TW201313845A - Coating composition and coated article - Google Patents

Abstract

The present invention provides a coating composition capable of forming a coating having high weather resistance and high alkali resistance as well as sufficiently high transparency, especially suitable for forming an anti-reflection layer. Coating composition of the present invention comprises a curable resin and a silica containing metal-oxide particles. The curable resin is composed of at least one of hydrolyzable condensation compound and its partially hydrolyzed products. The molecules of the hydrolyzable condensation compound has an organic chain and a hydrolyzable silyl group bonded to each of two ends of the organic chain. The organic chain is composed of one group or more selected from alkylene group that may have substituent group, fluoro-alkylene group that may have substituent group, and ether group, and the organic chain has at least one of the alkylene group and fluoro-alkylene group.

Description

Covered composition and coated product

The present invention relates to a coated composition used for forming an antireflection layer or the like, and a coated article comprising a film formed of a cured product of the coated composition.

In response to a transparent display substrate provided on an outermost surface of an advertising display device such as a digital electronic signboard or the like, which has been highly noticeable in recent years, measures for reducing the light reflectance of the surface have been sought. When the light reflectance in the transparent substrate is lowered, for example, in an advertisement display device, there is an advantage that the visibility of an image is improved, and in a solar cell, the amount of light extracted to the solar cell increases. The advantage of increased power generation efficiency. As described above, in order to reduce the light reflectance of the surface of the transparent substrate, an antireflection layer is conventionally provided on the surface of the substrate.

An example of the coating composition conventionally used for forming the antireflection layer is hydrolyzable organic decane or a partially hydrolyzed condensate thereof. For example, the coating composition described in Patent Document 1 contains the following in a mixed state of the hydrolyzable organodecane (A), the hydrolyzable organodecane (B), and the cerium oxide-based metal oxide particles described below. (A) and the first hydrolyzate after hydrolysis of the hydrolyzable organodecane of the following (B), and the hydrolyzable organodecane of the following (A) and the hydrolyzable organodecane of the following (C) are copolymerized. The terminal has a second hydrolyzate of a fluorine-substituted alkyl group.

(A) The general formula is a hydrolyzable organodecane represented by SiX ₄ (X is a hydrolyzable group).

(B) Hydrolyzable organodecane having two or more ruthenium dioxide atoms in its molecule, and a linear portion of a ruthenium dioxide atom has a water-repellent group and an alkoxy group bonded thereto.

(C) Hydrolyzable organodecane having a fluorine-substituted alkyl group.

Thereby, an antireflection layer having high antireflection property and excellent in chemical resistance and antifouling property can be formed.

However, in the case where the transparent substrate provided outside the room is provided with an antireflection layer, the antireflection layer may be easily deteriorated by exposure to ultraviolet rays or salt. Further, since the substrate disposed outside the house is required to have high strength, the substrate is often formed of tempered glass containing alkali ions. In the case where an antireflection layer is provided on a substrate formed of such a tempered glass, there is a problem that the antireflection layer is easily eroded by the alkali component and is easily deteriorated.

Therefore, it is sought to maintain good transparency of the antireflection layer and to improve its weather resistance and alkali resistance.

[Advanced technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-99828

The present invention has been made in view of the above circumstances, and an object thereof is to provide a coating film having sufficiently high transparency and a film having sufficiently high transparency, and particularly suitable for forming a coating composition for forming an antireflection layer.

Moreover, an object of the present invention is to provide a coated article comprising a film formed of a cured product of the coated composition.

The coating composition of the present invention contains a curable resin and a ceria-based metal oxide particle, and the curable resin is composed of at least one of a hydrolyzable condensable compound and a partially hydrolyzed product thereof, and the molecule of the hydrolyzable condensable compound And an organic chain and a hydrolyzable alkylene group respectively bonded to both ends of the organic chain, wherein the organic chain is selected from the group consisting of an alkyl group which may have a substituent, a fluorine alkyl group which may have a substituent, and an ether group More than one of the groups is constituted, and the organic chain has at least one of the alkylene group and the fluorine alkyl group.

The hydrolysis-condensable compound preferably contains a compound represented by the following structural formula (1).

R ¹ _q X _3-q Si-(CH ₂ ) _p -SiX _3-r R ¹ _r (1)

R ¹ represents an organic group, and in the case where a plurality of R ¹ are present in one molecule, the ones are the same or different from each other. X represents a hydrolyzable group, and a plurality of X in one molecule are the same or different from each other. p represents an integer from 1 to 10. q represents an integer from 0 to 2. r represents an integer from 0 to 2.

The coated article of the present invention comprises a film formed of the above-mentioned coated composition.

