CN102471666A - Hydrophilic coating agent and method for using same - Google Patents
Hydrophilic coating agent and method for using same Download PDFInfo
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- CN102471666A CN102471666A CN2010800304986A CN201080030498A CN102471666A CN 102471666 A CN102471666 A CN 102471666A CN 2010800304986 A CN2010800304986 A CN 2010800304986A CN 201080030498 A CN201080030498 A CN 201080030498A CN 102471666 A CN102471666 A CN 102471666A
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- coating agent
- wetting ability
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- tackifier
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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
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
-
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Disclosed is a coating-type hydrophilic coating agent which is ideal for the anti-fouling treatment of the exterior walls of buildings and the anti-fogging treatment of vinyl or glass agricultural greenhouses or similar and which is a one-part hydrophilic coating agent using sodium silicate [Na2O2 (SiO2)]. Also disclosed is a method for using the coating agent. The disclosed coating-type one-part hydrophilic coating agent is inexpensive and easy to use and has 1-70 parts by weight of inexpensive sodium silicate and 0.5-30 parts by weight of low-molecular hydrophilic organic compounds as main components. When applied to films for agricultural use or the external walls of buildings etc. the hydrophilic coating agent dries and the glass in the sodium silicate adheres rigidly onto the application surface, coating the surface, and due to the low-molecular hydrophilic organic compounds which are contained in the glass and distributed onto the application surface, water droplets and rain droplets run-off. When used diluted, the coating agent container becomes even smaller in size and easier to use. Furthermore, should the hydrophilic effect decrease, the hydrophilic properties can be maintained through reapplication.
Description
Technical field
The present invention relates to be suitable for the coating class wetting ability coating agent and the method for use thereof of antifouling processing of exterior wall such as antifog processing such as plastic greenhouse, greenhouse or dwelling house etc., at length relate to providing and use water glass [Na
2O2 (SiO
2)] the cheap wetting ability coating agent and the method for use thereof of 1 liquid formula.
Background technology
In the past; In plastic greenhouse and greenhouse; Because the temperature variation that dawn etc. are rapid etc. are adhered to water droplet mostly at plastic film for agricultural use (plastic greenhouse) or agricultural glass (greenhouse) in the inboard, if this water droplet is dropped in the booth and the surface of the farm crop in the greenhouse; The water droplet of farm crop adheres to the place and will turn white, and the commodity value of farm crop descends.Therefore, be necessary to apply antifog processing, make water droplet evenly bedew plastic film for agricultural use or agricultural glass inner side surface and flow down, water droplet is dropped on the farm crop in the inboard of plastic film for agricultural use or agricultural glass.In addition, according to circumstances, also be necessary to apply antifog processing in the outside of plastic film for agricultural use or agricultural glass.
Yet, in above-mentioned antifog processing, can use antifogging agent (being also referred to as drip agent).In antifogging agent, there is resin to sneak into the antifogging agent of type and application type (coating class).
And; Sneak into the antifogging agent of type as resin; For example; It is the antifogging agent of staple that proposition has with the such mineral colloid particle of tensio-active agent, metallic colloid, is the antifogging agent of staple and is the antifogging agent etc. of staple with the mixture of hindered amine compound and hydrotalcite-based compound with the reaction mixture of the dicarboxylicacid of carbonatoms 3～20 and fatty alcohol or fatty amine or polyvalent alcohol or oxyethane ring; Any a kind of resene antifogging agent is all mixing in advance goes in plastic film for agricultural use etc. and uses (for example, with reference to patent documentation 1,2,3).
In addition; As the application type antifogging agent; It is the antifogging agent of staple that proposition has with water-absorbent crosslinked resins such as unsaturated carboxylate type monomers; Be the antifogging agent of the wetting ability coating agent of staple with inorganic hydrophilic property colloidalmaterial and wetting ability organic cpds, any a kind of antifogging agent in the application type all carries out follow-up coating and uses (for example, with reference to patent documentation 4,5) in the plastic film for agricultural use in existing plastic greenhouse or greenhouse, agricultural glass etc.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 11-151788 specification sheets
Patent documentation 2: japanese kokai publication hei 9-31242 communique
Patent documentation 3: the special fair 6-99602 communique of Japan
Patent documentation 4: TOHKEMY 2007-237728 communique
Patent documentation 5: japanese kokai publication hei 10-248404 communique
Summary of the invention
Invent problem to be solved
Above-mentioned resin is sneaked into the antifogging agent of type, can not on existing plastic greenhouse and greenhouse, implement follow-up antifog processing, must change plastic film for agricultural use or agricultural glass when anti-fog effect deterioration with time etc. and spends a large amount of time and expense.
On the other hand, the antifogging agent of above-mentioned application type can be coated with in the plastic film for agricultural use in present plastic greenhouse or greenhouse, agricultural mode with spraying etc. on glass, can apply antifog processing simply.And, when anti-fog effect deterioration with time, can be coated with once more, than the antifogging agent of the type of sneaking into, the degree of freedom of the antifogging agent treatment process of application type is high.
Therefore, the antifogging agent that antifogging agent that we can say application type is sneaked into type than resin is more useful in after market (aftermarket) especially.
But; Because application type antifogging agent in the past is the water-absorbent crosslinked resin of polymkeric substance with high price is the antifogging agent of the application type of staple or the wetting ability coating agent that is staple with the inorganic hydrophilic property colloidalmaterial (colloid silica) and the wetting ability organic cpds of high price, so be to cost an arm and a leg.In addition, particularly the latter is the application type antifogging agent of the wetting ability coating agent of staple with inorganic hydrophilic property colloidalmaterial and wetting ability organic cpds, is actually 2 liquid formulas; Need container and increases that take up space of 2 liquid, transportation and expense certainly etc. are high, and; Must be at the scene during use with 2 liquid with the suitable proportion mixed diluting; Quite trouble in addition, also must be considered to select diluting water with the reaction of colloid silica.
