CN113463440A - Flame-retardant antifouling cellulose laminated composite board for rail transit interior decoration and preparation method thereof - Google Patents

Flame-retardant antifouling cellulose laminated composite board for rail transit interior decoration and preparation method thereof Download PDF

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CN113463440A
CN113463440A CN202110720174.5A CN202110720174A CN113463440A CN 113463440 A CN113463440 A CN 113463440A CN 202110720174 A CN202110720174 A CN 202110720174A CN 113463440 A CN113463440 A CN 113463440A
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cellulose
paper
formaldehyde resin
core layer
melamine
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CN113463440B (en
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咸漠
高薇
孔庆山
曹玉锦
陈泉
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31F—MECHANICAL WORKING OR DEFORMATION OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31F5/00—Attaching together sheets, strips or webs; Reinforcing edges
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T30/00—Transportation of goods or passengers via railways, e.g. energy recovery or reducing air resistance

Abstract

A flame-retardant antifouling cellulose laminated composite board for rail transit interior decoration and a preparation method thereof. The invention belongs to the field of rail transit interior trim. The invention aims to solve the technical problems that the existing cellulose laminated composite material has poor fireproof and antifouling performance and cannot meet the application requirements of rail transit interior materials. The flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration is formed by hot-pressing and curing a surface layer and a core layer which are arranged in a laminated manner; the surface layer is a plurality of layers of cellulose paper impregnated with modified melamine formaldehyde resin, and the core layer is formed by compounding a plurality of layers of alternately laminated aramid paper impregnated with modified melamine formaldehyde resin and cellulose paper impregnated with modified melamine formaldehyde resin. The composite board is formed by hot pressing of a plurality of cellulose materials which are impregnated with modified melamine formaldehyde resin with rapid infiltration and flame retardant property. The limiting oxygen index reaches 36.5; the combustion performance reaches A level; the pollution resistance reaches 5 grades, and the antifouling flame retardant property is excellent.

Description

Flame-retardant antifouling cellulose laminated composite board for rail transit interior decoration and preparation method thereof
Technical Field
The invention belongs to the field of rail transit interior trim, and particularly relates to a flame-retardant antifouling cellulose laminated composite board for rail transit interior trim and a preparation method thereof.
Background
The cellulose laminated composite board is a decorative material prepared by impregnating melamine formaldehyde resin with decorative paper and impregnating phenolic resin with multiple layers of cellulose paper through high temperature and high pressure, and can be used for trains, end wall boards, enclosing plates of electric cabinets, tea table boards and the like which run under complex environments due to the characteristics of high weather resistance, high stability, high wear resistance, impact resistance, strong decoration, water resistance and the like.
In recent years, the rail transit is rapidly developed in China, and has the characteristics of high personnel density, relatively closed environment and the like, the fireproof plate is used as a main decorative material in a vehicle, the material of the fireproof plate is researched and analyzed, a new technology is provided, and the fireproof plate has very important significance for improving the fireproof safe operation of a rail transit station and has wide application prospect. The melamine formaldehyde resin is prepared by taking melamine and formaldehyde as raw materials, is cured under a hot pressing condition, is transparent, has excellent characteristics of water resistance, organic solvent resistance, heat resistance and the like, and is an indispensable material for producing laminated composite boards. However, the melamine formaldehyde resin has some problems, such as a large number of rigid rings in the structure of the cured melamine formaldehyde resin and a large crosslinking density of the resin, which causes the cured melamine formaldehyde resin to have high brittleness, easy cracking, poor processability and the like in production application.
Aiming at the problems that the existing cellulose laminated composite material has poor performances such as fire resistance, pollution resistance and the like and cannot meet the application requirements of track traffic interior materials, the development of the cellulose laminated composite material with excellent comprehensive performance is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problems that the existing cellulose laminated composite material is poor in fireproof and antifouling performance and cannot meet the application requirements of track traffic interior materials, and provides a flame-retardant antifouling cellulose laminated composite board for track traffic interior and a preparation method thereof.
The flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration is formed by hot-pressing and curing a surface layer and a core layer which are arranged in a laminated manner; the surface layer is a plurality of layers of cellulose paper impregnated with modified melamine formaldehyde resin, and the core layer is formed by compounding a plurality of layers of aramid paper impregnated with modified melamine formaldehyde resin and cellulose paper impregnated with modified melamine formaldehyde resin which are alternately stacked.
