CN100592938C - Process for producing a layered article - Google Patents
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- CN100592938C CN100592938C CN200610009559A CN200610009559A CN100592938C CN 100592938 C CN100592938 C CN 100592938C CN 200610009559 A CN200610009559 A CN 200610009559A CN 200610009559 A CN200610009559 A CN 200610009559A CN 100592938 C CN100592938 C CN 100592938C
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Abstract
Disclosed is a process for producing a layered article including a substrate and an inorganic particle layer formed thereon, the process including: preparing a mixed inorganic particle dispersion comprising a liquid dispersion medium containing inorganic particles (A) and inorganic particles (B), the mixed inorganic particle dispersion being characterized by conditions (1) regarding particle size,(2) regarding volume fraction of inorganic particles and (3) regarding weight fraction; applying the mixed inorganic particle dispersion to a substrate, and removing the liquid dispersion medium fromthe mixed inorganic particle dispersion applied to form an inorganic particle layer on the substrate.
Description
Technical field
The present invention relates to a kind of method of making layered article, layered goods comprise base material and the inorganic particle layer that forms on it.
Background technology
The goods of being made by thermoplastic resin tend to the antistatic behaviour difference usually and the tendency of adsorbing stain are arranged.As for the repressed thermoplastic articles of absorption stain, JP 2004-307056A discloses a kind of film of anti-stain, this film is to be applied on the thermoplastic resin by the liquid that will comprise inorganic colloid, removes decentralized medium then and makes derived from the inorganic particle layer of inorganic colloid to form.
Summary of the invention
Therefore in above-mentioned anti-stain film, the bonding force between inorganic particulate is not very strong, when deformation of thin membrane or when film applied external force such as frictional force, inorganic particle layer may be peeled off.
Consider these problems of routine techniques, the invention is intended to provide a kind of method of making layered article, layered goods comprise the stabilized zone that base material and its are gone up the inorganic particulate that forms, and described layer has high strength.Another object of the present invention is to provide a kind of method of making layered article, and layered goods comprise the stabilized zone that base material and its are gone up the inorganic particulate that forms, and described layer has high strength and have good anti-dazzle property.
In the first embodiment, the invention provides:
A kind of method of making layered article, described layered article comprise base material and the inorganic particle layer that forms on it, and described method comprises:
Preparation mixed inorganic particle dispersion liquid, it comprises the liquid dispersion medium that contains inorganic particulate (A) and inorganic particulate (B), condition (1), (2) and (3) that provide below are provided described mixed inorganic particle dispersion liquid;
The mixed inorganic particle dispersion liquid is coated on the base material, and
From the mixed inorganic particle dispersion liquid that is coated with, remove liquid dispersion medium, on base material, to form inorganic particle layer:
Condition (1): the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, and the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and Da≤0.15 * Db;
Condition (2): 0.01≤Va/ (Va+Vb)≤0.40, and 0.60≤Vb/ (Va+Vb)≤0.99, wherein Va and Vb are respectively inorganic particulate (A) and inorganic particulate (B) volume fractions based on inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A) and volume summation (B); With
Condition (3): 0.01≤(Wa+Wb)/Wt≤0.20, wherein Wa and Wb are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A) and the weight of inorganic particulate (B), and Wt is the weight of mixed inorganic particle dispersion liquid.
In second embodiment, the invention provides:
A kind of method of making layered article, described layered article comprise base material and the inorganic particle layer that forms on it, and described method comprises:
Preparation mixed inorganic particle dispersion liquid, it comprises the liquid dispersion medium that contains inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C), condition (1), (2) and (3) that provide below are provided described mixed inorganic particle dispersion liquid;
Described mixed inorganic particle dispersion liquid is coated on the base material, and
From the mixed inorganic particle dispersion liquid that is coated with, remove liquid dispersion medium, on base material, to form inorganic particle layer:
Condition (1): the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, and the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and the average grain diameter Dc of inorganic particulate (C) is 0.4 to 10 μ m, and Da≤0.15 * Db;
Condition (2): 0.01≤Va/ (Va+Vb+Vc)≤0.45,0.45≤Vb/ (Va+Vb+Vc)≤0.98, and 0.01≤Vc/ (Va+Vb+Vc)≤0.45, wherein Va, Vb and Vc are respectively inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) volume fractions based on the inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A), (B) and volume summation (C); With
Condition (3): 0.01≤(Wa+Wb+Wc)/Wt≤0.30, wherein Wa, Wb and Wc are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A), the weight of inorganic particulate (B) and the weight of inorganic particulate (C), and Wt represents the weight of mixed inorganic particle dispersion liquid.
According to the present invention, can make a kind of layered article, described layered article comprises base material and the inorganic particle layer that forms on it, described layer has high strength.
Particularly, according to second embodiment of the present invention,, can form layered article with good anti-dazzle property by being the inorganic particulate (C) of 0.4 to 10 μ m in conjunction with average grain diameter Dc.
Description of drawings
Fig. 1 is the SEM image that shows the inorganic particulate laminar surface of the layered article of making among the embodiment 1.
Fig. 2 is the SEM image that shows the inorganic particulate laminar surface of the layered article of making among the embodiment 2.
Fig. 3 is the SEM image that shows the inorganic particulate laminar surface of the layered article of making in the comparative example 1.
The specific embodiment
At first, explain the method for first embodiment of the invention.
The material of base material can be a hard material, as glass or metal, but considers preferred thermoplastic resin from the easness of processing and processing.The example that forms the thermoplastic resin of base material comprises alkene-Ji resin, as polyvinyl resin, and acrylic resin, the copolymer of ethene and/or alpha-olefin and other polymerisable monomer; Chlorine-containing resins is as Corvic and polyvinylidene chloride resin; Fluorine resin, as proplast, the copolymer of tetrafluoroethene and other polymerisable monomer such as ethene and alpha-olefin; Mylar is as PETG and PEN; Acrylic resin, as polymethyl methacrylate, the copolymer of methyl methacrylate and other polymerisable monomer; Styrene-Ji resin is as the copolymer of polystyrene and styrene and other polymerisable monomer; Celluosic resin is as triacetyl cellulose and diacetyl cellulose; Polycarbonate resin; Polyamide; Polyurethane resin; And their mixture.
In order to prepare the layered article of the high grade of transparency, the preferred base material of making by following resin that uses: alkene-Ji resin, chlorine-containing resins, fluorine resin, mylar, acrylic resin, styrene-Ji resin, celluosic resin or polycarbonate resin.