On the other hand,, hope to use some wetting ability coating agent, the dirt of metope and rainwater are together flowed away, carry out soil release automatically recently at the exterior wall (external wall of house) of dwelling house etc.So,, do not invent out the wetting ability coating agent of cheap and safe aqueous solution class though propose that the high price wetting ability coating agent that uses hydrophilic polymer or titanium oxide etc. is arranged.
In addition, when implementing above-mentioned antifog processing or antifouling processing, more preferably handle and also carry out antimicrobial treatment (mildew-resistant-liver moss is handled) simultaneously with these.In many wetlands districts such as areas, Asia,, make middle light transmittance declines such as agricultural greenhouse especially because of adhering to of mould or liver moss; Residence outer wall outward appearances such as (external wall of house) is worsened, though prevent these generations aspect, antimicrobial treatment is useful; But in the antiseptic-germicide because of being exposed to outdoor dispersing or deterioration; Make it render a service a lot of of inactivation by cl concn, acidity, alkalescence, in antifog treatment agent or antifouling treatment agent, select suitable antiseptic-germicide and be not easy.
The present invention considers the premises and makes; A kind of 1 liquid formula wetting ability coating agent and method of use thereof is provided; This coating agent is the application type wetting ability coating agent that is suitable for use in antifog processing such as plastic greenhouse, greenhouse or the antifouling processing of external wall of house, and uses cheap water glass [Na
2O2 (SiO
2)].
Be used to solve the method for problem
In order to achieve the above object, wetting ability of the present invention coating agent is characterized in that, comprises the water glass [Na with 1～70 weight part
2O2 (SiO
2)] and the low molecular weight amphiphile water-based organic cpds of 0.5～30 weight part be the aqueous solution of staple; Above-mentioned low-molecular-weight organic compound has a kind of in carboxylic acid group, carboxylate group, hydroxyl, carboxamido-group, amino, the ammonium salt base at least, and is 1～18 wetting ability organic cpds (claim 1) for carbonatoms.
Wetting ability of the present invention coating agent is characterized in that, in the formation of claim 1, also has a kind of tackifier (claim 2) in carboxylic acid group, hydroxyl, phosphate, sulfate, carboxamido-group or the amino at least with what contain 0.1～15 weight part.
In addition; Wetting ability of the present invention coating agent; It is characterized in that, in the formation of claim 2, also contain the metal ion compound of 0.1～15 weight part; This metal ion compound and the reaction of above-mentioned water glass make above-mentioned wetting ability coating agent tackify, and further make tackify effect performance (claim 3) with the tackifier reaction.
In addition, wetting ability of the present invention coating agent is characterized in that, also contains the quaternary ammonium salt organic cpds (claim 4) of 0.005～1 weight part.
And; The method of use of wetting ability of the present invention coating agent; It is characterized in that, the one side coating at least of coating objects such as plastic film for agricultural use, agricultural glass, external wall of house with water with claim 1～4 in the diluent (claim 5) that obtains of each described wetting ability coating agent dilution.
The effect of invention
Wetting ability of the present invention coating agent is the water glass [Na that comprises the cheapness of 1～70 weight part
2O2 (SiO
2)] and 0.5～30 weight part have a kind of in carboxylic acid group, carboxylate group, hydroxyl, carboxamido-group, amino, the ammonium salt base at least, and than cheap carbonatoms 1 (formic acid etc.)～18 (Triple Pressed Stearic Acid (C of macromolecular organic compound
17H
35COOH) etc. low molecular weight amphiphile water-based organic cpds) is as the 1 liquid formula aqueous solution of staple, and the expense of in 1 container, holding formation, transportation and keeping etc. is cheap, and; Needn't mix 2 liquid at the scene in use, in addition, diluting water can be a water arbitrarily; And; The mistake that can 2 liquid mixture operations when using produce ratio of mixture, or by mixing order the performance difference that tells on, processing ease.
And, if coating is dry on the wall face of the medial surface of plastic film for agricultural use etc. or outer side, dwelling house, will on these coated faces, fits securely and be coated with above-mentioned coated face as thin Vitrea film.At this moment, in above-mentioned vitreum, carrying the carbonatoms of holding is 1 (formic acid etc.)～18 (Triple Pressed Stearic Acid (C
17H
35COOH) etc. low molecular weight amphiphile water-based organic cpds) is more cheap than macromolecular organic compound, is held in the vitreum through carrying, and in above-mentioned coated face, distributes equably, is incorporated into above-mentioned coated face securely.And, if on above-mentioned coating surface, adhere to water droplet or raindrop, the wetting ability through low molecular weight amphiphile water-based organic cpds then, water droplet or raindrop can not become big and flow down in that above-mentioned coated face is wetting equably, bring into play antifog or anti-fouling effect.In addition, when anti-fog effect or anti-fouling effect weakened, if be coated with the wetting ability coating agent once more, effect will be recovered simply.
Therefore, a kind of 1 liquid formula wetting ability coating agent can be provided, it is the application type wetting ability coating agent of antifouling processing that is applicable to antifog processing or the external wall of house in plastic greenhouse or greenhouse, and it uses water glass [Na
2O2 (SiO
2)] and processing ease.
In addition; When wetting ability of the present invention coating agent, through adding a certain amount of tackifier again, the cementability that improves when being coated with and adhere to dry back sodium silicate layer and base material film etc.; Make as the plastic film for agricultural use of base material etc. and adhere to more securely, improve the weather resistance of coating layer.In addition, because the tackifier water cut is many, so improve on the above-mentioned coated face of plastic film for agricultural use etc. for the water droplet that produces or the anti-fog effect (wetting ability) of raindrop anti-fog effect and anti-fouling effect also more raising more.
In addition; When wetting ability of the present invention coating agent, through with above-mentioned tackifier together, add a certain amount of metal ion compound; And water glass or have tackifier and the metal ion compound reaction of carboxylic acid group, sulfate, phosphate is further brought into play tackifying.At this moment, even reduce above-mentioned tackify dosage, also can obtain effect of sufficient.
