol resin for wood bonding is cured is optimal on the alkali side, and the curing rate is significantly deteriorated when neutralized. Therefore, even if this adhesive is bonded to a wood veneer to obtain a wood veneer, there is a problem that it takes a very long time to cure and the productivity is not good.
また、アルカリ汚染を防ぐための別な方法として、単板と単板とをレゾール型フェノール樹脂で接着する際に金属箔を介して接着する方法が提案されている（例えば、特許文献２参照。）。
しかしながら、この方法は金属箔を介する作業を要し、作業効率が良好ではない。
Further, as another method for preventing alkali contamination, a method of bonding a single plate and a single plate with a resol type phenolic resin via a metal foil has been proposed (for example, see Patent Document 2). ).
However, this method requires work through a metal foil, and the work efficiency is not good.
また、接着剤に含まれるフェノール樹脂分を減らせばアルカリ汚染は低減するが、フェノール樹脂分を減じた接着剤は、固形充填剤の量を増やしすぎると接着剤の粘度が著しく増加して使用が困難になるため、粘度低減用の水を大量に接着剤に入れる必要がある。その結果、樹脂分が水で希釈され、硬化遅延による硬化不良を誘引し、熱圧後の水蒸気圧による接着層の破裂（パンク）や接着不良に繋がる問題がある。
本発明は前記事情に鑑みてなされ、従来の高アルカリレゾール型フェノール樹脂と同様の生産性で、接着力が強く、アルカリ汚染の少ない単板積層材、合板を製造することができる接着剤の提供を目的とする。 The present invention has been made in view of the above circumstances, and provides an adhesive capable of producing a single-plate laminated material and a plywood having the same productivity as that of a conventional high alkali resol type phenolic resin, strong adhesion, and little alkali contamination. With the goal.
前記課題を達成するため、本発明は、レゾルシノール以外のフェノールとアルデヒドをアルカリ触媒存在下で反応させて得られる樹脂（Ａ）、レゾルシノールとアルデヒドをアルカリ触媒若しくは酸触媒下で反応させて得られる樹脂、又は、レゾルシノールとレゾルシノール以外のフェノールとアルデヒドをアルカリ触媒若しくは酸触媒下で反応させて得られる樹脂である樹脂（Ｂ）及び充填剤（Ｃ）を含有する木質材料用接着剤であり、該樹脂（Ａ）、該樹脂（Ｂ）及び充填剤（Ｃ）の含有比［〔（Ａ）＋（Ｂ）〕／（Ｃ）］が、固形分換算の質量比で１００／５０〜１００／２００の範囲内であり、前記樹脂（Ａ）と前記樹脂（Ｂ）との含有比（Ａ）／（Ｂ）が、固形分換算の質量比で１００／５〜１００／１００の範囲内であることを特徴とする木質材料用接着剤を提供する。 To achieve the above object, the present invention provides a resin (A) obtained by reacting a phenol other than resorcinol with an aldehyde in the presence of an alkali catalyst, and a resin obtained by reacting resorcinol with an aldehyde in the presence of an alkali catalyst or an acid catalyst. or a woody material for adhesives containing resin (B) and filler (C) is a resin obtained by the resorcinol and phenol with an aldehyde other than resorcinol is reacted under alkali catalyst or an acid catalyst, the resin (a), the resin (B) and filler content ratio of (C) [[(a) + (B)] / (C)] is, in a mass ratio of solid content in terms of 100 / 50-100 / 200 range der is, content ratio of the resin (a) and the resin (B) is (a) / (B), Ru der range of 100 / 5-100 / 100 in a mass ratio of solid basis That Providing wood material for adhesives symptoms.
本発明の木質材料用接着剤において、前記含有比［〔（Ａ）＋（Ｂ）〕／（Ｃ）］が、固形分換算の質量比で１００／６０〜１００／１２０の範囲内であることが好ましい。 In the adhesive for woody material of the present invention, the content ratio [[(A) + (B)] / (C)] is within a range of 100/60 to 100/120 in terms of mass ratio in terms of solid content. Is preferred.
本発明の木質材料用接着剤において、前記樹脂（Ａ）が、アルデヒドとレゾルシノール以外のフェノールとのモル比［（アルデヒド）／（レゾルシノール以外のフェノール）］で１．５〜３．０の範囲内であり、アルカリ触媒の存在下で反応させて得られる樹脂であることが好ましい。 In woody material for adhesives of the present invention, before Symbol resin (A), the molar ratio [(aldehyde) / (phenol other than resorcinol)] in the range of 1.5 to 3.0 of an aldehyde and non-resorcinol phenol It is preferable that it is resin obtained by making it react in presence of an alkali catalyst.
