TWI541303B - Coating compound and article coated with the coating compound - Google Patents

Description

Coating material composition, and coated article coated with the coating material composition

The present invention relates to a coating material composition and a coated article coated with the coating material composition.

On the uppermost surface of an image display device such as a display, a coating layer for use as a surface protection, reflection prevention, or the like is usually provided. On this coating layer, since there are many opportunities for a person to touch by hand, it is easy to attach a fingerprint. Therefore, the image display device has a problem that the attached fingerprint is conspicuous.

Therefore, a coating material composition has been developed since ancient times for forming a coating layer having a conspicuous fingerprint property (fingerprint resistance) even when touched with a finger.

For example, Patent Document 1 discloses a fingerprint-resistant coating material composition in which non-porous cerium oxide particles having a primary primary particle diameter of 50 nm or more and 200 nm or less, a tetrafunctional alkoxy decane, and The phenyl group is hydrolyzed with a decane compound, and the non-porous cerium oxide particles contained in the total solid content are 5% by mass or more and 30% by mass or less. In this case, since the fingerprint-resistant coating material composition contains a decane compound having a phenyl group to improve the lipophilicity of the coating layer, even if the coating layer is artificially Touching, it is not easy to produce conspicuous fingerprints.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2011-192506.

In recent years, devices such as smart phones and tablet computers with touch panel displays have become increasingly popular. In smart phones and tablets, not only do you need to touch your fingers, but you can also slide and pull your fingers on the display to enlarge and reduce the image. Therefore, in recent years, the coating layer provided on the image display device is required to have not only fingerprint resistance but also high sliding property when touched by a finger.

However, in the conventional technique disclosed in Patent Document 1, the slidability of the coating layer is insufficient.

In view of the above problems, an object of the present invention is to provide a coating material composition for forming a coating layer having both good fingerprint resistance and slidability, and a coating layer containing both good fingerprint resistance and slidability. Covered items.

The coating material composition according to the first aspect of the present invention includes: (a) porous cerium oxide particles; and (b) a reactive component having at least one of hydrolysis condensation reaction property and dehydration condensation reactivity; At least one selected from the condensation product of the reactive component, wherein the reactive component comprises: (b1) a tetrafunctional reactive decane compound; (b2) a reactive decane compound having a phenyl group; and (b3) Olefin with a phenyl group and a reactive group.

According to a second aspect of the present invention, in a first aspect of the present invention, The ratio of the (b3) component in the total solid content in the coating material composition is preferably in the range of from 1 to 15% by mass.

According to a third aspect of the present invention, in the first aspect or the second aspect of the present invention, the ratio of the component (b2) is 10% by mass or more and 30% based on the total solid content in the coating material composition. The range of mass % or less.

In a fourth aspect of the invention, in any one of the first to third aspects of the invention, the (b3) component has a weight average molecular weight of from 800 to 1200.

In a fifth aspect of the invention, in any one of the first to fourth aspects of the invention, the component (b3) comprises a sterol terminal diphenyl sulfoxane-dimethyl decane copolymer.

In a sixth aspect of the invention, in any one of the first to fifth aspects of the invention, the component (b2) contains a compound having an alkylene group between a ruthenium atom and a phenyl group.

A seventh aspect of the invention is a coated article comprising a coating layer formed of a coating material composition according to any one of the first to sixth aspects of the invention.

The coating material composition of the present invention can form a coating layer excellent in fingerprint resistance and slidability.

Further, in the coated article of the present invention, the coating layer provided in the coated article has good fingerprint resistance and slidability at the same time.

1‧‧‧covered items

2‧‧‧coating layer

3‧‧‧Substrate

4‧‧‧Intermediate

Fig. 1 is a cross-sectional view showing the structure of a coated article of the present invention.

The coating material composition of the present embodiment, comprising: (a) porous ceria particles; and (b) a reactive component having at least one of hydrolysis condensation reactivity and dehydration condensation reactivity, and reactivity At least one selected from the condensation products of the components.

Further, the reactive component contains: (b1) a tetrafunctional reactive decane compound; (b2) a reactive decane compound having a phenyl group; and (b3) an eucalyptus oil having a phenyl group and a reactive group.

Explain the various ingredients.

[(a) ingredient]

The component (a) is composed of porous ceria particles. The average primary particle diameter of the component (a) is preferably in the range of 30 nm or more and 100 nm or less. This average primary particle size is measured by dynamic light scattering. When the average primary particle diameter of the component (a) is within the above range, moderate unevenness can be formed on the surface of the coating layer composed of the coating material composition. Thereby, the transparency of the coating layer is continuously maintained, and the grease on the coating layer is easily smudged. Therefore, the finger marks of the coating layer will be less noticeable. Further, the component (a) can impart a moderate strength to the coating layer. Further, by including the component (a) in the coating layer, it is possible to lower the refractive index of the coating layer. Therefore, the coating layer is particularly suitable for use in anti-reflection applications. The pores of the component (a) are preferably more than 20%. The void ratio is the ratio of the volume of the pores within the particles relative to the volume of expression of the particles. The void ratio is measured based on a transmission electron microscope image.

