CN115094681B - Fingerprint-resistant impregnated paper and preparation method thereof - Google Patents
Fingerprint-resistant impregnated paper and preparation method thereof Download PDFInfo
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- CN115094681B CN115094681B CN202210784060.1A CN202210784060A CN115094681B CN 115094681 B CN115094681 B CN 115094681B CN 202210784060 A CN202210784060 A CN 202210784060A CN 115094681 B CN115094681 B CN 115094681B
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- formaldehyde resin
- melamine formaldehyde
- modified melamine
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- 238000002360 preparation method Methods 0.000 title abstract description 55
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 132
- 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 48
- 239000000853 adhesive Substances 0.000 claims abstract description 28
- 230000001070 adhesive effect Effects 0.000 claims abstract description 28
- 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
- 230000003666 anti-fingerprint Effects 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- -1 perfluoroalkyl ethanol Chemical compound 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
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 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
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 22
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 238000011109 contamination Methods 0.000 description 20
- 238000005299 abrasion Methods 0.000 description 19
- 238000001514 detection method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011056 performance test Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine 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
- 238000012360 testing method Methods 0.000 description 5
- 210000004243 sweat Anatomy 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
- 230000000694 effects 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
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 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 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 239000002313 adhesive film Substances 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000008092 positive effect Effects 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
- 239000004094 surface-active agent Substances 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 decorative surface decorative paper, in particular to fingerprint-resistant impregnated paper and a preparation method thereof. An anti-fingerprint impregnated paper is prepared by curing a base material impregnated modified melamine formaldehyde resin impregnating 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 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) impregnating the base material with the modified melamine formaldehyde resin impregnating adhesive, and drying to obtain the fingerprint-resistant impregnated paper. The fingerprint-resistant impregnated paper has excellent hydrophobic performance, pollution resistance, fingerprint resistance and wear resistance.
Description
Technical Field
The application relates to the technical field of furniture decorative surface decorative paper, in particular to fingerprint-resistant impregnated paper and a preparation method thereof.
Background
The impregnated paper is a kind of adhesive film paper with certain resin content and volatile matter content, which is obtained by impregnating amino resin into plain paper or printing paper and drying. The impregnated paper and the base material plate are glued by a hot pressing process, so that the decorative panel with excellent surface performance and attractive patterns can be manufactured. Accordingly, impregnated paper has been widely used in various finishing materials for finishing, furniture, cabinets, wardrobes, floors, and reinforced composite floors.
However, the decorative panel in the above-mentioned environment is often touched by both hands of a person, so that the impregnated paper on the surface of the decorative panel is easy to be stained with fingerprints, and the aesthetic property of the decorative panel is affected. Thus, there is a need for impregnated paper with 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 resistance impregnated paper and a preparation method thereof.
In a first aspect, the present application provides an anti-fingerprint impregnated paper, which adopts the following technical scheme:
an anti-fingerprint impregnated paper is prepared by curing a base material impregnated modified melamine formaldehyde resin impregnating 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 fluocinol;
5-10 parts of silica sol.
The melamine and formaldehyde are first methylolated through addition reaction, then the melamine is further condensed with methylolated melamine, or the methylolated melamine is subjected to self-condensation reaction, so that the melamine formaldehyde resin connected by methylene and ether bonds is generated.
By adopting the technical scheme, on one hand, the fluorine alcohol and the silica sol both contain hydroxyl groups, and in the total raw materials for preparing the melamine formaldehyde resin, the fluorine alcohol and the silica sol are grafted to the side chains of the melamine formaldehyde resin through the hydroxyl groups. Therefore, through the synergistic effect of fluorine and silicon molecules, the friction coefficient and the surface tension of the surface of the modified melamine formaldehyde resin are reduced, and the hydrophobicity, the pollution resistance, the fingerprint resistance and the friction resistance of the modified melamine formaldehyde resin are improved. On the other hand, the silica sol is grafted to the melamine formaldehyde resin side chain, so that the cohesive energy of the melamine formaldehyde resin side chain is improved, and the wear resistance of the modified melamine formaldehyde resin is further improved. Meanwhile, after the obtained modified melamine formaldehyde resin impregnating adhesive is cured, folds and corrugated structures are formed on the surface, so that the full scattering effect of light is realized, and the existence sense of fingerprints on impregnated paper is weakened.
