CN110450239B - Preparation method of novel formaldehyde-free impregnated membrane paper - Google Patents
Preparation method of novel formaldehyde-free impregnated membrane paper Download PDFInfo
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- CN110450239B CN110450239B CN201910764513.2A CN201910764513A CN110450239B CN 110450239 B CN110450239 B CN 110450239B CN 201910764513 A CN201910764513 A CN 201910764513A CN 110450239 B CN110450239 B CN 110450239B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
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- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of novel formaldehyde-free impregnated membrane paper, which comprises the following steps: s1, soaking base paper in a heat-sensitive multi-component isocyanate formaldehyde-free adhesive, and then taking out the soaked base paper and drying at the temperature of 60-120 ℃; and S2, after the impregnated paper is dried, veneering, wherein the hot pressing temperature is 110-220 ℃ when the impregnated paper is veneered, and the hot pressing is used for deblocking the isocyanate and the hydroxyl compound to react and crosslink, so that the curing and bonding of the impregnated paper and the artificial board substrate are completed. The preparation method of the novel formaldehyde-free impregnated membrane paper has the advantages of simple production process, easiness in operation and excellent performance, and realizes the aim of zero formaldehyde release of the veneer artificial board.
Description
Technical Field
The invention relates to the technical field of artificial board manufacturing, in particular to a preparation method of novel formaldehyde-free impregnated membrane paper.
Background
China is the first major artificial board producing country in the world and is also the first major furniture producing country. Currently, the yield of man-made boards exceeds 3 billion cubic meters. The artificial board is used for manufacturing furniture and needs to be subjected to facing treatment, common facings are those with melamine formal impregnated paper, veneers with wood, paint and the like, wherein the melamine paper facing has a far higher using effect than other facings, and is low in cost and high in processing efficiency.
With the increasing requirements of people on environmental protection, the production of artificial boards and the greening of products are more and more popularized, and more artificial board manufacturers begin to produce shaving boards, multilayer boards, fiber boards and the like without aldehyde. However, the finishing of the board, especially the sticker process, still only uses melamine formal impregnated bond paper. Namely, the substrate can realize the production of the aldehyde-free adhesive, and the veneer is still the veneer of the aldehyde-glue-impregnated paper, which becomes the last obstacle of the complete environmental protection of the board.
The melamine formaldehyde glue dipping glue film paper has mature production method and use method, is extremely simple, convenient and efficient, and has low cost, so the melamine formaldehyde glue dipping glue film paper becomes the most extensive method for plate facing. In order to avoid formaldehyde, attempts have been made to use other adhesives for impregnating the paper facer, but none are ideal. Because, after the panel veneer, must possess a series of characteristics: wear resistance, impact resistance, water resistance, hardness, glossiness and the like; at the same time, the process of finishing is also satisfactory, for example, the treated paper can be stored for a long time and cured rapidly during hot pressing, but the cost is also an important consideration.
At present, attempts are made to replace melamine formaldehyde acetal glue with diallyl phthalate, polyvinyl acetate, unsaturated resins and the like to produce impregnated paper for use in veneering. As a result, the performance or production efficiency cannot meet the corresponding requirements.
The industrial scale popularization of the artificial board without hydroformylation is realized by isocyanate adhesive, the direct use of the isocyanate adhesive can produce shaving boards, oriented structure shaving boards and fiber boards, and the use of isocyanate and water-soluble hydroxyl two components (commonly called API) can be used for producing multilayer boards and core-board boards. So some people try to use isocyanate to make formaldehyde-free impregnated bond paper, thereby completing the complete upgrade of the greening of the artificial board to furniture. However, the isocyanate adhesive has the characteristics of strong reactivity, need to be stored in a closed container independently, extremely strong bonding performance of products to various substances and the like, while the adhesive for impregnated paper needs to be a pre-polymerized mixture, and simultaneously needs to retain the activity capable of further reaction, but can not bond steel plates after completing the bonding to base materials, and no technology can be used for industrialization at present.
Disclosure of Invention
The invention aims to provide a preparation method of novel formaldehyde-free impregnated membrane paper, which has the advantages of simple production process, easy operation and excellent performance and realizes the aim of zero formaldehyde release of a veneer artificial board.
