CN101792564B - Anti-scratch coating and preparation method thereof - Google Patents

Anti-scratch coating and preparation method thereof Download PDF

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CN101792564B
CN101792564B CN2010101170745A CN201010117074A CN101792564B CN 101792564 B CN101792564 B CN 101792564B CN 2010101170745 A CN2010101170745 A CN 2010101170745A CN 201010117074 A CN201010117074 A CN 201010117074A CN 101792564 B CN101792564 B CN 101792564B
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coating
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aqueous solution
weak
substrate
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CN101792564A (en
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孙俊奇
刘小孔
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Jilin University
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Jilin University
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Abstract

The invention relates to a constructed elementary solution with negative charge, an anti-scratch coating prepared by the constructed elementary solution, and a preparation method for the constructed elementary solution and the anti-scratch coating. The constructed elementary solution is a complex solution comprising weak polyanions, calcium ions and carbonate ions. The preparation method of the anti-scratch coating is as follows: leading amino, carboxyl or hydroxide radical to the surface of substrates, alternatively placing the substrates in the constructed elementary solution and the weak polycations aqueous solution, utilizing a laminated assembly technology to prepare laminated assembly film coating with controllable thickness, and finally carrying out thermal treatment on the obtained coating under 80-250 DEG C for 0.5-20h to obtain the transparent anti-scratch coating with high hardness. The coating can be used as the anti-scratch coating of other functional film materials, has the characteristics of low cost, simple method and no need of complex apparatuses and devices. The size of the coating is not limited by the shape and size of the substrates, therefore, the coating is expected to have wide application in daily production and life.

Description

A kind of anti-scratch coating and preparation method thereof
Technical field
The invention belongs to the anti-scratch coating technical field, be specifically related to a kind of constructing primitive solution, constructing the anti-scratch coating of primitive formulations prepared from solutions of negative charge that have by this, and their preparation method.
Background technology
Existing research shows that polymer inorganic thing nano composite material can show excellent mechanical property.The mechanical property of matrix material is closely related with the degree of scatter of inorganic nano-filler wherein, and it is good more that inorganic nano-filler disperses, can big more degree on the mechanical property of reinforced composite.But nano level mineral filler is the important problem in polymer inorganic thing nano composite material mechanical property modification field because its big surface energy is easy to assemble so how to realize the homodisperse of inorganic nano-filler in polymer materials.The method of existing raising inorganic nano-filler degree of scatter in polymer materials mainly is that surface by utilizing polymkeric substance or the tensio-active agent at inorganic nano-filler carries out finishing; But inorganic nano-filler finishing meeting is made complex manufacturingization, increase production cost.And from existing report, this method can not be avoided the gathering of inorganic nano-filler in polymkeric substance fully.
At present the transparent anti-scratch coating of preparation high mechanical strength is based on sol-gel technique mostly, thus the organic inorganic hybridization coating that the presoma of silicon-dioxide is hydrolyzed in the polymer body material and prepares.This method will be with the presoma of silicon-dioxide as raw material, and comparatively expensive, the preparation process need carries out accuracy controlling to the hydrolysis of silicon-dioxide presoma, and is comparatively complicated, and preparation process need organic solvent.
Summary of the invention
First purpose of the present invention provide a kind of be used to prepare anti-scratch coating have negative charge construct primitive solution and this constructs the preparation method of primitive solution;
Second purpose of the present invention provides a kind ofly to be used the foregoing negative charge that has and constructs the anti-scratch coating of primitive formulations prepared from solutions and the preparation method of this coating.
The present invention has developed a kind of novel method of homodisperse inorganic nano-particle in polymeric coating of cheap and simple; Thereby can on various solid substrate, make the transparent anti-scratch coating of high mechanical strength, overcome defectives such as expensive raw materials among the preparation method of existing transparent anti-scratch coating, cost are higher, complicated operation, contaminate environment.
We find, as constructing primitive, utilize the stratiform package technique that it is assembled on solid substrate polyelectrolyte-inorganics original position mixture, can prepare the transparent high firmness anti-scratch coating that only contains the small amounts of inorganic filler.And in the preparation method, raw materials cost is cheap, and method is simple, does not have the restriction of substrate sizes shape, do not need complicated plant and instrument, and all preparation processes is all carried out environmental protection in the aqueous solution.These advantages all help its actual productive life and use.
A: of the present invention a kind of have a negative charge construct the primitive aqueous solution; It is the composite solution that comprises weak polyanion, calcium ion and carbanion; Wherein, The monomer concentration of weak polyanion is 0.02～1.5mol/L, and the concentration of calcium ion is 0.01～2mol/L, and the concentration of carbanion is 10%～90% of weak polyanion concentration.
