JP2004522628A - Method for reducing formaldehyde emissions from layered products containing formaldehyde - Google Patents

Method for reducing formaldehyde emissions from layered products containing formaldehyde Download PDF

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Publication number
JP2004522628A
JP2004522628A JP2002571270A JP2002571270A JP2004522628A JP 2004522628 A JP2004522628 A JP 2004522628A JP 2002571270 A JP2002571270 A JP 2002571270A JP 2002571270 A JP2002571270 A JP 2002571270A JP 2004522628 A JP2004522628 A JP 2004522628A
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Prior art keywords
formaldehyde
solution
veneer
urea
ammonium
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ロビン ユンガー
イングバー リンド
サルメ ピルホメン
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Akzo Nobel NV
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Akzo Nobel NV
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00Pretreatment of moulding material
    • B27N1/003Pretreatment of moulding material for reducing formaldehyde gas emission

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Veneer Processing And Manufacture Of Plywood (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Laminated Bodies (AREA)

Abstract

A method of reducing the emission of formaldehyde from formaldehyde laden layered products having at least 2 layers, at least one of which being a board or veneer, wherein prior to bonding the layers together, at least one side surface of said board or veneer is treated with a solution comprising an inorganic sulphur containing salt. The invention also relates to a board, a veneer and a flooring material obtainable by the method, to an aqueous solution comprising ammonium sulphite or bisulphite and urea for use in the method and to a process for preparation of the aqueous solution.

Description

【技術分野】
【0001】
本発明は少なくとも一つが板紙又はベニヤである、少なくとも二つの層を有するホルムアルデヒドを含む層状製品からのホルムアルデヒドの放出の低減方法に関する。また、本発明はその方法により得られる板紙、ベニヤ及び床材、その方法における使用のための亜硫酸アンモニウム又は重亜硫酸アンモニウム及び尿素を含む水溶液並びにその水溶液の調製方法に関する。本発明の方法はこれらの層を一緒に結合する前に無機硫黄含有塩を含む溶液による前記板紙又はベニヤの表面の少なくとも一つの処理を含む。
【背景技術】
【0002】
