CN101580683A - Modified urea-formaldehyde adhesive with low molar ratio for laminate flooring substrate - Google Patents
Modified urea-formaldehyde adhesive with low molar ratio for laminate flooring substrate Download PDFInfo
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- CN101580683A CN101580683A CNA2009101141218A CN200910114121A CN101580683A CN 101580683 A CN101580683 A CN 101580683A CN A2009101141218 A CNA2009101141218 A CN A2009101141218A CN 200910114121 A CN200910114121 A CN 200910114121A CN 101580683 A CN101580683 A CN 101580683A
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Abstract
The invention discloses a modified urea-formaldehyde adhesive with low molar ratio for a laminate flooring substrate, comprising the following components by weight: 300 portions of formaldehyde, 208-213 portions of carbamide, 21.5-29.5 portions of melamine, 0.0-2.0 portions of polyvinyl alcohol, 0.0-0.15 portions of triethanolamine, and 0.0-1.5 portions of borax. The preparation method comprising the following steps of: pouring the formaldehyde for one time, pouring the urea for two times and pouring the modifier for one time; sufficiently stirring and mixing the mixture and leading the mixture to react sequentially in a neutral or a alkalescent medium, a weak acidic medium and a alkalescent medium. The modified urea-formaldehyde adhesive is simple to be manufactured, is easy to be produced and operated, and can be produced in the glue department of an artificial board enterprise without needing to add equipments. The free formaldehyde content is 0.03-0.12%, the raw material has wide source, the cost is relatively low, and the laminate flooring substrate produced by the modified adhesive meets the requirement of the standard, and has good mechanic performance, low energy consumption and good waterproof performance.
Description
Technical field
The present invention relates to the modified urea-formaldehyde adhesive that the Wood-based Panel Production class is used, especially with the manufacture method of the melamine modified urea-formaldehyde glue that is applied to flooring substrate production usefulness.
Background technology
Laminated flooring entered the domestic market from 1994, emerge rapidly in market, floor with keen competition with its good performance and moderate price, and occupation rate is with about 30% speed increase every year on average in market, China floor.Present domestic laminated flooring manufacturing enterprise is numerous, and 2007 yearly capacities reach 22,000 ten thousand m
2As the base material of laminated flooring, mainly containing medium density fibre board (MDF) is MDF and homogeneous chipboard.At home and abroad have only at present a spot of laminated flooring with homogeneous chipboard as base material, the overwhelming majority laminated floorings be to produce as base material with MDF.Because it is low that urea-formaldehyde glue has a Joint strength height, quick solidifying, lighter color, cost, and raw material is easy to get, production technology ripe and advantage such as easy to use, and China MDF makes employing urea-formaldehyde resin adhesive 90% or more.Laminated flooring is widely used as one of main raw of interior decoration.Along with improving constantly of people's living standard, also more and more higher to the requirement of living environment, the theory of environment-friendly decorative material is rooted in the hearts of the people, and therefore, the formaldehyde of flooring product discharges problem and more and more is subjected to people's attention.Formaldehyde is a kind of very active chemical substance.Formaldehyde is gaseous state and volatilizees in air at normal temperatures, and it has special smell can stimulate people's eyes and respiratory mucosa.The European Community and Environmental Protection Agency (EPA) have been classified formaldehyde as the carcinogenic material of possibility, and China has also made standard and the rules about the restriction artificial board formaldehyde burst size.It is big to have a burst size of methanal with the artifical plate product of urea-formaldehyde resin manufacturing, how the shortcoming of water-fast, ageing resistance difference under current Environmental Safety is realized day by day the enhanced situation, reduces artifical plate product's burst size of methanal, overcoming shortcomings such as its poor water resistance, has been an instant problem.
At present both at home and abroad the operational path of production environmental protection E1 level flooring substrate is divided into two types substantially: a kind of method is to adopt the mol ratio that reduces tackiness agent, improve adhesive-preparing technology, urea-formaldehyde resin adhesive is carried out modification, adds formaldehyde-trapping agent in glue, the preferred consolidation agent, improves hardener dose etc.Another kind method is sheet material to be carried out the later stage ammonia cure handle.In the treatment chamber of special use, make the free formaldehyde reaction in ammonia and the sheet material generate six methynes, four ammoniums, this reaction can be in plate a step finish.