Preferable, the concentration of weak polyanion is 0.05～0.2mol/L, and the concentration of calcium ion is 0.05～0.15mol/L, and the concentration of carbanion is 40～90% of weak polyanion concentration;
Better, the concentration of weak polyanion is 0.08～0.12mol/L, and the concentration of calcium ion is 0.06～0.1mol/L, and the concentration of carbanion is 60～80% of weak polyanion concentration;
Best, the concentration of weak polyanion is 0.1mol/L, and the concentration of calcium ion is 0.07mol/L, and the concentration of carbanion is the 0.07mol/L of weak polyanion concentration.
Preferable, weak polyanion is the ROHM weak polyanion that ionization generates in water.
Above-mentioned be used to prepare the anti-scratch coating material construct the primitive aqueous solution, also can be described as polyelectrolyte-inorganics original position compound water solution, or be weak polyanion-lime carbonate (CaCO 3) compound aqueous solution, it is made by following method:
At first prepare the aqueous solution that monomer concentration is the weak polyanion of 0.02～1.5mol/L, again with Calcium Chloride Powder Anhydrous (CaCl 2) be dissolved in the weak polyanion aqueous solution that has prepared, make
Get CaCl 2Concentration be 0.01～2mol/L, obtain weak polyanion-CaCl 2Mixing solutions; With yellow soda ash (Na 2CO 310H 2O) soluble in water, compound concentration is the Na of weak polyanion concentration of aqueous solution 10～90% 2CO 3The aqueous solution; At last, with Na 2CO 3The aqueous solution pours into isopyknic weak polyanion-CaCl 2In the mixing solutions, promptly obtain comprising the weak polyanion-CaCO of weak polyanion, calcium ion and carbanion 3Composite solution, this weak polyanion-CaCO 3Composite solution has negative charge.
Preferable, at first prepare the aqueous solution that monomer concentration is the weak polyanion of 0.05～0.2mol/L, again with CaCl 2Be dissolved in the weak polyanion aqueous solution that has prepared, make CaCl 2Concentration be 0.05～0.15mol/L, obtain weak polyanion-CaCl 2Mixing solutions; With Na 2CO 310H 2O is soluble in water, and compound concentration is the Na of weak polyanion concentration of aqueous solution 40～90% 2CO 3The aqueous solution; At last, with Na 2CO 3The aqueous solution pours into isopyknic weak polyanion-CaCl 2In the mixing solutions, leave standstill 2～20h, promptly obtain comprising the weak polyanion-CaCO of weak polyanion, calcium ion and carbanion 3Composite solution;
Better, the concentration of the weak polyanion aqueous solution is 0.08～0.12mol/L, CaCl 2Concentration be 0.06～0.1mol/L, Na 2CO 3The concentration of the aqueous solution is weak polyanion concentration of aqueous solution 60～80%, and resulting composite solution leaves standstill 6～15h;
Best, the concentration of the weak polyanion aqueous solution is 0.1mol/L, CaCl 2Concentration be 0.07mol/L, Na 2CO 3The concentration of the aqueous solution is 0.07mol/L, and resulting composite solution leaves standstill 12h.
Preferable, the weak polyanion aqueous solution is the ROHM aqueous solution.
B: of the present invention a kind of have a negative charge construct the primitive aqueous solution; It is the composite solution that comprises weak polyanion, calcium ion and carbanion; Wherein, The monomer concentration of weak polyanion is 0.02～1.5mol/L, and the concentration of carbanion is 0.01～2mol/L, and the concentration of calcium ion is 10%～90% of weak polyanion concentration.
Preferable, the concentration of weak polyanion is 0.05～0.2mol/L, and the concentration of carbanion is 0.05～0.15mol/L, and the concentration of calcium ion is 40～90% of weak polyanion concentration;
Better, the concentration of weak polyanion is 0.08～0.12mol/L, and the concentration of carbanion is 0.06～0.1mol/L, and the concentration of calcium ion is 60～80% of weak polyanion concentration;
Best, the concentration of weak polyanion is 0.1mol/L, and the concentration of carbanion is 0.07mol/L, and the concentration of calcium ion is 0.07mol/L.
Preferable, weak polyanion is the ROHM weak polyanion that ionization generates in water.