Further, when wetting ability of the present invention coating agent, both possessed anti-fog effect and anti-fouling effect, brought into play the 1 liquid formula wetting ability coating agent that did not in the past have of antibacterial effect again through adding a certain amount of quaternary ammonium salt organic cpds again, just can providing.
In addition, in the method for use of wetting ability of the present invention coating agent, because each described wetting ability coating agent in the claim 1～4 is diluted with water; Be coated on the one side at least of coating objects such as plastic film for agricultural use; So, can either the miniaturized that concentrates type and realize its container etc. be processed in the wetting ability coating agent, again can be in use suitably dilute use with the water of necessary amount; At this moment, has the advantage that the operation that need not select diluting water, wetting ability coating agent becomes and is more prone to.
Embodiment
Then, specify the present invention.
Wetting ability of the present invention coating agent comprises the water glass [Na with 1～70 weight part
2O2 (SiO
2)] and the low molecular weight amphiphile water-based organic cpds of 0.5～30 weight part be the aqueous solution of 1 liquid formula of staple, low molecular weight amphiphile water-based organic cpds is that to have a kind of carbonatoms in carboxylic acid group, carboxylate group, hydroxyl, carboxamido-group, amino, the ammonium salt base at least be 1～18 wetting ability organic cpds (respective rights requires 1).
And; The wetting ability coating agent is directly with stoste or preferably with suitably (for example 20～40 times of ground) dilution of water (tap water etc.); At the medial surface (single face) that need carry out antifog processing (forming water droplet easily) at least (or medial surface and outer side (two-sided)) of the agricultural glass in the plastic film for agricultural use of plastic greenhouse or greenhouse, maybe need carry out the external wall of house face etc. of antifouling processing, promptly on the coated face of coating object with coatings such as sprayings.
Water glass [the Na of the wetting ability coating agent after the coating
2O2 (SiO
2)] be to carry the cheap and stable high inorganic materials of holding low molecular weight amphiphile water-based organic cpds, also be called as water glass (with SiO
2Dissolve the transparent adhering liquid (not being colloidal solution) that obtains with NaOH).
And, then dry if on above-mentioned coated face, be coated with the wetting ability coating agent through water glass, on above-mentioned coated face, form Vitrea film, fit in above-mentioned coated face securely, above-mentioned coated face is coated with by film equably.
The low molecular weight amphiphile water-based organic cpds of wetting ability coating agent is that carbonatoms is 1 (formic acid etc.)～18 (Triple Pressed Stearic Acid (C
17H
35COOH) etc. hydrophilic compounds); If the wetting ability coating agent that is coated with is dry; Then be evenly dispersed and carry and be held in the vitreum of water glass; Form the hydrophilic coating in the above-mentioned coated face, water droplet that adheres at above-mentioned coated face or raindrop by the wetting above-mentioned hydrophilic coated face of its wetting ability by dripization.
Therefore, when wetting ability of the present invention coating agent was coated with as antifogging agent at the plastic film for agricultural use of plastic greenhouse or the agricultural glass inner side in greenhouse etc., water droplet can not fall on plant etc., brings into play good anti-fog effect.In addition, wetting ability of the present invention coating agent is in coating such as the agricultural glass outer side in the plastic film for agricultural use of plastic greenhouse or greenhouse or external wall of house and during lining, raindrop flow down, and also flows away in metope adhered dust etc. simultaneously, brings into play good anti-fouling effect.
As the example of above-mentioned low molecular weight amphiphile water-based organic cpds, for example can enumerate the aliphatic organic compound of following (A1)～(A6).In addition, low molecular weight amphiphile water-based organic cpds is not limited to illustrative these aliphatic organic compounds.In addition, comprise aromatic organic cpds, general because deleterious compound is many, so, be not suitable for as low molecular weight amphiphile water-based organic cpds, and be excluded outside low molecular weight amphiphile water-based organic cpds.
(A1) only has the aliphatic organic compound of carboxyl
Formic acid, acetate, oxalic acid, toxilic acid, succsinic acid, phthalic acid, m-phthalic acid, terephthalic acid, propanedioic acid, fumaric acid, pentanedioic acid, propene dicarboxylic acid, hexanodioic acid, aconitic acid, pyruvic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, LAURIC ACID 99 MIN, tetradecanoic acid, palmitinic acid, margaric acid, Triple Pressed Stearic Acid etc. or their salt, perhaps aldose class or the aldose acids of its verivate, alditol acids, aldaric acid class or their salt of carboxylic acid anhydride (succinyl oxide etc.) or Glycerose, erythrose, glucose, pectinose, semi-lactosi etc.
(A2) has the aliphatic organic compound of carboxyl and hydroxyl
Hydrocerol A (following formula (1)), glyconic acid (following formula (2)), tartrate (following formula (3)), oxysuccinic acid, lactic acid etc. or their salt or their acid anhydrides.
(A3) have carboxyl and amino aliphatic organic compound (so-called amino acid)
Glycocoll (following formula (4)), L-Ala, l-arginine, l-asparagine, aspartic acid, halfcystine, Stimulina, L-glutamic acid, propalanine, glycocoll, sarkosine, kainic acid, Histidine, Isoleucine, leucine, Methionin, proline(Pro), Serine, Threonine, Xie Ansuan etc. or their salt.
(A4) have hydroxyl and amino aliphatic organic compound
The aminoglycoside of thanomin, diethylolamine (following formula (5)), trolamine, diethylolamine etc. or their salt or kantlex etc.
(A5) has the aliphatic organic compound of carboxamido-group
Ethanamide, urea, carboxylamine, N etc.
(A6) has the aliphatic organic compound of hydroxyl
The glycitols of terepthaloyl moietie, Ucar 35, glycol ether, trihydroxybutane etc. or glycerine, tetrahydroxybutane, Xylitol etc., the ketose class of fructose etc., pyrans carbohydrate; Furans carbohydrate etc.; Or the monose of glucose etc., the disaccharides of sucrose, sucrose etc., three carbohydrates of raffinose etc. etc.