The single layer of substrate material that base material both can be made up of individual layer also can be by multi-layer substrate two-layer or that multilayer is formed.The example of multi-layer substrate comprises: multi-layer substrate that the layer of being made by thermoplastic resin by every layer of two-layer or multilayer is formed and layer composite multi-layer base material of being made by the material (for example metal) beyond the thermoplastic resin by one or more layers the every layer layer of making by thermoplastic resin and one or more layers every layer of forming.
Shape, size and thickness to base material are not particularly limited.
The mixed inorganic particle dispersion liquid that in the method for first embodiment of the invention, uses meet the following conditions (1), (2) and (3):
Condition (1): the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, and the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and Da≤0.15 * Db;
Condition (2): 0.01≤Va/ (Va+Vb)≤0.40, and 0.60≤Vb/ (Va+Vb)≤0.99, wherein Va and Vb are respectively inorganic particulate (A) and inorganic particulate (B) volume fractions based on inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A) and volume summation (B); With
Condition (3): 0.01≤(Wa+Wb)/Wt≤0.20, wherein Wa and Wb are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A) and the weight of inorganic particulate (B), and Wt represents the weight of mixed inorganic particle dispersion liquid.
In the preparation of mixed inorganic particle dispersion liquid, selecting average grain diameter Da is 1 to 20nm inorganic particulate (A), and average grain diameter Db is 30 to 300nm inorganic particulate (B), thus the Da that satisfies condition≤0.15 * Db.Then two class inorganic particulates are mixed with the quantitative relationship of condition (2) definite above satisfying and (3).
The chemical composition of inorganic particulate (A) and inorganic particulate (B) can be identical or different.The example that is used as the inorganic particulate of inorganic particulate (A) or inorganic particulate (B) comprises: metallic, metal oxide particle, metal hydroxides particle, metal carbonate particle and metallic sulphate particles.The example of the metallic element of metallic comprises: gold, palladium, platinum and silver.The metallic element of metal oxide particle, metal hydroxides particle, metal carbonate particle and metallic sulphate particles comprises: silicon, aluminium, zinc, magnesium, calcium, barium, titanium, zirconium, manganese, iron, cerium, nickel and tin.Consider from the uniformity and the density of the inorganic particle layer that forms, be fit to adopt the oxide or the hydroxide particle of silicon or aluminium.
The spy uses metal oxide particle or metal hydroxides particle to suit in addition.Particularly, the oxide or the hydroxide particle of preferred silicon or aluminium.The use of such inorganic particulate makes and can form wherein inorganic particulate inorganic particle layer very fine and close and that evenly pile up.In order to form the inorganic particle layer of highly transparent, using silicon dioxide granule is preferably as inorganic particulate (A) and (B).
The method for preparing the mixed inorganic particle dispersion liquid but is not limited to typically, any in the following method [1] to [5]:
[1] with inorganic particulate (A) powder with inorganic particulate (B) powder joins in the common liquid dispersion medium and the method for disperseing therein.
[2] inorganic particulate (A) is dispersed in first kind of liquid dispersion medium, form first kind of dispersion liquid, and inorganic particulate (B) is dispersed in second kind of dispersion liquid of formation in second kind of liquid dispersion medium, then with first kind and second kind of method that dispersion liquid combines.
[3] inorganic particulate (A) is dispersed in forms dispersion liquid in the liquid dispersion medium, add the powder of inorganic particulate (B) then and its method of in dispersion liquid, disperseing.
[4] inorganic particulate (B) is dispersed in forms dispersion liquid in the liquid dispersion medium, add the powder of inorganic particulate (A) then and its method of in dispersion liquid, disperseing.
[5] in first kind of decentralized medium, grow the particle seed to obtain comprising first kind of dispersion liquid of inorganic particulate (A), and growth particle seed is to obtain comprising second kind of dispersion liquid of inorganic particulate (B), then with first kind and second kind of method that dispersion liquid combines in second kind of decentralized medium.
By using strong dispersion technology, disperse and the super-pressure dispersion as ultrasonic wave, make inorganic particulate to be evenly dispersed in very much in the mixed inorganic particle dispersion liquid.
In order to reach more uniform dispersion, wish that inorganic particulate is in colloidal state in inorganic particulate (A) dispersion liquid or in inorganic particulate (B) dispersion liquid or in the final mixed inorganic particle dispersion liquid of making.
In above-mentioned method [2] in [5], when inorganic particulate (A) dispersion liquid or inorganic particulate (B) dispersion liquid are colloidal aluminas, when perhaps inorganic particulate (A) dispersion liquid and inorganic particulate (B) dispersion liquid all are colloidal alumina, suitable is adds anion such as chlorion, sulfate ion and acetate ion as counter ion counterionsl gegenions, with the stable aluminium oxide particles that is easy to positively charged in colloidal alumina.PH value to colloidal alumina is not particularly limited, but considers from the stability of dispersion liquid, and the pH value is 2 to 6 to suit.
Even in method [1], when at least a in inorganic particulate (A) and the inorganic particulate (B) be aluminium oxide and mixed inorganic particle dispersion liquid when being in colloidal state, the anion that adds such as chlorion, sulfate ion and acetate ion in the mixed inorganic particle dispersion liquid suits.
In method [2] in [5], when inorganic particulate (A) dispersion liquid or inorganic particulate (B) dispersion liquid are cataloids, when perhaps inorganic particulate (A) dispersion liquid and inorganic particulate (B) dispersion liquid all are cataloid, suitable is adds cation such as ammonium ion, alkali metal ion and alkaline-earth metal ions as counter ion counterionsl gegenions in cataloid, be easy to electronegative silicon dioxide granule with stable.PH value to cataloid is not particularly limited, but considers from the stability of dispersion liquid, and the pH value is 8 to 11 to suit.
Even in method [1], when at least a in inorganic particulate (A) and the inorganic particulate (B) be silica and mixed inorganic particle dispersion liquid when being in colloidal state, the cation that adds such as ammonium ion, alkali metal ion and alkaline-earth metal ions in the mixed inorganic particle dispersion liquid suits.
