CN102391741B - Ammonia-removing and formaldehyde-removing paint - Google Patents
Ammonia-removing and formaldehyde-removing paint Download PDFInfo
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- CN102391741B CN102391741B CN201110217774.6A CN201110217774A CN102391741B CN 102391741 B CN102391741 B CN 102391741B CN 201110217774 A CN201110217774 A CN 201110217774A CN 102391741 B CN102391741 B CN 102391741B
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Abstract
The invention relates to the field of fine chemicals, and specifically relates to an ammonia-removing and formaldehyde-removing paint. The paint comprises an orange and tangerine plant peel extract, an emulsion, titanium dioxide, heavy calcium, calcined kaolin, saponite and auxiliary agents acceptable in paints. The paint provided by the invention does not release formaldehyde, and the volatile organic compound (VOC) content of the paint is low, such that the quality of the paint satisfies a national standard. As results of experiments, the formaldehyde-removing rate is 76.49-84.97%, and the ammonia-removing rate is 100%. With the paint, formaldehyde and ammonia in the air can be effectively and continuously removed.
Description
Technical field
The present invention relates to field of fine chemical, particularly a kind of except ammonia, except methanal paint.
Background technology
In recent years, along with the raising of China's expanding economy and living standards of the people, people's environmental consciousness and health requirements strengthen day by day, and the hazardous and noxious substances pollution on the environment in building and ornament materials, the impact that human health is caused also become increasingly conspicuous.Hazardous and noxious substances is mainly derived from the pollutents such as formaldehyde that building and ornament materials discharge, ammonia.Wherein, formaldehyde is mainly derived from the glued board being used for indoor ornamentation, Blockboard, paint, in the finishing material such as coating, is a kind of colourless easily molten irritant gas, hazard ratio to human body is larger, it can cause eyes, skin and and the hormesis of respiratory tract, cause neural system, immunity system, endocrine system dysfunction, there is embryotoxicity, teratogenesis, carcinogenesis simultaneously.Ammonia is a kind of colourless, has the gas of intense stimulus smell, is often adsorbed on a conjunctiva and skin mucosa, and human body produce is stimulated and inflammation, can corrode and tissue that stimulation contacts, mainly comes from fire retardant in finishing material, frostproofer, additive etc.
At present, all the purification of indoor environment has been done to deep research both at home and abroad, developed a series of air clearing product, as anion generator, plasma additive, formaldehyde absorbent etc.Formaldehyde absorbent such as gac, although can absorption portion formaldehyde, the material such as ammonia, absorbed dose is very limited, also can discharge the materials such as the formaldehyde that adsorbed, ammonia under certain condition, causes secondary pollution; Some formaldehyde absorbents itself are exactly synthetic chemical, when removing formaldehyde, self can discharge other dusty gas, and contaminate environment works the mischief to HUMAN HEALTH simultaneously.
Citrus, Rutaceae Citrus, for having the hesperidium aurantium of keratin pericarp, comprises orange, orange, mandarin orange, shaddock, lemon etc.Wherein, orange is the mature fruit of the multiple tangerine classes such as rutaceae tangerine produced in fujian province or Zhu's tangerine, and orange is often collectively referred to as oranges and tangerines together with mandarin orange, bright-colored, and sweet and sour taste is one of modal fruit in daily life.Orange contains more than 170 kind of plant compounds and more than 60 plants flavonoid compound, and most of materials are wherein all natural antioxidantss.Shaddock is the mature fruit of Citrus paradisi Macfadyen, modern pharmacology Epidemiological Analysis, and the pulp of shaddock and pericarp, be all rich in the dried immature fruit of citron orange, new orange peel, carotene, vitamin B group, vitamins C, mineral substance, carbohydrate and volatilization wet goods.Lemon, rich vitamin C, carbohydrate, calcium, phosphorus, iron, vitamins B
1, vitamins B
2, nicotinic acid, quininic acid, citric acid, oxysuccinic acid, Hesperidin, naringin, coumarin, a large amount potassium element and low amount sodium element etc.
Research shows, all contains the compositions such as a large amount of limonene, myrcene, phantol oxide compound I, germacrene D, phantol oxide compound II, sad and Palmitic acid in orange peel or pomelo peel.Wherein, sad and Palmitic acid has the effect that promotes Formaldehyde decomposition, absorbing ammonia, and the compositions such as limonene, myrcene have aromaticity, can improve smell.But in processing fruits process, citrus pericarp also rests on the roughing stage at present, is just discarded without profound level utilization, cause waste and the environmental pollution of resource.
Summary of the invention
In view of this, the invention provides a kind of except ammonia, except methanal paint.This coating comprises acceptable auxiliary agent in citrus peel extract, emulsion, titanium dioxide, coarse whiting, calcined kaolin, talcum powder and coating.In coating provided by the invention, add citrus pericarp,, containing artificial chemistry product, can effectively not remove the organic gass such as formaldehyde, ammonia.
In order to realize foregoing invention object, the invention provides following technical scheme:
, comprise acceptable auxiliary agent in citrus peel extract, emulsion, titanium dioxide, coarse whiting, calcined kaolin, talcum powder and coating; The preparation method of described citrus peel extract is: in citrus pericarp, add respectively calcium hydroxide aqueous solution and copper sulfate solution, soak respectively 12～24h, collect and soak rear citrus pericarp; In g/mL, the mass volume ratio of described citrus pericarp and described calcium hydroxide aqueous solution or copper sulfate solution is 1: 1.5～and 1: 2, the concentration of described calcium hydroxide aqueous solution is 5～10%, the concentration of described copper sulfate solution is 1～1.5%; After described immersion, after the squeezing of citrus pericarp, collect juice, with 300～500 mesh filter screens, filter, collect filtrate, obtain citrus peel extract.
The alkalescence of calcium hydroxide is stronger than sodium hydroxide, but because the solubleness of calcium hydroxide is more much smaller than sodium hydroxide, so the corrodibility of aqua calcis is less than sodium hydroxide, therefore, calcium hydroxide can be applied to field widely.In the present invention, adopt the calcium hydroxide aqueous solution that concentration is 5～10% to soak citrus pericarp, pericarp hardening is become fragile, oil vacuole is easily broken, is conducive to squeezing, extracts the active substance in citrus pericarp.
As preferably, described coating, in the preparation method of citrus peel extract, the concentration of calcium hydroxide aqueous solution is 6～8%.
The aqueous solution of copper sulfate has the effect of sterilization, deinsectization, test-results shows, it is that 1～1.5% copper sulfate solution soaks citrus pericarp that the present invention adopts concentration, fungi, bacterium or insect in citrus pericarp not only can be killed, but also the extraction yield of the active substance in citrus pericarp can be improved.
As preferably, described coating, in the preparation method of citrus peel extract, the concentration of copper sulfate solution is 1.1～1.3%.
As preferably, described coating, in the preparation method of citrus peel extract, soak time is 16～24h.
As preferably, described coating, in the preparation method of citrus peel extract, also comprises cleaning, air-dry step after immersion.
As preferably, described coating, in the preparation method of citrus peel extract, also comprises pulverizing, the step of sieving before squeezing.
Preferably, sieve and obtain the particle that particle diameter is less than or equal to 7mm.