Further defined, the preparation method of the modified melamine formaldehyde resin is as follows: adding a formaldehyde solution and a polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, adjusting the pH value to 7-10, heating to 65-105 ℃, continuing to react for 1-5 h after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5-2.0 h, adjusting the pH value to 7-9, cooling and discharging to obtain the modified melamine-formaldehyde resin.
Further limiting, the mass ratio of formaldehyde to melamine in the formaldehyde solution is (18-22): 10.
further limiting, the ratio of the amount of the polyvinyl alcohol to the amount of the melamine in the polyvinyl alcohol aqueous solution is (4-30): 100, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 1-20%.
Further limiting, the mass ratio of the benzoguanamine to the melamine is (0.5-25): 100.
further limiting, the cellulose paper is prepared by adopting chemi-mechanical pulp papermaking, and the gram weight of the cellulose paper is 70g/m2～200g/m2The cellulose paper of (1).
Further limited, the aramid paper is meta-aramid paper, and the gram weight is 29g/m2～110g/m2。
Further limiting, the surface layer is 1-3 cellulose paper impregnated with the modified melamine-formaldehyde resin, and the core layer is formed by compounding 6-30 layers of aramid paper impregnated with the modified melamine-formaldehyde resin and cellulose paper impregnated with the modified melamine-formaldehyde resin, wherein the number of the aramid paper layers accounts for 20-50% of the total number of the layers.
The preparation method of the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration comprises the following steps:
step 1: preparing modified melamine formaldehyde resin;
step 2: soaking the modified melamine formaldehyde resin obtained in the step 1 in cellulose paper, wherein the gluing amount is 80-110% of the dry weight of the cellulose paper, and drying to obtain surface cellulose paper;
and step 3: respectively dipping cellulose paper and aramid paper into modified melamine formaldehyde resin, wherein the gluing amount is 60-100% of the dry weight of the cellulose paper and the dry weight of the aramid paper, and drying to obtain core layer cellulose paper and core layer aramid paper;
and 4, step 4: and alternately laminating the multilayer core layer cellulose paper and the multilayer core layer aramid paper to form a core layer, covering the surface of the core layer with the multilayer surface layer cellulose paper, performing hot-pressing solidification in a hot press, and obtaining the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration by adopting a cold-in cold-out mode.
Further limiting, the preparation method of the modified melamine formaldehyde resin in the step 1 is as follows: adding a formaldehyde solution and a polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, adjusting the pH value to 7-10, heating to 65-105 ℃, continuing to react for 1-5 h after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5-2.0 h, adjusting the pH value to 7-9, cooling and discharging to obtain the modified melamine-formaldehyde resin.
Further limiting, the mass ratio of formaldehyde to melamine in the formaldehyde solution is (18-22): 10.
further limiting, the ratio of the amount of the polyvinyl alcohol to the amount of the melamine in the polyvinyl alcohol aqueous solution is (4-30): 100, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 1-20%.
Further limiting, the mass ratio of the benzoguanamine to the melamine is (0.5-25): 100.
and further limiting, in the step 4, the core layer is formed by compounding core layer cellulose paper and core layer aramid paper which are alternately stacked and have 6-30 total layers, wherein the number of the core layer aramid paper accounts for 20-50% of the total number of the layers.
Further defined, the parameters of the hot press curing in the step 4 are as follows: the temperature is 120-200 ℃, the pressure is 6-16 MPa, and the time is 10-60 min.
Compared with the prior art, the invention has the advantages that:
1) the laminated composite board is formed by hot pressing of a plurality of cellulose materials which are impregnated with modified melamine formaldehyde resin with rapid infiltration and flame retardant property. Compared with the traditional cellulose laminated composite board for the rail transit interior decoration, the limit oxygen index of the cellulose laminated composite board can reach 36.5; the combustion performance reaches A level; the burning smoke density is far higher than the standard index requirement, and the flame retardant property is excellent; meanwhile, the pollution resistance of the plate can reach 5 grades, and the plate has excellent pollution resistance. In addition, the cellulose laminated composite board also has good mechanical strength and impact resistance.