Therefore, the impregnated paper prepared by the modified melamine formaldehyde resin impregnating adhesive still has high hydrophobicity, pollution resistance and fingerprint resistance on the surface after abrasion.
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 fluohydrin is further optimized, the synergistic effect of fluorine and silicon molecules is improved, and the hydrophobic property, the pollution resistance and the fingerprint resistance of the impregnated paper prepared by the obtained modified melamine formaldehyde resin impregnating adhesive are further improved.
Preferably, the fluoroalcohol is perfluoroalkyl ethanol, hexafluoroisopropanol, hexafluorobutanol or perfluorobutyl ethanol.
By adopting the technical scheme, on one hand, the molecular weight of the perfluoroalkyl alcohol, hexafluoroisopropanol, hexafluorobutanol and perfluorobutyl alcohol is in the range of 100-300, the molecular weight is smaller, the modified melamine formaldehyde resin is grafted on the side chain of the melamine formaldehyde resin, the viscosity influence on the obtained modified melamine formaldehyde resin is smaller, the fluidity of the modified melamine formaldehyde resin is improved, the permeability and wettability of the obtained modified melamine formaldehyde resin impregnating adhesive to a substrate are improved, and the effect of enhancing the bonding strength of the substrate is achieved. On the other hand, 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-silicon molecules in the modified melamine formaldehyde resin is further improved, the friction coefficient and the surface tension of the surface of the modified melamine formaldehyde resin are further reduced, and the hydrophobicity, the oleophobic performance and the fingerprint resistance of the obtained modified melamine formaldehyde resin impregnating adhesive are improved.
Preferably, the silica sol is further subjected to a modification treatment, wherein the modification treatment comprises the following steps: adding polyethylene glycol into the silica sol, and stirring and mixing to obtain modified silica sol.
By adopting the technical scheme, polyethylene glycol can be adsorbed on the surface of the silica sol through hydrogen bonding, and the obtained modified silica sol has better hydrophilicity, is beneficial to improving the dispersibility and stability of the modified silica sol in a modified melamine formaldehyde resin mixed system, and not only improves the efficiency of grafting the modified silica sol to melamine formaldehyde resin side chains, but also further improves the hydrophobic, oleophobic and anti-fingerprint properties of the modified melamine formaldehyde resin, and can also improve the stability of the modified melamine formaldehyde resin. Meanwhile, the modified silica sol also has excellent film forming performance and hardness, and can improve the wear resistance of the obtained modified melamine formaldehyde resin.
Therefore, the impregnating adhesive and the impregnated paper prepared from the modified melamine formaldehyde resin have more excellent hydrophobic property, 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 not only improve the dispersibility of the modified silica sol, but also facilitate the grafting of the modified silica sol onto the side chain of the melamine formaldehyde resin, further improve the fold and ripple structure of the obtained modified melamine formaldehyde resin impregnating adhesive after curing, and weaken the existence sense of fingerprints on the impregnated paper.
Preferably, the polyethylene glycol has a molecular weight of 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, preserving heat at 70-85 ℃ for 20-30min, adding melamine, and stirring and mixing for 20-30min to obtain a mixture B;
a3: and adding silica sol and fluoroalcohol into the mixture B, and stirring and mixing for 120-240min to obtain the modified melamine formaldehyde resin.
By adopting the technical scheme, under the reaction of synthesizing melamine formaldehyde resin by formaldehyde and melamine as the main component, the silica 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 property, pollution resistance and fingerprint resistance. Meanwhile, the preparation method of the modified melamine formaldehyde resin has simple process and convenient operation, and can be used for mass production.
In a second aspect, the application provides a preparation method of fingerprint-resistant impregnated paper, which adopts the following technical scheme: the preparation method of the 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) impregnating the base material with the modified melamine formaldehyde resin impregnating adhesive, and drying to obtain the fingerprint-resistant impregnated paper.