アルデヒド、特にホルムアルデヒドをベースとする樹脂は、接着剤組成物に広く使用され、これらはパネル、デッキ等の如き構造材;家具、床材等の如き家庭用の備付け家具の製造に使用される。典型的には、これらの接着剤組成物は実質的にモル過剰のホルムアルデヒドを含む。この過剰のホルムアルデヒドの一部が製品の製造中に樹脂の硬化により放出される。しかしながら、ホルムアルデヒドは製造過程が完結された後でさえもこれらの製品から放出され続けることが公知である。こうして、インドア空気中のホルムアルデヒドが長年にわたって重大な関心事であった。
【0003】
幾つかの試みがホルムアルデヒド放出を低減するために長年にわたってなされていたが、全てが重大な機械上、化学上、環境上又は経済上の欠点を伴う。
【0004】
EP0027583はカルバミド樹脂で結合されたパーティクルボードからのホルムアルデヒドの放出の低減方法を開示している。そのボードはプレスに続いて熱分解性アンモニウム化合物、例えば、炭酸アンモニウムで処理される。次いでこうして処理されたボードが積み重ねられ、40℃から70℃までの温度で貯蔵され、その結果、アンモニアが放出され得る。
【0005】
更に、層状床材、例えば、3層の寄せ木張りの床は、異なる木材層がホルムアルデヒドをベースとする接着剤で接着することにより一緒に通常結合されるためにホルムアルデヒドを放出し得る。この上層は通常広葉樹からなり、中間層は針葉樹又は板紙、例えば、MDF、HDF又はパーティクルボードからなり、下層はベニヤからなる。この上層は表面を保護するために通常ホルムアルデヒドを含まないUVラッカー又は油で処理され、これはまたホルムアルデヒド放出のバリヤーとして機能し得る。寄せ木張りの床サンプルの異なる部分、例えば、前面、裏面、及び縁部は異なる放出速度を示す。例えば、裏面からのホルムアルデヒド放出は前面からの放出よりも20倍高いことがある。
【0006】
更に、スウェーデン規格SS270236(SS 1988)に従ってチャンバー試験で得られる必要とされるE1値を満足し得る寄せ木張りの床に対する増大する要望がある。寄せ木張りの床に関する放出試験が露出されていない裏面及びシールされた縁部を有するサンプルで行なわれた場合、得られた放出値はしばしば0.05mg/mを下まわって非常に低かった(E1に関する限界値は0.13mg/mである)。
【0007】
更に、ホルムアルデヒド放出測定について、新しい欧州規格、EN 717−1が提案され、それによれば、測定すべき全てのサンプルが露出された裏面及び部分的に露出された縁部を有するであろう。これは床製造業者が極めて低いホルムアルデヒド放出値を達成することを一層困難にする。
【0008】
更に、日本規格JAS SIS20を満足することについての要望があり、これはサンプルの裏面及び縁部がシールし得ないが、それらが完全に露出される場合のデシケーター測定を伴う。
【0009】
こうして、技術的解決がホルムアルデヒドをベースとする樹脂を含む木材をベースとする製品からのホルムアルデヒドの放出を低減して、これらの製品からのホルムアルデヒド放出に関する新しい一層厳格な規格を満足する要望について依然として探求される。
【発明の開示】
【発明が解決しようとする課題】
【0010】
それ故、本発明は上記問題が解決される、ホルムアルデヒドをベースとする樹脂を含む木材をベースとする製品からのホルムアルデヒドの放出の低減方法を提供する。
【課題を解決するための手段】
【0011】
本発明の方法は無機硫黄含有塩を含む溶液による、層を一緒に結合する前の、少なくとも二つの層を有する層状製品中に含まれる、板紙又はベニヤの表面の少なくとも一つの処理を含む。
【発明を実施するための最良の形態】
【0012】
“ホルムアルデヒドを含む層状製品”はホルムアルデヒドをベースとする樹脂を含む層状製品を本明細書中で意味し、この場合、これらの層がホルムアルデヒドをベースとする接着剤により互いに結合され、またこれらの層の一つ以上が板紙である場合には、板紙そのものがまたホルムアルデヒドをベースとする接着剤で結合されてもよい。
【0013】
好適には、溶液中の無機硫黄含有塩の濃度は約1重量%から約30重量%まで、好ましくは約5重量%から約20重量%まで、最も好ましくは約8重量%から約13重量%までである。溶液の形態の塩の適用が好ましいが、本発明によれば、それはまた所望により粉末の形態で適用されてもよい。環境上の理由のために、この溶液は水溶液であることが好適であるが、水以外の溶媒が使用されてもよい。この塩溶液はあらゆる通常の被覆技術、例えば、ロールコーティング、カーテンコーティング、又は噴霧被覆を使用することにより適用されてもよい。適用される塩溶液の量は、表面の一つのみが処理される場合には、好適には約30g/mから約90g/mまで、好ましくは約40g/mから約80g/mまで、最も好ましくは約55g/mから約65g/mまでである。表面の両方が処理されるべきである場合、面当りに適用される量は表面の一つのみが処理される場合の量の半分であることが好適である。処理される製品の水分バランスの乱れを避けるために、多量の塩溶液は望ましくない。
