CN1984972B - Films or structural exterior materials using coating composition having self-cleaning property and preparation method thereof - Google Patents
Films or structural exterior materials using coating composition having self-cleaning property and preparation method thereof Download PDFInfo
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- CN1984972B CN1984972B CN2005800239844A CN200580023984A CN1984972B CN 1984972 B CN1984972 B CN 1984972B CN 2005800239844 A CN2005800239844 A CN 2005800239844A CN 200580023984 A CN200580023984 A CN 200580023984A CN 1984972 B CN1984972 B CN 1984972B
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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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
- 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
Abstract
Disclosed is a coating composition comprising: (a) hydroxy group-containing inorganic particles having an average particle diameter of between 5 and 30 nm; (b) hydroxy group- containing inorganic particles having an average particle diameter of between 0.2 and 5 [mu]m; (c) an organosilane compound represented by the formula of RnSi(OR') 4-n (wherein R is a C1-C8 aminoalkyl group, glycidoxyalkyl group or isocyanatoalkyl group; R'is a C1-C6 lower alkyl group; and n is an integer of between 0 and 3); and (d) a solvent. A method for preparing the above coating composition, a substrate such as film or structural exterior material, having excellent self-cleaning property and staining resistance by using the above coating composition and methods for producing the same are also disclosed. The coating composition using hydroxy group-containing inorganic particles can improve the initial hydrophilicity of conventional coating agents. Additionally, the coating composition can form a hydrophilic coating layer having a contact angle with water of 30 DEG or less by using two kinds of inorganic particles having a different particles diameter. Particularly, the coating composition uses an organic solvent having erosive property to a substrate to be coated and a low boiling point, and thus can be applied to a conventional production line for structural exterior materials without adding a separate coating line. Therefore, the coating composition can provide structural materials having hydrophilicity, excellent self-cleaning property and long service life, when coated on substrates such as vinyl sidings.
Description
Technical field
The present invention relates to a kind of coating composition, have for example film of good self-cleaning performance and stain resistance or base material of structural exterior material and preparation method thereof by using above-mentioned composition with self-cleaning performance.
Background technology
Usually, when advertisement film and structural exterior material are exposed to outdoor environment for a long time, the serious problems that exist film and structural exterior material to fade by dust, flue dust and exhaust emission and owing to ultraviolet ray.Therefore, need outdoor film and outer material to present for example physical properties of self-cleaning performance and weathering resistance and long-term reliability especially.
The pollution on outdoor film and structural exterior material surface is mainly caused by the inorganic materials of the products of combustion of koniology, for example carbon black and for example clay particle.Usually, the pollutent that is deposited on outdoor film and structural exterior material surface can be cleaned by rainwater off and on, makes film and material recover its initial situation.Yet under the situation of drizzle, this pollutant is captured and adheres to described surface by rainwater.Then, this adherent pollutent appears at described surface with the form of grey dust spot bar, pollutent and stain when it becomes dry.In addition, because rainwater lacks, the generation of pollution substance increases in the air in dry season.Can not obtain any cleaning effect, thereby cause the successive sedimentation of pollutent by rainwater.Therefore, used coating material to solve the problems referred to above usually with stain resistance.
The most widely used method comprises the use photocatalyst granular.When with uviolizing photocatalyst granular surface, its surface shows strongly hydrophilic.Even also can keep several hours to a week though stop to shine this strong hydrophilicity state, initial hydrophobic state is recovered on its surface gradually.In addition, after the initial hydrophobic state of its surface recovery, can recover Superhydrophilic rapidly by uviolizing once more.In other words, do not need the continuity irradiation, intermittent irradiation is enough to keep surface hydrophilicity and stain resistance.Yet, the shortcoming of the method for this use photocatalytic coating is: because photocatalyst has the possibility of decomposing organic matter matter usually, so at the additional step that need apply priming paint before the coating photocatalyst on the plastic basis material that is formed by thermoplastic resin etc.
In addition, considered for example preferred stain resistance material of waterproof paint conduct of the fluoro-containing group of polytetrafluoroethylene (PTFE).When the water droplet on filming moved down owing to low surface tension, waterproof paint played the effect that dust is removed from upper layer.Yet water droplet is too little and can not move by gravity the time, described water droplet becomes dry with pollution substance, thereby forms local stain.
In addition, a kind of method that applies wetting ability grafting heteropolymer has been proposed.Yet present the contact angles of 30～40 degree by filming of forming of wetting ability grafting heteropolymer and water, and conventional mineral dust and water present 20～50 contact angles (Newspaper Daily Chemical Industry, 30,1995) of spending.Therefore, this heteropolymer can not purify stain and the pollutent that is formed by the mineral dust that is deposited on the surface effectively.In addition, because other hydrophilic coating that can obtain easily and glassware for drinking water have the contact angle of 50～70 degree, so its problem is: they can not prevent in the city effectively because the pollution of dust.
Simultaneously, the unknown can obtain the outer dress material (for example, vinyl wallboard) of routine building for the product with self-cleaning performance and stain resistance.For this character is provided, need stain-resistant coating.Yet, because vinyl wallboard material is normally hard and firm, so as general its very difficult scale operation of scroll film.
In addition, the structural exterior material is by comprising the production line production of extruding machine, correction card (being used for being shaped and cooling) and pressing machine (being used for cutting).This production line can randomly further comprise other supplementary device, makes described material by comprising the production line production of extruding machine, Embosser (Embo device), correction card (being used for being shaped and cooling), driling unit, tension device (being used for tension control) and pressing machine (being used for cutting).
For giving structural exterior material stain resistance, after above-mentioned production process, need to carry out extra applying step.Therefore, also need extra paint line, thereby reduce product production and improve production cost.In other words, aspect cost and workspace two, whole process is worthless.
Summary of the invention
Technical problem
Therefore, finished the present invention in view of the above problems.We find, because its initial stage wetting ability and surfaceness, comprise that the inorganic particle of possess hydrophilic property hydroxyl and the coating composition of other inorganic particle with different size help to improve wetting ability, thereby when forming the water coating, remove the pollutent that adheres to coating surface effectively good self-cleaning performance can be provided by moving down by rainwater on the surface.
We also find, to have corrodibility and have lower boiling organic solvent when being used for described coating composition the structural exterior material as solvent, can not increase any independent paint line and with described coating composition at the production line of any step application to above-mentioned structural exterior material.
Technical scheme
Therefore, an object of the present invention is to provide a kind of in order to coating composition of giving good self-cleaning performance and preparation method thereof, and a kind of use above-mentioned composition can self-cleaning base material.
Another object of the present invention provide a kind of do not increase any independent production line and in the conventional production line of structural exterior material by using above-mentioned composition to prepare the method for structural exterior material with stain resistance and self-cleaning performance.
According to an aspect of the present invention, the invention provides a kind of coating composition, it comprises: the hydroxy group-containing inorganic particles that (a) has the median size of 5～30nm; (b) has the hydroxy group-containing inorganic particles of the median size of 0.2～5 μ m; (c) organic silane compound of representing with following Chemical formula 1; (d) solvent.The present invention also provides a kind of method for preparing aforementioned coating composition.
[Chemical formula 1]
R
nSi(OR’)
4-n(I)
Wherein, R is C1～C8 aminoalkyl, glycidoxyalkyl or isocyanato-alkyl; R ' is C1～C6 low alkyl group; And n is 0～3 integer.
In addition, what the invention provides a kind of for example film or structural exterior material can self-cleaning base material, and it comprises: (a) base material; (b) coating by forming in described base material one or both sides coating aforementioned coating composition.