本発明の木質材料用接着剤において、前記樹脂（Ｂ）が、アルデヒドとレゾルシノール以外のフェノール、レゾルシノールのモル比［（アルデヒド）／〔（レゾルシノール以外のフェノール）＋（レゾルシノール）〕］で０．５０〜０．８０の範囲内とし、これらを反応させて得られる樹脂であることが好ましい。 In woody material for adhesives of the present invention, before Symbol resin (B), aldehyde and non-resorcinol phenol, the molar ratio of resorcinol [(aldehyde) / [(phenol other than resorcinol) + (resorcinol)]] 0. A resin obtained by reacting these in the range of 50 to 0.80 is preferable.
本発明の木質材料用接着剤において、前記樹脂（Ａ）は、樹脂固形分濃度が３５〜５５質量％の範囲内の樹脂溶液であり、前記樹脂（Ｂ）は、樹脂固形分濃度が５０〜７０質量％の範囲内の樹脂溶液であることが好ましい。 In woody material for adhesives of the present invention, before Symbol resin (A), a resin solid content of a resin solution in the range of 35 to 55 wt%, prior Symbol resin (B) is a resin solids concentration A resin solution within the range of 50 to 70% by mass is preferable.
また本発明は、本発明に係る前記木質材料用接着剤を木質単板に塗布した後、積層し圧着してなることを特徴とする木質板を提供する。 The present invention also provides a wood board, wherein the wood material adhesive according to the present invention is applied to a wood veneer and then laminated and pressure-bonded.
また本発明は、本発明に係る木質材料用接着剤を木質単板に塗布した後、積層し圧着して木質板を得ることを特徴とする木質板の製造方法を提供する。 Moreover, this invention provides the manufacturing method of the wooden board characterized by apply | coating the adhesive for wooden materials which concerns on this invention to a wooden single board, and laminating | stacking and crimping | bonding and obtaining a wooden board.
本発明によれば、従来の高アルカリレゾール型フェノール樹脂と同様の生産性で、接着力が強く、アルカリ汚染の少ない単板積層材、合板を製造することができる接着剤を提供できる。
また、本発明の接着剤は、含水率が高い木質単板（１５％程度）を用いた場合でも、パンク現象を起こすことなく、木質板を製造することができ、材料の選択の自由度が増し、且つ材料の乾燥工程を簡素化できることで、木質板の製造工程を簡素化、短縮化できる。更には木質単板の過乾燥による収縮や割れを抑制できるため単板の歩留まりを向上させることができる。
ADVANTAGE OF THE INVENTION According to this invention, the adhesive which can manufacture a single board laminated material and a plywood with the same productivity as the conventional high alkali resol type phenol resin, strong adhesive force, and little alkali contamination can be provided.
In addition, the adhesive of the present invention can produce a wood board without causing a puncture phenomenon even when a wood veneer (about 15%) having a high water content is used. Further, since the material drying process can be simplified, the wood board manufacturing process can be simplified and shortened. Furthermore, shrinkage and cracking due to overdrying of the wood veneer can be suppressed, so that the yield of veneer can be improved.
本発明に係る木質材料用接着剤は、レゾール型フェノール樹脂（Ａ）、レゾルシノール樹脂（Ｂ）及び充填剤（Ｃ）を含有する木質材料用接着剤であり、該レゾール型フェノール樹脂（Ａ）、レゾルシノール樹脂（Ｂ）及び充填剤（Ｃ）の含有比［〔（Ａ）＋（Ｂ）〕／（Ｃ）］が、固形分換算の質量比で１００／５０〜１００／２００の範囲内であることを特徴とする。 The wood material adhesive according to the present invention is a wood material adhesive containing a resol type phenol resin (A), a resorcinol resin (B) and a filler (C), the resole type phenol resin (A), The content ratio [[(A) + (B)] / (C)] of the resorcinol resin (B) and the filler (C) is in the range of 100/50 to 100/200 in terms of mass ratio in terms of solid content. It is characterized by that.
本発明に用いるレゾール型フェノール樹脂（Ａ）としては、特に限定されないが、例えば、フェノール、クレゾール、ビスフェノールＡ等のようなフェノールと、ホルムアルデヒド、パラホルムアルデヒド、グリオキザール等のようなアルデヒドとを、アルカリ触媒存在下で反応させて得られレゾール型フェノール樹脂の水溶液が挙げられる。また、前記レゾール型フェノール樹脂水溶液（Ａ）は、硬化性と樹脂粘度の点から不揮発分が３５〜５５質量％であることが好ましい。 Although it does not specifically limit as resol type phenol resin (A) used for this invention, For example, phenols, such as phenol, cresol, bisphenol A, and aldehydes, such as formaldehyde, paraformaldehyde, a glyoxal, are used as an alkaline catalyst. An aqueous solution of a resol-type phenolic resin obtained by reacting in the presence can be mentioned. Moreover, it is preferable that the said resole type phenol resin aqueous solution (A) is 35-55 mass% of non volatile matters from the point of sclerosis | hardenability and resin viscosity.