Than carbonatoms is the hydrophilic high molecular polymer more than 19, and these low molecular weight amphiphile water-based organic cpds are cheap, and the ratio of hydrophilic group is also high, and water droplet and raindrop are shown good hydrophilicity.For example, be 6 Hydrocerol A as the carbonatoms of an example of low molecular weight amphiphile water-based organic cpds, in 1 molecule, have 4 hydrophilic groups (OH base and COOH yl), the ratio height of hydrophilic group is to water droplet and raindrop demonstration good hydrophilicity.
In wetting ability of the present invention coating agent; Water glass is made as 1～70 weight part, low molecular weight amphiphile water-based organic cpds is made as 0.5～30 weight part, though be owing to be the base material of coating layer with the water glass; Add low molecular weight amphiphile water-based organic cpds and make its possess hydrophilic property; But the content of low molecular weight amphiphile water-based organic cpds for a long time, and coating layer is difficult to form vitreum, so low molecular weight amphiphile water-based organic cpds must moderately be less than water glass.In addition; Low molecular weight amphiphile water-based organic cpds is that carboxylic acid etc. is when showing the tart compound; Have water glass as silica-based and situation gelation by its addition, therefore than water glass, low molecular weight amphiphile water-based organic cpds is an addition still less; Infer that this is to show that the tart compound produces the part silica dioxide gel owing to add carboxylic acid etc., the cause that more good hydrophilicity and rapid-drying properties are brought into play.
But, reducing the addition of water glass from discoveries such as various experiments with respect to organism (particularly tackifier), the film strength of wetting ability coating agent increases and the effect of last much longer.And; Also having preferred water glass to be less than the situation of 10 weight parts, for example, is 0.5 weight part at the minimum addition of low molecular weight amphiphile water-based organic cpds; When the minimum addition of tackifier is 0.1 weight part; At water glass is not 10 weight parts but under the situation about 1 weight part, the weather resistance of the film (composite package) of dried wetting ability coating agent improves, wetting ability effect for a long time.Therefore, about water glass, in order to contain the scope that is less than 10 weight parts, and be made as 1～70 weight part.
And, with the water glass [Na of 1～70 weight part
2O2 (SiO
2)] and the low molecular weight amphiphile water-based organic cpds of 0.5～30 weight part be the wetting ability of the present invention coating agent of staple; Through carry the low molecular weight amphiphile water-based organic cpds of holding and distributing equably at above-mentioned coated face by water glass; Make above-mentioned coated face become the good hydrophilicity face, can carry out the antifog processing in plastic greenhouse or greenhouse and the antifouling processing of external wall of house face reliably.In addition, when anti-fog effect and anti-fouling effect weaken,, can recover the wetting ability of above-mentioned coated face at an easy rate through being coated with the wetting ability coating agent once more.
Therefore, the wetting ability coating agent of application type of the antifouling processing of the antifog processing that is applicable to plastic greenhouse or greenhouse and external wall of house can be provided, this wetting ability coating agent only needs 1 container; Do not account for redundant space, in addition, do not need the combination treatment when using like 2 liquid formulas; And; Through being coated with recovery effects at an easy rate again, use cheap water glass, be that in the past do not have cheap and easy operated.
And, especially when dilution is used, have that container is more small-sized, an advantage of processing ease etc.Just can obtain necessary amount simply with the water dilution when also having use, the advantage that does not take up space in the keeping after use (respective rights requires 5).In addition, preferably be made as 20～40 times dilution ratio in the practicality as stated.In addition, during wetting ability of the present invention coating agent, because staple is a water glass, so than being the situation of staple with colloid silica etc., diluting water can be considered reaction and select, can be tap water or well water etc.
(containing tackifier, metal ion compound)
Then, above-mentioned wetting ability coating agent also preferably adds and contains 0.1～15 weight part tackifier, and these tackifier have a kind of (respective rights requires 2) in carboxylic acid group, hydroxyl, phosphate, sulfate, carboxamido-group or the amino at least.In addition, also preferred and tackifier together add the metal ion compound of 0.1～15 weight part, make tackifying further bring into play (respective rights requires 3).
The tackifier that add; Both can be the natural type of tackifier that polyoses such as X 5363 or xanthane glue constitute with hydroxyl and carboxylic acid group etc.; Also can be natural type of semi-synthetic type of tackifier through chemically modified, also can be synthetic type of tackifier that make the polymerization of vinyl monomer formation that comprises hydroxyl, carboxylic acid group, carboxamido-group, amino, phosphate, sulfate etc.
And through containing tackifier, the cementability that the wetting ability coating agent is coated with dried sodium silicate layer and base material film etc. improves, and is attached to as the plastic film for agricultural use of base material more securely etc., and the weather resistance of coating layer improves.In addition, because the tackifier water cut is many, so, the water droplet that on above-mentioned coated faces such as plastic film for agricultural use, produces and the anti-fog effect (wetting ability) of raindrop are improved more anti-fog effect and anti-fouling effect also raising more.
But; Tackifier addition (content) is made as 0.1～15 weight part, and tackifier show the tackify effect with a spot of addition mostly though this is, in natural type; The lower tackifier of tackify effect such as gelatin, agar are also arranged, must select appropriate amount according to the tackifier of selecting.
As tackifier, can enumerate for example following (B1), (B2), (B3), (B4).In addition, also can consider these mixture (compsn) is used as tackifier.
(B1) natural type of tackifier
X 5363, starch, gum arabic, xanthane glue, gelatin, collagen protein, tamarind seed gum, agar, X 5189, pectin, pulullan, soybean polysaccharides, Viscogum BE, glucose sweet dew carbohydrate gum, chitosan, xylogen, semicellulose etc.
