CN1245517A - Material and process for surface treatment - Google Patents

Material and process for surface treatment Download PDF

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Publication number
CN1245517A
CN1245517A CN 97181728 CN97181728A CN1245517A CN 1245517 A CN1245517 A CN 1245517A CN 97181728 CN97181728 CN 97181728 CN 97181728 A CN97181728 A CN 97181728A CN 1245517 A CN1245517 A CN 1245517A
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China
Prior art keywords
treatment agent
film
matrix
organic acid
acid
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CN 97181728
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岩间克己
吉本敏雄
齐藤学
大高守康
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O Nobuhito
P & E International Inc
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O Nobuhito
P & E International Inc
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Priority to CN 97181728 priority Critical patent/CN1245517A/en
Publication of CN1245517A publication Critical patent/CN1245517A/en
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Abstract

A four-fluid and one-powder, coloring-type material for surface treatment composed of an aqueous emulsion of a polymer having hydroxyl or carboxyl groups, a granular siliceous material, a liquid treatment for a substrate, a liquid reinforcement for a substrate, and a colorant. The liquid treatment is a mixture mainly comprising a powdered siliceous material, a calcium-containing material comprising calcium hydroxide or calcium oxide, an organic acid or its salt having an acid dissociation constant of 3 to 5, and water. The liquid reinforcement is a mixture mainly comprising an aqueous solution of an alkali silicate and an organic acid or its salt having an acid dissociation constant of 3 to 5. The colorant which can form coatings excellent in smoothness, strength and water resistance on any substrate is a mixture mainly comprising the above reinforcement, a powdered siliceous material as a leveling agent and a pigment. Tack-free coatings can be formed in a short time and the workability in coating is excellent.

Description

Surface treatment agent and treatment process thereof
Technical field
The present invention relates to a kind of surface treatment agent and treatment process thereof, described surface treatment agent and treatment process system thereof are used for to handling as the surface of plastics, fabric, non-woven, timber, metal and pottery etc., to prevent its surface deterioration and painted.
Background technology
In the past, as being used for the surface as plastics, fabric, non-woven, timber, metal and pottery etc. is prevented surface deterioration and the surface treatment agent of handling such as painted, known have multiple: with polymer resinoids such as Resins, epoxy and varnish, lacquers is organic class coating of main composition, and is the mineral-type coating of main composition with inanimate matters such as silicate.
Yet, in various surface treatment agents in the past, because the weathering resistance of organic class coating is poor, so, in the occasion that requires to have weathering resistance, must use mineral-type coating.But, when mineral-type coating carries out surface treatment at the surperficial pending component materials to pottery, though can form good filming, but when the surperficial pending parts as materials such as plastics, metal, timber, fabric and non-wovens are carried out surface treatment, but can't form good filming, its purposes is restricted.
Knownly open the surface treatment method that clear 56-43359 communique is put down in writing just like the Japanese Patent Application Publication spy.
Described spy opens the surface treatment method that clear 56-43359 communique put down in writing: with water-soluble or water dispersible alkalimetal silicate glass and its basicity greater than the water-soluble alkali of this silicate glass, water, and the pigment of 5-90% (capacity) mix, the curable coating material that mixes gained is coated on the body materials such as timber and metal, glass, concrete, make it to solidify, form coating.
Yet, according to the described surface treatment method of the public clear 56-43359 communique of above-mentioned spy, for the pigment that makes easy cohesion is done good dispersion, strengthen the homogeneity of pigment color, must on its matrix, be carried with in the water-soluble of pigment or the water dispersible alkalimetal silicate glass, mix water-soluble alkali and the water of its basicity simultaneously, again with the mix proportions hybrid pigment of 5～90% (capacity) greater than this silicate glass.So, only partly forming stratiform at parts surface, above-mentioned pigment coated may peeling off because of produced by extraneous impact and stress etc. lacks water tolerance, can't obtain good painted coating.Have again, need the time by reaching fixed hardness, and need protect, so that the coating that forms that is coated with did not sustain damage before solidifying and water drenches.
On the other hand, add water and the surface treatment agent that forms as the treatment agent to the organic acid that contains a plurality of carboxyls of tool or organic acid salt, magnesium compound, microparticulate silica or water-soluble silicate, known have a surface treatment agent of being put down in writing on the special fair 1-320284 communique of Japanese Unexamined Patent Publication No.
A kind of like this surface treatment method of surface treatment method system of calcium-base inorganic members materials such as the described concrete of the special fair 1-320284 communique of this Japanese Unexamined Patent Publication No: add water to containing the organic acid with a plurality of carboxyls or the treatment agent of organic acid salt, magnesium compound, microparticulate silica or water-soluble silicate, with described surface treatment agent coating or be sprayed at as calcium-base inorganic members material surfaces such as concrete or mortars.Then, water carries out maintenance, makes by the calcium hydroxide in sodium compound and silicon-dioxide, the concrete and generates water-soluble silicate compound.Meanwhile, organic acid and organic acid salt and free magnesium ion and calcium ion reaction generate organic-magnesium and organic calcium.Then, these water-soluble silicon acid compounds and organic calcium infiltrate in the kapillary and space as calcium-base inorganic members materials such as concrete under the effect of osmotic pressure and capillary phenomenon.Under the catalyst action of residual organic acid that permeates and organic acid salt, the calcium hydroxide in the calcium-base inorganic members materials such as water-soluble silicon acid compound and concrete reacts, and generates the Calucium Silicate powder based compound.In addition, because organic-magnesium and organic calcium and water-soluble silicon acid compound react, generate the Calucium Silicate powder based compound, described Calucium Silicate powder based compound is filled pore and the space as body materials such as concrete, makes its surface densification.
Yet the surface treatment method of the calcium-base inorganic members material that special fair 1-320284 communique is put down in writing is to be object with body materials such as concrete, as this surface treatment method being used for plastics and timber, fabric etc., can't form well and film.Have, described organic acid and organic acid salt permeate, residue in kapillary and the space when participating in reaction again, and under this state, the state of Calucium Silicate powder based compound may be different.So, for obtaining certain densification state, need do careful proportioning setting and management of reaction atmosphere or the like, like this, make operation seem numerous and diverse.Have, for reaching required hardness, spended time is longer again, need carry out the operation of protectiveness, so that make the injury-free and water pouring before solidifying of coating form layers.
The present invention system does in view of the above problems, the objective of the invention is to: a kind of surface treatment agent and treatment process thereof are provided, by using surface treatment agent of the present invention and treatment process thereof, can form high-intensity filming at any body material, the anti-deteriorate performance and the construction that improve described substrate material surface at short notice easily are easy.
Purpose of the present invention more is: a kind of surface treatment agent and treatment process thereof are provided, use by described surface treatment agent and treatment process thereof, can form high-intensity filming at any body material, by this, can obtain excellent coating weatherability and water tolerance and painted easily at short notice.
Invention discloses
Surface treatment agent of the present invention comprises:
Coat the polymer water miscible liquid of the high adherence of substrate material surface as film like,
Be supported at described polymer water miscible liquid surface, to small part expose, with silicon oxide (SiO 2) be the silica powder of main composition,
Coat with film like the coating of aforementioned film like exposed portions serve polymer water miscible liquid surface and that cover the silica powder liquid matrix treatment agent and
Coat matrix strengthening agent on the described matrix treatment agent surface that the coating of aforementioned film like is formed at polymer water miscible liquid surface with film like;
The polymer water miscible liquid of described high adherence is selected from hydroxyl (OH) and carboxyl (at least a polymer water miscible liquid COOH) for containing;
Described matrix treatment agent is for containing with silicon oxide (SiO 2) be main composition the silica powder, be selected from calcium hydroxide (Ca (OH) 2) and calcium oxide (CaO) at least a calcareous material, contain that to be selected from acid dissociation exponent (pKa) be organic acid more than 3, below 5 and at least a and water (H in the organic acid salt 2O) liquid treatment agent;
Described matrix strengthening agent is organic acid more than 3, below 5 and at least a liquid treatment agent in the organic acid salt for containing the alkali silicate aqueous solution and being selected from acid dissociation exponent (pKa), and described matrix strengthening agent is coated above-mentioned matrix treatment agent surface with film like.
To contain be selected from hydroxyl (OH) and carboxyl (the polymer water miscible liquid of at least a high adherence COOH) is coated substrate material surface as film like, before described polymer water miscible liquid is solidified, by for example spraying method etc., makes with silicon oxide (SiO 2) be that the silica powder of main composition carries and holds on it, and the described silica powder of at least a portion is exposed to the surface.Liquid matrix treatment agent is coated polymer water miscible liquid surface, so that it covers described silica powder as film like.By the coating of described matrix treatment agent, along with the volatilization etc. moisture (H 2O) minimizing, under the catalyst action of organic acid and organic acid salt, (the Ca (OH) of the calcium hydroxide in the calcareous material of matrix treatment agent 2) and water and calcium oxide (CaO) chemical combination, generate calcium hydroxide.The calcium hydroxide of described generation and polymer water miscible liquid are carried the silicon oxide generation pozzolanic reaction in the silica powder of holding, and complexing generates Calucium Silicate powder (CaSiO 3), insoluble chain CaO-SiO-...-SiO-... SiO-CaO (C-O-S-O-C).Simultaneously, silicon oxide in the silica powder in the matrix treatment agent and the calcium hydroxide generation pozzolanic reaction that generates owing to the chemical combination of the calcium hydroxide in the calcareous material and water and calcium oxide, complexing generates insoluble chain C-O-S-O-C and Calucium Silicate powder.Again, silica powder and silica powder and silica powder silicon oxide each other become the Si-O-Si key by hydrogen bond and dehydration polymerization, form to have a plurality of hydroxyls (three-dimensional net structure of densification OH).The calcium hydroxide that generates owing to the chemical combination of the calcium hydroxide in the calcareous material and water and calcium oxide of an inclusion part thus.
Secondly, the matrix strengthening agent is coated the matrix treatment agent surface of doing the film like coating, having network structure as film like.Coating by described matrix strengthening agent, make that being selected from acid dissociation exponent (pKa) be under the effects such as organic acid more than 3, below 5 and at least a catalysis in the organic acid salt, alkali silicate and be supported between the matrix treatment agent network structure, the unreacted residual calcium hydroxide reaction, with alkali part inclusion of alkali silicate, be enclosed between the network structure, generate Calucium Silicate powder and C-O-S-O-C.Simultaneously, hydroxyl by the matrix treatment agent, with constitute combining of network structure C-O-S-O-C and Si-O-Si associative key, and by alkali silicate each other, the combination of silica powder and alkali silicate, the alkali part that makes alkali silicate is around between network structure, in the network structure that forms more in the densification, make that described network structure increases, one turns to fine and close three-dimensional net structure, thus, with alkali part inclusion of alkali silicate between network structure.