In first embodiment of the present invention, below be essential: the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, and the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and Da≤0.15 * Db.Herein, the average grain diameter Da of inorganic particulate (A) measures by dynamic light scattering method or Sears method.Measuring average grain diameter with dynamic light scattering method is to use commercially available particle diameter distributional analysis instrument to carry out.The Sears method, it is disclosed in Analytical Chemistry, vol.28, p.1981-1983, and 1956, be the analytical technology that is used to measure the silicon dioxide granule average grain diameter.It is a kind of like this method, wherein determines the pH value of cataloid from 3 amounts that are elevated to 9 NaOH that need by titration, and calculates the surface area of silicon dioxide granule based on titration results, determines spherolite of equal value at last directly.Spherolite of equal value directly is applied average grain diameter.The average grain diameter Db of inorganic particulate (B) is the bulb diameter of being measured by BET method or laser diffraction and scattering method of equal value.
The mixed inorganic particle dispersion liquid that uses in the first embodiment of the invention must meet the following conditions (2):
Condition (2): 0.01≤Va/ (Va+Vb)≤0.40, and 0.60≤Vb/ (Va+Vb)≤0.99, wherein Va and Vb are respectively inorganic particulate (A) and inorganic particulate (B) volume fractions based on inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A) and volume summation (B).
The volume fraction of inorganic particulate (A) and inorganic particulate (B) can use the density of inorganic particulate and weight to calculate.When inorganic particulate (A) and inorganic particulate (B) are identical chemical species, think that the weight fraction of inorganic particulate (A) and inorganic particulate (B) is respectively the volume fraction of inorganic particulate (A) and inorganic particulate (B).The density of inorganic particulate is measured with the helium pycnometry.By the inorganic particulate (A) of use in the suitable selection mixed inorganic particle dispersion liquid preparation and the density and the amount of inorganic particulate (B), (2) can satisfy condition.
The mixed inorganic particle dispersion liquid that is used for first embodiment of the invention must meet the following conditions (3):
Condition (3): 0.01≤(Wa+Wb)/Wt≤0.20, wherein Wa and Wb are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A) and the weight of inorganic particulate (B), and Wt represents the weight of mixed inorganic particle dispersion liquid.By the amount of inorganic particulate (A), inorganic particulate (B) and the liquid dispersion medium of use in the suitable selection mixed inorganic particle dispersion liquid preparation, (3) can satisfy condition.
The method of second embodiment of the invention then, is described.If the material in second embodiment is total with previously described first embodiment, then states such fact, and omit the detailed description of this material.
The base material that uses in the method for the base material that uses in the method for second embodiment and first embodiment is identical.
The mixed inorganic particle dispersion liquid that uses in the method for second embodiment meet the following conditions (1), (2) and (3):
Condition (1): the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, and the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and the average grain diameter Dc of inorganic particulate (C) is 0.4 to 10 μ m, and Da≤0.15 * Db;
Condition (2): 0.01≤Va/ (Va+Vb+Vc)≤0.45,0.45≤Vb/ (Va+Vb+Vc)≤0.98, and 0.01≤Vc/ (Va+Vb+Vc)≤0.45, wherein Va, Vb and Vc are respectively inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) volume fractions based on the inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A), (B) and volume summation (C); With
Condition (3): 0.01≤(Wa+Wb+Wc)/Wt≤0.30, wherein Wa, Wb and Wc are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A), the weight of inorganic particulate (B) and the weight of inorganic particulate (C), and Wt represents the weight of mixed inorganic particle dispersion liquid.
In the preparation of mixed inorganic particle dispersion liquid, selecting average grain diameter Da is 1 to 20nm inorganic particulate (A), and average grain diameter Db is 30 to 300nm inorganic particulate (B), thus the Da that satisfies condition≤0.15 * Db.Be of the quantitative relationship mixing of the inorganic particulate (C) of 0.4 to 10 μ m with two class inorganic particulates and average grain diameter Dc then with condition (2) definite above satisfying and (3).
Those that use in the inorganic particulate that uses in second embodiment (A) and inorganic particulate (B) and first embodiment are identical.In addition, the chemical composition of the inorganic particulate that uses in second embodiment (C) can be identical with inorganic particulate (A) or inorganic particulate (B), also can be different.Similar inorganic particulate (A) and (B), the example of inorganic particulate (C) comprising: metallic, metal oxide particle, metal hydroxides particle, metal carbonate particle and metallic sulphate particles.The example of the metallic element of metallic comprises: gold, palladium, platinum and silver.The metallic element of metal oxide particle, metal hydroxides particle, metal carbonate particle and metallic sulphate particles comprises: silicon, aluminium, zinc, magnesium, calcium, barium, titanium, zirconium, manganese, iron, cerium, nickel and tin.
Equally, as for inorganic particulate (C), the suitable oxide of metal or the particle of hydroxide of using.Especially, use metal oxide particle or metal hydroxides particle to suit.The average grain diameter Dc of inorganic particulate (C) is 0.4 to 10 μ m.Use have such average grain diameter inorganic particulate (C) can so that to inorganic particle layer have good anti-dazzle property.
The method for preparing the mixed inorganic particle dispersion liquid but is not limited to typically, any in the following method [1] to [9].
[1] method that joins inorganic particulate (A) powder, inorganic particulate (B) powder and inorganic particulate (C) powder in the common liquid dispersion medium and disperse therein.
[2] inorganic particulate (A) is dispersed in first kind of dispersion liquid of formation in first kind of liquid dispersion medium, inorganic particulate (B) is dispersed in second kind of dispersion liquid of formation in second kind of liquid dispersion medium, and inorganic particulate (C) is dispersed in the third liquid dispersion medium forms the third dispersion liquid, then the method that first kind, second kind and the third dispersion liquid are combined.
[3] a kind of inorganic particulate that will be selected from inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) is dispersed in and forms dispersion liquid in the liquid dispersion medium, adds two kinds of inorganic particulates of residue and they disperse in dispersion liquid with it method then in dispersion liquid.(this method is the improvement of method [1]).
[4] two kinds of inorganic particulates that will be selected from inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) are dispersed in and form dispersion liquid in the liquid dispersion medium, add remaining a kind of inorganic particulate then and with its method of disperseing in dispersion liquid in dispersion liquid.(this method is another improvement of method [1]).
[5] two kinds of inorganic particulates that will be selected from inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) are dispersed in respectively in the liquid dispersion medium separately, form first kind and second kind of dispersion liquid, then two kinds of dispersion liquids are combined, add the powder of remaining a kind of inorganic particulate at last and its method of in the dispersion liquid that merges, disperseing.
