CN101921574B - Adhesive and veneer prepared by same - Google Patents
Adhesive and veneer prepared by same Download PDFInfo
- Publication number
- CN101921574B CN101921574B CN200910086669A CN200910086669A CN101921574B CN 101921574 B CN101921574 B CN 101921574B CN 200910086669 A CN200910086669 A CN 200910086669A CN 200910086669 A CN200910086669 A CN 200910086669A CN 101921574 B CN101921574 B CN 101921574B
- Authority
- CN
- China
- Prior art keywords
- weight
- sodium hydroxide
- timber
- tackiness agent
- leachable
- 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.)
- Expired - Fee Related
Links
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention provides an adhesive. The adhesive comprises a polyethyleneimine aqueous solution and a sodium hydroxide extract of brown rot wood, and the polyethyleneimine aqueous solution and the extract are separately preserved. The invention further provides veneer comprising at least two layers of superposed wood single plates and an adhesive coating arranged between adjacent two layers of wood single plates, wherein the adhesive coating is a product formed by solidifying the adhesive provided in the invention. After the adhesive is solidified, the adhesive has better water resistance than the prior art, and the veneer prepared by the adhesive has the same dry bonding strength as the prior art. In addition, the invention turns waste into wealth by fully utilizing waste brown rot wood as raw materials.
Description
Technical field
The present invention relates to a kind of tackiness agent, also relate to a kind of wood veneer, this wood veneer adopts tackiness agent of the present invention to prepare.
Background technology
In the production of Wood composite material; Using maximum tackiness agents is with urea aldehyde, phenolic aldehyde and the melamine resin of formaldehyde as base-material; Thereby ubiquity formaldehyde discharges problem in production that synthesizing of tackiness agent reaches sheet material and application process; Because formaldehyde is harmful to people's health, therefore will pollute people's work environment and inhabitation place, the infringement people's is healthy.In addition, also brought all labile factors for tackiness agent market as the limited storage capacity of the petroleum resources of the raw material of above-mentioned resin and the fluctuation of petroleum chemicals price.This just forces the adhesives industry field to study and how to utilize renewable biomass and develop new type bonding agent functional, toxicological harmless.
Xylogen is present in the lignum, is one of composition that constitutes plant cell wall, in plant tissue, has the effect that strengthens cell walls and binder fibre.At occurring in nature, the reserves of xylogen are only second to Mierocrystalline cellulose, and all regenerate with 50,000,000,000 tons speed every year.Except using maximum xylogen that paper industry produced in the past; It is brown rot timber by the brown rot fungus rotten timber that China also exists a large amount of; The brown rot timber of particularly cultivating the Poria cocos Chinese medicinal materials and producing; Its staple is the xylogen that part-structure changes, and the reactive behavior of this xylogen is big than other industrial lignin.And usually these brown rot timber are utilized, and the peasant in the Poria cocos producing region remaining dote of will gathering mostly behind the Poria cocos abandons or is used as firewood and use, this is beyond doubt to the significant wastage of natural resources.
" Formaldehyde-Free Wood Adhesives from Decayed Wood " (Kaichang Li, Xinglian Geng, Macromol.Rapid Commun.2005; 26; Disclose a kind of formaldehyde-free wood tackiness agent with the dote preparation 529-532), this preparation method is that brown rot timber is crushed into powder (0.5 order); The powder (40g) of this pulverizing is mixed with the NaOH solution (600ml) of 1 weight %, and under agitation in 70 ℃ water-bath, placed 2 hours.With the suspension filtered that obtains, and with NaOH solution (400ml) the washing residuum of 1 weight % of heat.Filtrate is concentrated into the raw material that 16.5 weight % also are used as wood adhesive through Rotary Evaporators.At room temperature along with stirring this liquid concentrator with Peng Qinghuana (NaBH
4) (based on the dry weight of this liquid concentrator, NaBH
4Consumption be 0.1-4 weight %) handle preset time.Liquid concentrator after at room temperature will handling mixed 1 hour with 5: 1 weight ratio with polymine as linking agent, obtained tackiness agent.Have dry glue intensity preferably after using this tackiness agent gummed base material, but the water resistance after this tackiness agent curing is lower.
Summary of the invention
The objective of the invention is to overcome the lower defective of water resistance after above-mentioned tackiness agent of the prior art solidifies; A kind of back dry glue intensity and all higher tackiness agent of water resistance of solidifying is provided, a kind of wood veneer that uses tackiness agent gummed of the present invention and process also is provided.
The invention provides a kind of tackiness agent, said tackiness agent contains the sodium hydroxide leachable of polyethyleneimine: amine aqueous solution and brown rot timber, and said polyethyleneimine: amine aqueous solution and said leachable independently exist.
The present invention also provides a kind of wood veneer, and this wood veneer comprises stacked two-layer at least wood single-plate and the adhesive coating between the adjacent two layers wood single-plate, the product of said adhesive coating for being solidified to form by tackiness agent provided by the invention.
Adopt tackiness agent of the present invention to solidify and can obtain than the better water tolerance of prior art, the wood veneer that uses tackiness agent of the present invention to process simultaneously has the dry glue intensity suitable with prior art.Under preferable case, the water tolerance after the tackiness agent that the sodium hydroxide leachable of brown rot timber is further carried out obtaining behind acidylate or the epoxidation solidifies further improves, and the dry glue intensity of the wood veneer of being processed by this tackiness agent further improves.In addition, the present invention can make full use of depleted brown rot timber as raw material, realizes turning waste into wealth.
Embodiment
The term that this paper mentions " brown rot timber " is meant the timber of brown rot, is formed by the Mierocrystalline cellulose and the semicellulose of brown rot fungus destruction timber, and outward appearance is sorrel or brown, and matter is crisp, and there is crisscross block crack the centre.In the brown rot later stage, the timber of being injured is easy to twist with the fingers powdered, is called Powdered rottenly, or cries destructive rotten.