(B2) semi-synthetic type of tackifier (natural type of tackifier) through chemically modified
Natvosol, hydroxyethylmethyl-cellulose, methylcellulose gum, hydroxypropylcellulose, Vltra tears, can dissolve starch, cationization X 5363, hydroxypropylated starch phosphoric acid, Xylo-Mucine etc.
(B3) synthetic type tackifier
C974P and salt thereof, Z 150PH, SEPIGEL 305 etc. are by the organic cpds shown in the formula (6).
(X1)m-(X2)n-(X3)o-(CH2)p-(O)q-(COO)r-(X4)s (6)
(in the formula,
X1=CHCOOH or CHCOOR (R is an organic radical)
X2＝CHOH
X3＝CHNH2
X4=CHCONH2 or CHCONHR (R is an organic radical)
M, n, o, p, q, r, s are zero or integer)
Polyvinyl sulfonic acid, Vilaterm phosphoric acid and salt thereof etc. by the organic cpds shown in the formula (7).These organic cpds have and the same tackify effect of organic cpds shown in the above-mentioned general formula (6), and the organic cpds than shown in the above-mentioned general formula (6) shows stronger wetting ability.
(X1)m-(X2)n-(X3)o-(CH2)p-(O)q-(COO)r-(X4)
s-(X5)t-(X6)u (7)
(in the formula,
X1=CHCOOH or CHCOOR (R is an organic radical)
X2＝CHOH
X3＝CHNH2
X4=CHCONH2 or CHCONHR (R is an organic radical)
X5=CHSO3H, CHCH2SO3H or CH (C6H4) SO3H
X6＝CHPO3H
M, n, o, p, q, r, s, t, u are zero or integer)
Also have organic cpds such as Vinylpyrrolidone polymer, ethylene-vinyl alcohol, SEPIGEL 305, polyethylene oxide, polymine, polyether ester amides, naphthalene sulfonic acidformaldehyde condensation product, poly butyric ester, water class urethane resin, water class resol, water class polyurethane acrylic resin.
(B4) mineral-type tackifier
The mineral-type tackifier that with the wilkinite are representative also can be as tackifier utilization of the present invention.Promptly; Natural and synthetic tackifier are arranged in these mineral-type tackifier; Generally in the aqueous solution, exist, between particle, form hydrogen bond by the hydroxyl of particle surface and bring into play tackifying with particle, or by the electrostatic interaction of the charge generation of particle surface and bring into play tackifying.Therefore, this mineral-type tackifier also can with organic type of tackifier likewise as tackifier utilization of the present invention.
Object lesson as above-mentioned mineral-type tackifier; Crushed material that the natural stone of wilkinite, talcum, sepiolite, magnesium aluminum silicate etc. is pulverized or these refining thing or modifier can be enumerated, the synthetic swelling soil of LAPONITE (RockWoodAdditives company) etc. etc. can also be enumerated.
Then; When tackifying further being brought into play together adding metal ion compound with tackifier; In the wetting ability coating agent, add tackifier with carboxylic acid group, sulfate, phosphate; And add the metal ion compound of 0.1～15 weight part, the tackifier reaction and the tackify that make itself and water glass and have carboxylic acid group, sulfate, phosphate.
Particularly; Generate Calucium Silicate powder because of water glass and calcium ion reaction as the joint compound composition; So, with ionic calcium cpds such as calcium sulfate, lime carbonate, calcium chloride and the tackifier with carboxylic acid group, sulfate, phosphate together, be added in the wetting ability coating agent with 0.1～15 weight part; Generation is as the Calucium Silicate powder of the gelation of tackifier and be included in the wetting ability coating agent; Both made the tackifying performance, and with above-mentioned tackifier reaction, the tackify effect was further brought into play again with the water glass reaction.In addition, about mg ion, aluminum ion etc., because also expectation and the same effect of calcium ion, so, even these ionic compounds that add 0.1～15 weight part as metal ion compound, also can be expected same tackify effect.
In addition; The performance tackifying is well-known in technical fields such as ionomer because zine ion etc. are with the tackifier reaction that contains carboxylic acid; So; The zine ion compounds such as zinc sulfate, zinc chloride that can add 0.1～15 weight part are as above-mentioned metal ion compound, generate the coordination compound that is obtained by tackifier that contain carboxylic acid and zine ion and bring into play tackifying.In addition, about mg ion, aluminum ion etc., because also can expect the effect same with zine ion, so, even these ionic compounds that add 0.1～15 weight part as above-mentioned metals ion, also can be expected same tackify effect.
(interpolation of antiseptic-germicide)
Above-mentioned wetting ability coating agent also preferably contains the quarternary ammonium salt compound as antiseptic-germicide (respective rights requires 5) of 0.005～1 weight part.Antiseptic-germicide uses multiple antiseptic-germicides such as silver ions, carboxylic-acid, low mass molecule alcohol class, is being exposed to dispersing and deterioration of outdoor generation but be defined in, the antiseptic-germicide that the high cl concn of dilution water, alkaline condition can use down.
Wetting ability of the present invention coating agent; As antiseptic-germicide; The quarternary ammonium salt compound that uses can be exposed under the high cl concn of open air, dilution water, the alkaline condition through what contain 0.005～1 weight part; Both can carry out antifog processing and antifouling processing, also can carry out the antimicrobial treatment of farm plastic greenhouse and agricultural glass, external wall of house.
As quarternary ammonium salt compound, can enumerate the example of for example following (C1)～(C6).
(C1) the benzyl first and second oxygen ammoniums (benzethonium >
Benzethonium chloride (for example " HYAMINE 1622 " of LONZA Japan (strain)).