In addition, the invention provides a kind of method for preparing the structural exterior material, it comprises step: (a) apply with the one or both sides of aforementioned coating composition with the structural exterior material before material passes through cooling step; (b) will be in the cooling of structural exterior material or the cutting of step (a) coating.
As used herein, term " rudimentary " be meant have 6 or still less carbon atom, preferably have 5 or the still less atomic group or a compound of carbon atom.
Low alkyl group refers to the rudimentary saturated aliphatic hydrocarbon of straight or branched, and can be example with methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl and n-pentyl.
Hereinafter will illustrate in greater detail the present invention.
(1) coating composition according to the present invention can provide good self-cleaning performance by the hydroxy group-containing inorganic particles of uniting at least two kinds of different sizes of use.
Recently, majority has the outdoor film of stain resistance and the hydrophilic group that the structural exterior material comprises photocatalyst granular and introducing.Yet this film and material require can be protected the prime coat of base material.Otherwise there is the problem of the surperficial stain that is caused by part cleaning and shorter time length in it.
Yet, according to the present invention, for example inorganic particle of normally used silicon-dioxide and aluminum oxide is scattered in the dispersion medium of for example water, alcohol or ketone, make it have hydroxyl.With this, when water contact coating surface, it can improve moisture film formability and wetting properties, therefore presents wetting ability.
Except introducing aforesaid hydrophilic group, can also use other to have surfaceness promptly, have the inorganic particle of the median size bigger, further to improve the wetting ability of coating surface by surfaceness than normally used hydroxy group-containing inorganic particles.
In addition, according to coating composition of the present invention since with coating composition in the organosilane that comprises reaction and can form reticulated structure, therefore can show wetting ability and wear resistance simultaneously.
(2), use the base material (for example, structural exterior material) that will apply is had corrodibility and has the solvent of lower boiling organic solvent as coating composition according to the present invention.This organic solvent can corrode the part on conventional plastic basis material surface to form the structure of base material and the mutual grappling of coating.Therefore, the self-cleaning performance coating can exist with stable status, and can easily finish the curing of coating, thereby provides good stain resistance and self-cleaning performance simultaneously in long-time.
(3) in addition, can not increase any independent paint line and will coating composition according to the present invention at the production line of any step application to above-mentioned structural exterior material.Therefore, aspect cost and workspace, coating composition of the present invention is very economical.
More particularly, as shown in Figure 1, the conventional production line of structural exterior material comprises extruding machine, Embosser, correction card (being used for being shaped and cooling), driling unit, tension device (being used for tension control) and pressing machine (being used for cutting).Usually, base material also dry and the curing coating forms coating on the base material by coating composition is coated to.Therefore, form coating, need extra paint line, thereby improve owing to extra equipment causes required cost for going up at structural exterior material (for example, the vinyl wallboard).
According to the present invention, in order in the production line of the above-mentioned structural exterior material that does not need extra production line, to finish applying step, present high surface temperature promptly at material, before cooling step, with coating composition the structural exterior material is applied in the time of preferably just after extruding step.By applying, being contained in the coating composition and having lower boiling solvent coating is solidified easily, and additionally do not use heat or UV solidifying agent.In addition, applying device can be added any step in the step of above-mentioned production line, and can use coating composition in any step.
As the first kind of component that forms according to coating composition of the present invention, operable first kind of inorganic particle (a) comprises common use and inorganic particle well known by persons skilled in the art.The non-limitative example of first kind of inorganic particle comprises silicon-dioxide (SiO
2), aluminum oxide (Al
2O
3), SnO
2, MgO, CaO or its combination.
First kind of inorganic particle preferably has 5～30nm, more preferably the median size of 10～20nm.If the median size of inorganic particle is less than 5nm because raw-material expensive, so coating composition be do not have cost-benefit.If the median size of inorganic particle is greater than 30nm, this big particle size can reduce the particulate tamped density, thereby reduces the intensity of filming.
Based on the coating composition of 100wt%, have the suitable amount of inorganic particle of the median size of 5～30nm with 1～15wt%, more preferably the amount with 3～10wt% is present in according in the coating composition of the present invention.If this content is lower than 1wt%, the intensity of filming can reduce.On the other hand, if greater than 15wt%, can not forming fully, this content films.
As the second kind of component that forms according to coating composition of the present invention, operable second kind of inorganic particle (b) comprises common use and inorganic particle well known by persons skilled in the art.Second kind of inorganic particle preferably has the median size of 0.2～5 μ m.For improve the wetting ability of coating by above-mentioned surfaceness, more preferably second kind of inorganic particle has the median size of 1.5～2.0 μ m.If the median size of inorganic particle is lower than 0.2 μ m because raw-material expensive, so coating composition be do not have cost-benefit.If the median size of inorganic particle is greater than 5 μ m, can there be the problem of relevant package stability in coating composition.
Based on the coating composition of 100wt%, the suitable amount with 0.05～3wt% of inorganic particle with median size of 0.2～5 μ m is present in according in the coating composition of the present invention.If this content is lower than 0.05wt%, the wetting ability of filming can cause self-cleaning performance to reduce.On the other hand, if greater than 3wt%, filming, this content can break or separate.
Can be with two or more at least particulate in conjunction with using inorganic particle with different median sizes ((a) and (b)).In addition, inorganic particle preferably comprises the hydrophilic functional group to improve wetting ability.Reason is for this reason preferably used the inorganic particle of discrete form in the solvent of for example water, pure and mild ketone.
Formation is according to the organic silane compound (c) of the third component for being represented by above-mentioned Chemical formula 1 of coating composition of the present invention.
For the organosilane of wetting ability silane can improve with the bounding force of base material and can combine/inorganic hybrid nano reticulated structure organic to form with the inorganic particle with at least two kinds of different median sizes, thereby play silane coupling agent.
Operable organosilane comprise tetraalkoxysilane or after hydrolysis except the hydroxyl silane of possess hydrophilic property functional group also.The preferred silane that uses with one or two hydrophilic functional group.In above-mentioned Chemical formula 1, the hydrophilic functional group refers to ' R ' in the Chemical formula 1, and its special example comprises glycidoxyalkyl, aminoalkyl, isocyanato-alkyl etc.In addition, the hydrophilic functional group can comprise thiol group, amine oxide group, sulfoxide radicals, phosphate group, sulfuric acid alkali or their salt; Or the hydrophilic group of polyoxyethylene or polyoxypropylene.
More particularly, the non-limitative example of wetting ability silane comprises N-aminoethyl γ-An Bingjisanjiayangjiguiwan, N-aminoethyl γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-isocyano-propyl-triethoxysilicane, γ-isocyano-propyl trimethoxy silicane or its mixture.
Based on the coating composition of 100wt%, use organosilane according to suitable amount in the coating composition of the present invention with 1～15wt%.If this content is lower than 1wt%, can not forms and film.If this content is greater than 15wt%, wetting ability can reduce.
Formation is solvent (d) according to the 4th kind of component of coating composition of the present invention.Operable solvent comprises common use and solvent well known by persons skilled in the art, for example water, organic solvent and its mixture.
Described solvent preferably includes has 9.5Mpa to coated base material
0.5Or the solvent of littler solubility parameter (δ), described base material is preferably for example general plastic material of PVC.This solvent has some corrodibility to the base material of coating, makes the base material of coating closely to combine with coating.In addition, this solvent preferably includes at least a organic solvent of the mean boiling point (b.p.) with 60～150 ℃, by lower boiling advantage the curing of coating is finished easily.
Operable organic solvent comprises for example alcohol with 1～4 carbon atom of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or Pyranton; The ketone with 1～5 carbon atom of methyl ethyl ketone or methyl iso-butyl ketone (MIBK) for example; The acetic ester of methyl acetate or ethyl acetate for example; Cellosolve with 4～6 carbon atoms; Aromatic solvent or its mixture with 7 carbon atoms, but be not limited to them.