Under existing situation, brown rot timber generally includes in the forest by brown rot fungus destructive timber, and cultivate on the timber and obtain various brown rot fungus after remaining timber, for example on timber, cultivate the Poria cocos and the remaining dote in back of gathering.These timber are discarded perhaps as the firewood use by people usually.Because the xylogen in the brown rot timber mainly is the xylogen that part-structure changes, the reactive behavior of this xylogen is big than other industrial lignin.Therefore, this has caused the great wasting of resources undoubtedly.The present invention is through utilizing brown rot timber and prepare tackiness agent and prior art is further improved, can the better tackiness agent of obtained performance, and simplified the preparation method, and save employed Peng Qinghuana reagent, reduced cost thus.
Tackiness agent provided by the invention contains the sodium hydroxide leachable of polyethyleneimine: amine aqueous solution and brown rot timber, and said polyethyleneimine: amine aqueous solution and said leachable independently exist.
According to tackiness agent provided by the invention; Because said polyethyleneimine: amine aqueous solution and said leachable mix the afterreaction rapid speed, viscosity increases gradually, mobile variation; Cause gluing irregular; Therefore poor permeability need make them independently exist, just just mixing immediately or apply the purpose that pressing again reaches gummed respectively in use.
According to tackiness agent provided by the invention, under preferable case, the weight-average molecular weight of said polymine is 10000-100000, and the concentration of said polyethyleneimine: amine aqueous solution is 20-35 weight %, and the solid content of said leachable is 15-35 weight %.
Solid content as herein described is still continued to use implication as known in the art, is called non-volatile content again, is meant the per-cent that surplus materials quality after the sample drying drying is accounted for the sample total mass.
According to tackiness agent provided by the invention, under preferable case, the weight ratio of the polymine in the dry weight of said leachable and the polyethyleneimine: amine aqueous solution is 3-20: 1.Employing contains with the said polyethyleneimine: amine aqueous solution of this weight ratio and the tackiness agent of said leachable, compared with prior art, can make said tackiness agent have the dry glue intensity suitable with prior art, and water tolerance also improves to some extent.
According to tackiness agent provided by the invention, the preparation method of said leachable can adopt the method for well known to a person skilled in the art, for example this method comprises, aqueous sodium hydroxide solution is contacted with brown rot timber, filters then, obtains filtrate.The aperture of filtration unit filtering surface is the 30-50 micron, for example can adopt the middling speed qualitative filter paper.Under the preferable case, filter cake is washed with aqueous sodium hydroxide solution, washings that obtains and said filtrate are combined.Generally, the solid content of resulting filtrate is lower than above-mentioned preferable range 25-35 weight %, therefore, preferably carries out evaporation concentration and obtains this range of solid content.
Saidly aqueous sodium hydroxide solution is comprised with the condition that brown rot timber contacts the temperature of said contact is 20-100 ℃, the time of said contact is 0.5-5 hour, and the weight ratio of the sodium hydroxide in said brown rot timber and the said aqueous sodium hydroxide solution is 1-15: 1.The concentration of preferred said aqueous sodium hydroxide solution is 0.1-10 weight %, 0.5-2 weight % more preferably.
According to tackiness agent provided by the invention, under preferable case, the preparation method of said leachable also comprises; With resulting filtrate acetylize, said acetylizad method comprises, under the acetylization reaction condition; With contacting 10 minutes with excessive acetylation reagent-6 hours after the said filtrate drying; Remove unreacted acetylation reagent then, then the acetylate that obtains is dissolved in the aqueous sodium hydroxide solution, obtaining solid content is the acetylate solution of 15-35; Said acetylation reagent is one or more in Acetyl Chloride 98Min., acetyl bromide, ketene, thioacetic acid, diacetyl oxide-pyridine, diacetyl oxide-sulfuric acid and the acetic anhydride, and preferred said acetylation reagent is an acetic anhydride.
Said acetylization reaction condition comprises; The acetylize temperature is 80-140 ℃; The dry weight of said filtrate and the weight ratio of acetylation reagent are 1: 5-30, and the weight ratio of the sodium hydroxide in said acetylate and the aqueous sodium hydroxide solution is 5-150: 1, be preferably 5-60: 1; The concentration of preferred said aqueous sodium hydroxide solution is 0.1-10 weight %, more preferably 0.5-2 weight %.
According to tackiness agent provided by the invention; The reactive behavior of resultant acetylate increases after the acetylize to carrying out after the said filtrate drying; Thereby can improve the dry glue intensity of tackiness agent of the present invention, and further improve the water tolerance of tackiness agent of the present invention, further reduce the consumption of polymine with respect to said leachable.
The by product of above-mentioned dry thing and acetic anhydride reaction is an acetate, if contain acetate and excessive acetic anhydride, can impel the wood degradation that is glued together, thereby influence the intensity of timber itself in the tackiness agent of the present invention, therefore need remove by-product acetic acid and acetic anhydride.The method of removing acetate and acetic anhydride can adopt and well known to a person skilled in the art the whole bag of tricks, and the method that for example adopts heating to vacuumize or feed hot gas flow is carried out.
According to tackiness agent provided by the invention, under preferable case, the preparation method of said leachable also comprises; With resulting filtrate epoxidation, said process for epoxidation comprises, under epoxidation reaction condition; With contacting 10 minutes with excessive epoxidation reagent-6 hours after the said filtrate drying; Remove unreacted epoxidation reagent then, then the epoxide that obtains is dissolved in the aqueous sodium hydroxide solution, obtaining solid content is the epoxide solution of 15-35; Said epoxidation reagent is an epoxy chloropropane.Said method of removing unreacted epoxide can adopt the normally used method of those skilled in the art, for example the method through filtering, washing.
Said epoxidation reaction condition comprises; The epoxidation temperature is 20-90 ℃; The dry weight of said filtrate and the weight ratio of epoxidation reagent are 1: 2-10, and the weight ratio of the sodium hydroxide in said epoxide and the aqueous sodium hydroxide solution is 5-150: 1, be preferably 5-60: 1; The concentration of preferred said aqueous sodium hydroxide solution is 0.1-10 weight %, more preferably 0.5-2 weight %.