Use gas of the present invention carries out analysis of effective component to the method for chromatograph-mass spectrometer coupling to the citrus peel extract obtaining, and contains sad, Palmitic acid, limonene, myrcene, phantol oxide compound I, germacrene D, phantol oxide compound II etc. in described citrus peel extract.Wherein, sad and Palmitic acid has slightly acidic, can dissociate proton, promotes to a certain extent Formaldehyde decomposition Cheng Shui and carbonic acid gas.The mechanism of action is as follows:
Citrus peel extract provided by the invention is added in coating as paint additive, can effectively decompose the formaldehyde in coating, and degradation production is water and carbonic acid gas, to human body toxicological harmless.
Meanwhile, sad and Palmitic acid energy absorbing ammonia, forms salt, and its mechanism of action is as follows:
RCOOH+NH
3→RCOO
-+H
4N
+
The extracts such as limonene, myrcene, phantol oxide compound I, germacrene D, phantol oxide compound II have pleasant aromatising flavour, as paint additive, add in coating, can effectively improve construction and living environment.Therefore, the present invention adds above-mentioned citrus peel extract in coating to, the coating that make and can remove ammonia, removes formaldehyde.
In coating provided by the invention, the extraction yield of extract or pomelo peel extract is 72.5～76.1%.
As preferably, GC-MS detected result shows, in citrus peel extract, sad content is 1.35～2.13%, the content of Palmitic acid is 0.97～1.48%, the content of limonene is 48.25～51.20%, and the content of myrcene is 11.97～14.94%, and the content of phantol oxide compound I is 11.49～16.15%, the content of phantol oxide compound II is 6.15～11.14%, and the content of germacrene D is 8.12～8.74%.
As preferably, coating provided by the invention, by percentage to the quality, contains described citrus peel extract 1～3%.
As preferably, coating provided by the invention, by weight percentage, it consists of: citrus peel extract 1～3%, acrylate and vinyl acetate emulsion or benzene emulsion 23.5～44%, titanium dioxide 5～15%, coarse whiting 10～30%, calcined kaolin 5～15%, talcum powder 2～8%, surplus is described auxiliary agent.
As preferably, described coating is water soluble paint.
As preferably, described auxiliary agent comprises one or more the mixture in thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, ethylene glycol, sanitas, mould inhibitor.
As preferably, by weight percentage, described auxiliary agent consists of: Natvosol thickening material 0.3～0.9%, AMP-95 multifunctional assistant 0.05～0.15%, wetting dispersing agent 0.3～0.6%, defoamer 0.2～0.4%, film coalescence aid 0.8～1.5%, ethylene glycol 1～1.5%, sanitas 0.1～0.3%, mould inhibitor 0.1～0.3%.
The invention provides a kind of except ammonia, except methanal paint.This coating comprises acceptable auxiliary agent in citrus peel extract, emulsion, titanium dioxide, coarse whiting, calcined kaolin, talcum powder and coating.Coating provided by the invention, self is release formaldehyde not, and the content of organic volatile gas (VOC) is lower, and quality meets national standard; Evidence, coating formaldehyde clearance provided by the invention is 76.49～84.97%, the clearance of ammonia is 100%, can continuous and effective remove the organic volatile gases such as airborne formaldehyde, ammonia.
Embodiment
The invention discloses a kind ofly except ammonia, except methanal paint, those skilled in the art can use for reference content herein, suitably improve processing parameter and realize.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are all deemed to be included in the present invention.Method of the present invention and application are described by preferred embodiment, related personnel obviously can change methods and applications as herein described or suitably change and combination within not departing from content of the present invention, spirit and scope, realizes and apply the technology of the present invention.
, comprise acceptable auxiliary agent in citrus peel extract, emulsion, titanium dioxide, coarse whiting, calcined kaolin, talcum powder and coating; The preparation method of described citrus peel extract is: in citrus pericarp, add respectively calcium hydroxide aqueous solution and copper sulfate solution, soak respectively 12～24h, collect the citrus pericarp after soaking; In g/mL, the mass volume ratio of described citrus pericarp and described calcium hydroxide aqueous solution or copper sulfate solution is 1: 1.5～and 1: 2, the concentration of described calcium hydroxide aqueous solution is 5～10%, the concentration of described copper sulfate solution is 1～1.5%; After described immersion, after the squeezing of citrus pericarp, collect juice, with 300～500 mesh filter screens, filter, collect filtrate, obtain citrus peel extract.
The alkalescence of calcium hydroxide is stronger than sodium hydroxide, but because the solubleness of calcium hydroxide is more much smaller than sodium hydroxide, so the corrodibility of aqua calcis is less than sodium hydroxide, therefore, calcium hydroxide can be applied to field widely.In the present invention, adopt the calcium hydroxide aqueous solution that concentration is 5～10% to soak citrus pericarp, pericarp hardening is become fragile, oil vacuole is easily broken, is conducive to squeezing, extracts the active substance in citrus pericarp.
As preferably, described coating, in the preparation method of citrus peel extract, the concentration of calcium hydroxide aqueous solution is 6～8%.
The aqueous solution of copper sulfate has the effect of sterilization, deinsectization, test-results shows, it is that 1～1.5% copper sulfate solution soaks citrus pericarp that the present invention adopts concentration, fungi, bacterium or insect in orange peel or pomelo peel not only can be killed, but also the extraction yield of the active substance in citrus pericarp can be improved.
As preferably, described coating, in the preparation method of citrus peel extract, the concentration of copper sulfate solution is 1.1～1.3%.
As preferably, described coating, in the preparation method of citrus peel extract, soak time is 16～24h.
As preferably, described coating, in the preparation method of citrus peel extract, also comprises cleaning, air-dry step after immersion.
As preferably, described coating, in the preparation method of citrus peel extract, also comprises pulverizing, the step of sieving before squeezing.
Preferably, sieve and obtain the particle that particle diameter is less than or equal to 7mm.
In coating provided by the invention, the extraction yield of citrus peel extract is 72.5～76.1%.
As preferably, GC-MS detected result shows, in citrus peel extract, sad content is 1.35～2.13%, the content of Palmitic acid is 0.97～1.48%, the content of limonene is 48.25～51.20%, and the content of myrcene is 11.97～14.94%, and the content of phantol oxide compound I is 11.49～16.15%, the content of phantol oxide compound II is 6.15～11.14%, and the content of germacrene D is 8.12～8.74%.
As preferably, coating provided by the invention, by percentage to the quality, contains described citrus peel extract 1～3%.
As preferably, coating provided by the invention, by weight percentage, comprising: citrus peel extract 1～3%, acrylate and vinyl acetate emulsion or benzene emulsion 23.5～44%, titanium dioxide 5～15%, coarse whiting 10～30%, calcined kaolin 5～15%, talcum powder 2～8%, surplus is described auxiliary agent.
As preferably, described coating is water soluble paint.
As preferably, described auxiliary agent comprises one or more the mixture in thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, ethylene glycol, sanitas, mould inhibitor.
Acrylate and vinyl acetate emulsion claims again vinyl acetate emulsion, is to take the aqueous high molecular resin that vinyl acetate between to for plastic and butyl acrylate form as major function monomer copolymerization.
In coating provided by the invention, acrylate and vinyl acetate emulsion be take vinyl acetate between to for plastic and butyl acrylate and is formed as monomer copolymerization.
As preferably, the glass transition temp of acrylate and vinyl acetate emulsion (Tg) is 10～20 ℃.
Preferably, the glass transition temp of acrylate and vinyl acetate emulsion (Tg) is 18 ℃.
As preferably, the minimum film-forming temperature of acrylate and vinyl acetate emulsion (MFT) is 5～6 ℃.