Though the present invention does not have particular restriction to the content of above-mentioned solvent, based on 100wt% according to coating composition of the present invention, preferably use this solvent with the amount of 50～85wt%.If the content of solvent is lower than 50wt%, inadequate curing can appear.On the other hand, if the content of solvent greater than 85wt%, wetting ability can reduce.
Coating composition of the present invention may further include photocatalyst granular.
Photocatalyst granular produces the high reactivity type to quicken chemical reaction by the luminous energy to its irradiation.When usefulness had the rayed photocatalyst of the energy bigger than the band-gap energy of photocatalyst, photocatalyst produced electronics and hole, can produce strong redox reaction by it.In the redox reaction process, organic chemicals is broken down into harmless carbonic acid gas and water, thereby reduces the bounding force of dust to coatingsurface.In addition, it can prevent to be condensed and the wetting ability that causes reduces at the coatingsurface hydrophilic group with the passing of time by hydrophilic group, thereby keeps wetting ability for a long time.
When with uviolizing photocatalyst granular surperficial, its surface becomes strongly hydrophilic.Even also keep several hours to a week though stop to shine this strongly hydrophilic state, initial hydrophobicity state is little by little recovered on its surface.In addition, behind the initial hydrophobicity state of its surface recovery, by it can recover Superhydrophilic rapidly with uviolizing once more.In other words, do not need the continuity irradiation, intermittent irradiation is enough to keep its surperficial Superhydrophilic state.Therefore, be preferably with the coating composition of the present invention coating that is added with photocatalyst granular advertisement film or structural exterior material will be coated base material the time, by daytime the irradiation of sunlight coatingsurface can be transformed into the wetting ability state and also can continue to keep wetting ability.
The non-limitative example of operable photocatalyst granular comprises anatase titanium dioxide, rutile titanium dioxide, stannic oxide, tungstic oxide, ferric oxide, strontium titanate, ZnO, SnO
2, SrTiO
3, WO
3, Bi
2O
3, Fe
2O
3Or its mixture.Wherein, most preferably be titanium dioxide (TiO
2).Because titanium dioxide has the high band gap energy, so it needs ultraviolet ray with by optical excitation.In the excitation process, titanium dioxide does not absorb visible light, therefore can not produce the colour developing that is caused by the complementary color composition.
The middle suitable sources of using that excites of photocatalyst granular comprises for example interior lighting of luminescent lamp, glow-discharge lamp, mercury lamp, sunlight etc.Especially, the illuminating value during optical excitation is suitably 0.001mW/cm
2Or higher, be preferably 0.1mW/cm
2
Photocatalyst granular has 10～80nm, is preferably the median size of 15～60nm.If median size is lower than 10nm because raw-material expensive, so coating composition be do not have cost-benefit.If median size is greater than 80nm, owing to bleaching that scattering of light causes, so there is the problem of relevant film transparency.
Based on the coating composition of 100wt%, the suitable amount with 0.1～3wt% of photocatalyst is present in according in the coating composition of the present invention.If this content is lower than 0.1wt%, wetting ability can reduce, so self-cleaning performance reduces.On the other hand, if this content is higher than 3wt%, films and to break and separate.
Equally, coating composition according to the present invention may further include the hydrolysate of the functionalized with alkoxysilane aromatics UV absorption agent of being represented by following Chemical formula 2.
[Chemical formula 2]
Wherein, R
1And R
2Independently represent C1～C6 alkyl;
R
3Expression C1～C6 alkyl or aryl; OR
4Expression methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or acetoxyl;
R
5Expression C1～C12 alkyl or aryl;
X represents hydrogen atom or halogen atom;
L is 5～9 integer;
M is 1～3 integer; And
N is 0～2 integer.
The hydrolysate of above-mentioned functionalized with alkoxysilane UV absorption agent and organosilane coupling are so that the maximization of the consistency of coating composition, and it combines to keep weathering resistance for a long time with silylation materialization.The preparation method of the hydrolysate of above-mentioned functionalized with alkoxysilane UV absorption agent is disclosed among the Korean Patent Publication No. 2000-0009647.
Based on the coating composition of 100wt%, the suitable hydrolysate that uses above-mentioned functionalized with alkoxysilane UV absorption agent with the amount of 1～10wt% in coating composition according to the present invention.If this content is lower than 1wt%, can destroy the UV assimilation effect.If this content is greater than 10wt%, coating composition be do not have cost-benefit.
Except said components, coating composition according to the present invention may further include acid, solidifying agent, aqueous polyurethane emulsion or other additive.
Can be by ordinary method preparation well known by persons skilled in the art according to coating composition of the present invention.In a kind of preferred implementation, the method comprising the steps of: the inorganic particle that (a) will have 5～30nm median size adds and also mixes in the dispersion medium to form the dispersion of inorganic particle; (b) dispersion of the inorganic particle that will obtain from step (a) and other inorganic particle, organosilane, acid and the solvent represented by above-mentioned Chemical formula 1 with 0.2～5 μ m median size, and make the mixture reaction of generation; And, make the mixture reaction of generation then (c) with in the product of organic solvent adding by step (b) acquisition.
(1) at first, the inorganic particle with 1～15wt% mixes the dispersion that has the inorganic particle that comprises the wetting ability hydroxyl of 5～30nm median size with formation with the dispersion medium of 15～30wt%.
The dispersion medium that is used to form the inorganic particle dispersion can comprise water, alcohol or ketone.Because, alcohol can mix equably with the organic solvent that uses later, have lower boiling and easily finish the curing of coating, and can provide hydroxyl as the hydrophilic functional group, so dispersion medium is preferably for example alcohol of methyl alcohol, yet, can use other conventional solvent within the scope of the invention.
The dispersion of hydroxy group-containing inorganic particles has 10～40wt%, is preferably the solids content of 15～35wt%.
(2) then, in the alcohol of the dispersion of the inorganic particle that comprises the wetting ability hydroxyl of the median size of 1～15wt% and 15～30wt%, add other inorganic particle of 0.05～2wt%, the organosilane of 1～10wt%, acid and the solvent of 0.001～2wt% as hydrolyst with 0.2～5 μ m median size with 5～3nm.With the mixture thorough mixing that obtains and with it at 20～80 ℃ of sol gel reaction of carrying out 1～48 hour, cool to room temperature then.
Use have 0.2～5 μ m median size inorganic particle with control coating composition wetting ability and surfaceness.The present invention does not have particular restriction to the size and the kind of inorganic particle.
Temperature of reaction and time are suitably 20～80 ℃ and 1～48 hour respectively.Preferably, temperature of reaction and time are respectively 25～60 ℃ and 5～24 hours.
In above-mentioned reaction mixture, described acid is as catalysts, and the non-limitative example of acid comprises hydrofluoric acid, nitric acid, hydrochloric acid, acetate, sulfuric acid or its blended acid.Based on the present composition of 100wt%, according to using above-mentioned acid to exist with the amount of 0.001～2wt% in the coating composition of the present invention, still the content of acid is not limited thereto.The pH that preferred control adds the reaction mixture of acid is pH 1～5.If this mixture has 6 or higher pH value, coating composition can not show the binding property to base material, maybe can cause for example the bleach problem relevant with the coating feature.
(3) last, in reaction product, add organic solvent and make mixture room temperature sustained reaction 1 hour.
In this step, before adding organic solvent, can in reaction product, add the thermal curing catalyst of 1～4wt%.