Above-mentioned be used to prepare the anti-scratch coating material construct primitive solution, also can be described as polyelectrolyte-inorganics original position compound water solution, perhaps be weak polyanion-lime carbonate (CaCO 3) compound aqueous solution, it is made by following method:
At first prepare the aqueous solution that monomer concentration is the weak polyanion of 0.02～1.5mol/L, again with yellow soda ash (Na 2CO 310H 2O) be dissolved in the weak polyanion aqueous solution that has prepared, make Na 2CO 3Concentration be 0.01～2mol/L, obtain weak polyanion-Na 2CO 3Mixing solutions; With Calcium Chloride Powder Anhydrous (CaCl 2) soluble in water, compound concentration is the CaCl of weak polyanion concentration of aqueous solution 10～90% 2The aqueous solution; At last, with CaCl 2The aqueous solution pours into isopyknic weak polyanion-Na 2CO 3In the mixing solutions, promptly obtain comprising the weak polyanion-CaCO of weak polyanion, calcium ion and carbanion 3Composite solution, this weak polyanion-CaCO 3Composite solution has negative charge.
Preferable, at first prepare the aqueous solution that monomer concentration is the weak polyanion of 0.05～0.2mol/L, again with yellow soda ash (Na 2CO 310H 2O) be dissolved in the weak polyanion aqueous solution that has prepared, make Na 2CO 3Concentration be 0.05～0.15mol/L, obtain weak polyanion-Na 2CO 3Mixing solutions; With Calcium Chloride Powder Anhydrous (CaCl 2) soluble in water, compound concentration is the Na of weak polyanion concentration of aqueous solution 40～90% 2CO 3The aqueous solution; At last, with CaCl 2The aqueous solution pours into isopyknic weak polyanion-Na 2CO 3In the mixing solutions, leave standstill 2～20h, promptly obtain comprising the weak polyanion-CaCO of weak polyanion, calcium ion and carbanion 3Composite solution;
Better, the concentration of the weak polyanion aqueous solution is 0.08～0.12mol/L, Na 2CO 3Concentration be 0.06～0.1mol/L, CaCl 2The concentration of the aqueous solution is weak polyanion concentration of aqueous solution 60～80%, and resulting composite solution leaves standstill 6～15h;
Best, the concentration of the weak polyanion aqueous solution is 0.1mol/L, Na 2CO 3Concentration be 0.07mol/L, CaCl 2The concentration of the aqueous solution is 0.07mol/L, and resulting composite solution leaves standstill 12h.
Preferable, the weak polyanion aqueous solution is the ROHM aqueous solution.
The invention still further relates to a kind of preparation method of anti-scratch coating, it comprises the following step:
What 1, preparation had a negative charge constructs the primitive aqueous solution;
2, with the substrate that has electric charge behind the surface modification, alternately place have negative charge construct the primitive aqueous solution with have a positive charge construct the primitive aqueous solution, utilize the stratiform package technique to prepare the layered assembling film coating of controllable thickness;
3, the layered assembling film of controllable thickness is coated with is placed on thermal treatment under 80～250 ℃ of temperature condition, promptly in substrate, obtain anti-scratch coating.
Wherein, The described primitive aqueous solution of constructing that has positive charge is that this area utilizes the stratiform package technique to prepare in the layered assembling film coating procedure primitive aqueous solution of constructing commonly used; The preferable aqueous solution for polycation a little less than comprising; That its concentration is preferable is 0.1～10mg/mL; Its pH value is preferably 5.5～9.5, and what wherein said weak polycation was preferable is one or more the weak polycations that ionization generates in water in PAH hydrochloride (PAH), linear polyethylene base amine (LPEI) or the branched polyethylene base amine (PEI).
In the step 2; Have the preferable substrate of substrate of electric charge after the described finishing for handling through amino, carboxyl or the hydroxylation on surface; Substrate is the substrate that can be used for the multilayer film assembling; It does not receive the influence of shape with the size of substrate, and the substrate of plane, curved surface or irregular surface is all applicable, and preferable is glass, quartz, silicon single crystal, mica, plastics or various metal (like gold and silver, copper, iron, aluminium or zinc etc.) substrate; Described plastics preferable for terephthalic acid condensed ethandiol ester (PET), gather (4-methyl-1-pentene), Vilaterm, voltalef (PCTFE) or polytetrafluoroethylene (PTFE).
The substrate that has electric charge after the described finishing can be obtained by the surface treatment method of this area substrate that is used for the stratiform assembling commonly used.When immersing in the water, make the mica tape negative charge owing to aluminosilicate ionization goes out potassium ion, so mica does not need extra modification just can directly be used for the preparation of multilayer film like the mica of new strip off.