The component (a) preferably contains at least one of hollow cerium oxide particles and mesoporous particles.

The hollow cerium oxide particles are, for example, provided with a shell composed of a cerium oxide-based inorganic oxide, and are surrounded by a shell to form pores inside the hollow cerium oxide particles. The outer shell of the hollow ceria particles may be composed of a single layer formed of ceria, or may be a single layer formed of a composite oxide of an inorganic oxide other than ceria and ceria. Further, the outer shell of the hollow ceria particles may be composed of two or more layers laminated as described above. The thickness of the outer casing is, for example, 1 nm or more and 50 nm or less, preferably 5 nm or more and 20 nm or less. Further, the thickness of the outer shell is preferably in the range of 1/50 or more and 1/5 or less of the average primary particle diameter of the hollow cerium oxide particles. Further, the average primary particle diameter of the hollow cerium oxide particles is preferably in the range of 5 nm or more and 2 μm or less. When the average primary particle diameter is 5 nm or more, the refractive index of the coating layer can be effectively achieved. Further, when the average primary particle diameter is 2 μm or less, the anti-Glare generated by the hollow ceria particles can be suppressed, and the transparency of the coating layer can be effectively maintained. In particular, when the average primary particle diameter of the hollow cerium oxide particles is in the range of 30 nm or more and 100 nm or less, the coating layer has a low refractive index and transparency, and a good balance can be obtained. In this case, the coating layer can be particularly suitable for antireflection of a display or the like. Furthermore, the average primary particle size is measured by dynamic light scattering.

The porous ceria particles may also be in the form of a sol. The sol-like porous cerium oxide particles may, for example, be colloidal cerium oxide. The colloidal cerium oxide is not particularly limited, and examples thereof include water-dispersible colloidal cerium oxide, organic solvent-dispersible colloidal cerium oxide such as alcohol, and the like. In general, the colloidal cerium oxide contains 20% by mass or more and 50% by mass or less of cerium oxide as a solid component. When colloidal cerium oxide is used as coating When the raw material of the material composition is used, the amount of colloidal cerium oxide in the coating material composition is determined according to the ratio of cerium oxide in the colloidal cerium oxide.

The ratio of the component (a) in the coating material composition is not limited, and the ratio of the component (a) to the total amount of the solid component in the coating material composition is preferably 5% by mass or more and 30% by mass or less. When the ratio is 5% by mass or more, the refractive index of the coating layer can be further lowered. When the ratio is 30% by mass or less, the strength of the coating layer is further increased.

The coating material composition may further contain non-porous cerium oxide particles in addition to the component (a). Further, as a non-porous cerium oxide particle, it was observed by a scanning electron microscope that cerium oxide particles which could not be identified as pores except for defects were used. Further, the cerium oxide particles having a porosity of less than 10% are also regarded as non-porous cerium oxide particles. When the coating material composition contains non-porous ceria particles, the strength of the coating layer can be further increased. However, in order to further improve the slidability of the coating layer, it is preferred to reduce the ratio of the non-porous cerium oxide particles in the coating material composition, in particular, to make the coating material composition free of non-porous oxidizing.矽 particles. When the non-porous ceria particles are contained in the coating material composition, the ratio of the non-porous ceria particles to the total amount of the solid content of the coating material composition is preferably in the range of 5% by mass or less.

In addition, the ratio of the total amount of the component (a) to the total amount of the non-porous ceria particles is preferably in the range of 5% by mass to 35% by mass based on the total amount of the solid content of the coating material composition.

When non-porous ceria particles are used, the average primary particle diameter of the non-porous ceria particles is preferably in the range of 50 nm or more and 200 nm or less. Preferably, it is in the range of 80 nm or more and 120 nm or less. When the average primary particle diameter of the non-porous ceria particles is within the above range, moderate irregularities can be formed on the surface of the coating layer. Thereby, the transparency of the coating layer is continuously maintained, and the grease on the coating layer is easily smudged.

The non-porous ceria particles may also be in the form of a sol. The sol-like non-porous cerium oxide particles may, for example, be non-porous colloidal cerium oxide. The colloidal cerium oxide is not particularly limited, and examples thereof include water-dispersible colloidal cerium oxide, organic solvent-dispersible colloidal cerium oxide such as alcohol, and the like. In general, the colloidal cerium oxide contains 20% by mass or more and 50% by mass or less of cerium oxide as a solid component. When colloidal cerium oxide is used as a raw material of the coating material composition, the amount of colloidal cerium oxide in the coating material composition is determined according to the ratio of cerium oxide in the colloidal cerium oxide.

[(b) ingredients]

The component (b) has at least one selected from the group consisting of a reactive component of at least one of hydrolysis condensation reaction and dehydration condensation reactivity, and a condensation product of the reactive component. That is, the component (b) is composed of an unreacted reactive component or a mixture of a condensed product of a reactive component or a condensed product of an unreacted reactive component and a reactive component. Composition.