Preferably, in coating provided by the invention, acrylate and vinyl acetate emulsion outward appearance becomes milky white liquid, and solids content is 54～58%, is preferably 55%; Brookfield viscosity is 150～1600cp.s (3/60rpm/25 ℃); Average particle diameter is 0.18～0.45 μ m, is preferably 0.18～0.3 μ m; PH value (25 ℃) is 3.5～5.0 (25 ℃); Ion characteristic is negatively charged ion; Free monomer (% by weight) < 0.3; Glass transition temp (Tg) is 18 ℃; Minimum film-forming temperature (MFT) is 6 ℃; Wet proportion is 1.03～1.08; Dry proportion is 1.07～1.13.In coating provided by the invention, in acrylate and vinyl acetate emulsion, not containing APEO, do not contain formaldehyde yet.
Benzene emulsion (cinnamic acrylic ester emulsion) is to be made through emulsion copolymerization by vinylbenzene and acrylate monomer.Its solids content 40～50%, viscosity 800～2000mPas, it is 8～9 that level of residual monomers is less than 0.5%, pH value.Benzene emulsion sticking power is good, and glued membrane is transparent, and water-fast, oil resistant, heat-resisting, ageing-resistant performance is good.Specifically can be selected from silicone modified styrene-acrylate emulsion, organic fluorine modifying cinepazid emulsion.
Thickening material claims again jelling agent, can improve system viscosity, makes system keep even, stable suspended state or milkiness state, or forms gel.In emulsion paint is manufactured, thickening material plays many-sided coordinative role to the thickening of emulsion paint, stable and rheological property.In pigment, fillers dispersed stage, improve the viscosity of dispersed material and be beneficial to dispersion; In storage and transport process, improve paint stability, prevent that pigment, filler from sinking to the bottom caking; In construction, regulate emulsion paint viscosity, and present good rheological property etc.
Thickening material belongs to hydrophilic macromolecular compounds mostly, is by sources divided into animal class, plant, mineral substance, synthetic class or semi-synthetic class.Within simple minute, can be divided into natural and synthetic two large classes.Natural product great majority are to produce from plant and seaweeds containing polyose viscous substance, as starch, pectin, agar, gelatin, marine alga fat, carrageenin, dextrin, tragacanth gum, polysaccharide element derivative etc.; Synthetics has the derivatived celluloses such as methylcellulose gum, carboxymethyl cellulose, starch derivative, casein food grade, sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, low-molecular polyethylene wax, polyacrylamide etc.
Conventional thickening material has ether of cellulose and derivatives class, association type alkali swelling thickening material and polyurethane thickener.(1) ether of cellulose and derivative thereof: ether of cellulose and derivatives class thickening material thereof mainly contain Natvosol, methyl hydroxyethylcellulose, Type 3U, methylhydroxypropylcellulose etc.Hydrophobically modified Mierocrystalline cellulose is on Mierocrystalline cellulose hydrophilic skeleton, to introduce a small amount of long-chain hydrophobic alkyl, thereby becomes associative thickener, and the ether of cellulose thickening material kind that its thickening effectiveness can be much bigger with relative molecular mass is suitable.(2) alkali swelling type thickening material: alkali swelling thickening material is divided into two classes: non-association type alkali swelling thickening material and association type alkali swelling thickening material.(3) the non-polyurethane thickener of polyurethane thickener and hydrophobically modified: polyurethane thickener is a kind of hydrophobic grouping modification oxyethyl group urethane water-soluble polymers, belongs to non-ionic type associative thickener.Eco-friendly association type polyurethane thickener exploitation is generally paid attention to, and except the linear association type polyurethane thickener of introducing, also has pectination associative polyurethane thickening material above.In coating provided by the invention, the thickening material of interpolation does not limit.
Natvosol (HEC), is a kind of white or faint yellow, and tasteless, nontoxic fibrous or pulverulent solids is prepared through etherification reaction by alkali cellulose and oxyethane (or chloroethanol), belongs to non-ionic type soluble fiber element ethers.There is following character: 40 order sieving rate >=99; Softening temperature: 135～140 ℃; Performance density: 0.35～0.61g/mL; Decomposition temperature: 205～210 ℃; Combustionvelocity is slower; Balance is measured containing temperature: 23 ℃; During 50%rh 6%, during 84%rh 29%.
Because HEC has good thickening, suspension, dispersion, emulsification, bonding, film forming, protection moisture and the characteristics such as protective colloid are provided, the fields such as oil production, coating, building, medicine food, weaving, papermaking and macromolecular polymerization reaction have been widely used in.Natvosol, as a kind of tensio-active agent of non-ionic type, also has following character: HEC and dissolves in hot water or cold water, and high temperature or boil does not precipitate, and makes it have large-scale solvability and viscosity characteristics, and non-thermal gelation; Non-ionic type own can with on a large scale in other water-soluble polymerss, tensio-active agent, salt coexist, and are a kind of good colloid thickening materials containing high density electrolysis matter solution; Water retention capacity exceeds one times than methylcellulose gum, has good flow adjustment; The dispersive ability of HEC is compared dispersive ability with Vltra tears with generally acknowledged methylcellulose gum slightly poor, but protective colloid ability is stronger.
Therefore, in coating provided by the invention, the preferred Natvosol of thickening material (HEC).
Coating multifunctional assistant is the indispensable component of coating, and it can improvement of production process, keeps shelf-stable, improves execution conditions, improves the quality of products, and gives specific function.Rationally correctly select multifunctional assistant to reduce costs, increase economic efficiency.The multifunctional assistant adding in coating provided by the invention is not construed as limiting.
AMP-95 is a kind of 5% moisture content-2-amino-2-methyl-1-propanol that contains, and is also that current minority has one of lower molecular weight and overbasic industrial amine.Use AMP-95 as the multifunctional assistant of waterborne polymeric, except improving coating property, also can greatly reduce costs, because other amine of required amount ratio of AMP-95 is much lower.Not only have the excellent functions such as dispersion, thickening, adjusting pH value, nondiscoloration, but also possess antimicrobial (sterilization) characteristic, also can reduce VOC (volatile organic compounds) total amount, contribute to enhancing ring guaranteed cost simultaneously.In view of the foregoing, as preferably, in coating provided by the invention, add AMP-95 multifunctional assistant.
The outward appearance of wetting dispersing agent is limpid yellow liquid; Activated feedstock is a kind of modified polypropene acid sodium-salt; The content of active ingredient is 39～41%; Solids content is 40～45%; Ion characteristic is negatively charged ion; PH value is 7.0～9.0.Mineral dye is had to remarkable wetting and dispersive ability as ferric oxide and titanium dioxide etc.; Can improve colouring intensity, pigment stability in storage; In alkaline medium, strengthen water-base resin and emulsion consistency; There is good water-repellancy; Preferred wetting dispersing agent has not containing alkylphenol ethoxylate, not containing advantages such as solvents.The wetting dispersing agent adding in coating provided by the invention is not construed as limiting.
As preferably, in coating provided by the invention, add Akzo Nobel 645 as wetting dispersing agent, it is a kind of vinylformic acid sodium salt homopolymer.
Defoamer, is called again kilfoam, in industrial process, can produce many harmful foams, need to add defoamer.Be widely used in removing the harmful foam producing in the industry production processes such as latex, textile sizing, food fermentation, biological medicine, coating, petrochemical complex, papermaking, industry cleaning link.
