JP5845466B2 - Coating material composition and coated article coated with the coating material composition - Google Patents

Description

  A coating layer is often provided on the outermost surface of an image display device such as a display for the purpose of surface protection and antireflection. Since such a coating layer has many opportunities to be touched by a hand, finger marks are easily attached. For this reason, there is a problem that finger marks attached to the image display device are easily noticeable.

  Therefore, conventionally, a coating material composition for forming a coating layer having a property (fingerprint resistance) in which finger marks are not noticeable even when touched with a finger has been developed.

  For example, Patent Document 1 contains non-porous silica particles having an average primary particle diameter of 50 nm or more and 200 nm or less, a tetrafunctional alkoxysilane, and a hydrolyzable silane compound having a phenyl group, and is contained in the total solid content. A fingerprint-resistant coating material composition containing 5% by mass to 30% by mass of non-porous silica particles is disclosed. In this case, since the anti-fingerprint coating material composition contains a silane compound having a phenyl group, the oleophilicity of the coating layer is improved, so that even if a human finger touches the coating layer, the finger marks are less noticeable.

  Japanese Patent Publication No. 2011-195806

  In recent years, devices equipped with a touch panel display, such as smartphones and tablet terminals, have become widespread. In smartphones, tablet terminals, and the like, processes such as scrolling and image enlargement / reduction are performed not only by touching the display with a finger but also by sliding the finger on the display. Therefore, in recent years, a coating layer provided on an image display device is required to have not only fingerprint resistance but also high slipperiness when touched with a finger.

  However, in the prior art as disclosed in Patent Document 1, the slipperiness of the coating layer is not sufficient.

  The present invention has been made in view of the above reasons, and the object of the present invention is a coating material composition for forming a coating layer having both good fingerprint resistance and slipperiness, and fingerprint resistance. An object of the present invention is to provide a coated article having a coating layer having good sliding properties.

The coating material composition according to the first aspect of the present invention comprises:
Contains at least one selected from (a) porous silica particles, and (b) a reactive component having at least one of hydrolytic condensation reactivity and dehydration condensation reactivity, and a condensation product of this reactive component And the reactive component is
(B1) Tetrafunctional reactive silane compound (b2) A reactive silane compound having a phenyl group, and (b3) a reaction having hydrolysis reactivity that reacts with the phenyl group, the component (b1) and the component (b2). Containing a silicone oil having a functional group ,
The ratio of the component (b3) to the total solid content is in the range of 1 to 15% by mass .

In the second aspect of the present invention, in the first aspect of the present invention, the ratio of the component (b2) to the total solid content in the coating material composition is in the range of 10% by mass to 30% by mass. is there.

In the third aspect of the present invention, in the first or second aspect of the present invention, the weight average molecular weight of the component (b3) is in the range of 800 to 1200.

According to a fourth aspect of the present invention, in any one of the first to third aspects of the present invention, the component (b3) contains a silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects of the present invention, the component (b2) contains a compound having an alkylene group interposed between a silicon atom and a phenyl group. To do.

A coated article according to a sixth aspect of the present invention includes a coating layer formed from the coating material composition according to any one of the first to fifth aspects.

  From the coating material composition according to the present invention, a coating layer having both good fingerprint resistance and slipperiness can be formed.

  Moreover, in the coated product according to the present invention, both the fingerprint resistance and the slipperiness of the coating layer provided in the coated product are improved.

It is sectional drawing which shows an example of the structure of the covering goods which concern on this invention.

The coating material composition according to this embodiment is
Contains at least one selected from (a) porous silica particles, and (b) a reactive component having at least one of hydrolytic condensation reactivity and dehydration condensation reactivity, and a condensation product of this reactive component To do.

  The reactive component contains (b1) a tetrafunctional reactive silane compound, (b2) a reactive silane compound having a phenyl group, and (b3) a silicone oil having a phenyl group and a reactive group.

  Each of these components will be described.

[(A) component]
The component (a) is composed of porous silica particles. The average primary particle diameter of the component (a) is preferably in the range of 30 nm to 100 nm. This average primary particle diameter is measured by a dynamic light scattering method. When the average primary particle diameter of the component (a) is in the above range, moderate irregularities are formed on the surface of the coating layer formed from the coating material composition. Thereby, the fats and oils easily spread on the coating layer while the transparency of the coating layer is maintained. For this reason, the finger mark adhering to the coating layer is less noticeable. Moreover, moderate intensity | strength is provided to a coating layer by (a) component. Furthermore, when the component (a) is contained in the coating layer, the refractive index of the coating layer can be lowered. For this reason, a coating layer becomes a thing especially suitable for an antireflection use. The porosity of the component (a) is preferably 20% or more. The porosity is the ratio of the volume of voids in the particle to the apparent volume of the particle. The porosity is measured based on a transmission electron microscope image.