But all need introduce electric charge artificially for above-mentioned other substrates of mentioning, the treatment process of preferable substrate is following:
At first, several kinds of solvent cleaning that polarity is different are used in substrate successively, substrate is cleaned, as with toluene, acetone, chloroform, second alcohol and water substrate being cleaned successively with polarity of solvent order from small to large; Then, through in following three kinds of methods any one, promptly on substrate surface, introduce amino, carboxyl or hydroxyl etc. and help the group of multilayer film preparation, thereby make the surface of substrate have electric charge:
(1) self-assembling method
Quartzy and glass surface exists a large amount of silicon hydroxyls, introduces required group thereby make them be easy to use the terminal silane derivative that contains amino, carboxyl or hydroxyl to modify.For example, tri-alkoxy-3-aminosilane can be connected in quartz or glass surface through the method for self-assembly, at one deck amino of having modified quartzy or on glass.Because silicon face has the very thin zone of oxidation of one deck, so be applicable to that the surface modification method of quartzy and glass is all effective for silicon base.Because the ito glass surface is In 2O 3And SnO 2Mixture, also can modify the ITO surface with modifying quartzy method.The verivate that contains sulfydryl also can be in the ITO surface-assembled, and therefore, the mercapto derivatives that contains required group also is used for the finishing of ITO.Similarly; For the gold substrate of vapor deposition on glass or quartz; Mercapto derivatives with containing charged group can be introduced required group on their surface easily; And alternative SR is extremely abundant, can introduce carboxyl and amino respectively in the metallic surface like 3-thiohydracrylic acid and mercaptoethylamine.
(2) polyelectrolyte absorption method
Some polyelectrolyte, particularly polycation are easy to be adsorbed onto in some substrate and introduce amino, carboxyl or hydroxyl on its surface through mode physics or chemistry.Polyamine class (polyamines) material is one type owing to contain the polycation that is easy to protonated amino and induces positive charge easily, they can through the nitrogen-atoms on the amino with golden (or other metal base is like silver, copper, iron, aluminium, zinc etc.) thus compound and be adsorbed in securely and make the gold surface lotus that becomes positively charged on the gold surface.With H 2O 2/ H 2SO 4The clean quartz surfaces of handling with alkali lye (like NH 3The aqueous solution) the silicon hydroxyl on surface done deprotonation handle, can make its surface be easy to adsorb the last layer polycation.Only use H 2O 2/ H 2SO 4The clean quartz of handling also can directly adsorb the polyelectrolyte that contains amido, like the polyvinylamine (PEI) and the linear polyvinylamine (PVA) of cladodification.Polydiene propyl-dimethyl ammonium muriate (PDDA) and gather (N, N, N-trimethylammonium-2-methylacrylic acid ethyl ammonia) and also can both easily be adsorbed on the quartz with s.t..PEI (polyvinylamine) and PDDA (gathering diallyl Dimethyl Ammonium hydrochloride) be two kinds and the most frequently used introduce the polymkeric substance of positive charge at substrate surface, and the surface that they can be used in most substrates such as quartz, glass, silicon, gold (and metal base such as silver, copper, iron, aluminium, zinc) and ITO is passed through to adsorb and introduced electric charge.
(3) chemical reaction method
Still can not introduce the substrate of electric charge through self-assembly and polyelectrolyte absorption and can introduce electric charge by means of some special interfacial chemical reaction.For example, terephthalic acid condensed ethandiol ester (PET) is immersed 1mol/LNa2OH solution in 60 ℃ of hydrolysis after 20 minutes, the surface has just produced a large amount of carboxylate groups, and the HCl solution soaking with 0.1mol/L can be converted into carboxyl with carboxylate salt.In the time of in PET being immersed polypropylene-base amine (PAH) solution, can introduce amino at the pet sheet face through the absorption/reaction of PAH.Similarly, gather (4-methyl-1-pentene) and can use CrO 3/ H 2SO 4Mixing solutions (5mol/L CrO 3Be dissolved in 28vol%H 2SO 4In, temperature is 80 ℃) methyl oxidation that it is surperficial is carboxyl.Vilaterm also can be introduced the carboxylic acid group through this reaction.For voltalef (PCTFE), after hydroxyl is introduced on the surface, above polypropylene-base amine can be adsorbed at an easy rate.Polytetrafluoroethylene (PTFE) is a kind of plastics of very difficult modification, but can introduce amino through its surperficial allyl amine plasma polymerization.