The composition of defoamer: (1) active ingredient, effect: broken bubble, froth breaking, reduce surface tension; Representative: silicone oil, polyethers, higher alcohols, mineral oil, plant wet goods.(2) emulsifying agent, effect: make activeconstituents be dispersed into small-particle, be convenient to be dispersed in water, better play froth breaking, press down bubble effect.Representative: the ninth of the ten Heavenly Stems (pungent) base phenol polyethenoxy ether, soap salt, op series etc., tween series, this dish series etc.(3) carrier, effect: contribute to the combination of carrier and bubbling system, be easy to be distributed in bubbling system, both are combined, the surface tension of itself is low, contributes to press down bubble, and can reduce costs.Representative: the solvent beyond dewatering, as aliphatic hydrocarbon, aromatic hydrocarbon, oxo solvent etc.(4) emulsion adjuvant, effect: make emulsifying effectiveness better.Representative: dispersion agent: water drain silica etc.; Tackifier: CMC, polyvinyl ether etc.The defoamer adding in coating provided by the invention is not construed as limiting.
As preferably, in coating provided by the invention, add the CF-246 of England Blackburn company as defoamer.
Film coalescence aid claims again coalescing aid, can promote macromolecular compound plastic flow and recoverable deformation, improves coalescent performance, and the material of film forming within the scope of more extensive construction temperature is a kind of evanescent softening agent.Conventional is the strong solvent of ether alcohol class superpolymer, as propandiol butyl ether, 1-Methoxy-2-propyl acetate etc.General emulsion has film-forming temperature, when envrionment temperature during lower than emulsion film forming temperature emulsion be difficult for film forming, film coalescence aid can improve emulsion film forming mechanism, helps film forming.After film forming, film coalescence aid volatilization, can not affect the characteristic of filming.In industry, conventional film coalescence aid is alcohol ester-12 at present, the TEXNAL of Yi Siman.The film coalescence aid adding in coating provided by the invention is not construed as limiting.
As preferably, in coating provided by the invention, add alcohol ester-12 of Mitsui company as film coalescence aid.
Ethylene glycol (ethylene glycol) has another name called " glycol ", " 1,2 ethylene glycol ", is called for short EG.Molecular formula is C
2h
6o
2, chemical formula is (HOCH
2)
2, molecular weight is 62.07, is the simplest dibasic alcohol.Ethylene glycol is no color or smell, pleasantly sweet liquid, can dissolve each other with water, acetone, but solubleness is less in ethers, can be used as the raw material of solvent, frostproofer and synthetic terylene.In coating, mainly as antifreezing agent and solubility promoter, use.
Titanium dioxide formal name used at school is titanium dioxide (Titanium Dioxide), and molecular formula is TiO
2, relative molecular mass 79.90.Titanium dioxide stable chemical nature, does not react with most of material in the ordinary course of things, belongs to inert pigment, is considered at present the best a kind of white pigment of performance in the world.It has three kinds of crystallizations: plate titanium type, sharp titanium and rutile-type.Plate titanium type is unsettled crystal formation, without industrial utilization, be worth, anatase titanium dioxide (Anatase) is called for short A type, and rutile-type (Rutile) is called for short R type, all there is stable lattice, be important white pigment and porcelain glaze, relatively have superior whiteness, tinting strength, opacifying power, weathering resistance, thermotolerance and chemical stability with other white pigments, particularly there is no toxicity.
Titanium dioxide is a kind of intermediate oxide of slant acidity, under normal temperature, react with other elements and compound hardly, all inoperative to oxygen, ammonia, nitrogen, hydrogen sulfide, carbonic acid gas, sulfurous gas, water insoluble, fatty, also be insoluble to diluted acid and mineral acid, alkali, be only dissolved in hydrofluoric acid.But under light action, can there is continuous redox reaction in titanium dioxide, have photochemical activity.This kind of photochemical activity, under uviolizing, anatase thpe white powder is particularly evident, even if this character makes the photosensitized oxidation catalyzer of some mineral compound of titanium dioxide, is again some organic compound sensitized catalyzer.
Titanium dioxide is widely used at coating industry, and Rutile type Titanium Dioxide particularly is most ofly consumed by coatings industry.The coating of manufacturing with titanium dioxide, bright in luster, opacifying power is high, strong coloring force; low-consuming, wide in variety, to the stability of medium, can play a protective role, and can strengthen physical strength and the sticking power of paint film; prevent crackle, prevent that ultraviolet ray and moisture from seeing through, and extends the paint film life-span.
Titanium dioxide size-grade distribution is a comprehensive index, and it has a strong impact on titanium white powder pigment performance and product application performance, therefore, for opacifying power and dispersed discussion, can directly from size-grade distribution, analyze.The factor that affects titanium dioxide size-grade distribution is comparatively complicated, is first the size of hydrolysis initial size, by controlling and regulating hydrolysis process condition, makes initial size within the specific limits.Next is calcining temperature, and metatitanic acid is in the process of calcining, and particle experiences a transformation of crystal phase and growth stage, controls suitable temperature, makes to grow up particle within the specific limits.Be exactly finally the pulverizing of product, the adjusting to the transformation of Raymond mill and analyzer rotating speed conventionally, controls and pulverizes quality.The titanium dioxide adding in coating provided by the invention is not construed as limiting.
As preferably, in coating provided by the invention, add granularity and be the rutile titanium white powder of 0.2 μ m as titanium dioxide.
Water-ground limestone, is called for short coarse whiting, by natural carbonate mineral, as calcite, marble, Wingdale grind, is formed.Because its settling volume (1.1-1.9mL/g/) is less than the light calcium carbonate settling volume (2.4-2.8mL/g) of producing by chemical process, be therefore called as water-ground limestone.Water-ground limestone is conventional powdery mineral filler, have that chemical purity is high, inertia is large, be difficult for chemical reaction, Heat stability is good, at 400 ℃, can not decompose below, whiteness is high, oil absorbency is low, refractive index is low, matter is soft, dry, do not contain the advantages such as crystal water, the low wear(ing)value of hardness are little, nontoxic, tasteless, odorless, good dispersity.
In water-ground limestone, by weight percentage, contain CaCO
399.7%, Fe
2o
3≤ 0.005%, SiO
20.1%, Al
2o
3≤ 0.15%, whiteness 95%, 18～5 μ m.For white non-opaque pigment and filler, opacifying power is stronger, good dispersity.Because calcium carbonate color is white, relative latex in coating, solvent price is all cheap, and particle is thin, can be dispersed in coating, so be a large amount of pigment extenders that use.Along with the raising of environmental consciousness, architectural coating is used water-borne coatings in a large number, and calcium carbonate is due to hydrophilic, and low price, is widely used.Inserting of calcium carbonate can strengthen priming paint to the deposition of substrate surface and perviousness.In paste paint, calcium carbonate can make coating thickening, thickening, plays a kind of effect of filling and fill.So conventionally add water-ground limestone and light calcium carbonate in paste paint, add water-ground limestone and can reach 24.6～78.5%.In finish paint,, in finishing paint, half light and lustreless paint will adopt increases the way that pigment extender is cut down gloss, and calcium carbonate is exactly desirable delustring filler.Calcium carbonate can be used as wherein a kind of additive and brings into play its effect in multicolor finish, reaches and both reduces material cost, can improve again the object of decorative effect.Available light calcium carbonate in multicolor finish, i.e. precipitated chalk, its oil number is 80% left and right, granularity 15 μ m left and right, proportion 2.7 left and right, refractive index is 1.60 left and right.Also available water-ground limestone (calcite in powder) is that the grindings such as natural product marble form.In metal anti-corrosion paint, the suitable consumption of calcium carbonate is 30%.In metal anti-corrosion paint, calcium carbonate is pigment extender, also has rust inhibition.