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

  The hollow silica particle includes an outer shell made of, for example, a silica-based inorganic oxide, and a void surrounded by the outer shell is formed inside the hollow silica particle. The outer shell of the hollow silica particles may be composed of a single layer composed of silica or may be composed of a single layer composed of a composite oxide of silica and an inorganic oxide other than silica. Further, the outer shell of the hollow silica particles may be constituted by laminating two or more layers as described above. The thickness of the outer shell is, for example, 1 nm or more and 50 nm or less, preferably 5 nm or more and 20 nm or less. The thickness of the outer shell is preferably in the range of 1/50 to 1/5 of the average primary particle diameter of the hollow silica particles. The average primary particle diameter of the hollow silica particles is preferably in the range of 5 nm to 2 μm. When the average primary particle diameter is 5 nm or more, a reduction in the refractive index of the coating layer is effectively achieved. Further, when the average primary particle diameter is 2 μm or less, the diffuse reflection (Anti-Glare) due to the hollow silica particles is suppressed, so that the transparency of the coating layer is maintained well. In particular, when the average primary particle diameter of the hollow silica particles is in the range of 30 nm or more and 100 nm or less, the reduction in the refractive index of the coating layer and the maintenance of transparency can be achieved in a well-balanced manner. In this case, the coating layer is particularly preferably used for preventing reflection of a display or the like. The average primary particle diameter is measured by a dynamic light scattering method.

  The porous silica particles may be in a sol form. Examples of the sol-like porous silica include porous colloidal silica. The colloidal silica is not particularly limited, and examples thereof include water-dispersible colloidal silica and organic solvent-dispersible colloidal silica such as alcohol. Generally, such colloidal silica contains 20% by mass or more and 50% by mass or less of silica as a solid content. When colloidal silica is used as a raw material for the coating material composition, the blending amount of the colloidal silica in the coating material composition is determined based on the ratio of silica in the colloidal silica.

  Although there is no restriction | limiting in the ratio of the (a) component in a coating material composition, The ratio of the (a) component with respect to the solid content whole quantity in a coating material composition is the range of 5 mass% or more and 30 mass% or less especially. Is preferred. When this proportion is 5% by mass or more, the refractive index of the coating layer is further reduced. Moreover, the intensity | strength of a coating layer improves more that this ratio is 30 mass% or less.

  The coating material composition may further contain non-porous silica particles in addition to the component (a). Note that silica particles in which voids other than defects are not observed even when observed with a scanning electron microscope are regarded as non-porous silica particles. Silica particles with a porosity of less than 10% are also considered non-porous silica particles. When the coating material composition contains non-porous silica particles, the strength of the coating layer is further improved. However, in order to further improve the slipperiness of the coating layer, it is preferable that the ratio of the nonporous silica particles in the coating material composition is small, and particularly that the coating material composition does not contain nonporous silica particles. preferable. When the coating material composition contains non-porous silica particles, the ratio of the non-porous silica particles to the total solid content in the coating material composition is preferably in the range of 5% by mass or less.

  Moreover, it is preferable that the ratio of the total amount of the component (a) and the non-porous silica particles with respect to the total solid content of the coating material composition is in the range of 5% by mass to 35% by mass.

  When nonporous silica particles are used, the average primary particle size of the nonporous silica particles is preferably in the range of 50 nm to 200 nm, and more preferably in the range of 80 nm to 120 nm. When the average primary particle diameter of the non-porous silica particles is within the above range, the surface of the coating layer is moderately uneven, so that the fat on the coating layer spreads while maintaining the transparency of the coating layer. It becomes easy.

  The non-porous silica particles may be in a sol form. Examples of the sol-like non-porous silica include non-porous colloidal silica. The colloidal silica is not particularly limited, and examples thereof include water-dispersible colloidal silica and organic solvent-dispersible colloidal silica such as alcohol. Generally, such colloidal silica contains 20% by mass or more and 50% by mass or less of silica as a solid content. When colloidal silica is used as a raw material for the coating material composition, the blending amount of the colloidal silica in the coating material composition is determined based on the ratio of silica in the colloidal silica.

[Component (b)]
The component (b) consists of at least one selected from a reactive component having at least one of hydrolytic condensation reactivity and dehydration condensation reactivity and a condensation product of this reactive component. That is, the component (b) consists of an unreacted reactive component, a condensation product of a reactive component, or a mixture of an unreacted reactive component and a condensation product of a reactive component.

The reactive component includes the following (b1) component, (b2) component, and (b3) component; (b1) a tetrafunctional reactive silane compound,
(B2) a reactive silane compound having a phenyl group, and (b3) a silicone oil having a phenyl group and a reactive group.

