CN109306246A - A kind of shock proof automatically cleaning impregnated paper and preparation method thereof - Google Patents
A kind of shock proof automatically cleaning impregnated paper and preparation method thereof Download PDFInfo
- Publication number
- CN109306246A CN109306246A CN201811185497.3A CN201811185497A CN109306246A CN 109306246 A CN109306246 A CN 109306246A CN 201811185497 A CN201811185497 A CN 201811185497A CN 109306246 A CN109306246 A CN 109306246A
- Authority
- CN
- China
- Prior art keywords
- hot melt
- nano
- tio
- impregnated paper
- layer
- Prior art date
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- Granted
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- 238000004140 cleaning Methods 0.000 title claims abstract description 108
- 230000035939 shock Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- -1 melamine-formaldehyde compound Chemical class 0.000 claims abstract description 52
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims description 69
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- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical class CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 5
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/754—Self-cleaning
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to impregnated paper technical fields, and in particular to a kind of shock proof automatically cleaning impregnated paper and preparation method thereof, the dipping include the original paper layer set gradually from the bottom to top, hot melt adhesive stratum reticulare, printing lines layer, wear-resisting glue-line and nano-TiO2Self-cleaning layer, the mesh density of the hot melt adhesive stratum reticulare are 100-130/m2；The wear-resisting glue-line is made by melamine-formaldehyde compound adhesive；The nano-TiO2Self-cleaning layer is by nano-TiO2Self-cleaning coating is made.Impregnated paper of the invention is by being arranged nano-TiO in outer surface2Self-cleaning layer can be attached to the dust granule and spot on impregnated paper surface using its photocatalysis degradation, improve the self-cleaning performance and anti-pollution characteristic of impregnated paper；And by setting hot melt adhesive stratum reticulare, original paper layer can be improved and print the bonding force between lines layer, avoid the occurrence of interlayer disengaging, and the resilience and impact resistance of impregnated paper can be improved using the flexibility of hot melt adhesive stratum reticulare itself, it is damaged to be not easy large area due to impact.
Description
Technical field
The present invention relates to impregnated paper technical fields, and in particular to a kind of shock proof automatically cleaning impregnated paper and its preparation side
Method.
Background technique
Current impregnated paper is substantially mixed by non-woven fabrics wood pulp with PE and plant fiber, has stronger absorbability
It with antilysis ability, is widely used in the veneer of cabinet, wardrobe and composite floor board, mostly due to original paper layer, plain color layer
The phenomenon that Deng preparation, the bonding force of interlayer is insufficient, is easy to appear interlaminar separation, and anti-impact force is lower, is easy because of foreign impacts
Power and lead to that impregnated paper is whole to magnify parts against wear, or even fall off from cabinet, wardrobe, bottom plate in large area, service life is lower；
In addition, current impregnated paper resistance to soiling is lower, spot easy to attach and be difficult to clean off it is clean, influence using.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, it is shock proof certainly that the purpose of the present invention is to provide one kind
Impregnated paper is cleaned, the impregnated paper is by being arranged nano-TiO in outer surface2Self-cleaning layer can be degraded attached using its photocatalysis
In the dust granule and spot on impregnated paper surface, improve the self-cleaning performance and anti-pollution characteristic of impregnated paper；And pass through setting heat
Melten gel stratum reticulare can improve original paper layer and print the bonding force between lines layer, avoid the occurrence of interlayer disengaging, and can utilize hot melt
The flexibility of glue stratum reticulare itself improves the resilience and impact resistance of impregnated paper, and it is damaged to be not easy large area due to impact.
Another object of the present invention is to provide a kind of preparation method of shock proof automatically cleaning impregnated paper, operating procedure letters
Single, easy to control, high production efficiency, production cost is low, and Qualities of Paper Impregnated Thermosetting obtained is stablized, and is applicable to be mass produced.
The purpose of the invention is achieved by the following technical solution: a kind of shock proof automatically cleaning impregnated paper, including by down toward
On the original paper layer, hot melt adhesive stratum reticulare, the printing lines layer, wear-resisting glue-line and nano-TiO that set gradually2Self-cleaning layer, the hot melt
The mesh density of glue stratum reticulare is 100-130/m2；The wear-resisting glue-line is made by melamine-formaldehyde compound adhesive；The nanometer
TiO2Self-cleaning layer is by nano-TiO2Self-cleaning coating is made.
Impregnated paper of the invention is by being arranged nano-TiO in outer surface2Self-cleaning layer can be declined using its photocatalysis
Solution is attached to the dust granule and spot on impregnated paper surface, improves the self-cleaning performance and anti-pollution characteristic of impregnated paper, improving it makes
Use the service life；And by setting hot melt adhesive stratum reticulare, it can stablize with original paper layer, printing lines layer bonding, improve original paper layer, printing line
Bonding force between the floor of road avoids the occurrence of interlayer disengaging, improves the stability of impregnated paper, and can utilize hot melt adhesive stratum reticulare itself
Flexibility improves the resilience and impact resistance of impregnated paper, so that impregnated paper is not easy, large area is damaged due to impact or falls off.
Preferably, the hot melt adhesive stratum reticulare is made by polyurethane hot melt, and the polyurethane hot melt includes following weight
The raw material of part:
The application prepares polyurethane hot melt by using the raw material of mentioned kind, and bonding force is strong, can be with original paper layer, printing
The bonding of lines layer is stablized, and the phenomenon that improving the interlayer connective stability of impregnated paper, be less prone to interlaminar separation, improves impregnated paper
Stability；Wherein, hydroxyl, ehter bond isoreactivity group are contained in the xylene formaldehyde resin molecular structure of use, in molecular composition
Have 80% the above are diformazan benzenyl structure, there is excellent compatibility with polyurethane resin, polyurethane heat can be effectively improved
Thermoplasticity, the toughness of melten gel, and increase the adhesion strength of hot melt adhesive stratum reticulare, improve hot melt adhesive stratum reticulare and original paper layer, printing lines
Adhesion stability between layer, improves the layer stability of impregnated paper, is less prone to interlaminar separation phenomenon；By using two laurels
Sour dibutyl tin and triethylene diamine are that 2-3:1.5-2 compounds immixture with ratio, can promote polyurethane resin and dimethylbenzene
The cross-linking modified reaction of formaldehyde resin, rise catalytic action, while dibutyl tin dilaurate and triethylene diamine can all have compared with
Good photostability, weatherability, can effectively improve the stability of polyurethane hot melt, it is made to be not easy the qualitative change that is corroded or occurs.
Preferably, the polyurethane hot melt is made by following steps:
(1) xylene formaldehyde resin is added into polyurethane resin, stirs 30-40min at 50-60 DEG C, then proceedes to stir
It mixes, and is warming up to 85-90 DEG C, dibutyl tin dilaurate, triethylene diamine and crosslinking agent are added while stirring, after mixing
Material A is made；
(2) tackifying resin and solvent is added made from step (1) in material A, is 18000-22000Hz in supersonic frequency
Lower stirring 15-25min, adds antioxidant and curing agent after mixing evenly, and polyurethane-hot melt is made after being mixed evenly
Glue.