2) According to the invention, aramid fiber and other materials are used as core layers, and are laminated with the composite board prepared from the cellulose paper under a certain process condition, so that the problems of high brittleness, flammability and easiness in pollution of the laminated composite board are effectively solved, and the anti-pollution performance of the laminated composite board is effectively improved by introducing polyvinyl alcohol and benzoguanamine into melamine formaldehyde resin. The obtained plate has excellent mechanical strength and flame retardant property.
3) The invention adopts the structure that the aramid paper and the cellulose paper are alternately laminated, thereby not only ensuring the uniformity of the core layer structure, but also improving the shock resistance and the flame retardant property through the mutual cooperation of the two materials, and the cellulose paper is effectively protected by the non-combustible and heat-resistant aramid paper.
Detailed Description
Example 1: the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration is formed by hot-pressing and curing a surface layer and a core layer which are arranged in a laminated mode; the surface layer is 2 layers of cellulose paper impregnated with modified melamine formaldehyde resin, and the core layer is composed of 20 layers of cross-linked paperThe aramid paper impregnated with the modified melamine-formaldehyde resin and the cellulose paper impregnated with the modified melamine-formaldehyde resin are alternately laminated and compounded; wherein the aramid fiber paper has 10 layers, the cellulose paper has 10 layers, and the gram weight of the cellulose paper prepared by adopting chemi-mechanical pulp papermaking is 150g/m2The aramid paper is meta-aramid paper, and the gram weight of the aramid paper is 50g/m2；
The preparation method of the modified melamine formaldehyde resin comprises the following steps: adding a 37 wt% formaldehyde solution and a 10 wt% polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 2.5 hours after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5 hour, adjusting the pH value to 9, cooling and discharging to obtain modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 2:1, the ratio of the amount of polyvinyl alcohol to melamine in the polyvinyl alcohol aqueous solution is 1: 5, the mass ratio of benzoguanamine to melamine is 0.5: 10.
the preparation method of the flame-retardant antifouling cellulose laminated composite board for rail transit interior trim, which is described in preparation example 1, comprises the following steps:
step 1: adding a 37 wt% formaldehyde solution and a 10 wt% polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 2.5 hours after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5 hour, adjusting the pH value to 9, cooling and discharging to obtain modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 2:1, the ratio of the amount of polyvinyl alcohol to melamine in the polyvinyl alcohol aqueous solution is 1: 5, the mass ratio of benzoguanamine to melamine is 0.5: 10;
step 2: soaking the modified melamine formaldehyde resin obtained in the step 1 in cellulose paper, wherein the glue applying amount after soaking is 100% of the dry weight of the cellulose paper, and drying at 70 ℃ to obtain surface cellulose paper;
and step 3: respectively soaking cellulose paper and aramid fiber paper in modified melamine formaldehyde resin, wherein the glue applying amount after soaking is 65% of the dry weight of the cellulose paper and the dry weight of the aramid fiber paper, and drying at 70 ℃ to obtain core layer cellulose paper and core layer aramid fiber paper;
and 4, step 4: and (2) alternately laminating 10 layers of core layer cellulose paper and 10 layers of core layer aramid paper to form a core layer, covering 2 layers (one layer on each of the upper surface and the lower surface of the core layer) of surface layer cellulose paper on the surface of the core layer, then performing hot-pressing curing for 30min in a hot press at the temperature of 140-145 ℃ and the pressure of 10MPa, and obtaining the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration by adopting a cold-in and cold-out mode.
Example 2: the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration is formed by hot-pressing and curing a surface layer and a core layer which are arranged in a laminated mode; the surface layer is 2 layers of cellulose paper impregnated with modified melamine formaldehyde resin, and the core layer is formed by compounding 14 layers of aramid paper impregnated with modified melamine formaldehyde resin and cellulose paper impregnated with modified melamine formaldehyde resin in an alternating and laminated manner; wherein the aramid fiber paper has 6 layers, the cellulose paper has 8 layers, and the gram weight of the cellulose paper prepared by adopting chemi-mechanical pulp papermaking is 120g/m2The aramid paper is meta-aramid paper, and the gram weight of the aramid paper is 80g/m2；
The preparation method of the modified melamine formaldehyde resin comprises the following steps: adding a 37 wt% formaldehyde solution and a 20 wt% polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 2.5 hours after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5 hour, adjusting the pH value to 9, cooling and discharging to obtain the modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 2:1, the ratio of the amount of polyvinyl alcohol to melamine in the aqueous polyvinyl alcohol solution is 0.4:10, the mass ratio of benzoguanamine to melamine is 1: 10.
