CN115094681A - Fingerprint-resistant impregnated paper and preparation method thereof - Google Patents
Fingerprint-resistant impregnated paper and preparation method thereof Download PDFInfo
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- CN115094681A CN115094681A CN202210784060.1A CN202210784060A CN115094681A CN 115094681 A CN115094681 A CN 115094681A CN 202210784060 A CN202210784060 A CN 202210784060A CN 115094681 A CN115094681 A CN 115094681A
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- formaldehyde resin
- fingerprint
- modified melamine
- impregnated paper
- melamine
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- 238000002360 preparation method Methods 0.000 title abstract description 56
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 130
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims abstract description 96
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 24
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000853 adhesive Substances 0.000 claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 18
- 238000007598 dipping method Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003292 glue Substances 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- -1 perfluoroalkyl ethanol Chemical compound 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- JCMNMOBHVPONLD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F JCMNMOBHVPONLD-UHFFFAOYSA-N 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 21
- 230000003666 anti-fingerprint Effects 0.000 abstract description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000005299 abrasion Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001514 detection method Methods 0.000 description 12
- 238000011109 contamination Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- QXJCOPITNGTALI-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutan-1-ol Chemical compound OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F QXJCOPITNGTALI-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
- D21H27/28—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures treated to obtain specific resistance properties, e.g. against wear or weather
-
- 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
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application relates to the technical field of furniture facing decorative paper, in particular to fingerprint-resistant impregnated paper and a preparation method thereof. An anti-fingerprint impregnated paper is prepared by impregnating a base material with a modified melamine formaldehyde resin impregnating adhesive and curing; the modified melamine-formaldehyde resin impregnating adhesive comprises modified melamine-formaldehyde resin and a curing agent; the modified melamine formaldehyde resin is prepared from the following raw materials in parts by weight: 20-32 parts of formaldehyde, 5-10 parts of water, 48-70 parts of melamine, 2-10 parts of fluoroalcohol and 5-10 parts of silica sol; the preparation method comprises the following steps: stirring and mixing the modified melamine-formaldehyde resin and the curing agent to obtain modified melamine-formaldehyde resin impregnating adhesive; and (3) dipping the base material in the modified melamine formaldehyde resin dipping glue, and drying to obtain the fingerprint-resistant dipping paper. The fingerprint-resistant impregnated paper has excellent hydrophobic property, pollution resistance property, fingerprint resistance property and wear resistance.
Description
Technical Field
The application relates to the technical field of furniture facing decorative paper, in particular to fingerprint-resistant impregnated paper and a preparation method thereof.
Background
The impregnated paper is a kind of plain paper or printing paper which is impregnated with amino resin and dried to obtain a kind of film paper with a certain resin content and volatile matter content, and its surface is bright and soft. The impregnated paper and the substrate board are glued by a hot pressing process to manufacture the decorative panel with excellent surface performance and beautiful patterns. Therefore, the impregnated paper has been widely used in various finishing and decorating materials for finishing, furniture, cabinets, wardrobes, floors, and laminate flooring.
However, the decorative panel in the above environment is often touched by both hands of a person, so that the impregnated paper on the surface of the decorative panel is easily stained with fingerprints, which affects the beauty of the decorative panel. Therefore, there is a need for an impregnated paper having fingerprint resistance.
Disclosure of Invention
In order to improve the fingerprint adhesion resistance of the impregnated paper and improve the influence of fingerprints on the aesthetic property of a decorative panel, the application provides the fingerprint adhesion resistance impregnated paper and the preparation method thereof.
In a first aspect, the application provides an anti-fingerprint impregnated paper, which adopts the following technical scheme:
an anti-fingerprint impregnated paper is prepared by impregnating a base material with a modified melamine formaldehyde resin impregnating adhesive and curing;
the modified melamine-formaldehyde resin impregnating adhesive comprises modified melamine-formaldehyde resin and a curing agent;
the modified melamine formaldehyde resin is prepared from the following raw materials in parts by weight:
20-32 parts of formaldehyde;
5-10 parts of water;
48-70 parts of melamine;
2-10 parts of fluoroalcohol;
5-10 parts of silica sol.