Contained amino, carboxyl or the hydroxy functional group of substrate surface can with have with the polymkeric substance of its opposite charges (like positively charged diallyl Dimethyl Ammonium hydrochloride, polyvinylamine, the polypropylene-base amine of gathering; Electronegative Lewatit, ROHM, polymethyl acrylic acid) the generation electrostatic interaction; Also can interaction of hydrogen bond take place with the polymkeric substance (polyvinylamine, polypropylene-base amine etc.) or the carboxylic polymkeric substance (ROHM, polymethyl acrylic acid etc.) of amino-contained, these all help the assembling of film.
For glass, quartz and silicon base, preferable, the surface is through H 2O 2/ H 2SO 4Handle and just can carry out the preparation of multilayer film so that the surface has one deck silicon hydroxyl on its surface; Also available aforesaid method is the refabrication multilayer film after amino, carboxyl or hydroxy functional group are introduced in the surface.
In the step 3, what described heat treated temperature was preferable is 100～220 ℃; What heat treatment period was preferable is 0.5～20 hour, and better is 1～10 hour, and that best is 5h.
Best; Described anti-scratch coating preparation methods comprises the following step: the substrate that will pass through surface treatment (amino, carboxyl or hydroxylation) alternately places and comprises above-mentioned two kinds of solution of constructing primitive and respectively soak 2～30min; And with soaking or process of washing is removed the primitive of constructing that substrate surface soaks the back physical adsorption at every turn, thereby accomplish the preparation of the layered assembling film of one-period; Repeat above step 5～50 cycle, thereby in substrate, utilize the stratiform package technique to prepare the layered assembling film coating of controllable thickness; With 100～220 ℃ of thermal treatments of prepared coating warp 1～10 hour, promptly make the anti-scratch coating of transparent high firmness again.
The invention still further relates to the anti-scratch coating that makes by above-mentioned preparation method.
Except that specified otherwise, raw material that the present invention relates to and reagent are all commercially available to be got.
Positive progressive effect of the present invention is:
The present invention utilizes the stratiform package technique, has realized containing the preparation of the transparent high firmness anti-scratch coating of lower aq inorganic components.The surface that this coating can be deposited on other functionalization coatings is used for the anti-scraping protection of functionalized polymer coating.The preparation process of coating is simple, with low cost, need not adopt complicated instrument and raw material simultaneously again.The preparation process of this patent is fully based on the aqueous solution, so present technique is a kind of cheap preparation means of environmental protection.Anti-scratch coating of the present invention can be used as the resist of other functional film materials or surface optical device because its high firmness and strong substrate bonding strength show well anti-scraping performance.Therefore application of the present invention is expected to realize the application of transparent high firmness anti-scratch coating in extensive fields more.
Description of drawings
Fig. 1: sedimentary ROHM-CaCO on monocrystalline silicon piece 3The thickness of/PAH multilayer film coating and the graph of a relation of assembling the number of plies;
Fig. 2: through the ROHM-CaCO of heat treated 8 assembling cycles 3The transmission electron microscope photo of/PAH multilayer film;
Fig. 3: the ROHM-CaCO in 30 cycles 3The thermogravimetic analysis (TGA) of/PAH coating;
Fig. 4: the ROHM-CaCO in 20 cycles of deposition on the substrate of glass 3The ultraviolet-visible of/PAH multilayer film coating see through spectrum and photo thereof (dotted line be the ultraviolet-visible of substrate of glass itself through spectrum, solid line is the ROHM-CaCO that is assembled with 20 cycles 3The ultraviolet-visible of/PAH coating sees through spectrum; Illustration is the ROHM-CaCO that is assembled with 20 cycles on the glass substrate 3The photo of/PAH coating).
Fig. 5: through the ROHM-CaCO in heat treated 20 cycles 3The microphotograph of/PAH coating after the experiment of substrate adhesive power.
Fig. 6: left side figure be deposited on the substrate of glass through the poly propenoic acid allyl amine coating in heat treated 30 cycles photo through 80 all after dates of swiping; Right figure be deposited on the substrate of glass through heat treated 20 cycle ROHM-CaCO 3/ PAH coating is through the photo of the 1100 all after dates of swiping;
Fig. 7: left side figure is the photo of azobenzene polymer film through the 40 all after dates of swiping, and right figure is the ROHM-CaCO in 20 cycles that were assembled with on the nitrogen benzide film 3/ PAH coating after heat treatment again through the scraping 1100 all after dates photo.
Embodiment
Below come further to illustrate practical implementation of the present invention and result through some instances, rather than to limit the present invention with these instances.