When the coating film of the present invention is formed into a film, the film has sufficiently high transparency and exhibits high weather resistance and alkali resistance.

The coating composition of the present embodiment contains a curable resin and ceria-based metal oxide particles.

The curable resin is a resin component which is cured when the coating composition forms a film, and the cured resin of the curable resin constitutes a matrix of the film.

The curable resin is composed of at least one of a hydrolyzable condensable compound and a partially hydrolyzed condensate thereof. The molecule of the hydrolyzable condensable compound has an organic chain and a hydrolyzable decyl group bonded to both ends of the organic chain. The organic chain is selected from the group consisting of an alkylene group which may have a substituent, a fluorine-extended alkyl group which may have a substituent, and at least one or more of the ether groups. Further, the organic chain has at least one of an alkylene group which may have a substituent and a fluorine alkyl group which may have a substituent. That is, the organic chain has the following conditions: a case where only an alkylene group is formed, a case where only a fluorine alkyl group is formed, a case where an alkyl group and a fluorine alkyl group are formed, and two or more alkyl groups and The case where the ether group is composed, the case where two or more fluorine alkyl groups and an ether group are formed, and the case where the alkyl group, the fluorine alkyl group and the ether group are constituted. Further, in the present specification, the ether group is a divalent group composed only of oxygen, and the ether group is bonded to a carbon atom in an alkylene group or a fluorine alkyl group.

The coating composition contains such a curable resin to maintain the high transparency of the coating formed of the coating composition, and to improve the mechanical strength of the coating, and further to impart high weather resistance, alkali resistance, and salt water resistance to the coating. It can be considered that the proportion of the siloxane coupling in the film is small due to the presence of the organic chain as described above in the curable resin. In other words, it is presumed that the proportion of the siloxane coupling which is easily cut off by the external attack is reduced, so that the durability of the film is improved.

Among the hydrolyzable condensable compounds, the hydrolyzable alkylene group is represented by the following formula (2).

-SiX _3-m R ¹ _m (m is an integer from 0 to 2) ...(2)

X in the formula (2) represents a hydrolyzable group, and in the case where a plurality of X are present, a plurality of Xs may be the same or different from each other. R ¹ represents a monovalent hydroxyl group, and in the case where R ¹ is plural, a plurality of Rs may be the same or different from each other.

The R ¹ is not particularly limited as long as it is a monovalent hydroxyl group, and a monovalent hydroxyl group having 1 to 8 carbon atoms is suitable. Preferable examples of R ¹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. When the carbon number of R ¹ is 3 or more, R ¹ may be linear such as n-propyl or n-butyl, or may have a branch such as isopropyl, isobutyl or t-butyl.

Examples of X include an alkoxy group, an ethoxy group, an anthracenyl group (-ON=CR(R')), an alkenyloxy group (-OC(R)=C(R')R"), and an amine group. Aminooxy (-ON(R)R'), decyloxy (-N(R)-C(=O)-R') (wherein R, R', R" are, for example, each independently It is a hydrogen atom or a monovalent hydroxyl group, etc., a halogen or the like.

In the case where X is an alkoxy group, the hydrolyzable decyl group is represented, for example, by the following formula (2a).

-Si(OR ² ) _3-m R ¹ _m (m is an integer from 0 to 2) ... (2a)

R ¹ in the formula (2a) is a monovalent hydroxyl group as in the case of the formula (2), and in the case where a plurality of R ¹ are present, the plurality of Rs may be the same or different from each other. R ² in the formula (2a) is a monovalent hydroxyl group as in the case of the formula (2), and in the case where a plurality of R ² are present, the plurality of Rs may be the same or different from each other.

The R ² is not particularly limited as long as it is a monovalent hydroxyl group, but a monovalent hydroxyl group having 1 to 8 carbon atoms is suitable. Preferable examples of R ² include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. When the carbon number of R ² is 3 or more, R ² may have a linear form such as n-propyl or n-butyl, or may have a branch such as isopropyl, isobutyl or t-butyl. .

In the molecule which hydrolyzes the condensable compound, a hydrolyzable alkylene group is bonded to both ends of each organic group as described above, but a hydrolyzable decyl group may be further bonded to the organic group at a position other than the above. That is, the molecule of the hydrolyzable condensable compound may have two or more hydrolyzable alkylene groups. For example, in the case where the organic group has an alkylene group, a hydrolyzable decyl group may be bonded to the alkylene group as a substituent, and in the case where the organic group has a fluoroalkyl group, hydrolyzability may also be employed. A decyl group is bonded to the fluoroalkyl group as a substituent. The upper limit of the number of hydrolyzable alkylidene groups in the molecule of the hydrolysis-condensable compound is not particularly limited.