Thermal curing catalyst is used for changing the structure of organosilane so that organosilane can form the mesh nanometer structure with the inorganic particle coupling.In addition, thermal curing catalyst makes in the short period of time (90 ℃, 2 minutes) and solidifies.Usually, because thermal curing catalyst is actually alkalescence, so under suitable agitation condition, by using the dilution method that in can the solvent of catalyst-solvent, comprises the thermal curing catalyst of about 10wt% it to be added in the acid dispersion of inorganic particle, feasiblely can prevent the topical gel phenomenon with small proportion.
The non-limitative example of operable thermal curing catalyst comprises that for example acetate is received, the alkali metal carboxylate of potassium formiate; The hydroxy acid amine of acetate dimethylamine, acetate thanomin or formic acid xylidene(s) for example; The quaternary ammonium carboxylate of acetate tetramethylammonium, acetate benzyltrimethylammon.um or acetate trimethylammonium ethanol (choline acetate) for example; The amine of triethylamine, trolamine or paraffin for example; Or the alkali metal hydroxide of sodium hydroxid or ammonium hydroxide for example.
Based on the composition of 100wt%, use above-mentioned thermal curing catalyst with the amount of 1～10wt% according to suitable in the coating composition of the present invention.If this content is lower than 1wt%, the intensity of filming can reduce.On the other hand, if this content is higher than 10wt%, coating composition has poor package stability.
In addition, in this step, before adding organic solvent, the hydrolysate of the functionalized with alkoxysilane aromatics UV absorption agent of being represented by above-mentioned Chemical formula 2 that can add 1～10wt% amount in the sol gel reaction product is to improve weathering resistance.After adding described hydrolysate, preferably in stirring at room mixture 1～2 hour.Equally, for improving wetting ability can further add 0.001～1wt% in mixture aminosilane.
In this step, the aqueous polyurethane emulsion that can use the dispersion of photocatalyst granular of 0.1～3wt% and/or 1～10wt% is to improve wetting ability, weathering resistance and scratch-proofness.Titanium dioxide (the TiO that can have the median size of 10～80nm by use
2) and proper amount of solvent prepare the dispersion of photocatalyst granular, dispersion preferably has the solids content of 15wt%.In addition, operable aqueous polyurethane emulsion comprises the aqueous polyurethane emulsion with polyester backbone.Based on the composition of 100wt%, the preferred aqueous polyurethane emulsion that uses the amount of 1～10wt% in the coating composition.
In addition, in this step, the tensio-active agent that can randomly use 0.001～0.5wt% is to improve coating and sliding capability.Can use other additive that comprises various tensio-active agents, water tolerance improving agent, antioxidant, lubricant, heat absorbent, tinting material, static inhibitor or softening agent equally.If desired, coating composition according to the present invention may further include the leveling agent that for example improves the film smoothness, the surface tension that reduces composition to be to improve the additive of wettable wetting agent, UV absorption agent, dye leveller, radio-protector (IR absorption agent or IR tamper) etc.Operable tensio-active agent comprises at least a nonionogenic tenside, anion surfactant, cats product or amphoterics.
The present invention is not particularly limited the form of the coating composition of above-mentioned preparation.For easy to use, use the coating composition of liquid form usually.
As indicated above, the present invention also provide a kind of can self-cleaning base material, it comprises: (a) base material; And (b) coating that forms according to coating composition of the present invention of the one or both sides on described base material coatings.
As long as neither fluid neither gas, the present invention is not particularly limited the kind of base material.The non-limitative example of operable base material comprises structural exterior material, ceramic tile, plastics, glass, resin, film, pottery, metal, concrete, fiber, timber, paper, stone etc.More particularly, film, resin and structural exterior material are without any restrictedly comprising those skilled in the art's known whole plastic materials usually.Preferred film or the structural exterior material of using.
In addition, though the present invention is not particularly limited the thickness of the coating with self-cleaning performance that forms at substrate surface, coat-thickness is preferably in the scope of 0.01～50 μ m.If this thickness is lower than 0.01 μ m, film hardness is relatively poor.If this thickness is greater than 50 μ m, coating has relatively poor snappiness, breaks thereby cause filming producing.
Of the present invention can being not particularly limited by the ordinary method preparation by self-cleaning base material.In a kind of preferred implementation, can be prepared by a method comprising the following steps by self-cleaning base material: the one side in the two sides of coated base material is applied with coating composition; And the base material drying that makes coating.
Can use the common known coating method of any those skilled in the art that coating composition is coated on the base material.The present invention is not particularly limited the selection of coating method.Operable coating method comprises air knife method, intagliotype, reverse roll method, touches the roller method, scrapes the skill in using a kitchen knife in cookery, spraying method, dip coating, spread coating, rod are coated with method, spin-coating method or its combination.Can carry out the curing of coating 60～150 ℃ temperature in 4 seconds～2 minutes, but to it without limits.If solidification value is lower than 60 ℃, film can not complete drying.If solidification value is higher than 150 ℃, film and base material can be damaged.
Except aforesaid method, it is a kind of by extruding the method that step prepares the structural exterior material that the present invention also provides, and it comprises the steps: that (a) applies with the one or both sides of coating composition with the structural exterior material before material is passed through cooling step; And (b) will be in the cooling of structural exterior material or the cutting of step (a) coating.Be noted that because the structural exterior material has high surface temperature up to 100～250 ℃, just become dry and solidify so the coating of structural exterior material can be placed into water coolant up to it.Therefore, preferably (for example, extruding step, embossing step and forming step) before cooling step, the extrusion step that more preferably lucky externally material has 100～250 ℃ high surface temperature is carried out applying step afterwards.Yet the said temperature scope does not limit the scope of the invention.Antithesis, applying step can be carried out in room temperature.In addition, can applying device or applying step be added any step (any step that for example, adds the production line that comprises extruding machine-Embosser-correction card (being used for being shaped and cooling)-driling unit-tension device (being used for tension control) and pressing machine (being used for cutting)) in the structural exterior material production process in the mode that is different from aforesaid way.
As mentioned above, preparation according to the method for structural exterior material of the present invention without any need for special thermofixation or UV curing schedule.In addition, this method does not need independent wiring and the place thereof of being coated with.Therefore, can easily applying device be added the production line of the structural exterior material that uses at present, for example, add the production line of vinyl wallboard.
Aforesaid method can be applied to the whole plastic basis materials by the preparation of extrusion method.In addition, the present invention is not particularly limited coating composition, can use and can give for example coating composition of the required physical properties of stain resistance, self-cleaning performance, weathering resistance, scratch-proofness and other character of structural exterior material.More particularly, preferably described coating composition has 60～150 ℃ lower boiling or 9.5Mpa
0.5Or littler solubility parameter (δ), thereby solidify easily owing to lower boiling, and owing to corrodibility forms firm coating.Therefore, preferred use comprise the organic solvent that can satisfy above-mentioned condition according to coating composition of the present invention.When using coating composition according to the present invention to prepare the structural exterior material, coating composition of the present invention can be realized good stain resistance and self-cleaning performance simultaneously.
Operable coating method is with above-mentioned identical.The structural exterior material that obtains by aforesaid method has 0.01～50 μ m, is preferably the coat-thickness of 0.5～20 μ m.
After the coating, after having the extrusion step of the surface temperature up to 100～250 ℃, can finish the structural exterior material curing of coating just with 4 seconds or longer set time.If be 4 seconds set time, film can not become dry and solidify fully under 100 ℃ or lower solidification value.If solidification value is higher than 250 ℃, wetting ability can reduce.