前記アルカリ触媒としては、無機系では、アルカリ金属、アルカリ土類金属の酸化物や水酸化物等が挙げられ、有機系では、アミン、アンモニア等が挙げられる。 Examples of the alkali catalyst include inorganic metals such as oxides and hydroxides of alkali metals and alkaline earth metals, and organic solvents include amines and ammonia.
前記レゾール型フェノール樹脂（Ａ）において、フェノールとアルデヒドの反応比率は、木質板からのホルムアルデヒドの放出が少なく、生産環境、材料使用時の環境が良好となる点と硬化性の点から、ホルムアルデヒド（Ｆ）とフェノール（Ｐ）とを例にとると、（Ｆ）／（Ｐ）＝１．０〜３．５（モル比）であることが好ましく、（Ｆ）／（Ｐ）＝１．５〜３．０（モル比）であることがより好ましく、１．５〜２．５（モル比）であることが特に好ましい。 In the resol-type phenol resin (A), the reaction ratio of phenol and aldehyde is such that formaldehyde (formaldehyde) is produced from the point that the release of formaldehyde from the wooden board is small, the production environment and the environment when using the material are good, and the curability. Taking F) and phenol (P) as examples, it is preferable that (F) / (P) = 1.0 to 3.5 (molar ratio), and (F) / (P) = 1.5. -3.0 (molar ratio) is more preferable, and 1.5-2.5 (molar ratio) is particularly preferable.
本発明に用いるレゾルシノール樹脂（Ｂ）は、レゾルシノールとアルデヒドを必須の成分とし、これらを反応させて得られる。例えば、レゾルシノールとアルデヒドをアルカリ触媒若しくは酸触媒下で反応させて得られる樹脂、レゾルシノールとレゾルシノール以外のフェノールとアルデヒドをアルカリ触媒若しくは酸触媒下で反応させて得られる樹脂等が挙げられる。この場合、３者を一括仕込みし反応させても良いし、フェノールとアルデヒドを予め反応させて、その後レゾルシノールを加えて反応させても良い。 The resorcinol resin (B) used in the present invention is obtained by using resorcinol and aldehyde as essential components and reacting them. Examples thereof include resins obtained by reacting resorcinol and aldehyde in the presence of an alkali catalyst or acid catalyst, and resins obtained by reacting phenol and aldehyde other than resorcinol and resorcinol in the presence of an alkali catalyst or acid catalyst. In this case, the three parties may be charged together and reacted, or phenol and aldehyde may be reacted in advance, and then resorcinol may be added and reacted.
本発明に用いるレゾルシノール樹脂（Ｂ）は、レゾルシノールとレゾルシノール以外のフェノールとアルデヒドを反応させて得られる樹脂が好ましい。特に、アルデヒドと、レゾルシノール以外のフェノールと、レゾルシノールとをアルデヒドとフェノール、レゾルシノールの割合が、硬化性と樹脂保存安定性が良好となる点からモル比［（アルデヒド）／〔（フェノール）＋（レゾルシノール）〕］で０．５０〜０．８０の範囲内となるように配合して反応させた樹脂が好ましい。また、このレゾルシノール樹脂（Ｂ）は、硬化性と樹脂粘度の点から不揮発分が５０〜７０質量％の樹脂が好ましい。 The resorcinol resin (B) used in the present invention is preferably a resin obtained by reacting resorcinol and a phenol other than resorcinol and an aldehyde. In particular, the ratio of aldehyde, phenol other than resorcinol, and resorcinol to the ratio of aldehyde to phenol and resorcinol is such that the molar ratio [(aldehyde) / [(phenol) + (resorcinol )]] Is preferably a resin which is blended and reacted so as to be in the range of 0.50 to 0.80. The resorcinol resin (B) is preferably a resin having a nonvolatile content of 50 to 70% by mass from the viewpoint of curability and resin viscosity.
本発明に用いる充填剤（Ｃ）としては、特に限定されず、固形の粉末状のものであれば良く、有機物、無機物何れであっても良く、何れを併用しても良い。例えば、小麦粉、炭酸カルシウム、タンニン、リグニン、米粉、クルミ殻粉、籾殻、木粉、こんにゃく粉、椰子殻子、トウキビ粉、樹皮粉等が挙げられ、これらのなかでも、小麦粉、炭酸カルシウムが好ましい。 The filler (C) used in the present invention is not particularly limited as long as it is in the form of a solid powder, and may be either organic or inorganic, and may be used in combination. For example, wheat flour, calcium carbonate, tannin, lignin, rice flour, walnut shell flour, rice husk, wood flour, konjac flour, coconut shell, sugarcane powder, bark flour, etc. Among these, wheat flour and calcium carbonate are preferred. .