The following components (b1), (b2), and (b3) are contained in the reactive component. (b1) a tetrafunctional reactive decane compound; (b2) a reactive decane compound having a phenyl group; and (b3) an eucalyptus oil having a phenyl group and a reactive group.

The condensation product of the reactive component may include at least one of a hydrolyzed condensation product of the reactive component and a dehydrated condensation product of the reactive component. The hydrolysis-condensation product of the reactive component may include at least one of a complete hydrolysis condensation product of the reactive component and a partial hydrolysis condensation product. Further, the condensation product of the reactive component may include only the condensation product of the component (b1), the condensation product of only the component (b2), the condensation product of only the component (b3), and (b1) to (b3). At least one of the condensation products of at least two or more components of the component. Further, the component (b1), the component (b2), and the component (b3) are preferably mutually soluble.

The component (b1) is composed of a tetrafunctional reactive decane compound. The tetrafunctional reactive decane compound is a decane compound having four reactive groups bonded to a ruthenium atom. The reactive group is a functional group having a hydrolysis condensation reaction property or a dehydration condensation reaction property. When the reactive component contains the component (b1), the coating layer formed of the coating material composition can be sufficiently high in strength.

The component (b1) preferably contains a compound represented by the following formula (1).

Si(OR) ₄ ...(1)

The four R groups in the formula (1) are each independently H or a monovalent hydrocarbon group. The carbon number of the monovalent hydrocarbon group is preferably 1 or more and 8 or less. For example, R is preferably 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 R is an alkyl group, if the carbon number of the alkyl group is 3 or more, the alkyl group may be a linear chain such as n-propyl or n-butyl, or may have an isopropyl group, an isobutyl group, or the like. A branch of t-butyl or the like. Wherein R is a carbon number of 1 or more and 4 or less Methyl, ethyl, n-propyl, i-propyl or n-butyl is preferred. Further, preferred tetrafunctional alkoxydecanes may, for example, be tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetra-i-propoxydecane, tetra-n-butyl Oxydecane, etc.

The ratio of the component (b1) is preferably in the range of 30% by mass or more and 60% by mass or less based on the total amount of the solid content in the coating material composition. When the ratio is 30% by mass or more, the strength of the coating layer can be increased. When the ratio is 60% by mass or less, the coating material composition can contain an appropriate amount of the component (b2) and the component (b3), whereby the fingerprint resistance and slidability of the coating layer can be sufficiently improved.

Further, the reactive component may further contain at least one of a trifunctional reactive decane compound, a difunctional reactive decane compound, and a monofunctional reactive decane compound. However, in order to increase the strength of the coating layer, it is preferred that the reactive component does not contain a trifunctional or lower reactive decane compound. When the reactive component contains a trifunctional or lower reactive decane compound, the ratio thereof is preferably in the range of 5% by mass or less based on the total amount of the solid component.

The component (b2) is composed of a reactive decane compound having a phenyl group. When the reactive component contains the component (b2), the fingerprint resistance of the coating layer formed of the coating material composition can be improved. Since the surface of the coating layer is provided with a phenyl group derived from the component (b2), it is considered that the lipophilicity of the surface of the coating layer is improved. That is, since the lipophilicity of the surface of the coating layer is improved, even if the fat or oil adheres to the surface of the coating layer by a human finger or the like, the grease is easily smudged on the surface of the coating layer, so that the finger marks are not conspicuous.

The component (b2) is preferably a ruthenium atom having a phenyl group in the molecule and a reactive group. Further, the eucalyptus oil containing a phenyl group and a reactive group as the component (b3) is excluded from the component (b2).

The reactive group of the component (b2) may, for example, be an alkoxy group, an ethenyloxy group, an anthracenyl group (-ON=CR(R')) or an enoxy group (-OC(R)=C(R')R. "), an amine group, an amine group (-ON(R)R'), a guanamine group (-N(R)-C(=O)-R') (in these functional groups, R, R', R" each independently represents a hydrogen atom or a monovalent hydrocarbon group, a hydrolyzable group such as a halogen, and a hydroxyl group.

The number of germanium atoms in the molecule of one of the components (b2) may be one or plural. Further, the number of phenyl groups in one molecule of the component (b2) may be one or more. The phenyl group may be bonded to the substituent or may not be bonded. The number of reactive groups in the molecule of one of the components (b2) is preferably two or more. In this case, the strength of the coating layer formed by the coating material composition can be improved. In the molecule of the component (b2), the ruthenium atom may be directly bonded to the phenyl group, and the alkyl group may be interposed between the ruthenium atom and the phenyl group.

The component (b2) particularly preferably contains a compound having an alkyl group interposed between a ruthenium atom and a phenyl group. In this case, the lipophilicity of the coating layer is particularly enhanced, thereby further improving the fingerprint resistance. The reason is considered as follows. Since the phenyl group in the component (b2) contains π electrons, it generally acts to improve the miscibility of the component (b2) in the coating material composition and other components. However, if an alkylene group is interposed between a ruthenium atom and a phenyl group, since the alkylene group does not contain π electrons, the mixing property of the component (b2) and other components is lowered. Therefore, the component (b2) is easily disposed in the composition of the coating material. Unhardened coating on the surface. Therefore, the phenyl group is easily aligned on the surface layer of the coating layer, and it is considered that the coating layer can be particularly improved in lipophilicity.