Beneficial effect
Use at least two kinds of coating compositions according to the present invention with inorganic particle that comprises the wetting ability hydroxyl of different median sizes to utilize the advantage of hydrophilic group and surfaceness and can be provided for the good self-cleaning performance coating of outdoor film and structural exterior material.In addition, because coating composition use according to the present invention has lower boiling organic solvent, in conventional production line, can finish the coating of the general plastic basis material that comprises the vinyl wallboard for preparing by routine extrusion method so it does not need extra production line, finish required production cost of production stage and workspace thereby reduce.
Description of drawings
In conjunction with the accompanying drawings, by following detailed explanation, above and other objects of the present invention, feature and other advantage will become more apparent, wherein:
Fig. 1 is the synoptic diagram of a kind of embodiment of the ordinary method of demonstration production structural exterior material, and it is finished at the production line that comprises extruding machine, Embosser, correction card (being used for being shaped and cooling), driling unit, tension device (being used for tension control) and pressing machine (being used for cutting).
Embodiment
Hereinafter with detailed description preferred implementation of the present invention.Should be appreciated that the following examples only are illustrative and the invention is not restricted to them.
Specimen preparation. synthesizing of the hydrolysate of functionalized with alkoxysilane aromatics UV absorption agent.
The UV absorption agent Tinuvin 1130 (available from Ciba-Geigy company) based on benzothiazole of 30.5wt% is mixed and mixture is added in the reactor with the acetone of 42wt%.The internal temperature of reactor maintains 55～57 ℃ and stirring.Dropwise added γ-isocyanato-propyl-triethoxysilicane of 11.5wt% in 30 minutes in the introversive described mixture and 55～57 ℃ temperature sustained reaction 90 minutes.In the mixture that makes, add γ-glycidoxypropyltrime,hoxysilane of 11wt% and 55～57 ℃ temperature sustained reaction 30 minutes.In the solution that makes, add the water of 5wt% and 55～57 ℃ temperature sustained reaction 2 hours to obtain as the hydrolysate in the title of functionalized with alkoxysilane UV absorption agent.This hydrolysate has 52% solids content.
[embodiment 1～7] coating composition, and use the poster paper of this coating composition and structural exterior material
Preparation
Embodiment 1
1-1. coating composition
The silica dispersion with 30% solids content (MA-ST is available from TLSAN chemical company) that in reactor, adds 9wt%, it comprises and is scattered in the silicon-dioxide that has 10～20nm median size in the methyl alcohol (silicon-dioxide of 2.7wt% and the methyl alcohol of 6.3wt%); The silica dioxide granule of 0.09wt% (FineSil, Tokuyama Co.) with 1.7 μ m median sizes; The concentration of 0.01wt% is 10% nitric acid; The water of 1.01wt%; The methyl alcohol of 18wt%; Glycidoxypropyltrime,hoxysilane with 1.89wt%.This mixture after 24 hours, adds the MEK (methyl ethyl ketone) of EA (ethyl acetate), 54.5wt% of 10wt% and the toluene of 5wt% 50 ℃ of reactions successively.Then, said mixture is stirred 1 hour to form coating composition.
1-2. have the preparation of the structural exterior material of stain resistance
Utilize spraying method just the Embo-device in its production line (embossing step) coating composition that will obtain according to embodiment 1-1 afterwards be coated to vinyl wallboard product (LG Chemical Ltd. with the dried thickness of 2 μ m, LG Sideon) above, thereby preparation has the vinyl wallboard of stain resistance.
Embodiment 2
Except at room temperature not using outside the coating composition vinyl coating basal wall panel products (LG Chemical Ltd., LG Sideon), repeat embodiment 1 has stain resistance with preparation vinyl wallboard in the embossing step.
Embodiment 3
3-1. coating composition
The silica dispersion with 20% solids content (ST-C is available from TLSAN chemical company) that in reactor, adds 32wt%, it comprises and is scattered in the silicon-dioxide that has the 20nm median size in the water (silicon-dioxide of 6.4wt% and the methyl alcohol of 25.6wt%); The silica dioxide granule of 0.56wt% (FineSil T-32, Tokuyama Co.) with 1.7 μ m median sizes; The concentration of 0.05wt% is 67% nitric acid; The water of 60.62wt%; The glycidoxypropyltrime,hoxysilane of 4.48wt%; The ethylene diamide of 0.37wt% as thermal curing catalyst; Choline acetate with 1.92wt%.Said mixture is at room temperature stirred 3 hours to form coating composition.
3-2. the preparation of poster paper
Utilize rod be coated with method will according to the coating composition of embodiment 3-1 preparation with the dried thickness of 1 μ m be coated to white PVC poster paper (LG Chemical Ltd., Hi-Cast) on, and be coated with patch and solidified 2 minutes at 90 ℃, thus the preparation poster paper.
Embodiment 4
4-1. coating composition
The silica dispersion that in reactor, adds 32wt% with 20% solids content
(ST-C is available from TLSAN chemical company), it comprises and is scattered in the silicon-dioxide that has the 20nm median size in the water (silicon-dioxide of 6.4wt% and the methyl alcohol of 25.6wt%); The silica dioxide granule of 0.56wt% (FineSil T-32, Tokuyama Co.) with 1.7 μ m median sizes; The concentration of 0.05wt% is 67% nitric acid; The water of 40.62wt%; The glycidoxypropyltrime,hoxysilane of 4.48wt%; The ethylene diamide of 0.37wt% as thermal curing catalyst; Choline acetate with 1.92wt%.Said mixture is at room temperature stirred 3 hours to form coating composition.The coating composition of preparation further mixes with the titanium dioxide dispersion with 15% solids content (ST-21 is available from Isahara Industries Co.) of 20wt% so that final coating composition to be provided, and this titanium dioxide dispersion comprises and is scattered in the water (TiO of 3wt%
2Water with 17wt%) titanium dioxide that has the median size of 40nm in.
4-2. the preparation of poster paper
Except using coating composition, repeat embodiment 3-2 with the preparation poster paper according to embodiment 4-1.
Embodiment 5
5-1. coating composition
The silica dispersion with 20% solids content (ST-C is available from TLSAN chemical company) that in reactor, adds 32wt%, it comprises and is scattered in the silicon-dioxide that has the 20nm median size in the water (silicon-dioxide of 6.4wt% and the methyl alcohol of 25.6wt%); The silica dioxide granule of 0.56wt% (FineSil T-32, Tokuyama Co.) with 1.7 μ m median sizes; 4.48wt% glycidoxy propyl group trimethoxy silane; The concentration of 0.05wt% is 67% nitric acid; The water of 31.5wt%.Then, said mixture was 50 ℃ of sustained reactions 24 hours.After the reaction mixture, add 0.37wt% as the ethylene diamide of thermal curing catalyst and the choline acetate of 1.92wt%, and the mixture that obtains at room temperature stirred 3 hours.The aminopropyl Ethoxysilane, the tensio-active agent (BYK 333, BYK chemical company) of 0.19wt% and the methyl cellosolve of 4.16wt% that in the solution that makes, add 0.28wt%, and this mixture at room temperature stirred 1 hour.With the mixture that obtains further with the titanium dioxide dispersion with 15% solids content (ST-21 is available from Isahara Industries Co.) of 20wt%, (the PES A160-P of the urethane with 10% solid content of 3wt%, Takamasu Co.) and the UV absorption agent that obtains according to above-mentioned preparation embodiment of 1.5wt% mix preparing final coating composition, this titanium dioxide dispersion comprises and is scattered in the water (TiO of 3wt%
2Water with 17wt%) titanium dioxide that has the median size of 40nm in.
5-2. the preparation of poster paper
Except using coating composition, repeat embodiment 3-2 with the preparation poster paper according to embodiment 5-1.
Embodiment 6
6-1. coating composition
The silica dioxide granule that has the median size of 3 μ m except use replaces having the silica dioxide granule of median size of 1.7 μ m, repeats embodiment 5 to form coating composition.