  The condensation product of the reactive component can include at least one of a hydrolysis condensation product of the reactive component and a dehydration condensation product of the reactive component. The hydrolytic condensation product of the reactive component can include at least one of a complete hydrolytic condensation product and a partial hydrolytic condensation product of the reactive component. Further, the condensation product of the reactive component is a condensation product of only the component (b1), a condensation product of only the component (b2), a condensation product of only the component (b3), and the components (b1) to (b3). Among these, at least one of condensation products of two or more components may be included. Moreover, it is preferable that (b1) component, (b2) component, and (b3) component are compatible.

  The component (b1) is composed of a tetrafunctional reactive silane compound. The tetrafunctional reactive silane compound is a silane compound having four reactive groups bonded to a silicon atom. The reactive group is a functional group having hydrolytic condensation reactivity or dehydration condensation reactivity. When the reactive component contains the component (b1), sufficiently high strength is imparted to the coating layer formed from the coating material composition.

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

Si (OR) ₄ (1)
Four R in 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. In the case where R is an alkyl group, when the alkyl group has 3 or more carbon atoms, the alkyl group may be linear such as an n-propyl group, an n-butyl group, You may have a branch like an isopropyl group, an isobutyl group, t-butyl group. Among these, R is particularly preferably a methyl group having 1 to 4 carbon atoms, an ethyl group, an n-propyl group, an i-propyl group, or an n-butyl group. Examples of preferable tetrafunctional alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane.

  The ratio of the component (b1) to the total solid content in the coating material composition is preferably in the range of 30% by mass to 60% by mass. When this ratio is 30% by mass or more, the strength of the coating layer is improved. Further, when this ratio is 60% by mass or less, an appropriate amount of the component (b2) and the component (b3) are included in the coating material composition. Thereby, the fingerprint resistance and slipperiness of the coating layer are sufficiently improved.

  The reactive component may further contain at least one of a trifunctional reactive silane compound, a bifunctional reactive silane compound, and a monofunctional reactive silane compound. However, in order to improve the strength of the coating layer, it is preferable that the reactive component does not contain a trifunctional or lower functional silane compound ratio. Moreover, even when a reactive component contains the reactive silane compound below 3 functionals, it is preferable that the ratio is the range of 5 mass% or less with respect to solid content whole quantity.

  The component (b2) is composed of a reactive silane compound having a phenyl group. When the reactive component contains the component (b2), the fingerprint resistance of the coating layer formed from the coating material composition is improved. This is considered to be because the lipophilicity of the coating layer surface is improved by arranging the phenyl group derived from the component (b2) on the surface of the coating layer. In other words, since the lipophilicity of the coating layer surface is improved, even if oils and fats adhere to the surface of the coating layer from a human finger or the like, the oils and fats easily spread on the surface of the coating layer. It seems to be inconspicuous.

  The component (b2) preferably has a phenyl group and a silicon atom to which a reactive group is bonded in the molecule. The component (b2) excludes the silicone oil having a phenyl group and a reactive group as the component (b3).

  As the reactive group in the component (b2), an alkoxy group, an acetoxy group, an oxime group (—O—N═C—R (R ′)), an enoxy group (—O—C (R) ═C (R ′) R ″), an amino group, an aminoxy group (—O—N (R) R ′), an amide group (—N (R) —C (═O) —R ′) (in these groups, R, R ′, R ″ is, for example, each independently a hydrogen atom or a monovalent hydrocarbon group), hydrolyzable groups such as halogen, and hydroxyl groups.

  The number of silicon atoms in one molecule of component (b2) may be one or more. In addition, the number of phenyl groups in one molecule of the component (b2) may be one or more. The phenyl group may or may not be bonded to a substituent. The number of reactive groups in one molecule of component (b2) is preferably 2 or more. In this case, the strength of the coating layer formed from the coating material composition is improved. In the molecule of the component (b2), a silicon atom and a phenyl group may be directly bonded, or an alkylene group may be interposed between the silicon atom and the phenyl group.

  It is particularly preferable that the component (b2) contains a compound having an alkylene group interposed between a silicon atom and a phenyl group. In this case, the lipophilicity of the coating layer is particularly improved, whereby the fingerprint resistance is further improved. The reason is considered as follows. Since the phenyl group in the component (b2) contains π electrons, it normally functions to improve the miscibility between the component (b2) in the coating material composition and other components. However, when an alkylene group is interposed between the silicon atom and the phenyl group, the alkylene group does not contain π electrons, so that the miscibility between the component (b2) and other components is lowered. For this reason, it becomes easy to arrange | position (b2) component in the surface layer of the uncured coating film formed from a coating material composition. Therefore, it is considered that the phenyl group is easily oriented on the surface layer of the coating layer, and as a result, the lipophilicity of the coating layer is particularly improved.