(C2) < zephiran (benzalkonium) >
Benzalkonium chloride liquid (for example " the HYAMINE 3500-J " of LONZA Japan (strain)); Alkyl dimethyl benzyl ammonium chloride (for example " BARQUATMB-80/50 " of LONZA Japan (strain)); Alkyl dimethyl benzyl ammonium chloride (for example " the BARQUAT MS-100 " of LONZA Japan (strain)); Alkyl dimethyl ethylbenzylammonium chloride/alkyl-dimethyl Sulphonylbenzyl ammonium chloride mixt (for example " BARQUAT4280-Z/4250-Z " of LONZA Japan (strain)); Alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl benzyl ammonium chloride complex compound (for example " BARQUAT 1552 " of LONZA Japan (strain)); Alkyl dimethyl benzyl ammonium chloride (for example " the BARQUAT MX-80/50 " of LONZA Japan (strain)).
(C3) < dialkyl dimethyl >
Timbercote 2000 (for example " BARDAC2280/2250 " of LONZA Japan (strain)), dialkyl group (C8/C8, C8/C10, C10/C10) alkyl dimethyl ammonium chloride/benzalkonium chloride mixture (for example " the BARDAC 208M/205M " of LONZAJapan (strain)), the different nonyl dimethyl ammonium of decyl (for example " the BARDAC 2170P " of LONZA Japan (strain)).
(C4) < low bubble sexual type >
Quaternium 24 (for example " BARDACLF-80 " of LONZA Japan (strain)).
(C5) < non-chlorine type >
Didecyl dimethyl-volatile salt (for example " Carboquat " of LONZA Japan (strain)), didecyl methyl T 46155 propionic acid ammonium (for example " BARDAP 26 " of LONZA Japan (strain)).
(C6) < other >
Alkyl benzyl imidazole salts (for example " UNIQUATCB-50 " of LONZA Japan (strain)).
In addition; As antiseptic-germicide; Though it is because the minute quantity performance antibacterial effect of quarternary ammonium salt compound about with 500ppm that the addition of quarternary ammonium salt compound is made as 0.005～1 weight part; But add in order to make it have persistence even and also can continue and adjust addition for the water that the is flowed down effect that flows away for a long time.
Embodiment
Then, concrete embodiment is described.In addition, the present invention is not limited by embodiment.
(the 1st embodiment [confirming the embodiment of wetting ability effect])
In the present embodiment; In 300g water glass (No. 1 water glass that Fuji's chemical industry (strain) is produced), add 660g water (for example tap water); Add Hydrocerol A and 10g (trade(brand)name " CharmyV Quick " that Lion (strain) produce) tensio-active agent of 30g as low molecular weight amphiphile water-based organic cpds while stirring, obtaining 1kg is the wetting ability coating agent of the clear solution (stoste) of staple with the water glass of 30 weight parts (wt%) and the Hydrocerol A low molecular weight amphiphile water-based organic cpds of 3 weight parts (wt%).In addition; Same operation; Also obtain not adding fully the wetting ability coating agent (the only wetting ability coating agent of water glass and tensio-active agent) of low molecular weight amphiphile water-based organic cpds; Contain the wetting ability coating agent of 0.5 weight part (wt%) Hydrocerol A as low molecular weight amphiphile water-based organic cpds; Contain 3 weight parts (wt%) or 0.5 weight part (wt%) glyconic acid wetting ability coating agent, contain 3 weight parts (wt%) acetate, glycocoll, diethylolamine wetting ability coating agent stoste respectively as low molecular weight amphiphile water-based organic cpds as low molecular weight amphiphile water-based organic cpds.
Again respectively with resulting each the wetting ability coating agent stoste of 30 times water (30kg) dilution; These diluents are added respectively in the smooth salver; In the diluent of metal vessel, immerse the square plastic film for agricultural use of 10cm (agricultural of the trade(brand)name " Achilles haiberu (Ha ィ ベ one Le) " that Achilles (strain) produces is with PO (polyolefine) film), the plastic film for agricultural use of each wetting ability coating agent state that has been formed on the two sides separate application.
These plastic films for agricultural use tanned by the sun dry about 4 hours respectively again; Affirmation at separate application on the two sides behind each wetting ability coating agent; In the salver that has only added water, put into these plastic films for agricultural use; The two sides is immersed in the water, confirmed whether the mulch film of water forms (whether anti-drop property is arranged) at each plastic film for agricultural use through the two sides of coating, judge that each wetting ability coating agent has or not the wetting ability effect.
In addition, example, is operated by the situation of Mikado chemical industry (strain) as the 2 liquid formula wetting ability coating agents (trade(brand)name " Nurutobodon (ヌ Le ト ボ one De Application) ") of antifog-antifogging agent sale for coating too as a reference, judges to have or not hydrophilic effect.
Its result obtains the judged result like following table 1.The addition of table 1 is the concentration of (enrichment stage) before the dilution.In addition, the reference example in the table 1 representes to be coated with the situation of above-mentioned 2 liquid formula wetting ability coating agents.
[table 1]
| Low molecular weight amphiphile water-based organic cpds | Addition (wt%) | Have or not hydrophilic effect |
| Do not have and add (water glass+tensio-active agent) | 0 | Do not have |
| Hydrocerol A | 3 | Have |
| Hydrocerol A | 0.5 | Have |
| Glyconic acid | 3 | Have |
| Glyconic acid | 0.5 | Have |
| Acetate | 3 | Have |
| Glycocoll | 3 | Have |
| Diethylolamine | 3 | Have |
| Nurutobodon (trade(brand)name) | Have |
Can know from table 1, when being coated with 1 liquid formula wetting ability coating agent of the present invention, can obtaining good hydrophilicity, and can confirm to bring into play good anti-fog effect, anti-fouling effect.
(the 2nd embodiment [adding the embodiment of tackifier])
In the present embodiment; In 300g water glass (No. 1 water glass that Fuji's chemical industry (strain) is produced), add 660g water (for example tap water); Add 30g while stirring as the Hydrocerol A of low molecular weight amphiphile water-based organic cpds (Citric anhydride that Kishida chemistry (strain) is produced) and following the tackifier aluminum chloride and the tackifier of metal ion compound (or as), tensio-active agent; Obtaining 1kg is staple with the low molecular weight amphiphile water-based organic cpds of the Hydrocerol A of the water glass of 30 weight parts (wt%) and 3 weight parts (wt%); Also add the tackifier of 0.1～0.6 weight part (wt%), added the wetting ability coating agent of clear solution (stoste) of the aluminum chloride of 0.1 weight part (wt%) as required.