Water-ground limestone is divided into corase grind calcium carbonate (> 3 μ m), fine grinding calcium carbonate (1～3 μ m), calcium carbonate superfine powder (0.5～1 μ m) by its original median size (d).Can select as required.The coarse whiting adding in coating provided by the invention is not construed as limiting.
As preferably, in coating provided by the invention, add 600 order coarse whitings.
Calcined kaolin can be applicable to coating, papermaking, rubber and plastics pottery etc., and wherein paint and coating are the topmost Application Areass of China's high-quality calcined kaolin, account for respectively 60% and 30% left and right of domestic ultra-fine high-brightness high grade kaolinite consumption.Compare with calcined kaolin not, the kaolinic combination water-content of low temperature calcination reduces, silicon-dioxide and alchlor content all increase, and active site increases, and structure changes, particle diameter is less and even, fill NR sizing material with calcined kaolin not and compare, it is basically identical that low temperature calcination kaolin is filled the vulcanization characteristics curve of NR sizing material, and your the A type hardness tester that continues is constant, tensile strength improves, and both physicalies all reach the requirement of the nontransparent sole industry standard of sports shoes.The calcined kaolin adding in coating provided by the invention is not construed as limiting.
As preferably, in coating provided by the invention, add 3000 order ground calcined kaolins.
Talcum powder, for white or off-white color, fine, without the powder of grittiness, molecular weight is 260.8617, hand touches with greasy feeling.Odorless, tasteless.In water, the acid of rare ore deposit or rare alkali hydroxide solution, all do not dissolve.Talcous main component is the moisture Magnesium Silicate q-agent of talcum, and molecular formula is Mg
3[Si
4o
10] (OH)
2.Belong to oblique system.Crystal is the sheet of false six sides or rhombus, is generally fine and close bulk, foliated lamellar, radial, fibrous agrregate, crystal water white transparency or white, but because presenting even light red of light green, pale yellow, shallow palm fibre containing a small amount of impurity; In cleavage surface, be pearliness.Hardness is close to 1, and proportion is 2.7～2.8.Good physics, the chemical propertys such as talcum has oilness, anti-sticks, helps that stream, resistivity against fire, resistance to acid, insulativity, fusing point are high, chemical torpescence, opacifying power are good, softness, good luster, adsorptive power are strong.The talcum powder kind of adding in coating provided by the invention is not construed as limiting.
Sanitas refers to the medicament of natural or synthetic chemical composition inhibitory substance corruption, to take the microbial growth that corrupt substance is metabolism substrate, has lasting restraining effect.It can suppress the most incident Putrefaction under different situations, particularly when general sterilization functions is insufficient, still has the effect of persistence.Added food, medicine, pigment, biological sample etc., the corruption causing to postpone microorganism growth or chemical transformation.Nitrite and sulfurous gas are one of conventional sanitass.To fiber and Dormant oils, coal tar, tannin for the preservation of timber against decay, to formaldehyde, mercuric chloride, toluene, butyl p-hydroxybenzoate, nitrofurazone derivative or face cream resinoid for biological sample.
In coating industry, sanitas is generally selected the isothiazolinone of Kathon CG class and the mixture of methylisothiazolinone, also has in addition benzisothiazole-3-ketone.
Isothiazolinone is a kind of wide spectrum, efficient, low toxicity, non-oxidative bactericide, mainly by CMIT (CMI) and MIT (MI), formed, by disconnecting the key of bacterium and algae protein matter, play to kill livestock and act on.After it contacts with microorganism, can promptly irreversibly suppress its growth, thereby cause the death of microorganism cells, therefore common bacteria, fungi, algae etc. are had to very strong inhibition and killing action.The efficiency of killing livestock is high, and degradation property is good, has the features such as do not produce residual, operational safety, compatibleness is good, stability is strong, use cost is low.Can be miscible with chlorine and most of yin, yang ion and nonionogenic tenside.During high dosage, isothiazolinone has been peeled off unusual effect to biological clay.
Methylisothiazolinone is a kind of efficient germicide, and heat-resisting water-borne preservative has good effect for suppressing microbial growth, can anti-bacteria, the growth of fungi, mould and mould.
Benzisothiazole-3-ketone has good bactericidal property; under acid and alkaline environment, all can use; at 180 ℃, be to still have fabulous stability, have its configuration product of good safety performance and have good stability, it can provide long protection to material system.And do not contain heavy metal, chlorine, formaldehyde and inorganic salt.
In a lot of sanitass, all contain formaldehyde, as preferably, in coating provided by the invention, add not Tao Shi LXE containing formaldehyde as sanitas.
Mould inhibitor refers to that mould is had and killed or restraining effect, prevents the preparation that application goes mouldy.There are phenols (as phenol), chlorophenols (as Pentachlorophenol), organic mercury salt (as phenyl mercury oleate), organic copper salt (as copper 8-quinolinolate), organic tin salt (as chlorination three second or tributyl tin etc.), and inorganic salt copper sulfate, mercury chloride, Sodium Fluoride etc.Be mainly used in plastics, rubber, textiles, paint and insulating material etc.The kind of the mould inhibitor adding in coating provided by the invention is not construed as limiting.
As preferably, in coating provided by the invention, add Ke Laien DFX-1 as mould inhibitor.
As preferably, by weight percentage, described auxiliary agent comprises: Natvosol thickening material 0.3～0.9%, AMP-95 multifunctional assistant 0.05～0.15%, wetting dispersing agent 0.3～0.6%, defoamer 0.2～0.4%, film coalescence aid 0.8～1.5%, ethylene glycol 1～1.5%, sanitas 0.1～0.3%, mould inhibitor 0.1～0.3%.
The invention provides a kind of except ammonia, except methanal paint.This coating comprises acceptable auxiliary agent in citrus peel extract, emulsion, titanium dioxide, coarse whiting, calcined kaolin, talcum powder and coating.Coating provided by the invention, self is release formaldehyde not, and the content of organic volatile gas (VOC) is lower, and quality meets national standard; Evidence, coating formaldehyde clearance provided by the invention is 76.49～84.97%, the clearance of ammonia is 100%, can continuous and effective remove the organic volatile gases such as airborne formaldehyde, ammonia.
In coating provided by the invention, each composition all can be buied by market.Wherein, titanium dioxide: the rutile titanium white powder that U.S. Du Bang company produces; 600 order coarse whitings: the water-ground limestone that Guangdong Dongfanghong powder company limited produces; Acrylate and vinyl acetate emulsion, benzene emulsion: LG-DOW company produces; Film coalescence aid: Mitsui company produces; AMP-95 multifunctional assistant: U.S. An Ge company produces; Sanitas, mould inhibitor: German Clariant company produces.
Below in conjunction with embodiment, further set forth the present invention:
Embodiment 1 coating that contains citrus peel extract provided by the invention
Get orange peel 100g, adding concentration is that 5% calcium hydroxide aqueous solution 200mL soaks 24h, adding concentration is 1.5% copper sulfate solution 150mL again, soaks 24h, and grinding and sieving obtains the particle that particle diameter is less than 7mm, after squeezing, collect juice, with 420 mesh filter screens, filter, collect filtrate, obtain orange peel extract, extraction yield is 72.5%.