The present invention prepares polyurethane hot melt by using above-mentioned steps, can make polyurethane resin and xylene formaldehyde resin
Contact mixing sufficiently, and dibutyl tin dilaurate, triethylene diamine catalysis under and the facilitation of crosslinking agent under,
Promote polyurethane resin and xylene formaldehyde resin cross-linking polymerization, improves the thermoplasticity of polyurethane hot melt, toughness and viscous
Knotting strength improves the adhesion stability between hot melt adhesive stratum reticulare and original paper layer, printing lines layer, and the interlayer for improving impregnated paper is stablized
Property, it is less prone to interlaminar separation phenomenon.
Preferably, the tackifying resin is mixed by 2-4 parts of rosin glycerides and 1.5-2.5 parts of β-terpene resins；Institute
Stating antioxidant is by four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2.4- di-tert-butyls
Base] phosphite ester and thiodipropionic acid bis-dodecanol ester acetone is with mixture that weight ratio is that 2-3:0.8-1.2:1 is formed；It is described
Crosslinking agent is mixed by 3-4 parts of cumyl peroxides and 1-3 parts of diethylenetriamines；The curing agent is by laurylene base
The mixture that succinic anhydride and cyanoethylation diethylentriamine are formed with weight ratio for 2-3:0.8-1.2；The solvent is propylene
The mixture that sour methyl esters and water are formed with weight ratio for 1.5-2.5:1.
The present invention mutually compounds work with polyurethane resin, xylene formaldehyde resin by using the tackifying resin of mentioned kind
With can effectively increase the polymeric adhesive power of polyurethane resin, xylene formaldehyde resin, improve tack, effectively improve compound
The stickiness of hot melt adhesive；Wherein, the rosin glyceride of use is nontoxic, and flexibility is good, can effectively improve the material phase of hot melt adhesive
Mixcibility and flexibility after molding and elasticity, and tack is good, effectively improve the viscosity and weatherability of composite hot melt adhesive, and with
β-terpene resin mutually compounds, and hot melt adhesive obtained can be made to have excellent bonding force, enables polyurethane hot melt obtained and original
Adhesion stability between paper layer, hot melt adhesive stratum reticulare improves the layer stability of impregnated paper, is less prone to interlaminar separation phenomenon；
β-terpene resin of use is nontoxic, has preferable cementability and inoxidizability, can effectively improve the viscous of composite hot melt adhesive
Conjunction property can enable the bonding stabilization between obtained polyurethane hot melt and original paper layer, printing lines layer.
The present invention can effectively prevent or inhibit the oxidation of high polymer by using the antioxidant of mentioned kind, avoid high poly-
The oxidation of object causes macromolecular chain to be broken, be crosslinked, and then influences or destroy the performance of hot melt adhesive, and influences hot melt adhesive stratum reticulare and original
Paper layer, the printing direct adhesion stability of lines layer, can make hot melt adhesive obtained have excellent antioxidation, stability
Height is not influenced vulnerable to ambient light heat；Wherein, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi of use
Alcohol ester belongs to hindered phenol type antioxidant, all has with polyurethane resin, xylene formaldehyde resin, tackifying resin excellent compatible
Property, can effectively improve the inoxidizability of polyurethane hot melt, stability is high, and with three [2.4- di-tert-butyl-phenyl] phosphorous acid
Ester, thiodipropionic acid bis-dodecanol ester acetone can play synergistic effect, and the light of further raising polyurethane hot melt is stablized
Property and thermal stability, be avoided that polyurethane hot melt during following process be heated light influence, and then reduce hot melt adhesive net
Adhesion stability between layer and original paper layer, printing lines layer；Three [2.4- di-tert-butyl-phenyl] phosphite esters used belong to sub-
Phosphoric acid ester antioxidant, when being used alone, antioxygenic property is unstable, cannot play effect steady in a long-term, and with four [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] after pentaerythritol ester is mutually used in compounding with certain proportion, compound collaboration can be played
Effect, the photo and thermal stability of composite hot melt adhesive can be improved, effectively prevent polyurethane resin, xylene formaldehyde resin, thickening tree
Rouge heated light in heating processing is too long is influenced and is degraded, and avoids reducing between hot melt adhesive and original paper layer, printing lines layer
Bond properties；And the thiodipropionic acid bis-dodecanol ester acetone and four [β-(3,5- di-tert-butyl-hydroxy phenyl) third used
Acid] pentaerythritol ester and with excellent synergistic effect, the inoxidizability and stability of composite hot melt adhesive can be significantly improved.
The present invention can effectively facilitate polyurethane resin, xylene formaldehyde resin, increasing by using the crosslinking agent of mentioned kind
The cross-linked polymeric of viscosity resin forms stable hot melt adhesive system, and the crosslinking agent of mentioned kind is pollution-free, and heat resistance is good, no
Because hot melt adhesive is in its bond properties between original paper layer, printing lines layer that is influenced by heat in post-production heating process, stablize
Property it is high；Wherein, the cumyl peroxide of use can make polyurethane resin, xylene formaldehyde resin generate the bubble of fine and even
Hole touches reaction so that mixing between polyurethane resin, xylene formaldehyde resin, tackifying resin, promotes cross-linked polymeric effect,
Improve the heat resistance and weatherability of composite hot melt adhesive.
Curing agent of the present invention by using mentioned kind, the curing efficiency that hot melt adhesive can be improved and the stabilization after solidification
Property, the layer stability of impregnated paper is improved, interlaminar separation phenomenon is less prone to；Wherein, the dodecenylsuccinic anhydride of use with
Polyurethane resin, xylene formaldehyde resin, tackifying resin etc. are easily mixed reaction, and the hot melt adhesive layer after solidification has preferably tough
Property, heat resistance and impact resistance；The cyanoethylation diethylentriamine of use is harmless, and stability is high, can improve compound thermal
The toughness and impact resistance of melten gel make impregnated paper obtained mass lesions or will not fall off due to extraneous impact, improve
The impact resistance of impregnated paper.
The present invention is used as solvent by using methyl acrylate and water compounding, can sufficiently dissolve each material of hot melt adhesive, improves
The dispersibility of material, curing molding is fast, and hot melt adhesive stratum reticulare obtained can be made to have preferable toughness and weatherability, do not produced after molding
Stiff object sense improves the impact resistance of impregnated paper using the toughness and flexibility of hot melt adhesive stratum reticulare, makes impregnated paper obtained will not
It mass lesions or falls off due to extraneous impact.