The length of the organic chain in the molecule of the hydrolyzable condensable compound is not particularly limited, but it is preferably in the range of 1 to 10 atoms arranged side by side in the organic chain and sequentially bonded. In this case, the amount of the organic component constituting the cured product of the hydrolyzable condensable compound is appropriately suppressed, so that the UV resistance of the film formed of the coated composition is sufficiently improved. In addition, the good compatibility between the hydrolysis-condensable compound and the other components such as a solvent in the coating composition is ensured. Therefore, the transparency of the film formed of the coating composition is sufficiently good and the film is less likely to cause appearance spots.

The hydrolyzable condensable compound is particularly preferably a compound represented by the following structural formula (1). In this case, the alkali resistance, the salt water resistance, and the UV resistance of the film formed of the coating composition are extremely excellent, and the transparency of the film is sufficiently improved.

R ¹ _q X _3-q Si-(CH ₂ ) _p -SiX _3-r R ¹ _r (1)

R ¹ represents an organic group, and in the case where a plurality of R ¹ are present in one molecule, the two are the same or different from each other. X represents a hydrolyzable group, and a plurality of X in one molecule are the same or different from each other. The details of R ¹ and X in the formula (1) are the same as those in the formula (2).

In the formula (1), p represents an integer of 1 to 10, and particularly preferably an integer of 1 to 5. When the p is 10 or less, the amount of the organic component constituting the cured product of the hydrolyzable condensable compound is appropriately suppressed, so that the UV resistance of the film formed of the coated composition is sufficiently improved. In addition, since the good compatibility between the hydrolysis-condensable compound and the other components such as a solvent in the coating composition is ensured, the transparency of the coating film formed of the coating composition is sufficiently good and the coating film is less likely to cause appearance spots.

q in the formula (1) represents an integer of 0 to 2, and r represents an integer of 0 to 2. It is preferred that q and r are 0 or 1, and further preferably 0.

The ratio of the compound represented by the structural formula (1) to the entire hydrolyzable condensable compound is not particularly limited, but is preferably in the range of 20 to 100% by mass, particularly preferably in the range of 50 to 100% by mass.

In addition to the compound represented by the structural formula (1), the compound which can be contained in the hydrolysis-condensable compound is not particularly limited, and specific examples thereof include compounds represented by the following formulas (11) to (14).

[Chemical 1]

(H ₃ CO) ₃ Si-(CH ₂ ) ₂ -(CF ₂ ) ₆ -(CH ₂ ) ₂ -Si(OCH ₃ ) ₃ (11)

The coating composition is preferably a material that does not contain a matrix constituting the film, in addition to the curable resin. In other words, it is preferable that the coating composition contains only the curable resin as the material constituting the substrate.

In addition, the coating composition may further contain a material other than the curable resin, for example, in order to ensure high weather resistance, alkali resistance, salt water resistance, and the like of the coating film formed of the coating composition, for example, SiX ₄ (X is The hydrolyzable organic decane represented by the hydrolyzable group or the like, the hydrolysis condensate thereof (polysiloxane), epoxy decane or the like is used as a material constituting the matrix of the film. However, when these materials are mixed in the coating composition, the durability of the film is lowered and the mechanical strength of the film is lowered. Therefore, when the coating composition contains a material constituting the matrix of the coating film other than the curable resin, the ratio is preferably less than 5% by mass based on the total amount of the material constituting the matrix of the coating film.

On the other hand, the cerium oxide-based metal oxide particles can bring about a low refractive index of the coating film formed by the coating composition, and can also improve the strength of the coating film. Among the coating films formed of the coating composition, the cerium oxide-based metal oxide particles are dispersed in a matrix composed of a cured product of a curable resin.

Examples of the cerium oxide-based metal oxide particles include non-hollow particles and hollow particles. Non-hollow particles are particles with no voids inside. The hollow particle system has an outer shell formed of a cerium oxide-based metal oxide, and the inner side of the outer shell is formed as a hollow particle.

The non-hollow particles are not particularly limited, and examples thereof include cerium oxide particles having no voids therein. When the coating composition contains the cerium oxide particles, the mechanical strength of the coating film formed by the coating composition is improved, and the surface smoothness and crack resistance of the coating film can be improved. The form of the cerium oxide particles is not particularly limited, and may be, for example, a powder form or a sol form. In the case where the cerium oxide particles are in a colloidal form, that is, in the case of using colloidal cerium oxide, there is no particular limitation, but for example, a hydrophilic organic solvent such as water-dispersible colloidal cerium oxide or alcohol is used. Dispersive colloidal cerium oxide and the like. In general, the colloidal cerium oxide contains 20 to 50% by mass of cerium oxide as a solid component, and the value of the cerium oxide particles in the coating composition can be determined by this value. The content of the cerium oxide particles in the coating composition is not particularly limited, but is preferably in the range of 0.1 to 30% by mass based on the total amount of the solids in the coating composition. When the content of the cerium oxide particles is 0.1% by mass or more, the mechanical strength of the film is sufficiently improved, and the surface smoothness and crack resistance of the film are sufficiently improved, and when the content is 30% by mass or less, the content is 30% by mass or less. The increase in the refractive index of the film is moderately suppressed.

