CN1826396A - Adhesive composition comprising a formaldehyde-containing aminoplast resin and a catalysing compound - Google Patents
Adhesive composition comprising a formaldehyde-containing aminoplast resin and a catalysing compound Download PDFInfo
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- CN1826396A CN1826396A CN 200480021212 CN200480021212A CN1826396A CN 1826396 A CN1826396 A CN 1826396A CN 200480021212 CN200480021212 CN 200480021212 CN 200480021212 A CN200480021212 A CN 200480021212A CN 1826396 A CN1826396 A CN 1826396A
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Abstract
The invention relates to an adhesive composition comprising a formaldehyde-containing aminoplast resin and a catalysing compound, with the catalysing compound being an acid or is able to release an acid with a pKa lower than 4 and with the formaldehyde-containing aminoplast resin having a F/(NH2)2 ratio lower than or equal to 1. The catalysing compound comprises at most 11 wt.% of an ammonium salt. The invention also relates to a process for the preparation of board material using the adhesive composition according to the invention and to the board material thus obtainable.
Description
The present invention relates to a kind of aminoplast(ic) resin that contains formaldehyde and binding compositions of catalytic cpd of comprising.
For example EP-436.485-A2 discloses this binding compositions.This patent documentation has been described the method for quickening the curing amino plastics binder and has been reached by its wood based material that makes.The binding compositions of describing in the described patent application comprises urea-formaldehyde (UF) resin, and its F/U molar ratio is 1.11.Use ammonium sulfate as catalytic cpd.In order to quicken the curing of these aminoplast binders, use accelerator-scavenging agent system, urea-formaldehyde mixture is added in the tackiness agent as accelerator and formaldehyde purifying agent.The adding of formaldehyde purifying agent has prevented that the formaldehyde emission of the panel material that made by tackiness agent from increasing.
Consider environmental regulations, extremely important during panel material is made with later formaldehyde emission.For example, for shaving board, NEN EN 312-1 stipulates that it is a step that the potential amount of formaldehyde of the cellulose-containing material that every 100g does must not be higher than 8mg.The potential amount of formaldehyde refers to by the extracting method described in the DIN NEN 120, is also referred to as the Perforator test, and the amount of the formaldehyde that obtains; Bright its formaldehyde emission of the potential scale of the formaldehyde of material.It is the strict demand that the potential amount of formaldehyde of shaving board material must meet that the one-level of shaving board is required, and has illustrated that quantity discharged requires to be tending towards stricter.
Be surprised to find now, when use was produced panel material according to binding compositions of the present invention, formaldehyde emission was very low; For example, for shaving board, the material of the cellulose of doing according to the every 100g of the potential amount of the formaldehyde of DIN NEN 120 can be less than 10mg, in many cases even less than 8mg/.Simultaneously, the final performance to set time and panel material does not have disadvantageous effect.
Binding compositions according to the present invention is characterised in that, catalytic cpd is pKa less than 6 acid or can discharges pKa less than 6 acid (condition is the maximum 11wt% of ammonium salt that this catalytic cpd comprises), and contains the F/ (NH of the aminoplast(ic) resin of formaldehyde
2)
2Ratio is less than or equal to 1.
In EP 107260 A1, a kind of method of making sheet material is disclosed, the F/ (NH of use therein binding compositions
2)
2Molar ratio is between 0.50 and 1.25.EP 107260 A1 disclose the mixture of ammonium salt and strong acid as catalytic cpd.Disclosed catalytic cpd mixture comprises the ammonium salt above 11wt% among EP 107260 A1.
Can be pKa less than 6 acid or can discharge the compound of pKa according to catalytic cpd of the present invention less than 6 acid.The pKa of acid measures down at 25 ℃.
PKa is known less than 6 acid itself.The example of this acid is formic acid, lactic acid, oxoethanoic acid, toxilic acid, fumaric acid, (adjacent, and to) phthalic acid, Whitfield's ointment (salycicacid), right-toluenesulphonic acids, sulfuric acid, phosphoric acid, tartrate, uric acid, hydrochloric acid soln, acetate, phenylformic acid, succsinic acid and furancarboxylic acid.