Preferably, the melamine-formaldehyde compound adhesive includes the raw material of following parts by weight:
The mass fraction that the formalin is is 37wt%；
The curing agent is with weight ratio by hexa, phthalic anhydride and deionized water for 1-1.5:1.6-2.4:1 group
At mixture.
The present invention is 3-8:10-25 by the mixed proportion of strict control melamine and formaldehyde, and the two addition polymerization can be made poly-
The compound adhesive that activity is high, thermal stability is good, weatherability is good is made after conjunction, viscosity is high, and bonding force is strong, is coated on printing lines layer
Surface improves wear-resisting glue-line and prints the adhesion stability of lines layer, and is subject to the stream that nano alumina particles improve compound adhesive
Dynamic property and wearability so that compound adhesive is easy to coat, and can be such that wear-resisting glue-line obtained hasWearability, improve impregnated paper
Wearability；Meanwhile urea is added can effectively facilitate polymerizeing for melamine and formaldehyde, accelerate reaction process, helps generation three
Poly cyanamid glue；The para toluene sulfonamide of addition can effectively improve the toughness and plasticity of compound adhesive, improve the intensity of wear-resisting glue-line, keep away
There is the case where embrittlement in wear-resisting glue-line after exempting from curing molding；And it is compound as solidification by using hexa and phthalic anhydride
Agent can effectively improve the curing efficiency that compound adhesive is coated on after printing lines layer, improve the mouldability and stability of wear-resisting glue-line.
Preferably, the melamine-formaldehyde compound adhesive is prepared by following steps:
(1) hexa and phthalic anhydride are added into deionized water, stir 30-40min at 65-80 DEG C, be made solid
Agent, it is spare；
(2) formalin is stirred at 35-40 DEG C, melamine and urea is then added while stirring, it is stirred
85 DEG C are warming up in journey in 40-50min, insulation reaction 30-40min after addition is being cooled to 50-60 DEG C, and object is made
Expect A；
(3) it is added para toluene sulfonamide, nano alumina particles and water made from step (2) in material A, 40-55 DEG C
Material B is made in lower stirring 30-50min；
(4) in coating before use, curing agent made from step (1) is added into material B made from step (3), stirring
Uniformly, melamine-formaldehyde compound adhesive is made.
The present invention prepares melamine-formaldehyde compound adhesive by using above-mentioned steps, easy to operate, easy to control, production
High-efficient, production cost is low, and melamine-formaldehyde compound adhesive quality obtained is stablized, and is applicable to be mass produced, pass through by
Melamine and urea are added into formalin while stirring, and strict control reaction temperature and time, can improve trimerization
The contact area of cyanamide and formalin is sufficiently reacted, and the process of polymerization reaction is accelerated, and promotes to generate stable melamine
Para toluene sulfonamide and nano alumina particles are added again thereafter for amine-for-aldehyde compound adhesive, improve the intensity of wear-resisting glue-line and resistance to
Mill property, and curing agent is added before using compound adhesive, (curing agent is ready-to-use) effectively improves compound adhesive and is coated on printing line
Curing efficiency after the floor of road improves the mouldability and stability of wear-resisting glue-line.
Preferably, the nano-TiO2Self-cleaning coating includes the raw material of following parts by weight:
Tetraisopropoxy titanium of the invention is by the hydrolytic condensation under the catalysis of acetic acid, by containing for still aging postposition
The TiO of Nano grade2The coating semi-finished product of automatically cleaning particle, and promote levelling agent, dispersing agent and silane coupled using isopropanol
The dispersion mixing of agent and coating semi-finished product improves dispersibility, levelability and the adhesion strength of coating, improves nano-TiO2Automatically cleaning applies
Expect the adhesive force in wear-resisting glue-line corona surface, is formed and stablize impregnated paper, avoid the occurrence of interlaminar separation phenomenon.
It by using dispersing agent, prevents from mutually assembling between material, prevents the nano-TiO generated2Particle sedimentation and flocks,
And can have preferable compatibility between material, dispersion performance, compatibility and the thermal stability of coating can be improved, so that coating
There is preferable mobility when coating；By using levelling agent, the levelability and ductility of each material in coating are improved, so that applying
Material is easy to coat or be sprayed at the corona surface of wear-resisting glue-line；And by using silane coupling agent, the dispersed, viscous of coating can be improved
Conjunction property and adhesion improve nano-TiO so that coating is easily attached to the corona surface of wear-resisting glue-line2Self-cleaning layer and wear-resisting glue
The adhesion stability of layer, and then improve the layer stability of impregnated paper.
Utilize the TiO of tetraisopropoxy titanium Nano grade as made from the hydrolytic condensation under the catalysis of acetic acid2, can be in purple
The irradiation of outer light is lower to generate electron-hole pair, then be adsorbed on TiO2The H of material surface2O and O2Redox reaction occurs to generate
Hydroxyl free radical, using the hydroxyl free radical decomposing organic pollutant of high activity, and nano-TiO2The decomposition of self-cleaning layer is organic
It acts synergistically in terms of pollutant ability and surface super hydrophilic two, is easy to after the pollutant for being attached to coating surface can be made to be decomposed
It rinses or, realizing the self-cleaning surface performance of impregnated paper.
Preferably, the levelling agent is mixed by 1-1.5 parts of isophorones and 2-4 parts of modified polyorganosiloxanes；Described point
Powder is that 2-3 parts of neopelexes and 1.6-2.4 parts of sodium polymethacrylates mix.
The present invention improves the levelability and ductility of each material in coating by using the levelling agent of mentioned kind, so that
Coating is easy to coat or be sprayed at the corona surface of wear-resisting glue-line；And by using the dispersing agent of mentioned kind, can prevent material it
Between mutually assemble, prevent generate nano-TiO2Particle sedimentation and flocks, and can have preferable compatibility, energy between material
Dispersion performance, compatibility and the thermal stability of coating are improved, so that there is preferable mobility when coating coating.
The nano-TiO2Self-cleaning coating is made by following steps:
(1) tetraisopropoxy titanium is stirred at 25-35 DEG C, acetic acid and deionized water is added while stirring, stirs evenly
After stand 12-20h, be made contain nano-TiO2The material A of particle；
(2) material A made from step (1) is added into isopropanol, is stirred evenly, then add levelling agent, dispersion
Nano-TiO is made after homogeneous stirring 20-30min at room temperature in agent and silane coupling agent2Self-cleaning coating.
The present invention prepares nano-TiO by using above-mentioned steps2Self-cleaning coating, operating procedure is simple, easy to control, raw
Produce high-efficient, production cost is low, and coating quality obtained is stablized, and passes through tetraisopropoxy titanium and hydrolyzes contracting under the catalysis of acetic acid
It closes, by the TiO containing Nano grade of still aging postposition2The coating semi-finished product of automatically cleaning particle, subsequent recycling isopropyl
Alcohol promotes the dispersion mixing of levelling agent, dispersing agent and silane coupling agent and coating semi-finished product, improves dispersibility, the levelability of coating
And adhesion strength, improve nano-TiO2Self-cleaning coating forms in the adhesive force of wear-resisting glue-line corona surface and stablizes impregnated paper, avoid out
Existing interlaminar separation phenomenon.