At this moment, as the acid dissociation exponent (pKa) of organic acid and organic acid salt less than 3, the calcium hydroxide of silica powder and matrix treatment agent (Ca (OH) then 2) the pozzolanic reaction and the various reactions of polycondensation etc. very slow, the film forming required time is longer.Again, acid dissociation exponent (pKa) is greater than 5 as described, and excessive velocities is carried out in the various reactions of then above-mentioned pozzolanic reaction and polycondensation etc., and reaction is carried out partly, can't obtain roughly filming uniformly.In addition,, film to go up be full of cracks etc. takes place, peeling off after the powdered also can be taken place sometimes because contraction increases, equally can't film forming.For this reason, use organic acid and the organic acid salt of acid dissociation exponent (pka) greater than 3, less than 5.
Therefore, owing to be to use the polymer water miscible liquid, make the silica powder be supported on the body material securely, this silica powder as reflecting point, is made to form fine and close three-dimensional network structure, and lining forms and has filming of excellent in water resistance and weathering resistance on body material, so, can prevent the surface deterioration processing easily at short notice at any body material, improve workability.
Again, the present invention is a kind of surface treatment agent that comprises tinting material: described tinting material is the liquid matrix strengthening agent surface of coating the film like coating with film like.Described tinting material contain the invention described above the alkali silicate aqueous solution, pigment, be selected from least a in organic acid more than 3, below 5 and organic acid salt of acid dissociation exponent (pKa).
By matrix treatment agent and the matrix strongthener surface coated tinting material that becomes network structure, one densification in membranaceous coating, can be thus being selected under the effect such as at least a catalysis of acid dissociation exponent (pKa) in organic acid more than 3, below 5 and organic acid salt, make alkali silicate and the unreacted calcium hydroxide (Ca (OH) that residues in the matrix strongthener 2), constitute the C-O-S-O-C and the Si-O-Si key of network structure, fixing, form finer and close integrated network structure, with the alkali composition of alkali silicate and tinting material is airtight, inclusion is between network structure.
Therefore, surface treatment agent of the present invention is owing to be to use the polymer water miscible liquid, with carrying the silica powder held as reflecting point, makes to form fine and close three-dimensional net structure, simultaneously, pigment is fixed between the network structure, and lining forms and has filming of excellent in water resistance and weathering resistance on body material, so, can prevent surface deterioration and painted etc. processing easily at short notice at any body material, can improve painted aesthetic property, obtain identity, increase the popularity of using.
Have, the present invention is a kind of like this surface treatment agent again: wherein, contain metal oxide at least a in matrix treatment agent, matrix strengthening agent and the tinting material of the invention described above.
The burning system that contains in above-mentioned matrix treatment agent, matrix strengthening agent and tinting material at least a is by three-dimensional combination, is incorporated between the chain molecule of Si-O-Si associative key of network structure, forms network structure densification, firm membrane structure.
Therefore,, can make fine and close originally network structure fine and close more, increase weathering resistance, water tolerance and the intensity of formed substrate material surface owing to contain metal oxide.
Again, the present invention is a kind of like this surface treatment agent: contain in the matrix treatment agent of the invention described above, the content that is scaled calcium hydroxide is: be more than 0.2, below 2, be selected from least a calcareous material in calcium hydroxide and the calcium oxide based on the weight ratio of silica powder.
And, by its content that is scaled calcium hydroxide for count 0.2 or more based on the weight ratio of silica powder, below 2, be selected from the use of calcareous material at least a in calcium hydroxide and the calcium oxide, owing to selecting for use such matrix treatment agent can make the calcium hydroxide (Ca (OH) of ground silica material and calcium-base inorganic members material 2) do firm combination, form integrated; Simultaneously, the fixing of inclusion calcium hydroxide can be made, (under state OH), network structure can be easily formed at short notice having a plurality of hydroxyls.Again, if the content of calcareous material is less than at 0.2 o'clock based on silica powder weight ratio meter, then can't look to increasing the matrix treatment agent film portion intensity and with the reactivity of matrix strengthening agent, can't increase it at short notice as the sufficient intensity of filming.In addition, greater than based on 2 o'clock of silica powder weight ratio meter, the calcium hydroxide composition that is fixed between network structure increases as the content of calcareous material, can't look to increasing the matrix treatment agent intensity, water tolerance and with the reactivity of matrix strengthening agent; Can't improve as smoothness of filming and coating transaction capabilities; Calcium moving from the teeth outwards may be the reason that produces powder phenomenon-tion.For this reason, the content with calcareous material is set at based on more than 0.2, below 2 of silica powder weight ratio meter.
Therefore, because the content of setting calcareous material can make filming of ground silica material and polymer water miscible liquid make incorporate mortise in the scope more than 0.2, below 2 based on silica powder weight ratio meter.Simultaneously, (under state OH), can have the three-dimensional net structure of inclusion calcium hydroxide fixed densification having a plurality of hydroxyls; Can easily form at short notice and have the good film that excellent weathering resistance, water tolerance and high-intensity matrix treatment agent constitute.
Have again, the present invention is a kind of like this surface treatment agent: organic acid in its matrix treatment agent and organic acid salt contain based on the gross weight of silica powder and calcareous material than meter more than 0.01, below 0.1, be selected from least a in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and, contain based on the gross weight of silica powder and calcareous material than count more than 0.1, below 5, be selected from least a in arabic acid and the salt thereof.
As organic acid in the matrix treatment agent and organic acid salt, can contain based on the gross weight of silica powder and calcareous material than meter more than 0.01, below 0.1, be selected from least a in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and, contain based on the gross weight of silica powder and calcareous material than count more than 0.1, below 5, be selected from least a in arabic acid and the salt thereof.By this, can not make polymer water miscible liquid film modification ground, make the silica powder of matrix treatment agent and being swift in response, roughly carrying out equably of calcareous material, form the three-dimensional net structure of the densification of insoluble, mortise.Again, at least a content that is selected from glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof compares 0.01 of meter as the gross weight that is less than based on silica powder and calcareous material, then above-mentioned organic acid and organic acid salt and be supported at the silica powder on the polymer water miscible liquid reactivity, with the reactivity of polymer water miscible liquid and reactive low with matrix treatment agent self, be difficult to obtain firm integral structure; Hopeless increase coating strength and weathering resistance, the dispersiveness of also hopeless raising material; Be difficult to obtain roughly level and smooth filming uniformly, also be difficult to improve application property.On the other hand, be higher than gross weight based on silica powder and calcareous material than 0.1 of meter if be selected from least a content in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof, then present the residual state that unreacted organic acid and organic acid salt are arranged between network structure, can't obtain good intensity, water tolerance and weathering resistance; Simultaneously, cost increases.Therefore, the content that is selected from least a organic acid in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and organic acid salt is set at gross weight based on silica powder and calcareous material than more than 0.01 of meter, the scope below 0.1.On the other hand, as at least a content in arabic acid and the salt thereof is to be lower than based on the gross weight ratio of silica powder and calcareous material to count 0.1, the reactivity of then above-mentioned organic acid and organic acid salt and silica powder, with the reactivity of polymer water miscible liquid and reactive low with matrix treatment agent self, be difficult to obtain firm integral structure; Hopeless increase coating strength, water tolerance and weathering resistance.Otherwise, as at least a content in arabic acid and the salt thereof is that the gross weight that is higher than based on silica powder and calcareous material compares 5 of meter, then present the residual state that unreacted organic acid and organic acid salt are arranged between network structure, filming of forming is difficult to obtain good intensity, water tolerance and weathering resistance, simultaneously, cost increases.Therefore, the gross weight that at least a content that is selected from arabic acid and the salt thereof is set at based on silica powder and calcareous material compares more than 0.1 of meter, the scope below 5.
Thus, because use contain based on the gross weight of silica powder and calcareous material than meter more than 0.01, below 0.1, be selected from least a in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and, contain based on the gross weight of silica powder and calcareous material than count more than 0.1, below 5, be selected from least a organic acid and organic acid salt in arabic acid and the salt thereof, so, can form at short notice have excellent in water resistance, weathering resistance and high strength, level and smooth filming.
Again, the present invention is a kind of like this surface treatment agent: a kind of alkali silicate concentration of the alkali silicate water solution system of the invention described above that it contains is 15～40% the aqueous solution, the silicon oxide (SiO of described alkali silicate 2) to the mol ratio of alkali more than 5, below 7.5.
By its silicon oxide (SiO 2) to the mol ratio of alkali more than 5, below 7.5, concentration is the use of 15～40% the alkali silicate aqueous solution, alkali silicate can with hydroxyl (OH), the calcium hydroxide (Ca (OH) in the film of matrix treatment agent 2), after C-O-S-O-C and Si-O-Si key do the combination of short period of time, form finer and close integrated network structure, simultaneously, also quickened the combination between the alkali silicate.Again, silicon oxide (SiO as described 2) to the mol ratio of alkali less than 5, then inclusion residual alkali part between network structure increases, can not airtight inclusion alkali composition, the intensity that hopeless increase is filmed, water tolerance and weathering resistance.Silicon oxide (SiO as described 2) to the mol ratio of alkali greater than 7.5, then itself and matrix treatment agent is reactive low, the formation performance of the integrated and network structure of hopeless raising.For this reason, with described silicon oxide (SiO 2) mol ratio of alkali is set in below 5, more than 7.5.On the other hand, be lower than 15% as the concentration of the alkali silicate aqueous solution, then the absolute magnitude of the alkali silicate of itself and the reaction of matrix treatment agent reduces, and glue spread increases, and phenomenons such as sagging take place easily, sometimes, must repeat repeatedly to be coated with.Like this, make that also its processing property is low, cost increases.Simultaneously, inclusion residual alkali part between formed three-dimensional network structure is increased, can't be airtight, bag connects described alkali part, thereby, cause the intensity, water tolerance, weathering resistance etc. of described treat surface low.
On the other hand, be higher than 40% as the concentration of the alkali silicate aqueous solution, then because of moisture ratio is low, alkali silicate had promptly begun to carry out combination before coating.Simultaneously, because viscosity increases, can't obtain level and smooth filming, processing property is low.For this reason, the concentration of the alkali silicate aqueous solution is set in scope more than 15%, below 40%.