According to tackiness agent provided by the invention; To carrying out resulting epoxide behind the epoxidation after the said filtrate drying; Its reactive behavior increases; Thereby can improve the dry glue intensity of tackiness agent of the present invention, and further improve the water tolerance of tackiness agent of the present invention, further reduce the consumption of polymine with respect to said leachable.
Wood veneer provided by the invention comprises stacked two-layer at least wood single-plate and the adhesive coating between the adjacent two layers wood single-plate, the product of said adhesive coating for being solidified to form by tackiness agent of the present invention.
According to wood veneer provided by the invention, the number of plies of said wood single-plate is the number of plies known in those skilled in the art, is generally the odd number number of plies, for example is three layers to 13 layers, and common have three-ply-wood, five-ply board, nine plywood and ten three-ply-wood.
According to wood veneer provided by the invention, under the preferable case, the thickness of said wood single-plate is the 0.5-10 millimeter, and the preparation method of said wood veneer can carry out through following method, and wherein a kind of method is:
With the sodium hydroxide leachable of brown rot timber and the cemented surface that is coated in each wood single-plate after the polyethyleneimine: amine aqueous solution mixes immediately; Two-sided resin added be 300-450 gram/square metre; With the stacked assembly of all wood single-plates and displayed 30-100 minute; Carry out hot pressing compacting then, hot pressing pressure is that 0.5-2 MPa, hot pressing temperature are that hot pressing press time of 120-180 ℃, every millimeter wood single-plate thickness is 0.8-2 minute.
Another kind method is:
The cemented surface that the sodium hydroxide leachable and the polyethyleneimine: amine aqueous solution of brown rot timber is coated in each wood single-plate respectively; Two-sided resin added be 300-450 gram/square metre; With the stacked assembly of all wood single-plates and displayed 30-100 minute; Carry out hot pressing compacting then, hot pressing pressure is that 0.5-2 MPa, hot pressing temperature are that hot pressing press time of 120-180 ℃, every millimeter wood single-plate thickness is 0.8-2 minute.
The said cemented surface that the sodium hydroxide leachable and the polyethyleneimine: amine aqueous solution of brown rot timber are coated in each wood single-plate respectively; Can be for said leachable and the layering of polyethyleneimine: amine aqueous solution be applied; For example three layers of plywood glue is fashionable can be following several kinds of modes; The downside cemented surface of veneer applies said leachable or polyethyleneimine: amine aqueous solution on the upper strata; At the upside cemented surface coating polyethylene imines aqueous solution or the leachable of middle veneer, same also is coating like this at the downside cemented surface of middle veneer and the upside cemented surface of lower floor's veneer; Perhaps the downside cemented surface of veneer successively applies said leachable and polyethyleneimine: amine aqueous solution on the upper strata; At the upside cemented surface priority coating polyethylene imines aqueous solution and the said leachable of middle veneer, same also is coating like this at the downside cemented surface of middle veneer and the upside cemented surface of lower floor's veneer; In a word, be the cemented surface that preferably said leachable and the layering of polyethyleneimine: amine aqueous solution also alternately is coated in each wood single-plate.At last with upper strata, centre, the stacked assembly of lower floor's veneer, and compacting, wood veneer obtained.
As known in those skilled in the art, under preferable case, the fiber direction of adjacent veneer is orthogonal in the wood single-plate of above-mentioned stacked assembly.
Adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
1, the preparation of tackiness agent
Depleted Pinus massoniana Lamb brown rot timber after brown rot timber is selected for use and under 25-30 ℃, the condition of relative air humidity 60-80%, cultivated about 10 months of the Poria cocos and the Poria cocos of gathering.
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 10000), being mixed with concentration is 20 weight %.
The sodium hydroxide leachable of preparation brown rot timber:
It is that 70 ℃, weight are stirring reaction 2 hours in the 1 weight %NaOH aqueous solution of 19600 grams that the powder (0.5 sieve mesh) of the above-mentioned brown rot timber of 200 grams is immersed in temperature; (filter paper is Hangzhou Paper Co., Ltd of Xinhua with the suspension filtered that obtains; Two circle boards, middling speed qualitative filter paper 102), and with filter cake with the NaOH aqueous solution 400 gram washings 50 ℃, 1 weight %; Merge all filtrates; Obtain the sodium hydroxide leachable of brown rot timber, concentrate this leachable through rotary evaporation then, obtain the liquid concentrator that solid content is 25 weight %.
2, the preparation of wood veneer
The liquid concentrator that polyethyleneimine: amine aqueous solution and the above-mentioned solid content that makes that with above-mentioned concentration is 20 weight % is 25 weight % with the weight of Vilaterm ethamine and the ratio of the dry weight of liquid concentrator be mix at 1: 3 after; Be coated in the cemented surface of 3 layers of board using poplar board (270 millimeters long * 270 mm wides * 1.6 mm thick) rapidly; The total two-sided resin added of polyethyleneimine: amine aqueous solution and liquid concentrator be 300 the gram/square metre; With 3 layers of stacked assembly of wood single-plate and displayed 30 minutes; Carry out hot pressing compacting then, hot pressing pressure is that 0.5 MPa, hot pressing temperature are that hot pressing press time of 180 ℃, every millimeter wood single-plate thickness is 2.5 minutes.
Comparative Examples 1
1, the preparation of tackiness agent
Brown rot timber is selected for use under 25-30 ℃, the condition of relative air humidity 60-80% and is cultivated about 10 months of Poria cocos and gather back depleted Pinus massoniana Lamb brown rot timber;
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 10000), being mixed with concentration is 20 weight %.
According to prior art " Formaldehyde-Free Wood Adhesives from Decayed Wood " (Kaichang Li, Xinglian Geng, Macromol.Rapid Commun.2005,26, the method for describing in 529-532) prepares:
With powder (0.5 sieve mesh) and the weight of the above-mentioned brown rot timber of 200 grams is that the NaOH solution of 1 weight % of 20000 grams mixes, and under agitation in 70 ℃ water-bath, reacts 2 hours.With the suspension filtered that obtains, and, merge filtrate with the NaOH solution washing residuum of 70 ℃ 400 grams, 1 weight %.Filtrate is concentrated into 16.5 weight % through rotary evaporation, at room temperature along with stirring with this liquid concentrator and Peng Qinghuana (NaBH
4) (based on the dry weight of this liquid concentrator, NaBH
4Consumption be 2 weight %) mix, carried out reduction reaction 18 hours, obtain reduzate.