[6] inorganic particulate (A) is dispersed in first kind of dispersion liquid of formation in first kind of liquid dispersion medium, inorganic particulate (B) is dispersed in second kind of dispersion liquid of formation in second kind of liquid dispersion medium, and inorganic particulate (C) is dispersed in the third dispersion liquid of formation in the third liquid dispersion medium, then two kinds in first kind, second kind and the third dispersion liquid are combined, at last the method that remaining a kind of dispersion liquid and the previous dispersion liquid that merges are merged.(this method is the improvement of method [2]).
[7] in first kind of decentralized medium, grow the particle seed to obtain comprising first kind of dispersion liquid of inorganic particulate (A), and growth particle seed is to obtain comprising second kind of dispersion liquid of inorganic particulate (B) in second kind of decentralized medium, then first kind and second kind of dispersion liquid are combined, add the powder of inorganic particulate (C) at last and its method of in the dispersion liquid that merges, disperseing.
[8] in first kind of decentralized medium, grow the particle seed to obtain comprising first kind of dispersion liquid of inorganic particulate (A), and growth particle seed is to obtain comprising second kind of dispersion liquid of inorganic particulate (B) in second kind of decentralized medium, inorganic particulate (C) is dispersed in the third liquid dispersion medium to obtain the third dispersion liquid, then the method that first kind, second kind and the third dispersion liquid are combined.
[9] in first kind of decentralized medium, grow the particle seed to obtain comprising first kind of dispersion liquid of inorganic particulate (A), and growth particle seed is to obtain comprising second kind of dispersion liquid of inorganic particulate (B) in second kind of decentralized medium, inorganic particulate (C) is dispersed in the third liquid dispersion medium to obtain the third dispersion liquid, then two kinds in first kind, second kind and the third inorganic particulate dispersion liquid are combined, at last remaining dispersion liquid is joined the method in the dispersion liquid of previous merging.(this method is the improvement of method [8]).
By using strong dispersion technology, disperse and the super-pressure dispersion as ultrasonic wave, make inorganic particulate to be evenly dispersed in very much in the mixed inorganic particle dispersion liquid.
In order to reach more uniform dispersion, wish inorganic particulate in inorganic particulate (A) dispersion liquid, or in inorganic particulate (B) dispersion liquid, or in inorganic particulate (C) dispersion liquid, or be in colloidal state in the final mixed inorganic particle dispersion liquid that forms.
In above-mentioned method [2] in [9], when the intermediate inorganic particulate dispersion liquid that comprises inorganic particulate (A) dispersion liquid, inorganic particulate (B) dispersion liquid, inorganic particulate (C) dispersion liquid and contain the mixed dispersion liquid of two kinds of inorganic particulates is colloidal alumina, suitable is adds anion such as chlorion, sulfate ion and acetate ion as counter ion counterionsl gegenions, with the stable aluminium oxide particles that is easy to positively charged in colloidal alumina.PH value to colloidal alumina is not particularly limited, but considers from the stability of dispersion liquid, and the pH value is 2 to 6 to suit.
Even in method [1], when at least a in inorganic particulate (A), inorganic particulate (B) and the inorganic particulate (C) be aluminium oxide and the final mixed inorganic particle dispersion liquid that forms when being in colloidal state, the anion that adds such as chlorion, sulfate ion and acetate ion in the mixed inorganic particle dispersion liquid suits.
In above-mentioned method [2] in [9], when comprising inorganic particulate (A) dispersion liquid, inorganic particulate (B) dispersion liquid, inorganic particulate (C) dispersion liquid and contain the intermediate inorganic particulate dispersion liquid cataloid of mixed dispersion liquid of two kinds of inorganic particulates, suitable is adds cation such as ammonium ion, alkali metal ion and alkaline-earth metal ions as counter ion counterionsl gegenions in cataloid, be easy to electronegative silicon dioxide granule with stable.PH value to cataloid is not particularly limited, but considers from the stability of dispersion liquid, and the pH value is 8 to 11 to suit.
Even in method [1], when at least a in inorganic particulate (A), inorganic particulate (B) and the inorganic particulate (C) be silica and the final mixed inorganic particle dispersion liquid that forms when being in colloidal state, the cation that adds such as ammonium ion, alkali metal ion and alkaline-earth metal ions in the mixed inorganic particle dispersion liquid suits.
In second embodiment of the present invention, below be essential: the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and the average grain diameter Dc of inorganic particulate (C) is 0.4 to 10 μ m, and Da≤0.15 * Db.Herein, identical in the implication of average grain diameter Da and average grain diameter Db and measuring method and first embodiment.The average grain diameter Dc of inorganic particulate (C) is the bulb diameter of measuring by BET method, centrifugal sedimentation method or laser diffraction and scattering method of equal value.
The mixed inorganic particle dispersion liquid that uses in the second embodiment of the invention must meet the following conditions (2):
Condition (2): 0.01≤Va/ (Va+Vb+Vc)≤0.45,0.45≤Vb/ (Va+Vb+Vc)≤0.98, and 0.01≤Vc/ (Va+Vb+Vc)≤0.45, wherein Va, Vb and Vc are respectively inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) volume fractions based on the inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A), (B) and volume summation (C).
The volume fraction of inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) can use the density of inorganic particulate and weight to calculate.When inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) are identical chemical species, think that inorganic particulate (A), (B) and weight fraction (C) are respectively inorganic particulate (A), (B) and volume fraction (C).The density of inorganic particulate is measured with the helium pycnometry.
The mixed inorganic particle dispersion liquid that is used for second embodiment of the invention must meet the following conditions (3):
Condition (3): 0.01≤(Wa+Wb+Wc)/Wt≤0.30, wherein Wa, Wb and Wc are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A), the weight of inorganic particulate (B) and the weight of inorganic particulate (C), and Wt represents the weight of mixed inorganic particle dispersion liquid.
By the amount of inorganic particulate (A), inorganic particulate (B), inorganic particulate (C) and the liquid dispersion medium of use in the suitable selection mixed inorganic particle dispersion liquid preparation, (3) can satisfy condition.
In first and second embodiments of the present invention, can in the mixed inorganic particle dispersion liquid, add additive such as surfactant and organic bath, its purpose is, for example the stabilisation of inorganic particulate dispersion liquid.