6-2. the preparation of poster paper
Except using coating composition, repeat embodiment 3-2 with the preparation poster paper according to embodiment 6-1.
Embodiment 7
7-1. coating composition
Except the water of the silica dioxide granule with 1.7 μ m median sizes that uses 1.12wt% and 30.94wt% replaces the water of the silica dioxide granule with 1.7 μ m median sizes of 0.56wt% and 31.5wt%, repeat embodiment 5 to form coating composition.
7-2. the preparation of poster paper
Except using coating composition, repeat embodiment 3-2 with the preparation poster paper according to embodiment 7-1.
[comparative example 1～9] coating composition, and the preparation of using the poster paper and the structural exterior material of this coating composition
Comparative example 1
Except not using silicon-dioxide, repeat embodiment 1 and be coated with the vinyl wallboard of this coating composition so that coating composition and preparation to be provided with 10～20nm median size.
Comparative example 2
Except not using silicon-dioxide, repeat embodiment 1 and be coated with the vinyl wallboard of identical coating composition so that coating composition and preparation to be provided with 1.7 μ m median sizes.
Comparative example 3
Except the ethanol that do not use 10% water and 90% as the solvent, repeat embodiment 1 and be coated with the vinyl wallboard of identical coating composition so that coating composition and preparation to be provided.
Comparative example 4
Except not using aqueous silica dispersion (the median size 40nm of 20wt% with 15% solids content, ST-21 is available from Isahara Industries Co.) outside, repeat embodiment 5 and use the poster paper of identical coating composition so that coating composition and preparation to be provided.
Comparative example 5
Except not using silicon-dioxide, repeat embodiment 5 and use the poster paper of identical coating composition so that coating composition and preparation to be provided with 20nm median size.
Comparative example 6
Except the hydrolysate that does not use the UV absorption agent, repeat embodiment 5 and use the poster paper of identical coating composition so that coating composition and preparation to be provided.
Comparative example 7
The silicon-dioxide that has the 90nm median size except use replaces having the silicon-dioxide of 20nm median size, repeats embodiment 5 and uses the poster paper of this coating composition so that coating composition and preparation to be provided.
Comparative example 8
Except the aqueous silica dispersion of not using 20wt% and use the water dispersion (TiO of 6wt% of the same light granules of catalyst of 40wt% with 15% solid content
2Water with 34wt%) outside, repeat embodiment 5 and use the poster paper of this coating composition so that coating composition and preparation to be provided.
Comparative example 9
Except neither using silicon-dioxide also not use the silicon-dioxide with 1.7 μ m median sizes, repeat embodiment 5 and use the poster paper of identical coating composition so that coating composition and preparation to be provided with 20nm median size.
The evaluation of test example 1. wetting abilities and hydrophilic persistence
Carry out following test to estimate by using the poster paper that coating composition according to the present invention obtains and the wetting ability and the hydrophilic persistence of structural exterior material.
In this embodiment, use is available from the contact angle measuring apparatus of Kruss company.Each sample place outdoor environment and 1,3 and 6 months after measure the surface contact angle of each sample.
1.1 structural exterior material
To carry out above-mentioned test as sample by the vinyl wallboard of embodiment 1～2 and comparative example 1～3 preparation.The results are shown in the following table 1.
After this test, as can be seen by using the coating composition preparation do not contain inorganic particle vinyl wallboard, and present relatively poor wetting ability (referring to table 1) by the vinyl wallboard that use has a solvent preparation of improved composition according to comparative example 3 according to comparative example 1 with 10～20nm median size.More particularly, can expect that vinyl wallboard according to comparative example 1 does not have the wetting ability that the hydrophilic group by the silicon nanoparticle surface produces.In addition, can expect that vinyl wallboard according to comparative example 3 has too high boiling point or too poor corrodibility and can not form coating on base material, thereby present poor wetting ability.In addition, compare, do not use the vinyl wallboard of silica dioxide granule to present low wetting ability with 1.7 μ m median sizes with vinyl wallboard according to embodiment 1.Can expect that this lower wetting ability is caused by the low hydrophilic group content and the low surface roughness of silica sphere.
Antithesis, the vinyl wallboard that is coated with according to the composition of embodiment 1 and 2 presents the highest initial stage wetting ability and excellent hydrophilic persistence (referring to table 1).
Table 1
1-2. poster paper
To carry out above-mentioned test as sample by the poster paper of embodiment 3～7 and comparative example 4～9 preparations.The results are shown in the following table 2.
After the test, present 22 °～60 ° water contact angle by each poster paper that uses the coating composition preparation that does not contain photocatalyst granular according to embodiment 3 and comparative example 4,5 and 9.Other poster paper presents 5 ° or littler water contact angle.More particularly, compare with the poster paper that does not use photocatalyst granular, neither use photocatalyst granular not use also that wherein a kind of poster paper according to comparative example 9 presents lower initial stage wetting ability and hydrophilic persistence in two kinds of inorganic particles with different mean molecule particle diameters according to comparative example 5.In the sample that this test is tested, present minimum initial stage wetting ability and hydrophilic persistence according to the poster paper of comparative example 9.This means that the factor that influences wetting ability and hydrophilic persistence is two kinds of inorganic particles with different median sizes.
Therefore, can provide good wetting ability and hydrophilic persistence (referring to table 2) according to coating composition of the present invention as can be seen.
Table 2
The evaluation of test example 2. self-cleaning performances
Carry out following test to estimate by using according to the poster paper of coating composition preparation of the present invention and the self-cleaning performance of structural exterior material.
For carrying out this test, the earth and the sand that will have 10 μ m median sizes are scattered in the water, reach 5% solid content, and this dispersion are sprayed onto on each sample of vinyl wallboard and poster paper.Then, the sample drying of handling also is sprayed onto distilled water on each sample once more.After 6 months, remain in the content of each vinyl wallboard and lip-deep earth of poster paper and sand by visual inspection.Amount by earth and sand pollutent is divided into level Four with sample: good (totally), good (light contamination), not enough (pollution) and relatively poor (highly polluted).
2-1. structural exterior material
To carry out above-mentioned test as sample by the vinyl wallboard of embodiment 1～2 and comparative example 1～3 preparation.The results are shown in the following table 3.
After the test, can obtain the similar result of test-results to above-mentioned wetting ability and hydrophilic persistence.More particularly, the vinyl wallboard according to comparative example 1 for preparing by the coating composition that uses the inorganic particle that does not contain the median size with 10～20nm presents relatively poor self-cleaning performance.Antithesis, the vinyl wallboard according to embodiment 1 and 2 presents good self-cleaning performance (referring to table 3).
Table 3
| Sample (vinyl wallboard) | Self-cleaning performance |
| Embodiment 1 | Good |
| Embodiment 2 | Good |
| Comparative example 1 | Relatively poor |
| Comparative example 2 | Well |
| Comparative example 3 | Not enough |
2-2. poster paper
To carry out above-mentioned test as sample by the poster paper of embodiment 3～7 and comparative example 4～9 preparations.The results are shown in the following table 4.
After the test, present insufficient self-cleaning performance by each poster paper that uses the coating composition preparation that does not contain photocatalyst granular according to embodiment 3 and comparative example 4.In addition, use photocatalyst granular and the poster paper according to comparative example 5 that do not contain the inorganic particle with 1.7 μ m median sizes presents good self-cleaning performance.In addition, the photocatalyst granular that neither uses according to comparative example 9 does not use two kinds of wherein a kind of poster papers in the inorganic particle with different median sizes to present relatively poor self-cleaning performance again.This means the coating composition of inorganic particle that use only has a kind of median size owing to hydrophilic group presents wetting ability, but its wetting ability can not significantly improve owing to surfaceness, thereby present the self-cleaning performance of reduction.Use two kinds of coating compositions that good self-cleaning performance (referring to table 4) can be provided with inorganic particle of different median sizes antithesis.