The compound that can discharge acid refers in the preparation of binding compositions and/or the compound that reacts in the mode that forms acid in using, for example because this compound decomposition.Can discharge pKa and be the melamine salt of alkyl ester, one or more described acid of for example methyl ester or urea salt and by the methylolation urea or the melamine compound of one or more described acid estersization less than the examples of compounds of 6 acid.The methyl ester example is glyoxalic acid methylester, methyl citrate, methyl-formiate, methyl orthophosphoric acid and uric acid methyl esters.Usually can use the methyl esters of pKa less than 6 acid.
The example of melamine salt or urea salt is formic acid trimeric cyanamide, citric acid trimeric cyanamide, lactic acid urea and uric acid urea.Usually can use the melamine salt or the urea salt of pKa less than 6 acid.
The ester of methylolation urea or melamine compound can be synthetic according to following reaction:
Wherein, R-NH
2Being derived from trimeric cyanamide or urea, HO-X, to be derived from pKa can be H or CH less than 6 acid, Y
2OX, z are 1 or 2.
Preferably, the compound that can discharge acid in water 90 ℃ discharge at least 50% acid in following 1 minute.
Should not surpass 11wt% according to the ammonium salt that catalytic cpd of the present invention comprised.In the context of the present invention, the mixture of various ammonium salts also contained in term " ammonium salt ".Known ammonium salt example is ammonia chloride and ammonium sulfate.Have been found that these salt particularly at the setting up period of binding compositions, can form relative unstable compounds with formaldehyde reaction, for example vulkacit H (HMTA).This reaction reduces the formation of the bonding network of the desirable three-dimensional of setting up period, causes the performance reduction of the finished product, as shows as chemical resistant properties reduction, hydrolytic resistance reduction, internal bond strength reduces or meet the bloated increase of the water capacity.And for example the compound of HMTA can decompose, thus short-term and/or cause formaldehyde emissions chronically, as indicated in potential measurement examination (Perforator test) according to the formaldehyde of NEN-EN 120.As a result, the use of ammonium salt causes negative impact may for main purpose of the present invention-reduction formaldehyde emission, works as the F/ (NH of used binding compositions especially
2)
2Molar ratio is less than or equal at 1 o'clock.Preferably, catalytic cpd according to the present invention comprises the ammonium salt of maximum 10wt% or 8wt%; More preferably, catalytic cpd according to the present invention comprises the ammonium salt of maximum 6wt% or 4wt%; Especially, catalytic cpd according to the present invention comprises the ammonium salt of maximum 2wt% or 1wt%; Most preferably, catalytic cpd according to the present invention comprises the ammonium salt of maximum 0.5wt% or 0.1wt%, or even does not have an ammonium salt at all.
In the preferred embodiment according to binding compositions of the present invention, catalytic cpd comprises the primary amine salt of maximum 11wt%, and (primary amine is to have R-NH
2The compound of structure) or secondary amine salt (secondary amine is the compound with RR '-NH structure, and wherein R and R ' are not hydrogen).In other preferred embodiment, these primary amine salt or secondary amine salt with in addition lower amount have for example above-described ammonium salt amount.
Certainly, catalytic cpd can also comprise one or more aforesaid acid and one or more aforementioned compounds that can discharge acid.Catalytic cpd can also comprise more than one acid or more than one the compound that can discharge acid.
For example when hope at room temperature stores for some time with binding compositions, can use the compound that can discharge acid.In this case, the preferred selection only is being higher than resolvent compound under the temperature of room temperature, so that katalysis only takes place during making panel material.
Preferably, catalytic cpd is pKa less than 5 acid, maybe can discharge the compound of pKa less than 5 acid.Such advantage is that easier pH with binding compositions drops to the level of hope, is generally 7, or even lower, for example 6.Another advantage is that the pKa by reducing can realize shorter gel time.Gel time is defined as to be introduced 5 gram catalytic resins in the water in the test tubes and stirs in boiling water in the test tube after the material, carries out the required time of gelling.
Also more preferably, catalytic cpd is pKa less than 4 acid, maybe can discharge the compound of pKa less than 4 acid.Such advantage is, compares and uses pKa maybe can discharge the compound of the acid of pKa between 4 and 6, the pH value of easier like this reduction binding compositions in the acid between 4 and 6; Another advantage is that the amount of catalyzer to be measured is than using pKa to lack at the compound that the acid between 4 and 6 maybe can discharge the acid of pKa between 4 and 6; Because this catalyzer adds with the form dosage of the aqueous solution usually, so the water in the final binding compositions is less, and this is desired, is favourable because binding compositions has high as far as possible solids content.