In order to realize the aim, the invention provides a preparation method of novel aldehyde-free impregnated membrane paper, which comprises the following steps:
s1, soaking base paper in a heat-sensitive multi-component isocyanate formaldehyde-free adhesive, and then taking out the soaked base paper and drying at the temperature of 60-120 ℃;
and S2, after the impregnated paper is dried, veneering, wherein the hot pressing temperature is 110-220 ℃ when the impregnated paper is veneered, and the hot pressing is used for deblocking the isocyanate and the hydroxyl compound to react and crosslink, so that the curing and bonding of the impregnated paper and the artificial board substrate are completed.
Preferably, the heat-sensitive multi-component isocyanate aldehyde-free adhesive comprises a mixture B, a filler, an internal release agent and an auxiliary agent, and the solid content of the heat-sensitive multi-component isocyanate aldehyde-free adhesive is 20-70%;
the mixture B mainly comprises heat-sensitive blocked isocyanate A which can be dispersed in water, acrylic resin containing hydroxyl and polyalcohol; the filler comprises one or more of metal powder, metal oxide and nonmetallic mineral, the internal mold release agent is polyurethane internal mold release agent, and the polyol comprises one or more of polyether polyol, polyester polyol, vegetable oil polyol and hydroxyl compound thereof.
Preferably, the heat-sensitive multicomponent isocyanate aldehyde-free adhesive has a solids content of 30 to 50%.
Preferably, the preparation method of the heat-sensitive blocked isocyanate A comprises the following steps: self-polymerizing isocyanate monomer or reacting with polyol to generate prepolymer, wherein the average functionality of-NCO is more than 2; then reacting the prepolymer with a hydrophilic modifier to prepare emulsifiable isocyanate, wherein the-NCO functionality is 2-4, and the mass fraction is 1-15%; blocking-NCO groups of the emulsifiable isocyanate by using a blocking agent to obtain blocked emulsifiable isocyanate A; finally, preparing the closed emulsifiable isocyanate into dispersion liquid through high-speed shearing;
the hydrophilic modifier is nonionic, anionic, cationic or mixed type, the hydrophilic modifier is one or more of polyoxyethylene alcohol ether, sulfonate, quaternary ammonium salt, polyethylene glycol monomethyl ether and 2, 2-dimethylolpropionic acid, and the sealant is one or more of phenol, caprolactam, butanone oxime and sodium sulfite.
Preferably, the isocyanate monomer is one or more of diisocyanate, monomer or derivative of polyisocyanate or prepolymer, and the isocyanate monomer is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene dicyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, methylcyclohexyl diisocyanate, and polymethylene polyphenyl isocyanate.
Preferably, the isocyanate monomer is an aliphatic isocyanate or a hydrogenated isocyanate with yellowing resistance, and the isocyanate monomer is one or more of hexamethylene dicyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate and cyclohexane dimethylene diisocyanate.
Preferably, the polyhydric alcohol is one or more of glycerol, glycol, dihydroxy polyether, trihydroxy polyether and polyethylene glycol adipate, the filler is one or more of aluminum oxide, calcium carbonate, titanium dioxide and mica powder, and the internal mold release agent is zinc stearate.
Preferably, the heat-sensitive multi-component isocyanate aldehyde-free adhesive also comprises an external release agent, a catalyst and a leveling agent, wherein the external release agent is coated on a steel plate intermittently during the release time;
the external mold release agent is an organic silicon mold release agent, the catalyst is dibutyltin dilaurate, and the flatting agent is polyether modified polysiloxane.
Preferably, the emulsifiable isocyanate A has a-NCO functionality of 2 to 3 and a mass fraction of 4 to 10%.
Preferably, the drying temperature of the base paper is 90-110 ℃ after the base paper is soaked in the heat-sensitive multi-component isocyanate formaldehyde-free adhesive, and the dried impregnated paper is immediately sealed and stored; the temperature of the impregnated paper is 140-200 ℃ when the paper is pasted.
Therefore, the preparation method of the novel formaldehyde-free impregnated membrane paper has the following technical effects:
(1) the invention solves the problem that the traditional impregnated bond paper must use aldehyde glue, namely triamine glue and urea-formaldehyde glue, and is the last difficulty of no hydroformylation of artificial board furniture and decoration.
(2) the-NCO group in the isocyanate adhesive and the hydroxyl group are condensed to form a carbamate bond, and the crosslinking and curing are very stable, so that the chemical bond adhesive has extremely strong bonding force, good waterproofness and high temperature resistance, and is incomparable to other adhesives.