Embodiment 1: the preparation of transparent high firmness anti-scratch coating on glass or monocrystal silicon substrate
A. base treatment: the solid substrate glass of being selected for use or the treatment process of monocrystalline silicon piece substrate are following: successively with the ultrasonic 10min that handles respectively of toluene, acetone, chloroform, ethanol and zero(ppm) water, to remove the various impurity that substrate surface adheres to, then at 98%H 2SO 4With 30% (mass concentration) H 2O 2(v: v=7: heated and boiled in the mixing solutions 3) (30min) is not overflowed to there being bubble.A large amount of distilled water flushings are used in the cooling back, dry up with nitrogen again, and are for use.A large amount of silicon hydroxyls are contained on glass of handling like this or quartz substrate surface; With being soaked in 30min in the 1mg/mL polydimethyl allyl ammonium chloride (PDDA) at the bottom of glass of having handled or the silicon wafer-based; Make its surface have the quaternised amino of positive charge, like this preparation of the substrate of the modified layered assembling film that can be used for constructing based on electrostatic force through self-assembled modified one deck.
B. construct the preparation of primitive solution
(1) primitive of constructing that has a negative charge is ROHM-lime carbonate (CaCO 3) composite solution, its compound method is following: the monomer concentration of at first preparing 60mL is the ROHM aqueous solution of 0.1M, again with the Calcium Chloride Powder Anhydrous (CaCl of 0.4662g 2) be dissolved in the polyacrylic acid solution that has prepared, obtain ROHM-CaCl 2Mixing solutions.With 1.2018g yellow soda ash (Na 2CO 310H 2O) be dissolved in 60mL water in make Na 2CO 3The aqueous solution.At last, with the Na that is prepared 2CO 3The aqueous solution pours into ROHM-CaCl 2Mixing solutions in, left standstill 12 hours, obtain ROHM-CaCO 3Composite solution is tested resulting ROHM-CaCO through Zeta-potential 3Mixture has negative charge.
(2) have PAH hydrochloride (PAH) aqueous solution that primitive is 1mg/mL of constructing of positive charge, its pH value is 8.15.
B. transparent high firmness anti-scratch coating preparation: have the substrate of polydiene propyl-dimethyl ammonium muriate PDDA to operate as follows above-mentioned finishing: ROHM-CaCO is immersed in (1) 3In the composite solution 20 minutes, take out three steps deionized water rinse through 3 minutes, 2 minutes, 1 minute; (2) immerse in the 1mg/mL PAH solution prepare 20 minutes again, take out three steps deionized water rinse through 3 minutes, 2 minutes, 1 minute.
Said process is a deposition cycle of film coating, and above-mentioned (1) (2) two processes that repeat just obtain (ROHM-CaCO 3/ PAH) n multilayer film coating, n represents the cycle life of sedimentary multilayer film coating.Resulting coating at 180 ℃ of thermal treatment 5h, has just been made transparent high firmness anti-scratch coating.Effect embodiment:
We with following method to ROHM-CaCO 3The structure and the performance of/PAH multilayer film coating characterize:
We utilize the ROHM-CaCO to different deposition cycle 3The tangent plane of/PAH multilayer film has carried out the sign of ESEM, has obtained the thickness of different cycles film and the graph of a relation (as shown in Figure 1) of the deposition number of plies, has confirmed the successful assembling of multilayer film, proves ROHM-CaCO simultaneously 3/ PAH multilayer film shows the growth pattern of exponential form.ROHM-CaCO 3The transmission electron microscope photo of/PAH multilayer film (as shown in Figure 2) shows to be evenly distributed with in the film and is of a size of～CaCO of 2nm 3Nanoparticle, the gathering that has no between the nanoparticle.We adopt the ROHM-CaCO of the method for thermogravimetic analysis (TGA) to 30 cycles 3/ PAH film characterizes (as shown in Figure 3), and the result shows CaCO 3The weight fraction of composition in film is merely 4.2%.
Be assembled with ROHM-CaCO 3The uv-vis spectra of the glass substrate of/PAH multilayer film coating and photo (as shown in Figure 4) thereof show that this coating has good visible light transmissive performance.