Thereby, owing to used silicon oxide (SiO 2) to the mol ratio of alkali more than 5, below 7.5, concentration is 15～40% the alkali silicate aqueous solution, so, can make described alkali silicate and matrix treatment agent make integrated reacting by this at short notice, form fine and close network structure.
Moreover the present invention is a kind of like this surface treatment agent: metal oxide content wherein of the present invention is based on more than 0.1, below 5 of the weight ratio meter of the alkali silicate aqueous solution.
Because its content of mixing is the metal oxide more than 0.1, below 5 based on the weight ratio meter of the alkali silicate aqueous solution, can make described metal oxide promptly between the chain molecule of formed network structure Si-O-Si associative key, be connected to form fine and close three-dimensional net structure.Again, be less than based on 0.1 of the weight ratio meter of the alkali silicate aqueous solution as metal oxide content, the connection state of then described three-dimensional net structure densification weakens, the formed coating strength of hopeless raising this moment, water tolerance and weathering resistance.Again, greater than based on 5 of alkali silicate aqueous solution weight ratio meter, the metal oxide that does not then participate in connecting between chain molecule is supported between the network structure as metal oxide content, becomes Restzustand, hopeless raising coating strength, water tolerance and weathering resistance.Simultaneously, because the color dyes of metal oxide causes color bad on filming, cost increases.So, metal oxide content of the present invention is set at the scope more than 0.1, below 5 based on the weight ratio meter of the alkali silicate aqueous solution.
Therefore and since fusion its content be the metal oxide 0.1 or more, 5 below based on the weight ratio meter of the alkali silicate aqueous solution, can make the network structure densification more of script densification, increase weathering resistance, water tolerance and the intensity of filming that forms.
Again, the present invention is a kind of like this surface treatment agent: wherein, organic acid in the matrix strengthening agent of the invention described above and at least a material of tinting material and organic acid salt contain its content for based on more than 0.01 of weight ratio meter of the alkali silicate aqueous solution, below 0.1, be selected from least a in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and, contain based on the weight ratio of the alkali silicate aqueous solution count more than 0.1, below 5, be selected from organic acid at least a in arabic acid and the salt thereof and organic acid salt.
So, as at least a organic acid and the organic acid salt that are contained in matrix strengthening agent and the tinting material, make it contain content and be more than 0.01 of weight ratio meter based on the alkali silicate aqueous solution, 0.1 below, be selected from glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, at least a in propionic acid and the salt thereof and, contain based on the weight ratio of the alkali silicate aqueous solution and count more than 0.1, below 5, be selected from least a in arabic acid and the salt thereof, thus, can make in alkali silicate and matrix treatment agent or the matrix strengthening agent film hydroxyl (OH), calcium hydroxide (Ca (OH) 2), C-O-S-O-C and Si-O-Si key do the short period of time in conjunction with after, form finer and close network structure.Simultaneously, also can quicken the combination between the alkali silicate, can obtain easily at short notice and weathering resistance, water tolerance and high-intensity filming matrix treatment agent or being integral of matrix strengthening agent, that have excellence.Again, as the content that is selected from least a organic acid in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and salt thereof is less than based on 0.01 of the weight ratio meter of the alkali silicate aqueous solution, make that then the reactivity and the reactivity worth between the alkali silicate of the matrix treatment agent of itself and alkali silicate or matrix strengthening agent are low, cause integrated degree low.Simultaneously, the formed intensity of filming of hopeless raising, water tolerance and weathering resistance; The dispersiveness of material is also low, is difficult to obtain roughly smoothly filming uniformly; The hopeless raising of application property.
Again, as the content that is selected from least a organic acid in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof or its salt is greater than based on 0.1 of the weight ratio meter of the alkali silicate aqueous solution, then present the residual state that unreacted organic acid and organic acid salt are arranged between network structure, formed filming is difficult to obtain good intensity, water tolerance and weathering resistance, simultaneously, cost also increases.For this reason, be set at more than 0.01, below 0.1 of weight ratio meter with being selected from least a content in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof based on the alkali silicate aqueous solution.
On the other hand, be selected from least a content in arabic acid and the salt thereof as less than based on 0.1 of the weight ratio meter of the alkali silicate aqueous solution, then the reaction of alkali silicate and matrix treatment agent or matrix strengthening agent and the reaction between the alkali silicate can not fully be carried out, the formed intensity of filming of hopeless raising, water tolerance and weathering resistance.Again, be selected from least a content in arabic acid and the salt thereof as greater than based on 5 of the weight ratio meter of the alkali silicate aqueous solution, then present the residual state that unreacted organic acid and organic acid salt are arranged between network structure, formed filming is difficult to obtain good intensity, water tolerance and weathering resistance, simultaneously, cost also increases.So, be set at more than 0.1 of weight ratio meter based on the alkali silicate aqueous solution, the scope below 5 with being selected from least a content in arabic acid and the salt thereof.
Thereby, be selected from least a in glyconic acid, blue or green enzyme spore acid, lactic acid, acetate, propionic acid and salt thereof based on the weight ratio meter of the alkali silicate aqueous solution more than 0.01, below 0.1 owing to used its content to be set at, and content be set at based on the weight ratio meter of the alkali silicate aqueous solution be selected from least a organic acid or organic acid salt in arabic acid and the salt thereof more than 0.1, below 5, can form at short notice have high weathering resistance, water tolerance and high-intensityly smoothly film.
The present invention be again a kind of in the invention described above the matrix treatment agent and matrix strengthening agent at least a in contain the surface treatment agent of pigment.
Owing to contain pigment in the matrix treatment agent, by this, can make pigment by inclusion, be fixed in the Calucium Silicate powder (CaSiO that the reaction owing to matrix treatment agent and polymer water miscible liquid and silica powder generates 3) between and between the network structure, and can be from the sur-face peeling of body material.And so on, it is uniformly good painted that body material can be done roughly, and can increase intensity, water tolerance and weathering resistance.Simultaneously, can strengthen attractive in appearance and the acquisition identity, increase the popularity of using because of painted.In addition, by making the matrix strengthening agent contain pigment, can make pigment when the reaction of matrix treatment agent and matrix strengthening agent by inclusion, fixing, and can be from the sur-face peeling of body material.Thus, can carry out roughly evenly good paintedly, when improving coating weatherability, water tolerance and intensity, improve painted aesthetic measure, obtain identity and increase the popularity of use.
Therefore,, can carry out complicated painted and toning, improve colour, increase attractive in appearance and identity owing in matrix treatment agent and matrix strengthening agent, all contain pigment.
Therefore, because make in the matrix treatment agent and matrix strengthening agent at least a among all contain pigment, can make the pigment can be from the sur-face peeling of body material, really be supported at its surface, obtain roughly evenly, have good painted of color, improve painted aesthetic measure, obtain identity and increase the popularity of using.
Again, the present invention is a kind of like this surface treatment agent: wherein, the pigment of the invention described above comprise based on the gross weight of silica powder and calcareous material than or the weight ratio of the alkali silicate aqueous solution count mineral-type pigment more than 0.1, below 12.
As pigment, since use its content for based on the gross weight of silica powder and calcareous material than or the weight ratio of the alkali silicate aqueous solution be mineral-type pigment more than 0.1, below 12, by this, can easily form have excellent weathering resistance, water tolerance and high strength, have high color, high identity, even, level and smooth painted filming roughly.Described filming is difficult for peeling off from substrate material surface.As the mineral-type pigment content be lower than based on the gross weight of silica powder and calcareous material than or the weight ratio meter of the alkali silicate aqueous solution 0.1, then tinctorial property is low, is to obtain the colour developing set, must form thick film; At this moment, the danger of peeling off is arranged again; Simultaneously, cause processing property lowly to reach the increase of cost.In addition, as the mineral-type pigment content greater than based on the gross weight of silica powder and calcareous material than or the weight ratio meter of the alkali silicate aqueous solution 12, then existing can't the pigment of inclusion between network structure, at this moment, the loss of pigment might or take place, or hinders the formation of network structure; Simultaneously, although hopeless increase color developing, cost still increases.In addition, pigment dyestuff is difficult to increase the weathering resistance of filming, and might hinder the formation of network structure.For this reason, the content of mineral-type pigment is set at based on the gross weight of silica powder and calcareous material than or the scope more than 0.1, below 12 of the weight ratio meter of the alkali silicate aqueous solution.
Therefore, since use its content for based on the gross weight of silica powder and calcareous material than or the weight ratio of the alkali silicate aqueous solution be mineral-type pigment more than 0.1, below 12, can easily form have excellent weathering resistance, water tolerance and high strength, have high color, high identity, smoothly, painted filming uniformly roughly, described filming is difficult for peeling off from substrate material surface.
Have, the present invention is a kind of like this surface treatment agent again: wherein at least a in matrix strengthening agent of the invention described above and the tinting material to contain its content be porous matter amorphous dust more than 1.0, below 15 for the weight ratio based on the alkali silicate aqueous solution.
Mixing in matrix strengthening agent and tinting material at least a and containing its content is porous matter amorphous dust more than 1.0, below 15 for the weight ratio based on the alkali silicate aqueous solution.By this, porous matter amorphous dust and unreacted, residual calcium hydroxide and silicon oxide are reacted, generate Calucium Silicate powder, C-O-S-O-C and Si-O-Si associative key, and form fine and close network structure thus.And the contraction during owing to this network structure of formation is restrained, and can prevent trickle check surface etc.Simultaneously, can obtain its level and smooth performance and improve, have the well behaved film of glossy.Again, be lower than based on 1.0 of the weight ratio meter of the alkali silicate aqueous solution generation of be full of cracks in the time of then can not preventing to shrink, the also hopeless raising smoothness of filming as the content of porous matter amorphous dust.Again, be higher than based on 15 of the weight ratio meter of the alkali silicate aqueous solution as the content of porous matter amorphous dust, then viscosity increases, and the processing property of filming is low, and simultaneously, thickness increases, and cost increases.For this reason, the content of setting porous matter amorphous dust is based on more than 1.0, below 15 of alkali silicate aqueous solution weight ratio meter.
Therefore, owing in matrix strengthening agent and tinting material at least a, mixed its content for to count more than 1.0 based on the weight ratio of the alkali silicate aqueous solution, porous matter amorphous dust below 15, so, contraction in the time of can restraining network structure formation, prevent that trickle surface from producing be full of cracks etc., simultaneously, can improve its smoothness, obtain having the glossy good film.