The melamine and formaldehyde are subjected to hydroxymethylation through an addition reaction, and then the melamine and the hydroxymethylated melamine are subjected to condensation reaction, or the hydroxymethylated melamine is subjected to self-condensation reaction to generate the melamine-formaldehyde resin connected by methylene and ether bonds.
By adopting the technical scheme, on one hand, the fluorine alcohol and the silicon dioxide sol both contain hydroxyl, and in the total raw materials for preparing the melamine formaldehyde resin, the fluorine alcohol and the silicon dioxide sol are grafted to the side chain of the melamine formaldehyde resin through the hydroxyl. Therefore, the friction coefficient and the surface tension of the surface of the modified melamine-formaldehyde resin are reduced through the synergistic effect of fluorine and silicon molecules, and the hydrophobicity, pollution resistance, fingerprint resistance and abrasion resistance of the modified melamine-formaldehyde resin are improved. On the other hand, the silica sol is grafted to the side chain of the melamine formaldehyde resin, so that the cohesive energy of the side chain of the melamine formaldehyde resin is improved, and the wear resistance of the modified melamine formaldehyde resin is further improved. Meanwhile, after the obtained modified melamine formaldehyde resin impregnated glue is cured, a fold and ripple structure is formed on the surface, so that the full scattering effect of light is realized, and the existence sense of fingerprints on the impregnated paper is weakened.
Therefore, the impregnated paper prepared by the modified melamine formaldehyde resin impregnated adhesive has high hydrophobic and pollution-resistant performances and fingerprint-resistant performances after being worn.
Preferably, the weight ratio of the silica sol to the fluoroalcohol is 1 (0.5-1).
By adopting the technical scheme, the weight ratio of the silica sol to the fluoroalcohol is further optimized, the synergistic effect of the fluorine-silicon molecules is favorably improved, and the hydrophobic property, the pollution resistance and the fingerprint resistance of the impregnated paper prepared by the obtained modified melamine formaldehyde resin impregnated adhesive are further adopted.
Preferably, the fluoroalcohol is perfluoroalkyl alcohol, hexafluoroisopropanol, hexafluorobutanol or perfluorobutyl alcohol.
By adopting the technical scheme, on one hand, the perfluoroalkyl alcohol, the hexafluoroisopropanol, the hexafluorobutanol and the perfluorobutyl alcohol have the molecular weight within the range of 100-300 and are grafted to the side chain of the melamine formaldehyde resin, so that the influence on the viscosity of the obtained modified melamine formaldehyde resin is small, the fluidity of the modified melamine formaldehyde resin is favorably improved, the permeability and wettability of the obtained modified melamine formaldehyde resin impregnating adhesive to a base material are improved, and the effect of enhancing the bonding strength of the base material is achieved. On the other hand, the perfluoroalkyl alcohol, hexafluoroisopropanol, hexafluorobutanol or perfluorobutyl alcohol is grafted on the side chain of the modified melamine-formaldehyde resin, so that the synergistic effect of fluorine and silicon molecules in the modified melamine-formaldehyde resin is further improved, the friction coefficient and surface tension of the surface of the modified melamine-formaldehyde resin are further reduced, and the hydrophobic and oleophobic properties and the fingerprint resistance of the obtained modified melamine-formaldehyde resin impregnating adhesive are improved.
Preferably, the silica sol is further subjected to modification treatment, and the modification treatment comprises the following steps: adding polyethylene glycol into the silica sol, stirring and mixing to obtain the modified silica sol.
By adopting the technical scheme, the polyethylene glycol can be adsorbed on the surface of the silicon dioxide sol through the hydrogen bond effect, the obtained modified silicon dioxide sol has better hydrophilicity, the dispersibility and stability of the modified silicon dioxide sol in a modified melamine formaldehyde resin mixed system can be improved, the efficiency of grafting the modified silicon dioxide sol to a melamine formaldehyde resin side chain is improved, the hydrophobic, oleophobic and anti-fingerprint properties of the modified melamine formaldehyde resin are further improved, and the stability of the modified melamine formaldehyde resin can be improved. Meanwhile, the modified silica sol also has excellent film forming performance and hardness, and the wear resistance of the modified melamine formaldehyde resin can be improved.