Be that the polyethyleneimine: amine aqueous solution of 20 weight % mixed 1 hour with 1: 3 weight ratio with resulting reduzate at room temperature, obtain tackiness agent above-mentioned concentration.
2, the preparation of wood veneer
The above-mentioned tackiness agent that obtains is coated in the cemented surface of 3 layers of board using poplar board (270 millimeters long * 270 mm wides * 1.6 mm thick); Two-sided resin added be 300 the gram/square metre; With 3 layers of stacked assembly of board using poplar board and displayed 30 minutes; Carry out hot pressing compacting then, hot pressing pressure is that 0.5 MPa, hot pressing temperature are that 180 ℃, hot pressing press time are 1.5 minutes.
Embodiment 2
1, the preparation of tackiness agent
Brown rot timber is selected the poplar brown rot material after continuous rotten transverse hole fungus destruction was removed mycelia and foreign material after 5 months that receives in prepared in laboratory according to GB/T 13942.1-92 for use;
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 100000), being mixed with concentration is 35 weight %.
The sodium hydroxide leachable of preparation brown rot timber:
It is that 100 ℃, weight are stirring reaction 0.5 hour in the 1 weight %NaOH aqueous solution of 1600 grams that the powder (0.5 sieve mesh) of the above-mentioned brown rot timber of 300 grams is immersed in temperature; (filter paper is Hangzhou Paper Co., Ltd of Xinhua with the suspension filtered that obtains; Two circle boards, middling speed qualitative filter paper 102), and with filter cake with the NaOH aqueous solution 400 gram washings 30 ℃, 1 weight %; Merge all filtrates; Obtain the sodium hydroxide leachable of brown rot timber, concentrate this leachable through rotary evaporation then, obtain the liquid concentrator that solid content is 35 weight %.
2, the preparation of wood veneer
Get three layers of board using poplar board, be of a size of 270 millimeters long * 270 mm wides * 1.6 mm thick.
On the downside cemented surface of the downside cemented surface of upper strata board using poplar board, middle board using poplar board, respectively applying above-mentioned concentration is the polyethyleneimine: amine aqueous solution of 35 weight %; The liquid concentrator that on the upside cemented surface of middle board using poplar board upside cemented surface and lower floor's board using poplar board, respectively to apply the above-mentioned solid content that makes be 35 weight %; The weight ratio of polymine and liquid concentrator dry weight is 1: 15; Two-sided resin added be 350 the gram/square metre; With upper strata, centre and the stacked assembly of lower floor's board using poplar board and displayed 100 minutes, carry out the hot pressing compacting then then, hot pressing pressure is that 2 MPas, hot pressing temperature are that 120 ℃, hot pressing press time are 2.5 minutes.
Embodiment 3
1, the preparation of tackiness agent
It is that 25-30 ℃, relative air humidity are the Pinus massoniana Lamb brown rot timber of cultivating under the condition of 60-80% after 7 week of Poria cocos fungi, top layer Poria cocos mycelia and foreign material were removed in the back that brown rot timber is selected for use in temperature;
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 50000), being mixed with concentration is 30 weight %.
The sodium hydroxide leachable of preparation brown rot timber:
It is that 20 ℃, weight are stirring reaction 5 hours in the 1 weight %NaOH aqueous solution of 3600 grams that the powder (0.5 sieve mesh) of the above-mentioned brown rot timber of 200 grams is immersed in temperature; (filter paper is Hangzhou Paper Co., Ltd of Xinhua with the suspension filtered that obtains; Two circle boards, middling speed qualitative filter paper 102), and with filter cake with the NaOH aqueous solution 400 gram washings 40 ℃, 1 weight %; Merge all filtrates; Obtain the sodium hydroxide leachable of brown rot timber, concentrate this leachable through rotary evaporation then, obtain the liquid concentrator that solid content is 15 weight %.
2, the preparation of wood veneer
Get three layers of board using poplar board, be of a size of 270 millimeters long * 270 mm wides * 1.6 mm thick.
Upside cemented surface at lower floor's board using poplar board applies the polyethyleneimine: amine aqueous solution that above-mentioned concentration is 30 weight %; The liquid concentrator that then the above-mentioned solid content that makes of coating is 15 weight % on this polymine aqueous coating; Upside cemented surface at middle board using poplar board applies the polyethyleneimine: amine aqueous solution that above-mentioned concentration is 30 weight %; The liquid concentrator that then the above-mentioned solid content that makes of coating is 15 weight % on this polymine aqueous coating; The weight ratio of polymine and liquid concentrator dry weight is 1: 10, two-sided resin added be 450 grams/square metre, then with upper strata, centre and the stacked assembly of lower floor's board using poplar board and displayed 70 minutes; Carry out hot pressing compacting then, hot pressing pressure is that 1.5 MPas, hot pressing temperature are that 150 ℃, hot pressing press time are 3 minutes.
Embodiment 4
1, the preparation of tackiness agent
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 10000), being mixed with concentration is 20 weight %.
Method according to the sodium hydroxide leachable of preparation brown rot timber among the embodiment 1 prepares liquid concentrator, and liquid concentrator is carried out vacuum-drying, obtains dry thing.
Get dry thing and mix with 1: 5 weight ratio, be heated to 100 ℃, and under this temperature, reacted 6 hours with acetic anhydride.Through filtering (filter paper is Hangzhou Paper Co., Ltd of Xinhua, two circle boards, middling speed qualitative filter paper 102), be heated to 120 ℃ and be evacuated to-0.003 MPa and remove unreacted acetic anhydride and by-product acetic acid, obtain acetylate.Then this acetylate is dissolved in the aqueous sodium hydroxide solution of 1 weight % (weight ratio of the sodium hydroxide in acetylate and the aqueous sodium hydroxide solution is 5: 1), obtaining solid content is the acetylate solution of 25 weight %.