The purpose of the invention is achieved by the following technical solution: a kind of preparation of above-mentioned shock proof automatically cleaning impregnated paper
Method includes the following steps:
(1) original paper layer is taken, netted polyurethane hot melt is coated in original paper layer upper surface, while covering printing lines layer,
Polyurethane hot melt forms hot melt adhesive stratum reticulare after dry solidification, then composite layer is made；
(2) melamine-formaldehyde compound adhesive is coated in the upper surface of printing lines layer, forms wear-resisting glue after dry solidification
Layer；
(3) wear-resisting glue-line upper surface made from step (2) is subjected to surface corona processing, while by nano-TiO2Automatically cleaning
Coating is sprayed at corona surface, forms nano-TiO after solidification2Automatically cleaning impregnated paper is then made in self-cleaning layer.
In the step (1), the coating thickness of the polyurethane hot melt is 25-75 μm, and the temperature of dry solidification is 80-
95℃；In the step (2), the coating thickness of the melamine-formaldehyde compound adhesive is 25-75 μm, the temperature of dry solidification
It is 35-60 DEG C；In the step (3), the nano-TiO2The coating thickness of self-cleaning coating is 30-50 μm, and solidification temperature is
45-55℃。
The present invention prepares nano-TiO by using above-mentioned steps2Self-cleaning coating, operating procedure is simple, easy to control, raw
Produce high-efficient, production cost is low, and Qualities of Paper Impregnated Thermosetting obtained is stablized, and is suitble to large-scale production, is improved using polyurethane hot melt
Bonding force between original paper layer, printing lines layer avoids the occurrence of interlayer disengaging, improves the stability of impregnated paper, and can utilize shape
At hot melt adhesive stratum reticulare itself flexibility improve impregnated paper resilience and impact resistance so that impregnated paper is not easy due to impact
Large area is damaged or falls off；After coating prepares wear-resisting glue-line, surface corona processing is carried out to wear-resisting glue-line upper surface, can be improved
The adhesive force of wear-resisting glue-line, and then improve nano-TiO2Self-cleaning coating avoids the occurrence of interlayer in wear-resisting glue-line adhesion stability
It is detached from；And utilize nano-TiO obtained2Self-cleaning layer is attached to the dust granule on impregnated paper surface in photocatalysis decline solution
And spot, the self-cleaning performance and anti-pollution characteristic of impregnated paper are improved, its service life is improved.
The beneficial effects of the present invention are: impregnated paper of the invention is by being arranged nano-TiO in outer surface2Self-cleaning layer,
The dust granule and spot on impregnated paper surface can be attached in photocatalysis decline solution using it, improves the automatically cleaning of impregnated paper
Performance and anti-pollution characteristic improve its service life；And by setting hot melt adhesive stratum reticulare, it can be with original paper layer, printing lines layer bonding
Stablize, improve the bonding force between original paper layer, printing lines layer, avoids the occurrence of interlayer disengaging, improve the stability of impregnated paper,
And the resilience and impact resistance of impregnated paper can be improved using the flexibility of hot melt adhesive stratum reticulare itself, so that impregnated paper is not easy because of punching
It hits and large area is damaged or fall off.
The preparation method operating procedure of impregnated paper of the present invention is simple, and easy to control, high production efficiency, production cost is low, system
The Qualities of Paper Impregnated Thermosetting obtained is stablized, and large-scale production is suitble to, and improves original paper layer using polyurethane hot melt, prints between lines layer
Bonding force avoids the occurrence of interlayer disengaging, improves the stability of impregnated paper, and can utilize the softness of the hot melt adhesive stratum reticulare itself formed
Property improve the resilience and impact resistance of impregnated paper so as to be not easy due to impact large area damaged or fall off for impregnated paper；It is coating
After preparing wear-resisting glue-line, surface corona processing is carried out to wear-resisting glue-line upper surface, the adhesive force of wear-resisting glue-line, Jin Erti can be improved
High nano-TiO2Self-cleaning coating avoids the occurrence of interlayer disengaging in wear-resisting glue-line adhesion stability；And utilize nano-TiO obtained2
Self-cleaning layer is attached to the dust granule and spot on impregnated paper surface in photocatalysis decline solution, improves the automatically cleaning of impregnated paper
Performance and anti-pollution characteristic improve its service life.
Detailed description of the invention
Fig. 1 is perspective view of the invention；
Appended drawing reference are as follows: 1-original paper layer, 2-hot melt adhesive stratum reticulares, 3-printing lines layers, 4-wear-resisting glue-lines, 5-nanometers
TiO2Self-cleaning layer.
Specific embodiment
For the ease of the understanding of those skilled in the art, make below with reference to 1 couple of present invention of examples and drawings further
Illustrate, the content that embodiment refers to not is limitation of the invention.
Embodiment 1
A kind of shock proof automatically cleaning impregnated paper, including the original paper layer 1, hot melt adhesive stratum reticulare 2, print set gradually from the bottom to top
Brush lines layer 3, wear-resisting glue-line 4 and nano-TiO2Self-cleaning layer 5, the mesh density of the hot melt adhesive stratum reticulare 2 is 100-130/
m2；The wear-resisting glue-line 4 is made by melamine-formaldehyde compound adhesive；The nano-TiO2Self-cleaning layer 5 is by nano-TiO2From clear
Clean coating is made.
Embodiment 2
The hot melt adhesive stratum reticulare is made by polyurethane hot melt, and the polyurethane hot melt includes the original of following parts by weight
Material:
The tackifying resin is mixed by 2 parts of rosin glycerides and 1.5 parts of β-terpene resins；The antioxidant is
By four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2.4- di-tert-butyl-phenyl] phosphite esters
The mixture formed with thiodipropionic acid bis-dodecanol ester acetone with weight ratio for 2:0.8:1；The crosslinking agent is by 3 parts of peroxidating
Diisopropylbenzene (DIPB) and 1 part of diethylenetriamines mix；The curing agent is by dodecenylsuccinic anhydride and cyanoethylation two
Ethylene triamine is with the mixture that weight ratio is that 2:0.8 is formed；It with weight ratio is 1.5:1 group that the solvent, which is methyl acrylate and water,
At mixture.
The polyurethane hot melt is made by following steps:
(1) xylene formaldehyde resin is added into polyurethane resin, stirs 40min at 50 DEG C, then proceedes to stir, and rise
Dibutyl tin dilaurate, triethylene diamine and crosslinking agent is added to 85 DEG C in temperature while stirring, and material A is made after mixing；
(2) tackifying resin and solvent is added made from step (1) in material A, is stirred in the case where supersonic frequency is 18000Hz
25min adds antioxidant and curing agent after mixing evenly, and polyurethane hot melt is made after being mixed evenly.