Therefore, the impregnating adhesive and the impregnating paper prepared by the modified melamine formaldehyde resin have more excellent hydrophobicity, pollution resistance, wear resistance and fingerprint resistance.
Preferably, the weight ratio of the silica sol to the polyethylene glycol is 1 (0.02-0.06).
By adopting the technical scheme, a small amount of polyethylene glycol can improve the dispersibility of the modified silica sol, and is also beneficial to grafting the modified silica sol to the side chain of the melamine formaldehyde resin, so that the cured fold and ripple structure of the obtained modified melamine formaldehyde resin impregnated glue is further improved, and the existence sense of fingerprints on the impregnated paper is weakened.
Preferably, the molecular weight of the polyethylene glycol is 400-800.
Preferably, the preparation method of the modified melamine formaldehyde resin comprises the following steps:
a1: mixing formaldehyde and water to obtain a mixture A;
a2: adjusting the pH value of the mixture A to 8-9.5, keeping the temperature at 70-85 ℃ for 20-30min, adding melamine, and stirring and mixing for 20-30min to obtain a mixture B;
a3: adding the silica sol and the fluorine alcohol into the mixture B, stirring and mixing for 120-240min to obtain the modified melamine-formaldehyde resin.
By adopting the technical scheme, under the reaction that the melamine formaldehyde resin is mainly synthesized by formaldehyde and melamine, the silicon dioxide sol and the fluoroalcohol are introduced into the side chain of the melamine formaldehyde resin, so that the obtained modified melamine formaldehyde resin has excellent hydrophobic and pollution-resistant properties and fingerprint-resistant properties. Meanwhile, the preparation method of the modified melamine formaldehyde resin has the advantages of simple process, convenience in operation and capability of large-scale production.
In a second aspect, the application provides a preparation method of fingerprint-resistant impregnated paper, which adopts the following technical scheme: a preparation method of fingerprint-resistant impregnated paper comprises the following preparation steps:
s1 glue mixing: stirring and mixing the modified melamine-formaldehyde resin and the curing agent to obtain modified melamine-formaldehyde resin impregnating adhesive;
s2 gum dipping: and (3) dipping the base material in the modified melamine formaldehyde resin dipping glue, and drying to obtain the fingerprint-resistant dipping paper.
By adopting the technical scheme, the modified melamine-formaldehyde resin impregnating adhesive prepared by adding raw materials such as curing agent and the like into the modified melamine-formaldehyde resin has excellent permeability and wettability, has high bonding strength to a base material, and has excellent hydrophobic, oleophobic, fingerprint-resistant and wear-resistant properties after being dried, cured and formed into a film. Meanwhile, the fold and ripple structure formed on the surface of the base material is beneficial to realizing the full scattering effect of light, and further weakens the existing sense of fingerprints on the impregnated paper.
In summary, the present application has the following beneficial effects:
1. in the process of synthesizing the melamine-formaldehyde resin from formaldehyde and melamine, the fluoroalcohol and the silica sol are grafted to the side chain of the melamine-formaldehyde resin through hydroxyl groups, and the friction coefficient and the surface tension of the surface of the modified melamine-formaldehyde resin are reduced through the synergistic effect of fluorine and silicon molecules, so that the impregnated paper obtained by impregnating the impregnated glue prepared from the modified melamine-formaldehyde resin has excellent hydrophobicity, pollution resistance, fingerprint resistance and wear resistance;
2. in the application, fluoroalkyl ethanol, hexafluoroisopropanol or perfluorobutanol with the molecular weight within the range of 100-300 is preferably grafted on the side chain of the modified melamine-formaldehyde resin, so that the influence on the viscosity of the obtained modified melamine-formaldehyde resin is small, and the improvement on the permeability and wettability of the obtained modified melamine-formaldehyde resin impregnating adhesive on a base material is facilitated;
3. according to the preparation method, the polyethylene glycol modified silica sol is adopted, so that the dispersity and stability of the modified silica sol in a modified melamine-formaldehyde resin mixed system are improved, the modified silica sol is favorably promoted to be grafted on the side chain of the melamine-formaldehyde resin, and the hydrophobicity, pollution resistance, fingerprint resistance and wear resistance of the finally obtained modified melamine-formaldehyde resin impregnating compound are improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation of modified Melamine-Formaldehyde resin
Preparation example 1
A modified melamine formaldehyde resin, the components and their respective weights are shown in Table 1, and is prepared by the following steps:
a1: mixing formaldehyde and diethylene glycol to obtain a mixture A;
a2: adjusting the pH value of the mixture A to 8, keeping the temperature at 70 ℃ for 20min, adding melamine, and stirring and mixing for 20min to obtain a mixture B;
a3: and adding the silica sol and the fluoroalcohol into the mixture B, and stirring and mixing for 120min to obtain the modified melamine-formaldehyde resin.