We utilize nano-hardness tester to ROHM-CaCO 3The hardness and the Young's modulus of/PAH multilayer film coating are tested, and its hardness and Young's modulus are respectively 1.60 ± 0.01GPa and 15.33 ± 0.12GPa.By contrast, the hardness and the Young's modulus that have a poly propenoic acid allyl amine straight polymer coating of same thickness are respectively 0.48 ± 0.01GPa and 12.62 ± 0.17GPa.So ROHM-CaCO 3The hardness of/PAH coating is 2.2 times of poly propenoic acid allyl amine coating of straight polymer, and Young's modulus is 1.2 times of poly propenoic acid allyl amine coating.We are to 20 cycle ROHM-CaCO 3The substrate adhesive power of/PAH coating has carried out monitoring (as shown in Figure 5) according to international standard ASTM D 3359, and the result shows that the substrate adhesive power of this figure layer is a highest level 5B level.
We utilize the scraping experiment to ROHM-CaCO 3The anti-scraping performance of/PAH coating characterizes, and itself and the poly propenoic acid allyl amine straight polymer coating with same thickness are contrasted.We swipe testing sample through the reciprocating metal cylinder (diameter 1.6cm) that is with ramie cloth, the pressure that metal cylinder is applied to sample surfaces is 1.12 * 10 4Pa, its speed that sample is swiped is the 20cm/s/ cycle.As shown in Figure 6, after 80 cycle scrapings, tangible breakage has taken place in poly propenoic acid allyl amine coating, and ROHM-CaCO 3Any cut does not appear in/PAH coating.Proof ROHM-CaCO 3/ PAH coating has well anti-scraping performance.
Embodiment 2: the preparation of transparent high firmness anti-scratch coating on the azobenzene polymer multilayer film
The processing of substrate of glass is identical with embodiment 1; At first have the sheet glass of polydiene propyl-dimethyl ammonium muriate PDDA to operate as follows finishing: (1) with its immerse a kind of concentration be the 0.5mg/mL polyelectrolyte that contains azobenzene group (PAC-azoBNS, it is a kind of red-purple dyestuff, chemical structural formula is as follows; Compound method is referring to document: Langmuir 2006; 22,7894.) 20min in the solution takes out the three steps deionized water rinse through 3 minutes, 2 minutes, 1 minute; (2) immerse 20min in the polydiene propyl-dimethyl ammonium muriate PDDA solution of the 1mg/mL prepare again, take out three steps deionized water rinse through 3 minutes, 2 minutes, 1 minute; 15 cycles of (1) (2) two processes just obtain (PAC-azoBNS/ polydiene propyl-dimethyl ammonium muriate PDDA) 15 multilayer films more than repeating.Then according on (PAC-azoBNS/ polydiene propyl-dimethyl ammonium muriate PDDA) 15 multilayer films, preparing the ROHM-CaCO of 20 assembling cycles with embodiment 1 identical method 3/ PAH coating, then with it at 180 ℃ of thermal treatment 5h.
Figure GSA00000046733900091
We are same utilize with embodiment 1 in same scraping test and verify ROHM-CaCO 3/ PAH coating is for the anti-scraping protective value of PAC-azoBNS/ polydiene propyl-dimethyl ammonium muriate PDDA multilayer film.As shown in Figure 7, come off from substrate of glass fully after (PAC-azoBNS/ polydiene propyl-dimethyl ammonium muriate PDDA) 15 multilayer films scraping, and preparation above that has the ROHM-CaCO in 20 cycles through 40 cycles 3After/PAH the coating, after 1100 scrapings, sample surfaces is not seen any stroke of damage.This result shows ROHM-CaCO 3/ PAH coating can be used as the anti-scraping supercoat of other functional film materials.
Embodiment 3:
A. the metal aluminium flake is adopted in substrate, and successively with the ultrasonic 10min that handles respectively of toluene, acetone, chloroform, ethanol and zero(ppm) water, to remove the various impurity that substrate surface adheres to, a large amount of distilled water flushings are used in the back, dry up with nitrogen again, and are for use with it.The aluminium flake of having handled is soaked in 30min in the 1mg/mL polydimethyl allyl ammonium chloride (polydiene propyl-dimethyl ammonium muriate PDDA); Make its surface have the quaternised amino of positive charge, like this preparation of the aluminium flake of the modified layered assembling film that can be used for constructing based on electrostatic force through self-assembled modified one deck.
B. construct the preparation of primitive solution
(1) primitive of constructing that has a negative charge is ROHM-lime carbonate (CaCO 3) composite solution, its collocation method is following: at first preparing the 60mL monomer concentration is the ROHM aqueous solution of 0.08mol/L, again with 0.9654g yellow soda ash Na 2CO 310H 2O is dissolved in the ROHM aqueous solution that has prepared, wherein Na 2CO 3Concentration be 0.056mol/L, obtain ROHM-Na 2CO 3Mixing solutions; With 0.373g calcium chloride (CaCl 2) be dissolved in the 60mL water, its concentration is 0.056mol/L; At last, with CaCl 2The aqueous solution pours into weak polyanion-Na 2CO 3In the mixing solutions, leave standstill 12h, promptly obtain comprising the ROHM-CaCO of ROHM, calcium ion and carbanion 3Composite solution; Test resulting ROHM-CaCO through Zeta-potential 3Mixture has negative charge.