The tackifier that add are 3g or 1g (the xanthane glue FJ level that Yongbuntsura (transliteration of ュ Application グ Block Application Star ウ ラ one) AG company produces) xanthane glue or 6g or 1g (trade(brand)name " Carbopol ETD2050 " that daylight chemicals (strain) produces) CARBOPOPLS or 3g or 1g (the refining X 5363 that MRC polysaccharide (strain) produces) X 5363 or 1g (LAPONITE that RockWoodAdditives company produces) synthetic swelling soil.Aluminum chloride 0.1g, tensio-active agent as the ionizable metal salt compound are the trade(brand)name " Charmy V Quick " that 10g Lion (strain) produces.
Each hydrophilizing agent aqueous solution that will obtain again dilutes with 5 times of water (5kg) respectively; In smooth salver, add these diluents respectively; In the diluent of salver, immerse the 10cm square plastic film for agricultural use identical, be formed on the plastic film for agricultural use of each wetting ability coating agent state of two sides separate application with the 1st embodiment.
Again these plastic films for agricultural use were tanned by the sun respectively dry about 24 hours; Affirmation in two sided coatings behind each wetting ability coating agent; Band (cover tape) (correction band " CLK-15 " of Mitsubishi's pencil (strain)) revised in the surface applying of these plastic films for agricultural use to be divested again; Whether the coating layer of wetting ability coating agent is peeled off and is carried out belt stripping test through this moment, confirms whether the sticking power of the coating layer epithelium of wetting ability coating agent is improved by tackifier.
Its result obtains the affirmation result like following table 2.In addition, the addition of table 2 is the tackifier weight parts (concentration) of (enrichment stage) before the dilution.In addition, the coating layer sticking power high (coating is not peeled off) of the coating layer sticking power low (coating is peeled off) of " * " of table 2 expression wetting ability coating agent, " zero " expression wetting ability coating agent.
[table 2]
| Tackifier | Addition (wt%) | Sticking power |
| Do not have and add (water glass+tensio-active agent+Hydrocerol A) | 0 | × |
| X 5363 | 0.3 | ○ |
| X 5363 | 0.1 | ○ |
| CARBOPOPLS | 0.6 | ○ |
| CARBOPOPLS | 0.1 | ○ |
| Xanthane glue | 0.3 | ○ |
| Xanthane glue | 0.1 | ○ |
| LAPONITE (trade(brand)name) | 0.1 | ○ |
| Aluminum chloride+CARBOPOPLS | 0.1+0.6 | ○ |
| Nurutobodon (trade(brand)name) | ?- | ○ |
Can know from table 2; Confirmed through adding (interpolation) tackifier (or metallic compound and tackifier); 1 liquid formula wetting ability coating agent of the present invention; The cementability that is coated with dried sodium silicate layer and base material film improves, and more securely attached to as on the plastic film for agricultural use of base material etc., the weather resistance of coating layer improves.And, because the water cut of tackifier is many, so, the water droplet that on above-mentioned coated faces such as plastic film for agricultural use, produces and the anti-fog effect (wetting ability) of raindrop are improved more, anti-fog effect and anti-fouling effect improve more.In addition, tackifier usually carry out gelation with the addition about 1wt%, but also have through being tackifier (CARBOPOPLS etc.) acid, that alkalescence weakens tackifying.Therefore, preferably strengthen addition under these circumstances.
(the 3rd embodiment [adding the embodiment of quaternary ammonium salt organic cpds (antiseptic-germicide)])
In the present embodiment; In 300g water glass (No. 1 water glass that Fuji's chemical industry (strain) is produced), add 660g water; (xanthane glue (the xanthane glue FJ level that YongbuntsuraAG company produces) or 6g CARBOPOPLS (trade(brand)name " Carbopol ETD2050 " that daylight chemicals (strain) produces) or 3g X 5363 (the refining X 5363 that MRC polysaccharide (strain) produces), 10g tensio-active agent (trade(brand)name " Charmy V Quick " that Lion (strain) produces) obtain the 1kg clear solution as the Hydrocerol A of low molecular weight amphiphile water-based organic cpds (Citric Acid, usp, Anhydrous Powder that Kishida chemistry (strain) is produced), 3g tackifier to add 30g while stirring.In this clear solution, add 0.15g quaternary ammonium salt organic cpds (antiseptic-germicide) (BARDAP 26 of the BARDAC 2280 of LONZAJapan (strain) or the Carboquat of the said firm or the said firm) again.Thus; Obtaining 1kg is staple with the low molecular weight amphiphile water-based organic cpds of 30 weight parts (wt%) water glass and 3 weight parts (wt%) Hydrocerol A, has added the wetting ability coating agent of clear solution (stoste) of quaternary ammonium salt organic cpds (antiseptic-germicide) of tackifier and 0.005～0.015 weight part (wt%) of 0.3～0.6 weight part (wt%) again.
Each hydrophilizing agent aqueous solution that will obtain again dilutes with 30 times of water (30kg); In smooth salver, add this diluent; In the diluent of salver, immerse the 10cm square plastic film for agricultural use identical, be formed on two sided coatings and be added with the plastic film for agricultural use of the wetting ability coating agent state of tackifier and quaternary ammonium salt organic cpds (antiseptic-germicide) with the 1st, the 2nd embodiment.
Again this plastic film for agricultural use was exposed to the sun dry about 24 hours; Affirmation in two sided coatings behind the wetting ability coating agent; Can produce in the outdoor environment of liver moss in reality; With the plastic film for agricultural use that does not form the wetting ability coating layer (no coated film) together, be placed into till producing liver moss on the film of this nothing coating, carry out the exposure test that antibacterial effect is confirmed.