2, the preparation of wood veneer
With above-mentioned concentration be 20 weight % polyethyleneimine: amine aqueous solution and the above-mentioned acetylate solution that makes with the weight of Vilaterm ethamine and the ratio of acetylate weight be mix at 1: 3 after; Be coated in the cemented surface of 3 layers of board using poplar board (270 millimeters long * 270 mm wides * 1.6 mm thick) rapidly; The total two-sided resin added of polyethyleneimine: amine aqueous solution and acetylate solution be 300 the gram/square metre; With 3 layers of stacked assembly of wood single-plate and displayed 30 minutes; Carry out hot pressing compacting then, hot pressing pressure is that 0.5 MPa, hot pressing temperature are that hot pressing press time of 180 ℃, every millimeter wood single-plate thickness is 2.5 minutes.
Embodiment 5
Method according to embodiment 4 prepares tackiness agent and wood veneer, and different is, is that polyethyleneimine: amine aqueous solution and the acetylate solution that makes of 20 weight % is to mix at 1: 5 with the polymine and the weight ratio of acetylate with concentration.
Embodiment 6
1, the preparation of tackiness agent
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 100000), being mixed with concentration is 35 weight %.
Method according to the sodium hydroxide leachable of preparation brown rot timber among the embodiment 2 prepares liquid concentrator, and liquid concentrator is carried out vacuum-drying, obtains dry thing.
Get dry thing and mix with 1: 30 weight ratio, be heated to 140 ℃, and under this temperature, reacted 3 hours with acetic anhydride.Through filtering (filter paper is Hangzhou Paper Co., Ltd of Xinhua, two circle boards, middling speed qualitative filter paper 102), be heated to 120 ℃ and be evacuated to-0.003 MPa and remove unreacted acetic anhydride, obtain acetylate.This acetylate is dissolved in the aqueous sodium hydroxide solution of 1 weight % (weight ratio of the sodium hydroxide in acetylate and the aqueous sodium hydroxide solution is 30: 1) then, and obtaining solid content is the acetylate solution of 35 weight %.
2, the preparation of wood veneer
Get three layers of board using poplar board, be of a size of 270 millimeters long * 270 mm wides * 1.6 mm thick.
On the downside cemented surface of the downside cemented surface of upper strata board using poplar board, middle board using poplar board, respectively applying above-mentioned concentration is the polyethyleneimine: amine aqueous solution of 35 weight %; On the upside cemented surface of middle board using poplar board upside cemented surface and lower floor's board using poplar board, respectively apply the acetylate solution that the above-mentioned solid content that makes is 35 weight %; The weight ratio of polymine and acetylate is 1: 15; Two-sided resin added be 350 the gram/square metre; With upper strata, centre and the stacked assembly of lower floor's board using poplar board and displayed 100 minutes, carry out the hot pressing compacting then then, hot pressing pressure is that 2 MPas, hot pressing temperature are that 120 ℃, hot pressing press time are 2.5 minutes.
Embodiment 7
Method according to embodiment 6 prepares tackiness agent and wood veneer, and different is, is that polyethyleneimine: amine aqueous solution and the acetylate solution that makes of 35 weight % is to mix at 1: 20 with the polymine and the weight ratio of acetylate with concentration.
Embodiment 8
1, the preparation of tackiness agent
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 50000), being mixed with concentration is 30 weight %.
Method according to the sodium hydroxide leachable of preparation brown rot timber among the embodiment 3 prepares liquid concentrator, and liquid concentrator is carried out vacuum-drying, obtains dry thing.
Get dry thing and mix with 1: 20 weight ratio, be heated to 80 ℃, and under this temperature, reacted 30 minutes with acetic anhydride.Through filtering (filter paper is Hangzhou Paper Co., Ltd of Xinhua, two circle boards, middling speed qualitative filter paper 102), be heated to 120 ℃ and be evacuated to-0.003 MPa and remove unreacted acetic anhydride, obtain acetylate.Then this acetylate is dissolved in the aqueous sodium hydroxide solution of 1 weight % (weight ratio of the sodium hydroxide in acetylate and the aqueous sodium hydroxide solution is 60: 1), obtaining solid content is the acetylate solution of 15 weight %.
2, the preparation of wood veneer
Get three layers of board using poplar board, be of a size of 270 millimeters long * 270 mm wides * 1.6 mm thick.
Upside cemented surface at lower floor's board using poplar board applies the polyethyleneimine: amine aqueous solution that above-mentioned concentration is 30 weight %; Then on this polymine aqueous coating, apply the above-mentioned acetylate solution that makes; Upside cemented surface at middle board using poplar board applies the polyethyleneimine: amine aqueous solution that above-mentioned concentration is 30 weight %; Then on this polymine aqueous coating, apply the above-mentioned acetylate solution that makes; The weight ratio of polymine and acetylate is 1: 10, two-sided resin added be 450 grams/square metre, then with upper strata, centre and the stacked assembly of lower floor's board using poplar board and displayed 70 minutes; Carry out hot pressing compacting then, hot pressing pressure is that 1.5 MPas, hot pressing temperature are that 150 ℃, hot pressing press time are 3 minutes.
Embodiment 9
Method according to embodiment 8 prepares tackiness agent and wood veneer, and different is, is that polyethyleneimine: amine aqueous solution and the acetylate solution that makes of 30 weight % is to mix at 1: 12 with the polymine and the weight ratio of acetylate with concentration.
Embodiment 10
1, the preparation of tackiness agent
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 10000), being mixed with concentration is 20 weight %.
Method according to the sodium hydroxide leachable of preparation brown rot timber among the embodiment 1 prepares liquid concentrator, and liquid concentrator is carried out vacuum-drying, obtains dry thing.
Get dry thing and mix with 1: 2 weight ratio, at room temperature reacted 6 hours with epoxy chloropropane.Obtain epoxide through filtration (filter paper is Hangzhou Paper Co., Ltd of Xinhua, two circle boards, middling speed qualitative filter paper 102), washing.Then this epoxide is dissolved in the aqueous sodium hydroxide solution of 1 weight % (weight ratio of the sodium hydroxide in epoxide and the aqueous sodium hydroxide solution is 5: 1), obtains the epoxide that solid content is 25 weight %.