Further, examples of the hollow particles include hollow ceria particles. The hollow ceria particle system is provided with a shell (case) made of a ceria-based inorganic oxide, and has void particles formed therein. The outer shell composed of the cerium oxide-based inorganic oxide is formed, for example, of only cerium oxide, or a composite oxide composed of an inorganic oxide other than cerium oxide and cerium oxide, or has a composition of cerium oxide. A two-layer structure of a layer and a layer composed of a composite oxide. The outer casing may be porous having pores formed therein, and the pores of the outer casing may be closed to seal the cavity as described below.

The outer casing may also have a plurality of layers including a first layer and a second layer covering the first layer. In this case, the pores formed in the first layer are occluded by the second layer, thereby densifying the outer casing and sealing the void inside the outer casing.

The thickness of the first layer is preferably in the range of 1 to 50 nm, and particularly preferably in the range of 5 to 20 nm. When the thickness of the first layer is 1 nm or more, the strength of the outer casing is sufficiently increased to maintain the shape of the hollow particles. Further, when the second layer is formed, the partially hydrolyzed product of the organic ruthenium compound or the like is less likely to enter the pores of the core particles, and the core particle constituent component is easily removed. Further, when the thickness of the first layer is 50 nm or less, the ratio of the voids in the hollow ceria particles is appropriately maintained, so that the refractive index of the film can be sufficiently lowered by the hollow ceria particles.

Further, the total thickness of the outer shell is preferably in the range of 1/50 to 1/5 of the average particle diameter of the hollow cerium oxide particles. Moreover, especially in the case of densifying the outer casing, the thickness of the second layer is preferably in the range of 20 to 49 nm.

The solvent used in the preparation of the hollow ceria particles, the gas immersed in the drying, and the like are present in the void. Moreover, the material for the precursor before the cavity is formed may remain in the cavity. Precursor materials are also slightly attached to the outer shell and remain in the majority of the cavity. Here, the precursor substance is a porous substance remaining after removing a part of its constituent components from the core particles for forming the first layer. As the core particles, porous composite oxide particles composed of an inorganic oxide other than cerium oxide and cerium oxide can be used. The inorganic oxide may be selected from the group consisting of Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , Ce ₂ O ₃ , P ₂ O ₅ , Sb ₂ O ₃ , MoO ₃ , ZnO _{2 .} One or two or more of WO ₃ and the like. As the inorganic oxide of two or more kinds, TiO ₂ -Al ₂ O ₃ , TiO ₂ -ZrO ₂ and the like are exemplified. Further, the above solvent or gas is also present in the pores of the porous substance. When the amount of removal of the constituent component at this time is increased, the volume of the void is increased, and hollow cerium oxide particles having a low refractive index can be obtained, and the coating film formed of the coating composition containing the hollow cerium oxide particles is a low refractive index. And excellent anti-reflection performance.

The average particle diameter of the hollow cerium oxide particles is preferably in the range of 5 nm to 2 μm. As described above, when the average particle diameter is 5 nm or more, the refractive index of the film can be sufficiently lowered by the hollow ceria particles. Further, when the average particle diameter is 2 μm or less, the transparency of the film is sufficiently improved, and the function of diffusion-reflection (Anti-Glare) is suppressed. In the case where the film is required to have particularly high transparency, the average particle diameter of the hollow cerium oxide particles is preferably in the range of 5 to 100 nm. Further, the average particle diameter is a value measured by a dynamic light scattering method.

The ratio of the hollow particles of the coating composition is not particularly limited, and is preferably in the range of 25 to 75% by mass based on the total solid content in the coating composition, and more preferably in the range of 30 to 70% by mass. When the ratio of the hollow particles is 75% by mass or less, the mechanical strength of the film formed of the coating composition is sufficiently improved, and when the ratio is 70% by mass or less, the effect is more remarkable. In addition, when the ratio is 25% by mass or more, the refractive index of the film can be sufficiently lowered by the hollow particles, and when the ratio is 30% by mass or more, the effect is more remarkable.