The alkylene group is not particularly limited, but is preferably a linear or branched alkylene group having a carbon number of 2 or more and 5 or less. In this case, the fingerprint resistance of the coating layer is particularly improved. This system is considered to be because the alkylene group has a carbon number of 5 or less, and the alkyl group does not easily hinder the lipophilicity of the phenyl group. Further, since the alkyl group has 2 or more carbon atoms, the alkyl group is The decrease in the miscibility of the components and other components plays an effective role.

Further, the number of reactive groups in one molecule of the component (b2) is particularly preferably three. In this case, the reaction of the reactive component increases the crosslinking density of the cured product, whereby the mechanical strength of the coating layer can be particularly enhanced.

In the molecule of the component (b2), it is particularly preferable that the number of reactive groups in the molecule of one of the (b2) components is three between the alkyl group and the phenyl group.

The weight average molecular weight of the component (b2) is preferably in the range of 200 or more and 300 or less. In this case, the fingerprint resistance of the coating layer becomes particularly good. This is considered to be because the molecular weight is moderately small, and the component (b2) is more easily aligned on the surface of the coating film. Further, the weight average molecular weight was measured by a gel permeation chromatography (GPC). At this time, the weight average molecular weight was calculated based on the calibration curve measured by standard polystyrene.

The component (b2) preferably contains an alkoxydecane compound having a phenyl group. Examples of the phenyl alkoxydecane compound include phenyltrimethoxydecane, phenyltriethoxysilane, diphenyldimethoxydecane, and diphenyl. a phenyl alkoxy decane such as bis-ethoxy decane or triphenyl ethoxy decane; bis (p-tolyl) dimethoxy decane, bis (p-tolyl) diethoxy decane, etc. An alkyl-substituted phenyl alkoxy decane comprising a ruthenium atom, a phenyl group bonded to the ruthenium atom, and a substituent bonded to the phenyl group; 1,4-bis(triethoxydecylalkyl) a bis alkoxy fluorenyl benzene containing two fluorene atoms and a phenyl group interposed between two fluorene atoms, such as benzene; a methyl phenyl dimethoxy decane or the like containing a ruthenium atom and a direct bond with the ruthenium atom a phenyl group, an alkyl phenyl alkoxy decane having an alkyl group, a phenylethyltrimethoxy decane or the like having a phenyl group, a ruthenium atom, and a carbon number between the phenyl group and the ruthenium atom It is a linear or branched alkyl phenethylalkyl alkoxy decane of 2 or more and 5 or less.

The component (b2) is preferably a trifunctional phenethylalkyl alkoxydecane such as phenethyltrimethoxydecane. In this case, the strength of the coating layer formed by the coating material composition can be improved.

Further, the component (b2) preferably contains a hydroxydecane compound having a phenyl group. The phenyl group-containing hydroxydecane compound has a structure in which an alkoxy group in the above phenyl group-containing alkoxydecane compound is substituted with a hydroxyl group. The phenyl group-containing hydroxydecane compound can be obtained by hydrolyzing a phenylalkanefluorodecane compound.

The component (b2) is particularly preferably a trifunctional phenethyl hydroxydecane such as phenethyltrihydroxydecane. In this case, the strength of the coating layer formed by the coating material composition can be improved.

The ratio of the component (b2) is preferably in the range of 10% by mass to 30% by mass based on the total amount of the solid content in the coating material composition. This ratio When it is 10% by mass or more, the lipophilic property of the surface of the coating layer can be exhibited, so that the fingerprint resistance of the coating layer can be improved. When the ratio is 30% by mass or less, the strength of the coating layer can be increased.

The component (b3) is composed of an eucalyptus oil having a phenyl group and a reactive group. When the reactive component contains the component (b3), the fingerprint resistance of the coating layer formed by the coating material composition can be maintained, and the slidability of the coating layer can be further improved. This is because the coating layer contains the oil of the component (b3), and the slidability of the coating layer can be improved. Further, since the component (b3) contains a phenyl group, the coating layer can maintain high fingerprint resistance. Further, since the component (b3) contains a reactive group, the molecule of the component (b3) is fixed to the coating layer by reacting with the component (b1) and the component (b2). Therefore, the decrease in the strength of the coating layer caused by the use of the component (b3) can be suppressed. Further, the durability of the coating layer can be improved, and therefore, the coating layer can maintain good slidability for a long period of time.

The reactive group of the component (b3) may, for example, be an alkoxy group, an ethyloxy group, a fluorenyl group (-ON=CR(R')), or an enoxy group (-OC(R)=C(R')R. "), an amine group, an amine group (-ON(R)R'), a guanamine group (-N(R)-C(=O)-R') (in these functional groups, R, R', R" each independently represents a hydrogen atom or a monovalent hydrocarbon group, a hydrolyzable group such as a halogen, and a hydroxyl group.