The silica sol is transparent liquid, the content of silica is 28-32%, the pH value is 5-7, and the granularity is 10 nm; the fluoroalcohol is perfluoroalkyl alcohol.
Preparation examples 2 to 3
A modified melamine-formaldehyde resin which differs from preparation example 1 in that the components and their respective weights are shown in table 1.
TABLE 1 Components and weights (kg) thereof in preparation examples 1-3
Preparation example 4
A modified melamine-formaldehyde resin which is different from that in production example 2 in that the fluorine alcohol is hexafluoroisopropanol.
Preparation example 5
A modified melamine-formaldehyde resin which is different from preparation example 2 in that the fluoroalcohol is hexafluorobutanol.
Preparation example 6
A modified melamine formaldehyde resin is different from the preparation example 2 in that the silica sol is also subjected to modification treatment, and the modification treatment comprises the following steps: adding polyethylene glycol into the silica sol, stirring and mixing for 6 hours at 50 ℃ to obtain the modified silica sol.
The molecular weight of the polyethylene glycol is 200.
Preparation examples 7 to 10
A modified melamine formaldehyde resin was different from preparation example 6 in that the weights of silica sol and polyethylene glycol are shown in Table 2.
TABLE 2 weight (kg) of silica sol and polyethylene glycol in preparation examples 7 to 10
Preparation examples 11 to 14
A modified melamine-formaldehyde resin which is different from preparation example 8 in that the molecular weight of polyethylene glycol in the step of modifying the silica sol is shown in Table 3.
TABLE 3 molecular weights of polyethylene glycols in preparation examples 11 to 14
Preparation example 15
A modified melamine-formaldehyde resin which is different from the modified melamine-formaldehyde resin prepared in preparation example 12 in that the modified melamine-formaldehyde resin is prepared by the following steps:
a1: mixing formaldehyde and diethylene glycol to obtain a mixture A;
a2: adjusting the pH value of the mixture A to 9.5, keeping the temperature at 85 ℃ for 30min, adding melamine, and stirring and mixing for 30min to obtain a mixture B;
a3: and adding the silica sol and the fluoroalcohol into the mixture B, and stirring and mixing for 240min to obtain the modified melamine-formaldehyde resin.
The modified melamine-formaldehyde resins obtained in preparation examples 1 to 15 of the present application were subjected to storage stability detection, pre-curing degree detection and volatile content detection, and the detection standards and detection results were as follows:
and (3) detecting the storage stability: the days when the modified melamine-formaldehyde resin in a sealed package was stored at room temperature (10-20 ℃) in the dark until the viscosity did not exceed 1500 cps were expressed, and the larger the days was, the better the storage stability was expressed.
And (3) detecting the pre-curing degree and the volatile content: reference is made to LYT 1143-2006.
And (3) detecting the release amount of formaldehyde: reference is made to GB/T15102-2017.
Tests show that the modified melamine-formaldehyde resins obtained in preparation examples 1 to 15 of the present application have a storage stability of 55 days or more, a precuring degree of 52 to 56%, a volatile matter content of 6.5 to 8%, and a formaldehyde emission of 0.2 mg/L.