The melamine-formaldehyde compound adhesive includes the raw material of following parts by weight:
The mass fraction that the formalin is is 37wt%；
The mixing that the curing agent is made of hexa, phthalic anhydride and deionized water with weight ratio for 1:1.6:1
Object.
The melamine-formaldehyde compound adhesive is prepared by following steps:
(1) hexa and phthalic anhydride are added into deionized water, stir 40min at 65 DEG C, curing agent is made, it is standby
With；
(2) formalin is stirred at 35 DEG C, is then added melamine and urea while stirring, in whipping process
85 DEG C are warming up in 50min, insulation reaction 40min after addition is being cooled to 60 DEG C, and material A is made；
(3) para toluene sulfonamide, nano alumina particles and water is added made from step (2) in material A, is stirred at 40 DEG C
50min is mixed, material B is made；
(4) in coating before use, curing agent made from step (1) is added into material B made from step (3), stirring
Uniformly, melamine-formaldehyde compound adhesive is made.
The nano-TiO2Self-cleaning coating includes the raw material of following parts by weight:
The levelling agent is mixed by 1.5 parts of isophorones and 4 parts of modified polyorganosiloxanes；The dispersing agent is 3 part ten
Dialkyl benzene sulfonic acids sodium and 2.4 parts of sodium polymethacrylates mix.
The nano-TiO2Self-cleaning coating is made by following steps:
(1) tetraisopropoxy titanium is stirred at 25 DEG C, acetic acid and deionized water is added while stirring, it is quiet after mixing evenly
12h is set, is made and contains nano-TiO2The material A of particle；
(2) material A made from step (1) is added into isopropanol, is stirred evenly, then add levelling agent, dispersion
Nano-TiO is made after homogeneous stirring 20min at room temperature in agent and silane coupling agent2Self-cleaning coating.
A kind of preparation method of such as above-mentioned shock proof automatically cleaning impregnated paper, includes the following steps:
(1) original paper layer is taken, netted polyurethane hot melt is coated in original paper layer upper surface, while covering printing lines layer,
Polyurethane hot melt forms hot melt adhesive stratum reticulare after dry solidification, then composite layer is made；
(2) melamine-formaldehyde compound adhesive is coated in the upper surface of printing lines layer, forms wear-resisting glue after dry solidification
Layer；
(3) wear-resisting glue-line upper surface made from step (2) is subjected to surface corona processing, while by nano-TiO2Automatically cleaning
Coating is sprayed at corona surface, forms nano-TiO after solidification2Automatically cleaning impregnated paper is then made in self-cleaning layer.
In the step (1), the coating thickness of the polyurethane hot melt is 25 μm, and the temperature of dry solidification is 80 DEG C；
In the step (2), the coating thickness of the melamine-formaldehyde compound adhesive is 25 μm, and the temperature of dry solidification is 35 DEG C；Institute
It states in step (3), the nano-TiO2The coating thickness of self-cleaning coating is 30 μm, and solidification temperature is 45 DEG C.
Embodiment 3
The hot melt adhesive stratum reticulare is made by polyurethane hot melt, and the polyurethane hot melt includes the original of following parts by weight
Material:
The tackifying resin is mixed by 2.5 parts of rosin glycerides and 1.8 parts of β-terpene resins；The antioxidant
It is by four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2.4- di-tert-butyl-phenyl] phosphorous acid
The mixture that ester and thiodipropionic acid bis-dodecanol ester acetone are formed with weight ratio for 2.2:0.9:1；The crosslinking agent is by 3.2 parts
Cumyl peroxide and 1.5 parts of diethylenetriamines mix；The curing agent is by dodecenylsuccinic anhydride and cyanogen
Ethylization diethylentriamine is with the mixture that weight ratio is that 2.2:0.9 is formed；The solvent is methyl acrylate and water with weight
Than the mixture formed for 1.8:1.
The polyurethane hot melt is made by following steps:
(1) xylene formaldehyde resin is added into polyurethane resin, stirs 38min at 52 DEG C, then proceedes to stir, and rise
Dibutyl tin dilaurate, triethylene diamine and crosslinking agent is added to 86 DEG C in temperature while stirring, and material A is made after mixing；
(2) tackifying resin and solvent is added made from step (1) in material A, is stirred in the case where supersonic frequency is 19000Hz
23min adds antioxidant and curing agent after mixing evenly, and polyurethane hot melt is made after being mixed evenly.
The melamine-formaldehyde compound adhesive includes the raw material of following parts by weight:
The mass fraction that the formalin is is 37wt%；
The curing agent is made of hexa, phthalic anhydride and deionized water with weight ratio for 1.2:1.8:1 mixed
Close object.
The melamine-formaldehyde compound adhesive is prepared by following steps:
(1) hexa and phthalic anhydride are added into deionized water, stir 38min at 69 DEG C, curing agent is made, it is standby
With；
(2) formalin is stirred at 36 DEG C, is then added melamine and urea while stirring, in whipping process
85 DEG C are warming up in 48min, insulation reaction 38min after addition is being cooled to 58 DEG C, and material A is made；
(3) para toluene sulfonamide, nano alumina particles and water is added made from step (2) in material A, is stirred at 43 DEG C
45min is mixed, material B is made；
(4) in coating before use, curing agent made from step (1) is added into material B made from step (3), stirring
Uniformly, melamine-formaldehyde compound adhesive is made.
The nano-TiO2Self-cleaning coating includes the raw material of following parts by weight:
The levelling agent is mixed by 1.4 parts of isophorones and 3.5 parts of modified polyorganosiloxanes；The dispersing agent is 2.8
Part neopelex and 2.2 parts of sodium polymethacrylates mix.
The nano-TiO2Self-cleaning coating is made by following steps:
(1) tetraisopropoxy titanium is stirred at 28 DEG C, acetic acid and deionized water is added while stirring, it is quiet after mixing evenly
14h is set, is made and contains nano-TiO2The material A of particle；
(2) material A made from step (1) is added into isopropanol, is stirred evenly, then add levelling agent, dispersion
Nano-TiO is made after homogeneous stirring 22min at room temperature in agent and silane coupling agent2Self-cleaning coating.
A kind of preparation method of such as above-mentioned shock proof automatically cleaning impregnated paper, includes the following steps:
(1) original paper layer is taken, netted polyurethane hot melt is coated in original paper layer upper surface, while covering printing lines layer,
Polyurethane hot melt forms hot melt adhesive stratum reticulare after dry solidification, then composite layer is made；
(2) melamine-formaldehyde compound adhesive is coated in the upper surface of printing lines layer, forms wear-resisting glue after dry solidification
Layer；
(3) wear-resisting glue-line upper surface made from step (2) is subjected to surface corona processing, while by nano-TiO2Automatically cleaning
Coating is sprayed at corona surface, forms nano-TiO after solidification2Automatically cleaning impregnated paper is then made in self-cleaning layer.