A kind of like this surface treatment method of surface treatment method system of the present invention:
With the surface treatment agent of the invention described above have hydroxyl (OH) and carboxyl (the polymer water miscible liquid of at least a high adherence is coated substrate material surface COOH), forms film like;
Again before this polymer water miscible liquid is solidified, upload at above-mentioned polymer water miscible liquid film and to hold with silicon oxide (SiO 2) be the silica powder of main composition, make its at least a portion expose described polymer water miscible liquid film surface;
Then, be coated with the matrix treatment agent of above-mentioned surface treatment agent, form film, make it cover aforementioned silica powder at described polymer water miscible liquid film surface;
Coat the surface of described matrix treatment agent film again above the matrix strengthening agent with described surface treatment agent, form described matrix strengthening agent film.
Thereby, owing to the silica powder is supported at the surface of body material, be coated with polymer water miscible liquid film again, after this film surface is with film like coated substrates treatment agent, again the matrix strengthening agent is coated described matrix treatment agent film surface, form film, so, no matter which kind of body material carries out the anti-degradation treatment of substrate material surface and painted processing etc. all easily, improve workability.
Therefore, only be to carry with the polymer water miscible liquid to hold the silica powder, after the coated substrates treatment agent, the coated substrates strengthening agent can carry out the surface of any body material easily and prevent degradation treatment and painted processing etc. again, improves workability.
Again, a kind of like this surface treatment method of surface treatment method system of the present invention:
With the surface treatment agent of the invention described above have hydroxyl (OH) and carboxyl (the polymer water miscible liquid of at least a high adherence COOH) is coated substrate material surface, forms film like;
Again before this polymer water miscible liquid is solidified, upload at above-mentioned polymer water miscible liquid film and to hold with silicon oxide (SiO 2) be the silica powder of main composition, make its at least a portion expose this polymer water miscible liquid film surface;
Then,, form film, make it cover aforementioned silica powder at described polymer water miscible liquid film surface coated substrates treatment agent;
Again the matrix strengthening agent of described surface treatment agent is coated the surface of described matrix treatment agent film, formed described matrix strengthening agent film;
Described tinting material is coated aforementioned substrates strengthening agent film surface, form described tinting material film.
Owing to be that order is carried out following coating operation: back, the surface coating polymer water miscible liquid film that the silica powder is supported at body material, at this polymer water miscible liquid film surface with film like coated substrates treatment agent, then, again matrix strengthening agent and tinting material are coated described matrix treatment agent film surface in proper order, film forming, so, no matter which kind of body material, carry out the anti-degradation treatment of substrate material surface and painted processing etc. all easily, can improve workability.
Therefore, only be to carry with the polymer water miscible liquid to hold after the silica powder coated substrates treatment agent, order coated substrates treatment agent, matrix strengthening agent and tinting material, so, to any body material, can carry out surperficial anti-degradation treatment and painted processing etc. easily, improve workability.
The best mode that carries out an invention
Be detailed description the present invention, below, the 1st embodiment of the present invention is described.
Surface treatment agent is the surface treatment agent of three liquid, one powder-type of the liquid matrix strengthening agent of the liquid matrix treatment agent of the polymer water miscible liquid that contains the water slurry shape, particulate silica powder, water slurry shape and water slurry shape.
Polymer water miscible liquid system will have hydroxyl (OH) and carboxyl (the macromolecule latex liquefaction back of at least a high adherence COOH), have water miscible water miscible liquid, for example wherein having used propylene is that polymer, propylene-styrene multipolymer, vinyl acetate between to for plastic are the macromolecular material of polymer, vinyl acetate-ethylene copolymer etc.
Again, the solid component content of described polymer water miscible liquid is with more than 15%, be advisable below 30%.Here,, then be difficult to obtain the adherence firm with body material if the solid component content is less than 15%, simultaneously, silica powder as described below to carry the power of holding low, must do repeatedly stacked, multiple coating, operation is low.Have again, if the solid component content greater than 30%, then viscosity increases, the coating trivial operations is difficult to obtain roughly thickness uniformly, operability is low.For this reason, the solid component content of polymer water miscible liquid is set in the scope more than 15%, below 30%.
And, the thickness scope that described polymer water miscible liquid can be more than substrate material surface be coated with as 200 μ m, below the 1000 μ m.
On the other hand, the silica powder can use fumed silica, silica, sintered pearlite etc.Be preferably, use after dehydration fever is handled adjusting the silica powder that its calcium oxide activity is enhanced.Particularly, use the sintered pearlite of foaming and intumescing, its reactivity worth height, the contraction in forming of can preventing to film is restrained the generation of be full of cracks, so desirable especially.Again, fumed silica is for roughly being the globular particulate, from the addition that can reduce water etc., improves the angle of operability, and fumed silica is desirable especially.In addition, the particle diameter of this silica powder should be greater than the thickness of polymer water miscible liquid film.Be preferably, the particle diameter of described silica powder is about scope more than 2 times, below 3 times of polymer water miscible liquid film thickness, so that the silica powder that at least a portion is carried hold is exposed to described polymer water miscible liquid film surface.For example, if when polymer water miscible liquid film thickness is 3 μ m, then described silica powder should use its particle diameter at the silica powder more than the 6.0 μ m, below the 10.0 μ m.Here, the silica powder particle size is less than 6.0 μ m as described, then the silica powder almost completely buries in polymer water miscible liquid film, can't react with following matrix treatment agent, makes the operation that described film carries the exposed portions serve of holding this silica powder also become difficult.Again, the silica powder particle size is greater than 10.0 μ m as described, and the silica powder that then is exposed to polymer water miscible liquid film partly becomes greatly, causes the power of holding of carrying relatively of film to reduce, and simultaneously, can not make smoothing processing to substrate material surface.For this reason, the about scope more than 2 times, below 3 times that described silica powder particle size is set at polymer water miscible liquid thickness is advisable.
The matrix treatment agent is a kind of containing with silicon oxide (SiO 2) be main composition the silica powder, be selected from calcium hydroxide (Ca (OH) 2) and calcium oxide (CaO) at least a calcareous material, calcareous material as lime, cement etc., be selected from least a and water of acid dissociation exponent (pKa) in organic acid more than 3, below 5 and organic acid salt, and be the mixture of main composition with above-mentioned composition.
Again, as with silicon oxide (SiO 2) be the silica powder of main composition, as the silica granule material, can use pyrolysis method silicon oxide, silica, sintered pearlite etc.Be preferably, use silica powder through the dehydration fever processing is regulated, its calcium oxide activity is enhanced.Particularly, the sintered pearlite of foaming and intumescing, its reactivity worth height.Again, fumed silica is for roughly being the globular particulate, from the addition that can reduce water etc., improves the angle of operability, and fumed silica is desirable especially.In addition, the particle diameter of this silica powder is to be advisable less than 5.0 μ m.
On the other hand, as being selected from calcium hydroxide (Ca (OH) 2) and calcium oxide (CaO) at least a calcareous material, can use calcium hydroxide, calcium oxide, cement etc., particularly, calcium hydroxide is from regulating proportioning and processing ease aspect, and is particularly desirable.
As acid dissociation exponent (pKa) at organic acid more than 3, below 5 and organic acid salt, can use to be selected from glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid arabic acid and salt (particularly calcium salt) thereof etc., its acid dissociation exponent (pKa), or mix use wherein multiple at a kind of organic acid and organic acid salt more than 3, below 5.
Here, as acid dissociation exponent (pKa) less than 3, then when coating the matrix treatment agent on the calcium-base inorganic members material, then because calcium hydroxide (the Ca (OH) of matrix treatment agent and calcium-base inorganic members material 2) reaction, with the reaction of silica powder calcareous material, and polycondensation when forming three-dimensional net structure etc. very slow, film formation time is longer, transaction capabilities is low.Again, as acid dissociation exponent (pKa) greater than 5, (the Ca (OH) of calcium hydroxide in then described matrix treatment agent and the calcium-base inorganic members material 2) the reaction and the polycondensation uniform velocity when forming three-dimensional net structure of reaction, silica powder and calcareous material too fast, be reflected at the part and carry out, can't obtain equally roughly to film uniformly.In addition, because of contraction increases, film be full of cracks etc. can take place.Thus,, film and powdered may take place peel off, can not form and film according to the occasion difference.For this reason, use acid dissociation exponent (pKa) at organic acid more than 3, below 5 and organic acid salt.
Matrix treatment agent system is suitably mixed: the silica powder, count more than 0.2 based on the weight ratio of this silica powder, calcareous material below 2, as acid dissociation exponent (pKa) more than 3, organic acid below 5 and organic acid salt, gross weight ratio based on silica powder and calcareous material is counted more than 0.01,0.1 the following glyconic acid that is selected from, the acid of blue or green enzyme spore, lactic acid, acetate, at least a organic acid and organic acid salt in propionic acid arabic acid and the salt thereof, gross weight ratio based on silica powder and calcareous material is counted more than 0.1, at least a and water in arabic acid below 5 and the salt thereof, the aqueous solution that is adjusted to pulpous state forms.
Here, as based on as described in silica powder weight ratio meter, be lower than 0.2 as the content of the calcareous material of calcium hydroxide composition, then the reactivity of itself and the contained silica powder of holding, with the reactivity shortcoming of polymer water miscible liquid, the intensity of the film portion of hopeless increase matrix treatment agent, reactivity between also hopeless increase itself and the matrix strengthening agent, can't be integrated at short notice, increase enough coating strengths.Again, be higher than 2 as the content as the calcareous material of calcium hydroxide based on this silica powder weight ratio meter, then because the part that contains of silica powder correspondingly reduces, the point of reflecting point and network structure also correspondingly reduces.Follow above-mentioned minimizing, the intensity of matrix treatment agent film, water tolerance, weathering resistance and be short of with the reactivity of matrix strengthening agent, powder phenomenon-tion might take place in the smoothness that hopeless raising is filmed and the operability of filming, and can not get good filming.For this reason, the addition that calcareous material is scaled calcium hydroxide is set at: count scope more than 0.2, below 2 based on the weight ratio of silica powder.