When the mixed inorganic particle dispersion liquid contained surfactant, its content was up to 0.1 weight portion usually based on the decentralized medium of 100 weight portions.Kind to the surfactant that uses is not particularly limited, and can be anion surfactant, cationic surfactant, non-ionic surface active agent or amphoteric surfactant.
The example of anion surfactant comprises the alkali metal salt of carboxylic acid; Particularly, Sodium Caprylate, potassium octanoate, sodium caprate, sodium n-caproate, myristic acid sodium, potassium oleate, stearic acid tetramethyl-ammonium and odium stearate.The alkali metal salt that especially preferably contains the carboxylic acid of 6 to 10 carbon atoms.
The example of cationic surfactant comprises the cetyl trimethyl ammonium chloride, two (octadecyl) alkyl dimethyl ammonium chloride, N-octadecyl bromination pyridine and spermaceti base triethyl group phosphonium bromide.
The example of non-ionic surface active agent comprises sorbitan fatty esters and fatty glyceride.
Examples of amphoteric surfactants comprises 2-alkyl-N-carboxy ethyl-N-hydroxyethyl imidazolinium betaine and lauramido propyl betaine.
When the mixed inorganic particle dispersion liquid contained organic bath, its content was up to 0.01 weight portion usually based on the decentralized medium of 100 weight portions.The organic bath of Shi Yonging is to have Ionized ionic group but be not the organic compound of surfactant herein.The example comprises paratoluenesulfonic acid sodium salt, benzene sulfonic acid sodium salt, fourth potassium sulfonate, phenyl sodium hypophosphite and diethyl sodium phosphate.Preferred organic bath is a benzene sulfonic derivative.
In first and second embodiments of the present invention, the method that the mixed inorganic particle dispersion liquid is applied on the base material is not particularly limited.Can described liquid be applied on the substrate surface described method such as notch board coating, oppositely coating, brush roller coat, spraying, contact coating, mouthful pattern coating and the coating of dipping/roller scraping article with conventional method.
Before the mixed inorganic particle dispersion liquid is applied to base material, substrate surface is carried out preliminary treatment suit, described preliminary treatment such as sided corona treatment, ozone treatment, plasma treatment, burning (flaming), electron beam treatment, tackify coating and cleaning.
Another kind of available base material is by form the layered article that inorganic cover film prepares on base material, described inorganic cover film is the liquid that contains inorganic substances that is different from the mixed inorganic particle dispersion liquid that uses among the present invention by coating on the basad material, and dry then described liquid forms.As for base material, can use before the material that provides as the example of base material.As for the liquid that contains inorganic substances, the suitable liquid that adopts colloidal alumina, contains clay mineral, described clay mineral have the characteristic of in decentralized medium swelling or division.
When adopting the suitable mixed inorganic particle dispersion liquid of method on being coated in base material, removing liquid dispersion medium, on base material, form inorganic particle layer.The removal of liquid dispersion medium can be undertaken by heating under normal pressure or decompression.The pressure and the heating-up temperature that are used to remove liquid dispersion medium can be according to the material (that is, the inorganic particulate (A) in first embodiment, inorganic particulate (B) and the liquid dispersion mediums that use; Inorganic particulate in second embodiment (A), inorganic particulate (B), inorganic particulate (C) and liquid dispersion medium) suitably select.For example, when decentralized medium is water, can preferably under about 60 ℃ temperature, carry out drying typically at from 50 to 80 ℃.
In the present invention, by the kind of suitable selection base material and inorganic particulate (A) and the kind (B) that is used to form inorganic particle layer, can make the layered article that is fit to various application.For example, when with titanium oxide, its so-called photosemiconductor, during as inorganic particulate, the layered article that obtains will be the film with special light absorption band.Such material is suitable as has the controlled material of good smooth transmission.
When use has the inorganic particulate of porous, can in the hole, introduce the materials with function that is fit to give such as optical function, electric function, magnetic function and biological function.The introducing of such material in the hole can be carried out before or after the inorganic particle layer on the base material forms.
Embodiment
Explain the present invention below with reference to embodiment, but scope of the present invention is not limited to embodiment.
The embodiment of I, first embodiment
At first, provide embodiment and comparing embodiment about first embodiment of the invention.What show below is the testing experiment program of using among the embodiment.
The outward appearance of＜inorganic particulate laminar surface 〉
The surface of inorganic particle layer is observed with SEM (SEM), and uses the uniformity and the consistency of SEM image evaluation inorganic particle layer.
The intensity of＜inorganic particle layer 〉
Intensity in order to following method evaluation layer shape goods inorganic particle layer.
With cleaning the inorganic particulate laminar surface 20 times before and after the laboratory tissue paper (trade name: Kimwipe, by Crecia Co., Ltd. makes), and measure clean before and after the variation of mist degree.This variation is more little, and inorganic particle layer intensity is high more.Mist degree is according to JIS K7105, by the direct-reading mist degree computer (HGM-2DF that is used for illuminant-C; By Suga Test Instruments Co., Ltd. makes) measure.
＜base material 〉
Use the thick three-layer thin-film of being made up of A layer, B layer and C layer of 130 μ m as base material, described A layer, B layer and C layer are settled in this order one by one.A layer, B layer and C layer are respectively by polyvinyl resin (trade name: Sumikathene F208-0; By Sumitomo Chemical Co., Ltd. makes), ethylene/hexene-1 copolymer (trade name: Excellen FX CX2001; By SumitomoChemical Co., Ltd. makes) and another ethylene/hexene-1 copolymer (trade name: Sumikathene EFV201; By Sumitomo Chemical Co., Ltd. makes) make.Thickness proportion is A layer/B layer/C layer=2/6/2.
By synthetic saponite (trade name: Sumecton SA with 1 weight portion; By KunimineIndustries, Co., Ltd. makes) be dispersed in the ion exchange water of 99 weight portions and prepare first kind of dispersion liquid.Then, by with first kind of dispersion liquid of 9.000 weight %, colloidal alumina (trade name: the Aluminasol 520 of 9.000 weight %; By Nissan Chemical Industries, Ltd. makes; The average grain diameter that the BET method is measured: 20nm; Solid concentration: 20 weight %; Water), cataloid (trade name: the Snowtex 20 of 2.400 weight % decentralized medium:; By Nissan Chemical Industries, Ltd. makes; The average grain diameter that the BET method is measured: 20nm; Solid concentration: 20 weight %; Water), the Sodium Caprylate of 0.014 weight % is (available from Tokyo Chemical Industry Co. decentralized medium:, Ltd.), paratoluenesulfonic acid sodium salt (available from Nacalai Tesque Inc.) and the ion exchange water of 79.584 weight % of 0.002 weight % mix, and prepares second kind of dispersion liquid.C laminar surface to base material carries out sided corona treatment, subsequently second kind of decentralized medium is applied on the surface of sided corona treatment and dry.So, on the C laminar surface, form cover layer.Regulate the amount of second kind of decentralized medium of coating, make that the weight of the cover layer per unit area on the dried C laminar surface is 0.2g/m
2Drying is to carry out under 60 ℃ in dryer temperature.In following examples, use the cover film of so making as base material.