2, the preparation of wood veneer
With above-mentioned concentration be 20 weight % polyethyleneimine: amine aqueous solution and the above-mentioned epoxide solution that makes with the Vilaterm ethamine and the weight ratio of epoxide be mix at 1: 3 after; Be coated in the cemented surface of 3 layers of board using poplar board (270 millimeters long * 270 mm wides * 1.6 mm thick) rapidly; The total two-sided resin added of polyethyleneimine: amine aqueous solution and epoxide solution be 300 the gram/square metre; With 3 layers of stacked assembly of wood single-plate and displayed 30 minutes; Carry out hot pressing compacting then, hot pressing pressure is that 0.5 MPa, hot pressing temperature are that hot pressing press time of 180 ℃, every millimeter wood single-plate thickness is 2.5 minutes.
Embodiment 11
Method according to embodiment 10 prepares tackiness agent and wood veneer, and different is, is that polyethyleneimine: amine aqueous solution and the epoxide solution that makes of 20 weight % is to mix at 1: 5 with the polymine and the weight ratio of epoxide with concentration.
Embodiment 12
1, the preparation of tackiness agent
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 100000), being mixed with concentration is 35 weight %.
Method according to the sodium hydroxide leachable of preparation brown rot timber among the embodiment 2 prepares liquid concentrator, and liquid concentrator is carried out vacuum-drying, obtains dry thing.
Get dry thing and mix with 1: 10 weight ratio, be heated to 70 ℃ and reacted 3 hours down with epoxy chloropropane.Obtain epoxide through filtration (filter paper is Hangzhou Paper Co., Ltd of Xinhua, two circle boards, middling speed qualitative filter paper 102), washing.Then this epoxide is dissolved in the aqueous sodium hydroxide solution of 1 weight % (weight ratio of the sodium hydroxide in epoxide and the aqueous sodium hydroxide solution is 30: 1), obtaining solid content is the epoxide solution of 35 weight %.
2, the preparation of wood veneer
Get three layers of board using poplar board, be of a size of 270 millimeters long * 270 mm wides * 1.6 mm thick.
On the downside cemented surface of the downside cemented surface of upper strata board using poplar board, middle board using poplar board, respectively applying above-mentioned concentration is the polyethyleneimine: amine aqueous solution of 35 weight %; On the upside cemented surface of middle board using poplar board upside cemented surface and lower floor's board using poplar board, respectively apply the above-mentioned epoxide solution that makes; The weight ratio of polymine and epoxide is 1: 15; Two-sided resin added be 350 the gram/square metre; With upper strata, centre and the stacked assembly of lower floor's board using poplar board and displayed 100 minutes, carry out the hot pressing compacting then then, hot pressing pressure is that 2 MPas, hot pressing temperature are that 120 ℃, hot pressing press time are 2.5 minutes.
Embodiment 13
Method according to embodiment 12 prepares tackiness agent and wood veneer, and different is, is that polyethyleneimine: amine aqueous solution and the epoxide solution that makes of 35 weight % is to mix at 1: 20 with the polymine and the weight ratio of epoxide with concentration.
Embodiment 14
1, the preparation of tackiness agent
Get commercially available polyethyleneimine: amine aqueous solution (weight-average molecular weight is 50000), being mixed with concentration is 30 weight %.
Method according to the sodium hydroxide leachable of preparation brown rot timber among the embodiment 3 prepares liquid concentrator, and liquid concentrator is carried out vacuum-drying, obtains dry thing.
Get dry thing and mix with 1: 5 weight ratio, be heated to 90 ℃ and reacted 30 minutes down with epoxy chloropropane.Obtain epoxide through filtration (filter paper is Hangzhou Paper Co., Ltd of Xinhua, two circle boards, middling speed qualitative filter paper 102), washing.Then this epoxide is dissolved in the aqueous sodium hydroxide solution of 1 weight % (weight ratio of the sodium hydroxide in epoxide and the aqueous sodium hydroxide solution is 60: 1), obtaining solid content is the epoxide solution of 15 weight %.
2, the preparation of wood veneer
Get three layers of board using poplar board, be of a size of 270 millimeters long * 270 mm wides * 1.6 mm thick.
Upside cemented surface at lower floor's board using poplar board applies the polyethyleneimine: amine aqueous solution that above-mentioned concentration is 30 weight %; Then on this polymine aqueous coating, apply the above-mentioned epoxide solution that makes; Upside cemented surface at middle board using poplar board applies the polyethyleneimine: amine aqueous solution that above-mentioned concentration is 30 weight %; Then on this polymine aqueous coating, apply the above-mentioned epoxide solution that makes; The weight ratio of polymine and epoxide is 1: 10, two-sided resin added be 450 grams/square metre, then with upper strata, centre and the stacked assembly of lower floor's board using poplar board and displayed 70 minutes; Carry out hot pressing compacting then, hot pressing pressure is that 1.5 MPas, hot pressing temperature are that 150 ℃, hot pressing press time are 3 minutes.
Embodiment 15
Method according to embodiment 14 prepares tackiness agent and wood veneer, and different is, is that polyethyleneimine: amine aqueous solution and the epoxide solution that makes of 50 weight % is to mix at 1: 12 with weight ratio with concentration.
Performance test
1, dry glue intensity
Detect the dry glue intensity of wood veneer according to IV class wood veneer classification among the GB/T 17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels ".
2, water tolerance
According to the wet bonding strength of I class wood veneer classification detection wood veneer among the GB/T 17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels ", wet bonding strength is high more, and water tolerance is good more.
Resulting wood veneer in embodiment 1-15 and the Comparative Examples 1 is carried out performance test according to above-mentioned testing method, and gained is the result list in the table 1.