On the other hand, be selected from glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, at least a organic acid in propionic acid and the salt thereof and the content of organic acid salt, as the gross weight that is lower than based on silica powder and calcareous material compares 0.01 of meter, the reactivity of the calcareous material of then contained silica powder of holding and matrix treatment agent is low, simultaneously, can't carry out fully by reaction and polycondensation that silica powder and calcareous material carry out, the intensity of the formed film of hopeless raising, the dispersiveness of water tolerance and weathering resistance and material, be difficult to obtain roughly even, level and smooth films, and is difficult to improve application property.Again, the content that is selected from least a organic acid in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and organic acid salt is as being higher than gross weight based on silica powder and calcareous material than 0.1 of meter, the existing residual state that unreacted organic acid and organic acid salt are arranged in then between network structure, when being difficult to obtain good film intensity, water tolerance and weathering resistance, cost also increases.For this reason, with being selected from glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and at least a organic acid of salt and the content of organic acid salt, be set at based on the gross weight of silica powder and calcareous material and be advisable than the scope of counting more than 0.01, below 0.1.
Again, at least a content that is selected from arabic acid and salt thereof compares 0.1 of meter as the gross weight that is lower than based on silica powder and calcareous material, the reactivity of the calcareous material of then contained silica powder of holding and matrix treatment agent is low, simultaneously, intensity, water tolerance and the weathering resistance of the formed film of hopeless raising can not be fully carried out in reaction and polycondensation by silica powder and calcareous material; The dispersiveness of hopeless raising material; Be difficult to obtain roughly even, level and smooth filming, also be difficult to improve application property.As at least a content that is selected from arabic acid and salt thereof compares 5 of meter as the gross weight that is higher than based on silica powder and calcareous material, then present the residual state that unreacted organic acid and organic acid salt are arranged between network structure, be difficult to obtain good film intensity, water tolerance and weathering resistance, simultaneously, cost also increases.For this reason, the gross weight that at least a content that is selected from arabic acid and salt thereof is set at based on silica powder and calcareous material compares more than 0.1, below 5 of meter.
These organic acids or organic acid salt are water-soluble, can make good mixing with silica powder and calcareous material, and have surfactivity and restrain the foaming effect.When mixing with silica powder and calcareous material, the tackify that can prevent bubbles causes can be done roughly evenly, good mixing, dispersion.
On the other hand, the matrix strengthening agent is a kind of with the alkali silicate aqueous solution with to be selected from least a in organic acid more than 3, below 5 and organic acid salt of acid dissociation exponent (pKa) be the mixture of main composition.
The alkali silicate of the alkali silicate aqueous solution can use sodium silicate, lithium silicates, potassium silicate etc.Sodium silicate is because of buying especially easily, and cheap, so desirable especially.Again, lithium silicates is because of having excellent in water resistance, so, under the occasion that needs enhanced water resistance especially, be advisable to use lithium silicates.
Again, in the alkali silicate, silicon oxide (SiO 2) for alkali (M 2O M: lithium (Li), potassium (K), sodium (Na) or caesium (Cs)) mol ratio is more than 5, below 7.5.Here, as silicon oxide (SiO 2) for alkali (M 2O) mol ratio is less than 5, and then alkali part is increased relatively, because the coating of matrix strengthening agent, the residual alkali part that is supported between the formed network structure along with reaction increases, thereby, hopeless increase coating strength, water tolerance and weathering resistance.And as silicon oxide (SiO 2) for alkali (M 2O) mol ratio is then preferentially carried out owing to silicon oxide polycondensation each other greater than 7.5, and to cohesion efflorescence direction progress, its viscosity increases.Thus, make the reactive low of itself and matrix treatment agent, the formation performance of integrated performance of hopeless raising and network structure.For this reason, with silicon oxide (SiO 2) for alkali (M 2O) mol ratio is set in more than 5, is advisable below 7.5.
The alkali silicate aqueous solution is the solution of 15～40% concentration of alkali silicate.Here, be leaner than 15% as the concentration of the alkali silicate aqueous solution, then the absolute magnitude of the alkali silicate of itself and the reaction of matrix treatment agent reduces, and for obtaining desirable weathering resistance, water tolerance and intensity, just must increase glue spread.Yet, increase glue spread, phenomenons such as sagging easily take place again.For preventing the generation of sagging phenomenon, be necessary to repeat repeatedly to be coated with, like this, may cause the low and cost increase of transaction capabilities.Have, institute's inclusion, residual alkali part are increased between the three-dimensional net structure of formation, hopeless increase coating strength, water tolerance and weathering resistance again.In addition, thick in 40% as the concentration of the alkali silicate aqueous solution, then the moisture ratio is low, might be before coating, and combination has promptly taken place in alkali silicate, like this, causes viscosity to increase, and can not obtain level and smooth filming, and operation is low.For this reason, the scope that the concentration of the alkali silicate aqueous solution is set in more than 15%, below 40% is advisable.
Again, as the matrix treatment agent, as acid dissociation exponent (pKa) at organic acid more than 3, below 5 and organic acid salt, can use to be selected from glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid arabic acid and salt (particularly calcium salt) thereof etc., its acid dissociation exponent (pKa), or mix use wherein multiple at a kind of organic acid and organic acid salt more than 3, below 5.
Here, the acid dissociation exponent of organic acid and organic acid salt (pKa) is less than 3 as described, then when coating the matrix strengthening agent on the matrix treatment agent, the reaction of matrix strengthening agent and matrix treatment agent, and alkali silicate between reaction etc. very slow, film formation time is longer, and transaction capabilities is low.Again, acid dissociation exponent (pKa) is greater than 5 as described, the reaction of then described matrix strengthening agent and matrix treatment agent, and alkali silicate between the excessive velocities of reaction etc., being reflected at the part carries out, and can't obtain roughly to film uniformly.In addition, because contraction increases and films be full of cracks etc. takes place, according to the occasion difference, described matrix strengthening agent is filmed and is taken place to peel off after the powdered, can not form and film.For this reason, use acid dissociation exponent (pKa) at organic acid more than 3, below 5 and organic acid salt.
As the alkali silicate aqueous solution in the matrix treatment agent and acid dissociation exponent (pKa) more than 3, organic acid below 5 and organic acid salt, can use based on the weight ratio of the alkali silicate aqueous solution and count more than 0.01,0.1 it is following, be selected from glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, at least a in propionic acid arabic acid and the salt thereof etc., its acid dissociation exponent (pKa) is more than 3, organic acid below 5 or organic acid salt, count more than 0.1 based on the weight ratio of the alkali silicate aqueous solution with using, be selected from least a in arabic acid and the salt thereof below 5, regulated by suitable mixing.
Here, as the blending ratio that is selected from least a organic acid of glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and salt thereof and organic acid salt is less than counting 0.01 based on the weight ratio of the alkali silicate aqueous solution, then reaction between alkali silicate and the matrix treatment agent and the reaction between the alkali silicate can not fully be carried out, the integrated performance of hopeless raising itself and matrix treatment agent, also intensity, water tolerance, weathering resistance and the dispersiveness of hopeless raising material.Thereby, be difficult to obtain roughly even, level and smooth filming, be difficult to improve application property.
Again, as the blending ratio that is selected from least a organic acid of glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and salt thereof and organic acid salt is greater than based on 0.1 of the weight ratio meter of the alkali silicate aqueous solution, then present the residual state that unreacted organic acid and organic acid salt are arranged between network structure, be difficult to obtain good coating strength, water tolerance and weathering resistance.Simultaneously, cost also increases.The blending ratio that for this reason will be selected from least a organic acid of glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and salt thereof and organic acid salt is set at the scope of counting more than 0.01, below 0.1 based on the weight ratio of the alkali silicate aqueous solution and is advisable.
Again, as the blending ratio that is selected from least a organic acid of arabic acid and salt thereof and organic acid salt is less than based on 0.1 of the weight ratio meter of the alkali silicate aqueous solution, then reaction between alkali silicate and the matrix treatment agent and the reaction between the alkali silicate can not fully be carried out, and the integrated performance of hopeless raising itself and matrix treatment agent, also can't improve coating strength, water tolerance and weathering resistance.Yet, as the blending ratio that is selected from least a organic acid of arabic acid and salt thereof and organic acid salt is greater than based on 5 of the weight ratio meter of the alkali silicate aqueous solution, then present the residual state that unreacted organic acid and organic acid salt are arranged between network structure, be difficult to obtain good coating strength, water tolerance and weathering resistance.Simultaneously, cost also increases.The blending ratio that for this reason will be selected from least a organic acid of arabic acid and salt thereof and organic acid salt is set at the scope of counting more than 0.1, below 5 based on the weight ratio of the alkali silicate aqueous solution and is advisable.
In addition, these organic acids or organic acid salt can carry out good mixing with the alkali silicate aqueous solution, and can not take place to bubble and tackified phenomenon.
Below, the effect of above-mentioned the 1st embodiment is described.
At first, the polymer water miscible liquid of liquid state by for example spraying or disperse, or by brushing and the coating process of roller coat etc., is coated with into the film like that 200 μ m are above, 1000 μ m are following.Here, less than 200 μ m, then be difficult to obtain firm adherence for body material as thickness, silica powder simultaneously as described below to carry the power of holding low, must do repeatedly stacked coating, operation is low.Again, surpass 1000 μ m as thickness, then under the effect of the impact in the external world and stress etc., the danger of filming and peeling off from body material.For this reason, the coating of thickness is with more than the 200 μ m, be advisable below the 1000 μ m.
Secondly, before described polymer water miscible liquid is solidified, the silica powder is carried hold on it.That is, the silica powder is sprayed on the polymer water miscible liquid films by the device of for example sandblast machine etc., the silica powder that at least a portion is carried hold not by moistening, be exposed to polymer water miscible liquid film, and rest part is buried and carry and hold on it.Again, when the described silica powder of spraying, suitably regulate spraying pressure, be supported at polymer water miscible liquid film so that the silica powder can expose a part at least.For example, if when the median size of employed silica powder is the ground silica of 5.0 μ m, the spraying pressure of then selecting for use is 5kg/cm 2
Secondly, firmly be carried with on the film coated surface of silica powder at high adherence because of described polymer water miscible liquid, by for example spraying and spreading etc., or the coating process of use brushing or roller coat etc., with about 5～10kg/m 2The glue spread of (thickness that 2.5 μ m are above, 5.0 μ m are following) is coated with the matrix treatment agent that has been pre-mixed raw material, and drying is so that it covers the exposed portions serve of silica powder.
Here, glue spread is as being less than 5kg/m 2(2.5 μ m thickness) then can not get enough intensity; As glue spread greater than 10kg/m 2(5.0 μ m thickness) then has the danger that comes off.So glue spread is to be about 5～10kg/m 2(thickness that 2.5 μ m are above, 5.0 μ m are following) is advisable.