[embodiment 1]
By with the cataloid (trade name: SnowtexST-XS of 15g as inorganic particulate (A); By Nissan Chemical Industries, Ltd. makes; The average grain diameter that the Sears method is measured: 4-6nm; Solid concentration: 20 weight %; Decentralized medium: water) and 25g as the cataloid (trade name: Snowtex ST-ZL of inorganic particulate (B); By Nissan Chemical Industries, Ltd. makes; The average grain diameter that the BET method is measured: 78nm; Solid concentration: 40 weight %; Decentralized medium: water) mix, use magnetic stirrer subsequently, preparation mixed inorganic particle dispersion liquid with 60g water.Provided inorganic particulate (A) in the table 1 and (B) for the ratio of whole inorganic particulate.Use wire bar applicator that the mixed inorganic particle dispersion liquid is coated on the cover layer of base material.Then, by removing decentralized medium, obtain inorganic particle layer wherein and be positioned at layered article on the base material 60 ℃ of dryings.The inorganic particle layer of the layered article that obtains has the good uniformity and consistency (referring to Fig. 1) and good intensity.
[embodiment 2]
By 5g is mixed with 70g water as the Snowtex ST-ZL of inorganic particulate (B) as the Snowtex ST-XS of inorganic particulate (A) and 25g, use magnetic stirrer subsequently, preparation mixed inorganic particle dispersion liquid.Provided inorganic particulate (A) in the table 1 and (B) for the ratio of whole inorganic particulate.Use wire bar applicator that the mixed inorganic particle dispersion liquid is coated on the cover layer of base material.Then, by removing decentralized medium, obtain inorganic particle layer wherein and be positioned at layered article on the base material 60 ℃ of dryings.The inorganic particle layer of the layered article that obtains has the good uniformity and consistency (referring to Fig. 2) and good intensity.
[comparing embodiment 1]
25g is mixed with 75g water as the Snowtex ST-ZL of inorganic particulate (B), use magnetic stirrer subsequently, preparation inorganic particulate dispersion liquid.Provided the ratio of inorganic particulate (B) in the table 1 for whole inorganic particulate.Use wire bar applicator that the inorganic particulate dispersion liquid is coated on the cover layer of base material.Then, by removing decentralized medium, obtain inorganic particle layer wherein and be positioned at layered article on the base material 60 ℃ of dryings.The inorganic particle layer of the layered article that obtains, this layer only is made up of inorganic particulate (B), has the good uniformity, but consistency poor (referring to Fig. 3).In addition, the intensity of this layer is also not enough.
The embodiment of II, second embodiment
Embodiment and comparing embodiment about second embodiment of the invention are provided below.
Assessment is as the characteristic of anti-dazzle film in the following method that provides.
＜glossiness 〉
Glossiness is to use gloss meter (GM-3D is by Murakami Color Research LaboratoryCo., and Ltd. makes) to measure under 60 ° of incidence angles.
＜anti-dazzle property 〉
Visual observation fluorescent lamp reflected image state.The situation of fluorescent lamp reflected image clear-cut is judged as " anti-dazzle property is poor ", and represents with symbol " * ".There is a little unsharp situation to be judged as " anti-dazzle property is medium " fluorescent lamp reflected image profile, with symbol " Δ " expression.The unsharp situation of fluorescent lamp reflected image profile is judged as " anti-dazzle property is good ", with symbol " zero " expression.
The outward appearance of＜inorganic particulate laminar surface 〉
Observe the surface of inorganic particle layer with SEM (SEM), and use the uniformity and the consistency of SEM image evaluation inorganic particle layer.
The intensity of＜inorganic particle layer 〉
Intensity in order to following method evaluation layer shape goods inorganic particle layer.
With cleaning the inorganic particulate laminar surface 20 times before and after the laboratory tissue paper (trade name: Kimwipe, by Crecia Co., Ltd. makes), and measure clean before and after the variation of mist degree.This variation is more little, and inorganic particle layer intensity is high more.Mist degree is according to JIS K7105, by the direct-reading mist degree computer (HGM-2DF that is used for illuminant-C; By Suga Test Instruments Co., Ltd. makes) measure.
＜pencil hardness 〉
Under the load of 1kgf, measure the pencil hardness of inorganic particle layer according to JIS K5400.
[embodiment 3]
Prepare the mixed inorganic particle dispersion liquid by following method: with the cataloid (trade name: Snowtex ST-XS of 35g as inorganic particulate (A); By Nissan Chemical Industries, Ltd. makes; The average grain diameter that the Sears method is measured: 4-6nm; Solid concentration: 20 weight %; Water), 140g is as the cataloid (trade name: Snowtex ST-ZL of inorganic particulate (B) decentralized medium:; By Nissan Chemical Industries, Ltd. makes; The average grain diameter that the BET method is measured: 78nm; Solid concentration: 40 weight %; Decentralized medium: water) and 14g as the SiO 2 powder (trade name: Seahoster KE-P100 of inorganic particulate (C); By Nippon Shokubai Co., Ltd. makes; Average grain diameter by the measurement of laser diffraction and scattering method: 1.01 μ m) join in the 511g pure water, use high shear fluid processor (trade name: Microfluidizer subsequently; Make by Microfluidics) depress in adding of 20MPa and carry out dispersion treatment.Inorganic particulate (A), (B) have been provided in the table 3 and (C) for the ratio of whole inorganic particulate.(by Fuji Photo Film Co., Ltd. makes to use wire bar applicator that the mixed inorganic particle dispersion liquid is coated on triacetylcellulose film; Pencil hardness: HB).Then, at 60 ℃ of dry decentralized media, thereby form inorganic particle layer.The glossiness of the inorganic particle layer that obtains is 55.4.The profile of fluorescent lamp reflected image is unintelligible.Inorganic particle layer has high strength and pencil hardness is H.The outward appearance of inorganic particle layer is good.The non-dizzy film of so making of only being made up of inorganic particulate has good static electricity resistance, weatherability and solvent resistance.