Adopt ammonia cure to handle base material and can reach the environmental requirement of E1 level, the physical and mechanical property of sheet material does not have disadvantageous effect yet, but residual ammonia has brought new indoor pollution problem in the base material.Mainly reduce burst size of methanal both at home and abroad at present by the modified urea-formaldehyde glue that hangs down mol ratio.A lot of researchs and production show, reduce the content of free formaldehyde in the urea-formaldehyde resin, it is one of main path that reduces the sheet material burst size of methanal, change the urea formaldehyde molar ratio simultaneously, adjust the reaction process of resin, the heat pressing process etc. that adds urea in batches and improve making sheet also is effectively approach.MDF develops to low mol ratio direction with urea-formaldehyde resin at present, but low excessively mol ratio also can cause the performance of resin to reduce, and package stability descends, and set time is elongated, and pressing cycle increases, and production efficiency reduces, and has improved manufacturing cost.The key that reduces formaldehyde, urea mol ratio is to select a suitable ratio, and it can guarantee that tackiness agent has good performance, the requirement that the burst size of methanal of plank is up to state standards.In addition, adding properties-correcting agent, formaldehyde-trapping agent in the glue process also is popular in the world in recent years way.As use ring texture amine, amides, ammonium salt etc., and add by the synthetic copolymerization of resin, later stage and catch the release that can reduce free formaldehyde effectively, strengthen the bonding strength and the water resistance of resin simultaneously.Therefore, these methods also are in continuous research at present, progressively improve the also stage of broadened application scope.
Summary of the invention
The purpose of this invention is to provide a kind of ultralow mol ratio prescription modified urea-formaldehyde adhesive, the glue product color is shallow, low content of free formaldehyde content, set time are moderate.The flooring substrate fiberboard that makes meets the wood-based plate that GB18580-2001 " burst size of methanal in indoor decorating material wood-based plate and the goods thereof " E1 grade standard requires, and particularly the 24h thickness swelling rate is lower than 10%.
The technical solution used in the present invention is:
Modified urea-formaldehyde adhesive with low molar ratio for laminate of the present invention comprises the component of following weight proportion: 300 parts in formaldehyde, 208～213 parts in urea, 21.5～29.5 parts of trimeric cyanamides, 0.0～2.0 part of polyvinyl alcohol, 0.0～0.15 part of trolamine, 0.0～1.5 part of borax.
Weight proportion is preferred: 300 parts in formaldehyde, 210～213 parts in urea, 26.5～29.5 parts of trimeric cyanamides, 0.0～1.0 part of polyvinyl alcohol, 0.12～0.15 part of trolamine, 0.1～1.5 part of borax.
The manufacture method of modified urea-formaldehyde adhesive with low molar ratio for laminate of the present invention is that formaldehyde once drops into, under 45～90 temperature, urea adds at twice, properties-correcting agent once drops into, and after fully mixing, reacts in neutrality or weakly alkaline, slightly acidic, weak alkaline medium successively.At least a in the preferred trimeric cyanamide of properties-correcting agent, the polyvinyl alcohol.For the first time, for the second time the urea add-on is respectively the urea total amount: 40～50%, 50～60%.
Technological process is carried out following steps successively:
1. in reactor, add formaldehyde, trimeric cyanamide, start stirring, be warmed up to 45～65 ℃, be incubated 20-30 minute.
2. detect the pH value, transfer pH=8.0～9.0, add urea for the first time, continue to be warmed up to 80～90 ℃, be incubated 10～30 minutes.
3. check the pH value, three adjust pHs are up to 4.2～5.0, reach that to be coated with-4 glasss of viscosity be 12～16 seconds.
4. add trolamine, add adjusting PH with base=8.0～9.0, add urea for the second time, be incubated 20～40 minutes.
5. add the borax postcooling.
6. be cooled to 39 ℃, transfer pH=7.0～8.0, blowing.
Advantage of the present invention is:
1, the manufacturing of this modified urea-formaldehyde glue is simple, is easy to production operation, and is less demanding to equipment, manufacturing condition, and the glue department of most of artificial plate enterprise need not increase equipment just can be produced, and need not to increase facility investment.
2, manufacturing has good bonding strength to this modified urea-formaldehyde glue to fiberboard, and free formaldehyde content is 0.03%～0.12%, and the raw material supplied materials is wide, and cost is relatively low.