【0014】
本発明の無機硫黄塩は非常に高い水溶解度を有し、一方、炭酸塩はかなり制限された水溶解度を有する。こうして、ホルムアルデヒド放出の所望の低減をもたらす有効な塩溶液を得るために、亜硫酸塩溶液の量と較べて多量の炭酸塩溶液が、処理すべき表面に適用されることが必要とされ、これは処理される製品、ひいては仕上げられた層状製品の水分バランスに悪影響し得る。
【0015】
更に、本発明の無機硫黄塩は仕上げられた層状製品、特にその外面を変色せず、一方、炭酸塩は仕上げられた製品の外層、特にオーク表面に対し変色作用を有するかもしれない。
【0016】
好適な無機硫黄含有塩として、亜硫酸塩又は重亜硫酸塩、例えば、アルカリ金属の亜硫酸塩もしくは重亜硫酸塩又は亜硫酸アンモニウムもしくは重亜硫酸アンモニウムが挙げられる。水溶性の亜硫酸塩又は重亜硫酸塩が好ましい。亜硫酸アンモニウム又は重亜硫酸アンモニウムが使用されることが好ましく、亜硫酸アンモニウムが最も好ましい。
【0017】
ホルムアルデヒドをベースとする樹脂で調製された材料及び製品により放出されるホルムアルデヒドの量の低減方法は全てのホルムアルデヒドをベースとする樹脂に適用可能であり、例えば、それは尿素−ホルムアルデヒド樹脂、メラミン−ホルムアルデヒド樹脂、フェノール−ホルムアルデヒド樹脂等だけでなく、これらからつくられたコポリマー、ブレンド及び混合物に適用可能である。
【0018】
本発明の好ましい実施態様において、尿素が無機硫黄含有塩溶液に添加される。たとえ該無機硫黄含有塩が単独でホルムアルデヒドの放出を有効に低減するとしても、該塩溶液への尿素の添加はホルムアルデヒド放出の低減を更に改良する。好適には、尿素対硫黄含有塩の重量比は約1:10から約1:1まで、好ましくは約2:10から約8:10まで、最も好ましくは約3:10から約6:10までである。
【0019】
本発明に従って処理される板紙はあらゆる種類の板紙、例えば、パーティクルボード、チップボール、又は繊維板であってもよく、それはホルムアルデヒドをベースとする樹脂又はその他のホルムアルデヒドをベースとしない樹脂をベースとする接着剤で結合されてもよい。
【0020】
本発明に従って処理されるベニヤはあらゆる種類の木材ベニヤ、好ましくは未処理のベニヤであってもよい。
【0021】
これらの板紙又はベニヤは結合段階の前に所望の含水量に塩溶液の適用後に状態調節されてもよい。更に、ベニヤ又は板紙の表面の一つのみが本発明の利益を得るために塩溶液で被覆されることを必要とするが、適用方法に応じて、表面の両方が所望により被覆されてもよい。
前記層は既知の通常の技術のいずれかを使用することにより、例えば、接着及びプレスにより結合し得る。
【0022】
本発明の方法により処理された板紙又はベニヤは層状製品の裏面又は層を構成することが好ましい。これは層状製品の裏面からのホルムアルデヒドの放出のかなりの低減を生じる。
【0023】
本発明の層状製品はあらゆる木材をベースとする層状製品であってもよい。好適には、それは床材、好ましくは寄木張りの床、最も好ましくは3層の寄木張りの床である。
【0024】
本発明の塩水溶液は亜硫酸アンモニウム又は重亜硫酸アンモニウム及び尿素を含む。それは亜硫酸アンモニウム及び尿素を含むことが好ましい。
この塩と尿素の重量比は好適には約1:10から約1:1まで、好ましくは約2:10から約8:10まで、最も好ましくは約3:10から約6:10までである。
好適には、本溶液中のアンモニウム塩及び尿素の濃度は約1重量%から約30重量%まで、好ましくは約5重量%から約20重量%まで、最も好ましくは約8重量%から約13重量%までである。
【0025】
本発明の塩溶液の調製方法は、溶液中の塩及び尿素の所望の濃度を生じる、混合比で塩、尿素及び水の混合を含む。
【0026】
本発明の塩溶液の調製方法の好ましい実施態様において、前記アンモニウム塩は尿素及び所望の塩濃度を有する溶液を受け取るのに必要とされる追加の水との混合の前に水溶液の形態である。
【0027】
本発明の塩溶液の調製方法の更に好ましい実施態様において、前記アンモニウム塩及び尿素の両方は所望の塩濃度を有する本発明の水溶液を調製するための互いの混合の前に水溶液の形態である。
【0028】
本発明が下記の非限定実施例により更に説明される。部数及び%は、特にことわらない限り、夫々重量部、重量%に関する。
【実施例】
【0029】
本発明の実施例に使用した亜硫酸アンモニウム溶液を、亜硫酸アンモニウム溶液(35−36重量%)19.7kg及び尿素3.0kgを水と混合して10重量%の塩水溶液を得ることにより調製した。
【0030】