本発明に係る木質材料用接着剤は、前述した必須成分であるレゾール型フェノール樹脂（Ａ）、レゾルシノール樹脂（Ｂ）及び充填剤（Ｃ）の含有比［〔（Ａ）＋（Ｂ）〕／（Ｃ）］が、固形分換算の質量比で１００／５０〜１００／２００の範囲内となるように、均一に混合して調製され、必要に応じて水を添加しても良い。
前記含有比［〔（Ａ）＋（Ｂ）〕／（Ｃ）］において、樹脂成分〔（Ａ）＋（Ｂ）〕１００質量部に対して充填剤（Ｃ）が５０質量部未満であると、アルカリ汚染の発生を抑えることが困難となる。また樹脂成分〔（Ａ）＋（Ｂ）〕１００質量部に対して充填剤（Ｃ）が２００質量部を超えるとパンク発生や接着不良に繋がる。前記含有比［〔（Ａ）＋（Ｂ）〕／（Ｃ）］は、アルカリ汚染低減、接着良好とする為に、１００／６０〜１００／１２０の範囲内であることがより好ましい。
前記レゾール型フェノール樹脂（Ａ）とレゾルシノール樹脂（Ｂ）との含有比（Ａ）／（Ｂ）が、固形分換算の質量比で１００／５〜１００／１００の範囲内であることが好ましい。
本発明に係る木質材料用接着剤は、硬化剤や硬化促進剤を入れなくても良いが、レゾルシノール樹脂（Ｂ）成分の硬化性を上げるためにレゾルシノール樹脂成分に対して硬化剤としてアルデヒドを１〜１０質量部入れても良い。またレゾール型フェノール樹脂（Ａ）成分の硬化促進剤としてアルカリ金属の炭酸塩を入れても良い。アルカリ金属の炭酸塩としては、例えば、炭酸カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸水素カリウム等が挙げられる。
The adhesive for wood material according to the present invention is a content ratio [[(A) + (B)] / resor type phenol resin (A), resorcinol resin (B) and filler (C) which are the essential components described above. (C)] is prepared by uniformly mixing so that the mass ratio in terms of solid content is in the range of 100/50 to 100/200, and water may be added as necessary.
In the content ratio [[(A) + (B)] / (C)], the filler (C) is less than 50 parts by mass with respect to 100 parts by mass of the resin component [(A) + (B)]. It becomes difficult to suppress the occurrence of alkali contamination. Moreover, when a filler (C) exceeds 200 mass parts with respect to 100 mass parts of resin components [(A) + (B)], it will lead to generation | occurrence | production of puncture and adhesion failure. The content ratio [[(A) + (B)] / (C)] is more preferably in the range of 100/60 to 100/120 in order to reduce alkali contamination and improve adhesion.
The content ratio (A) / (B) of the resole-type phenol resin (A) to the resorcinol resin (B) is preferably in the range of 100/5 to 100/100 in terms of mass ratio in terms of solid content.
The wood material adhesive according to the present invention does not require a curing agent or a curing accelerator, but in order to increase the curability of the resorcinol resin (B) component, 1 aldehyde is used as a curing agent for the resorcinol resin component. -10 mass parts may be added. An alkali metal carbonate may be added as a curing accelerator for the resol type phenol resin (A). Examples of the alkali metal carbonate include potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.
本発明に係る木質材料用接着剤は、レゾール型フェノール樹脂（Ａ）とレゾルシノール樹脂（Ｂ）を併用することで、接着力を強化し、更に、多量の固形充填剤を配合する（樹脂成分〔（Ａ）＋（Ｂ）〕１００質量部に対して充填剤（Ｃ）５０〜２００質量部）ことにより、アルカリ汚染を低減させた。その結果、本発明によれば、従来の高アルカリレゾール型フェノール樹脂と同様の生産性で、接着力が強く、アルカリ汚染の少ない単板積層材、合板を製造することができる木質材料用接着剤を提供できる。 The adhesive for wood materials according to the present invention reinforces the adhesive force by using the resole phenolic resin (A) and the resorcinol resin (B) in combination, and further contains a large amount of solid filler (resin component [ (A) + (B)] By 100 parts by mass of filler (C) 50 to 200 parts by mass), alkali contamination was reduced. As a result, according to the present invention, the adhesive for wood materials that can produce a single-plate laminated material and a plywood that have the same productivity as the conventional high alkali resol type phenolic resin, strong adhesion, and little alkali contamination. Can provide.