[embodiment 4]
By 70g is joined in the 476g pure water as the Seahoster KE-P100 of inorganic particulate (C) as the Snowtex ST-ZL of inorganic particulate (B) and 14g as Snowtex ST-XS, the 140g of inorganic particulate (A), use Microfluidizer to depress subsequently and carry out dispersion treatment, preparation mixed inorganic particle dispersion liquid in adding of 20MPa.Provided in the table 3 inorganic particulate (A), (B) and (C) for the ratio of whole inorganic particulate.Use this mixed inorganic particle dispersion liquid, on triacetylcellulose film, form inorganic particle layer in the mode identical with embodiment 3.The glossiness of the inorganic particle layer that obtains is 61.6.The profile of fluorescent lamp reflected image is unintelligible.Inorganic particle layer has high strength and pencil hardness is H.The outward appearance of inorganic particle layer is good.The non-dizzy film of so making of only being made up of inorganic particulate has good static electricity resistance, weatherability and solvent resistance.
[embodiment 5]
By 70g is joined in the 462g pure water as the Seahoster KE-P100 of inorganic particulate (C) as the Snowtex ST-ZL of inorganic particulate (B) and 28g as Snowtex ST-XS, the 140g of inorganic particulate (A), use Microfluidizer to depress subsequently and carry out dispersion treatment, preparation mixed inorganic particle dispersion liquid in adding of 20MPa.Inorganic particulate (A), (B) have been provided in the table 3 and (C) for the ratio of whole inorganic particulate.Use this mixed inorganic particle dispersion liquid, on triacetylcellulose film, form inorganic particle layer in the mode identical with embodiment 3.The glossiness of the inorganic particle layer that obtains is 41.2.The profile of fluorescent lamp reflected image is unintelligible.Inorganic particle layer has high strength and pencil hardness is H.The outward appearance of inorganic particle layer is good.The non-dizzy film of so making of only being made up of inorganic particulate has good static electricity resistance, weatherability and solvent resistance.
[embodiment 6]
By with 35g as Snowtex ST-XS, the 70g of inorganic particulate (A) as the Snowtex ST-ZL of inorganic particulate (B) and 106g SiO 2 powder (trade name: Seahoster KE-W50 as inorganic particulate (C); By Nippon Shokubai Co., Ltd. makes; Average grain diameter by the measurement of centrifugal sedimentation method: 0.55 μ m) join in the 139g pure water, use magnetic stirrer subsequently, preparation mixed inorganic particle dispersion liquid.Inorganic particulate (A), (B) have been provided in the table 3 and (C) for the ratio of whole inorganic particulate.Use this mixed inorganic particle dispersion liquid, on triacetylcellulose film, form inorganic particle layer in the mode identical with embodiment 3.The glossiness of the inorganic particle layer that obtains is 26.1.The profile of fluorescent lamp reflected image is unintelligible.Inorganic particle layer has high strength and pencil hardness is H.The outward appearance of inorganic particle layer is good.The non-dizzy film of so making of only being made up of inorganic particulate has good static electricity resistance, weatherability and solvent resistance.
[embodiment 7]
Prepare the mixed inorganic particle dispersion liquid by following method: with 70g as Snowtex ST-XS, the 140g of inorganic particulate (A) as Snowtex ST-ZL, the 14g of inorganic particulate (B) as the Seahoster KE-P100 of inorganic particulate (C) and 14g SiO 2 powder (trade name: Seahoster KE-P50 as inorganic particulate (C); By Nippon Shokubai Co., Ltd. makes; Average grain diameter by the measurement of laser diffraction and scattering method: 0.54 μ m) join in the 462g pure water, use Microfluidizer to depress subsequently and carry out dispersion treatment in adding of 20MPa.Inorganic particulate (A), (B) have been provided in the table 3 and (C) for the ratio of whole inorganic particulate.Use this mixed inorganic particle dispersion liquid, on triacetylcellulose film, form inorganic particle layer in the mode identical with embodiment 3.The glossiness of the inorganic particle layer that obtains is 32.8.The profile of fluorescent lamp reflected image is unintelligible.Inorganic particle layer has high strength and pencil hardness is H.The outward appearance of inorganic particle layer is good.The non-dizzy film of so making of only being made up of inorganic particulate has good static electricity resistance, weatherability and solvent resistance.
[reference example 1]
By 70g is joined in the 245g pure water as the Snowtex ST-ZL of inorganic particulate (B) as the Snowtex ST-XS of inorganic particulate (A) and 140g, use magnetic stirrer subsequently, preparation mixed inorganic particle dispersion liquid.Provided inorganic particulate (A) in the table 3 and (B) and (C) for the ratio of whole inorganic particulate.Use this mixed inorganic particle dispersion liquid, on triacetylcellulose film, form inorganic particle layer in the mode identical with embodiment 3.The glossiness of the inorganic particle layer that obtains is 125.7.The clear-cut of fluorescent lamp reflected image means the anti-dazzle property deficiency of inorganic particle layer.Inorganic particle layer has high strength and pencil hardness is H.The outward appearance of inorganic particle layer is good.
[comparing embodiment 2]
By 140g is joined in the 546g pure water as the Seahoster KE-P100 of inorganic particulate (C) as the Snowtex ST-ZL of inorganic particulate (B) and 14g, use Microfluidizer to depress subsequently and carry out dispersion treatment, preparation mixed inorganic particle dispersion liquid in adding of 20MPa.Provided inorganic particulate (B) in the table 3 and (C) for the ratio of whole inorganic particulate.Use this mixed inorganic particle dispersion liquid, on triacetylcellulose film, form inorganic particle layer in the mode identical with embodiment 3.The glossiness of the inorganic particle layer that obtains is 85.4.The profile of fluorescent lamp reflected image has a little unintelligible.Leaving away of inorganic particle layer appears in the evaluation process of inorganic particle layer intensity.Pencil hardness is low to HB.The outward appearance of inorganic particle layer is good.