3, modified urea-formaldehyde glue of the present invention has been started laminated flooring production and has been fallen aldehyde, the new situation of water resistance aspect.Utilize modified adhesive of the present invention, the flooring substrate of producing, its important quality index such as burst size of methanal, thickness swelling rate, MOR, dimensional stability and buckling deformation etc. all meet GB/T11718-1999 " medium density fibre board (MDF) " standard premium grads and the requirement of GB18580-2001 " burst size of methanal in indoor decorating material wood-based plate and the goods thereof " E1 grade standard.
4, the E1 level flooring substrate that utilizes glue of the present invention to cooperate heat pressing process to produce, mechanical property is good, and the glue consumption is low, good waterproof performance, production cost has very strong market competition advantage.
Embodiment
Embodiment 1
1, composition of raw materials
| Raw material | Weight (kg) | Content (%) | Remarks |
| Formaldehyde | 15000 | 37.0 | |
| Urea | 10650 | 46.3 | U1＝5050 U2＝5600 |
| Trimeric cyanamide | 1075 | 99.9 | |
| Polyvinyl alcohol | 0 | 1799# (polymerization degree model) | |
| Trolamine | 0 | 85 | |
| Borax | 0 | 95 | Technical grade |
| Formic acid | In right amount | 15 | |
| Sodium hydroxide | In right amount | 40 |
Annotate: the mol ratio of formaldehyde and urea+trimeric cyanamide is 0.99
Concrete reactions steps comprises:
1. add formaldehyde at reactor, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds trimeric cyanamide, starts stirring, is warmed up to 45～65 ℃, is incubated 20～30 minutes.
2. detect the pH value, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the first time, continues to be warmed up to 80～90 ℃, is incubated 10～30 minutes.
3. check the pH value, add formic acid solution adjust pH to 4.2～5.0 three times, reach that to be coated with-4 glasss of viscosity be 12～16 seconds.
4. the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the second time, is incubated 20～40 minutes postcooling.
5. be cooled to 39 ℃, the hydro-oxidation sodium solution is transferred pH=7.0～8.0, blowing.
Product quality indicator:
| Viscosity | (14.2S T-4 cup, 25 ℃) | Density | 1.20kg/m 3 |
| Solids content | 53.0％ | Set time | 216S |
| The pH value | 8.33 | Outward appearance | The oyster white homogeneous liquid |
| Free formaldehyde | 0.12％ | Working life | 25 days |
The E1 glue reaction times: 6 hours, production cost: 1726 yuan/ton.
Embodiment 2
1, preferred feedstock prescription
| Raw material | Weight (kg) | Content (%) | Remarks |
| Formaldehyde | 15000 | 37.0 | |
| Urea | 10400 | 46.3 | U1＝4800 U2＝5600 |
| Trimeric cyanamide | 1475 | 99.9 | |
| Polyvinyl alcohol | 0 | 1799# (polymerization degree model) | |
| Trolamine | 6 | 85 | |
| Borax | 50 | 95 | Technical grade |
| Formic acid | In right amount | 15 | |
| Sodium hydroxide | In right amount | 40 |
Annotate: the mol ratio of formaldehyde and urea+trimeric cyanamide is 0.99
Concrete reactions steps comprises:
1. add formaldehyde at reactor, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds trimeric cyanamide, starts stirring, is warmed up to 45～65 ℃, is incubated 20～30 minutes.
2. detect the pH value, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the first time, continues to be warmed up to 80～90 ℃, is incubated 10～30 minutes.
3. check the pH value, add formic acid solution adjust pH to 4.2～5.0 three times, reach that to be coated with-4 glasss of viscosity be 12～16 seconds.
4. add trolamine, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the second time, is incubated 20～40 minutes.
5. add the borax postcooling.
6. be cooled to 39 ℃, the hydro-oxidation sodium solution is transferred pH=7.0～8.0, blowing.
Product quality indicator:
| Viscosity | (15.9S T-4 cup, 25 ℃) | Density | 1.21kg/m 3 |
| Solids content | 53.9％ | Set time | 238S |
| The pH value | 8.45 | Outward appearance | The oyster white homogeneous liquid |
| Free formaldehyde | 0.06％ | Working life | 25 days |
The E1 glue reaction times: 6 hours, production cost: 1819 yuan/ton.
