CN1496297A - Method of reducing emission of formaldehyde from formaldehyde layered products - Google Patents
Method of reducing emission of formaldehyde from formaldehyde layered products Download PDFInfo
- Publication number
- CN1496297A CN1496297A CNA028063775A CN02806377A CN1496297A CN 1496297 A CN1496297 A CN 1496297A CN A028063775 A CNA028063775 A CN A028063775A CN 02806377 A CN02806377 A CN 02806377A CN 1496297 A CN1496297 A CN 1496297A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- empiecement
- solution
- urea
- aqueous solution
- 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.)
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Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE 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
- B27N1/00—Pretreatment of moulding material
- B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
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
The present invention relates to the method for a kind of reduction formaldehyde emission from the laminar product that has formaldehyde, wherein said laminar product has two-layer at least, and wherein at least one deck be plate or empiecement.The invention still further relates to plate, empiecement and the flooring material that can obtain by described method, relate to the aqueous solution of using in the method that contains ammonium sulfite or ammonium bisulfite and urea, and the method for preparing this aqueous solution.Before method of the present invention is included in each layer is bonded together, with a kind of described plate of solution-treated of the salt that contains inorganic sulfur or at least one surface of empiecement.
Based on aldehyde particularly the resin of formaldehyde be widely used in the adhesive composition, described adhesive composition is used to make construction material such as panelling, decorative panel etc.; Household furniture such as furniture, flooring material etc.Usually these adhesive compositions contain the formaldehyde of a large amount of molar excess.The part excess formaldehyde discharges when resin solidification in process of producing product.Even but known be that formaldehyde still continues to discharge from these products after production process is finished.Therefore the formaldehyde in the room air has become subject matter for many years.
Carried out the discharging that many trials reduce formaldehyde for many years, but all trials all have tangible machinery, chemistry, environment or economical disadvantages.
EP0 027 583 discloses a kind of method that reduces the discharging of formaldehyde from the chip glued board of carbamide resin bonding.Described plate can be handled with heat decomposable ammonium compounds such as ammonium carbonate, suppresses subsequently.The plate that to handle is like this stacked under 40-70 ℃ temperature and is stored then, thereby ammonia is discharged.
In addition, owing to different wood layers bonds together with carboxaldehyde radicals binding agent gummed usually, the stratiform flooring material may formaldehyde emission as three layers of parquet floor.Top layer is made up of hardwood usually, and the middle level is cork or plate, for example MDF, HDF or chip glued board, and bottom is the empiecement plate.Top layer usually with the UV-lacquer that does not contain formaldehyde or oil processing to protect the surface, simultaneously as a kind of barrier of formaldehyde emissions.The different piece of parquet floor sample as front, the back side and edge, has different rate of discharges.For example, may be from the formaldehyde of back side discharging than high 20 times from the formaldehyde that discharges previously.
In addition, increase day by day for the demand of the parquet floor that can meet desired E1 value, wherein said E1 value is to obtain in laboratory test according to Svensk Standard SS270236 (SS1988).When the sample that has the unexposed back side and a sealing the margin when application carried out the emission testing of parquet floor, the discharge value that obtains was very low, is usually less than 0.05mg/m
3(boundary value of E1 is 0.13mg/m
3).
In addition, for determining of formaldehyde emissions, having proposed a new European standard is EN717-1, and according to this standard, all samples that will measure all will have the back side of exposure and the edge that part exposes.This makes that floor manufacturer is more difficult and reaches extremely low formaldehyde emissions value.
Moreover, also there is requirement to meet Nippon Standard JAS SIS20, this standard comprises that a drier (desiccator) measures, wherein the back side of sample and edge can not seal, but expose fully.
Therefore, still seeking to reduce the technical scheme that formaldehyde discharges from the wood-based product of containing formaldehyde based resin, thereby satisfying the discharge standard of new stricter formaldehyde from these products.
Correspondingly, the invention provides a kind of method that formaldehyde discharges that reduces from the wood-based product of containing formaldehyde based resin, utilize this method can solve the top problem of being mentioned.
With the solution-treated plate of salt that contains inorganic sulfur or at least one surface of empiecement, wherein said plate or empiecement were included in the laminar product with at least two surfaces before method of the present invention was included in each layer bonded together.
" laminar product that has formaldehyde " refers to contain the laminar product of formaldehyde based resin here, and wherein each layer bonds together mutually by the carboxaldehyde radicals binding agent, and when one or more layers was plate, described plate equally also can bond with the carboxaldehyde radicals binding agent.