  The alkylene group is not particularly limited, but is particularly preferably a linear or branched alkylene group having 2 to 5 carbon atoms. In this case, the fingerprint resistance of the coating layer is particularly improved. This is because when the alkylene group has 5 or less carbon atoms, the alkylene group is less likely to inhibit the lipophilic effect of the phenyl group, and when the alkylene group has 2 or more carbon atoms, it depends on the alkylene group. (B2) It is thought that it is because the effect | action which reduces the miscibility with the component other than that expresses effectively.

  Moreover, it is especially preferable that the number of reactive groups in one molecule of the component (b2) is 3. In this case, the crosslink density of the cured product formed by the reaction of the reactive component is improved, and thereby the mechanical strength of the coating layer is particularly increased.

  It is particularly preferred if an alkylene group is interposed between the silicon atom and the phenyl group in the component (b2) molecule and the number of reactive groups in one molecule of the (b2) component is three.

  The weight average molecular weight of the component (b2) is preferably in the range of 200 to 300. In this case, the fingerprint resistance of the coating layer is particularly good. This is considered to be because the component (b2) is more easily oriented to the coating film surface due to the reasonably low molecular weight. The weight average molecular weight is measured by gel permeation chromatography (GPC). At this time, the weight average molecular weight is calculated based on a calibration curve obtained from standard polystyrene.

The component (b2) preferably contains a phenyl group-containing alkoxysilane compound. As a phenyl group-containing alkoxysilane compound,
Phenylalkoxysilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane;
Di (p-tolyl) dimethoxysilane, di (p-tolyl) diethoxysilane, etc., a silicon atom, a phenyl group bonded to the silicon atom, and an alkyl substituent bonded to the phenyl group Having an alkyl-substituted phenylalkoxysilane;
Bisalkoxysilylbenzene having two silicon atoms and a phenylene group interposed between these silicon atoms, such as 1,4-bis (triethoxysilyl) benzene;
An alkylphenylalkoxysilane having a silicon atom and a phenyl group and an alkyl group directly bonded to the silicon atom, such as methylphenyldimethoxysilane;
Phenalkylalkylsilanes having a phenyl group, a silicon atom, and a linear or branched alkylene group having 2 to 5 carbon atoms interposed between the phenyl group and the silicon atom, such as phenethyltrimethoxysilane Etc. are mentioned.

  The component (b2) preferably contains a trifunctional phenealkylalkoxysilane such as phenethyltrimethoxysilane. In this case, the strength of the coating layer formed from the coating material composition is improved.

  In addition, the component (b2) preferably includes a phenyl group-containing hydroxysilane compound. The phenyl group-containing hydroxysilane compound has a structure formed by replacing the alkoxy group in the phenyl group-containing alkoxysilane compound with a hydroxy group. The phenyl group-containing hydroxysilane compound is obtained by hydrolyzing the phenyl group-containing alkoxysilane compound.

  The component (b2) also preferably contains a trifunctional phenalkylalkylsilane such as phenethyltrihydroxysilane. In this case, the strength of the coating layer formed from the coating material composition is improved.

  The ratio of the component (b2) to the total solid content in the coating material composition is preferably in the range of 10% by mass to 30% by mass. When this ratio is 10% by mass or more, the surface of the coating layer exhibits lipophilic performance, and thus the fingerprint resistance of the coating layer is improved. Moreover, the intensity | strength of a coating layer improves that this ratio is 30 mass% or less.

  The component (b3) is composed of a silicone oil having a phenyl group and a reactive group. When the reactive component contains the component (b3), the good anti-fingerprint property of the coating layer formed from the coating material composition is maintained, and the slipping property of the coating layer is further improved. This is because the coating layer contains the component (b3) which is a silicone oil, so that the slipping property of the coating layer is improved. Further, since the component (b3) has a phenyl group, the coating layer has a high fingerprint resistance. It is thought that sex is maintained. Further, since the component (b3) has a reactive group, the molecule of the component (b3) is fixed in the coating layer by reacting with the component (b1) and the component (b2). For this reason, the fall of the intensity | strength of the coating layer by using (b3) component is suppressed. Furthermore, the durability of the coating layer is improved, so that the good slipperiness of the coating layer is maintained over a long period of time.

  As the reactive group in the component (b3), an alkoxy group, an acetoxy group, an oxime group (—O—N═C—R (R ′)), an enoxy group (—O—C (R) ═C (R ′) R ″), amino groups, aminoxy groups (—O—N (R) R ′), amide groups (—N (R) —C (═O) —R ′) (in these groups R, R ′, R "" Is, for example, each independently a hydrogen atom or a monovalent hydrocarbon group), hydrolyzable groups such as halogen, and hydroxyl groups.