The fingerprint-resistant impregnated paper obtained in the examples of the present application and the impregnated paper obtained in the comparative examples were subjected to the detection of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the detection criteria were as follows:
detecting a hydrophilic angle: the water contact angle was measured using a domestic contact angle measuring instrument Alpha developed by bethon science.
And (3) detecting the surface wear resistance: refer to 4.42 surface abrasion resistance determination in GB/T17657-2013-method 1.
And (3) detecting the surface pollution resistance: referring to a 4.41 surface pollution resistance performance determination-method 2 in GB/T17657-2013, marking as an initial surface pollution resistance performance; and then, carrying out surface anti-pollution performance detection on the impregnated paper with the surface subjected to surface wear resistance detection, and recording the surface anti-pollution performance as the wear surface anti-pollution performance.
Detecting the fingerprint resistance of the surface: adopting artificial sweat test, soaking the impregnated paper in artificial sweat for 24h, then airing, detecting sweat traces on the surface of the impregnated paper, and recording as initial surface fingerprint resistance; and then, carrying out surface fingerprint resistance detection on the impregnated paper with the surface subjected to surface wear resistance detection, and recording as the wear surface fingerprint resistance.
Examples
Example 1
An anti-fingerprint impregnated paper is prepared by impregnating a base material with a modified melamine formaldehyde resin impregnating adhesive and curing;
the modified melamine-formaldehyde resin impregnating compound is prepared by mixing 100kg of modified melamine-formaldehyde resin, 0.1kg of curing agent, 0.3kg of release agent and 0.3kg of penetrating agent.
The preparation steps of the fingerprint-resistant impregnated paper are as follows:
s1 glue mixing: mixing the modified melamine-formaldehyde resin, the curing agent, the release agent and the penetrating agent, and stirring and mixing for 7min at 40 ℃ to obtain modified melamine-formaldehyde resin impregnating adhesive;
s2 gum dipping: and (3) dipping the base material in the modified melamine formaldehyde resin dipping glue, and drying to obtain the fingerprint-resistant dipping paper.
Wherein, the modified melamine formaldehyde resin is prepared from the preparation example 1.
Examples 2 to 3
An anti-fingerprint impregnated paper is different from the impregnated paper in example 1 in that the total raw materials for preparing the melamine formaldehyde resin are different in each component and the corresponding weight, that is, the modified melamine formaldehyde resin is prepared by the preparation examples in Table 4.
Table 4 preparation of modified melamine formaldehyde resins from examples 2 to 3
| Example 1 | Example 2 | Example 3 |
| Preparation example 1 | Preparation example 2 | Preparation example 3 |
The fingerprint-resistant impregnated papers obtained in examples 1 to 3 were subjected to the tests of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the test results are shown in table 5.
TABLE 5 results of testing the properties of examples 1 to 3
As can be seen from the results of the performance tests in Table 5, the anti-fingerprint impregnated papers obtained in examples 1 to 3 of the present application have excellent hydrophobic properties, surface stain resistance, surface abrasion resistance and surface anti-fingerprint properties. Meanwhile, after being worn, the coating still has excellent surface pollution resistance and surface fingerprint resistance.
Example 4
A fingerprint impregnated paper is different from the impregnated paper in example 2 in that the fluorine alcohol in the total raw materials for preparing the melamine formaldehyde resin is hexafluoroisopropanol, namely, the modified melamine formaldehyde resin is prepared from the preparation example 4.
Example 5
A fingerprint impregnated paper is different from the impregnated paper in example 2 in that the fluorine alcohol in the total raw materials for preparing the melamine formaldehyde resin is hexafluorobutanol, namely, the modified melamine formaldehyde resin is prepared from the preparation example 5.
The fingerprint-resistant impregnated papers obtained in examples 4 to 5 were subjected to the tests of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the test results are shown in table 6.
TABLE 6 results of testing each property of examples 4 to 5
From the performance detection results in table 6, it can be seen that, in the total raw materials for preparing the melamine formaldehyde resin, the fluoroalcohol is perfluoroalkyl alcohol, hexafluoroisopropanol or hexafluorobutanol, and the obtained fingerprint-resistant impregnated paper has relatively excellent hydrophobic performance.