In the step (1), the coating thickness of the polyurethane hot melt is 37 μm, and the temperature of dry solidification is 83 DEG C；
In the step (2), the coating thickness of the melamine-formaldehyde compound adhesive is 37 μm, and the temperature of dry solidification is 42 DEG C；Institute
It states in step (3), the nano-TiO2The coating thickness of self-cleaning coating is 35 μm, and solidification temperature is 48 DEG C.
Embodiment 4
The hot melt adhesive stratum reticulare is made by polyurethane hot melt, and the polyurethane hot melt includes the original of following parts by weight
Material:
The tackifying resin is mixed by 3 parts of rosin glycerides and 2 parts of β-terpene resins；The antioxidant be by
Four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2.4- di-tert-butyl-phenyl] phosphite esters and
Thiodipropionic acid bis-dodecanol ester acetone is with the mixture that weight ratio is that 2.5:1:1 is formed；The crosslinking agent is by 3.5 parts of peroxidating
Diisopropylbenzene (DIPB) and 2 parts of diethylenetriamines mix；The curing agent is by dodecenylsuccinic anhydride and cyanoethylation two
Ethylene triamine is with the mixture that weight ratio is that 2.5:1 is formed；It with weight ratio is that 2:1 is formed that the solvent, which is methyl acrylate and water,
Mixture.
The polyurethane hot melt is made by following steps:
(1) xylene formaldehyde resin is added into polyurethane resin, stirs 35min at 55 DEG C, then proceedes to stir, and rise
Dibutyl tin dilaurate, triethylene diamine and crosslinking agent is added to 87 DEG C in temperature while stirring, and material A is made after mixing；
(2) tackifying resin and solvent is added made from step (1) in material A, is stirred in the case where supersonic frequency is 20000Hz
20min adds antioxidant and curing agent after mixing evenly, and polyurethane hot melt is made after being mixed evenly.
The melamine-formaldehyde compound adhesive includes the raw material of following parts by weight:
The mass fraction that the formalin is is 37wt%；
The mixing that the curing agent is made of hexa, phthalic anhydride and deionized water with weight ratio for 1.3:2:1
Object.
The melamine-formaldehyde compound adhesive is prepared by following steps:
(1) hexa and phthalic anhydride are added into deionized water, stir 35min at 73 DEG C, curing agent is made, it is standby
With；
(2) formalin is stirred at 37 DEG C, is then added melamine and urea while stirring, in whipping process
85 DEG C are warming up in 45min, insulation reaction 35min after addition is being cooled to 55 DEG C, and material A is made；
(3) para toluene sulfonamide, nano alumina particles and water is added made from step (2) in material A, is stirred at 46 DEG C
40min is mixed, material B is made；
(4) in coating before use, curing agent made from step (1) is added into material B made from step (3), stirring
Uniformly, melamine-formaldehyde compound adhesive is made.
The nano-TiO2Self-cleaning coating includes the raw material of following parts by weight:
The levelling agent is mixed by 1.3 parts of isophorones and 3 parts of modified polyorganosiloxanes；The dispersing agent is 2.5 parts
Neopelex and 2 parts of sodium polymethacrylates mix.
The nano-TiO2Self-cleaning coating is made by following steps:
(1) tetraisopropoxy titanium is stirred at 30 DEG C, acetic acid and deionized water is added while stirring, it is quiet after mixing evenly
16h is set, is made and contains nano-TiO2The material A of particle；
(2) material A made from step (1) is added into isopropanol, is stirred evenly, then add levelling agent, dispersion
Nano-TiO is made after homogeneous stirring 25min at room temperature in agent and silane coupling agent2Self-cleaning coating.
A kind of preparation method of such as above-mentioned shock proof automatically cleaning impregnated paper, includes the following steps:
(1) original paper layer is taken, netted polyurethane hot melt is coated in original paper layer upper surface, while covering printing lines layer,
Polyurethane hot melt forms hot melt adhesive stratum reticulare after dry solidification, then composite layer is made；
(2) melamine-formaldehyde compound adhesive is coated in the upper surface of printing lines layer, forms wear-resisting glue after dry solidification
Layer；
(3) wear-resisting glue-line upper surface made from step (2) is subjected to surface corona processing, while by nano-TiO2Automatically cleaning
Coating is sprayed at corona surface, forms nano-TiO after solidification2Automatically cleaning impregnated paper is then made in self-cleaning layer.
In the step (1), the coating thickness of the polyurethane hot melt is 50 μm, and the temperature of dry solidification is 87 DEG C；
In the step (2), the coating thickness of the melamine-formaldehyde compound adhesive is 50 μm, and the temperature of dry solidification is 48 DEG C；Institute
It states in step (3), the nano-TiO2The coating thickness of self-cleaning coating is 40 μm, and solidification temperature is 50 DEG C.
Embodiment 5
The hot melt adhesive stratum reticulare is made by polyurethane hot melt, and the polyurethane hot melt includes the original of following parts by weight
Material:
The tackifying resin is mixed by 3.5 parts of rosin glycerides and 2.3 parts of β-terpene resins；The antioxidant
It is by four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2.4- di-tert-butyl-phenyl] phosphorous acid
The mixture that ester and thiodipropionic acid bis-dodecanol ester acetone are formed with weight ratio for 2.8:1.1:1；The crosslinking agent is by 3.8 parts
Cumyl peroxide and 2.5 parts of diethylenetriamines mix；The curing agent is by dodecenylsuccinic anhydride and cyanogen
Ethylization diethylentriamine is with the mixture that weight ratio is that 2.8:1.1 is formed；The solvent is methyl acrylate and water with weight
Than the mixture formed for 2.3:1.
The polyurethane hot melt is made by following steps:
(1) xylene formaldehyde resin is added into polyurethane resin, stirs 32min at 58 DEG C, then proceedes to stir, and rise
Dibutyl tin dilaurate, triethylene diamine and crosslinking agent is added to 89 DEG C in temperature while stirring, and material A is made after mixing；
(2) tackifying resin and solvent is added made from step (1) in material A, is stirred in the case where supersonic frequency is 21000Hz
18min adds antioxidant and curing agent after mixing evenly, and polyurethane hot melt is made after being mixed evenly.
The melamine-formaldehyde compound adhesive includes the raw material of following parts by weight:
The mass fraction that the formalin is is 37wt%；
The curing agent is made of hexa, phthalic anhydride and deionized water with weight ratio for 1.4:2.2:1 mixed
Close object.