本発明はまた、前述した本発明に係る前記木質材料用接着剤を木質単板に塗布した後、積層し圧着してなることを特徴とする木質板、及び前記木質材料用接着剤を木質単板に塗布した後、該木質単板とは別の木質単板を積層し圧着して木質板を得ることを特徴とする木質板の製造方法を提供する。本発明に係る木質板及びその製造方法に用いる木質単板等は、木材加工分野等で用いられる各種の木質単板等の中から適宜選択して使用でき、材質、厚さ、形状、積層枚数等は特に限定されない。また本発明に係る木質板の製造方法において、接着剤を塗布するのは木質単板の片面及び両面の何れでも良く、各接着層に少なくとも一層塗布してあればよい。
例えば、木質板として合板を製造する場合には、適当な木質単板の両面に、本発明の木質材料用接着剤を塗布し、塗布していない木質単板と共に所定の枚数を重ね合わせる。次いで、重ね合わせた板を、冷圧して圧締した後、プレスから取り出す。次いで、冷圧によって仮接着した板を１２０〜１５０℃で熱圧によって硬化させる。次いで、耳きり、表面仕上げ、選別、検査等の工程を経て合板を完成させる。
The present invention also provides a wood board, wherein the wood material adhesive according to the present invention described above is applied to a wood board and then laminated and pressure-bonded, and the wood material adhesive is made of wood wood. Provided is a method for producing a wood board, which is obtained by laminating and pressing a wood board different from the wood board after being applied to the board. The wood board and the wood veneer used in the manufacturing method according to the present invention can be used by appropriately selecting from various wood veneers used in the wood processing field, etc., and the material, thickness, shape, number of laminated sheets Etc. are not particularly limited. In the method for producing a wood board according to the present invention, the adhesive may be applied on one side or both sides of the wood board, and it is sufficient that at least one layer is applied to each adhesive layer.
For example, when manufacturing a plywood as a wood board, the wood material adhesive of the present invention is applied to both sides of a suitable wood board, and a predetermined number of sheets are overlapped together with the wood wood board not applied. Next, the superposed plates are cooled and pressed, and then removed from the press. Next, the plate temporarily bonded by cold pressure is cured at 120 to 150 ° C. by hot pressure. Next, the plywood is completed through processes such as ear trimming, surface finishing, sorting, and inspection.
通常、木質板を製造する場合には、十分乾燥させた木質単板（含水率は通常５％以下）を用いる。これは、含水率が高い単板に接着剤を塗布し、積層、加熱圧着すると、水蒸気圧によりパンク現象が発生するからである。しかしながら、本発明の接着剤を用いると、含水率が高い木質単板（１５％程度）を用いてもパンク現象を起こすことなく木質板を製造することができる。 Usually, when producing a wooden board, a sufficiently dried wooden board (water content is usually 5% or less) is used. This is because a puncture phenomenon occurs due to water vapor pressure when an adhesive is applied to a single plate having a high water content, laminated, and thermocompression bonded. However, when the adhesive of the present invention is used, a wood board can be produced without causing a puncture phenomenon even if a wood board having a high water content (about 15%) is used.
以下、本発明に関して実施例、比較例により説明する。なお、以下に記載の部及び％は、特に断りのない限り質量基準である。 Hereinafter, the present invention will be described with reference to examples and comparative examples. In addition, the part and% as described below are based on mass unless otherwise specified.
［レゾール型フェノール樹脂（Ａ）の合成］
フェノール１０００グラム、４０％ホルムアルデヒド水溶液１４３５グラム及びイオン交換水６００グラムを還流装置の付いたフラスコに入れ攪拌を開始し、５０％水酸化ナトリウム水溶液６００グラムを徐々に加えながら８０℃迄昇温し５時間反応させてレゾール型フェノール樹脂水溶液を得た。得られたレゾール型フェノール樹脂水溶液は不揮発分４５％、粘度２００ｍＰａ・ｓ、ｐＨ１２．８であった。
[Synthesis of resol type phenol resin (A)]
1000 grams of phenol, 1435 grams of 40% aqueous formaldehyde solution and 600 grams of ion-exchanged water were placed in a flask equipped with a reflux apparatus, and stirring was started. The temperature was raised to 80 ° C. while gradually adding 600 grams of 50% aqueous sodium hydroxide solution. By reacting for a time, a resol type phenol resin aqueous solution was obtained. The obtained aqueous resol type phenolic resin solution had a non-volatile content of 45%, a viscosity of 200 mPa · s, and a pH of 12.8.