The coating composition preferably contains the above-mentioned ceria-based metal oxide particles as a filler, but may contain a filler other than the above-described ceria-based metal oxide particles. However, in order to ensure high weather resistance, alkali resistance, salt water resistance, and the like of the coating film formed of the coating composition, the content of the filler other than the cerium oxide-based metal oxide particles is preferably as small as possible, and the ratio is relatively large with respect to the coating. The total amount of the filler in the composition is preferably less than 5% by mass.

The coating composition preferably contains water as a solvent or a mixed solvent containing an aqueous and hydrophilic solvent as a solvent. The amount of water in the coating composition is preferably at least the amount necessary for the hydrolysis reaction of the curable resin. The hydrophilic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, and diacetone alcohol. , glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetonide; An ester such as ethyl acetate, butyl acetate or ethyl acetate, xylene, toluene or the like.

The ratio of the solvent in the coating composition is appropriately adjusted in accordance with the viscosity, the film forming property, and the like of the coating composition, and is preferably in the range of 10.0 to 99.9% by mass based on the entire coating composition.

The coating composition preferably contains a catalyst that promotes a hydrolysis reaction of the curable resin. As the catalyst, an acid such as hydrochloric acid, acetic acid or maleic acid, an amine compound such as sodium hydroxide (NaOH), ammonia, triethylamine, dibutylamine, hexylamine, octylamine or dibutylamine, and a salt of an amine compound are exemplified. Bases such as quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, such as potassium fluoride, fluoride fluoride, solid acid catalyst or solid base a medium (for example, an ion exchange resin catalyst, etc.), a metal salt of an organic carboxylic acid such as iron-2-ethylhexanoate, titanium naphthenate, zinc stearate or dibutyltin diacetate, titanium tetrabutoxide, Organic titanium esters such as tetraisopropyl titanium, dibutoxy-(bis-2,4-pentanedione) titanium, diisopropoxy (bis-2,4-pentanedione) titanium, tetrabutoxy Zirconium, tetraisopropoxy zirconium, dibutoxy-(bis-2,4-pentanedione) zirconium, diisopropoxy (bis-2,4-pentanedione) zirconium and other organic zirconium esters, three An organoaluminum compound such as an alkoxy aluminum compound such as aluminum isopropoxide or an aluminum chelate compound such as an aluminum acetonate complex, γ-aminopropyltrimethoxydecane or γ-aminopropyltriethoxydecane , N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane, N-( - aminoethyl) [gamma] aminopropyl triethoxy silane-substituted amine such as an alkyl silicon oxide. These catalysts may be used alone or in combination of two or more.

The proportion of the catalyst in the coating composition is appropriately set, but it is preferably in the range of 0.1 to 10% by mass based on the curable resin.

The coating composition may contain various components in addition to the above-described components, without departing from the spirit of the invention.

The coated composition is applied onto a suitable substrate, and a hydrolysis reaction is carried out by a curable resin in the coated composition on the substrate, and dried, and a cured product of the coated composition is provided on the substrate. The film formed. Thereby, as shown in FIG. 1, the coated article 3 provided with the base material 2 and the film 1 is obtained.

The substrate is not particularly limited, and examples thereof include an inorganic substrate typified by glass, a metal substrate, and an organic substrate typified by polycarbonate or polyethylene terephthalate. The shape of the substrate is not particularly limited, and examples thereof include a plate shape and a film shape. Further, one or more layers may be formed on the surface of the substrate.

The coated composition is applied to the surface of the substrate by an appropriate method. In this case, the coating method is not particularly limited, and examples thereof include brush coating, spray coating, dipping (dipping, dip coating), roll coating, casting coating, curtain coating, knife coating, and rotation. Various usual coating methods such as coating, flat coating, sheet coating, single coating, die coating, and rod coating.

After the coated composition applied on the surface of the substrate is dried, it is preferably subjected to heat treatment. By this heat treatment, the mechanical strength of the film is further improved. The temperature during the heat treatment is not particularly limited, and is preferably in the range of 60 to 300 ° C. In this case, the heating time is preferably in the range of 10 seconds to 20 minutes.

The thickness of the film formed on the surface of the substrate is appropriately set in accordance with the intended use or purpose, and is preferably in the range of 50 to 150 nm.

As described above, the film formed on the substrate has high transparency, and further has excellent alkali resistance, salt water resistance, and UV resistance. Therefore, even if the coated article having such a substrate and a film is exposed to the outside, the film is not easily deteriorated. Therefore, the high transparency and strength of the film can be maintained for a long period of time.