the preparation method of the flame-retardant antifouling cellulose laminated composite board for rail transit interior trim, which is described in preparation example 2, comprises the following steps:
step 1: adding a 37 wt% formaldehyde solution and a 20 wt% polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 2.5 hours after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5 hour, adjusting the pH value to 9, cooling and discharging to obtain the modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 2:1, the ratio of the amount of polyvinyl alcohol to the amount of melamine in the polyvinyl alcohol aqueous solution is 0.4:10, and the ratio of the amount of benzoguanamine to the amount of melamine is 1: 10;
step 2: soaking the modified melamine formaldehyde resin obtained in the step 1 in cellulose paper, wherein the glue applying amount after soaking is 80% of the dry weight of the cellulose paper, and drying at 70 ℃ to obtain surface cellulose paper;
and step 3: respectively soaking cellulose paper and aramid fiber paper in modified melamine formaldehyde resin, wherein the glue applying amount after soaking is 60% of the dry weight of the cellulose paper and the dry weight of the aramid fiber paper, and drying at 70 ℃ to obtain core layer cellulose paper and core layer aramid fiber paper;
and 4, step 4: and (2) alternately laminating 8 layers of core layer cellulose paper and 6 layers of core layer aramid paper to form a core layer, covering 2 layers (one layer on each of the upper surface and the lower surface of the core layer) of surface layer cellulose paper on the surface of the core layer, then performing hot-pressing curing for 30min in a hot press at the temperature of 140-145 ℃ and the pressure of 10MPa, and obtaining the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration by adopting a cold-in and cold-out mode.
Example 3: the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration is formed by hot-pressing and curing a surface layer and a core layer which are arranged in a laminated mode; the surface layer is 2 layers of cellulose paper impregnated with modified melamine formaldehyde resin, and the coreThe layers are formed by compounding 30 layers of aramid paper impregnated with modified melamine-formaldehyde resin and cellulose paper impregnated with modified melamine-formaldehyde resin; wherein the aramid fiber paper has 15 layers, the cellulose paper has 15 layers, and the gram weight of the cellulose paper prepared by adopting chemi-mechanical pulp papermaking is 200g/m2The aramid paper is meta-aramid paper, and the gram weight of the aramid paper is 29g/m2；
The preparation method of the modified melamine formaldehyde resin comprises the following steps: adding a 37 wt% formaldehyde solution and a 10 wt% polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 2.5 hours after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5 hour, adjusting the pH value to 9, cooling and discharging to obtain modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 2:1, the ratio of the amount of polyvinyl alcohol to melamine in the polyvinyl alcohol aqueous solution is 1.2:10, the mass ratio of benzoguanamine to melamine is 2: 10.
the preparation method of the flame-retardant antifouling cellulose laminated composite board for rail transit interior trim, which is described in preparation example 3, comprises the following steps:
step 1: adding a 37 wt% formaldehyde solution and a 10 wt% polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 2.5 hours after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5 hour, adjusting the pH value to 9, cooling and discharging to obtain modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 2:1, the ratio of the amount of polyvinyl alcohol to the amount of melamine in the polyvinyl alcohol aqueous solution is 1.2:10, and the ratio of the amount of benzoguanamine to the amount of melamine is 5: 10;
step 2: soaking the modified melamine formaldehyde resin obtained in the step 1 in cellulose paper, wherein the glue applying amount after soaking is 85% of the dry weight of the cellulose paper, and drying at 60 ℃ to obtain surface cellulose paper;
and step 3: respectively soaking cellulose paper and aramid fiber paper in modified melamine formaldehyde resin, wherein the glue applying amount after soaking is 65% of the dry weight of the cellulose paper and the dry weight of the aramid fiber paper, and drying at 60 ℃ to obtain core layer cellulose paper and core layer aramid fiber paper;
and 4, step 4: and (2) alternately laminating 15 layers of core layer cellulose paper and 15 layers of core layer aramid paper to form a core layer, covering 1 layer of surface layer cellulose paper on the upper surface and the lower surface of the core layer respectively, then performing hot-pressing solidification for 30min in a hot press at the temperature of 140-145 ℃ and the pressure of 10MPa, and obtaining the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration by adopting a cold-in and cold-out mode.