Because the volatilizations of the moisture that generates after the coating that above-mentioned matrix is handled etc., the blending ratio of silica powder and calcareous material, organic acid and organic acid salt and moisture become the state that moisture reduces.By this, at acid dissociation exponent (pKa) under the katalysis of organic acid more than 3, below 5 and organic acid salt, the exposed portions serve of carrying the silica powder of holding reaches, the silica powder of matrix treatment agent and, the calcium hydroxide of calcareous material and calcium oxide and hydrate, the calcium hydroxide that generates plays pozzolanic reaction, generates CaO-SiO-insoluble, chain compound ...-SiO-...-SiO-... CaO (C-O-S-O-C) and Calucium Silicate powder.Simultaneously, the silica powder of matrix treatment agent and silica powder and silica powder form the Si-O-Si associative key by hydrogen bond and dehydrating condensation each other, form the three-dimensional net structure of complexing.
Again, the silica powder is the occasion of porous matter perlite powder etc., and because of surfactivity effect, perviousness and the diffustivity of organic acid and organic acid salt, silica powder and calcareous material react by continuous infiltration.
In addition, when forming three-dimensional net structure, the inclusion shape is made in filming of exsiccant film like matrix treatment agent, surrounds the part of unreacted calcium hydroxide, and it is supported in the network structure, becomes a plurality of hydroxyls (state OH) that has.
Next is at film coated surface coating, the dried base strengthening agent of described matrix treatment agent.As the situation of matrix treatment agent, described coating process can use arbitrary method.Again, the solid component content is the coating of 15～30% matrix strengthening agent, and its glue spread makes and is roughly 5～10m at every turn 2/ kg (thickness that 3.5 μ m are above, 7 μ m are following).Here, glue spread is as being less than 5m 2/ kg (3.5 μ m thickness) then can not get enough intensity; As glue spread greater than 10m 2/ kg (7.0 μ m thickness) then has the danger that comes off, and matrix strengthening agent surplus, the waste of coating, causes cost to increase.So the glue spread of matrix strengthening agent is to be about 5～10m 2/ kg (thickness that 3.5 μ m are above, 7.0 μ m are following) is advisable.
Because the coating of above-mentioned matrix strengthening agent, the volatilization of coating back moisture causes moisture to reduce, thus, be selected under the effect such as at least a catalyzer of acid dissociation exponent (pKa) in organic acid more than 3, below 5 and organic acid salt, alkali silicate and the calcium hydroxide and the silicon oxide that are supported between the matrix treatment agent network structure react, and generate Calucium Silicate powder and insoluble C-O-S-O-C with water tolerance and weathering resistance.Have, the C-O-S-O-C of the hydroxyl of alkali silicate and matrix treatment agent and formation network structure and the reaction of Si-O-Si associative key form network structure, simultaneously, also make interreaction between the alkali silicate, do the combination of Si-O-Si key, form network structure again.Then, the unreacted silicon oxide reaction of the silica powder during alkali silicate and matrix treatment agent are filmed, when forming network structure, described alkali silicate also between unreacted silicon oxide, reacts, and makes the network structure densification.By these reactions, matrix strengthening agent and matrix treatment agent form one, and the network structure that forms the densification with complicated three-dimensional structure is filmed.
Therefore, in any body material, can easily form at short notice roughly evenly, level and smooth, have the incorporate of high strength, excellent in water resistance and weathering resistance and film, improve application property.
Have again,, be integrally formed securely because filming of inanimate matter is by coating, so, also can obtain acid resistance and thermotolerance.
Again, in described the 1st embodiment, at least a in matrix treatment agent and the matrix strengthening agent also can contain pigment.
As above-mentioned pigment, for example can use, zinc yellow, red lead, yellow lead, cadmium red, cadmium yellow, cobalt blue, dimension profit Dean pigment, white lead, ultramarine, titanium dioxide, iron oxide black, red iron oxide, aluminum oxide is white, titanium is black, the mineral dye of lithopone, carbon black etc.; , quinoline a word used for translation ketone purple red as alizarine lake, indanthrene blue, eosine lake, quinoline a word used for translation ketone, copper phthalocyanine series pigments, Naphthol are green, the pigment dyestuff of Dai Mengdehei etc. etc.No matter be natural or synthetic pigment, can use one of them.Good especially is to use the mineral dye with alkali resistance and weathering resistance.
In the time of in being contained in above-mentioned pigment as the matrix treatment agent, pigment is carried to be held, fixed packet is connected to formed Calucium Silicate powder (CaSiO 3) between and network structure between.Thus, the painted of inanimate matter filmed mortise on body material, and can not peel off from any substrate material surface.Can carry out roughly even, good painted; Can strengthen painted attractive in appearancely, obtain identity; Increase the popularity of using.Again, held, be fixed between the network structure, so desirable especially because thickness can carry well less than the tinting pigment of 0.5 μ m.
In addition, contain pigment in making the matrix strengthening agent, when matrix strengthening agent and matrix treatment agent reacted, pigment is carried to be held, is fixed between the network structure.Thus, on the painted mortise body material of filming of inanimate matter, and can not peel off from any substrate material surface.Can carry out roughly even, good painted; Can strengthen painted attractive in appearancely, obtain identity; Increase the popularity of using.Again, the situation that contains pigment in the matrix strengthening agent is the same with the matrix treatment agent, is held, is fixed between the network structure because thickness can carry well less than the tinting pigment of 0.5 μ m, so desirable especially.
Have again, also can make in matrix treatment agent and the matrix strengthening agent and all contain pigment.By this, can do complicated painted and toning, can further improve its color performance, increase attractive in appearance and identity.
Therefore, by the interpolation of pigment, can make pigment not peel off and obtain certain bonding from substrate material surface; Body material can do roughly evenly, good, have the painted of excellent colouristic properties; Can strengthen painted attractive in appearancely, obtain identity, increase the popularity of using.
Also can contain metal oxide in above-mentioned matrix treatment agent and the matrix strengthening agent again.Here, described metal oxide can use zinc oxide, aluminum oxide, titanium oxide, magnesium oxide etc., the particularly preferred silicon oxide with hyperergy energy that is to use.
When containing metal oxide in the matrix treatment agent, the content of described metal oxide is for to count more than 0.1, below 5 based on the gross weight ratio of silica powder and calcareous material.When containing metal oxide in the matrix strengthening agent, the content of described metal oxide is for to count more than 0.1, below 5 based on the weight ratio of the alkali silicate aqueous solution.Here, in the matrix treatment agent, as described the content of metal oxide be lower than based on the gross weight of silica powder and calcareous material than meter 0.1 and when in the matrix strengthening agent, containing metal oxide, the content of described metal oxide is lower than 0.1 o'clock based on the weight ratio meter of the alkali silicate aqueous solution, then the connection state of bridge formation shape reduces between the chain molecule of the Si-O-Si associative key of network structure, hopeless further raising intensity, water tolerance and weathering resistance.Again, in the matrix treatment agent, the content of metal oxide is higher than based on the gross weight of silica powder and calcareous material than 5 of meter as described, reach when in the matrix strengthening agent, containing metal oxide, the content of described metal oxide is higher than 5 o'clock based on the weight ratio meter of the alkali silicate aqueous solution, the metal oxide that does not then participate in connecting between chain molecule becomes the state that residues between the network structure, hopeless further raising intensity, water tolerance and weathering resistance.Moreover the color dyes of metal oxide causes color bad on filming easily, and cost increases., be preferably for this reason, in the matrix treatment agent, the content of described metal oxide be set in based on the gross weight of silica powder and the calcareous material scope more than 0.1, below 5 than meter; When perhaps containing metal oxide in the matrix strengthening agent, the content of described metal oxide is set in more than 0.1 of weight ratio meter based on the alkali silicate aqueous solution, the scope below 5.
Owing to contain metal oxide, can make it rapidly between the chain molecule of the Si-O-Si of network structure associative key, (M: metal) associative key connects, and makes network structure densification more with Si-O-M-O-Si.
Therefore, owing to contain metal oxide, can make fine and close network structure densification more, and further increase the weathering resistance of filming.Water tolerance and intensity.
Also can contain porous matter amorphous dust in the matrix strengthening agent again.Here, three-dimensional porous matter amorphous dust can be perlite powder, diatomite, silica-gel powder, mica etc., but good especially be the sintered pearlite powder.
Owing to contain described porous matter amorphous dust, described porous matter amorphous dust and unreacted residual calcium hydroxide and silicon oxide reaction generate Calucium Silicate powder, C-O-S-O-C and Si-O-Si associative key, form fine and close three-dimensional net structure.Simultaneously, the contraction when forming owing to this network structure is restrained, and has prevented trickle check surface etc., can improve smoothness, obtains having the glossy good film.
Here, the content of porous matter amorphous dust is preferably in the scope of counting based on the weight ratio of the alkali silicate aqueous solution more than 1.0, below 15.Be less than based on 1.0 of the weight ratio meter of the alkali silicate aqueous solution as the content of this porous matter amorphous dust, then can't restrain the be full of cracks that causes because of contraction, hopeless raising smoothness.Again, greater than more than 15 of weight ratio meter based on the alkali silicate aqueous solution, then viscosity increases as the content of porous matter amorphous dust, and the operability that forms of filming is low, and thickness increases, and cost increases.For this reason, the content of porous matter amorphous dust is set at based on the weight ratio of the alkali silicate aqueous solution and counts scope more than 1.0, below 15.
Below, the 2nd embodiment of the present invention is described.
The 2nd embodiment ties up in the surface treatment agent of three liquid, one powder type of above-mentioned the 1st embodiment and adds tinting material, makes it to become the surface treatment agent that four liquid, one powder the calcium-base inorganic members of colour pattern.
Promptly, the surface treatment agent of present embodiment system is except polymer water miscible liquid, silica powder, matrix treatment agent and the matrix strengthening agent of above-mentioned the 1st embodiment, the more painted mold base material surface of four liquid, the one powder treatment agent that forms at the film coated surface coating tinting material of matrix strengthening agent.
Above-mentioned tinting material is a kind of with the alkali silicate aqueous solution, pigment and to be selected from least a in organic acid more than 3, below 5 and organic acid salt of acid dissociation exponent (pKa) be the liquid form mixt of main composition.