Table 4
| Sample (poster paper) | Self-cleaning performance |
| Embodiment 3 | Not enough |
| Embodiment 4 | Good |
| Embodiment 5 | Good |
| Embodiment 6 | Good |
| Embodiment 7 | Good |
| Comparative example 4 | Not enough |
| Comparative example 5 | Well |
| Comparative example 6 | Good |
| Comparative example 7 | Good |
| Comparative example 8 | Good |
| Comparative example 9 | Relatively poor |
The evaluation of test example 3. weathering resistancies
Carry out following test to estimate by using according to the poster paper of coating composition preparation of the present invention and the weathering resistance of structural exterior material.
Use QUV accelerationizations weather-resistant tester (UVB 313 lamps, 60 ℃) to test as each vinyl wallboard of sample and poster paper 1000 hours with the mensuration yellowness index and observe each sample and whether break.
3-1. structural exterior material
To be used as the sample that carries out above-mentioned test by the vinyl wallboard of embodiment 1～2 and comparative example 1～3 preparation.The results are shown in the following table 5.
After the test, do not occur breaking according to whole vinyl wallboards of the foregoing description and comparative example, and aspect yellowness index, present relative good result (referring to table 5).
Table 5
3-2. poster paper
To carry out above-mentioned test as sample by the poster paper of embodiment 3～7 and comparative example 4～9 preparations.The results are shown in the following table 6.
After the test, aspect yellowness index, the whole poster papers that are coated with according to the coating composition of embodiment 3～7 and comparative example 4～9 present relative good result (referring to table 6).Specifically, be coated with the coating composition that do not contain the UV absorption agent according to embodiment 3 with 4 and the poster paper of comparative example 6 present relative high yellowness index, but it does not present other sign that any demonstration weathering resistance reduces.
Therefore, the poster paper for preparing according to coating composition of the present invention by use as can be seen not only has good self-cleaning performance but also has good weathering resistance.
Table 6
The evaluation of test example 4. scratch-proofnesss
Carry out following test to estimate by using according to the poster paper of coating composition preparation of the present invention and the scratch-proofness of structural exterior material.
Vinyl wallboard according to embodiment 1～2 and comparative example 1～3 is used as sample.According to each sample of SteelWool (#0000) experimental test, and under the heavy burden of 200g, measure the number of point that cut occurs.The results are shown in following table 7.
After the test, has relatively poor scratch-proofness by what use the coating composition preparation do not contain silica dioxide granule according to the vinyl wallboard of comparative example 1 and the vinyl wallboard according to comparative example 3 of coating composition preparation that has the improved composition of organic solvent by use as can be seen with 10～20nm median size.This means to be used for, thereby relatively poor scratch-proofness is provided according to the having high boiling point or base material is not had enough corrosive organic solvents and make the reticulated structure of coating not form of the coating composition of comparative example 3.
Antithesis, the vinyl wallboard according to embodiment 1 and 2 presents good scratch-proofness (referring to table 7).
Table 7
| Sample (vinyl wallboard) | Scratch-proofness |
| Embodiment 1 | 10 times |
| Embodiment 2 | 6 times |
| Comparative example 1 | 2 times |
| Comparative example 2 | 5 times |
| Comparative example 3 | 2 times |
The evaluation of test example 5. turbidity
Carry out following test to estimate turbidity according to coating composition of the present invention.
Poster paper according to embodiment 3～7 and comparative example 4～9 is used as sample.Use reflecting ﹠ transmitting instrument (HR-100, Murakami Co.), test each transparent PVC membrane sample, and measure the ratio of transmitted light and the degree of dispersion of incident light, i.e. turbidity (% turbidity) according to ASTM D-1003 method.The results are shown in following table 8.
Usually, for realizing antiglare effect, need low-luster and high turbidity.Under the situation of show and colour, consider visibility out of doors, allow the highest 20% turbidity.
After the test, the poster paper that is coated with according to the embodiment 5 of coating composition of the present invention shows about 10% turbidity, and shows 5%～20% turbidity value (referring to table 8) according to the poster paper of comparative example.
Table 8
| Sample (poster paper) | Turbidity (% turbidity) |
[0215]?
| Embodiment 3 | 9? |
| Embodiment 4 | 9? |
| Embodiment 5 | 10? |
| Embodiment 6 | 34? |
| Embodiment 7 | 23? |
| Comparative example 4 | 8? |
| Comparative example 5 | 5? |
| Comparative example 6 | 9? |
| Comparative example 7 | 20? |
| Comparative example 8 | 17? |
| Comparative example 9 | 5? |
The evaluation of test example 6. glossiness
Carry out following test to estimate glossiness according to coating composition of the present invention.
Poster paper according to embodiment 3～7 and comparative example 4～9 is used as sample.Use is measured the surface gloss of transparent each PVC membrane sample available from the glossometer of BYKGardner company by the relative value of measuring 60 ° of reflected light and 60 ° of incident lights.The results are shown in the following table 9.
Usually, by gloss (80% or higher), semi-gloss (40-80%) and tarnish (40% or lower) with the surface gloss classification.For giving anti-dazzle property, surface gloss is preferably in 20%～40% scope.
After the test, the poster paper that is coated with according to coating composition of the present invention shows good surface gloss.
Table 9
| Sample (poster paper) | Glossiness |
| Embodiment 3 | 29? |
| Embodiment 4 | 29? |
| Embodiment 5 | 30? |
| Embodiment 6 | 8? |
| Embodiment 7 | 9? |
| Comparative example 4 | 15? |
| Comparative example 5 | 75? |
| Comparative example 6 | 30? |
| Comparative example 7 | 20? |
| Comparative example 8 | 22? |
| Comparative example 9 | 74? |
Industrial applicability
From above as can be seen, can give the stain resistance that conventional outdoor film and structural exterior material are produced by self-cleaning performance according to coating composition of the present invention, make described film and material can keep clean outward appearance, and save and clean their required labor force and costs.Therefore, expectation can be extensively according to coating composition of the present invention and is used for the field of outdoor film and structural exterior material effectively.
Though described the present invention in conjunction with being considered to the most practical and most preferred embodiment at present, should be appreciated that to the invention is not restricted to disclosed embodiment and accompanying drawing.Antithesis, the present invention plans to cover the essence of appended claims and the various modifications and variations in the scope.
Claims (11)
1. coating composition with self-cleaning performance, it comprises:
(a) first kind of inorganic particle of the hydroxyl of 1-15wt% with 5～30nm median size;
(b) second kind of inorganic particle of the hydroxyl of 0.05-3wt% with 0.2～5 μ m median size;
(c) organic silane compound of representing by following Chemical formula 1 of 1-15wt%;
(d) solvent of 50-85wt%;
(e) photocatalyst granular of 0.1-3wt%;
(f) hydrolysate of the functionalized with alkoxysilane aromatics UV absorption agent of representing by following Chemical formula 2 of 1～10wt%;
(g) acid of 0.001～2wt%;
(h) thermal curing catalyst of 1～10wt%; And
(i) aqueous polyurethane emulsion of 1～10wt%:
[Chemical formula 1]
R
nSi(OR’)
4-n(1)
Wherein, R is C1～C8 aminoalkyl, glycidoxyalkyl or isocyanato-alkyl;
R ' is C1～C6 low alkyl group; And
N is 0～3 integer;
[Chemical formula 2]
Wherein, R
1And R
2Represent C1～C6 alkyl independently;
R
3Expression C1～C6 alkyl or aryl;
OR
4Expression methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or acetoxyl;
R
5Expression C1～C12 alkyl or aryl;
X represents hydrogen atom or halogen atom;
L is 5～9 integer;
M is 1～3 integer; And
N is 0～2 integer.