  The weight average molecular weight of the component (b3) is preferably in the range of 800 to 1200, and more preferably in the range of 900 to 1000. In these cases, the slipperiness of the coating layer is particularly high. This is because the viscosity of the coating material composition is moderately suppressed because the weight average molecular weight of the component (b3) is in the above range, and as a result, the surface of the coating layer formed from the coating material composition has a finger or the like. It is thought that this is because the coefficient of friction when sliding is lowered.

  The component (b3) particularly preferably contains a silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer. In this case, the fingerprint resistance of the coating layer is further improved, and the slipping property of the coating layer is further improved. This is because the lipophilicity of the surface of the coating layer is effectively improved by the diphenylsiloxane part in the silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer, and further, the dimethylsiloxane part in the silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer This is considered to be because the slipperiness of the surface of the coating layer is effectively improved.

  The silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer is represented by the following formula (2).

  In Formula (2), each of m and n is 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 mole percentage of the diphenylsiloxane portion relative to the entire constitutional unit of the silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer, that is, the value of {n / (m + n + 2)} × 100 (mol%) in the formula (2) is 10 to 25 mol. %, Preferably in the range of 14 to 18 mol%. In these cases, the effect of improving the lipophilicity of the surface of the coating layer by the phenylsiloxane portion and the effect of improving the slipperiness of the surface of the coating layer by the dimethylsiloxane portion are both effectively exhibited. Thereby, the fingerprint resistance and slipperiness of a coating layer become high with good balance.

  The ratio of the component (b3) to the total solid content in the coating material composition is preferably in the range of 1% by mass to 15% by mass. When this ratio is 1% by mass or more, the slipperiness of the coating layer is particularly improved. Moreover, the transparency of a coating layer becomes difficult to fall that this ratio is 15 mass% or less.

[Solvent]
The coating material composition preferably contains a solvent. In this case, it is preferable to use an appropriate solvent that can be easily volatilized by heating or the like. Specific examples of the solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol Glycol ethers such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone, esters such as ethyl acetate, butyl acetate and ethyl acetoacetate, xylene, And toluene.

  The ratio of the solvent in the coating material composition is 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 easily applied, the thickness of the coating layer is easily adjusted, and the stability of the coating material composition is ensured. It is more preferable if the ratio of the solvent is in the range of 70% by mass to 99% by mass.

[Preparation of coating material composition]
An example of a method for preparing the coating material composition will be described. First, a liquid mixture is prepared by blending a reactive component, a solvent, water, and an acid catalyst. The amount of water used is preferably such that the molar ratio of water to hydrolyzable groups in the reactive component is in the range of 1.0 to 3.0. Subsequently, the condensation reaction of the reactive components in the mixed solution is allowed to proceed. The condensation reaction is preferably allowed to proceed under a temperature condition of 20 ° C. or more and 60 ° C. or less. Subsequently, the component (a) is added to the mixed solution, and a solvent is further added as necessary. In addition, after adding (a) component to a liquid mixture, you may advance the condensation reaction of a reactive component. In that case, the coating material composition is more easily formed into a film, and the strength of the coating layer formed from the coating material composition is further improved. In addition, after the condensation reaction of the reactive component proceeds, the component (a) may be added to the mixed solution, and then the condensation reaction of the reactive component may further proceed. In this way, a coating material composition is obtained.

  Although the weight average molecular weight of (b) component in a coating material composition is not specifically limited, It is preferable that it is the range of 1000 or more and 5000 or less. When the weight average molecular weight is 1000 or more, the coating material composition is easily formed into a film. Moreover, the fall of the intensity | strength of a coating layer is suppressed as this weight average molecular weight is 5000 or less. In the preparation of the coating material composition, when the condensation reaction of the reactive component proceeds, it is desirable that the reaction conditions are appropriately adjusted so that the weight average molecular weight of the component (b) is in a desired range.

[Coated products]
In the present embodiment, as shown in FIG. 1, the coated article 1 includes a base material 3 and a coating layer 2 formed from a coating material composition.

  The material of the substrate 3 is not particularly limited, and examples thereof include inorganic materials typified by glass, metal materials, and organic materials typified by polycarbonate and polyethylene terephthalate. The shape of the substrate 3 is not particularly limited, and examples thereof include a plate shape and a film shape.

  The use of the base material 3 and the coated product 1 is not particularly limited. For example, the base material 3 and the coated product 1 are applied to a member constituting the outermost surface of an image display device such as a display, a protective cover such as a display, and the like. It is preferable. In particular, it is preferably applied to a member having many opportunities to touch a human hand, such as a member constituting the outermost surface of the touch panel display or a protective cover of the touch panel display.