比較例に使用した炭酸アンモニウム溶液を、尿素31.6kg、重炭酸アンモニウム40.0kg及び炭酸アンモニウム28.4kgを水と混合して27.8重量%の塩水溶液を得ることにより調製した。
【0031】
[例1(参考例)]
トウヒ類のベニヤ(厚さ2mm)を熱硬化性尿素−ホルムアルデヒド樹脂及び硬化剤でマツ類のコアー材料の両面に接着した。
[例2(比較例)]
トウヒ類のベニヤ(厚さ2mm)を両面で炭酸アンモニウム溶液で前処理し、次いで4時間乾燥させ、その後に例1と同じ方法で接着し、プレスした。
[例3]
トウヒ類のベニヤ(厚さ2mm)を両面で無機亜硫酸塩溶液で前処理し、乾燥させ、次いで例2と同じ方法で接着し、プレスした。
【0032】
[例4(比較例)]
接着及びプレス後に、サンプルを周囲温度で15分間放置し、次いでベニヤの裏面(接着剤ラインから離れて面する面)を炭酸アンモニウム溶液で噴霧した以外は、例1の操作を繰り返した。
[例5]
ベニヤの裏面を亜硫酸アンモニウム溶液で噴霧した以外は、例4の操作を繰り返した。
【0033】
上記例に従って調製したサンプルからのホルムアルデヒド放出を24時間の状態調節後に現場及び実験室用の放出セル(FLEC)で測定した。これらの結果を下記の表1に示す。
【0034】
【表1】
【0035】
表1からわかるように、処理ベニヤを含むサンプルからのホルムアルデヒド放出は未処理ベニヤを含むサンプルのホルムアルデヒド放出と較べて一般にかなり低下された。加えて、本発明の塩溶液によるベニヤの処理はベニヤが炭酸アンモニウム溶液で処理される場合のホルムアルデヒド放出と較べてホルムアルデヒド放出の一層大きな低下を生じる。この改良は使用された亜硫酸アンモニウム溶液の濃度が炭酸塩溶液の濃度のわずかに約1/3であるという事実及び亜硫酸アンモニウム溶液の適用量(g/m)が適用された炭酸アンモニウム溶液の量よりも少なかったという事実を考慮して一層明らかになる。
【0036】
[例6]
縁部接着した14mmの3層の寄せ木張りの床の製造用のトウヒ類のベニヤを両面で亜硫酸アンモニウム溶液で前処理した。このベニヤを約7%の含水量まで状態調節し、その後に熱硬化性尿素−ホルムアルデヒド樹脂及び硬化剤で、マツ類のコアー材料に接着した。トネリコ類の面ラメラを同じ尿素−ホルムアルデヒド樹脂/硬化剤混合物でコアー材料の上部に接着した。
[例7(比較例)]
トウヒ類のベニヤを炭酸アンモニウム溶液で前処理した以外は、例6を繰り返した。
[例8(参考例)]
使用したトウヒ類のベニヤを塩溶液で処理しなかった以外は、寄せ木張りの床サンプルを例6及び7と同じ方法で調製した。
【0037】
プレスし、周囲温度に冷却し、上層をラッカー又は油で処理した後の例6、7及び8の全てに従って調製したサンプルを、ホルムアルデヒド不透過性プラスチック中に包装した。前面及び裏面を露出し、縁部をシールして、ホルムアルデヒド放出をスウェーデン規格SS 270236 (SS 1988)に従って1mチャンバー中で測定した。これらの結果を下記の表2に示す。
【0038】
【表2】
【0039】
明らかに、本発明に従って無機亜硫酸塩溶液によるベニヤの前処理は、予期しないことに多量のかなり濃厚な塩溶液を使用することを必要としないでホルムアルデヒドの放出を一層有効に低減する。多量の塩溶液の使用は多量の水がベニヤに供給されることをもたらし、これが製品の水分バランスに悪影響を有し得る。
【Technical field】
[0001]
The present invention relates to a method for reducing the emission of formaldehyde from a layered product comprising formaldehyde having at least two layers, at least one of which is paperboard or veneer. The invention also relates to the paperboard, veneer and flooring material obtained by the method, to an aqueous solution containing ammonium sulfite or ammonium bisulfite and urea for use in the method and to a method for preparing the aqueous solution. The method of the present invention comprises at least one treatment of the paperboard or veneer surface with a solution containing an inorganic sulfur-containing salt before bonding the layers together.