Further, since the coating composition forms a film having a low refractive index, the film is suitable as an antireflection layer. In other words, when the refractive index of the substrate is higher than the refractive index of the film, the film can be directly formed on the substrate, whereby the film can exhibit antireflection performance. Further, when the refractive index of the substrate is lower than the refractive index of the film, an intermediate layer having a higher refractive index than the film is formed on the substrate, and then a film is formed on the intermediate layer, that is, the film can exhibit antireflection performance. The intermediate layer can be formed using well known high refractive index materials. In addition, the refractive index of the intermediate layer is preferably 1.60 or more. In this case, the difference in refractive index between the film formed by the coating composition is sufficiently increased, so that the film exhibits excellent antireflection properties. . Further, in order to alleviate the coloration of the film, the intermediate layer may be composed of a plurality of layers having different refractive indices.

An example of a transparent substrate in which a film formed by coating a composition is used as an antireflection layer includes a substrate constituting the outermost surface of the display device and a side mirror of the automobile. , front glass, side glass, rear glass, other vehicle glass, building material glass, and a substrate constituting the outermost surface of the solar cell. Since the film formed of the coating composition has alkali resistance, salt water resistance, and UV resistance, the coating composition is particularly suitable for a substrate which constitutes the outermost surface of the display device disposed outside the room, and constitutes the outermost surface of the solar cell. A substrate or the like is placed on a substrate outside the house to form a film. Further, since the film has high alkali resistance, the substrate is also a tempered glass containing an alkali ion.

The present invention is not limited to the above embodiments, and various modifications can be made without departing from the scope of the invention.

[Examples]

Hereinafter, the present invention will be described based on examples. Further, the invention is not limited to the embodiments.

[Example 1]

5.26 parts by mass of bis-triethoxydecylethane (GELEST, Inc., No. SIB1817.0), and 72.23 parts by mass of propylene glycol monomethyl ether, and then blended with 0.11 parts by mass of a 0.1 N aqueous solution of nitric acid, stirred with stirring These were uniformly mixed to obtain a mixture.

To the mixture, a hollow cerium oxide particle dispersion (manufactured by Nippon Chemical Co., Ltd., isopropyl alcohol solvent, 20% solids, average particle diameter: 40 nm) was added to the mixture to make hollow cerium oxide particles/mixture (condensation). The ratio of the compound conversion) was 60/40 by mass based on the solid content. These were uniformly mixed at room temperature, and further stirred and mixed at 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Embodiment 2]

4.6 parts by mass of bisglycidyl decylethane (GELEST, Inc., No. SIB1817.0), and 70.39 parts by mass of propylene glycol monomethyl ether, and then mixed with 0.11 parts by mass of a 0.1 N aqueous solution of nitric acid, stirred with stirring These were uniformly mixed to obtain a mixture.

To the mixture, a hollow cerium oxide particle dispersion (a total of 20% by weight, an average particle diameter of 40 nm) of 1 7.5 parts by mass of a hollow cerium oxide particle dispersion (manufactured by Nisko Catalyst Chemical Co., Ltd.) was added to thereby condense hollow cerium oxide particles/mixture (condensation) The ratio of the compound conversion) was 70/30 by mass based on the solid content. These were uniformly mixed at room temperature, and further stirred and mixed at 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Example 3]

5.92 parts by mass of bisglycidyl decylethane (GELEST, Inc., No. SIB1817.0), and 72.82 parts by mass of propylene glycol monomethyl ether, and then mixed with 0.11 parts by mass of a 0.1 N aqueous solution of nitric acid, stirred with stirring These were uniformly mixed to obtain a mixture.

To the mixture, 13.75 parts by mass of a hollow cerium oxide particle dispersion (a total of 20% by weight of an isopropanol solvent, a solid content of 20 nm, an average particle diameter of 40 nm) was added to the mixture, whereby the hollow cerium oxide particles/mixture (condensed) The ratio of the compound conversion) was 55/45 by mass based on the solid content. The mixture was uniformly mixed at room temperature, and further stirred and mixed at a constant temperature of 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Example 4]

2.33 parts by mass of bis(triethoxyethoxy)alkylethane (GELEST, Inc., No. SIB1817.0), and 69.86 parts by mass of propylene glycol monomethyl ether, and then mixed with 0.11 parts by mass of a 0.1 N aqueous solution of nitric acid, stirred with stirring These were uniformly mixed to obtain a mixture.

To the mixture, 20 parts by mass of a hollow cerium oxide particle dispersion (manufactured by Nippon Chemical Co., Ltd., an isopropanol solvent, 20% solids, and an average particle diameter of 40 nm) was added to the mixture to thereby condense hollow cerium oxide particles/mixture (condensation) The ratio of the compound conversion) was 80/20 by mass based on the solid content. The mixture was uniformly mixed at room temperature, and further stirred and mixed at a constant temperature of 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Example 5]

Coupling bis-triethoxy decylethane (GELEST, Inc., No. SIB1817.0) 10.52 parts by mass, and 76.97 parts by mass of propylene glycol monomethyl ether, and then blending 0.11 parts by mass of a 0.1 N aqueous solution of nitric acid with stirring These were uniformly mixed to obtain a mixture.