  The coating layer 2 can be formed on the base material 3 by applying and forming a coating material composition on the base material 3. The coating method of the coating material composition is not particularly limited. For example, brush coating, spray coating, dipping (dipping, dip coating), roll coating, gravure coating, flow coating, curtain coating, knife coating, spin coating, table Various usual coating methods such as a coat, a sheet coat, a sheet coat, a die coat, and a bar coat can be mentioned.

  It is preferable to advance the condensation reaction of the component (b) in the coating material composition by performing a heat treatment on the coating material composition applied onto the substrate 3. Thereby, the mechanical strength of the coating layer 2 further improves. The heating temperature during the heat treatment is not particularly limited, but is preferably a relatively low temperature of 60 ° C. or higher and 300 ° C. or lower. The heating time is preferably in the range of 5 minutes to 120 minutes. When the heating temperature is 300 ° C. or lower, the thermal decomposition of the phenyl group in the component (b) is suppressed, so that the high fingerprint resistance of the coating material composition is maintained. Even when the heating temperature is relatively low, the mechanical strength of the coating layer 2 is equivalent to that when the heating temperature is high. For this reason, it becomes possible to reduce cost and the deterioration of the base material 3 by high temperature is suppressed. Furthermore, when a base material 3 having a low thermal conductivity is used, such as a glass base material 3, if the heating temperature is high, the temperature rises and cooling takes time, so the processing speed is slowed down. If the heating temperature is low, the processing speed increases.

  The thickness of the coating layer 2 is appropriately set according to the use of the coated product 1, the purpose of forming the coating layer 2, and the like, but is particularly preferably in the range of 50 nm to 5 μm. Moreover, when the coating layer 2 is formed for antireflection use, it is preferable that the thickness of the coating layer 2 is in the range of 50 nm or more and 100 nm or less.

  Since it is easy to lower the refractive index of the coating layer 2 by preparing the composition of the coating material composition, the coating layer 2 is particularly suitable for antireflection applications. In this case, for example, when the refractive index of the substrate 3 is less than 1.65, a layer (intermediate layer 4) having a refractive index of 1.65 or more is first formed on the surface of the substrate 3, and this intermediate layer It is preferable that the coating layer 2 is formed on 4. A known high refractive index material is used as a material for forming the intermediate layer 4. If 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 becomes large, and thus the antireflection performance of the coated product 1 becomes high.

  The reflectance on the surface of the coating layer 2 of the coated product 1 is preferably in the range of 1.5% or more and 3% or less from the viewpoint of making it difficult to visually recognize finger marks. In particular, if the reflectance is 2% or more and 3% or less, the color tone change of the finger print on the coating layer 2 is reduced. For this reason, the finger print is more difficult to be visually recognized. Moreover, it is preferable that the haze of the coating layer 2 is 1% or less.

[Example 1]
Methyl silicate (partially hydrolyzed condensation product of tetramethoxysilane. Colcoat, methyl silicate 51 (trade name) 147 parts by mass, isopropyl alcohol 2450 parts by mass, phenethyl trimethoxysilane (Gelest, SIP6722.6 (product) Name)) 43 parts by mass, silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer (manufactured by Gelest, PDS-1615, diphenylsiloxane ratio 14-18 mol%, weight average molecular weight 900-1000, OH ratio 3.4-4.8% ) 8 parts by mass and 165 parts by mass of a 0.1N nitric acid aqueous solution were mixed, and these were mixed well with a disper to obtain a mixed solution. This mixture was allowed to stand at room temperature for 96 hours to allow the condensation polymerization reaction to proceed. Then, when the weight average molecular weight of the resin component in a liquid mixture was measured, it was 1340.

  Next, porous silica particles (isopropyl alcohol-dispersed porous silica fine particles, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: Sururia 4110, solid content: 20% by mass, average primary particle diameter: 60 nm, outer shell thickness: about 10 nm) Was added in an amount of 188 parts by mass in terms of solid content.

  Next, the mixed solution was mixed with an IPA / butyl acetate / butyl cellosolve mixed solvent (a mixture prepared in advance so that 5% by mass in the total amount of the diluted mixed solution was butyl acetate and 2% by mass in the total amount was butyl cellosolve. The mixture was diluted with a solvent and the mixture was allowed to stand for 1 hour to obtain a coating material composition having a total solid content of 3% by mass. The solid content ratios of the components in the coating material composition are shown in the following table.

  Moreover, the base material made from a polyethylene terephthalate provided with the intermediate | middle layer (hard-coat layer) of refractive index 1.67 was prepared. The surface of this substrate was cleaned with a UV-ozone cleaner (excimer lamp, manufactured by Ushio Electric, model H0011). Subsequently, the coating material composition was applied onto the hard coat layer of the substrate by a wire bar coater. Subsequently, the coating material composition on the substrate was heated at 120 ° C. for 5 minutes in an oxygen atmosphere. As a result, a coated product having a coating layer having a thickness of 100 nm was obtained.