The concentration that contains the salt of inorganic sulfur in the solution suitably is extremely about 30wt% of about 1wt%, is preferably about 5wt% to about 20wt%, and most preferably is about 8wt% to about 13wt%.Though it is preferred using salt by the solution form, according to the present invention if desired, also can use powder type.Because the reason of environment, though other solvent beyond dewatering also can be used, described solution suitably is the aqueous solution.Paint-on technique such as roller coat, curtain coating or spraying that described salting liquid can be used any routine apply.When only handling one when surperficial, the amount of coated salting liquid suitably is about 30g/m
2To about 90g/m
2, be preferably about 40g/m
2To about 80g/m
2, and most preferably be about 55g/m
2To about 65g/m
2When if two surfaces are all processed, the coated weight of each side half of the amount when only having a surface processed suitably then.For fear of the disturbance of the water balance of treatment product, a large amount of salting liquids is undesirable.
Inorganic sulfosalt of the present invention has very high water solubility, and carbonate has very limited water solubility.Thereby therefore in order to obtain the reduction that effective salting liquid causes desirable formaldehyde emissions, compare with sulfite solution, more substantial carbonate solution need be coated on the institute surface to be processed, and the water balance of its possibility product that negative effect is handled, even the water balance of final laminar product.
In addition, inorganic sulfosalt of the present invention can not make final laminar product particularly its outer surface fade, and carbonate may particularly have decolourization in the oak surface to the skin of final products.
The suitable salt that contains inorganic sulfur comprises sulphite or bisulfites, for example alkali metal sulfite or bisulfites or ammonium sulfite or ammonium bisulfite.Water-soluble sulfite or bisulfites are preferred.Preferred use ammonium sulfite or ammonium bisulfite, and most preferably be ammonium sulfite.
Reduction can be applied to all carboxaldehyde radicals resins, the copolymer, blend and the mixture that for example can be used for Lauxite, melamino-formaldehyde resin, phenolic resins etc. and made by them by the method for the formaldehyde amount that discharges in the material of formaldehyde based resin preparation and the product.
In a preferred embodiment of the invention, in the solution of the salt that contains inorganic sulfur, add urea.Though the salt itself that contains inorganic sulfur just can effectively reduce the discharging of formaldehyde, in salting liquid, add the reduction degree that urea has further improved formaldehyde emission.Urea is about 1: 10 to about 1: 1 suitably with the weight ratio that contains sulfosalt, is preferably about 2: 10 to about 8: 10, and most preferably is about 3: 10 to about 6: 10.
According to the present invention plate to be processed can be the plate of any kind of, for example chip glued board, chipboard or fiberboard, and it can bond with the binding agent based on formaldehyde based resin or other non-formaldehyde based resin.
According to the present invention empiecement to be processed can be preferably untreated empiecement for the wooden empiecement of any kind of.
Plate or empiecement can be adjusted to desirable moisture after bonding was applying salting liquid before the stage.In addition, though empiecement or plate have only a surface to need to use salting liquid coated with realizing benefit of the present invention, according to painting method, if desired, two surfaces can be coated.
Can use any known routine techniques such as gluing or compacting etc. bonds together each layer.
Back surfaces or layer that plate of handling according to the inventive method or empiecement preferably constitute layered product.This will cause obviously reducing from the formaldehyde of laminar product back side discharging.
According to the present invention, layered product can be any wooden laminar product.It is a flooring material suitably, is preferably parquet floor, and most preferably is three layers of parquet floor.
According to the present invention, the aqueous solution of salt contains ammonium sulfite or ammonium bisulfite and urea.Preferably contain ammonium sulfite and urea.
The weight ratio of salt and urea is about 1: 10 to about 1: 1 suitably, is preferably about 2: 10 to about 8: 10, and most preferably is about 3: 10 to about 6: 10.
The concentration of ammonium salt and urea suitably is extremely about 30wt% of about 1wt% in the solution, is preferably about 5wt% to about 20wt%, and most preferably is about 8wt% to about 13wt%.
According to the present invention, the preparation method of salting liquid comprises by mixing ratio salt-mixture, urea and water, thereby obtains salt and urea desirable concentration in solution.
According to the present invention, in salting liquid preparation method's a preferred embodiment, before mixing with urea with for the required additional water that adds of solution that obtains having desired salinity, ammonium salt is the form of the aqueous solution.
According to the present invention, in salting liquid preparation method's further preferred embodiment, ammonium salt and urea are mixed with the form that the aqueous solution with desirable salinity of the present invention is the aqueous solution before mutually.