Embodiment 3
1, composition of raw materials
| Raw material | Weight (kg) | Content (%) | Remarks |
| Formaldehyde | 15000 | 37.0％ | |
| Urea | 10400 | 46.3％ | U1＝4800 U2＝5600 |
| Trimeric cyanamide | 1475 | 99.9％ | |
| Polyvinyl alcohol | 100 | 1799# (polymerization degree model) | |
| Trolamine | 7.5 | 85％ | |
| Borax | 75 | 85％ | Technical grade |
| Formic acid | In right amount | 15％ | |
| Sodium hydroxide | In right amount | 40％ |
Annotate: the mol ratio of formaldehyde and urea+trimeric cyanamide is 0.99
Concrete reactions steps comprises:
1. add formaldehyde, polyvinyl alcohol at reactor, be warmed up to 45-55 ℃ to dissolving fully.
2. the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds trimeric cyanamide, starts stirring, is warmed up to 55～65 ℃, is incubated 20～30 minutes.
3. detect the pH value, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the first time, continues to be warmed up to 80～90 ℃, is incubated 10～30 minutes.
4. check the pH value, add the formic acid solution adjust pH up to 4.2～5.0 three times, reach that to be coated with-4 glasss of viscosity be 12～16 seconds.
5. add trolamine, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the second time, is incubated 20～40 minutes.
6. add the borax postcooling.
7. be cooled to 39 ℃, the hydro-oxidation sodium solution is transferred pH=7.0～8.0, blowing.
Product quality indicator:
| Viscosity | (15.1S T-4 cup, 25 ℃) | Density | 1.21kg/m 3 |
| Solids content | 53.2％ | Set time | 250S |
| The pH value | 8.37 | Outward appearance | The oyster white homogeneous liquid |
| Free formaldehyde | 0.03％ | Working life | 25 days |
The E1 glue reaction times: 6 hours, production cost: 1890 yuan/ton.
Embodiment 4
The modified urea-formaldehyde glue of embodiment 1 is used to produce the production of E1 level flooring substrate.
Carry out following technology during production:
Resin added is pressed 230kg/m
3, the applying wax amount is pressed 10.8kg/m
3, the ammonium sulfate solidifying agent is by 2.5% of dried glue amount, and on the continuous flat production line, press speed 270mm/s distinguishes hot pressing temperatures for 5 and is respectively: 220,232,225,205,185.By GB/T17657-1999 " wood-based plate and face artificial board physicochemical property experimental technique " product performance are detected, burst size of methanal detects with perforation method.
Use the flooring substrate fiberboard of above-mentioned explained hereafter 13.3mm specification, according to the method described above with its physicochemical property of Equipment Inspection and burst size of methanal.
Detected result is as seeing Table 1
Table 1 flooring substrate fibreboard performance detected result
| Specification | Resin added (kg/m 3) | Hardener dose (%) | Density (kg/m 3) | MOR (Mpa) | Thickness swelling rate (%) | Internal bond strength (Mpa) | Burst size of methanal (mg/100g) |
| 13.3mm | 235 | 2.5 | 812 | 30.71 | 8.87 | 1.39 | 5.65 |
| The GB requirement | 450～ 880 | ≥20 | ≤10 | ≥0.55 | ≤9 |
As can be seen from Table 1, when the mol ratio of modified urea-formaldehyde glue of the present invention was 0.99, the burst size of methanal of the flooring substrate of the 13.3mm of production was 5.65mg/100g, was lower than the E1 level requirement less than 9mg/100g of national standard.Thickness swelling rate is 8.87%, be lower than that national standard requires less than 10%.
Embodiment 5
The modified urea-formaldehyde glue of embodiment 2 is used to produce the production of E1 level flooring substrate.
Carry out following technology during production:
Resin added is pressed 235kg/m
3, the applying wax amount is pressed 10.5kg/m
3, the ammonium sulfate solidifying agent is by 2.5% of dried glue amount, and on the continuous flat production line, press speed 260mm/s distinguishes hot pressing temperatures for 5 and is respectively: 225,230,228,205,185.By GB/T17657-1999 " wood-based plate and face artificial board physicochemical property experimental technique " product performance are detected, burst size of methanal detects with perforation method.