Since the fluoroalcohol is perfluoroalkyl alcohol, hexafluoroisopropanol, hexafluorobutanol or perfluorobutyl alcohol in the embodiment of the application, the obtained fingerprint-resistant impregnated paper has similar effects on hydrophobicity, surface pollution resistance, surface wear resistance and surface fingerprint resistance. Therefore, in the examples of the present application, the fluoroalcohol is the perfluoroalkyl group ethanol, hexafluoroisopropanol or hexafluorobutanol, which is only taken as an example for brief description, but does not affect the application of other fluoroalcohols in the present application.
Examples 6 to 10
The fingerprint impregnated paper is different from the impregnated paper in example 2 in that in the total raw materials for preparing the melamine formaldehyde resin, the silica sol is also subjected to modification treatment, namely, the modified melamine formaldehyde resin is prepared by the preparation examples in Table 7.
TABLE 7 preparation of modified Melamine-Formaldehyde resins in examples 6-10
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 |
| Preparation example 6 | Preparation example 7 | Preparation example 8 | Preparation example 9 | Preparation example 10 |
The fingerprint-resistant impregnated papers obtained in examples 6 to 10 were subjected to the tests of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the test results are shown in table 8.
TABLE 8 results of testing the properties of examples 6 to 10
From the results of the property measurements in table 8, it is understood that the impregnated papers obtained in examples 6 to 10 have better hydrophobic property, surface stain resistance, surface abrasion resistance and surface fingerprint resistance than the impregnated paper obtained in example 2.
Among them, the impregnated papers obtained in examples 7 to 9 are better in hydrophobic property, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance than the impregnated papers obtained in examples 6 and 10, and the reason for this is analyzed probably because the weight of silica sol and polyethylene glycol in the modification treatment of silica sol is controlled, the obtained modified silica sol has a certain particle size and better dispersibility, the grafting ratio in the modified melamine formaldehyde resin is higher, and the film forming property of the obtained impregnated glue on the surface of the impregnated paper is better, so that the impregnated paper has more excellent hydrophobic property, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance.
Examples 11 to 14
An impregnated paper for fingerprints is different from example 8 in that the molecular weight of polyethylene glycol in the total raw materials for preparing melamine formaldehyde resin is different, that is, the modified melamine formaldehyde resin is prepared by the preparation examples in table 9.
TABLE 9 preparation of modified Melamine-Formaldehyde resins in examples 11-14
| Example 11 | Example 12 | Example 13 | Example 14 |
| Preparation example 11 | Preparation example 12 | Preparation example 13 | Preparation example 14 |
The fingerprint-resistant impregnated papers obtained in examples 11 to 14 were subjected to the tests of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the test results are shown in Table 9.
TABLE 9 results of examining the properties of examples 11 to 14
From the results of the property measurements in Table 9, it can be seen that the impregnated papers obtained in examples 11 to 14 have better hydrophobic properties and surface abrasion resistance than the impregnated paper obtained in example 8.
Among them, the impregnated papers obtained in examples 11 to 13 were superior to those obtained in examples 8 and 14 in hydrophobic property and surface abrasion resistance, and the reason for this was analyzed to be that the molecular weight of polyethylene glycol in the modification treatment of silica sol was controlled, which positively affects the particle size and dispersibility of the resulting modified silica sol, and the graft ratio in the modified melamine-formaldehyde resin was increased, so that the impregnated papers had superior hydrophobic property and surface abrasion resistance.
Example 15
A fingerprint impregnated paper is different from example 12 in that the preparation step of the melamine formaldehyde resin is different, namely, the modified melamine formaldehyde resin is prepared by the preparation example 15.
The fingerprint-resistant impregnated paper obtained in example 15 was subjected to the tests of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the test results are shown in table 10.
TABLE 10 test results of various properties of example 15
Comparative example
Comparative example 1
An impregnated paper which differs from example 2 in that, in the total raw material for preparing the modified melamine formaldehyde resin, an equal amount of fluoroalcohol is used instead of silica sol.