Further describe the present invention by following non-limiting embodiment.If not indicated otherwise, part and percentage refer to weight portion and percentage by weight respectively.
Embodiment
The ammonium sulfite solution of Ying Yonging prepares with the aqueous solution that 3.0kg urea and water obtain the salt of 10wt% by mixing 19.7kg ammonium sulfite solution (35-36wt%) in embodiments of the present invention.
The sal volatile of using in comparative example prepares by the aqueous solution that mixing 31.6kg urea, 40.0kg carbonic hydroammonium and 28.4kg ammonium carbonate and water obtain the salt of 27.8wt%.
Embodiment 1 (reference example):With heat cured Lauxite and curing agent dragon spruce empiecement (2mm is thick) is bonded on two surfaces of pine core.
Embodiment 2 (comparative example):Before pressing the gluing and compacting of the identical method of embodiment 1, with sal volatile preliminary treatment is carried out on two surfaces of dragon spruce empiecement (2mm is thick), placed then dry 4 hours.
Embodiment 3:With two surfaces of inorganic sulfite solution preliminary treatment dragon spruce empiecement (2mm is thick), place dryly, it is gluing and suppress press the identical method of embodiment 2 then.
Embodiment 4 (comparative example):Repeat the process of embodiment 1, just after gluing and compacting, sample was placed 15 minutes at ambient temperature, spray the back side (side of glue-line dorsad) of empiecement then with sal volatile.
Embodiment 5:Repeat the process of embodiment 4, just spray the back side of empiecement with ammonium sulfite solution.
After adjusting through 24 hours, (FLEC) measures the formaldehyde emission of the sample for preparing according to the foregoing description with scene and discharging pond, laboratory (Field andLaboratory Emission Cell).The result is as shown in table 1 below.
Table 1
| Embodiment | Handle empiecement | Concentration of salt solution wt% | Salting liquid coated weight g/m 2Each treatment surface | Discharge capacity μ g/m after 24 hours 2h |
| ?1 | Be untreated | 733 | ||
| ?2 | Use the sal volatile preliminary treatment | 27.8 | ?31 | 44 |
| ?3 | Use the ammonium sulfite solution preliminary treatment | 10 | ?29 | ＜10 |
As can be seen from Table 1, compare with the sample that comprises the empiecement that is untreated, usually the formaldehyde that is discharged from the sample of the empiecement that comprises processing is obviously lower.In addition, compare, handle empiecement with salting liquid of the present invention and cause formaldehyde emission reduction by a larger margin with the empiecement of handling with sal volatile.When the concentration of considering applied ammonium sulfite solution only is the coated weight (g/m of about 1/3rd and ammonium sulfite solution of carbonate solution concentration
2) when being lower than coated weight true of sal volatile, it is more obvious that this improvement will become.
Embodiment 6:Preliminary treatment is carried out in two sides of the dragon spruce empiecement of using when making the gluing 14mm3 layer parquet floor in edge with ammonium sulfite solution.Described empiecement was adjusted to about 7% moisture before being glued on the pine core with thermoset urea aldehyde resin and curing agent.The surface of ash thin slice also is glued to above the core with identical Lauxite/curing agent mixture.
Embodiment 7 (comparative example):Repeat embodiment 6, just with sal volatile preliminary treatment dragon spruce empiecement.
Embodiment 8 (reference example):Preparing the parquet floor sample by embodiment 6 mode identical with 7, is that applied dragon spruce empiecement need not be handled by any salting liquid.
According to embodiment 6,7 and 8 the preparation all samples after being pressed and being cooled to room temperature, and top layer with the lacquer or oil processing after, be wrapped in the impermeable plastics of formaldehyde.According to Svensk Standard SS270236 (SS1988) at 1m
3Indoor under the situation that exposes front and the back side and sealing the margin, measure the discharge capacity of formaldehyde.The result is as shown in table 2 below.
Table 2
| Embodiment | Handle empiecement | Concentration of salt solution wt% | Salting liquid coated weight g/m 2Each treatment surface | Discharge capacity mg formaldehyde/m 3Air |
| 6 | Use the ammonium sulfite solution preliminary treatment | 10 | ?29 | 0.02 |
| 7 | Use the sal volatile preliminary treatment | 27.8 | ?31 | 0.02 |
| 8 | Be untreated | 0.05 |
Clearly, under the situation that need not use denseer in a large number salting liquid, more effectively reduced the discharge capacity of formaldehyde with inorganic sulfite solution preliminary treatment empiecement of the present invention unexpectedly.Use a large amount of salting liquids to cause more substantial water is provided on empiecement, and this water balance to product have negative effect.