(3) The invention improves the molecular weight through prepolymerization, the prepolymer enables the molecular size and the structure to be more suitable for the adhesive, reduces the quantity of-NCO groups, ensures the controllability of reaction, and enables the demoulding to be easy and feasible under the condition of adding the demoulding agent.
(4) The invention solves the problem that the isocyanate adhesive is dispersed in water by grafting the hydrophilic group.
(5) The invention enables the aldehyde-free adhesive to coexist with the hydroxyl compound and to be stored for a long time by blocking the remaining amount of-NCO groups. The deblocking temperature of the sealant is between 80 ℃ and 220 ℃, and the conventional finishing temperature is between 110 ℃ and 200 ℃, which is in the interval.
(6) In the mixture B, the hydroxyl acrylic resin and the polyol are reactants, are components of the adhesive film and are providers of various properties of the adhesive film. Other components such as various resins and fillers are intended to improve the overall properties of the adhesive film. The catalyst is used to obtain a desired reaction rate.
(7) The adhesive film paper veneer can completely realize greening from the aldehyde-free base material to the aldehyde-free veneer, and avoids the release of free formaldehyde.
(8) The non-formaldehyde glue impregnated bond paper prepared by the invention has simple production process and easy operation, the dried impregnated bond paper can be stored for a long time only at the high temperature of not higher than 80 ℃, and is even superior to the formaldehyde glue impregnated bond paper, and the polyurethane glue layer of the plate obtained after hot pressing of the veneer has high bonding strength, scratch resistance, wear resistance, high temperature resistance and good water resistance.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The embodiments of the present invention will be further explained below.
A preparation method of novel aldehyde-free impregnated membrane paper comprises the following steps:
s1, soaking the base paper in a heat-sensitive multi-component isocyanate formaldehyde-free adhesive, taking out the soaked base paper and drying at 60-120 ℃, more preferably 90-110 ℃, wherein the dried impregnated paper is immediately sealed and stored.
S2, after the impregnated paper is dried, veneering is carried out, the hot pressing temperature is 110-220 ℃ when the impregnated paper is veneered, the temperature is more preferably 140-200 ℃ when the impregnated paper is veneered, and the hot pressing is used for deblocking isocyanate and hydroxyl compound reaction crosslinking, so that the curing and bonding of the impregnated paper and the artificial board base material are completed.
The heat-sensitive multi-component isocyanate aldehyde-free adhesive comprises a mixture B, a filler, an internal release agent and an auxiliary agent, wherein the solid content of the heat-sensitive multi-component isocyanate aldehyde-free adhesive is 20-70%. Preferably, the heat-sensitive multicomponent isocyanate aldehyde-free adhesive has a solids content of 30 to 50%.
The heat-sensitive multi-component isocyanate formaldehyde-free adhesive also comprises an external release agent, a catalyst and a leveling agent, wherein the external release agent is coated on a steel plate intermittently in the release time. The internal mold release agent and the external mold release agent are used together to enhance the mold release effect, and the external mold release agent is an organic silicon mold release agent. The catalyst and the flatting agent can improve the paper veneer effect and improve the working efficiency, the catalyst is dibutyltin dilaurate, and the flatting agent is polyether modified polysiloxane.
The mixture B mainly comprises heat-sensitive blocked isocyanate A which can be dispersed in water, acrylic resin containing hydroxyl and polyalcohol; with regard to the-NCO to-OH ratio, an excess of isocyanate groups is ensured. The polyhydric alcohol can improve the performance of paper, such as toughness, glossiness, plumpness and the like, and ensure the further optimization of the formaldehyde-free glue.
The filler comprises one or more of metal powder, metal oxide and nonmetallic mineral, the internal mold release agent is polyurethane internal mold release agent, and the polyol comprises one or more of polyether polyol, polyester polyol, vegetable oil polyol and hydroxyl compound thereof.
The polyhydric alcohol is one or more of glycerol, glycol, dihydroxy polyether, trihydroxy polyether and polyethylene glycol adipate, the filler is one or more of aluminum oxide, calcium carbonate, titanium dioxide and mica powder, and the internal mold release agent is zinc stearate.