GC-MS detected result shows, in orange peel extract, sad content is 1.35%, the content of Palmitic acid is 0.97%, the content of limonene is 48.60%, the content of myrcene is 13.58%, the content of phantol oxide compound I is 11.58%, and the content of phantol oxide compound II is 6.22%, and the content of germacrene D is 8.12%.
Accurately take orange peel extract 1.0g provided by the invention, acrylate and vinyl acetate emulsion 24.5g, Natvosol thickening material 0.3g, AMP-95 multifunctional assistant 0.05g, wetting dispersing agent 0.3g, defoamer 0.2g, film coalescence aid 0.8g, ethylene glycol 1.5g, titanium dioxide 5g, 600 order coarse whiting 30g, calcined kaolin 5g, talcum powder 2g, sanitas 0.1g, mould inhibitor 0.1g, measures 29.15mL water.
First at stirring tank, first add water, then order adds Natvosol thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, middling speed dispersion after ethylene glycol; Then add titanium dioxide, 600 order coarse whitings, orange peel extract provided by the invention, calcined kaolin, after talcum powder, high speed dispersion to fineness is less than 50 μ m; After turning low speed, add acrylate and vinyl acetate emulsion, sanitas, mould inhibitor stirs, and obtains.
Embodiment 2 coating that contains citrus peel extract provided by the invention
Get pomelo peel 100g, adding concentration is that 10% calcium hydroxide aqueous solution 150mL soaks 12h, adding concentration is 1.2% copper sulfate solution 180mL again, soaks 14h, and grinding and sieving obtains the particle that particle diameter is less than or equal to 7mm, after squeezing, collect juice, with 360 mesh filter screens, filter, collect filtrate, obtain pomelo peel extract, extraction yield is 74.3%.
GC-MS detected result shows, in pomelo peel extract, sad content is 1.69%, the content of Palmitic acid is 1.35%, the content of limonene is 48.25%, the content of myrcene is 11.97%, the content of phantol oxide compound I is 13.01%, and the content of phantol oxide compound II is 6.15%, and the content of germacrene D is 8.21%.
Accurately take pomelo peel extract 2.0g provided by the invention, benzene emulsion 25g, Natvosol thickening material 0.5g, AMP-95 multifunctional assistant 0.15g, wetting dispersing agent 0.45g, defoamer 0.4g, film coalescence aid 1.5g, ethylene glycol 1.2g, titanium dioxide 15g, 600 order coarse whiting 20g, calcined kaolin 15g, talcum powder 8g, sanitas 0.3g, mould inhibitor 0.3g, measures 10.2mL water.
First at stirring tank, first add water, then order adds Natvosol thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, middling speed dispersion after ethylene glycol; Then add titanium dioxide, 600 order coarse whitings, pomelo peel extract provided by the invention, calcined kaolin, after talcum powder, high speed dispersion to fineness is less than 50 μ m; After turning low speed, add benzene emulsion, sanitas, mould inhibitor stirs, and obtains.
Embodiment 3 coating that contains citrus peel extract provided by the invention
Get Pericarpium citri sinensis 100g, adding concentration is that 7% calcium hydroxide aqueous solution 180mL soaks 16h, adding concentration is 1% copper sulfate solution 200mL again, soaks 18h, and grinding and sieving obtains the particle that particle diameter is less than or equal to 7mm, after squeezing, collect juice, with 300 mesh filter screens, filter, collect filtrate, obtain Pericarpium citri sinensis extract, extraction yield is 73.8%.
GC-MS detected result shows, in Pericarpium citri sinensis extract, sad content is 1.47%, the content of Palmitic acid is 1.24%, the content of limonene is 49.56%, the content of myrcene is 14.22%, the content of phantol oxide compound I is 15.49%, and the content of phantol oxide compound II is 9.10%, and the content of germacrene D is 8.71%.
Accurately take Pericarpium citri sinensis extract 3.0g provided by the invention, acrylate and vinyl acetate emulsion 28.2g, Natvosol thickening material 0.5g, AMP-95 multifunctional assistant 0.1g, wetting dispersing agent 0.6g, defoamer 0.3g, film coalescence aid 1g, ethylene glycol 1.5g, titanium dioxide 10g, 600 order coarse whiting 28g, calcined kaolin 10g, talcum powder 5g, sanitas 0.2g, mould inhibitor 0.2g, measures 11.4mL water.
First at stirring tank, first add water, then order adds Natvosol thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, middling speed dispersion after ethylene glycol; Then add titanium dioxide, 600 order coarse whitings, Pericarpium citri sinensis extract provided by the invention, calcined kaolin, after talcum powder, high speed dispersion to fineness is less than 50 μ m; After turning low speed, add acrylate and vinyl acetate emulsion, sanitas, mould inhibitor stirs, and obtains.
Embodiment 4 coating that contains citrus peel extract provided by the invention
Get lemon peel 100g, adding concentration is that 9% calcium hydroxide aqueous solution 170mL soaks 18h, adding concentration is 1.3% copper sulfate solution 170mL again, soaks 22h, and grinding and sieving obtains the particle that particle diameter is less than or equal to 7mm, after squeezing, collect juice, with 400 mesh filter screens, filter, collect filtrate, obtain lemon peel extract, extraction yield is 76.1%.
GC-MS detected result shows, in lemon peel extract, sad content is 2.13%, the content of Palmitic acid is 1.27%, the content of limonene is 46.11%, the content of myrcene is 14.13%, the content of phantol oxide compound I is 16.15%, and the content of phantol oxide compound II is 11.14%, and the content of germacrene D is 8.35%.
Accurately take lemon peel extract 2.5g provided by the invention, benzene emulsion 32.3g, Natvosol thickening material 0.9g, AMP-95 multifunctional assistant 0.15g, wetting dispersing agent 0.5g, defoamer 0.35g, film coalescence aid 1.4g, ethylene glycol 1g, titanium dioxide 8g, 600 order coarse whiting 10g, calcined kaolin 12g, talcum powder 4g, sanitas 0.1g, mould inhibitor 0.1g, measures 26.7mL water.
First at stirring tank, first add water, then order adds Natvosol thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, middling speed dispersion after ethylene glycol; Then add titanium dioxide, 600 order coarse whitings, lemon peel extract provided by the invention, calcined kaolin, after talcum powder, high speed dispersion to fineness is less than 50 μ m; After turning low speed, add benzene emulsion, sanitas, mould inhibitor stirs, and obtains.
Embodiment 5 coating that contains citrus peel extract provided by the invention
Get mandarin orange skin 100g, adding concentration is that 8% calcium hydroxide aqueous solution 190mL soaks 21h, adding concentration is 1.1% copper sulfate solution 190mL again, soaks 20h, and grinding and sieving obtains the particle that particle diameter is less than or equal to 7mm, after squeezing, collect juice, with 500 mesh filter screens, filter, collect filtrate, obtain mandarin orange peel extract, extraction yield is 75.5%.
GC-MS detected result shows, in mandarin orange peel extract, sad content is 1.77%, the content of Palmitic acid is 1.48%, the content of limonene is 51.20%, the content of myrcene is 14.94%, the content of phantol oxide compound I is 13.15%, and the content of phantol oxide compound II is 7.14%, and the content of germacrene D is 8.74%.
Accurately take mandarin orange peel extract 1.5g provided by the invention, acrylate and vinyl acetate emulsion 23.5g, Natvosol thickening material 0.7g, AMP-95 multifunctional assistant 0.05g, wetting dispersing agent 0.4g, defoamer 0.25g, film coalescence aid 1.2g, ethylene glycol 1.2g, titanium dioxide 13g, 600 order coarse whiting 30g, calcined kaolin 8g, talcum powder 6g, sanitas 0.2g, mould inhibitor 0.2g, measures 13.8mL water.