[Background Art]
[0002]
Aldehydes, especially formaldehyde-based resins, are widely used in adhesive compositions and are used in the manufacture of structural materials such as panels, decks, etc .; and household furnishings, such as furniture, flooring and the like. Typically, these adhesive compositions contain a substantial molar excess of formaldehyde. Some of this excess formaldehyde is released by the curing of the resin during the manufacture of the product. However, it is known that formaldehyde continues to be released from these products even after the manufacturing process has been completed. Thus, formaldehyde in indoor air has been a major concern for many years.
[0003]
Several attempts have been made over the years to reduce formaldehyde emissions, but all have significant mechanical, chemical, environmental or economic disadvantages.
[0004]
EP 0027583 discloses a method for reducing the emission of formaldehyde from particleboard bonded with carbamide resins. The board is treated with a pyrolytic ammonium compound, for example, ammonium carbonate, following pressing. The boards thus treated are then stacked and stored at a temperature from 40 ° C. to 70 ° C., so that ammonia can be released.
[0005]
In addition, layered flooring, such as a three-layer parquet floor, can release formaldehyde because the different wood layers are usually bonded together by bonding with a formaldehyde-based adhesive. The upper layer is usually made of hardwood, the middle layer is made of softwood or paperboard, for example MDF, HDF or particleboard, and the lower layer is made of veneer. This top layer is treated with a formaldehyde-free UV lacquer or oil to protect the surface, which may also serve as a barrier for formaldehyde emission. Different portions of the parquet floor sample, eg, front, back, and edges, exhibit different release rates. For example, formaldehyde emission from the back side may be 20 times higher than emission from the front side.
[0006]
Furthermore, there is an increasing demand for parquet floors that can meet the required E1 values obtained in chamber tests according to the Swedish standard SS270236 (SS1988). If the emission test for parquet flooring has been performed with samples having a rear surface and sealed edges that are not exposed, resulting release values were very low often drops below 0.05 mg / m 3 ( The limit value for E1 is 0.13 mg / m 3 ).
[0007]
In addition, for formaldehyde emission measurements, a new European standard, EN 717-1, has been proposed, according to which all samples to be measured will have an exposed backside and partially exposed edges. This makes it more difficult for the floor manufacturer to achieve very low formaldehyde emission values.
[0008]
In addition, there is a need to meet Japanese Standard JAS SIS 20, which involves a desiccator measurement where the back and edges of the sample cannot be sealed but they are fully exposed.
[0009]
Thus, technical solutions still seek to reduce formaldehyde emissions from wood-based products containing formaldehyde-based resins and meet new, more stringent standards for formaldehyde emissions from these products. Is done.
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0010]
The present invention therefore provides a method for reducing the emission of formaldehyde from wood-based products comprising formaldehyde-based resins, which solves the above problems.
[Means for Solving the Problems]
[0011]
The method of the present invention comprises at least one treatment of the paperboard or veneer surface contained in the layered product having at least two layers, prior to bonding the layers together, with a solution comprising an inorganic sulfur-containing salt.
BEST MODE FOR CARRYING OUT THE INVENTION
[0012]
“Layered product comprising formaldehyde” means herein a lamellar product comprising a resin based on formaldehyde, in which case the layers are bonded to one another by a formaldehyde-based adhesive and If one or more is paperboard, the paperboard itself may also be bonded with a formaldehyde-based adhesive.