Comparative example 2
The impregnated paper is different from the impregnated paper in example 2 in that in the total raw materials for preparing the modified melamine formaldehyde resin, an equivalent amount of acidic nano silica aqueous dispersion is adopted to replace silica sol, wherein the silica content of the silica dispersion is 25%, the pH value is 2-6, and the particle size is 10 nm.
Comparative example 3
An impregnated paper which differs from example 2 in that, in the total raw material for preparing the modified melamine formaldehyde resin, equivalent BNK-4046 fluorosilicone surfactant is used instead of fluoroalcohol.
The impregnated papers obtained in the above comparative examples 1 to 3 were subjected to the tests of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the test results are shown in table 11.
TABLE 11 results of testing the properties of comparative examples 1 to 3
From the results of the performance tests in table 11, it is understood that the impregnated papers obtained in comparative examples 1 to 3 are significantly reduced in the hydrophobic property, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, compared to the impregnated paper obtained in example 1. Therefore, in the total raw materials for preparing the melamine formaldehyde resin, the fluoroalcohol and the silica sol are grafted to the side chain of the melamine formaldehyde resin, so that the hydrophobic property, the surface pollution resistance, the surface wear resistance and the surface fingerprint resistance of the obtained modified melamine formaldehyde resin can be improved. Therefore, the impregnated paper prepared by the modified melamine formaldehyde resin impregnated glue still has very high hydrophobic property, surface pollution resistance and surface fingerprint resistance after being worn.
Further analysis of example 1 and comparative example 3 revealed that, although the impregnated paper obtained in comparative example 3 had better hydrophobic property, surface stain resistance and surface fingerprint resistance than those of comparative examples 1 and 2, the hydrophobic property, surface stain resistance and surface fingerprint resistance after abrasion were lower than those of example 1. Therefore, the surface of the impregnated paper obtained by grafting the fluoroalcohol and the silica sol to the melamine formaldehyde resin side chain still has high hydrophobic property, surface pollution resistance and surface fingerprint resistance after being abraded.
The modified melamine formaldehyde resins prepared in comparative examples 1 to 3 were subjected to storage stability test, pre-cure degree test and volatile content test, and the test results were as follows:
tests show that the modified melamine-formaldehyde resins obtained in comparative examples 1 to 3 have storage stability days of 45 to 48 days, pre-curing degree of 48 to 50%, volatile matter content of 8 to 9%, and formaldehyde emission of 0.2 mg/L.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The fingerprint-resistant impregnated paper is characterized by being prepared by curing a base material impregnated modified melamine formaldehyde resin impregnated adhesive;
the modified melamine-formaldehyde resin impregnating adhesive comprises modified melamine-formaldehyde resin and a curing agent;
the modified melamine formaldehyde resin is prepared from the following raw materials in parts by weight:
20-32 parts of formaldehyde;
5-10 parts of water;
48-70 parts of melamine;
2-10 parts of fluoroalcohol;
5-10 parts of silica sol.
2. The fingerprint resistant impregnated paper of claim 1, wherein the weight ratio of the silica sol to the fluoroalcohol is 1 (0.5-1).
3. The fingerprint resistant impregnated paper of claim 1, wherein the fluoroalcohol is perfluoroalkyl ethanol, hexafluoroisopropanol, hexafluorobutanol or perfluorobutyl ethanol.
4. The fingerprint-resistant impregnated paper according to claim 1, wherein the silica sol is further subjected to a modification treatment, the modification treatment comprising the steps of: and adding polyethylene glycol into the silica sol, and stirring and mixing to obtain the modified silica sol.
5. The fingerprint-resistant impregnated paper according to claim 4, wherein the weight ratio of the silica sol to the polyethylene glycol is 1 (0.02-0.06).
6. The fingerprint-resistant impregnated paper as claimed in claim 4, wherein the molecular weight of the polyethylene glycol is 400-800.