［レゾルシノール樹脂（Ｂ）の合成］
フェノール２８０部、４０％ホルマリン２９０部に５０％水酸化ナトリウム２０部を加えて８０℃で１時間反応したのち、レゾルシノールを２８０部加え９０℃にて反応しメタノールにて粘度、不揮発分を調整した。得られたレゾルシノール樹脂は粘度５００ｍＰａ・ｓ、不揮発分６０％であった。これをレゾルシノール樹脂（Ｂ）とする。
[Synthesis of Resorcinol Resin (B)]
After adding 20 parts of 50% sodium hydroxide to 280 parts of phenol and 290 parts of 40% formalin and reacting at 80 ° C. for 1 hour, adding 280 parts of resorcinol and reacting at 90 ° C., the viscosity and nonvolatile content were adjusted with methanol. . The obtained resorcinol resin had a viscosity of 500 mPa · s and a non-volatile content of 60%. This is referred to as resorcinol resin (B).
［実施例１］
前記［レゾール型フェノール樹脂（Ａ）の合成］で得られたレゾール型フェノール樹脂水溶液１００部、前記［レゾルシノール樹脂（Ｂ）の合成］で得られたレゾルシノール樹脂（Ｂ）１０部、充填剤（Ｃ）として炭酸カルシウム１９部と小麦粉８部を用い、水を添加して粘度調整を行い（粘度２３ｄＰａ・Ｓ／２５℃）、実施例１の木質材料用接着剤を調製した。
この実施例１の木質材料用接着剤において、樹脂成分［（Ａ）＋（Ｂ）］１００部に対する充填剤（Ｃ）の配合量は５３部である。
木質材料としてカラマツ材から作ったサイズ３０ｃｍ×３０ｃｍのロータリー単板を用い、２．１ｍｍ厚の原板（ｘ１）、３．０ｍｍ厚の糊心単板（ｘ２）及び２．１ｍｍ厚の中板単板（ｘ３）を作製し、次いで、前記糊心単板（ｘ２）に前記木質材料用接着剤を片面当たり１９ｇの割合で、両面に塗布し、原板（ｘ１）／糊心単板（ｘ２）／中板単板（ｘ３）／糊心単板（ｘ２）／原板（ｘ１）〔＝２．１／３．０／２．１／３．０／２．１ｍｍ〕の５プライの１２ｍｍ構成で１サンプルセットして、０．９８ＭＰａにて３０分間冷圧後、１２０℃、０．９８ＭＰａにて２４０秒間熱圧して合板を成形テストし、次いで後述する耐アルカリ汚染性試験及び合板性能試験を行った。得られた結果を表１に示す。なお、前記単板（ｘ１）、（ｘ２）及び（ｘ３）の含水率はそれぞれ５％であった。
[Example 1]
100 parts of a resole phenol resin aqueous solution obtained in [Synthesis of resole phenol resin (A)], 10 parts of resorcinol resin (B) obtained in [synthesis of resorcinol resin (B)], filler (C ), 19 parts of calcium carbonate and 8 parts of wheat flour were used to adjust the viscosity by adding water (viscosity 23 dPa · S / 25 ° C.) to prepare an adhesive for woody material of Example 1.
In the adhesive for woody material of Example 1, the blending amount of the filler (C) with respect to 100 parts of the resin component [(A) + (B)] is 53 parts.
Using a rotary single plate of 30cm x 30cm size made from larch as a wood material, 2.1mm thick original plate (x1), 3.0mm thick glue core single plate (x2) and 2.1mm thick single plate A plate (x3) was prepared, and then the adhesive for wood material was applied to both sides of the glue core single plate (x2) at a rate of 19 g per side, and the original plate (x1) / glue core single plate (x2) / 5mm ply 12mm configuration: single plate (x3) / single core plate (x2) / original plate (x1) [= 2.1 / 3.0 / 2.1 / 3.0 / 2.1mm] 1 sample set, cold press at 0.98 MPa for 30 minutes, then hot press at 120 ° C. and 0.98 MPa for 240 seconds to test the plywood, then perform alkali contamination resistance test and plywood performance test described later It was. The obtained results are shown in Table 1. In addition, the moisture content of the said single plate (x1), (x2), and (x3) was 5%, respectively.
［実施例２］
充填剤（Ｃ）として、炭酸カルシウム３０部、小麦粉２０部とし、樹脂成分［（Ａ）＋（Ｂ）］１００部に対する充填剤（Ｃ）の配合量を９８部としたこと以外は、実施例１と同様にして木質材料用接着剤を調製し、それを用いて合板を作製した。
[Example 2]
Example, except that the filler (C) is 30 parts of calcium carbonate, 20 parts of flour, and the amount of filler (C) to 100 parts of resin component [(A) + (B)] is 98 parts. In the same manner as in No. 1, a wood material adhesive was prepared, and a plywood was produced using the adhesive.