By adopting the technical scheme, the modified melamine formaldehyde resin impregnating adhesive prepared by adding raw materials such as a curing agent and the like into the modified melamine formaldehyde resin has excellent permeability and wettability, higher bonding strength to a base material, and excellent hydrophobic, oleophobic, fingerprint resistance and wear resistance after being dried, cured and formed into a film. Meanwhile, the corrugation and the corrugated structure formed on the surface of the base material are beneficial to realizing the full scattering effect of light, and further weaken the existence sense of fingerprints on the impregnated paper.
In summary, the application has the following beneficial effects:
1. because the fluorine alcohol and the silicon dioxide sol are grafted to the side chain of the melamine formaldehyde resin through the hydroxyl in the process of synthesizing the melamine formaldehyde resin from the formaldehyde and the melamine, 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, the impregnated paper prepared by adopting the modified melamine formaldehyde resin is impregnated with the impregnated adhesive, and has excellent hydrophobic property, pollution resistance, fingerprint resistance and wear resistance;
2. in the application, fluoroalkyl ethanol, hexafluoroisopropanol or perfluorobutanol with molecular weight in the range of 100-300 is preferably grafted on the side chain of the modified melamine formaldehyde resin, so that the viscosity of the obtained modified melamine formaldehyde resin is less influenced, and the permeability and wettability of the obtained modified melamine formaldehyde resin impregnating adhesive to a substrate are improved;
3. according to the application, polyethylene glycol modified silica sol is adopted, so that the dispersibility and stability of the modified silica sol in a modified melamine formaldehyde resin mixed system are improved, the grafting of the modified silica sol on melamine formaldehyde resin side chains is promoted, and the hydrophobic property, the pollution resistance, the fingerprint resistance and the wear resistance of the finally obtained modified melamine formaldehyde resin impregnating adhesive are improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example of modified Melamine Formaldehyde resin
Preparation example 1
The modified melamine formaldehyde resin has the components and the corresponding weights 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, preserving heat at 70 ℃ for 20min, adding melamine, stirring and mixing for 20min to obtain a mixture B;
a3: and adding silica sol and fluoroalcohol into the mixture B, stirring and mixing for 120min to obtain the modified melamine formaldehyde resin.
Silica sol is transparent liquid, the silica content is 28-32%, the pH value is 5-7, and the granularity is 10nm; the fluoroalcohol is perfluoroalkyl ethanol.
PREPARATION EXAMPLES 2-3
A modified melamine formaldehyde resin was different from that of preparation example 1 in that the respective components and their respective weights are shown in Table 1.
TABLE 1 Components in preparation examples 1-3 and weights (kg)
Preparation example 4
A modified melamine formaldehyde resin differs from preparation 2 in that the fluoroalcohol is hexafluoroisopropanol.
Preparation example 5
A modified melamine formaldehyde resin is different from preparation example 2 in that the fluoroalcohol is hexafluorobutanol.
Preparation example 6
The modified melamine formaldehyde resin is different from the preparation example 2 in that the silica sol is further subjected to modification treatment, and the modification treatment comprises the following steps: adding polyethylene glycol into the silica sol, and stirring and mixing for 6 hours at 50 ℃ to obtain the modified silica sol.
The polyethylene glycol has a molecular weight of 200.
Preparation examples 7 to 10
A modified melamine formaldehyde resin is different from that of preparation example 6 in that the weight of silica sol and polyethylene glycol is shown in Table 2.
TABLE 2 weight (kg) of silica sol and polyethylene glycol in preparation examples 7-10
PREPARATION EXAMPLES 11 to 14
A modified melamine formaldehyde resin was different from preparation example 8 in that the step of modifying the silica sol was such that the molecular weight of polyethylene glycol was as shown in Table 3.