[0013]
Suitably, the concentration of the inorganic sulfur-containing salt in the solution is from about 1% to about 30% by weight, preferably from about 5% to about 20% by weight, most preferably from about 8% to about 13% by weight. Up to. Although the application of the salt in the form of a solution is preferred, it may also, if desired according to the invention, be applied in the form of a powder. For environmental reasons, this solution is preferably an aqueous solution, but solvents other than water may be used. The salt solution may be applied by using any conventional coating technique, for example, roll coating, curtain coating, or spray coating. The amount of salt solution applied is suitably from about 30 g / m 2 to about 90 g / m 2 , preferably from about 40 g / m 2 to about 80 g / m 2 if only one of the surfaces is treated. 2 , most preferably from about 55 g / m 2 to about 65 g / m 2 . If both surfaces are to be treated, it is preferred that the amount applied per surface is half that when only one of the surfaces is treated. Large amounts of salt solution are not desirable to avoid disturbing the moisture balance of the product being processed.
[0014]
The inorganic sulfur salts of the present invention have a very high water solubility, while the carbonates have a rather limited water solubility. Thus, in order to obtain an effective salt solution that results in the desired reduction of formaldehyde emissions, it is necessary that a large amount of carbonate solution compared to the amount of sulfite solution be applied to the surface to be treated. It can adversely affect the moisture balance of the product being processed, and thus of the finished layered product.
[0015]
In addition, the inorganic sulfur salts of the present invention do not discolor the finished layered product, especially its outer surface, while carbonates may have a discoloring effect on the outer layer of the finished product, especially the oak surface.
[0016]
Suitable inorganic sulfur-containing salts include sulfites or bisulfites, such as alkali metal sulfites or bisulfites or ammonium sulfite or ammonium bisulfite. Water soluble sulfites or bisulfites are preferred. Preferably, ammonium sulfite or bisulfite is used, with ammonium sulfite being most preferred.
[0017]
The methods of reducing the amount of formaldehyde released by materials and products prepared with formaldehyde-based resins are applicable to all formaldehyde-based resins, for example, urea-formaldehyde resins, melamine-formaldehyde resins. And phenol-formaldehyde resins, as well as copolymers, blends and mixtures made therefrom.
[0018]
In a preferred embodiment of the invention, urea is added to the inorganic sulfur-containing salt solution. Even though the inorganic sulfur-containing salt alone effectively reduces formaldehyde emission, the addition of urea to the salt solution further improves the reduction in formaldehyde emission. Suitably, the weight ratio of urea to sulfur-containing salt is from about 1:10 to about 1: 1, preferably from about 2:10 to about 8:10, most preferably from about 3:10 to about 6:10. It is.
[0019]
The paperboard treated according to the present invention may be any type of paperboard, for example, particleboard, chipboard, or fiberboard, which is based on formaldehyde-based resins or other non-formaldehyde-based resins. It may be bonded with an adhesive.
[0020]
The veneer treated according to the invention may be any type of wood veneer, preferably untreated veneer.
[0021]
These paperboards or veneers may be conditioned after application of the salt solution to the desired moisture content before the bonding step. Furthermore, only one of the surfaces of the veneer or paperboard needs to be coated with the salt solution to obtain the benefits of the present invention, but depending on the method of application, both surfaces may be coated as desired. .
The layers may be joined using any of the known conventional techniques, for example, by gluing and pressing.
[0022]
The paperboard or veneer treated according to the method of the present invention preferably constitutes the back or layer of the layered product. This results in a considerable reduction in the emission of formaldehyde from the back of the layered product.
[0023]
The layered product of the present invention may be any wood-based layered product. Suitably it is a flooring, preferably a parquet, most preferably a three-layer parquet.
[0024]
The aqueous salt solution of the present invention contains ammonium sulfite or bisulfite and urea. It preferably comprises ammonium sulphite and urea.
The weight ratio of the salt to urea is suitably from about 1:10 to about 1: 1, preferably from about 2:10 to about 8:10, and most preferably from about 3:10 to about 6:10. .