[Example 2]
In Example 1, the amount of methyl silicate and silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer used was changed so that the solid content ratio of these components in the coating material composition would be the value shown in the table below. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, and the coating material composition was prepared and the coating product was obtained further.

  When preparing the coating material composition, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1 and found to be 1290.

[Example 3]
In Example 1, the amount of methyl silicate and silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer used was changed so that the solid content ratio of these components in the coating material composition would be the value shown in the table below. did. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, and the coating material composition was prepared and the coating product was obtained further.

  When preparing the coating material composition, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1, and it was 1415.

[Example 4]
In Example 1, the amount of methyl silicate and silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer used was changed so that the solid content ratio of these components in the coating material composition would be the value shown in the table below. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, and the coating material composition was prepared and the coating product was obtained further.

  When preparing the coating material composition, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1 and found to be 1387.

[Example 5]
In Example 1, the amounts of methyl silicate and phenethyl trimethoxysilane used were changed so that the solid content ratio of these components in the coating material composition would be the value shown in the table below. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, the coating material composition was prepared, and also the coated article was obtained.

  When preparing the coating material composition, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1 and found to be 1278.

[Example 6]
In Example 1, the amounts of methyl silicate and phenethyl trimethoxysilane used were changed so that the solid content ratio of these components in the coating material composition would be the value shown in the table below. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, the coating material composition was prepared, and also the coated article was obtained.

  When the coating material composition was prepared, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1, and it was 1301.

[Example 7]
In Example 1, the amount of the porous silica particles and methyl silicate used was changed so that the solid content ratio of these components in the coating material composition would be the value shown in the table below. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, and the coating material composition was prepared and the coating article was further obtained.

  When the coating material composition was prepared, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1 and found to be 1297.

[Example 8]
In Example 1, the amount of the porous silica particles and methyl silicate used was changed so that the solid content ratio of these components in the coating material composition would be the value shown in the table below. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, the coating material composition was prepared, and also the coated article was obtained.

  When the coating material composition was prepared, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1 and found to be 1274.

[Example 9]
In Example 1, the use amount of the non-porous silica particles and methyl silicate was changed so that the solid content ratios of these components in the coating material composition were values shown in the following table. Further, the amount of isopropyl alcohol used was adjusted so that the solid content concentration of the mixed solution was the same as in Example 1.

  Other than that was processed by the same method and conditions as Example 1, the coating material composition was prepared, and also the coated article was obtained.

  When preparing the coating material composition, the weight average molecular weight of the resin component in the mixed solution was measured in the same manner as in Example 1 and found to be 1307.

[Comparative Example 1]
132 parts by mass of methyl silicate, 2473 parts by mass of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxysilane, and 165 parts by mass of 0.1N nitric acid aqueous solution were blended, and these were mixed well with a disper to obtain a mixed solution. This mixture was allowed to stand at room temperature for 96 hours. Then, when the weight average molecular weight of the resin component in a liquid mixture was measured, it was 1259.

  Next, 188 parts by mass of porous silica particles as solid content is added to the mixed solution, and non-porous silica particles (isopropyl alcohol-dispersed non-porous silica fine particles, manufactured by Nissan Chemical Industries, Ltd., product number IPA-ST-ZL 50 parts by mass of a solid content of 30% by mass and an average primary particle size of 100 nm).

  Thereafter, the coating material composition was prepared by performing the same treatment and conditions as in Example 1, and a coated product was obtained.

[Comparative Example 2]
A mixed solution was obtained by blending 162 parts by mass of methyl silicate, 2443 parts by mass of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxysilane, and 165 parts by mass of a 0.1N nitric acid aqueous solution, and thoroughly mixing them with a disper. This mixture was allowed to stand at room temperature for 96 hours. Then, when the weight average molecular weight of the resin component in a liquid mixture was measured, it was 1211.

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

  Thereafter, a coating material composition was prepared by carrying out the treatment under the same method and conditions as in Example 1, and further a coated product was obtained.

[Comparative Example 3]
153 parts by mass of methyl silicate, 2452 parts by mass of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxysilane, 6 parts by mass of alkylsilane (KBM3103 (trade name) manufactured by Shin-Etsu Silicone), and 165 parts by mass of 0.1N nitric acid aqueous solution These were mixed well with a disper to obtain a mixed solution. This mixture was allowed to stand at room temperature for 96 hours. Then, when the weight average molecular weight of the resin component in a liquid mixture was measured, it was 1253.

  Next, 188 parts by mass of porous silica particles in terms of solid content was added to the mixed solution.

  Thereafter, a coating material composition was prepared by carrying out the treatment under the same method and conditions as in Example 1, and further a coated product was obtained.