TABLE 3 molecular weight of polyethylene glycols in preparation examples 11-14
Preparation example 15
A modified melamine formaldehyde resin, which differs from preparation example 12 in that the modified melamine formaldehyde resin is prepared as follows:
a1: mixing formaldehyde and diethylene glycol to obtain a mixture A;
a2: adjusting the pH value of the mixture A to 9.5, preserving the temperature at 85 ℃ for 30min, adding melamine, and stirring and mixing for 30min to obtain a mixture B;
a3: and adding silica sol and 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 and volatile content detection, and the detection standards and detection results were as follows:
storage stability detection: the number of days when the modified melamine formaldehyde resin in the sealed package is stored at room temperature (10-20 ℃) in the dark until the viscosity is not more than 1500 centipoise is represented, and the larger the number of days is, the better the storage stability is represented.
Detection of the pre-curing degree and the volatile content: reference is made to LYT1143-2006.
Formaldehyde release amount detection: refer to GB/T15102-2017.
The detection shows that the modified melamine formaldehyde resin obtained in preparation examples 1-15 has storage stability of more than 55 days, pre-curing degree of 52-56%, volatile content of 6.5-8% and formaldehyde release of 0.2mg/L.
The anti-fingerprint impregnated paper obtained in the embodiment of the application and the impregnated paper obtained in the comparative example are subjected to hydrophilic angle, surface contamination resistance, surface wear resistance and surface anti-fingerprint performance detection, and the detection standards are as follows:
hydrophilic angle detection: the water contact angle is measured by adopting a domestic contact angle measuring instrument Alpha developed by Becton sciences.
And (3) surface wear resistance detection: reference is made to GB/T17657-2013 for 4.42 surface wear resistance determination-method 1.
Surface contamination resistance performance detection: reference to 4.41 surface contamination resistance performance measurement in GB/T17657-2013-method 2, noted as initial surface contamination resistance performance; then, the surface wear resistance of the impregnated paper is detected, and then the surface contamination resistance is detected, and the surface contamination resistance is recorded as the wear surface contamination resistance.
Surface fingerprint resistance detection: adopting an artificial sweat test, soaking the impregnated paper in the artificial sweat for 24 hours, then airing, detecting sweat marks on the surface of the impregnated paper, and marking the sweat marks as initial surface fingerprint resistance; then, the surface wear resistance of the impregnated paper is detected, and then the surface fingerprint resistance is detected, and the surface fingerprint resistance is recorded as the wear surface fingerprint resistance.
Examples
Example 1
An anti-fingerprint impregnated paper is prepared by curing a base material impregnated modified melamine formaldehyde resin impregnating adhesive;
the modified melamine formaldehyde resin impregnating adhesive 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) impregnating the base material with the modified melamine formaldehyde resin impregnating adhesive, and drying to obtain the fingerprint-resistant impregnated paper.
Wherein, the modified melamine formaldehyde resin is prepared by the preparation example 1.
Examples 2 to 3
An impregnated paper resistant to fingerprints is different from example 1 in that each component and its corresponding weight are different in the total raw material for preparing melamine formaldehyde resin, i.e., modified melamine formaldehyde resin is prepared from the preparation examples of table 4.
Table 4 preparation examples of modified Melamine Formaldehyde resins in examples 2-3
| Example 1 | Example 2 | Example 3 |
| Preparation example 1 | Preparation example 2 | Preparation example 3 |
The anti-fingerprint impregnated papers obtained in examples 1 to 3 were subjected to measurements of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface anti-fingerprint properties, and the measurement results are shown in Table 5.
TABLE 5 results of various Performance tests for examples 1-3
As can be seen from the results of the performance tests shown in Table 5, the anti-fingerprint impregnated papers obtained in examples 1 to 3 of the present application have good hydrophobic properties, surface contamination resistance, surface abrasion resistance and surface anti-fingerprint properties. Meanwhile, after abrasion, the surface anti-fouling performance and the surface anti-fingerprint performance are excellent.
Example 4
The impregnated paper for fingerprints is different from example 2 in that in the total raw material for preparing melamine formaldehyde resin, the fluoroalcohol is hexafluoroisopropanol, i.e. the modified melamine formaldehyde resin is prepared from preparation example 4.
Example 5
The impregnated paper for fingerprints is different from example 2 in that in the total raw material for preparing melamine formaldehyde resin, the fluoroalcohol is hexafluorobutanol, i.e., the modified melamine formaldehyde resin is prepared from preparation example 5.