(2) have branched polyethylene base amine (PEI) solution that primitive is 2mg/mL of constructing of positive charge, the pH value is 7.5.
B. transparent high firmness anti-scratch coating preparation: have the aluminium flake of polydiene propyl-dimethyl ammonium muriate PDDA to operate as follows above-mentioned finishing: ROHM-CaCO is immersed in (1) 3In the composite solution 20 minutes; Taking-up was immersed in the 2mg/mL branched polyethylene base amine PEI solution for preparing 20 minutes through 3 minutes, 2 minutes, 1 minute three step deionized water rinses (2) again, take out through 3 minutes, 2 minutes, 1 minute three go on foot the deionized water rinse.
Said process is a deposition cycle of film coating, and above-mentioned (1) (2) two 20 cycles of process that repeat just obtain (ROHM-CaCO 3/ PAH) 20 multilayer film coatings, with resulting coating at 160 ℃ of thermal treatment 5h.Just in the substrate of metal aluminium flake, made the coating of the anti-scraping of transparent high firmness through aforesaid method.

Claims (4)

1. the preparation method of an anti-scratch coating, its step is following:
What 1) preparation had a negative charge constructs the primitive aqueous solution;
2) with the substrate that has electric charge behind the surface modification, alternately place have negative charge construct the primitive aqueous solution with have a positive charge construct the primitive aqueous solution, utilize the stratiform package technique to prepare the layered assembling film coating of controllable thickness;
3) layered assembling film of controllable thickness is coated with is placed on thermal treatment under 80～250 ℃ of temperature condition, promptly in substrate, obtain anti-scratch coating;
Wherein, The primitive aqueous solution of constructing that has negative charge described in the step 1) is the composite solution that comprises weak polyanion, calcium ion and carbanion; Wherein, The concentration of weak polyanion is 0.02～1.5mol/L, and the concentration of calcium ion is 0.01～2mol/L, and the concentration of carbanion is 10%～90% of weak polyanion concentration;
Perhaps; The primitive aqueous solution of constructing that has negative charge described in the step 1) is the composite solution that comprises weak polyanion, calcium ion and carbanion; Wherein, The concentration of weak polyanion is 0.02～1.5mol/L, and the concentration of carbanion is 0.01～2mol/L, and the concentration of calcium ion is 10%～90% of weak polyanion concentration; Weak polyanion is the ROHM weak polyanion that ionization generates in water;
The aqueous solution that the primitive aqueous solution is weak polycation of constructing that has positive charge; Its concentration is 0.1～10mg/mL; The pH value is 5.5～9.5, and weak polycation is one or more the weak polycations that ionization generates in water in PAH hydrochloride, linear polyethylene base amine or the branched polyethylene base amine.
2. the preparation method of a kind of anti-scratch coating as claimed in claim 1; It is characterized in that: have the substrate of electric charge after the finishing; Be meant by solvent polarity order from small to large and substrate cleaned successively with multiple solvent; On substrate surface, introduce amino, carboxyl or the oh group that helps the multilayer film preparation through self-assembling method, polyelectrolyte absorption method or chemical reaction method then, thereby make the surface of substrate have electric charge.
3. the preparation method of a kind of anti-scratch coating as claimed in claim 1; It is characterized in that: be alternately to place the primitive aqueous solution of constructing that has negative charge respectively to soak 2～30min the substrate that has electric charge after the finishing with the primitive aqueous solution of constructing that has positive charge; And with soaking or process of washing is removed the primitive of constructing that substrate surface soaks the back physical adsorption at every turn, thereby accomplish the preparation of the layered assembling film of one-period; Repeat above step 5～50 cycle, thereby in substrate, utilize the stratiform package technique to prepare the layered assembling film coating of controllable thickness; With 100～220 ℃ of thermal treatments of prepared coating warp 1～10 hour, promptly make the anti-scratch coating of transparent high firmness again.
4. the anti-scratch coating that obtains by each described preparation method of claim 1～3.
CN2010101170745A 2010-03-04 2010-03-04 Anti-scratch coating and preparation method thereof Expired - Fee Related CN101792564B (en)

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