Use the flooring substrate fiberboard of above-mentioned explained hereafter 13.3mm specification, according to the method described above with its physicochemical property of Equipment Inspection and burst size of methanal.
Detected result is as seeing Table 1
Table 1 flooring substrate fibreboard performance detected result
| Specification | Resin added (kg/m 3) | Hardener dose (%) | Density (kg/m 3) | MOR (Mpa) | Thickness swelling rate (%) | Internal bond strength (Mpa) | Burst size of methanal (mg/100g) |
| 13.3mm | 235 | 2.5 | 841 | 26.0 | 7.11 | 1.42 | 5.92 |
| The GB requirement | 450～880 | ≥20 | ≤10 | ≥0.55 | ≤9 |
As can be seen from Table 1, when the mol ratio of modified urea-formaldehyde glue of the present invention was 0.99, the burst size of methanal of the flooring substrate of the 13.3mm of production was 5.92mg/100g, was lower than the E1 level requirement less than 9mg/100g of national standard.Thickness swelling rate is 7.11%, be lower than that national standard requires less than 10%.
Embodiment 6
The embodiment of the invention 3 modified urea-formaldehyde glues are used for E1 level laminated flooring
Resin added is pressed 236kg/m
3, the applying wax amount is pressed 11kg/m
3, the ammonium sulfate solidifying agent is by 2.5% of dried glue amount, and on the continuous flat production line, press speed 260mm/s distinguishes hot pressing temperatures for 5 and is respectively: 225,230,228,205,185.By GB/T17657-1999 " wood-based plate and face artificial board physicochemical property experimental technique " product performance are detected, burst size of methanal detects with perforation method.
Use the flooring substrate fiberboard of above-mentioned explained hereafter 13.3 specifications, according to the method described above with its physicochemical property of Equipment Inspection and burst size of methanal.
Detected result is as seeing Table 2
Table 2 flooring substrate fibreboard performance detected result
| Specification | Resin added (kg/m 3) | Hardener dose (%) | Density (kg/m 3) | MOR (Mpa) | Thickness swelling rate (%) | Internal bond strength (Mpa) | Burst size of methanal (mg/100g) |
| 13.3mm | 236 | 2.5 | 822 | 30.15 | 6.91 | 1.57 | 4.98 |
| The GB requirement | 450～880 | ≥20 | ≤10 | ≥0.55 | ≤9 |
As can be seen from Table 2, when the mol ratio of modified urea-formaldehyde glue of the present invention was 0.99, the burst size of methanal of the flooring substrate of the 13.3mm of production was 4.98mg/100g, was lower than the E1 level requirement less than 9mg/100g of national standard.Thickness swelling rate is 6.91%, low national standard require less than 10%.
Claims (6)
1. flooring substrate modified urea-formaldehyde adhesive with low molar ratio for laminate is characterized in that comprising the component of following weight proportion: 300 parts in formaldehyde, 208～213 parts in urea, 21.5～29.5 parts of trimeric cyanamides, 0.0～2.0 part of polyvinyl alcohol, 0.0～0.15 part of trolamine, 0.0～1.5 part of borax.
2. modified urea-formaldehyde adhesive with low molar ratio for laminate according to claim 1 is characterized in that described weight proportion is preferred: 300 parts in formaldehyde, 210～213 parts in urea, 26.5～29.5 parts of trimeric cyanamides, 0.0～1.0 part of polyvinyl alcohol, 0.12～0.15 part of trolamine, 0.1～1.5 part of borax.
3. modified urea-formaldehyde adhesive with low molar ratio for laminate according to claim 1 and 2 is characterized in that: at least a in the preferred trimeric cyanamide of properties-correcting agent, the polyvinyl alcohol.
4. the preparation method of modified urea-formaldehyde adhesive with low molar ratio for laminate according to claim 1 and 2, it is characterized in that: formaldehyde once drops into, under 45～90 temperature, urea adds at twice, properties-correcting agent once drops into, after fully mixing, in neutrality or weakly alkaline, slightly acidic, weak alkaline medium, react successively.
5. the preparation method of modified urea-formaldehyde adhesive with low molar ratio for laminate according to claim 4 is characterized in that: for the first time, the urea add-on is respectively the urea total amount for the second time: 40～50%, 50～60%.