The weight average molecular weight of the component (b3) is preferably in the range of 800 or more and 1200 or less, more preferably in the range of 900 or more and 1,000 or less. In this case, the slidability of the coating layer becomes extremely high. Since the weight average molecular weight of the component (b3) is in the above range, the viscosity of the coating layer can be appropriately controlled, and as a result, the finger can be applied to the surface of the coating layer formed by the coating material composition. The coefficient of friction during movement is reduced.

The component (b3) is particularly preferably a decyl alcohol terminal diphenyl sulfoxane-dimethyl decane copolymer. In this case, the slidability of the coating layer can be improved while improving the fingerprint resistance of the coating layer. This is to improve the lipophilicity of the surface of the coating layer by the diphenyl fluorinane moiety in the sterol terminal diphenyl siloxane-dimethyl oxane copolymer, and by the sterol terminal diphenyl. The dimethyloxane portion of the oxime-dimethyl methoxy olefin copolymer effectively improves the slidability of the surface of the coating layer.

The sterol terminal diphenyl siloxane-dimethyl oxa oxide copolymer is represented by the following formula (2).

In the formula (2), m and n are each an integer of 1 or more. m is preferably an integer of 5 or more and 8 or less. Further, n is preferably an integer of 1 or more and 3 or less.

Further, the molar percentage of the diphenyloxane moiety relative to the total amount of the monomers constituting the sterol terminal diphenyloxane-dimethyloxane copolymer, that is, in the formula (2) The value of {n(m+n+2)} x 100 (mol%) is preferably in the range of 10 to 25 mol%, particularly preferably in the range of 14 to 18 mol%. In this case, the portion of the diphenyloxane moiety is used to improve the lipophilicity of the surface of the coating layer, and the portion of the dimethyloxane portion is used to increase the sliding of the surface of the coating layer. Sex can work together. Thereby, the fingerprint resistance and slidability of the coating layer can further achieve a better balance.

The ratio of the component (b3) is preferably from 1% by mass to 15% by mass based on the total amount of the solid content in the coating material composition. When the ratio is 1% by mass or more, the slidability of the coating layer can be particularly improved. Further, if the ratio is 15% by mass or less, the transparency of the coating layer can be prevented from being lowered.

[solvent, etc.]

The coating material composition preferably contains a solvent. In this case, it is preferred to use a suitable solvent which can be easily volatilized by heating. Specific examples of the solvent are alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, diacetone alcohol, etc.; ethylene glycol monomethyl ether, Glycol ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, acetamidine acetone; ethyl acetate, butyl acetate Esters such as ester, ethyl acetate and the like; xylene; toluene and the like.

The ratio of the solvent in the coating material composition can be appropriately set. In particular, the ratio of the solvent in the coating material composition is preferably in the range of 50% by mass or more and 99.8% by mass or less. In this case, the coating material composition is easy to apply, and the thickness of the coating layer can be easily adjusted, and the stability of the coating material composition can be further ensured. The ratio of the solvent is more preferably in the range of 70% by mass or more and 99% by mass or less.

[Modulation of coating material composition]

A method of preparing a coating material composition will be described by way of an example. First, a reactive component, a solvent, water, and an acid catalyst are mixed to prepare a mixed solution. The amount of water used is preferably in the range of 1.0 or more and 3.0 or less with respect to the hydrolyzable group in the reactive component. Then, the reactive component in the mixed solution is subjected to a condensation reaction. The condensation reaction is preferably carried out at a temperature of from 20 ° C to 60 ° C. Next, the component (a) is added to the mixed solution, and a solvent is added as needed. Further, the reactive component may be subjected to a condensation reaction after the addition of the component (a). In this case, the strength of the coating layer formed by the coating material composition can be further enhanced while the coating material composition can be easily formed into a film. Further, after the reactive component is subjected to a condensation reaction, the component (a) may be added to the mixed solution, and then the reactive component may be further subjected to a condensation reaction. Thereby, a coating material composition can be obtained.

The weight average molecular weight of the component (b) in the coating material composition is not particularly limited, but is preferably in the range of 1,000 or more and 5,000 or less. The coating material composition having a weight average molecular weight of 1,000 or more can be easily formed into a film. Moreover, when the weight average molecular weight is 5,000 or less, the decrease in the strength of the coating layer can be suppressed. In the preparation process of the coating material composition, when the reactive component is subjected to a condensation reaction, the reaction conditions can be appropriately adjusted depending on the weight average molecular weight range of the desired component (b).

[covered items]

In the present embodiment, as shown in Fig. 1, the coated article 1 has a substrate 3 and a coating layer 2 formed of a coating material composition.

The material of the substrate 3 is not particularly limited, and may be, for example, glass. The inorganic materials, metal materials, and organic materials represented by polycarbonate or polyethylene terephthalate. Moreover, the shape of the base material 3 is not particularly limited, and examples thereof include a flat plate shape and a film shape.