2. coating composition according to claim 1, wherein, described solvent comprises having 60 ℃～at least a organic solvent of 150 ℃ mean boiling point.
3. coating composition according to claim 1, wherein, described solvent comprises that plastics are had 9.5Mpa
0.5Or the organic solvent of littler solubility parameter.
One kind can self-cleaning base material, comprising:
(a) base material; And
(b) coating that forms as each defined coating composition in the claim 1～3 by one or both sides coating at described base material.
5. according to claim 4 can self-cleaning base material, wherein, described base material is selected among film, structural exterior material, ceramic tile, plastics, glass, resin, pottery, metal, concrete, fiber, timber, paper and the stone.
6. according to claim 4 can self-cleaning base material, wherein, described coating has the thickness of 0.01～50 μ m.
7. one kind prepares the method with coating composition of self-cleaning performance as claimed in claim 1, and it comprises the steps:
(a) first kind of inorganic particle that will have 5～30nm median size adds in the dispersion medium and mixes to prepare the dispersion of first kind of inorganic particle;
(b) dispersion of first kind of inorganic particle that will obtain from described step (a) and second kind of inorganic particle, organic silane compound, acid and the solvent represented by following Chemical formula 1 with 0.2 μ m～5 μ m median sizes, and make the mixture reaction that obtains;
(c) in the reaction product of step (b), add thermal curing catalyst and the hydrolysate of the functionalized with alkoxysilane aromatics UV absorption agent represented by following Chemical formula 2, and react; And
(d) dispersion with organic solvent, aqueous polyurethane emulsion and photocatalyst granular adds in the reaction product that is obtained by step (c):
[Chemical formula 1]
R
nSi(OR’)
4-n(1)
Wherein, R is C1～C8 aminoalkyl, glycidoxyalkyl or isocyanato-alkyl;
R ' is C1～C6 low alkyl group; And
N is 0～3 integer;
[Chemical formula 2]
Wherein, R
1And R
2Represent C1～C6 alkyl independently;
R
3Expression C1～C6 alkyl or aryl;
OR
4Expression methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or acetoxyl;
R
5Expression C1～C12 alkyl or aryl;
X represents hydrogen atom or halogen atom;
L is 5～9 integer;
M is 1～3 integer; And
N is 0～2 integer.
8. method according to claim 7, wherein, described step (a) and the dispersion medium that (b) uses and solvent are to be selected from least a in water, the pure and mild ketone.
9. method for preparing the structural exterior material, it comprises the steps:
(a) before material passes through cooling step, the one side in the two sides of structural exterior material is applied with the coating composition that each limited in the claim 1 to 3 with self-cleaning performance; And
(b) will be in the cooling of structural exterior material or the cutting of step (a) coating.
10. method according to claim 9, wherein, described structural exterior material is selected from the plastic basis material that extrudes at least one step process in step, embossing step and the forming step for using.
11. method according to claim 9, wherein, the structural exterior material in the described step (a) has 100 ℃～250 ℃ surface temperature.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040073799 | 2004-09-15 | ||
| KR20040073799 | 2004-09-15 | ||
| KR10-2004-0073799 | 2004-09-15 | ||
| KR1020050033621A KR100876529B1 (en) | 2004-09-15 | 2005-04-22 | Film or building exterior material using self-cleaning coating composition and method for producing same |
| KR10-2005-0033621 | 2005-04-22 | ||
| KR1020050033621 | 2005-04-22 | ||
| PCT/KR2005/002038 WO2006031012A1 (en) | 2004-09-15 | 2005-06-29 | Films or structural exterior materials using coating composition having self-cleaning property and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1984972A CN1984972A (en) | 2007-06-20 |
| CN1984972B true CN1984972B (en) | 2011-05-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800239844A Expired - Fee Related CN1984972B (en) | 2004-09-15 | 2005-06-29 | Films or structural exterior materials using coating composition having self-cleaning property and preparation method thereof |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4712802B2 (en) |
| KR (1) | KR100876529B1 (en) |
| CN (1) | CN1984972B (en) |
| MX (1) | MX2007001244A (en) |
| RU (1) | RU2340644C2 (en) |
| TW (1) | TWI297032B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100782321B1 (en) * | 2007-04-20 | 2007-12-06 | 그린닉스주식회사 | A composition of paint and varnish for easy cleaning |
| US20100092765A1 (en) * | 2008-10-10 | 2010-04-15 | 3M Innovative Properties Company | Silica coating for enhanced hydrophilicity |
| KR101450917B1 (en) * | 2009-07-15 | 2014-10-14 | 엘지전자 주식회사 | Cooking appliance |
| CN101985250B (en) * | 2009-07-29 | 2013-08-28 | 财团法人工业技术研究院 | Weather-resistant self-cleaning coating and forming method thereof |
| US9428666B2 (en) * | 2013-03-22 | 2016-08-30 | Empire Technology Development Llc | Hydrophilic self-cleaning coating compositions |
| BR112015028758A2 (en) * | 2013-05-17 | 2017-07-25 | 3M Innovative Properties Co | easy to clean surface and same method of manufacture |
| KR101889615B1 (en) * | 2016-12-05 | 2018-08-17 | 김응서 | self-cleaning olefin sheet |
| JP7101570B2 (en) * | 2018-08-31 | 2022-07-15 | シャープ株式会社 | Photocatalyst paint, method for manufacturing photocatalyst paint, and method for manufacturing photocatalyst |
| US20220194857A1 (en) * | 2019-04-11 | 2022-06-23 | Wellture Finetech Co., Ltd. | Nano inorganic composition and coating method using same |
| CN114479657A (en) * | 2021-12-23 | 2022-05-13 | 江苏云睿汽车电器系统有限公司 | Self-purification nano coating and preparation method thereof |
| CN115895004B (en) * | 2022-11-10 | 2023-12-08 | 江苏凯伦建材股份有限公司 | Self-cleaning coiled material and preparation method and application thereof |
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- 2005-06-28 TW TW094121686A patent/TWI297032B/en not_active IP Right Cessation
- 2005-06-29 JP JP2007522412A patent/JP4712802B2/en not_active Expired - Fee Related
- 2005-06-29 RU RU2007102677/04A patent/RU2340644C2/en not_active IP Right Cessation
- 2005-06-29 CN CN2005800239844A patent/CN1984972B/en not_active Expired - Fee Related
- 2005-06-29 MX MX2007001244A patent/MX2007001244A/en active IP Right Grant
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| US6756124B2 (en) * | 2000-04-13 | 2004-06-29 | Jsr Corporation | Coating composition, method for producing the same, cured product and coating film |
| WO2004011554A1 (en) * | 2002-07-26 | 2004-02-05 | Matsushita Electric Works, Ltd. | Photocatalyst-containing silicone resin composition, and coated article having cured coating film therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100876529B1 (en) | 2008-12-31 |
| JP4712802B2 (en) | 2011-06-29 |
| RU2340644C2 (en) | 2008-12-10 |
| MX2007001244A (en) | 2008-10-24 |
| CN1984972A (en) | 2007-06-20 |
| JP2008506831A (en) | 2008-03-06 |
| TWI297032B (en) | 2008-05-21 |
| RU2007102677A (en) | 2008-07-27 |
| KR20060047423A (en) | 2006-05-18 |
| TW200613481A (en) | 2006-05-01 |
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