Its result obtains the test-results like following table 3.In addition, the addition of table 3 is the tackifier weight parts (concentration) of (enrichment stage) before the dilution.
[table 3]
| Quaternary ammonium salt organic cpds (antiseptic-germicide) | Addition (wt%) | Antibacterial effect |
| The film that does not have coating | 0 | × |
| Do not have and add (water glass+tensio-active agent+Hydrocerol A+tackifier) | 0 | △ |
| BARDAC?2280 | 0.015 | ○ |
| BARDAC?2280 | 0.005 | ○ |
| Carboquat | 0.015 | ○ |
| BARDAP?26 | 0.015 | ○ |
Can know from table 3, confirm that sufficient antibacterial effect is also brought into play in 1 liquid formula wetting ability coating agent of the present invention through adding (interpolation) quaternary ammonium salt organic cpds.In addition, " * " of table 3 is illustrated in plastic film for agricultural use surface generation liver moss, " △ " expression part generation liver moss, " zero " expression of being coated with the wetting ability coating agent and do not produce liver moss fully.
Utilizability in the industry
The present invention can be applicable to the cheapness 1 liquid formula wetting ability coating agent and the method for use thereof of application type of the antifouling processing of antifog processing such as plastic greenhouse, greenhouse and external wall of house.
Claims (5)
1. wetting ability coating agent is characterized in that:
Comprise water glass [Na with 1～70 weight part
202 (Si0
2)] and the low molecular weight amphiphile water-based organic cpds of 0.5～30 weight part be the aqueous solution of staple,
Said low molecular weight amphiphile water-based organic cpds has a kind of in carboxylic acid group, carboxylate group, hydroxyl, carboxamido-group, amino, the ammonium salt base at least, is that carbonatoms is 1～18 wetting ability organic cpds.
2. wetting ability as claimed in claim 1 coating agent is characterized in that:
What also contain 0.1～15 weight part has a kind of tackifier in carboxylic acid group, hydroxyl, phosphate, sulfate, carboxamido-group or the amino at least.
3. wetting ability as claimed in claim 2 coating agent is characterized in that:
The metal ion compound that also contains 0.1～15 weight part, said metal ion compound and said water glass react and the performance tackifying, and react with said tackifier, and the tackify effect is further brought into play.
4. like each described wetting ability coating agent in the claim 1～3, it is characterized in that:
The quaternary ammonium salt organic cpds that also contains 0.005～1 weight part.
5. the method for use of a wetting ability coating agent is characterized in that:
On the one side at least of coating objects such as plastic film for agricultural use, agricultural glass, external wall of house coating with water with claim 1～4 in the diluent that obtains of each described wetting ability coating agent dilution.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009197088 | 2009-08-27 | ||
| JP2009-197088 | 2009-08-27 | ||
| JP2010-158385 | 2010-07-13 | ||
| JP2010158385A JP4787907B2 (en) | 2009-08-27 | 2010-07-13 | Hydrophilic coating agent and method of using the same |
| PCT/JP2010/004645 WO2011024378A1 (en) | 2009-08-27 | 2010-07-20 | Hydrophilic coating agent and method for using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102471666A true CN102471666A (en) | 2012-05-23 |
Family
ID=43627500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800304986A Pending CN102471666A (en) | 2009-08-27 | 2010-07-20 | Hydrophilic coating agent and method for using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4787907B2 (en) |
| KR (1) | KR20120060778A (en) |
| CN (1) | CN102471666A (en) |
| TW (1) | TW201120201A (en) |
| WO (1) | WO2011024378A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108835705A (en) * | 2018-08-29 | 2018-11-20 | 佛山市森昂生物科技有限公司 | A kind of preparation method of high damp-proof tobacco humectant material |
| CN110978701A (en) * | 2019-11-21 | 2020-04-10 | 徐蕾 | Moss-inhibiting film, multi-layer moss-inhibiting film and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177944B (en) * | 2014-08-21 | 2017-01-18 | 河北晨阳工贸集团有限公司 | Internal wall paint |
| KR101655991B1 (en) | 2016-05-13 | 2016-09-09 | 주식회사 리폼테크 | Insulator for coating apparatus |
| KR20220161632A (en) | 2021-05-28 | 2022-12-07 | 주식회사 유니온바이오테크 | Antifogging wovenfilm using Bentonite materials |
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-
2010
- 2010-07-13 JP JP2010158385A patent/JP4787907B2/en not_active Expired - Fee Related
- 2010-07-20 CN CN2010800304986A patent/CN102471666A/en active Pending
- 2010-07-20 KR KR1020117025282A patent/KR20120060778A/en not_active Application Discontinuation
- 2010-07-20 WO PCT/JP2010/004645 patent/WO2011024378A1/en active Application Filing
- 2010-08-20 TW TW099127882A patent/TW201120201A/en unknown
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| US4588025A (en) * | 1983-11-07 | 1986-05-13 | Showa Aluminum Corporation | Aluminum heat exchanger provided with fins having hydrophilic coating |
| JPS62227968A (en) * | 1986-03-28 | 1987-10-06 | Usui Internatl Ind Co Ltd | Heat-resistant, corrosion-resistant paint |
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| CN108835705A (en) * | 2018-08-29 | 2018-11-20 | 佛山市森昂生物科技有限公司 | A kind of preparation method of high damp-proof tobacco humectant material |
| CN110978701A (en) * | 2019-11-21 | 2020-04-10 | 徐蕾 | Moss-inhibiting film, multi-layer moss-inhibiting film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4787907B2 (en) | 2011-10-05 |
| KR20120060778A (en) | 2012-06-12 |
| TW201120201A (en) | 2011-06-16 |
| JP2011068857A (en) | 2011-04-07 |
| WO2011024378A1 (en) | 2011-03-03 |
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Application publication date: 20120523 |