The substrate 3 and the coated article 1 are not particularly limited. For example, the substrate 3 and the coated article 1 are preferably used as components on the outermost surface of an image display device such as a display, and are used as a protective case for a display or the like. The components on the outermost surface of the touch panel display, the protective cover of the touch panel display, and the parts that are more likely to be touched by the human hand are particularly suitable.

The coating layer 2 can be formed on the substrate 3 by coating a coating material composition on the substrate 3 to form a film layer. The coating method of the coating material composition is not particularly limited, and examples thereof include brush coating, spray coating, dipping (immersion, dip coating), roll coating, gravure printing, flow coating, shower coating, blade coating, and spin coating. Common coating methods such as table coating, sheet coating, sheet coating, die coating, and bar coating.

Preferably, the component (b) in the coating material composition is subjected to a condensation reaction by subjecting the coating material composition coated on the substrate 3 to heat treatment. Thereby, the mechanical strength of the coating layer 2 can be further improved. The heating temperature at the time of heat treatment is not particularly limited, but is preferably a relatively low temperature of 60 ° C or more and 300 ° C or less. Further, the heating time is preferably in the range of 5 minutes or more and 120 minutes or less. When the heating temperature is 300 ° C or lower, thermal decomposition of the phenyl group in the component (b) can be suppressed, and high fingerprint resistance of the coating material composition can be maintained. Further, even if the heating temperature is relatively low, the mechanical strength of the coating layer 2 is equivalent to the case of the heating temperature at a high temperature. Therefore, the cost can be reduced, and the deterioration of the substrate 3 by the high temperature can be suppressed. Furthermore, when using a substrate made of glass 3 or the like In the case of the substrate 3 having a low thermal conductivity, if it is heated to a high temperature, it takes time to increase and decrease the temperature, and the processing speed is delayed, and conversely, if the heating temperature is low, the processing speed can be accelerated.

The thickness of the coating layer 2 can be appropriately set depending on the use of the coated article 1 and the purpose of forming the coating layer 2, and is particularly preferably in the range of 50 nm or more and 5 μm or less. Further, when the coating layer 2 is formed for use as an antireflection, the thickness of the coating layer 2 is preferably in the range of 50 nm or more and 100 nm or less.

By blending the composition of the coating material composition, the refractive index of the coating layer 2 can be easily lowered, and therefore, the coating layer 2 is particularly suitable for use for preventing reflection. In this case, for example, when the refractive index of the substrate 3 is less than 1.65, it is preferred to first form a layer (intermediate layer 4) having a refractive index of 1.65 or more on the substrate 3, and form a coating on the intermediate layer 4. Cloth layer 2. A conventional high refractive index material can be used as a material for forming the intermediate layer 4. When the refractive index of the intermediate layer 4 is 1.65 or more, the difference in refractive index between the coating layer 2 and the intermediate layer 4 is increased, so that the reflection preventing performance of the coated article 1 can be improved.

The surface reflectance of the coating layer 2 of the coated article 1 is preferably in the range of 1.5% or more and 3% or less from the viewpoint of less likely to cause finger marks. In particular, when the reflectance is 2% or more and 3% or less, the change in color tone of the finger marks on the coating layer 2 is small. Therefore, the finger marks are less recognizable. Further, the haze of the coating layer 2 is preferably 1% or less.

[Example 1]

Methyl silicate (partial hydrolysis of tetramethoxy decane) Condensation product. 5% by mass of methyl silicate 51 (trade name), 245 parts by mass of isopropyl alcohol, phenethyltrimethoxydecane (made by Gelest, SIP 6722.6 (trade name)), 43 parts by mass, sterol end Diphenyloxane-dimethyloxane copolymer (PDS-1615 (trade name), manufactured by Gelest Co., Ltd., diphenyl decane ratio 14-18 mol%, weight average molecular weight 900~1000, OH The ratio of 3.4 to 4.8%) of the mass portion and the 165 mass portion of the 0.1 N nitric acid aqueous solution were all mixed in a disperser to obtain a mixed solution. The mixture was allowed to stand at room temperature for 96 hours to carry out a polycondensation reaction. Next, the weight average molecular weight of the resin component in the mixed liquid was measured and found to be 1,340.

Next, the porous cerium oxide particles (isopropyl alcohol dispersed porous cerium oxide fine particles, manufactured by Catalyst Chemical Co., Ltd., trade name: Sluja 4110, solid content: 20% by mass, average primary particle diameter: 60 nm, outer shell thickness About 10 nm), 188 mass parts were added to the mixed liquid in terms of solid content.

Next, the mixed solution was diluted with a mixed solvent of IPA/butyl acetate/ethylene glycol butyl ester (the mixed solvent was previously prepared so that 5% of the total amount of the diluted mixed solution was butyl acetate, and 2 of the total amount was The mixture was allowed to stand for 1 hour to obtain a coating material composition of 3% by mass based on the total solid content. The solid content ratio of the components in this coating material composition is as shown later.