The anti-fingerprint impregnated papers obtained in examples 4 to 5 were subjected to measurements of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface anti-fingerprint properties, and the measurement results are shown in Table 6.
TABLE 6 results of various Performance tests for examples 4-5
As can be seen from the performance detection results in Table 6, the obtained fingerprint-resistant impregnated paper has excellent hydrophobic performance, and the fluoroalcohol is perfluoroalkyl ethanol, hexafluoroisopropanol or hexafluorobutanol in the total raw materials for preparing the melamine formaldehyde resin.
In the embodiment of the application, the fluoroalcohol is perfluoroalkyl ethanol, hexafluoroisopropanol, hexafluorobutanol or perfluorobutyl ethanol, and the obtained fingerprint-resistant impregnated paper has similar hydrophobic property, surface pollution resistance, surface wear resistance and surface fingerprint resistance. Therefore, in the embodiment of the present application, only the fluoroalcohol is taken as perfluoroalkyl ethanol, hexafluoroisopropanol or hexafluorobutanol as an example for brief description, but the application of other fluoroalcohols in the present application is not affected.
Examples 6 to 10
The impregnated paper for fingerprints is different from example 2 in that the silica sol is also modified in the total raw material for preparing the melamine formaldehyde resin, that is, the modified melamine formaldehyde resin is prepared from the preparation examples of table 7.
Table 7 preparation examples of modified Melamine Formaldehyde resins in examples 6 to 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 anti-fingerprint impregnated papers obtained in examples 6 to 10 were subjected to hydrophilic corner, surface contamination resistance, surface abrasion resistance and surface anti-fingerprint properties, and the test results are shown in Table 8.
TABLE 8 results of various Performance tests for examples 6-10
As can be seen from the results of the performance tests shown in table 8, the impregnated papers obtained in examples 6 to 10 have better hydrophobic properties, surface contamination 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 were 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 reasons for this were probably due to the control of the weight of silica sol and polyethylene glycol in the silica sol modification treatment, the silica sol obtained in the modification treatment had a certain particle size and better dispersibility, and the grafting ratio in the modified melamine formaldehyde resin was higher, and the film forming property of the obtained impregnated gel on the surface of the impregnated paper was better, so that the impregnated paper had more excellent hydrophobic property, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance.
Examples 11 to 14
The impregnated paper for fingerprint is different from example 8 in that the molecular weight of polyethylene glycol is different in the total raw material for preparing melamine formaldehyde resin, i.e., modified melamine formaldehyde resin is prepared from the preparation examples of table 9.
Table 9 preparation examples 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 anti-fingerprint impregnated papers obtained in examples 11 to 14 were subjected to measurements of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface anti-fingerprint properties, and the measurement results are shown in Table 9.
TABLE 9 results of various Performance tests for examples 11-14
As is clear from the results of the performance tests shown in Table 9, the impregnated papers obtained in examples 11 to 14 have better water repellency and surface abrasion resistance than the impregnated paper obtained in example 8.
Among them, the impregnated papers obtained in examples 11 to 13 were better in hydrophobic property and surface abrasion resistance than the impregnated papers obtained in examples 8 and 14, and the reason for this analysis was probably that controlling the molecular weight of polyethylene glycol in the silica sol modification treatment had a positive effect on the particle size and dispersibility of the obtained modified silica sol, and the grafting ratio in the modified melamine formaldehyde resin was improved, so that the impregnated papers had more excellent hydrophobic property and surface abrasion resistance.
Example 15
The impregnated paper for fingerprints is different from example 12 in that the melamine formaldehyde resin is prepared in a different step, i.e. the modified melamine formaldehyde resin is prepared from preparation example 15.
The impregnated paper with fingerprint resistance obtained in example 15 was subjected to hydrophilic corner, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the test results are shown in table 10.
Table 10 results of various Performance tests of example 15
Comparative example
Comparative example 1
Impregnated paper differs from example 2 in that in the total raw material for preparing the modified melamine formaldehyde resin, equal amounts of fluoroalcohol are used instead of silica sol.