Preferably, catalytic cpd is monoprotic acid or methyl ester, one or more pKa less than 4 monacid melamine salt or urea salt or by methylolation urea or the melamine compound of one or more pKa less than 4 monoprotic acid esterification.Monoprotic acid is the acid that can only discharge a hydrogen ion (proton).
Particularly preferably, catalytic cpd is the melamine salt of formic acid or methyl ester, formic acid or urea salt or by the methylolation urea or the melamine compound of formic acid esterification.
Most preferably, catalytic cpd is a formic acid.Yet in another preferred embodiment, catalytic cpd is an acetate.
Can be with catalytic cpd according to the present invention, be pKa less than 6 acid or can discharge the compound of pKa less than 6 acid, to be attached in the binding compositions than known catalysts (for example ammonium sulfate) degree more or less, wherein as indicated in above, the ammonium salt total amount that catalytic cpd comprised should be greater than 11wt%; Yet in a preferred embodiment of the invention, this point is not implemented, and does not use other catalyzer.
Though theoretical explanation is not clear, imagination is that the shock absorption of pKa low-down (discharging) acid is limited, and is unfavorable to the performance according to binding compositions of the present invention.Therefore preferably, catalytic cpd is pKa greater than-14 acid or can discharges the compound of pKa greater than-14 acid; More preferably, described pKa is greater than-10, and also more preferably pKa is greater than-6, and most preferably pKa is greater than-3.
In the present invention, use the condensation product of at least a aminocompound and free formaldehyde type compound as aminoplast(ic) resin.
As the aminocompound in these aminoplast(ic) resins, acyclic is all suitable with the heterocyclic aminocompound.Acyclic aminocompound example is urea, thiocarbamide or ethyl carbamide.As heterocyclic amino compounds, for example use compound, such as senior condensation product, cyanurodiamide, cyanuramide, tricyanic acid and the urea groups trimeric cyanamide of trimeric cyanamide, melam, trimeric cyanamide with triazine structure.Preferably, use urea and/or trimeric cyanamide.More specifically, use urea and trimeric cyanamide mixture, wherein the molar ratio of trimeric cyanamide/urea can be between 0.01 and 2, change between 0.02 and 1 especially.
As the formaldehyde type compound, can use the compound that reacts in the mode identical with formaldehyde.Example is formaldehyde, Paraformaldehyde 96 and trioxane.Paraformaldehyde 96 is the polymkeric substance or the oligopolymer form of formaldehyde, and it decomposites formaldehyde in depolymerization reaction.The polymerization degree is that the Paraformaldehyde 96 of n can produce n formaldehyde molecule, is n formaldehyde equivalent thus.
The aminoplast(ic) resin example is: melamine/formaldehyde resin, urea/formaldehyde resin, trimeric cyanamide/urea/formaldehyde resin, urea/phenol/formaldehyde resins and trimeric cyanamide/urea/phenol/formaldehyde resins.
Have been found that especially to use and comprise wherein F/ (NH
2)
2Ratio is less than or equal to the binding compositions of 1 aminoplast(ic) resin, and the formaldehyde emission of final panel material obviously reduces.Preferably, F/ (NH
2)
2Ratio is less than 0.98; More preferably less than 0.96; Also more preferably less than 0.95; Particularly preferably less than 0.94; Most preferably less than 0.92.F/ (NH
2)
2Ratio is existing formaldehyde equivalent and NH
2The molar ratio of base.
In aminoplast(ic) resin, F/ (NH
2)
2Ratio is preferably more than or equals 0.7, more preferably greater than 0.75, also more preferably greater than 0.78, particularly preferably more than or equal to 0.8, most preferably greater than 0.82.