[Comparative Example 4]
153 parts by mass of methyl silicate, 2452 parts by mass of isopropyl alcohol, 43 parts by mass of phenethyltrimethoxysilane, 6 parts by mass of alkylsiloxane (KF-96 (trade name) manufactured by Shin-Etsu Silicone), and 165 parts by mass of 0.1N nitric acid aqueous solution The liquid mixture was obtained by mix | blending and mixing these well with a disper. This mixture was allowed to stand at room temperature for 96 hours. Then, when the weight average molecular weight of the resin component in a liquid mixture was measured, it was 1356.

  Next, 188 parts by mass of porous silica particles in terms of solid content was added to the mixed solution.

  Thereafter, the coating material composition was prepared by performing the same treatment and conditions as in Example 1, and a coated product was obtained.

[Comparative Example 5]
Formulated with 153 parts by weight of methyl silicate, 2452 parts by weight of isopropyl alcohol, 43 parts by weight of phenethyltrimethoxysilane, 6 parts by weight of acrylic graft polymer (US270 (trade name) manufactured by Toa Gosei Co., Ltd.), and 165 parts by weight of 0.1N nitric acid aqueous solution These were mixed well with a disper to obtain a mixed solution. This mixture was allowed to stand at room temperature for 96 hours. Then, when the weight average molecular weight of the resin component in a liquid mixture was measured, it was 1321.

  Next, 188 parts by mass of porous silica particles in terms of solid content was added to the mixed solution.

  Thereafter, a coating material composition was prepared by carrying out the treatment under the same method and conditions as in Example 1, and further a coated product was obtained.

[Evaluation test]
About the coating layer formed in Examples 1-9 and Comparative Examples 1-5, the evaluation test shown below was implemented. The results are shown in the table below.

(Slippery)
Using a friction tester (manufactured by Kato Tech Co., Ltd., model number KES-SE), the dynamic friction coefficient of the surface of the coating layer was measured. Silicone rubber was used as the friction element, the load applied to the friction element was 25 g, and the sliding speed of the friction element was 1 cm / sec.

(Fingerprint visibility)
Finger traces were attached to the coating layer by pressing the abdominal surface of the finger on the surface of the coating layer. The result of visually observing the finger marks was evaluated according to the following evaluation criteria.
1. Fingerprints can be clearly seen.
2. Finger traces can be seen in a blurred manner.
3. Although the shape of the fingerprint on the finger print cannot be visually recognized, the distinction between the part having the finger print and the other part can be clearly recognized.
4). It is not possible to clearly distinguish the part with the finger print from the other part.
5. Fingerprints are hardly visible.

(Haze)
The haze value of the coating layer was measured using a haze meter (Nippon Denshoku Industries Co., Ltd., model number NDH2000).

(Mechanical strength)
The steel wool was slid on the coating layer at a speed of 5 cm / sec while pressing the steel wool # 0000 on the surface of the coating layer with a load of 250 g / cm ² (about 24.5 kPa). Thereby, the steel wool was reciprocated 10 times on the coating layer. Subsequently, the coating layer was observed to confirm the presence / absence of peeling of the coating layer, the surface shape, the state of scratches, and the like. The results were evaluated according to the following evaluation criteria.
1. The coating layer was completely peeled off.
2. Clear scratches were found on the entire surface of the coating layer.
3. The entire surface of the coating layer was slightly scratched.
4). Although no scratch was observed in the coating layer, a dent was formed.
5. No scratches or dents were observed in the coating layer.

1 Coated product 2 Coating layer 3 Base material 4 Intermediate layer

Claims (6)

Contains at least one selected from (a) porous silica particles, and (b) a reactive component having at least one of hydrolytic condensation reactivity and dehydration condensation reactivity, and a condensation product of this reactive component And the reactive component is
(B1) Tetrafunctional reactive silane compound (b2) A reactive silane compound having a phenyl group, and (b3) a reaction having hydrolysis reactivity that reacts with the phenyl group, the component (b1) and the component (b2). Containing a silicone oil having a functional group ,
The coating material composition whose ratio of the said (b3) component with respect to the total solid content is the range of 1-15 mass% . Relative to the total solid content of the coating material composition, wherein (b2) the proportion of component, the coating composition of claim 1 in the range of 10% by weight to 30% by weight. The coating material composition according to claim 1 or 2, wherein the (b3) component has a weight average molecular weight in the range of 800 to 1200. The coating material composition according to any one of claims 1 to 3 , wherein the component (b3) contains a silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer. The coating material composition according to any one of claims 1 to 4 , wherein the component (b2) contains a compound having an alkylene group interposed between a silicon atom and a phenyl group. A coated article comprising a coating layer formed from the coating material composition according to any one of claims 1 to 5 .

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