Claims (16)
1. the method for reduction formaldehyde emission from the laminar product that has formaldehyde, wherein said laminar product has two-layer at least, and wherein one deck is plate or empiecement at least, wherein before each layer bonded together, with a kind of described plate of solution-treated of the salt that contains inorganic sulfur or at least one surface of empiecement.
2. the process of claim 1 wherein that described solution is the aqueous solution.
3. claim 1 or 2 each methods, the content range of the inorganic sulfosalt of wherein said solution is about 5%wt% about 20wt% extremely.
4. each method of claim 1-3, wherein said inorganic sulfosalt is ammonium sulfite or ammonium bisulfite.
5. each method of claim 1-4, wherein said solution further contains urea.
6. the method for claim 5, wherein the weight ratio of urea and inorganic sulfite is about 3: 10 to about 6: 10.
7. each method of aforementioned claim, wherein plate of handling according to each method of claim 1-6 or the empiecement back surfaces or the layer that constitute layered product.
8. each method of claim 1-7, wherein said laminar product is a flooring material.
9. the method for claim 8, wherein said material is a parquet floor.
10. plate that can obtain according to each method of claim 1-6
11. empiecement that can obtain according to each method of claim 1-6.
12. flooring material that can obtain according to each method of claim 1-9.
13. the flooring material of claim 12, wherein said material are parquet floor.
14. one kind is used for each the aqueous solution of method of claim 1-9, the wherein said aqueous solution contains ammonium sulfite or ammonium bisulfite and urea.
15. the aqueous solution of claim 14 wherein contains ammonium sulfite.
16. the claim 14 or 15 each the aqueous solution, wherein the weight ratio of urea and sulphite is about 3: 10 to about 6: 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01850045 | 2001-03-12 | ||
| EP01850045.4 | 2001-03-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1496297A true CN1496297A (en) | 2004-05-12 |
| CN1320988C CN1320988C (en) | 2007-06-13 |
Family
ID=8184866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028063775A Expired - Fee Related CN1320988C (en) | 2001-03-12 | 2002-03-04 | Method of reducing emission of formaldehyde from formaldehyde layered products |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP1368168B1 (en) |
| JP (1) | JP2004522628A (en) |
| CN (1) | CN1320988C (en) |
| AT (1) | ATE409558T1 (en) |
| CA (1) | CA2440349C (en) |
| CZ (1) | CZ20032392A3 (en) |
| DE (1) | DE60229111D1 (en) |
| DK (1) | DK1368168T3 (en) |
| EE (1) | EE200300376A (en) |
| ES (1) | ES2315346T3 (en) |
| NO (1) | NO20034001D0 (en) |
| PL (1) | PL363912A1 (en) |
| SI (1) | SI1368168T1 (en) |
| SK (1) | SK11242003A3 (en) |
| WO (1) | WO2002072323A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331910C (en) * | 2005-04-19 | 2007-08-15 | 湖南大学 | Method for removing free formaldehyde in amino resin modified by hydroxylic acrylic ester |
| CN101351313B (en) * | 2005-07-27 | 2011-06-01 | 克罗诺普拉斯技术股份公司 | Method for preparing timber product emitting little chemical compound and timber products produced therefor |
| CN106367965A (en) * | 2008-12-19 | 2017-02-01 | 圣戈班艾德福斯公司 | Canvas including an agent capable of trapping formaldehyde and manufacturing process |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7678224B2 (en) | 2003-03-25 | 2010-03-16 | Akzo Nobel N.V. | Method for reducing emissions and method for producing a wooden product |
| EP1606089B1 (en) * | 2003-03-25 | 2013-01-02 | Akzo Nobel Coatings International BV | Method for reducing emissions and method for producing a wooden product |
| WO2006104455A1 (en) | 2005-04-01 | 2006-10-05 | Akzo Nobel Coatings International B.V. | Method of reducing the emission of aldehyde from wood based products |
| JP5198787B2 (en) * | 2006-04-25 | 2013-05-15 | 株式会社オーシカ | Aldehyde deodorant composition |
| US8173219B2 (en) | 2006-06-09 | 2012-05-08 | Georgia-Pacific Chemicals Llc | Porous fiberglass materials having reduced formaldehyde emissions |