Further, a substrate made of polyethylene terephthalate having an intermediate layer (hard coat layer) having a refractive index of 1.67 was prepared. The surface of the substrate was washed with a UV-ozone cleaning machine (Excimer Lamp, manufactured by USHIO Electric Co., model H0011). net. Next, a coating material composition was applied on the hard coat layer of the substrate by wire bar coating. Next, the coating material composition on the substrate was heated at 120 ° C for 5 minutes in an oxygen atmosphere. Thereby, a coated article having a coating layer having a thickness of 100 nm was obtained.

[Embodiment 2]

The amount of the methyl decanoate and the decyl alcohol terminal diphenyl sulfoxane-dimethyl methoxy olefin copolymer used in Example 1 was changed so that the solid content ratio in the coating material composition of the composition became the following table. The value shown. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the coating material composition was prepared, the weight average molecular weight of the resin component in the mixed liquid was measured to be 1,290, as in the case of Example 1.

[Example 3]

The amount of the methyl decanoate and the decyl alcohol terminal diphenyl sulfoxane-dimethyl methoxy olefin copolymer used in Example 1 was changed so that the solid content ratio in the coating material composition of the composition became the following table. The value shown. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the coating material composition is prepared, it is the same as in the case of the first embodiment. The weight average molecular weight of the resin component in the mixed liquid was measured to be 1415.

[Example 4]

The amount of the methyl decanoate and the decyl alcohol terminal diphenyl sulfoxane-dimethyl methoxy olefin copolymer used in Example 1 was changed so that the solid content ratio in the coating material composition of the composition became the following table. The value shown. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the composition of the coating material was prepared, the weight average molecular weight of the resin component in the mixed liquid was measured to be 1387 as in the case of Example 1.

[Example 5]

The amount of methyl decanoate or phenethyltrimethoxydecane used in Example 1 was changed, and the solid content ratio in the coating material composition of the component was changed to the value shown in the following table. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the composition of the coating material was prepared, the weight average molecular weight of the resin component in the mixed liquid was measured and found to be 1278 as in the case of Example 1.

[Embodiment 6]

The amount of methyl decanoate or phenethyltrimethoxydecane used in Example 1 was changed, and the solid content ratio in the coating material composition of the component was changed to the value shown in the following table. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the coating material composition was prepared, the weight average molecular weight of the resin component in the mixed liquid was measured to be 1301 as in the case of Example 1.

[Embodiment 7]

The amount of the porous cerium oxide particles and methyl decanoate used in Example 1 was changed, and the solid content ratio in the coating material composition of the component was changed to the value shown in the following table. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the composition of the coating material was prepared, the weight average molecular weight of the resin component in the mixed liquid was measured to be 1297 as in the case of Example 1.

[Embodiment 8]

The amount of the porous cerium oxide particles and methyl decanoate used in Example 1 was changed, and the solid content ratio in the coating material composition of the component was changed to the value shown in the following table. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the composition of the coating material was prepared, the weight average molecular weight of the resin component in the mixed liquid was measured to be 1274 as in the case of Example 1.

[Embodiment 9]

The amount of the porous cerium oxide particles and methyl decanoate used in Example 1 was changed, and the solid content ratio in the coating material composition of the component was changed to the value shown in the following table. Further, the amount of use of isopropyl alcohol was adjusted so that the solid content concentration of the mixed liquid was the same as in Example 1.

Otherwise, the treatment was carried out in the same manner and under the same conditions as in Example 1 to prepare a coating material composition, and further, a coated article was obtained.

Further, when the composition of the coating material was prepared, the weight average molecular weight of the resin component in the mixed liquid was measured to be 1307 as in the case of Example 1.

[Comparative Example 1]

Taking 13 parts by mass of methyl silicate, 2473 parts by weight of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxydecane, and 0.1N The 165 mass portions of the aqueous nitric acid solution were all placed in a disperser and thoroughly mixed to obtain a mixed solution. The mixture was allowed to stand at room temperature for 96 hours. Next, the weight average molecular weight of the resin component in the mixed liquid was measured and found to be 1259.

Then, in the mixed solution, 188 parts by mass of porous cerium oxide particles and 50 parts by mass of non-porous cerium oxide particles (isopropyl alcohol dispersed non-porous cerium oxide fine particles) are added in terms of solid content. Nissan Chemical Industries, Ltd., product number IPA-ST-ZL, solid content: 30% by mass, average primary particle diameter: 100 nm).

Thereafter, the coating material composition was prepared by the same method and conditions as in Example 1, and a coated article was further obtained.

[Comparative Example 2]

Taking 162 parts by mass of methyl silicate, 2443 parts by mass of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxydecane, and 165 parts by mass of 0.1 N aqueous solution of nitric acid, all of them were placed in a disperser and thoroughly mixed. A mixture was obtained. The mixture was allowed to stand at room temperature for 96 hours. Next, the weight average molecular weight of the resin component in the mixed liquid was measured and found to be 1211.

Next, in the mixed solution, 188 parts by mass of porous cerium oxide particles were added in terms of solid content.

Thereafter, the coating material composition was prepared by the same method and conditions as in Example 1, and a coated article was further obtained.