And as the matrix strengthening agent, the alkali silicate aqueous solution is preferably, and sets wherein silicon oxide (SiO 2) to alkali (M 2O) mol ratio be more than 5, below 7.5, alkali silicate concentration is 15～40% solution.Again, same with the matrix strengthening agent, acid dissociation exponent (pKa) is preferably at organic acid more than 3, below 5 and organic acid salt, mix its content for count more than 0.01 based on the weight ratio of the alkali silicate aqueous solution, below 0.1, be selected from least a in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid arabic acid and the salt thereof and, its content is for counting at least a in arabic acid and the salt thereof of being selected from 0.1 or more, below 5 based on the weight ratio of the alkali silicate aqueous solution, suitable mixed preparing forms.
In addition,, as mentioned above,, be preferably, have the mineral-type pigment of alkali resistance and weathering resistance equally no matter be mineral-type pigment or organic class pigment, also no matter be natural or synthetic pigment as pigment.
Be coated with above-mentioned tinting material with spraying method and dispersion method or with methods such as roller coat and brushings in matrix strengthening agent film coated surface, make its glue spread roughly become 5～10m 2/ kg (thickness is more than the 10 μ m, below the 40 μ m), and dry.Carry out above-mentioned coating repeatedly, can increase painted thickness of filming.
So, in matrix treatment agent and network structure one because of membranaceous coating, the matrix strengthening agent surface coated tinting material of densification, by this, and at acid dissociation exponent (pKa) more than 3, under the organic acid below 5 and the katalysis of organic acid salt, the hydroxyl of alkali silicate and matrix strengthening agent (OH) and the C-O-S-O-C and the Si-O-Si associative key that constitute network structure combine, simultaneously, also combination between alkali silicate is mutual, alkali part of alkali silicate and tinting material surround, be fixed between the network structure, form fine and close three-dimensional net structure, and integrated, form to carry in the network structure of having held baroque densification the painted of pigment and film.
Therefore, to any body material, all can obtain roughly even, good substrate material surface; Can obtain weathering resistance, water tolerance and the high strength of excellent film coated surface at short notice easily; Can carry out paintedly, improve painted aesthetic property, obtain identifiability; Increase the popularity of using.
Have again, film owing to form inanimate matter in described film coated surface, so, also can obtain acid resistance and thermotolerance.
Again, by the coating process of tinting material, can give above-mentioned body material with insight etc., or can be used as separation line, mural painting etc., the popularity of its use is improved.
Have, as embodiment 1, at least a in matrix treatment agent and the tinting material also can be mixed with the porous matter amorphous dust of perlite powder, diatomite, silica-gel powder, mica etc. again.
By the interpolation of above-mentioned porous matter amorphous dust, porous matter amorphous dust and unreacted residual calcium hydroxide and silicon oxide reaction generate Calucium Silicate powder, C-O-S-O-C and Si-O-Si associative key, make to form fine and close three-dimensional net structure.Simultaneously, the contraction when this network structure forms is restrained, and can prevent trickle check surface thus, improves smoothness, obtains having the film of good gloss.
Again, as mentioned above, the content of porous matter amorphous dust is to count more than 1.0 based on the weight ratio of the alkali silicate aqueous solution, to be advisable below 15.
Below, just use aluminium metal sheet and contaminated concrete as above-mentioned body material, just substrate material surface is carried out the surface-treated test and do an explanation.
At first, as the polymer water miscible liquid, be the emulsion 100cc of 50% propylene-styrene multipolymer to the solid component content, add the water of 150cc, it is 20% polymer water miscible liquid that preparation obtains the solid component content, with this polymer water miscible liquid with 5～10kg/m 2Glue spread, coat aluminium metal sheet and contaminated concrete surface.
Again, the contaminated coagulation soil series makes following state: aforesaid propylene-styrene copolymer resin in 25 ℃, humidity are 50% atmosphere, be impregnated in concrete, make it be in the state of pollution.Again, concrete test film, the ratio above-mentioned according to table 1, be configured as after 20cm * 20cm * 3cm size, successively in 25 ℃ wet air, placed two, in 20 ℃ water, placed seven, at 25 ℃, relative humidity is the indoor seasoning of 65%RH, carries out maintenance and makes.
Table 1
Raw material Use level (Kg/m 3)
The unit cement calcium carbonate fine aggregate coarse aggregate water yield ????180 ????120 ????803 ????944 ????195
The slump (cm) ????21
Secondly, after coating polymer water miscible liquid, the silica powder that with median size is 0.5mm is immediately used sandblast machine again, to be about 5kg/cm as the silica powder 2Spraying pressure be sprayed into above-mentioned polymer water miscible liquid film coated surface.Under the spraying of above-mentioned silica powder, filming by the polymer water miscible liquid about half of the contained silica powder of holding of described polymer water miscible liquid film is buried, and second half exposes above-mentioned film surface.Thereafter, under normal temperature, an atmospheric pressure environment (25 ℃, humidity 50%), drying makes polymer water miscible liquid curing of coating.
Then, suitably mix various raw materials, make various matrix treatment agents as shown in table 2.To be about 5～10m 2The glue spread of/kg is applied to described polymer water miscible liquid film coated surface with spread coating with described matrix treatment agent, makes its covering be exposed to the silica powder of this polymer water miscible liquid film coated surface.Under normal temperature, an atmospheric pressure environment (25 ℃, humidity 50%), drying.
Here, as calcareous material, use calcium oxide and portland cement.Again, as the silica powder, using its particle diameter is the perlite powder of 0.5～5.0 μ m, or to use its particle diameter be the ground silica of 0.5～3.0 μ m.In addition, metal oxide uses zinc oxide.
Table 2
Figure A9718172800271
The test method system operation during with regard to coating strength, water tolerance and concrete reactivity and coating etc. is studied.Its evaluation is shown in the 4 stages evaluation of table 3.Evaluation result is shown in table 4.
Table 3
*Metewand Smoothness Intensity Water tolerance Reactive Operation
????◎ ????????○ ????????△ ????????× The hollow trace in no hollow trace surface, surface visible significantly sometimes concavo-convex have concavo-convex, apparent hollow trace Justify the seamless seamless scratch that has of coin wiping with one hundred days and justify the scratch that has of coin wiping with one hundred days with the wiping of one hundred days circle coin with the wiping of one hundred days circle coin Immersion is wiped not fall to soak and is wiped to fall to soak to fall in the water slightly to melt But but but finger touch can not finger touch in 2 hours in the finger touch 2 hours in the finger touch 60 minutes in 30 minutes Sometimes must wait for extremely smoothly smoothly, but inhomogeneous
Table 4
Figure A9718172800291
Result shown in the table 4 shows, specimen coding 2～5, particularly, the sample of specimen coding 2～4, its content that is scaled the calcareous material of calcium hydroxide is calcium hydroxide and the calcium oxide as calcium cpd more than 0.2, below 2 based on the weight ratio meter of silica powder, to concrete coating with after smoothly the filming of high strength, enhanced water resistance 30 minutes, shown to refer to touch possible hyperergy that its coating operation is also easy.Yet, can see, though the content that does not contain such calcareous material, described calcium hydroxide composition as calcareous material is level and smooth for the weight ratio meter based on the silica powder is less than 0.2 specimen coding 1, its coating operability is also good, can not obtain required intensity.Itself and concrete reactivity are also poor, must dry about 2 hour, and the manipulation require spended time.
Understand that thus the doping level of calcareous material must make its content that is scaled the calcium hydroxide composition be the scope more than 0.2, below 2 based on the weight ratio meter of silica powder.
Again, change the raw material of silica powder, make its proportioning become the balance proportioning of the best specimen coding of proportioning 3, test.Its result, owing to used perlite powder, so filming of formation is level and smooth more, reactive high, operation is good.While also can further reduce moisture content with the specimen coding 9 of fumed silica, obtains the best filming.
Based on the balance proportioning of specimen coding 9, change the wherein weight ratio of organic acid and organic acid salt again.At this moment, the filming of specimen coding 9,13 shown based on the gross weight of silica powder and calcareous material than meter, wherein the content of the acid of blue or green enzyme spore and calcium salt thereof is the scope more than 0.01, below 0.1, the content of arabic acid and salt thereof is more than 0.1, below 5, has shown the good result of filming.
Have again, the organic acid and the organic acid salt of specimen coding 13 is substituted by acid of blue or green enzyme spore and calcium salt thereof; In specimen coding 14, used acid dissociation exponent (pKa) at glyconic acid more than 3, below 5 and calcium salt thereof; In specimen coding 15, used acid dissociation exponent (pKa) at propionic acid more than 3, below 5 and calcium salt thereof.As a result, all can obtain good filming.
Again, change the addition of zinc oxide, its result, its addition then can obtain good filming as in the scope that based on solid composition 25 is 1～5 weight ratio.
Secondly, about the matrix strengthening agent, test with regard to its intensity, water tolerance, reactivity and operability equally.Again, as the matrix treatment agent, the specimen coding 9 that use properties is the best is coated on the concrete with spread coating.
In addition, as the matrix strengthening agent, be with concentration be 30%, SiO 2/ Na 2O be 4.0 the sodium silicate aqueous solution and, concentration is 40%, SiO 2/ Na 2O be 4.0 methylamine be aqueous silicate solution by shown in the table 5, suitably add Purified Water (ion exchanged water), fusion is mixed with its concentration and is 20%, SiO 2/ Na 2The alkali silicate aqueous solution that the mol ratio of O is different.Each alkali silicate aqueous solution as shown in table 6 with brushing and roller coat, is coated matrix treatment agent surface, test.It the results are shown in table 7.
Table 5
20% sodium silicate solution SiO 2/Na 2The O mol ratio ????4.0 ????5.0 ????6.0 ????7.5 ????9.0
Mol ratio 4.030% sodium silicate ????100 ????100 ????100 ????100 ????100
Mol ratio 4.040% methylamine is a silicate ????- ????18 ????36 ????63 ????90
Purified Water ????50 ????67 ????74 ????117 ????164
Table 6
Figure A9718172800301
Table 7
Figure A9718172800311
Can understand from result shown in the table 7, use SiO 2/ Na 2O is than the specimen coding 23～28 that is 5.0～7.5, particularly, with organic acid and organic acid salt is acid of blue or green enzyme spore and calcium salt thereof, its content is than more than 0.01, below 0.1 of meter based on the alkali silicate aqueous solution, the content of employed arabic acid and salt thereof is based on the specimen coding 0.1 or more, 5 below 24～28 of the alkali silicate aqueous solution than meter, can obtain good filming.Again, at SiO 2/ Na 2O is than being that sample is preferably in 4.0 the sample, and wherein organic acid and organic acid salt contains proportional higher specimen coding 22; And at SiO 2/ Na 2O is than being in 9.0 the sample, preferably sample be wherein organic acid and organic acid salt contain proportional lower specimen coding 29.Its reason can be thought: in the bigger alkali silicate aqueous solution of silica content ratio, carry out the mutual polycondensation of silicon oxide apace, the catalyst action of organic acid and organic acid salt fails to show as outward appearance visible effect.