| US8043383B2 (en) | 2006-06-30 | 2011-10-25 | Georgia-Pacific Chemicals Llc | Reducing formaldehyde emissions |
| DE102007038041A1 (en) * | 2007-08-10 | 2009-02-12 | Kronotec Ag | Method for preventing the emission of aldehydes and volatile organic compounds from wood-based materials |
| JP2009074058A (en) * | 2007-08-29 | 2009-04-09 | Asahi Fiber Glass Co Ltd | Aldehyde scavenger and building material using the same |
| PT2272644T (en) | 2009-07-06 | 2017-01-10 | SWISS KRONO Tec AG | Method of reducing the emissions of aldehydes and fleeting organic compounds in wooden materials |
| GB201105583D0 (en) | 2011-04-01 | 2011-05-18 | Dynea Oy | System for form pressing with high production efficiency |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1598199A (en) * | 1976-12-10 | 1981-09-16 | Meyer C B | Adhesive resins containing sulphur |
| DE3344239C2 (en) * | 1983-12-07 | 1986-07-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München | Process for reducing the formaldehyde release from chipboard and fiberboard veneered with finishing layers |
| DE3427694A1 (en) * | 1984-07-27 | 1986-02-06 | Basf Ag, 6700 Ludwigshafen | Formaldehyde-binding agents, the use thereof in the production of wood chip materials, and a process for the production of wood chip materials having reduced formaldehyde emission |
| JPS62114629A (en) * | 1985-11-14 | 1987-05-26 | Mitsui Toatsu Chem Inc | Aqueous solution of formaldehyde absorbent |
| US5635583A (en) * | 1995-06-06 | 1997-06-03 | Borden Chemical, Inc. | Catalytic composition and method for curing urea-formaldehyde resin |
-
2002
- 2002-03-04 DK DK02701853T patent/DK1368168T3/en active
- 2002-03-04 PL PL02363912A patent/PL363912A1/en not_active Application Discontinuation
- 2002-03-04 SK SK1124-2003A patent/SK11242003A3/en unknown
- 2002-03-04 WO PCT/SE2002/000377 patent/WO2002072323A1/en active Application Filing
- 2002-03-04 CA CA002440349A patent/CA2440349C/en not_active Expired - Fee Related
- 2002-03-04 ES ES02701853T patent/ES2315346T3/en not_active Expired - Lifetime
- 2002-03-04 CN CNB028063775A patent/CN1320988C/en not_active Expired - Fee Related
- 2002-03-04 AT AT02701853T patent/ATE409558T1/en not_active IP Right Cessation
- 2002-03-04 JP JP2002571270A patent/JP2004522628A/en active Pending
- 2002-03-04 EE EEP200300376A patent/EE200300376A/en unknown
- 2002-03-04 DE DE60229111T patent/DE60229111D1/en not_active Expired - Fee Related
- 2002-03-04 CZ CZ20032392A patent/CZ20032392A3/en unknown
- 2002-03-04 EP EP02701853A patent/EP1368168B1/en not_active Expired - Lifetime
- 2002-03-04 SI SI200230782T patent/SI1368168T1/en unknown
-
2003
- 2003-09-10 NO NO20034001A patent/NO20034001D0/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331910C (en) * | 2005-04-19 | 2007-08-15 | 湖南大学 | Method for removing free formaldehyde in amino resin modified by hydroxylic acrylic ester |
| CN101351313B (en) * | 2005-07-27 | 2011-06-01 | 克罗诺普拉斯技术股份公司 | Method for preparing timber product emitting little chemical compound and timber products produced therefor |
| CN106367965A (en) * | 2008-12-19 | 2017-02-01 | 圣戈班艾德福斯公司 | Canvas including an agent capable of trapping formaldehyde and manufacturing process |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1368168A1 (en) | 2003-12-10 |
| SK11242003A3 (en) | 2004-05-04 |
| CA2440349C (en) | 2008-02-05 |
| PL363912A1 (en) | 2004-11-29 |
| CZ20032392A3 (en) | 2004-02-18 |
| WO2002072323A1 (en) | 2002-09-19 |
| EP1368168B1 (en) | 2008-10-01 |
| JP2004522628A (en) | 2004-07-29 |
| SI1368168T1 (en) | 2009-04-30 |
| ES2315346T3 (en) | 2009-04-01 |
| CA2440349A1 (en) | 2002-09-19 |
| DE60229111D1 (en) | 2008-11-13 |
| EE200300376A (en) | 2003-10-15 |
| NO20034001L (en) | 2003-09-10 |
| NO20034001D0 (en) | 2003-09-10 |
| DK1368168T3 (en) | 2009-02-02 |
| CN1320988C (en) | 2007-06-13 |
| ATE409558T1 (en) | 2008-10-15 |
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Granted publication date: 20070613 Termination date: 20100304 |