[Comparative Example 3]

3% by mass of methyl silicate, 2452 parts by weight of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxydecane, and 6 parts by mass of alkyl decane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name KBM3103), and 0.1 The 165 mass portions of the aqueous solution of N nitric acid were all placed in a disperser and thoroughly mixed to obtain a mixed solution. The mixture was allowed to stand at room temperature for 96 hours. Next, the weight average molecular weight of the resin component in the mixed liquid was measured and found to be 1,253.

Next, in the mixed solution, 188 parts by mass of porous cerium oxide particles were added in terms of solid content.

Thereafter, the coating material composition was prepared by the same method and conditions as in Example 1, and a coated article was further obtained.

[Comparative Example 4]

Take 153 parts by mass of methyl silicate, 2452 parts by weight of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxydecane, and alkyloxane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name KF-96) 6 mass The 165 mass portions of the 0.1% nitric acid aqueous solution were placed in a disperser and thoroughly mixed to obtain a mixed liquid. The mixture was allowed to stand at room temperature for 96 hours. Next, the weight average molecular weight of the resin component in the mixed liquid was measured and found to be 1356.

Next, in the mixed solution, 188 parts by mass of porous cerium oxide particles were added in terms of solid content.

Thereafter, the treatment was carried out in the same manner and under the same conditions as in the first embodiment. A coating material composition is obtained to further obtain a coated article.

[Comparative Example 5]

Taking 153 parts by mass of methyl silicate, 2452 parts by mass of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxydecane, and 6 parts by mass of acrylic graft polymer (manufactured by Toagosei Co., Ltd., trade name US270) And 165 mass portions of a 0.1 N aqueous solution of nitric acid were all placed in a disperser and thoroughly mixed to obtain a mixed solution. The mixture was allowed to stand at room temperature for 96 hours. Next, the weight average molecular weight of the resin component in the mixed liquid was measured and found to be 1321.

Next, in the mixed solution, 188 parts by mass of porous cerium oxide particles were added in terms of solid content.

Thereafter, the coating material composition was prepared by the same method and conditions as in Example 1, and a coated article was further obtained.

[evaluation experiment]

The following evaluation experiments were performed on the coating layers formed in Examples 1 to 9 and Comparative Examples 1 to 5. The results are shown in the table below.

(slidability)

The dynamic friction coefficient of the surface of the coating layer was measured using a friction feeling tester (manufactured by Kato Tech Co., model KES-SE). As the friction member, a friction rubber made of silicone rubber was used, and when the load of the friction was 25 g, the sliding speed of the friction was 1 cm/sec.

(fingerprint recognition)

The finger pad is pressed on the surface of the coating layer to adhere the finger marks. The results of the finger marks were visually observed and evaluated according to the following evaluation criteria.

1. Finger marks can be clearly identified.

2. It can blur the finger marks.

3. Although the shape of the fingerprint in the finger mark cannot be recognized, the part with the finger mark and the difference from the other part can be clearly identified.

4. The part with the finger mark and its difference from the other part cannot be clearly identified.

5. Finger marks are almost indistinguishable.

(haze)

The coating layer haze value was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model NDH 2000).

(Mechanical strength)

A load of 250 g/cm ² (about 24.5 kPa) was applied to the surface of the coating layer by steel wool #0000, and the steel wool was slid at a speed of 5 cm/sec on the surface of the coating layer. In this way, the steel wool was brought back and forth 10 times on the surface of the coating layer. Next, the coating layer was observed, and it was confirmed whether the coating layer had peeling, surface shape, and damage. As a result, evaluation was performed based on the following evaluation criteria.

1. The coating layer is completely peeled off.

2. A clear damage is produced on the entire coating layer.

3. Subtle damage is caused on the entire coating layer.

4. Although the damage is not recognized on the coating layer, there is an indentation.

5. No damage or indentation can be identified on the coating.

1‧‧‧covered items

2‧‧‧coating layer

3‧‧‧Substrate

4‧‧‧Intermediate

Claims (5)

A coating material composition comprising: (a) porous ceria particles; and (b) a condensation component having at least one of hydrolysis condensation reaction and dehydration condensation reactivity, and condensation with the reactive component At least one selected from the group consisting of the following components: (b1) a tetrafunctional reactive decane compound; (b2) a reactive decane compound having a phenyl group; and (b3) having a phenyl group and The reactivity of the eucalyptus oil and the ratio of the component (b3) to the total solid content in the coating material composition is in the range of 1 to 15% by mass, and the component (b3) contains the sterol terminal diphenyl sulfoxane a dimethyl methoxy alkane copolymer. The coating material composition according to the first aspect of the invention, wherein the ratio of the component (b2) is from 10% by mass to 30% by mass based on the total solid content of the coating material composition. . The coating material composition according to claim 1, wherein the weight average molecular weight of the component (b3) is in the range of 800 to 1200. The coating material composition according to claim 1, wherein the component (b2) contains a compound having an alkylene group between a halogen atom and a phenyl group. A coated article having a coating layer formed of the coating material composition according to any one of claims 1 to 4.