Suitably, the concentration of ammonium salts and urea in the solution is from about 1% to about 30% by weight, preferably from about 5% to about 20% by weight, most preferably from about 8% to about 13% by weight. %.
[0025]
The method of preparing a salt solution of the present invention involves mixing salt, urea and water in a mixing ratio to produce the desired concentration of salt and urea in the solution.
[0026]
In a preferred embodiment of the process for preparing a salt solution according to the invention, said ammonium salt is in the form of an aqueous solution before mixing with urea and the additional water required to receive a solution having the desired salt concentration.
[0027]
In a further preferred embodiment of the method for preparing a salt solution according to the invention, both said ammonium salt and urea are in the form of an aqueous solution before mixing with each other to prepare an aqueous solution according to the invention having the desired salt concentration.
[0028]
The present invention is further described by the following non-limiting examples. Parts and percentages relate to parts by weight and% by weight, respectively, unless otherwise stated.
【Example】
[0029]
The ammonium sulfite solution used in the examples of the present invention was prepared by mixing 19.7 kg of ammonium sulfite solution (35-36 wt%) and 3.0 kg of urea with water to obtain a 10 wt% aqueous salt solution.
[0030]
The ammonium carbonate solution used in the comparative example was prepared by mixing 31.6 kg of urea, 40.0 kg of ammonium bicarbonate and 28.4 kg of ammonium carbonate with water to obtain a 27.8% by weight aqueous salt solution.
[0031]
[Example 1 (reference example)]
Spruce veneers (2 mm thick) were adhered to both sides of a pine core material with a thermosetting urea-formaldehyde resin and a curing agent.
[Example 2 (Comparative Example)]
A spruce veneer (2 mm thick) was pretreated on both sides with an ammonium carbonate solution, then dried for 4 hours, then glued and pressed in the same manner as in Example 1.
[Example 3]
A spruce veneer (2 mm thick) was pretreated on both sides with an inorganic sulphite solution, dried and then glued and pressed in the same manner as in Example 2.
[0032]
[Example 4 (Comparative Example)]
After bonding and pressing, the procedure of Example 1 was repeated, except that the sample was left at ambient temperature for 15 minutes and then the backside of the veneer (the side facing away from the adhesive line) was sprayed with an ammonium carbonate solution.
[Example 5]
The procedure of Example 4 was repeated except that the back of the veneer was sprayed with an ammonium sulfite solution.
[0033]
Formaldehyde release from samples prepared according to the above examples was measured in a field and laboratory release cell (FLEC) after conditioning for 24 hours. The results are shown in Table 1 below.
[0034]
[Table 1]
[0035]
As can be seen from Table 1, the formaldehyde emissions from the samples containing the treated veneers were generally significantly reduced as compared to those of the samples containing the untreated veneers. In addition, treatment of the veneer with the salt solution of the present invention results in a greater reduction in formaldehyde emission as compared to when the veneer is treated with an ammonium carbonate solution. This improvement is due to the fact that the concentration of the ammonium sulphite solution used is only about 1/3 of the concentration of the carbonate solution and the amount of ammonium sulphite solution applied (g / m 2 ) It becomes even more evident in view of the fact that it was less.
[0036]
[Example 6]
A spruce veneer for the production of a three-sided parquet flooring of 14 mm with edge bonding was pretreated on both sides with an ammonium sulphite solution. The veneer was conditioned to a moisture content of about 7% and then adhered to the pine core material with a thermosetting urea-formaldehyde resin and a curing agent. Ash lamellae were adhered to the top of the core material with the same urea-formaldehyde resin / hardener mixture.
[Example 7 (Comparative Example)]
Example 6 was repeated except that the spruce veneers were pretreated with an ammonium carbonate solution.
[Example 8 (Reference example)]
Parquet floor samples were prepared in the same manner as Examples 6 and 7, except that the spruce veneers used were not treated with a salt solution.
[0037]
Samples prepared according to all of Examples 6, 7 and 8, after pressing, cooling to ambient temperature and treating the upper layer with lacquer or oil, were packaged in formaldehyde impermeable plastic. Exposing the front and back, to seal the edges was measured at 1 m 3 chamber in formaldehyde emission according to the Swedish standard SS 270236 (SS 1988). The results are shown in Table 2 below.