Comparative example: the cellulose laminated composite board of the embodiment is formed by hot-pressing and curing 20 layers of cellulose paper impregnated with modified melamine formaldehyde resin, wherein the cellulose paper is prepared by adopting chemimechanical pulp papermaking and has the gram weight of 120g/m2The cellulose paper of (a);
the preparation method of the modified melamine formaldehyde resin comprises the following steps: fully and uniformly mixing 37 wt% of formaldehyde solution and melamine, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 3 hours after the solution in the reaction kettle returns to be clear, adjusting the pH value to 9, cooling and discharging to obtain modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 20: 9;
the preparation method of the cellulose laminated composite sheet of the comparative example was carried out as follows:
step 1: fully and uniformly mixing 37 wt% of formaldehyde solution and melamine, heating to 60 ℃, adjusting the pH value to 8, heating to 85 ℃, continuing to react for 3 hours after the solution in the reaction kettle returns to be clear, adjusting the pH value to 9, cooling and discharging to obtain modified melamine-formaldehyde resin; wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is 20: 9;
step 2: soaking the modified melamine formaldehyde resin obtained in the step 1 in cellulose paper, wherein the glue applying amount after soaking is 65% of the dry weight of the cellulose paper, and drying at 70 ℃ to obtain surface cellulose paper;
and step 3: and (3) carrying out hot-pressing solidification on 20 layers of surface cellulose paper in a hot press at the temperature of 140-145 ℃ and the pressure of 10MPa for 30min, and obtaining the cellulose laminated composite board by adopting a cold-in cold-out mode.
The flame-retardant antifouling cellulose laminated composite board for rail transit interior trim of the embodiments 1 to 3 and the cellulose laminated composite board of the comparative example were subjected to surface pollution resistance test and impact resistance test by selecting coffee and ink as pollution sources according to the regulations of the national standard GB/T17657-2013 physicochemical property test methods for artificial boards and veneered artificial boards, and the test results are shown in Table 1.
The flame-retardant antifouling cellulose laminated composite sheet for rail transit interior trim of examples 1 to 3 and the cellulose laminated composite sheet of the comparative example were subjected to combustion performance and smoke density tests as specified in standard TB/T3237-2010 "technical conditions for flame retardancy of interior materials for motor train units", and the test results are shown in table 1.
TABLE 1
Figure BDA0003136218940000071

Claims (10)

1. The flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration is characterized by being formed by hot-pressing and curing a surface layer and a core layer which are arranged in a laminated mode; the surface layer is a plurality of layers of cellulose paper impregnated with modified melamine formaldehyde resin, and the core layer is formed by compounding a plurality of layers of aramid paper impregnated with modified melamine formaldehyde resin and cellulose paper impregnated with modified melamine formaldehyde resin which are alternately stacked.
2. The laminated composite board of flame-retardant antifouling cellulose for rail transit interior decoration as claimed in claim 1, wherein the preparation method of the modified melamine formaldehyde resin is as follows: adding a formaldehyde solution and a polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, adjusting the pH value to 7-10, heating to 65-105 ℃, continuing to react for 1-5 h after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5-2.0 h, adjusting the pH value to 7-9, cooling and discharging to obtain the modified melamine-formaldehyde resin.
3. The laminated composite board of flame-retardant antifouling cellulose for rail transit interior decoration as claimed in claim 2, wherein the mass ratio of formaldehyde to melamine in the formaldehyde solution is (18-22): 10, the ratio of the amount of polyvinyl alcohol to the amount of melamine in the polyvinyl alcohol aqueous solution is (4-30): 100, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 1-20%, and the mass ratio of the benzoguanamine to the melamine is (0.5-25): 100.