6. according to the preparation method of claim 4,5 described modified urea-formaldehyde adhesive with low molar ratio for laminate, its feature comprises the step that next coming in order carry out:
1. add formaldehyde in reactor, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds trimeric cyanamide, starts stirring, is warmed up to 45～65 ℃, is incubated 20～30 minutes.
2. detect the pH value, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the first time, continues to be warmed up to 80～90 ℃, is incubated 10～30 minutes.
3. check the pH value, add the formic acid solution adjust pH up to 4.2～5.0 three times, reach that to be coated with-4 glasss of viscosity be 12～16 seconds.
4. add trolamine, the hydro-oxidation sodium solution is transferred pH=8.0～9.0, adds urea for the second time, is incubated 20～40 minutes.
5. add the borax postcooling.
6. cool off 39 ℃, the hydro-oxidation sodium solution is transferred pH=7.0～8.0 blowings.
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| CN102134468A (en) * | 2010-01-26 | 2011-07-27 | 北京建筑材料科学研究总院有限公司 | Method for preparing adhesive for grade-E0 medium density fiberboards |
| CN102235077A (en) * | 2010-04-28 | 2011-11-09 | 幸世成 | Preparation method of water-proof and moisture-proof solid wood floor |
| CN102775946A (en) * | 2012-07-18 | 2012-11-14 | 广西华峰林业股份有限公司 | MDF(Medium-density fiber)-E1-level urea-formaldehyde resin adhesive |
| CN103087662A (en) * | 2013-01-18 | 2013-05-08 | 安徽省阜阳沪千人造板制造有限公司 | Special adhesive for heel plates |
| CN103264428A (en) * | 2013-05-16 | 2013-08-28 | 福建汇洋林业投资股份有限公司 | Production process of low-density light reinforced floor |
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| CN104031221A (en) * | 2012-07-27 | 2014-09-10 | 大亚木业(江西)有限公司 | Method for preparing melamine-modified urea-formaldehyde resin adhesive |
| CN104497937A (en) * | 2014-11-28 | 2015-04-08 | 广西丰林木业集团股份有限公司 | Low-molar ratio modified adhesive for laminate flooring base material and preparation method thereof |
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| CN107880230A (en) * | 2017-12-11 | 2018-04-06 | 云南新泽兴人造板有限公司 | A kind of adhesive-preparing technology of ultralow mole of glue |
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| CN102235077A (en) * | 2010-04-28 | 2011-11-09 | 幸世成 | Preparation method of water-proof and moisture-proof solid wood floor |
| CN102775946A (en) * | 2012-07-18 | 2012-11-14 | 广西华峰林业股份有限公司 | MDF(Medium-density fiber)-E1-level urea-formaldehyde resin adhesive |
| CN104031221A (en) * | 2012-07-27 | 2014-09-10 | 大亚木业(江西)有限公司 | Method for preparing melamine-modified urea-formaldehyde resin adhesive |
| CN104031221B (en) * | 2012-07-27 | 2016-04-20 | 大亚木业(江西)有限公司 | A kind of manufacture method of cyanurotriamide modified urea resin glue |
| CN103087662A (en) * | 2013-01-18 | 2013-05-08 | 安徽省阜阳沪千人造板制造有限公司 | Special adhesive for heel plates |
| CN103087662B (en) * | 2013-01-18 | 2014-10-29 | 安徽省阜阳沪千人造板制造有限公司 | Special adhesive for heel plates |
| CN103264428A (en) * | 2013-05-16 | 2013-08-28 | 福建汇洋林业投资股份有限公司 | Production process of low-density light reinforced floor |
| CN103496025A (en) * | 2013-09-26 | 2014-01-08 | 广西三威林产工业有限公司 | Method for manufacturing ultra-low formaldehyde emission medium-to-high density fiberboard |
| CN103496025B (en) * | 2013-09-26 | 2015-11-25 | 广西三威林产工业有限公司 | The manufacture method of ultra-low formaldehyde emission medium-to-high density fiberboard |
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| CN107880230A (en) * | 2017-12-11 | 2018-04-06 | 云南新泽兴人造板有限公司 | A kind of adhesive-preparing technology of ultralow mole of glue |
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Application publication date: 20091118 |