The invention still further relates to by material and mix, and be cured the method for preparing panel material with binding compositions according to the present invention with cellulose.This being solidificated in the pressing machine finished, produce panel material by under High Temperature High Pressure, in pressing machine, utilizing tackiness agent, this tackiness agent comprises according to binding compositions of the present invention, and this binding compositions comprises according to catalytic cpd of the present invention and aminoplast(ic) resin.Preferably, tackiness agent is gone up substantially or even almost all or all is made up of binding compositions according to the present invention.When producing plywood panel, in binding compositions, add thickening material usually in advance.This thickening material can comprise and anyly is dispersed in easily in the tackiness agent and mainly plays the filling effect of enhancing tackiness agent and guarantee that tackiness agent mainly remains on the material of the lip-deep effect of used glued board.
Preferably, present method is applied in the production of glued board, shaving board, MDF plate (medium-density fiberboard), HDF plate (high density fiberboard), OSB plate (directional structure board) or artificial board of straw (Straw Board).
Usually only before the production of plate, carry out by catalyzer being added to prepare in the resin according to tackiness agent of the present invention.This resin is at room temperature enough stable, can stored for several weeks.
Usually the pH of aminoplast(ic) resin is 8 or higher.If add, so preferably determine the addition of catalytic cpd by the pH of binding compositions according to catalytic cpd of the present invention.Preferably, add, make that the pH after adding is 7.5 or 7.0 or lower according to catalytic cpd of the present invention.Preferably, add after the catalytic cpd, the pH of mixture is between 6.5 and 5.5.In alternative embodiment, the catalytic cpd of interpolation with respect to aminoplast(ic) resin 0.5 and 7wt% between (recording) according to dried catalytic cpd/dried aminoplast(ic) resin.As guiding theory, think that the pH reduction that brings according to binding compositions of the present invention causes gel time to reduce usually, also makes stability in storage reduce.
For the preparation plywood panel, after adding the catalysis acid compound, the pH of adhesive mixture is preferably between 7.0 and 6.5.Perhaps for producing glued board, the catalytic cpd according to the present invention that is added with respect to aminoplast(ic) resin 0.2 and 1wt% between (also recording) according to dried catalytic cpd/dried aminoplast(ic) resin.
Add catalytic cpd after 10 seconds-4 hours, use this tackiness agent to produce panel material; Preferably after 30 seconds-120 minutes.
Can divide antacid compound as catalytic cpd if use, this tackiness agent can be used to produce panel material after the longer time so.This tackiness agent used after 30 seconds-30 hours.
The operable time-dependent of tackiness agent is in many factors, and those skilled in the art can easily determine.This time-dependent is in employed catalytic cpd, temperature and pH etc.
During the preparation panel material, pressing conditions depends on the type of panel material.For example in producing glued board, the pressure that uses is 1-2MPa, is 1-5MPa for shaving board pressure, and preferred 2-4MPa is 2-7MPa for MDF pressure, preferred 3-6MPa.Produce the temperature of panel material, for normally 80-140 ℃ of glued board, for normally 180-230 ℃ of shaving board and OSB, for normally 170-230 ℃ of MDF.For shaving board, MDF and OSB, the press time of use with second every mm thickness of slab represent.For the OSB plate, the press time is 4-12sec/mm normally, preferred 6-10sec/mm.For shaving board, the normally used press time is 4-12sec/mm, preferred 5-10sec/mm.The press time of manufacturing MDF plate is 5-17sec/mm, particularly 6-14sec/mm normally.The press time of making plywood panel usually is 30-70sec/mm, particularly 40-60sec/mm.
In preparation tackiness agent process, in binding compositions, add wax usually, so that final panel material is more water-fast.Usually this kind wax is emulsive wax or solid state wax, and for example produces in petrochemical industry.
The invention still further relates to the panel material that obtains according to the compound of binding compositions of the present invention and cellulose by compression.
According to the present invention, this blank material, the particularly potential amount of the formaldehyde of shaving board material test according to so-called Perforator that (DIN NEN 120) be measured as can be less than 10mg/100g; Preferably, the potential amount of this formaldehyde is less than 8mg/100g; Such advantage is, is 1 grade according to the potential amount of formaldehyde of (wood shavings) of the present invention panel material according to NEN EN 312-1.More preferably, the potential amount of formaldehyde is less than 7mg/100g, particularly preferably less than 6.5mg/100g or even less than 6mg/100g.Most preferably, according to the potential amount of the formaldehyde of panel material of the present invention less than 5mg/100g.