[comparing embodiment 3]
By 280g is joined in the 392g pure water as the Seahoster KE-P100 of inorganic particulate (C) as the Snowtex ST-XS of inorganic particulate (A) and 28g, use Microfluidizer to depress subsequently and carry out dispersion treatment, preparation mixed inorganic particle dispersion liquid in adding of 20MPa.Provided inorganic particulate (A) in the table 3 and (C) for the ratio of whole inorganic particulate.Use this mixed inorganic particle dispersion liquid, on triacetylcellulose film, form inorganic particle layer in the mode identical with embodiment 3.The glossiness of the inorganic particle layer that obtains is 46.4.The profile of fluorescent lamp reflected image is unintelligible.Inorganic particle layer has high strength and pencil hardness is H.In outward appearance is observed, find many crackles.
Table 1
| Da(nm) | Db(nm) | Va/(Va+Vb) | Vb/(Va+Vb) | (Wa+Wb)/Wt | |
| Embodiment 1 | 4～6 | 78 | 0.23 | 0.77 | 0.13 |
| Embodiment 2 | 4～6 | 78 | 0.09 | 0.97 | 0.11 |
| Comparing embodiment 1 | - | 78 | 0.00 | 1.00 | 0.10 |
Table 2
| Haze change | Outward appearance | |
| Embodiment 1 | +2.0 | Well |
| Embodiment 2 | +2.0 | Well |
| Comparing embodiment 1 | +9.7 | Difference |
Table 3
| Da [nm] | Db [nm] | Dc [μm] | Va/V | Vb/V | Vc/V | (Wa+Wb+Wc) /Wt | |
| Embodiment 3 | 4-6 | 78 | 1.01 | 0.09 | 0.73 | 0.18 | 0.11 |
| Embodiment 4 | 4-6 | 78 | 1.01 | 0.17 | 0.67 | 0.17 | 0.12 |
| Embodiment 5 | 4-6 | 78 | 1.01 | 0.14 | 0.57 | 0.29 | 0.14 |
| Embodiment 6 | 4-6 | 78 | 0.55 | 0.13 | 0.50 | 0.38 | 0.16 |
| Embodiment 7 | 4-6 | 78 | *1 | 0.14 | 0.57 | 0.29 | 0.14 |
| Reference example 1 | 4-6 | 78 | - | 0.20 | 0.80 | 0.00 | 0.10 |
| Comparing embodiment 2 | - | 78 | 1.01 | 0.00 | 0.80 | 0.20 | 0.10 |
| Comparing embodiment 3 | 4-6 | - | 1.01 | 0.67 | 0.00 | 0.33 | 0.12 |
V＝Va+Vb+Vc
*1:Dc=1.01 the combination of the particle of the particle of μ m and Dc=0.54 μ m.
Table 4
| Glossiness | Anti-dazzle property | Haze change | Pencil hardness | Outward appearance | |
| Embodiment 3 | 55.4 | ○ | +0.4 | H | Well |
| Embodiment 4 | 61.6 | ○ | +0.5 | H | Well |
| Embodiment 5 | 41.2 | ○ | +0.8 | H | Well |
| Embodiment 6 | 26.1 | ○ | +0.6 | H | Well |
| Embodiment 7 | 32.8 | ○ | +0.3 | H | Well |
| Reference example 1 | 125.7 | × | Free of data | H | Well |
| Comparing embodiment 2 | 85.4 | Δ | +1.5 | HB | Well |
| Comparing embodiment 3 | 46.4 | ○ | +0.0 | H | Difference |
Claims (5)
1, a kind of method of making layered article, described layered article comprise base material and the inorganic particle layer that forms on it, and described method comprises:
Preparation mixed inorganic particle dispersion liquid, it comprises the liquid dispersion medium that contains inorganic particulate (A) and inorganic particulate (B), condition (1), (2) and (3) that provide below are provided described mixed inorganic particle dispersion liquid;
The mixed inorganic particle dispersion liquid is coated on the base material, and
From the mixed inorganic particle dispersion liquid that is coated with, remove liquid dispersion medium, on base material, to form inorganic particle layer:
Condition (1): the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, and the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and Da≤0.15 * Db;
Condition (2): 0.01≤Va/ (Va+Vb)≤0.40, and 0.60≤Vb/ (Va+Vb)≤0.99, wherein Va and Vb are respectively inorganic particulate (A) and inorganic particulate (B) volume fractions based on inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A) and volume summation (B); With
Condition (3): 0.01≤(Wa+Wb)/Wt≤0.20, wherein Wa and Wb are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A) and the weight of inorganic particulate (B), and Wt is the weight of mixed inorganic particle dispersion liquid.
2, method according to claim 1, wherein inorganic particulate (A) and inorganic particulate (B) all are silica.
3, a kind of method of making layered article, described layered article comprise base material and the inorganic particle layer that forms on it, and described method comprises:
Preparation mixed inorganic particle dispersion liquid, it comprises the liquid dispersion medium that contains inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C), condition (1), (2) and (3) that provide below are provided described mixed inorganic particle dispersion liquid;
Described mixed inorganic particle dispersion liquid is coated on the base material, and
From the mixed inorganic particle dispersion liquid that is coated with, remove liquid dispersion medium, on base material, to form inorganic particle layer:
Condition (1): the average grain diameter Da of inorganic particulate (A) is 1 to 20nm, and the average grain diameter Db of inorganic particulate (B) is 30 to 300nm, and the average grain diameter Dc of inorganic particulate (C) is 0.4 to 10 μ m, and Da≤0.15 * Db;
Condition (2): 0.01≤Va/ (Va+Vb+Vc)≤0.45,0.45≤Vb/ (Va+Vb+Vc)≤0.98, and 0.01≤Vc/ (Va+Vb+Vc)≤0.45, wherein Va, Vb and Vc are respectively inorganic particulate (A), inorganic particulate (B) and inorganic particulate (C) volume fractions based on the inorganic particulate that is used to prepare the mixed inorganic particle dispersion liquid (A), (B) and volume summation (C); With
Condition (3): 0.01≤(Wa+Wb+Wc)/Wt≤0.30, wherein Wa, Wb and Wc are respectively the weight of inorganic particulate in the mixed inorganic particle dispersion liquid (A), the weight of inorganic particulate (B) and the weight of inorganic particulate (C), and Wt represents the weight of mixed inorganic particle dispersion liquid.
4, method according to claim 3, wherein inorganic particulate (A) and inorganic particulate (B) all are silica.
5, according to claim 3 or 4 described methods, wherein inorganic particulate (C) is a silica.
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