7. The fingerprint-resistant impregnated paper according to claim 1, wherein the modified melamine formaldehyde resin is prepared by the following method:
a1: mixing formaldehyde and water to obtain a mixture A;
a2: adjusting the pH value of the mixture A to 8-9.5, keeping the temperature at 70-85 ℃ for 20-30min, adding melamine, and stirring and mixing for 20-30min to obtain a mixture B;
a3: adding the silica sol and the fluorine alcohol into the mixture B, stirring and mixing for 120-240min to obtain the modified melamine-formaldehyde resin.
8. The method for preparing the fingerprint resistant impregnated paper according to any one of claims 1 to 7, comprising the steps of:
s1 glue mixing: stirring and mixing the modified melamine-formaldehyde resin and the curing agent to obtain modified melamine-formaldehyde resin impregnating adhesive;
s2 gum dipping: and (3) dipping the base material in the modified melamine formaldehyde resin dipping glue, and drying to obtain the fingerprint-resistant dipping paper.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117107549A (en) * | 2023-10-10 | 2023-11-24 | 江苏璞丽达数码科技有限公司 | Fingerprint-resistant wear-resistant nano decorative paper and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061577A (en) * | 1988-11-28 | 1991-10-29 | Allied-Signal Inc. | Magnetic coating compositions containing fluoropolyols |
| JP2011152659A (en) * | 2010-01-26 | 2011-08-11 | Ibiden Kenso Co Ltd | Decorative melamine sheet and method for producing the same |
| CN102154930A (en) * | 2011-03-23 | 2011-08-17 | 天津市鑫源森达新材料科技有限公司 | Preparation method of impregnated paper for decorative surface on high-glossiness furniture |
| CN102643303A (en) * | 2012-04-13 | 2012-08-22 | 阜新恒通氟化学有限公司 | Preparation method of fluoride anti-fingerprint agent |
| KR101406932B1 (en) * | 2013-12-31 | 2014-06-19 | 설태윤 | Polyurea coating composition modified by functional alchol for floor-waterproof, and construction method using the same |
| CN110951212A (en) * | 2019-12-21 | 2020-04-03 | 北华大学 | Preparation method of nano silicon dioxide modified melamine formaldehyde resin |
| CN114686087A (en) * | 2022-04-29 | 2022-07-01 | 深圳德诚达光电材料有限公司 | High-wear-resistance fluorine-containing anti-fingerprint agent and preparation method thereof |
-
2022
- 2022-07-05 CN CN202210784060.1A patent/CN115094681B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061577A (en) * | 1988-11-28 | 1991-10-29 | Allied-Signal Inc. | Magnetic coating compositions containing fluoropolyols |
| JP2011152659A (en) * | 2010-01-26 | 2011-08-11 | Ibiden Kenso Co Ltd | Decorative melamine sheet and method for producing the same |
| CN102154930A (en) * | 2011-03-23 | 2011-08-17 | 天津市鑫源森达新材料科技有限公司 | Preparation method of impregnated paper for decorative surface on high-glossiness furniture |
| CN102643303A (en) * | 2012-04-13 | 2012-08-22 | 阜新恒通氟化学有限公司 | Preparation method of fluoride anti-fingerprint agent |
| KR101406932B1 (en) * | 2013-12-31 | 2014-06-19 | 설태윤 | Polyurea coating composition modified by functional alchol for floor-waterproof, and construction method using the same |
| CN110951212A (en) * | 2019-12-21 | 2020-04-03 | 北华大学 | Preparation method of nano silicon dioxide modified melamine formaldehyde resin |
| CN114686087A (en) * | 2022-04-29 | 2022-07-01 | 深圳德诚达光电材料有限公司 | High-wear-resistance fluorine-containing anti-fingerprint agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高于洋等: "十三氟辛醇接枝改性三聚氰胺树脂的合成及其疏水性能", vol. 52, no. 5, pages 501 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117107549A (en) * | 2023-10-10 | 2023-11-24 | 江苏璞丽达数码科技有限公司 | Fingerprint-resistant wear-resistant nano decorative paper and preparation method thereof |
| CN117107549B (en) * | 2023-10-10 | 2024-03-12 | 江苏璞丽达数码科技有限公司 | Fingerprint-resistant wear-resistant nano decorative paper and preparation method thereof |
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