First at stirring tank, first add water, then order adds Natvosol thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, middling speed dispersion after ethylene glycol; Then add titanium dioxide, 600 order coarse whitings, mandarin orange peel extract provided by the invention, calcined kaolin, after talcum powder, high speed dispersion to fineness is less than 50 μ m; After turning low speed, add acrylate and vinyl acetate emulsion, sanitas, mould inhibitor stirs, and obtains.
Embodiment 6 coating that contains citrus peel extract provided by the invention
Get pomelo peel 100g, adding concentration is that 10% calcium hydroxide aqueous solution 150mL soaks 12h, adding concentration is 1.2% copper sulfate solution 180mL again, soaks 14h, and grinding and sieving obtains the particle that particle diameter is less than or equal to 7mm, after squeezing, collect juice, with 360 mesh filter screens, filter, collect filtrate, obtain pomelo peel extract, extraction yield is 74.3%.
GC-MS detected result shows, in pomelo peel extract, sad content is 1.69%, the content of Palmitic acid is 1.35%, the content of limonene is 48.25%, the content of myrcene is 11.97%, the content of phantol oxide compound I is 15.37%, and the content of phantol oxide compound II is 10.28%, and the content of germacrene D is 8.21%.
Accurately take pomelo peel extract 1.0g provided by the invention, benzene emulsion 44g, Natvosol thickening material 0.7g, AMP-95 multifunctional assistant 0.05g, wetting dispersing agent 0.6g, defoamer 0.25g, film coalescence aid 1.2g, ethylene glycol 1.2g, titanium dioxide 13g, 600 order coarse whiting 10g, calcined kaolin 8g, talcum powder 2g, sanitas 0.2g, mould inhibitor 0.2g, measures 15.8mL water.
First at stirring tank, first add water, then order adds Natvosol thickening material, multifunctional assistant, wetting dispersing agent, defoamer, film coalescence aid, middling speed dispersion after ethylene glycol; Then add titanium dioxide, 600 order coarse whitings, pomelo peel extract provided by the invention, calcined kaolin, after talcum powder, high speed dispersion to fineness is less than 50 μ m; After turning low speed, add benzene emulsion, sanitas, mould inhibitor stirs, and obtains.
7 pairs of coating qualities provided by the invention of embodiment detect
The coating that the embodiment of the present invention 1 to 6 provides send national building materials test center, and detected result is in Table 1.
Table 1 coating purifying formaldehyde provided by the invention rate detects
The quality of 8 pairs of coating provided by the invention of embodiment detects
According to the detection method of limits of harmful substances national standard in GB18582-2008 indoor decorating and refurnishing materials interior wall coating, the coating that the embodiment of the present invention 1 to 6 is provided is delivered Beijing Wei Liang chemistry institute Institute of Analysis and is detected, and the results are shown in Table 2.
Table 2 coating objectionable impurities provided by the invention detects
As shown in Table 2, coating provided by the invention all meets national standard.
Embodiment 9 detects the formaldehyde removal effect of coating provided by the invention
Handled object is as timber building materials such as () main adhesive plate, fiberboard or decorative sheets, paper, fiber, fibre product, resin forming product etc.
By the coating making in embodiment 1 to 6, according to the measuring method of following burst size of methanal, the formaldehyde performance of removing of coating provided by the invention is evaluated.
The preparation of test film: the two sides 6 F2 adhesive plates (specification is 35cm * 35cm * 0.55cm), evenly apply respectively the coating that embodiment 1 to 6 makes, after drying at room temperature, pack in plastics bag sealing 24h into.From being coated with the F2 adhesive plate of the coating that embodiment 1 to 6 makes, with 15cm * 5cm * 0.55cm, be cut into test film.
The preparation of comparison film: be cut into comparison film according to 15cm * 5cm * 0.55cm from the F2 adhesive plate of uncoated coating provided by the invention.
Crystallizing dish (the diameter 120mm that fills 300mL distilled water is placed in bottom at moisture eliminator (the about 10L of big or small 240mm, internal volume that meets JIS R3503 regulation), high 60mm), above it, be covered with porcelain plate, place respectively above-mentioned test film and comparison film, place 24h in 20～25 ℃, the formaldehyde absorption that F2 adhesive plate is separated out in distilled water as test soln.
In test soln, concentration of formaldehyde is measured with luminous point colorimeter colorimetric assay according to acetylacetone method.
The formaldehyde diffusing capacity that formaldehyde diffusing capacity (mg/L) is comparison film.
The formaldehyde diffusing capacity of formaldehyde diffusing capacity-comparison film that formaldehyde reduction (mg/L) is test film.
Formaldehyde is removed rate (%)=formaldehyde reduction (mg/L)/formaldehyde diffusing capacity (mg/L) * 100.
The results are shown in Table 3.
Table 3 coating provided by the invention is except effect of formaldehyde
As shown in Table 3, the coating that the embodiment of the present invention 1 to 6 provides is release formaldehyde not, and the rate of removing of formaldehyde reaches 76.49～84.97%, can effectively remove the formaldehyde that upholstery and furniture are separated out.
Embodiment 10 detects the formaldehyde removal effect of coating provided by the invention
The wood-based plate of 7 25cm * 25cm (seven lis of plates) is put into respectively to the encloses container of 20L, after 24h, with 4160 type Formaldehyde instrument, measured and record two concentration of formaldehyde values in encloses container; Then take out wood-based plate, will be wherein one apply common coating (not adding Pericarpium Kaki extract provided by the invention, the auxiliary agent in the coating that the auxiliary agent in coating provides with embodiment 1 to 6) as a control group, every 1h, apply one time, apply altogether 3 times; All the other 6 as test group, respectively and the coating that provides of the embodiment of the present invention 4 to 9, every 1h, applies one time, applies altogether 3 times.After 24h finish-drying, put into again encloses container, after airtight 24h, then measure and record the concentration of formaldehyde value in encloses container with 4160 type Formaldehyde instrument.After 36h, 48h, 60h, 72h, 5d, 7d, 11d, 18d, 30d, 60d, 90d, measure and record concentration of formaldehyde respectively.
Detecting instrument: be the U.S.'s 4160 type Formaldehyde instrument that national standard metering is assert, display density value numeral in the time of detection.The numerical value that 4160 type Formaldehyde instrument are measured and the deviation of laboratory chemical process detected value, generally in 5%.
Measure numerical standard: the content of measured value formaldehyde in indoor air is international standard value ppm, applicable China standard, need be converted into milligram value (mg/m
3).
The highest limit value of national regulation indoor formaldehyde concentration (GB/T 18883-2002) 0.10mg/m
3.Milligram with the reduction formula of ppm is: 1ppm=1.247mg/m
3.
Measurement result is in Table 4.
Table 4 coating provided by the invention is except effect of formaldehyde
As shown in Table 4, common coating also has certain effect of formaldehyde that removes, and the formaldehyde clearance when 24h is 8.24%; After 5d, formaldehyde clearance reaches minimum, is 18.09%; Pass in time, remove formaldehyde rate and do not rise counter falling, this shows, it is very limited that common coating absorbs the amount of formaldehyde, the formaldehyde of separating out in the follow-up period can not absorb interior finish, or on the contrary the formaldehyde absorbing in the past is again discharged and made the return trip empty in gas.The coating that the embodiment of the present invention 1 to 6 provides in the time, keeps good formaldehyde clearance at 24h to 90d always, is 76.57～84.63%, can effectively remove the formaldehyde discharging in interior finish.