To the mixture, a hollow cerium oxide particle dispersion (manufactured by Nippon Chemical Co., Ltd., an isopropanol solvent, 20% solids, an average particle diameter of 40 nm) was added in an amount of 5.0 parts by mass, whereby hollow cerium oxide particles/mixture (condensation) was added. The ratio of the compound conversion) was 40/60 by mass based on the solid content. The mixture was uniformly mixed at room temperature, and further stirred and mixed at a constant temperature of 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Embodiment 6]

搀 bis bis ethoxy decyl ethane (GELEST, Inc., No. SIB1832.0) 4.44 parts by mass, and 76.05 parts by mass of propylene glycol monomethyl ether, and then blended with 0.11 parts by mass of a 0.1 N aqueous solution of nitric acid, stirred with stirring These were uniformly mixed to obtain a mixture.

To the mixture, a hollow cerium oxide particle dispersion (a total of 20% by weight, an average particle diameter of 40 nm) was added to a hollow cerium oxide particle dispersion (manufactured by Nippon Kasei Chemical Co., Ltd., 15.0 parts by mass), whereby hollow cerium oxide particles/mixture (condensed) The ratio of the compound conversion) was 60/40 by mass based on the solid content. These were uniformly mixed at room temperature, and further stirred and mixed for 1 hour under a constant temperature of 25 ° C to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Comparative Example 1]

搀 聚 polymethoxy methoxy hydride (Mitsubishi Chemical Co., Ltd., product name methyl phthalate 51) 5.26 parts by mass, and propylene glycol monomethyl ether 73.57 parts by mass, and then 0.11 parts by weight of 0.1N aqueous solution of nitric acid, These were uniformly mixed with a stirrer to obtain a mixture.

To the mixture, a hollow cerium oxide particle dispersion (manufactured by Nippon Chemical Co., Ltd., isopropyl alcohol solvent, 20% solids, average particle diameter: 40 nm) was added to the mixture to make hollow cerium oxide particles/mixture (condensation). The ratio of the compound conversion) was 60/40 by mass based on the solid content. The mixture was uniformly mixed at room temperature, and further stirred and mixed at a constant temperature of 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Comparative Example 2]

4.6 parts by mass of polytrimethoxyethoxyalkylene, 0.49 parts by mass of polymethoxymethoxy alkane (product name methyl phthalate 51 manufactured by Mitsubishi Chemical Corporation), and 72.4 parts by mass of propylene glycol monomethyl ether. Further, 7.51 parts by mass of a 0.1 N aqueous solution of nitric acid was further blended, and the mixture was uniformly mixed with a stirrer to obtain a mixture.

To the mixture, a hollow cerium oxide particle dispersion (manufactured by Nippon Chemical Co., Ltd., isopropyl alcohol solvent, 20% solids, average particle diameter: 40 nm) was added to the mixture to make hollow cerium oxide particles/mixture (condensation). The ratio of the compound conversion) was 60/40 by mass based on the solid content. The mixture was uniformly mixed at room temperature, and further stirred and mixed at a constant temperature of 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[Comparative Example 3]

4.6 parts by mass of bis-triethoxyethoxyalkylethane, γ-glycidoxypropyltrimethoxydecane (manufactured by Momentive Performance Materials Japan Co., Ltd., No. TSL3350), 0.34 parts by mass, and propylene glycol monomethyl ether 72.55 parts by mass, 7.51 parts by mass of a 0.1 N aqueous solution of nitric acid was further blended, and the mixture was uniformly mixed with a stirrer to obtain a mixture.

To the mixture, a hollow cerium oxide particle dispersion (manufactured by Nippon Chemical Co., Ltd., isopropyl alcohol solvent, 20% solids, average particle diameter: 40 nm) was added to the mixture to make hollow cerium oxide particles/mixture (condensation). The ratio of the compound conversion) was 60/40 by mass based on the solid content. These were uniformly mixed at room temperature, and further stirred and mixed at a constant temperature of 25 ° C for 1 hour to prepare a coating composition.

The coated composition was allowed to stand for one hour from the point of preparation of the coated composition. Next, the coated composition was applied onto the surface of the tempered glass from which the stain had been removed in advance by a spin coater, and the coated composition was heated at 200 ° C for 10 minutes to form a film having a thickness of 150 nm. Thereby, a coated product composed of tempered glass and a film covering the tempered glass is obtained.