Comparative example 2
An impregnated paper differs from example 2 in that in the total raw material for preparing the modified melamine formaldehyde resin, an equal amount of acidic nano silica aqueous dispersion is used instead of silica sol, wherein the silica content of the silica dispersion is 25%, the pH value is 2-6, and the particle size is 10nm.
Comparative example 3
Impregnated paper differs from example 2 in that equivalent amounts of BNK-4046 fluorosilicone surfactant are used instead of the fluoroalcohol in the total stock for preparing the modified melamine formaldehyde resin.
The impregnated papers obtained in comparative examples 1 to 3 were subjected to measurements of hydrophilic angle, surface contamination resistance, surface abrasion resistance and surface fingerprint resistance, and the measurement results are shown in Table 11.
Table 11 results of various Performance tests of comparative examples 1 to 3
From the results of the performance tests shown in Table 11, it is understood that the impregnated papers obtained in comparative examples 1 to 3 were significantly reduced in all of the hydrophobic property, the surface contamination resistance, the surface abrasion resistance and the surface fingerprint resistance, relative to the impregnated paper obtained in example 1. Therefore, 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, 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 impregnating adhesive still has high hydrophobic performance, surface pollution resistance and surface fingerprint resistance on the surface after abrasion.
As is clear from further analysis of example 1 and comparative example 3, although the impregnated paper obtained in comparative example 3 has better hydrophobic property, surface contamination resistance property and surface fingerprint resistance property than those of comparative examples 1 and 2, the hydrophobic property, surface contamination resistance property and surface fingerprint resistance property after abrasion are lower than those of example 1. Therefore, the fluoroalcohol and the silica sol are grafted to the melamine formaldehyde resin side chain, and the obtained impregnated paper still has high hydrophobic property, surface pollution resistance and surface fingerprint resistance on the surface after abrasion.
The modified melamine formaldehyde resins prepared in comparative examples 1 to 3 were subjected to storage stability test, pre-cure degree and volatile content test, and the test results were as follows:
the modified melamine formaldehyde resin obtained in comparative examples 1-3 has a storage stability of 45-48 days, a pre-curing degree of 48-50%, a volatile content of 8-9% and a formaldehyde release of 0.2mg/L.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (4)
1. The fingerprint-resistant impregnated paper is characterized by being prepared by curing a base material impregnated modified melamine formaldehyde resin impregnating 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 fluocinol;
5-10 parts of silica sol;
the fluoroalcohol is any one of perfluoroalkyl ethanol, hexafluoroisopropyl alcohol and hexafluorobutanol;
silica sol is transparent liquid, the silica content is 28-32%, the pH value is 5-7, and the granularity is 10nm;
the silica sol is also subjected to modification treatment, wherein the modification treatment comprises the following steps: adding polyethylene glycol into the silica sol, and stirring and mixing to obtain modified silica sol;
the molecular weight of the polyethylene glycol is 400-800.
2. The fingerprint resistant impregnated paper according to claim 1, wherein the weight ratio of silica sol to fluoroalcohol is 1 (0.5-1).
3. The fingerprint-resistant impregnated paper according to claim 1, wherein the modified melamine formaldehyde resin is prepared by the process of:
a1: mixing formaldehyde and water to obtain a mixture A;
a2: adjusting the pH value of the mixture A to 8-9.5, preserving heat at 70-85 ℃ for 20-30min, adding melamine, and stirring and mixing for 20-30min to obtain a mixture B;
a3: and adding silica sol and fluoroalcohol into the mixture B, and stirring and mixing for 120-240min to obtain the modified melamine formaldehyde resin.
4. A method for preparing an anti-fingerprint impregnated paper according to any one of claims 1-3, 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) impregnating the base material with the modified melamine formaldehyde resin impregnating adhesive, and drying to obtain the fingerprint-resistant impregnated paper.
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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.日用化学工业.2022,第52卷(第5期),第501页左栏第2段-右栏第4段，第503页右栏倒数第1段-第504页左栏第1段及图1,6,7. * |
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