4. the laminated composite board of claim 1, wherein the cellulose paper is prepared by chemical mechanical pulp papermaking and has a grammage of 70g/m2～200g/m2The aramid paper is meta-aramid paper, and the gram weight of the aramid paper is 29g/m2～110g/m2。
5. The laminated composite board of the flame-retardant antifouling cellulose for the rail transit interior decoration as claimed in claim 1, wherein the surface layer is 1-3 layers of cellulose paper impregnated with the modified melamine-formaldehyde resin, and the core layer is formed by compounding 6-30 layers of aramid paper impregnated with the modified melamine-formaldehyde resin and cellulose paper impregnated with the modified melamine-formaldehyde resin, wherein the number of aramid paper layers accounts for 20-50% of the total number of layers.
6. The preparation method of the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration according to any one of claims 1 to 5, which is characterized by comprising the following steps:
step 1: preparing modified melamine formaldehyde resin;
step 2: soaking the modified melamine formaldehyde resin obtained in the step 1 in cellulose paper, wherein the gluing amount is 80-110% of the dry weight of the cellulose paper, and drying to obtain surface cellulose paper;
and step 3: respectively dipping cellulose paper and aramid paper into modified melamine formaldehyde resin, wherein the gluing amount is 60-100% of the dry weight of the cellulose paper and the dry weight of the aramid paper, and drying to obtain core layer cellulose paper and core layer aramid paper;
and 4, step 4: and alternately laminating the multilayer core layer cellulose paper and the multilayer core layer aramid paper to form a core layer, covering the surface of the core layer with the multilayer surface layer cellulose paper, performing hot-pressing solidification in a hot press, and obtaining the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration by adopting a cold-in cold-out mode.
7. The preparation method of the flame-retardant antifouling cellulose laminated composite board for rail transit interior decoration according to claim 6, wherein the preparation method of the modified melamine formaldehyde resin in step 1 is as follows: adding a formaldehyde solution and a polyvinyl alcohol aqueous solution into a reaction kettle, starting stirring, adding melamine, fully and uniformly mixing, adjusting the pH value to 7-10, heating to 65-105 ℃, continuing to react for 1-5 h after the solution in the reaction kettle returns to clear, then adding benzoguanamine, reacting until the solution returns to clear again, continuing to react for 0.5-2.0 h, adjusting the pH value to 7-9, cooling and discharging to obtain the modified melamine-formaldehyde resin.
8. The preparation method of the flame-retardant antifouling cellulose laminated composite board for the rail transit interior decoration, according to claim 7, is characterized in that the mass ratio of the formaldehyde solution to the melamine is (18-22): 10, the ratio of the amount of polyvinyl alcohol to the amount of melamine in the polyvinyl alcohol aqueous solution is (4-30): 100, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 1-20%, and the mass ratio of the benzoguanamine to the melamine is (0.5-25): 100.
9. the preparation method of the flame-retardant antifouling cellulose laminated composite board for the rail transit interior, according to claim 6, is characterized in that in the step 4, the core layer is formed by compounding core layer cellulose paper and core layer aramid paper which are alternately laminated and have 6-30 total layers, wherein the number of the core layer aramid paper accounts for 20-50% of the total number of the layers.
10. The preparation method of the flame-retardant antifouling cellulose laminated composite board for rail transit interior decoration according to claim 6, wherein the parameters of the hot-press curing in the step 4 are as follows: the temperature is 120-200 ℃, the pressure is 6-16 MPa, and the time is 10-60 min.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090155593A1 (en) * 2007-12-18 2009-06-18 O'brien Kevin Francis Through color high pressure decorative laminate and method of making same
CN101992653A (en) * 2009-08-13 2011-03-30 沁阳永威装饰材料有限公司 Fireproof decorative sheet and manufacturing method thereof
CN205021710U (en) * 2015-05-29 2016-02-10 佛山市源逵装饰材料有限公司 Melamine multiply -plywood
CN105623571A (en) * 2016-02-25 2016-06-01 广西大学 Method for preparing melamine modified urea-formaldehyde resin adhesive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090155593A1 (en) * 2007-12-18 2009-06-18 O'brien Kevin Francis Through color high pressure decorative laminate and method of making same
CN101992653A (en) * 2009-08-13 2011-03-30 沁阳永威装饰材料有限公司 Fireproof decorative sheet and manufacturing method thereof
CN205021710U (en) * 2015-05-29 2016-02-10 佛山市源逵装饰材料有限公司 Melamine multiply -plywood
CN105623571A (en) * 2016-02-25 2016-06-01 广西大学 Method for preparing melamine modified urea-formaldehyde resin adhesive

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