［実施例３］
実施例２と同様にして木質材料用接着剤を調製し、それを用いて合板を作製した。但し、合板の作製に使用した単板の含水率は１５％とした。
[Example 3]
A wood material adhesive was prepared in the same manner as in Example 2, and a plywood was produced using the adhesive. However, the moisture content of the veneer used for producing the plywood was 15%.
［実施例４］
レゾール型フェノール樹脂水溶液（Ａ）６５部、レゾルシノール樹脂（Ｂ）４５部、充填剤（Ｃ）として炭酸カルシウム５５部と小麦粉５０部とし、樹脂成分［（Ａ）＋（Ｂ）］１００部に対する充填剤（Ｃ）の配合量を１８７部としたこと以外は、実施例１と同様にして木質材料用接着剤を調製し、それを用いて合板を作製した。但し、合板の作製に使用した単板の含水率は１５％とした。
[Example 4]
Resor type phenolic resin aqueous solution (A) 65 parts, resorcinol resin (B) 45 parts, filler (C) 55 parts calcium carbonate and flour 50 parts, filling 100 parts of resin component [(A) + (B)] A wood material adhesive was prepared in the same manner as in Example 1 except that the blending amount of the agent (C) was 187 parts, and a plywood was produced using the adhesive. However, the moisture content of the veneer used for producing the plywood was 15%.
［比較例１］
レゾルシノール樹脂（Ｂ）を用いず、レゾール型フェノール樹脂水溶液１００部、炭酸ナトリウム４部、充填剤（Ｃ）として炭酸カルシウム１７部、小麦粉７部とし、樹脂成分［（Ａ）＋（Ｂ）］１００部に対する充填剤（Ｃ）の配合量を５３部として接着剤を調製し、それ以外は実施例１と同様にして合板を作製した。
[Comparative Example 1]
Resorcinol resin (B) is not used, 100 parts of resole type phenol resin aqueous solution, 4 parts of sodium carbonate, 17 parts of calcium carbonate as filler (C), 7 parts of flour, resin component [(A) + (B)] 100 A plywood was produced in the same manner as in Example 1 except that the amount of the filler (C) relative to the part was 53 parts, and the adhesive was prepared.
［比較例２］
比較例１と同様にして木質材料用接着剤を調製し、それを用いて合板を作製した。但し、合板の作製に使用した単板の含水率は１５％とした。
[Comparative Example 2]
A wood material adhesive was prepared in the same manner as in Comparative Example 1, and a plywood was produced using the adhesive. However, the moisture content of the veneer used for producing the plywood was 15%.
［比較例３］
充填剤（Ｃ）として、炭酸カルシウム１７部、小麦粉７部とし、樹脂成分［（Ａ）＋（Ｂ）］１００部に対する充填剤（Ｃ）の配合量を４７部としたこと以外は、実施例１と同様にして木質材料用接着剤を調製し、それを用いて合板を作製した。但し、合板の作製に使用した単板の含水率は１５％とした。
[Comparative Example 3]
Example, except that the filler (C) is 17 parts calcium carbonate, 7 parts flour, and the amount of filler (C) to 47 parts resin component [(A) + (B)] is 47 parts. In the same manner as in No. 1, a wood material adhesive was prepared, and a plywood was produced using the adhesive. However, the moisture content of the veneer used for producing the plywood was 15%.
［比較例４］
レゾール型フェノール樹脂水溶液（Ａ）６５部、レゾルシノール樹脂（Ｂ）４５部、充填剤（Ｃ）として炭酸カルシウム６０部と小麦粉５８部とし、樹脂成分［（Ａ）＋（Ｂ）］１００部に対する充填剤（Ｃ）の配合量を２１０部としたこと以外は、実施例１と同様にして木質材料用接着剤を調製し、それを用いて合板を作製した。但し、合板の作製に使用した単板の含水率は１５％とした。
[Comparative Example 4]
Resor type phenolic resin aqueous solution (A) 65 parts, resorcinol resin (B) 45 parts, filler (C) 60 parts calcium carbonate and 58 parts flour, filling 100 parts of resin component [(A) + (B)] A wood material adhesive was prepared in the same manner as in Example 1 except that the compounding amount of the agent (C) was 210 parts, and a plywood was produced using the adhesive. However, the moisture content of the veneer used for producing the plywood was 15%.
前記実施例１〜４、比較例１〜４においてそれぞれ作製した合板について、耐アルカリ汚染性の評価、パンク有無、ホルムアルデヒド放散量、引張剪断力、平均木破率及び合格率の各項目について、下記の測定方法及び評価基準で調べた。その結果を表１と表２にまとめて記す。
なお、比較例１と３ではアルカリ汚染がみられた。比較例２と４では、パンクが発生しホルムアルデヒド放散量試験、合板性能試験（特類試験）を実施できなかった。
About the plywood produced in Examples 1 to 4 and Comparative Examples 1 to 4, respectively, evaluation of alkali contamination resistance, presence / absence of puncture, formaldehyde emission amount, tensile shear force, average tree breakage rate, and acceptance rate are as follows. The measurement method and evaluation criteria were used. The results are summarized in Tables 1 and 2.