Again, as the zinc oxide of metal oxide, its content is 1.0～5.0 o'clock based on sodium silicate aqueous solution weight ratio meter, can obtain good especially filming.
Below, study with same evaluation method with regard to tinting material.As alkali silicate, be with concentration be 30%, SiO 2/ Na 2O be 4.0 the sodium silicate aqueous solution and, concentration is 40%, SiO 2/ Na 2O is that 4.0 methylamine is an aqueous silicate solution, presses proportioning shown in the table 8, suitably adds Purified Water (ion exchanged water), and fusion is mixed with its concentration and is 20%, SiO 2/ Na 2The alkali silicate aqueous solution that the mol ratio of O is different.Pigment uses red iron oxide.Have again,, suitably mix the perlite powder of particle diameter 0.5 μ m～5 μ m as the porous matter amorphous dust of surface smoothing material.Again, as the matrix treatment agent, the specimen coding 9 that performance is the best is applied on the concrete with spread coating.As the matrix strengthening agent, the same the best specimen coding 24 of use properties is applied to matrix treatment agent surface equally.Again the tinting material that respectively cooperates ratio as shown in table 9 is used and brushed and roller coat, coat matrix strengthening agent surface, test.Estimate 3 sections evaluation assessments that adopt shown in table 3 and table 10, it the results are shown in table 11.
Table 8
20% sodium silicate solution SiO 2/Na 2The O mol ratio ????4.0 ????5.0 ????7.5 ????9.0
Mol ratio 4.0 30% sodium silicates ????100 ????100 ????100 ????100
Mol ratio 4.0 40% methylamines are silicate ????- ????18 ????63 ????90
Purified Water ????50 ????67 ????117 ????164
Table 9
Table 10
* metewand Surface smoothing The gloss tint permanence
????× ????????○ ????????◎ Check surface, lacking the smoothness surface does not have be full of cracks, and the good surface of smoothness does not have be full of cracks, and smoothness is very good Tint permanence is poor, and is glossy, and the good gloss of tint permanence is splendid, and tint permanence is splendid
Table 11
Figure A9718172800331
Can understand from result shown in the table 11,, use SiO as the matrix strengthening agent 2/ Na 2O is than the specimen coding 34～39 that is 5.0～7.5, particularly, use acid of blue or green enzyme spore and calcium salt thereof with organic acid and organic acid salt system, its content be based on more than 0.01 of alkali silicate aqueous solution meter, below 0.1, the content of employed arabic acid and salt thereof is for the sample based on the specimen coding more than 0.1, below 5 35,36,38,39,43～45 of alkali silicate aqueous solution meter, can obtain good filming.Again, in the prescription of these samples, as long as acid dissociation exponent (pKa) is more than 3, below 5, to acid of blue or green enzyme spore and salt and unrestricted thereof.As specimen coding 43～45 as seen, use glyconic acid and salt, lactic acid and salt thereof, acetate, propionic salt also can obtain same good filming.
Study with regard to specimen coding 31～33,40～42 again, then can understand, with porous matter amorphous dust by the mixed of counting 1.0～15.0 based on the weight ratio of the alkali silicate aqueous solution, then can obtain its surface and not chap, surface working is very level and smooth, have good the filming of glossy.In addition, do not see that sintered pearlite powder and diatomite have difference on surface smoothing and glossiness, these two kinds of materials all can make good filming.
Again, as the occasion of matrix strengthening agent, at SiO 2/ Na 2O is than being that sample is preferably in 4.0 the sample, organic acid and organic acid salt contain proportional higher specimen coding 33.Again, at SiO 2/ Na 2The O ratio is 9.0 o'clock, and containing of organic acid and organic acid salt proportionally do not see that too big difference is arranged.Its reason can be thought: the acid dissociation exponent that organic acid had is roughly in the cause of identical level.As porous matter amorphous dust, promptly use mica also can obtain to have well filming of high surface smoothing and high gloss again.
Utilizability on the industry
As mentioned above, surface conditioning agent of the present invention and processing method thereof can be used in the concrete member surface such as plastics, fabric, non-weaving cloth, timber, metal, pottery and concrete or mortar etc. is prevented deteriorated and painted etc. surface treatment.

Claims (13)

1. a surface treatment agent is characterized in that, described surface treatment agent comprises:
Coat the polymer water miscible liquid of the high adherence of substrate material surface with film like,
Be supported at above-mentioned polymer water miscible liquid film surface, to small part be exposed to this film surface, with silicon oxide (SiO 2) be the silica powder of main composition,
With film like coat the polymer water miscible liquid surface of aforementioned film like coating and cover silica powder exposed portions serve the matrix treatment agent and
Coat the matrix strengthening agent on the described matrix treatment agent surface on the thin-filmy polymeric water miscible liquid surface that aforementioned coating forms with film like;
The polymer water miscible liquid of described high adherence is selected from hydroxyl (OH) and carboxyl (at least a polymer water miscible liquid COOH) for containing;
Described matrix treatment agent is for containing with silicon oxide (SiO 2) be main composition the silica powder, be selected from calcium hydroxide (Ca (OH) 2) and calcium oxide (CaO) at least a calcareous material, contain that to be selected from acid dissociation exponent (pKa) be organic acid more than 3, below 5 and at least a and water (H in the organic acid salt 2O) the liquid treatment agent that forms;
Described matrix strengthening agent is organic acid more than 3, below 5 and at least a liquid treatment agent in the organic acid salt for containing the alkali silicate aqueous solution and being selected from acid dissociation exponent (pKa), and described matrix strengthening agent is coated above-mentioned matrix treatment agent surface with film like.
2. surface treatment agent as claimed in claim 1, it is characterized in that, to contain the alkali silicate aqueous solution, pigment and be selected from acid dissociation exponent (pKa) be organic acid more than 3, below 5 and at least a liquid treatment agent in the organic acid salt matrix strengthening agent surface with the film like coating described, is coated with the tinting material of film like.
3. surface treatment agent as claimed in claim 1 or 2 is characterized in that, at least a metal oxide that contains in described matrix treatment agent, matrix strengthening agent and the tinting material.
4. as each described surface treatment agent of claim 1～3, it is characterized in that described matrix treatment agent contains and is selected from least a in calcium hydroxide and the calcium oxide, as to be scaled calcium hydroxide content and is: based on the weight ratio of silica powder is calcareous material more than 0.2, below 2.
5. as each described surface treatment agent of claim 1～4, it is characterized in that described matrix treatment agent contains:
Based on the gross weight of silica powder and calcareous material than meter more than 0.01, below 0.1, be selected from least a organic acid in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and organic acid salt and
Based on the gross weight of silica powder and calcareous material than count more than 0.1, below 5, be selected from least a organic acid and organic acid salt in arabic acid and the salt thereof.
6. as each described surface treatment agent of claim 1～5, it is characterized in that a kind of alkali silicate concentration of described alkali silicate water solution system is 15～40% the aqueous solution, the silicon oxide (SiO of described alkali silicate 2) to the mol ratio of alkali more than 5, below 7.5.
7. as each described surface treatment agent of claim 3～6, it is characterized in that described metal oxide content is based on more than 0.1, below 5 of the weight ratio meter of the alkali silicate aqueous solution.
8. as each described surface treatment agent of claim 1～7, it is characterized in that at least a the containing in described matrix strengthening agent and the tinting material:
Based on alkali silicate aqueous solution weight ratio meter more than 0.01, below 0.1, be selected from least a organic acid in glyconic acid, the acid of blue or green enzyme spore, lactic acid, acetate, propionic acid and the salt thereof and organic acid salt and
Based on alkali silicate aqueous solution weight ratio count more than 0.1, below 5, be selected from least a organic acid and organic acid salt in arabic acid and the salt thereof.
9. as each described surface treatment agent of claim 1～8, it is characterized in that at least a pigment that contains in described matrix treatment agent and the matrix strengthening agent.
10. as each described surface treatment agent of claim 1～9, it is characterized in that, described pigment be content based on the weight ratio of the gross weight of silica powder and calcareous material or alkali silicate count more than 0.1, the mineral-type pigment of 12 following scopes.
11. each described surface treatment agent as claim 1～9, it is characterized in that, at least a in described matrix strengthening agent and the tinting material contain based on the weight ratio of the alkali silicate aqueous solution count more than 1.0, the porous matter amorphous dust of 15 following scopes.
12. the surface treatment method of a body material, it is characterized in that, will as each described surface treatment agent of claim 1 and 3-11, contain be selected from hydroxyl (OH) and carboxyl (the polymer water miscible liquid of at least a tool high adherence COOH) is coated substrate material surface, forms film;
Before described polymer water miscible liquid is solidified, will contain with silicon oxide (SiO 2) be that the silica powder of main composition is supported on this polymer water miscible liquid film, make at least a portion in the described silica powder be exposed to described polymer water miscible liquid film surface;
Then, at the matrix treatment agent of described polymer water miscible liquid film surface coating, form film as each described surface treatment agent of claim 1 and 3～11;
The matrix strengthening agent of described surface treatment agent is coated above-mentioned matrix treatment agent film surface, form described matrix strengthening agent film.
13. a surface treatment method is characterized in that,
Will as each described surface treatment agent of claim 1 and 3-11, contain be selected from hydroxyl (OH) and carboxyl (the polymer water miscible liquid of at least a tool high adherence is coated substrate material surface COOH), forms film;
Before described polymer water miscible liquid is solidified, will contain with silicon oxide (SiO 2) be that the silica powder of main composition is supported on this polymer water miscible liquid film, make at least a portion in the described silica powder be exposed to described polymer water miscible liquid film surface;
Then, at the matrix treatment agent of described polymer water miscible liquid film surface coating, form film as each described surface treatment agent of claim 1 and 3～11;
The matrix strengthening agent of described surface treatment agent is coated above-mentioned matrix treatment agent film surface, form described matrix strengthening agent film;
To coat aforementioned substrates strengthening agent film surface as the tinting material of each described surface treatment agent of claim 2～11, form described tinting material film.
CN 97181728 1997-02-10 1997-02-10 Material and process for surface treatment Pending CN1245517A (en)

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