Panel material according to the present invention has excellent in mechanical properties: according to the internal break intensity of panel material of the present invention, be also referred to as internal bond strength or IB usually usually, passed through the V100 test of NEN-EN1087-1.
The production of glued board has special status in framework of the present invention, because be used for the F/ (NH of the aminoplast(ic) resin in the binding compositions of known Manufacturing Technology of Plywood
2)
2Molar ratio is usually than the panel material that is used to prepare other type, and for example shaving board, MDF plate, HDF plate or OSB plate wants high.And the formaldehyde emission of glued board usually depends on different standards.Therefore, the invention still further relates to the method for producing the glued board material, this method comprises uses binding compositions and with its curing, wherein this binding compositions comprises aminoplast(ic) resin and the catalytic cpd that contains formaldehyde, to be pKa maybe can discharge pKa less than 6 acid less than 6 acid to this catalytic cpd, contains the F/ (NH of the aminoplast(ic) resin of formaldehyde
2)
2Ratio is less than or equal to 1.2, preferably is less than or equal to 1.1.
The binding compositions that is used to prepare glued board according to the present invention can comprise preferred embodiment described above.Especially, the maximum 11wt% of the ammonium salt that catalytic cpd comprised in the preferred binding compositions; More preferably, as pointing out in the preferred embodiment of front that the volume that is comprised is lower.
The invention still further relates to the glued board material that obtains by the method according to this invention.Advantage according to glued board material of the present invention is that the quantity discharged of formaldehyde is lower than the glued board material of producing in a known way, in this glued board material of producing in a known way, and the F/ (NH in the aminoplast(ic) resin of binding compositions
2)
2Higher, and/or do not use pKa less than 6 acid as catalyzer.Simultaneously, glued board material according to the present invention also has excellent mechanical property, for example according to the tensile strength of the NEN 314-1 7kg/cm at least that can meet the requirements
2Strict standard.
Further explain the present invention with reference to following examples, but be not limited to this.
Embodiment 1
The resin of shaving board is produced in preparation
50% formalin of 26.6 weight parts is added in the reactor that is preheating to 50 ℃.With 2 molar sodium hydroxides the pH of formaldehyde solution is transferred to 8.0-8.5.After this urea that adds 13.1 weight parts, and the temperature of mixture is raised to 99 ℃.One reaches the temperature of hope, promptly with 2 mole of acetic acid or formic acid pH is dropped to 4.5-5.0.Keep this temperature and pH, be increased to the 200-300 centipoise up to viscosity.After this, pH is increased to 9.0-9.5, and the temperature of mixture is dropped to 90 ℃ with 2 molar sodium hydroxides.Add 50% formaldehyde solution of the trimeric cyanamide and 17.6 weight parts of 26.5 weight parts.This reaction mixture remained on this temperature and pH following 1 hour, added the urea of 16.3 weight parts then.Then, the temperature of mixture is dropped to 50 ℃, and discharge tackiness agent.
F/ (the NH of the muf resin that obtains
2)
2Be 0.9.
Embodiment 2-4 and Comparative experiment A-B
Different catalyzer is added in the muf resin that makes according to the step described in the embodiment 1, reach 6 up to pH, and measure the Abes tensile strength after gel time, the boiling, the internal bond strength of the shaving board after the boiling and the potential amount of formaldehyde of shaving board.Being prepared as follows of shaving board: a certain amount of catalyzer is added in the resin, makes gel time be about 60 seconds at 100 ℃.To thoroughly mix with a certain amount of fragment (dragon spruce) through catalytic resin with mixing machine, make that doing wood goes up existence 10% dried resin.The water-content of used timber is 2.2%.After the mixing, resinification fragment is transferred in the molding pressure machine, in pressing machine with its uniform distribution and compacting gently, to form the cake of forming by fragment and resin.Remove after the mould side, it is on the substrate in 190 ℃ the mould that this cake is placed on temperature, and it further is compacted to specific thicknesses, and the density that obtains is 650kg/m
3For the thickness of slab of 16mm, use the neutralizing factor of 11sec/mm.After the compacting,, and be sawn into and be used for determining potential amount of formaldehyde and the required size of internal break intensity the cooling of this plate.