Example 1
A preparation method of novel aldehyde-free impregnated membrane paper comprises the following steps:
(1) the preparation method comprises the following steps of adopting wannate series PAPI produced by Wanhua chemical group Limited company, adopting dihydroxy polyether GE-220 and trihydroxy polyether GEP-560S produced by high-bridge petrochemical chemical industry, wherein the using amount of the two polyethers is 2: 1;
the three are prepolymerized to obtain a prepolymer, wherein the mass fraction of-NCO groups is 14%, and the functionality is 2.3. And a modifier of polyoxyethylene alcohol ether is further added, and the mass fraction of NCO groups is further reduced to 10 percent. At this time, the blocking agent butanone oxime is further added to block the residual-NCO groups. The resultant was dispersed in water by high-speed stirring and shearing. Preparing the thermosensitive isocyanate aqueous dispersion A, wherein the weight fraction ratio of water to colloid is 1: 1.
(2) The mixture B comprises hydroxy acrylic resin DB3717 which is produced by Hubei double bond fine chemical industry and glycerol which is purchased from the market.
(3) And adding aluminum oxide powder filler for increasing the wear resistance and a catalyst T12 into the A and the B at the same time, and shearing and mixing at a high speed to prepare the aldehyde-free impregnation liquid. Wherein the proportion of the aldehyde-free glue component A, the hydroxy acrylic resin, the glycerol, the aluminum oxide, the T12, the polyether modified polysiloxane and the water is 50: 60: 3: 5: 0.05: 2: 120.
(4) Soaking the base paper in the prepared formaldehyde-free glue, draining off the glue solution, and drying at 100 ℃.
(5) Taking a 18mm aldehyde-free straw board produced by Wanhua ecological board industry GmbH as a base material, and carrying out hot pressing at 180 ℃, under 1.2MPa and for 30 s.
(6) After hot pressing the facing, drying the board to obtain the artificial board without the aldehyde impregnated bond paper facing.
The veneer key performance is detected as follows:
according to the two indexes, the advantage of high bonding strength of the polyurethane adhesive is very outstanding and is far higher than the requirement that the national standard is more than or equal to 0.6 MPa. In the free formaldehyde release test, no free formaldehyde release was detected since the substrate straw board was also bonded using an isocyanate adhesive as was the case with the bond paper. In addition, the adhesive layer of the cured adhesive film paper has excellent cold-hot cycle resistance, scratch resistance, pollution corrosion resistance, crack resistance, and luster and texture.
Therefore, the preparation method of the novel formaldehyde-free impregnated membrane paper has the advantages of simple production process, easiness in operation and excellent performance, and realizes the aim of zero formaldehyde release of the veneer artificial board.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (9)
1. The preparation method of the novel aldehyde-free impregnated membrane paper is characterized by comprising the following steps:
s1, soaking base paper in a heat-sensitive multi-component isocyanate formaldehyde-free adhesive, and then taking out the soaked base paper and drying at the temperature of 60-120 ℃;
s2, after drying the impregnated paper, pasting the impregnated paper, wherein the hot pressing temperature is 110-220 ℃ when pasting the impregnated paper, and the hot pressing is used for deblocking isocyanate and hydroxyl compound reaction crosslinking, so as to finish curing and bonding the impregnated paper and the artificial board base material;
the heat-sensitive multi-component isocyanate aldehyde-free adhesive comprises a mixture B, a filler, an internal release agent and an auxiliary agent, wherein the solid content of the heat-sensitive multi-component isocyanate aldehyde-free adhesive is 20-70%, and the main component of the mixture B comprises heat-sensitive blocked isocyanate A which can be dispersed in water, acrylic resin containing hydroxyl and polyhydric alcohol;
the preparation method of the heat-sensitive blocked isocyanate A comprises the following steps: self-polymerizing isocyanate monomer or reacting with polyol to generate prepolymer, wherein the average functionality of-NCO is more than 2; then reacting the prepolymer with a hydrophilic modifier to prepare emulsifiable isocyanate, wherein the-NCO functionality is 2-4, and the mass fraction is 1-15%; blocking-NCO groups of the emulsifiable isocyanate by using a blocking agent to obtain blocked emulsifiable isocyanate A; finally, preparing the closed emulsifiable isocyanate into dispersion liquid through high-speed shearing;
the hydrophilic modifier is nonionic, anionic, cationic or mixed type, the hydrophilic modifier is one or more of polyoxyethylene alcohol ether, sulfonate, quaternary ammonium salt, polyethylene glycol monomethyl ether and 2, 2-dimethylolpropionic acid, and the sealant is one or more of phenol, caprolactam, butanone oxime and sodium sulfite.