The melamine-formaldehyde compound adhesive is prepared by following steps:
(1) hexa and phthalic anhydride are added into deionized water, stir 32min at 76 DEG C, curing agent is made, it is standby
With；
(2) formalin is stirred at 38 DEG C, is then added melamine and urea while stirring, in whipping process
85 DEG C are warming up in 42min, insulation reaction 32min after addition is being cooled to 52 DEG C, and material A is made；
(3) para toluene sulfonamide, nano alumina particles and water is added made from step (2) in material A, is stirred at 51 DEG C
35min is mixed, material B is made；
(4) in coating before use, curing agent made from step (1) is added into material B made from step (3), stirring
Uniformly, melamine-formaldehyde compound adhesive is made.
The nano-TiO2Self-cleaning coating includes the raw material of following parts by weight:
The levelling agent is mixed by 1.1 parts of isophorones and 2.5 parts of modified polyorganosiloxanes；The dispersing agent is 2.2
Part neopelex and 1.8 parts of sodium polymethacrylates mix.
The nano-TiO2Self-cleaning coating is made by following steps:
(1) tetraisopropoxy titanium is stirred at 32 DEG C, acetic acid and deionized water is added while stirring, it is quiet after mixing evenly
18h is set, is made and contains nano-TiO2The material A of particle；
(2) material A made from step (1) is added into isopropanol, is stirred evenly, then add levelling agent, dispersion
Nano-TiO is made after homogeneous stirring 28min at room temperature in agent and silane coupling agent2Self-cleaning coating.
A kind of preparation method of such as above-mentioned shock proof automatically cleaning impregnated paper, includes the following steps:
(1) original paper layer is taken, netted polyurethane hot melt is coated in original paper layer upper surface, while covering printing lines layer,
Polyurethane hot melt forms hot melt adhesive stratum reticulare after dry solidification, then composite layer is made；
(2) melamine-formaldehyde compound adhesive is coated in the upper surface of printing lines layer, forms wear-resisting glue after dry solidification
Layer；
(3) wear-resisting glue-line upper surface made from step (2) is subjected to surface corona processing, while by nano-TiO2Automatically cleaning
Coating is sprayed at corona surface, forms nano-TiO after solidification2Automatically cleaning impregnated paper is then made in self-cleaning layer.
In the step (1), the coating thickness of the polyurethane hot melt is 62 μm, and the temperature of dry solidification is 91 DEG C；
In the step (2), the coating thickness of the melamine-formaldehyde compound adhesive is 62 μm, and the temperature of dry solidification is 54 DEG C；Institute
It states in step (3), the nano-TiO2The coating thickness of self-cleaning coating is 45 μm, and solidification temperature is 53 DEG C.
Embodiment 6
The hot melt adhesive stratum reticulare is made by polyurethane hot melt, and the polyurethane hot melt includes the original of following parts by weight
Material:
The tackifying resin is mixed by 4 parts of rosin glycerides and 2.5 parts of β-terpene resins；The antioxidant is
By four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2.4- di-tert-butyl-phenyl] phosphite esters
The mixture formed with thiodipropionic acid bis-dodecanol ester acetone with weight ratio for 3:1.2:1；The crosslinking agent is by 4 parts of peroxidating
Diisopropylbenzene (DIPB) and 3 parts of diethylenetriamines mix；The curing agent is by dodecenylsuccinic anhydride and cyanoethylation two
Ethylene triamine is with the mixture that weight ratio is that 3:1.2 is formed；It with weight ratio is 2.5:1 group that the solvent, which is methyl acrylate and water,
At mixture.
The polyurethane hot melt is made by following steps:
(1) xylene formaldehyde resin is added into polyurethane resin, stirs 30min at 60 DEG C, then proceedes to stir, and rise
Dibutyl tin dilaurate, triethylene diamine and crosslinking agent is added to 90 DEG C in temperature while stirring, and material A is made after mixing；
(2) tackifying resin and solvent is added made from step (1) in material A, is stirred in the case where supersonic frequency is 22000Hz
15min adds antioxidant and curing agent after mixing evenly, and polyurethane hot melt is made after being mixed evenly.
The melamine-formaldehyde compound adhesive includes the raw material of following parts by weight:
The mass fraction that the formalin is is 37wt%；
The curing agent is made of hexa, phthalic anhydride and deionized water with weight ratio for 1.5:2.4:1 mixed
Close object.
The melamine-formaldehyde compound adhesive is prepared by following steps:
(1) hexa and phthalic anhydride are added into deionized water, stir 30min at 80 DEG C, curing agent is made, it is standby
With；
(2) formalin is stirred at 40 DEG C, is then added melamine and urea while stirring, in whipping process
85 DEG C are warming up in 40min, insulation reaction 30min after addition is being cooled to 50 DEG C, and material A is made；
(3) para toluene sulfonamide, nano alumina particles and water is added made from step (2) in material A, is stirred at 55 DEG C
30min is mixed, material B is made；
(4) in coating before use, curing agent made from step (1) is added into material B made from step (3), stirring
Uniformly, melamine-formaldehyde compound adhesive is made.
The nano-TiO2Self-cleaning coating includes the raw material of following parts by weight:
The levelling agent is mixed by 1 part of isophorone and 2 parts of modified polyorganosiloxanes；The dispersing agent is 2 part 12
Sodium alkyl benzene sulfonate and 1.6 parts of sodium polymethacrylates mix.
The nano-TiO2Self-cleaning coating is made by following steps:
(1) tetraisopropoxy titanium is stirred at 35 DEG C, acetic acid and deionized water is added while stirring, it is quiet after mixing evenly
20h is set, is made and contains nano-TiO2The material A of particle；
(2) material A made from step (1) is added into isopropanol, is stirred evenly, then add levelling agent, dispersion
Nano-TiO is made after homogeneous stirring 30min at room temperature in agent and silane coupling agent2Self-cleaning coating.
A kind of preparation method of such as above-mentioned shock proof automatically cleaning impregnated paper, includes the following steps:
(1) original paper layer is taken, netted polyurethane hot melt is coated in original paper layer upper surface, while covering printing lines layer,
Polyurethane hot melt forms hot melt adhesive stratum reticulare after dry solidification, then composite layer is made；
(2) melamine-formaldehyde compound adhesive is coated in the upper surface of printing lines layer, forms wear-resisting glue after dry solidification
Layer；
(3) wear-resisting glue-line upper surface made from step (2) is subjected to surface corona processing, while by nano-TiO2Automatically cleaning
Coating is sprayed at corona surface, forms nano-TiO after solidification2Automatically cleaning impregnated paper is then made in self-cleaning layer.
In the step (1), the coating thickness of the polyurethane hot melt is 75 μm, and the temperature of dry solidification is 95 DEG C；
In the step (2), the coating thickness of the melamine-formaldehyde compound adhesive is 75 μm, and the temperature of dry solidification is 60 DEG C；Institute
It states in step (3), the nano-TiO2The coating thickness of self-cleaning coating is 50 μm, and solidification temperature is 55 DEG C.