Table 1
| Leachable: polyethyleneimine: amine aqueous solution (weight) | Dry glue intensity (MPa) | Wet bonding strength (MPa) | |
| Embodiment 1 | 3∶1 | 1.28 | 0.40 |
| Comparative Examples 1 | 3∶1 | 1.24 | 0.25 |
| Embodiment 2 | 15∶1 | 0.80 | 0.10 |
| Embodiment 3 | 10∶1 | 0.87 | 0.15 |
| Embodiment 4 | 3∶1 | 1.50 | 0.85 |
| Embodiment 5 | 5∶1 | 1.30 | 0.50 |
| Embodiment 6 | 15∶1 | 1.32 | 0.78 |
| Embodiment 7 | 20∶1 | 0.88 | 0.25 |
| Embodiment 8 | 10∶1 | 1.02 | 0.72 |
| Embodiment 9 | 12∶1 | 1.90 | 0.20 |
| Embodiment 10 | 3∶1 | 1.65 | 0.93 |
| Embodiment 11 | 5∶1 | 1.35 | 0.60 |
| Embodiment 12 | 15∶1 | 1.45 | 0.85 |
| Embodiment 13 | 20∶1 | 0.95 | 0.35 |
| Embodiment 14 | 10∶1 | 1.80 | 1.05 |
| Embodiment 15 | 12∶1 | 1.10 | 0.30 |
Data from embodiment 1-15 and Comparative Examples 1 and table 1 can find out that the preparation method of tackiness agent of the present invention is simple, and the water tolerance after the tackiness agent of the present invention curing is better.Through respectively with embodiment 1,4,5,10 and 11 and embodiment 2,6,7,12 and 13, embodiment 3,8,9,14 and 15 compare and can find out; The sodium hydroxide leachable of brown rot timber is further carried out after resulting tackiness agent solidifies behind acetylize or the epoxidation, and dry glue intensity and water tolerance further improve; And under the situation that the consumption of polymine reduces, dry glue intensity and water tolerance are still quite or raising.
Claims (11)
1. a tackiness agent is characterized in that, said tackiness agent contains the sodium hydroxide leachable of polyethyleneimine: amine aqueous solution and brown rot timber; Said polyethyleneimine: amine aqueous solution and said leachable are independently preserved; Said brown rot timber is meant the timber of brown rot, is formed by the Mierocrystalline cellulose and the semicellulose of brown rot fungus destruction timber, wherein; The weight-average molecular weight of said polymine is 10000-100000; The concentration of said polyethyleneimine: amine aqueous solution is 20-35 weight %, and the solid content of said leachable is 15-35 weight %, and the weight ratio of the polymine in the dry weight of said leachable and the polyethyleneimine: amine aqueous solution is 3-20:1.
2. tackiness agent according to claim 1, wherein, the preparation method of said leachable comprises, aqueous sodium hydroxide solution is contacted with brown rot timber, filters then, obtains filtrate.
3. tackiness agent according to claim 2; Wherein, aqueous sodium hydroxide solution is comprised with the condition that brown rot timber contacts that the temperature of contact is 20-100 ℃; The time of contact is 0.5-5 hour, and the weight ratio of the sodium hydroxide in brown rot timber and the aqueous sodium hydroxide solution is 1-15:1.
4. according to claim 2 or 3 described tackiness agents, wherein, the concentration of said aqueous sodium hydroxide solution is 0.1-10 weight %.
5. tackiness agent according to claim 2, wherein, the preparation method of said leachable also comprises; With resulting filtrate acetylize, said acetylizad method comprises, under the acetylization reaction condition; With contacting 10 minutes with excessive acetylation reagent-6 hours after the said filtrate drying; Remove unreacted acetylation reagent then, then the acetylate that obtains is dissolved in the aqueous sodium hydroxide solution, obtaining solid content is the acetylate solution of 15-35 weight %; Said acetylation reagent is one or more in Acetyl Chloride 98Min., acetyl bromide, ketene, thioacetic acid, diacetyl oxide-pyridine, diacetyl oxide-sulfuric acid and the acetic anhydride.
6. tackiness agent according to claim 5; Wherein, Said acetylization reaction condition comprises that the acetylize temperature is 80-140 ℃, and the dry weight of said filtrate and the weight ratio of acetylation reagent are 1:5-30; The weight ratio of the sodium hydroxide in said acetylate and the aqueous sodium hydroxide solution is 5-150:1, and the concentration of said aqueous sodium hydroxide solution is 0.1-10 weight %; Said acetylation reagent is an acetic anhydride.
7. tackiness agent according to claim 2, wherein, the preparation method of said leachable also comprises; With resulting filtrate epoxidation, said process for epoxidation comprises, under epoxidation reaction condition; With contacting 10 minutes with excessive epoxidation reagent-6 hours after the said filtrate drying; Remove unreacted epoxidation reagent then, then the epoxide that obtains is dissolved in the aqueous sodium hydroxide solution, obtaining solid content is the epoxide solution of 15-35 weight %; Said epoxidation reagent is an epoxy chloropropane.
8. tackiness agent according to claim 7; Wherein, Said epoxidation reaction condition comprises that the epoxidation temperature is 20-90 ℃, and the dry weight of said filtrate and the weight ratio of epoxidation reagent are 1:2-10; The weight ratio of the sodium hydroxide in said epoxide and the aqueous sodium hydroxide solution is 5-150:1, and the concentration of said aqueous sodium hydroxide solution is 0.1-10 weight %.
9. wood veneer; This wood veneer comprises stacked two-layer at least wood single-plate and the adhesive coating between the adjacent two layers veneer; It is characterized in that said adhesive coating is by any product that described tackiness agent is solidified to form among the claim 1-8.
10. wood veneer according to claim 9; Wherein, The thickness of said wood single-plate is the 0.5-10 millimeter, and the preparation method of said wood veneer comprises, with the sodium hydroxide leachable of brown rot timber and the cemented surface that is coated in each wood single-plate after the polyethyleneimine: amine aqueous solution mixes immediately; Two-sided resin added be 300-450 gram/square metre; Stacked assembly was also displayed 30-100 minute, carried out hot pressing compacting then, and hot pressing pressure is that 0.5-2 MPa, hot pressing temperature are that hot pressing press time of 120-180 ℃, every millimeter wood single-plate thickness is 0.8-2 minute.