Embodiment 11 detects the organic volatile gas removal effect of coating provided by the invention
The solution that discharges the objectionable impuritiess such as benzene, ammonia is sprayed into respectively in the climate box of 7 airtight same volumes, wherein in 6 climate boxs, place the sheet glass be coated with the coating that the embodiment of the present invention 1 to 6 makes, in the integral point time period, the portable ammonia organic gas of the TLV FALCON PID monitor that detects ，Huo Yong U.S. product with ammonia detector tube detects.
Test group: select 1 airtight proofing box (about 1m
3, inside is provided with ultraviolet source), in proofing box, be placed with the sheet glass that surface-coated has the 50cm * 50cm of the coating that in the present invention, embodiment 1 makes.Spray into benzene, control constant temp (23 ℃ ± 2), humidity (60%), through 30min, make ammonia fully volatilize and fill the air.
Control group: select airtight proofing box (the about 1m with test group formed objects
3, inside is provided with ultraviolet source), in proofing box, be placed with the sheet glass of 50cm * 50cm, apply common coating.Spray into ammonia, control constant temp (23 ℃ ± 2), humidity (60%), through 30min, make benzene fully volatilize and fill the air.
After 24h, the air sampling with atmosphere sampling instrument to each airtight proofing box, and carry out blank determination with the absorption liquid of on-the-spot unsampled blank absorption tube.According to the portable ammonia organic gas of benzene,toluene,xylene health test method > > test ammonia concentration in air ，Huo Yong U.S. TLV FALCON detector in the atmosphere of GB/T11737-2001 < < residential district, detect and record.
Measurement result is in Table 5.
Table 5 coating provided by the invention is except organic volatile gas effect
As shown in Table 5, the coating that embodiment 1 provided by the invention makes has good removal effect to airborne ammonia, and clearance is 100%.The coating that embodiment 2 to 6 provided by the invention makes also has the close effect of coating making with embodiment 1, can effectively remove airborne ammonia equally.Wherein, the coating that embodiment 2 to 6 makes is 100% to the clearance of ammonia
Comprehensive the above results, coating provided by the invention is 100% to the clearance of ammonia, has preferably except ammonia effect.
Embodiment 12 coating provided by the invention is removed the detection test of formaldehyde and ammonia
Test group: the coating that the embodiment of the present invention 1 provides;
Control group: the common coating that does not add citrus peel extract provided by the invention.
Detect in test group and control group coating 7 days, 15 days, within 30 days, discharge afterwards the amount of ammonia and formaldehyde, the results are shown in Table 6.
In table 6 coating, discharge the amount of ammonia and formaldehyde
Test-results by table 6 shows, coating provided by the invention, and after test 7 days, the amount that discharges ammonia, formaldehyde with control group does not have significant difference; After 15 days, compare with control group, the burst size of test group coating formaldehyde declines 37.5%, and the burst size of ammonia declines 43.75%, with control group significant difference (P < 0.05); After 30 days, compare with control group, the clearance of test group coating formaldehyde is 77.14%, and the clearance of ammonia is 100%, with control group difference extremely significantly (P < 0.01).
The coating that the embodiment of the present invention 2 to 6 is provided removes according to the method described above ammonia, removes the effect detection of formaldehyde, result and above-mentioned test-results have consistence, the coating that the embodiment of the present invention 2 to 6 provides all can effectively be removed ammonia and formaldehyde, and the test-results of control group is had to significant difference.
Comprehensive above-mentioned test-results, the coating that the embodiment of the present invention 1 to 6 provides can effectively be removed ammonia and formaldehyde.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a coating, is characterized in that, by weight percentage, it consists of: citrus peel extract 1～3%, acrylate and vinyl acetate emulsion or benzene emulsion 23.5～44%, titanium dioxide 5～15%, coarse whiting 10～30%, calcined kaolin 5～15%, talcum powder 2～8%, surplus is auxiliary agent; By weight percentage, described auxiliary agent consists of: Natvosol thickening material 0.3～0.9%, AMP-95 multifunctional assistant 0.05～0.15%, wetting dispersing agent 0.3～0.6%, defoamer 0.2～0.4%, film coalescence aid 0.8～1.5%, ethylene glycol 1～1.5%, sanitas 0.1～0.3%, mould inhibitor 0.1～0.3%; The preparation method of described citrus peel extract is: in citrus pericarp, add respectively calcium hydroxide aqueous solution and copper sulfate solution, soak respectively 12～24h, collect the citrus pericarp after soaking; In g/mL, the mass volume ratio of described citrus pericarp and described calcium hydroxide aqueous solution or copper sulfate solution is 1:1.5～1:2, and the concentration of described calcium hydroxide aqueous solution is 5～10%, and the concentration of described copper sulfate solution is 1～1.5%; After citrus pericarp squeezing after described immersion, collect juice, with 300～500 mesh filter screens, filter, collect filtrate, obtain citrus peel extract.
2. coating as claimed in claim 1, is characterized in that, in the preparation method of described citrus peel extract, the concentration of calcium hydroxide aqueous solution is 6～8%.
3. coating as claimed in claim 1, is characterized in that, in the preparation method of described citrus peel extract, the concentration of copper sulfate solution is 1.1～1.3%.
4. coating as claimed in claim 1, is characterized in that, in the preparation method of described citrus peel extract, soak time is 16～24h.
5. coating as claimed in claim 1, is characterized in that, in the preparation method of described citrus peel extract, also comprises cleaning, air-dry step after immersion.
6. coating as claimed in claim 1, is characterized in that, also comprises pulverizing, the step of sieving before described squeezing.
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| CN108690442A (en) * | 2018-06-24 | 2018-10-23 | 南京市雨花台区绿宝工业设计服务中心 | A kind of preparation method except formaldehyde composite coating |
| CN111117462A (en) * | 2020-01-06 | 2020-05-08 | 深圳市美施美克新材料有限公司 | Two-component environment-friendly coating rich in d-limonene and preparation method thereof |
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| CN101343451A (en) * | 2007-07-12 | 2009-01-14 | 上海汉邦化工有限公司 | Healthy inner wall paint without VOC and preparing method |
| CN101397431A (en) * | 2007-12-03 | 2009-04-01 | 三棵树涂料股份有限公司 | Environment friendly coating |
| CN102051095A (en) * | 2011-01-22 | 2011-05-11 | 中山市丽莎涂料有限公司 | Low-carbon energy-saving latex paint and preparation method thereof |
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| EP0093198A1 (en) * | 1982-04-22 | 1983-11-09 | OECE - INDUSTRIE CHIMICHE - S.p.A. | Additive compound designed to reduce the harmful effects produced by polyurethane paints and varnishes and the finishes obtained therewith |
| CN101343451A (en) * | 2007-07-12 | 2009-01-14 | 上海汉邦化工有限公司 | Healthy inner wall paint without VOC and preparing method |
| CN101397431A (en) * | 2007-12-03 | 2009-04-01 | 三棵树涂料股份有限公司 | Environment friendly coating |
| CN102051095A (en) * | 2011-01-22 | 2011-05-11 | 中山市丽莎涂料有限公司 | Low-carbon energy-saving latex paint and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN102391741A (en) | 2012-03-28 |
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