2. The method for preparing the novel aldehyde-free impregnated film paper according to claim 1, wherein the method comprises the following steps: the filler comprises one or more of metal powder, metal oxide and nonmetallic mineral, the internal mold release agent is polyurethane internal mold release agent, and the polyol comprises one or more of polyether polyol, polyester polyol, vegetable oil polyol and hydroxyl compound thereof.
3. The method for preparing the novel aldehyde-free impregnated film paper according to claim 1, wherein the method comprises the following steps: the solid content of the heat-sensitive multi-component isocyanate aldehyde-free adhesive is 30-50%.
4. The method for preparing the novel aldehyde-free impregnated film paper according to claim 1, wherein the method comprises the following steps: the isocyanate monomer is one or more of diisocyanate, polyisocyanate monomer or derivative or prepolymer, and the isocyanate monomer is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene dicyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, methylcyclohexyl diisocyanate and polymethylene polyphenyl isocyanate.
5. The method for preparing the novel aldehyde-free impregnated film paper according to claim 1, wherein the method comprises the following steps: the isocyanate monomer is aliphatic isocyanate or hydrogenated isocyanate with yellowing resistance, and the isocyanate monomer is one or more of hexamethylene dicyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate and cyclohexane dimethylene diisocyanate.
6. The method for preparing the novel aldehyde-free impregnated film paper according to claim 2, wherein the method comprises the following steps: the polyhydric alcohol is one or more of glycerol, glycol, dihydroxy polyether, trihydroxy polyether and polyethylene glycol adipate, the filler is one or more of aluminum oxide, calcium carbonate, titanium dioxide and mica powder, and the internal mold release agent is zinc stearate.
7. The method for preparing the novel aldehyde-free impregnated film paper according to claim 2, wherein the method comprises the following steps: the heat-sensitive multi-component isocyanate formaldehyde-free adhesive also comprises an external release agent, a catalyst and a leveling agent, wherein the external release agent is coated on a steel plate intermittently in the demolding time;
the external mold release agent is an organic silicon mold release agent, the catalyst is dibutyltin dilaurate, and the flatting agent is polyether modified polysiloxane.
8. The method for preparing the novel aldehyde-free impregnated film paper according to claim 1, wherein the method comprises the following steps: the emulsifiable isocyanate A has the-NCO functionality of 2-3 and the mass fraction of 4-10%.
9. The method for preparing the novel aldehyde-free impregnated film paper according to claim 1, wherein the method comprises the following steps: after being soaked in the thermosensitive multi-component isocyanate formaldehyde-free adhesive, the base paper is dried at the temperature of 90-110 ℃, and the dried impregnated paper is immediately sealed and stored; the temperature of the impregnated paper is 140-200 ℃ when the paper is pasted.
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| CN111531660B (en) * | 2020-05-09 | 2022-02-08 | 中国林业科学研究院木材工业研究所 | Low-formaldehyde impregnated bond paper facing artificial board and preparation method thereof |
| CN111411543B (en) * | 2020-05-09 | 2022-01-28 | 中国林业科学研究院木材工业研究所 | Adhesive for formaldehyde-free impregnated bond paper and preparation method thereof |
| CN113492445B (en) * | 2021-06-25 | 2022-05-17 | 广州市盈尔安防火材料有限公司 | Weather-proof and corrosion-proof solid wood composite plywood and preparation process thereof |
| CN113733262A (en) * | 2021-08-30 | 2021-12-03 | 雪宝家居集团有限公司 | Surface dipping wear-resistant treatment process for environment-friendly plate |
| CN114293402B (en) * | 2022-01-06 | 2023-01-17 | 阳光王子(寿光)特种纸有限公司 | Aldehyde-free hot-pressing impregnation decorative paper and preparation method thereof |
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| EP2931824B1 (en) * | 2012-12-14 | 2018-10-17 | Dow Global Technologies LLC | Solid, self-bondable isocyantate-containing organic polymers and methods for using same |
| CN106393297B (en) * | 2016-11-01 | 2019-08-06 | 南京林业大学 | Manufacturing method of wear-resistant polyurethane impregnated decorative paper veneer formaldehyde-free glue-based wood-based panel |
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Denomination of invention: A new preparation method of formaldehyde free dipping film paper Effective date of registration: 20220627 Granted publication date: 20210625 Pledgee: Rizhao Bank Co.,Ltd. Yantai Zhifu sub branch Pledgor: Wanhua Ecological Technology Co.,Ltd. Registration number: Y2022980009126 |