[0038]
[Table 2]
[0039]
Obviously, the pretreatment of the veneer with an inorganic sulphite solution according to the invention more effectively reduces the emission of formaldehyde without having to use unexpectedly large amounts of rather concentrated salt solutions. The use of a large amount of salt solution results in a large amount of water being supplied to the veneer, which can have an adverse effect on the moisture balance of the product.

Claims (16)

少なくとも一つが板紙又はベニヤである、少なくとも2層を有するホルムアルデヒドを含む層状製品からのホルムアルデヒドの放出の低減方法であって、これらの層を一緒に結合する前に、前記板紙又はベニヤの表面の少なくとも一つを無機硫黄含有塩を含む溶液で処理することを特徴とする上記方法。A method for reducing the release of formaldehyde from a layered product comprising formaldehyde having at least two layers, at least one of which is paperboard or veneer, wherein at least one of the surfaces of the paperboard or veneer is bonded prior to bonding the layers together. The above method, wherein one is treated with a solution containing an inorganic sulfur-containing salt. 前記溶液が水溶液である請求項1記載の方法。The method of claim 1, wherein said solution is an aqueous solution. 前記溶液が約5重量%から約20重量%までの範囲の無機硫黄塩含量を有する請求項1又は2のいずれか1項記載の方法。3. The method according to claim 1, wherein the solution has an inorganic sulfur salt content ranging from about 5% to about 20% by weight. 前記無機硫黄塩が亜硫酸アンモニウム又は重亜硫酸アンモニウムである請求項1から3のいずれか1項記載の方法。The method according to any one of claims 1 to 3, wherein the inorganic sulfur salt is ammonium sulfite or ammonium bisulfite. 前記溶液が更に尿素を含む請求項1から4のいずれか1項記載の方法。The method according to any one of claims 1 to 4, wherein the solution further comprises urea. 尿素対無機亜硫酸塩の重量比が約3:10から約6:10までである請求項5記載の方法。The method of claim 5, wherein the weight ratio of urea to inorganic sulfite is from about 3:10 to about 6:10. 請求項1から6のいずれか1項記載の方法により処理された板紙又はベニヤが層状製品の裏面又は層を構成する請求項1から6のいずれか1項記載の方法。7. The method according to any one of the preceding claims, wherein the paperboard or veneer treated by the method according to any one of the preceding claims constitutes the back or layer of a layered product. 前記層状製品が床材である請求項1から7のいずれか1項記載の方法。The method according to any one of claims 1 to 7, wherein the layered product is flooring. 前記材料が寄せ木張りの床材である請求項8記載の方法。9. The method of claim 8, wherein said material is parquet flooring. 請求項1から6のいずれか1項記載の方法により得られる板紙。Paperboard obtained by the method according to any one of claims 1 to 6. 請求項1から6のいずれか1項記載の方法により得られるベニヤ。Veneer obtained by the method according to any one of claims 1 to 6. 請求項1から9のいずれか1項記載の方法により得られる床材。A flooring obtained by the method according to any one of claims 1 to 9. 前記材料が寄せ木張りの床材である請求項12記載の床材。13. The flooring of claim 12, wherein said material is a parquet flooring. 亜硫酸アンモニウム又は重亜硫酸アンモニウム及び尿素を含むことを特徴とする請求項1から9のいずれか1項記載の方法に有益な水溶液。Aqueous solution useful in the process according to any of the preceding claims, comprising ammonium sulfite or bisulfite and urea. 亜硫酸アンモニウムを含む請求項14記載の水溶液。The aqueous solution according to claim 14, comprising ammonium sulfite. 尿素対亜硫酸塩の重量比が約3:10から約6:10までである請求項14又は15のいずれか1項記載の水溶液。16. The aqueous solution of any one of claims 14 or 15, wherein the weight ratio of urea to sulfite is from about 3:10 to about 6:10.
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