The numerical value that records is listed in the table below.
| Embodiment or experiment | MUF | Catalyzer | Gel time 2) | Abes 4)(V100) tensile strength | IB (V100) 5) | The potential amount of F 6) (Perforator) |
| F/(NH 2) 2 1) | [second] | [N] | N/mm 2 | [mg/100g] |
| A | 1.1 | Ammonium sulfate | 60 3) | - | 1.1 | 11 |
| B | 1.1 | Formic acid | 52 | - | 1.2 | 18 |
| 2 | 0.9 | Acetate | 69 | 121 | - | - |
| 3 | 0.9 | Formic acid | 58 | 116 | 1.0 | 5 |
| 4 | 0.9 | Oxalic acid | 56 | 91 | - | - |
1) as among the embodiment 1, obtain 1.1 ratio by the preparation resin, difference is to regulate the addition of formaldehyde so that the F/ (NH that obtains wishing
2)
2Molar ratio.
2) for measuring gel time, 5 grams in water are transferred in the test tube through catalytic resin.In boiling water, stir the material in the test tube, up to forming gel.The association time is gel time.
3) in 5 gram resins, add 3% ammonium sulfate (doing/do), after this, according to 2) the measurement gel time.
4) for measuring tensile strength, 2mg is placed between two beech thin plates (0.75 * 20 * 117mm) through catalytic resin, 140 ℃ solidify 60 seconds (ABES methods (Automated Bonding Evaluation) down, after this, measure tensile strength after the boiling according to the program of describing among the US 5176028 by professor's Ph..E.Humphrey exploitation.
5) after two hours, measuring internal bond strength according to NEN-EN 1087-1 (V100 test) boiling according to EN 319.For the shaving board for preparing herein, the specification that is used in the bearing plate material under the wet condition of indication equals 0.14N/mm at least among the EN 312-5
2
6) measure the potential amount of formaldehyde according to NEN-EN 120 (Perforator test).
Comparative experiment A adopts 1.1 standard F/ (NH
2)
2, ammonium sulfate as Catalyst Production with reference to material; The potential amount of formaldehyde is 11mg/100g, makes us undesirably high.
Contrast experiment B shows, in shaving board, and 1.1 normal F/ (NH
2)
2Ratio and formic acid cause the potential amount of formaldehyde than common taller of this resin system as the combination of catalyzer.
Embodiment 2 shows, when the pKa of acid value was between 4 and 5, gel time was increased to the outline high value more common than this type of resin, but the accessible mechanical properties of the finished product that use this binding compositions to produce can be very good, shown in the ABES tensile strength, although F/ is (NH
2)
2Ratio is less than 1.
Embodiment 3 show monobasic formic acid with less than 1 F/ (NH
2)
2The combination of ratio causes the tensile strength height of panel material, and IB is good and the potential amount of formaldehyde is very low.Consider contrast experiment B, the potential amount of formaldehyde that embodiment 3 is low is wondrous especially.
See that from embodiment 4 compare with embodiment 3, monobasic formic acid causes higher tensile strength than binary oxalic acid.
Embodiment 5 and contrast experiment
The resin of glued board is produced in preparation
37.6% formalin of 593 weight parts is added in the glass reactor.With 2 moles of hydrogen oxide compounds (sodium) pH of formaldehyde solution is transferred to 7.5-8.1, after this is metered into the urea of 194 weight parts and the trimeric cyanamide of 41 weight parts.
Temperature is raised to 90 ℃.The temperature that reaches hope dropped to 4.8-5.2 with 2 moles of formic acid with pH after 5 minutes.Room temperature is issued to after the cloud point, with 2 moles of hydrogen oxide compounds (sodium) pH is increased to 8.5, and the temperature of reaction mixture is dropped to 88 ℃.Then, 37.6% formaldehyde solution that adds the trimeric cyanamide and 396 weight parts of 380 weight parts.Keep reaction mixture under this temperature and pH 1 hour, after this, it is cooled to 78 ℃.Add the urea of 152 weight parts then, and to be concentrated to viscosity be 50 centipoises.Subsequently, this mixture is cooled to 30 ℃.
F/ (the NH of the muf resin that obtains
2)
2Be 1.1.