11. wood veneer according to claim 9; Wherein, the preparation method of said wood veneer comprises, the cemented surface that the sodium hydroxide leachable and the polyethyleneimine: amine aqueous solution of brown rot timber is coated in each wood single-plate respectively; Two-sided resin added be 300-450 gram/square metre; Stacked assembly was also displayed 30-100 minute, carried out hot pressing compacting then, and hot pressing pressure is that 0.5-2 MPa, hot pressing temperature are that hot pressing press time of 120-180 ℃, every millimeter wood single-plate thickness is 0.8-2 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910086669A CN101921574B (en) | 2009-06-17 | 2009-06-17 | Adhesive and veneer prepared by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910086669A CN101921574B (en) | 2009-06-17 | 2009-06-17 | Adhesive and veneer prepared by same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101921574A CN101921574A (en) | 2010-12-22 |
| CN101921574B true CN101921574B (en) | 2012-10-24 |
Family
ID=43336799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910086669A Expired - Fee Related CN101921574B (en) | 2009-06-17 | 2009-06-17 | Adhesive and veneer prepared by same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101921574B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693441B (en) * | 2015-02-13 | 2017-04-19 | 华南理工大学 | Method for preparing paper-making fixing agent and application thereof |
| CN106625910A (en) * | 2016-12-17 | 2017-05-10 | 浦北县建业胶合板有限责任公司 | Bamboo, wood and vine compound plywood and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049367A (en) * | 1989-08-09 | 1991-02-20 | 陈晓森 | The decorating paste that utilizes waste paper pulp to produce is prepared the method for the senior spraying pulp of inner, external wall |
| EP0183872B1 (en) * | 1984-11-26 | 1991-09-18 | Valtion Teknillinen Tutkimuskeskus | Method for preparing adhesive compositions, especially used in the preparation of wood constructions, wood board and similar products |
| US5417888A (en) * | 1988-02-11 | 1995-05-23 | Commonwealth Scientific And Industrial Research | Tannin extraction and processing |
| CN1764696A (en) * | 2003-06-05 | 2006-04-26 | 氦克逊特种化学品公司 | Emulsions for lignocellulosic products, methods of their manufacture, improved lignocellulosic products and methods for their manufacture |
| KR20070033065A (en) * | 2005-09-20 | 2007-03-26 | 박종철 | Composition of Functional Doping Adhesive |
-
2009
- 2009-06-17 CN CN200910086669A patent/CN101921574B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0183872B1 (en) * | 1984-11-26 | 1991-09-18 | Valtion Teknillinen Tutkimuskeskus | Method for preparing adhesive compositions, especially used in the preparation of wood constructions, wood board and similar products |
| US5417888A (en) * | 1988-02-11 | 1995-05-23 | Commonwealth Scientific And Industrial Research | Tannin extraction and processing |
| CN1049367A (en) * | 1989-08-09 | 1991-02-20 | 陈晓森 | The decorating paste that utilizes waste paper pulp to produce is prepared the method for the senior spraying pulp of inner, external wall |
| CN1764696A (en) * | 2003-06-05 | 2006-04-26 | 氦克逊特种化学品公司 | Emulsions for lignocellulosic products, methods of their manufacture, improved lignocellulosic products and methods for their manufacture |
| KR20070033065A (en) * | 2005-09-20 | 2007-03-26 | 박종철 | Composition of Functional Doping Adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101921574A (en) | 2010-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nemli et al. | Suitability of kiwi (Actinidia sinensis Planch.) prunings for particleboard manufacturing | |
| Nemli et al. | Evaluation of the physical and mechanical properties of particleboard made from the needle litter of Pinus pinaster Ait. | |
| Hashim et al. | Characterization of raw materials and manufactured binderless particleboard from oil palm biomass | |
| Khazaeian et al. | Suitability of sorghum stalk fibers for production of particleboard | |
| CN104772795B (en) | A kind of battenboard and production method thereof | |
| CN100522526C (en) | Technique for producing medium density fiberboard by using modified bulrush | |
| CN106272865B (en) | The method of full Eucalyptus leftover pieces production weatherability oriented wood chipboard | |
| CN106346589A (en) | Method for manufacturing anti-insect and anti-mold oriented strand board with full eucalyptus leftover materials | |
| CN106313265B (en) | The method of full Eucalyptus leftover pieces production high temperature resistant oriented wood chipboard | |
| CN104690803B (en) | Manufacturing method of fiber boards of non-formaldehyde soybean meal | |
| CN106584636A (en) | Production technique for formaldehyde-free damp-proof high-density fiberboard | |
| CN105082302A (en) | Manufacturing method of high-strength chipboard | |
| CN102604587A (en) | Formaldehyde-free adhesive and method for producing formaldehyde-free particle boards by using same | |
| CN102896682A (en) | Method for preparing solid wood particleboard of soybean protein adhesive | |
| CN103331796B (en) | Preparation method of tea polyphenol modified phenolic resin artificial board | |
| CN102782147B (en) | Fungal modified chitosan adhesives and wood composites made from the adhesives | |
| CN101921574B (en) | Adhesive and veneer prepared by same | |
| CN101497205A (en) | Vacuum pressure impregnating and glue-applying technique | |
| Talaei et al. | A comparative study on the mechanical and physical properties of plywood panels prepared by chitosan as bio-adhesive | |
| JPWO2013190777A1 (en) | Bagasse molded body | |
| CN103320082B (en) | Plant-based polyester polyol adhesive, and preparation method and application thereof | |
| CN108501478A (en) | A kind of compound laminated veneer lumber of high intensity eucalyptus poplar and its manufacturing method | |
| Eshraghi et al. | Waste paperboard in composition panels | |
| CN101245172B (en) | Urea formaldehyde condensate additive agent, production method and urea formaldehyde condensate adhesive agent | |
| CN201702827U (en) | High-strength laminated veneer lumber for electromechanical packaging box |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121024 Termination date: 20150617 |
|
| EXPY | Termination of patent right or utility model |