[evaluation experiment]

The evaluation experiments shown below were carried out for the coated articles obtained in the respective examples and comparative examples. The results are shown in Table 1 below.

(refractive index measurement)

The refractive index of the coating of the coated article was derived using a simple ellipsometer (manufactured by FILMTRICS, model F20).

(Abrasion resistance measurement)

The surface of the film was rubbed with an abrasion tester (manufactured by Shinto Scientific Co., Ltd., model HEIDON-14DR, steel wool #0000, 500 g load, 10 reciprocating). The change in the appearance of the film before and after the test was visually confirmed, and the case where the residual amount of the film in the experimental range was 50% or more was evaluated as "○", and the case where the residual amount was less than 50% was "x".

(transmittance measurement)

Using a spectrophotometer (manufactured by Hitachi, Ltd., model U-4100), the spectral transmittance in the range of 300-1500 nm at the time of irradiating light to the film was measured, and the transmission in the range of 400-1100 nm was derived based on the result. The average of the rates. In addition, in the case where the tempered glass alone, the transmittance was 91.3%.

(UV (UV) test)

Using a SUPER UV test apparatus (manufactured by Iwasaki Electric Co., Ltd., model SUV-W151), the film in the coated product was irradiated with ultraviolet light of 100 mW/cm ² at an ambient temperature of 80 ° C and a humidity of 70 RH%. Irradiation was carried out under conditions of 24 hours.

Next, the transmittance of the coated article was measured by the same method as in the case of the above-mentioned "transmittance measurement", and the amount of decrease in transmittance compared with the case of the above "transmittance measurement" was calculated.

(High temperature and high humidity experiment)

The coated product was exposed to an atmosphere of a temperature of 85 ° C and a humidity of 80% for 500 hours using a small-scale environmental test apparatus (manufactured by Espec Corporation, model SH-241).

Next, the transmittance of the coated article was measured by the same method as in the case of the above-mentioned "transmittance measurement", and the amount of decrease in transmittance compared with the case of the above "transmittance measurement" was calculated.

Based on the results, Examples 1 to 6 showed good light transmittance. Further, the amount of decrease in transmittance after UV irradiation is small, and the UV resistance is high. Further, since the amount of decrease in the transmittance after the high-temperature and high-humidity test was also small, it was evaluated that even if the alkali component was eluted from the tempered glass, the deterioration of the film was less likely to occur. As described above, the film systems of Examples 1 to 6 exhibited high durability.

Further, in Examples 1 to 4, the refractive index of the film was greatly reduced and the light transmittance was particularly good. Further, in addition to Example 4 in which the proportion of hollow cerium oxide was large, the abrasion resistance of the film in each of the examples was also high. Therefore, it was evaluated that the film strength was improved by using a specific hydrolysis-condensing compound in the present embodiment.

On the other hand, in Comparative Examples 1 and 2 in which the coating composition contained a considerable amount of polymethoxymethoxyoxane, the transparency after the high-temperature and high-humidity test was largely lowered. Further, in Comparative Example 3 in which the coating composition contained a considerable amount of γ-glycidoxypropyltrimethoxydecane, the transparency after the UV resistance test and after the high temperature and high humidity test was greatly lowered. Further, in Comparative Example 3, the abrasion resistance was low, and it was evaluated that the film was softened by using a considerable amount of γ-glycidoxypropyltrimethoxydecane.

1. . . Film

2. . . Substrate

3. . . Coating product

Fig. 1 is a schematic cross-sectional view showing a coated article according to an embodiment of the present invention.

1. . . Film

2. . . Substrate

3. . . Coating product

Claims (3)

A coating composition comprising a curable resin and a ceria-based metal oxide particle, wherein the curable resin is composed of at least one of a hydrolyzable condensable compound and a partially hydrolyzed product thereof, and the hydrolyzable condensable compound The molecule has an organic chain and a hydrolyzable decyl group bonded to both ends of the organic chain, and the organic chain is selected from the group consisting of an alkyl group which may have a substituent, a fluorine alkyl group which may have a substituent, and an ether group. More than one of the groups, and the organic chain has at least one of the alkylene group and the fluorine alkyl group. The coated composition of claim 1, wherein the hydrolyzable condensable compound contains a compound represented by the following structural formula (1), R ¹ _q X _3-q Si-(CH ₂ ) _p -SiX _3-r R ¹ _r (1) R ¹ represents an organic group, and in the case where a plurality of R ¹ are present in one molecule, these may be the same or different from each other, X represents a hydrolyzable group, and a plurality of X in one molecule They may be the same or different from each other, p represents an integer from 1 to 10, q represents an integer from 0 to 2, and r represents an integer from 0 to 2. A coated article comprising a film formed of the coated composition of the first or second aspect of the patent application.