Preparation glued board (5 layers)
Catalyzer is added in the aforesaid resin, up to reach 160 seconds of expectation at 100 ℃ of following gel times.Add flour then, to reach the viscosity of about 2000cPs.This adhesive mixture is used to prepare 5 layers of glued board.Use water-content to be adjusted to 10% red lauan thin plate at last.For every block of plate, used thickness is 2 deck panels of 3 layers of core thin plate and the 1.8mm of 3.7mm.With adhesive mixture that these thin plates are intersected with each other stacked, this adhesive mixture is fully distributed in the inter-engagement place, and consumption is 200g/m
2
Use tackiness agent and stacked after, under the pressure of 10bar with this compoboard cold reduction 30 minutes.After the heated press, under 120 ℃ temperature, compress/solidify 12 minutes.From pressing machine, take out plate and cooling then.
After plank is produced, measure formaldehyde emission and IB according to Japanese Agricultural Standard JAS (being used for structural plywood JAS 987 2000) as quickly as possible.
| Embodiment or experiment | MUF | Catalyzer | Gel time 2) (100℃) | Abes 4) (V100) tensile strength | IB after the circulation boiling test 4) (JAS) | The F quantity discharged 5)(JAS) moisture eliminator |
| F/(NH 2) 2 1) | [second] | [N] | [kg/cm 2] | [mg/100ml] | ||
| C | 1.2 | NH 4Cl | 160 6) | 137 | 8.8 | 0.4 |
| 5 | 1.1 | HCOOH | 160 | 124 | 7.7 | 0.3 |
1) as preparing resin among the embodiment 5, obtaining ratio is 1.2, increases the feasible F/ (NH that reaches hope of add-on of formaldehyde
2)
2Molar ratio.
2) for measuring gel time, 5 grams in water are transferred in the test tube through catalytic resin.In boiling water, stir material in the test tube, up to forming gel.The association time is gel time.
3) for measuring the ABES tensile strength, 2mg is placed between two beech thin plates (0.75 * 20 * 117mm) through catalytic resin, 140 ℃ solidify 60 seconds (ABES methods (Automated Bonding Evaluation) down, after this, measure tensile strength after the boiling according to the program of describing among the US 5176028 by professor's Ph..E.Humphrey exploitation.
4) after the circulation boiling test below, measure the internal bond strength (tensile strength IB) of 5 layers of glued board specimen
1. in boiling water, soaked 4 hours
In ventilated drying oven 60 ± 3 ℃ dry 16-20 hour down
3. in boiling water, soaked 4 hours again
4. in 20 ℃ water, cool off.
After the step 3, intersect in 4 hours and measure IB, as the Shear Tensile Strength under the wet condition.
According to JAS (JAS 987 2000 that is used for structural plywood), the I type specification value minimum of moisture-proof plywood panel is 7.0kg/cm
2
5) measure formaldehyde emission according to the moisture eliminator method described in the JAS (JAS 987 2000 that is used for structural plywood).Here the test panel with 10 150 * 50mm was placed on 300ml moisture eliminator waterborne interior 24 hours excessively.After this measure the formaldehyde of aqueous phase.
6) in order to obtain gel time, in the contrast experiment, in resin, add the formic acid solution of solid-state ammonium chloride or 50%.Under one situation of back, be about 6.6 through the pH of acidifying resin.
Embodiment 5 shows, according to formaldehyde (F) quantity discharged of glued board of the present invention, i.e. 0.3mg/100ml is significantly less than the F quantity discharged of the known glued board as shown in the contrast experiment, still meet the JAS standard according to the IB after the boiling in the mechanical property, particularly water of glued board of the present invention simultaneously.
Claims (17)
1. a binding compositions comprises the aminoplast(ic) resin and the catalytic cpd that contain formaldehyde, it is characterized in that the described F/ (NH that contains the aminoplast(ic) resin of formaldehyde
2)
2Ratio is less than or equal to 1, and described catalytic cpd is pKa less than 6 acid or can discharges pKa less than 6 acid that prerequisite is that the ammonium salt that described catalytic cpd comprises mostly is 11wt% most.
2. binding compositions as claimed in claim 1 is characterized in that described catalytic cpd is pKa less than 5 acid or can discharges pKa less than 5 acid.