In Comparative Examples 1 and 3, alkali contamination was observed. In Comparative Examples 2 and 4, puncture occurred and the formaldehyde emission test and the plywood performance test (special test) could not be performed.
＜耐アルカリ汚染性の評価＞
得られた合板で１０ｃｍ角の試験片を作製し、厚さ方向に下半分を水に浸積し、上半分は空気中に晒した状態で７２時間放置した後、表面の染みの程度を目視で調べ、以下の評価基準に照らして耐アルカリ汚染性を比較した。パンクした合板は、パンクしていない部位で耐アルカリ汚染性の評価を行った。
◎：殆ど赤褐色の染みがない。
○：赤褐色の染みがあるが僅かである。
×：部分的に若しくは全体的に赤褐色の染みがある。
<Evaluation of resistance to alkali contamination>
A test piece of 10 cm square was prepared with the obtained plywood, the lower half was immersed in water in the thickness direction, and the upper half was left in the air for 72 hours, and then the degree of surface stain was visually observed. And compared alkali resistance against the following evaluation criteria. The punctured plywood was evaluated for resistance to alkali contamination at a non-punctured portion.
A: Almost no reddish brown stain.
○: There is a reddish-brown stain but slight.
X: There is a reddish brown stain partially or entirely.
＜パンク有無＞
得られた合板を長さ３０ｃｍ×５ｃｍの試験片に丸鋸で切断し接着層を観察、パンクの有無を判定した。
<Punk presence>
The obtained plywood was cut into a test piece having a length of 30 cm × 5 cm with a circular saw, the adhesive layer was observed, and the presence or absence of puncture was determined.
＜ホルムアルデヒド放散量＞
ホルムアルデヒド放散量は「合板の日本農林規格」におけるホルムアルデヒド放散量試験にて測定した。
<Formaldehyde emission>
Formaldehyde emission was measured by a formaldehyde emission test in “Japanese Agricultural Standard for Plywood”.
＜引張剪断力、平均木破率及び合格率＞
引張剪断力、平均木破率、合格率は、「合板の日本農林規格」における「構造用合板の規格（特類）」にて測定した。
<Tensile shear force, average wood breaking rate and acceptance rate>
The tensile shear force, the average tree breakage rate, and the acceptance rate were measured according to “Standard for plywood for construction (special)” in “Japanese Agricultural Standard for Plywood”.
Claims (7)
該樹脂（Ａ）、該樹脂（Ｂ）及び充填剤（Ｃ）の含有比［〔（Ａ）＋（Ｂ）〕／（Ｃ）］が、固形分換算の質量比で１００／５０〜１００／２００の範囲内であり、
前記樹脂（Ａ）と前記樹脂（Ｂ）との含有比（Ａ）／（Ｂ）が、固形分換算の質量比で１００／５〜１００／１００の範囲内であることを特徴とする木質材料用接着剤。 Resin (A) obtained by reacting phenol and aldehyde other than resorcinol in the presence of an alkali catalyst, resin obtained by reacting resorcinol and aldehyde in the presence of an alkali catalyst or acid catalyst, or phenol and aldehyde other than resorcinol and resorcinol Is an adhesive for woody material containing a resin (B) and a filler (C), which are resins obtained by reacting the catalyst in the presence of an alkali catalyst or an acid catalyst ,
Content ratio of the resin (A), the said resin (B) and filler (C) [[(A) + (B)] / (C)] is, in a mass ratio of the solid content basis 100 / 50-100 / range der of 200 is,
Wood-containing ratio (A) / (B), characterized in der Rukoto the range of 100 / 5-100 / 100 in a mass ratio on solid basis of the resin (A) and the resin (B) Adhesive for materials.
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| JPH0331384A (en) * | 1989-06-28 | 1991-02-12 | Aica Kogyo Co Ltd | Resorcinol-based resin adhesive of two-pack type |
| JP2518709B2 (en) * | 1989-12-25 | 1996-07-31 | アイカ工業株式会社 | Coating adhesion method |
| JPH10338862A (en) * | 1997-06-06 | 1998-12-22 | Aica Kogyo Co Ltd | Quickly curing adhesive and adhering method |
| JPH11209563A (en) * | 1998-01-20 | 1999-08-03 | Mitsui Chem Inc | Phenolic resin composition |
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| JP4426176B2 (en) * | 2002-12-25 | 2010-03-03 | 株式会社サンベーク | Phenolic resin adhesive composition |
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