The adhesion strength of the progress of impregnated paper made from above-described embodiment 1-5 shock resistance test, hot melt adhesive stratum reticulare is tested,
And nano-TiO2The self-cleaning performance of self-cleaning layer is tested, and it is shown that test result is as follows:
There are above-mentioned data it is found that impregnated paper of the invention is by being arranged nano-TiO in outer surface2Self-cleaning layer can utilize
It is attached to the dust granule and spot on impregnated paper surface in photocatalysis decline solution, improve impregnated paper self-cleaning performance and
Oil, anti-pollution are refused in anti-pollution characteristic, impregnated paper surface, do not adhere to spot, and service life is high；And by setting hot melt adhesive stratum reticulare, it can be with
Original paper layer, printing lines layer bonding are stablized, and the adhesion strength between hot melt adhesive stratum reticulare and original paper layer, printing lines layer is preferable, does not have
There is interlayer to be detached from, the high stability of impregnated paper, and improves the rebound of impregnated paper using the flexibility of hot melt adhesive stratum reticulare itself
Property and impact resistance, impact resistance it is preferable so as to be not easy due to impact large area damaged or fall off for impregnated paper；And it is received using containing
The wear-resisting glue-line of sharp aluminium oxide can make to be made and obtaining impregnated paper has preferable wearability, and it is impaired to be not easy friction.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of shock proof automatically cleaning impregnated paper, it is characterised in that: including set gradually from the bottom to top original paper layer, hot melt adhesive
Stratum reticulare, printing lines layer, wear-resisting glue-line and nano-TiO2Self-cleaning layer, the mesh density of the hot melt adhesive stratum reticulare are 100-130
A/m2；The wear-resisting glue-line is made by melamine-formaldehyde compound adhesive；The nano-TiO2Self-cleaning layer is by nano-TiO2From clear
Clean coating is made.
2. a kind of shock proof automatically cleaning impregnated paper according to claim 1, it is characterised in that: the hot melt adhesive stratum reticulare by
Polyurethane hot melt is made, and the polyurethane hot melt includes the raw material of following parts by weight:
3. a kind of shock proof automatically cleaning impregnated paper according to claim 2, it is characterised in that: the tackifying resin is by 2-
4 parts of rosin glycerides and 1.5-2.5 parts of β-terpene resins mix；The antioxidant is by four [β-(the tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyl) propionic acid] pentaerythritol ester, three [2.4- di-tert-butyl-phenyl] phosphite esters and thio-2 acid double 12
Alcohol ester acetone is with the mixture that weight ratio is that 2-3:0.8-1.2:1 is formed；The crosslinking agent by 3-4 parts of cumyl peroxides and
1-3 parts of diethylenetriamines mix；The curing agent is by dodecenylsuccinic anhydride and cyanoethylation diethylentriamine
It is the mixture that 2-3:0.8-1.2 is formed with weight ratio；The solvent be methyl acrylate and water with weight ratio for 1.5-2.5:1
The mixture of composition.
4. a kind of shock proof automatically cleaning impregnated paper according to claim 1, it is characterised in that: the melamine-first
Aldehyde compound adhesive includes the raw material of following parts by weight:
The mass fraction that the formalin is is 37wt%；
The curing agent is what 1-1.5:1.6-2.4:1 was formed with weight ratio by hexa, phthalic anhydride and deionized water
Mixture.
5. a kind of shock proof automatically cleaning impregnated paper according to claim 4, it is characterised in that: the melamine-first
Aldehyde compound adhesive is prepared by following steps:
(1) hexa and phthalic anhydride are added into deionized water, stir 30-40min at 65-80 DEG C, curing agent is made,
It is spare；
(2) formalin is stirred at 35-40 DEG C, is then added melamine and urea while stirring, in whipping process
85 DEG C are warming up in 40-50min, insulation reaction 30-40min after addition is being cooled to 50-60 DEG C, and material A is made；
(3) para toluene sulfonamide, nano alumina particles and water is added made from step (2) in material A, is stirred at 40-55 DEG C
30-50min is mixed, material B is made；
(4) it stirs evenly in coating before use, being added curing agent made from step (1) into material B made from step (3),
Melamine-formaldehyde compound adhesive is made.
6. a kind of shock proof automatically cleaning impregnated paper according to claim 1, it is characterised in that: the nano-TiO2From clear
Clean coating includes the raw material of following parts by weight:
7. a kind of shock proof automatically cleaning impregnated paper according to claim 6, it is characterised in that: the levelling agent is by 1-
1.5 parts of isophorones and 2-4 parts of modified polyorganosiloxanes mix；The dispersing agent be 2-3 part neopelexes with
1.6-2.4 part sodium polymethacrylate mixes.
8. a kind of shock proof automatically cleaning impregnated paper according to claim 6, it is characterised in that: the nano-TiO2From clear
Clean coating is made by following steps:
(1) tetraisopropoxy titanium is stirred at 25-35 DEG C, acetic acid and deionized water is added while stirring, it is quiet after mixing evenly
12-20h is set, is made and contains nano-TiO2The material A of particle；
(2) material A made from step (1) is added into isopropanol, is stirred evenly, then add levelling agent, dispersing agent and
Nano-TiO is made after homogeneous stirring 20-30min at room temperature in silane coupling agent2Self-cleaning coating.
9. a kind of preparation method of such as described in any item shock proof automatically cleaning impregnated papers of claim 1-8, it is characterised in that:
Include the following steps:
(1) original paper layer is taken, netted polyurethane hot melt is coated in original paper layer upper surface, while covering printing lines layer, poly- ammonia
Ester hot melt adhesive forms hot melt adhesive stratum reticulare after dry solidification, then composite layer is made；
(2) melamine-formaldehyde compound adhesive is coated in the upper surface of printing lines layer, forms wear-resisting glue-line after dry solidification；
(3) wear-resisting glue-line upper surface made from step (2) is subjected to surface corona processing, while by nano-TiO2Self-cleaning coating
It is sprayed at corona surface, forms nano-TiO after solidification2Automatically cleaning impregnated paper is then made in self-cleaning layer.
10. a kind of preparation method of shock proof automatically cleaning impregnated paper according to claim 9, it is characterised in that: described
In step (1), the coating thickness of the polyurethane hot melt is 25-75 μm, and the temperature of dry solidification is 80-95 DEG C；The step
Suddenly in (2), the coating thickness of the melamine-formaldehyde compound adhesive is 25-75 μm, and the temperature of dry solidification is 35-60 DEG C；Institute
It states in step (3), the nano-TiO2The coating thickness of self-cleaning coating is 30-50 μm, and solidification temperature is 45-55 DEG C.
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| CN111335069A (en) * | 2020-03-25 | 2020-06-26 | 福建省闽清双棱纸业有限公司 | Impregnated paper and preparation method thereof |
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