3. binding compositions as claimed in claim 1 is characterized in that described catalytic cpd is monoprotic acid or methyl ester, one or more pKa less than 4 monacid melamine salt or urea salt or by methylolation urea or the melamine compound of one or more pKa less than 4 monoprotic acid esterification.
4. binding compositions as claimed in claim 3 is characterized in that described catalytic cpd is the melamine salt of formic acid or methyl ester, formic acid or urea salt or by the methylolation urea or the melamine compound of formic acid esterification.
5. binding compositions as claimed in claim 4 is characterized in that described catalytic cpd is a formic acid.
6. binding compositions as claimed in claim 1 is characterized in that described catalytic cpd is an acetate.
7. as each described binding compositions among the claim 1-6, it is characterized in that the pH of described binding compositions is less than or equal to 7.
8. binding compositions as claimed in claim 7, the pH that it is characterized in that described binding compositions is 6.5-5.5.
9. one kind by with the compound of cellulose and the method for mixing and its curing is prepared panel material according to each described binding compositions among the claim 1-8.
10. the panel material that obtains according to claim 9.
11. panel material as claimed in claim 10, the potential amount of the formaldehyde of described panel material is less than 8mg/100g according to DINNEN 120.
12. panel material as claimed in claim 11, the potential amount of the formaldehyde of described panel material is less than 6.5mg/100g according to DINNEN 120.
13. as each described panel material among the claim 10-12, the internal bond strength of wherein said panel material meets the specification of the bearing plate material that uses that being used for of stipulating among the EN 312-5 measure according to NEN-EN 1087-1 (V100) under wet condition.
14. method for preparing the glued board material, described method comprises the application binding compositions, and with described composition curing, it is characterized in that using according to each described binding compositions among the claim 1-8, wherein contain the F/ (NH of the aminoplast(ic) resin of formaldehyde
2)
2Ratio is less than 1.2.
15. the glued board material that obtains according to the method for claim 14.
16. glued board material as claimed in claim 15, the tensile strength of described glued board material is at least 7kg/cm according to JAS
2
17. as claim 15 or 16 described glued board materials, the formaldehyde emission of described glued board material is no more than 0.3mg/100ml water according to JAS.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1024010 | 2003-07-28 | ||
| NL1024010 | 2003-07-28 | ||
| NL1024036 | 2003-08-04 | ||
| NL1024319 | 2003-09-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1826396A true CN1826396A (en) | 2006-08-30 |
| CN100580047C CN100580047C (en) | 2010-01-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200480021212A Expired - Fee Related CN100580047C (en) | 2003-07-28 | 2004-07-27 | Adhesive composition comprising formaldehyde-containing aminoplast resin and catalysing compound |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688102B (en) * | 2007-07-05 | 2013-12-11 | 阿克佐诺贝尔国际涂料股份有限公司 | Hardener composition, adhesive system and method of gluing |
| CN109462985A (en) * | 2016-06-30 | 2019-03-12 | 胡坦斯·阿尔伯图斯化学厂有限公司 | The aqueous alkaline adhesive ingredient hardened by means of carbon dioxide gas and its application, manufacture the corresponding molding material mixture of casting and forming body, corresponding casting and forming body and the method for manufacturing casting and forming body |
| CN109642138A (en) * | 2016-07-27 | 2019-04-16 | 催化系统C.E.D.有限责任公司 | The hardening of bonding system |
-
2004
- 2004-07-27 CN CN200480021212A patent/CN100580047C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688102B (en) * | 2007-07-05 | 2013-12-11 | 阿克佐诺贝尔国际涂料股份有限公司 | Hardener composition, adhesive system and method of gluing |
| CN109462985A (en) * | 2016-06-30 | 2019-03-12 | 胡坦斯·阿尔伯图斯化学厂有限公司 | The aqueous alkaline adhesive ingredient hardened by means of carbon dioxide gas and its application, manufacture the corresponding molding material mixture of casting and forming body, corresponding casting and forming body and the method for manufacturing casting and forming body |
| CN109642138A (en) * | 2016-07-27 | 2019-04-16 | 催化系统C.E.D.有限责任公司 | The hardening of bonding system |
| CN109642138B (en) * | 2016-07-27 | 2021-10-15 | 催化系统C.E.D.有限责任公司 | Hardening of adhesive systems |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100580047C (en) | 2010-01-13 |
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