JP2011195806A - Fingerprint-resistant coating film-formed article and fingerprint-resistant coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fingerprint-resistant coating film-formed article including a coating film on which fingerprint stains are hardly made conspicuous and which has practically-sufficient mechanical strength and to provide a fingerprint-resistant coating material composition for forming the coating film of the fingerprint-resistant coating film-formed article.SOLUTION: The fingerprint-resistant coating film-formed article is obtained by forming the coating film, which contains non-porous silica fine particle, a hydrolysate or a partially-hydrolyzed material of tetrafunctional alkoxysilane, and a hydrolysate or a partially-hydrolyzed material of a hydrolyzable silane compound having a phenyl group, on the outermost surface of a base material. The two-dimensional surface roughness Ra of the outermost surface of the coating film is 5-20 nm. The fingerprint-resistant coating material composition for forming the coating film contains the non-porous silica fine particles, the hydrolysate or the partially-hydrolyzed material of tetrafunctional alkoxysilane and the hydrolyzable silane compound having the phenyl group. The non-porous silica fine particles have 50-200 nm average primary particle diameter and accounts for 5-30 mass% of the total solid content.

Description

  The present invention relates to a fingerprint-resistant coating film-formed product and a fingerprint-resistant coating material composition.

  In a display typified by a display device, the antireflection coating formed on the outermost surface has a problem that fingerprint stains are easily attached and the attached fingerprint stains are easily noticeable. For this reason, conventional antireflection coatings have a basic performance of antireflection performance and surface strength that prevents scratches (ie, scratch resistance), as well as surface water and oil repellency that can easily remove fingerprint stains (ie, Antifouling properties have been required.

For example, in Japanese Patent Application Laid-Open No. 2003-266581 (Patent Document 1), a coating material composition is mixed with a hydrolyzable organosilicon compound having a fluorine atom in the molecule, thereby providing water and oil repellency on the surface of the coating film. Is granted.
Japanese Patent Laid-Open No. 2003-266581

  However, in recent years, in displays such as touch panels and mobile phones, it has become more desirable that the attached fingerprint stains are less noticeable or are less likely to adhere than the fingerprint stains can be easily removed. .

  On the other hand, in products other than display devices, a highly glossy surface treatment is applied to give a high-quality appearance. For example, a high gloss surface coating is increasing on the surface of a small electric product housing represented by a housing of a mobile phone, but the attached fingerprint is easily noticeable, and there is a problem of impairing the sense of quality. In addition, there is a similar problem that various fingerprints that transmit or reflect light (for example, reflection parts such as a clear reflector for illumination, and transmission parts such as a protective cover) are easily noticeable. Furthermore, in a usage environment where such fingerprints are attached, the coating film is also required to have practically sufficient mechanical strength.

  The present invention has been made in view of the above problems, and fingerprint antifouling coating products and antifingerprinting coatings provided with a coating film that has a mechanical strength that is practically sufficient with less noticeable fingerprint stains. It is an object to provide a fingerprint-resistant coating material composition to be formed.

  In order to solve the above-mentioned problems, the anti-fingerprint film-forming product of the first invention comprises a non-porous silica fine particle, a hydrolyzate or partial hydrolyzate of a tetrafunctional alkoxysilane, and a hydrolyzate having a phenyl group. A coating film containing a hydrolyzate or partial hydrolyzate of a degradable silane compound is provided on the outermost surface of the substrate, and the two-dimensional surface roughness Ra of the outermost surface of the coating film is 5 nm to 20 nm. It is what.

  The fingerprint-resistant coating material composition of the second invention is a fingerprint-resistant coating material composition for forming a coating film of the fingerprint-resistant coating film-formed product of the first invention, and is a non-porous silica fine particle And a tetrafunctional alkoxysilane and a hydrolyzable silane compound having a phenyl group, and the non-porous silica fine particles have an average primary particle diameter of 50 nm to 200 nm, and are contained in the total solid content. It contains 5 mass% to 30 mass%.

  The fingerprint-resistant coating material composition of the third invention is the second invention, wherein the non-porous silica fine particles are contained in an amount of 5% by mass to 25% by mass in the total solid content, and further the porous silica fine particles are all solid. It is characterized by containing 5 mass% to 30 mass% in the minute.

  The fingerprint-resistant coating material composition of the fourth invention is characterized in that, in the third invention, the porous silica fine particles have an average primary particle diameter of 30 nm to 100 nm.

  ADVANTAGE OF THE INVENTION According to this invention, in addition to making the attached fingerprint stain | pollution | contamination hard to be conspicuous, the fingerprint-resistant coating-film formation product provided with the coating film which has mechanical strength can be obtained.

It is a figure which shows the atomic force microscope image of the coating-film surface of an Example, (a) is Example 1, (b) is Example 2, (c) is Example 3, (d) is Example 4. An atomic force microscope image is shown.

  Hereinafter, the best mode for carrying out the present invention will be described.

  The anti-fingerprint film-forming product according to the present invention comprises a non-porous silica fine particle, a hydrolyzate or partial hydrolyzate of a tetrafunctional alkoxysilane, a hydrolyzate of a hydrolyzable silane compound having a phenyl group, or A coating film containing a partial hydrolyzate is provided on the outermost surface of the substrate, and the two-dimensional surface roughness Ra of the outermost surface of the coating film is 5 nm to 20 nm.

  The reason why the attached fingerprint stains are conspicuous is that the oil and fat component in the fingerprint stains exists as micro oil droplets on the coating film, and the transmitted light or reflected light is scattered by the oil droplets, thereby changing to diffused light. In order to make the fingerprint stain inconspicuous, the present inventors only need to make the oil and fat component not become oil droplets on the surface of the coating but spread and get wet.For improving the wettability of the oil and fat component of this fingerprint stain, It has been found that it is effective that a phenyl group exists on the surface of a coating film made of a silane compound and that the coating film surface has a nanoscale surface roughness. By setting the two-dimensional surface roughness Ra of the outermost surface of the coating film to 5 nm to 20 nm, it is possible to obtain the effect of spreading and spreading fingerprint stains by increasing the surface area without increasing haze due to light scattering. That is, if the two-dimensional surface roughness (Ra) is less than 5 nm, the wetting and spreading effect due to the increase in surface area is difficult to obtain, and if it exceeds 20 nm, the haze may increase due to light scattering. Further, by including non-porous silica fine particles as an essential component, a practically sufficient mechanical strength can be achieved while obtaining fingerprint resistance. The two-dimensional surface roughness (Ra) is more preferably 6 to 12 nm.

  The method for setting the two-dimensional surface roughness (Ra) of the coating film to the above range is not limited, but 5% by mass of non-porous silica fine particles having an average primary particle diameter of 50 nm to 200 nm, preferably 80 nm to 120 nm in the coating film. It is preferable to achieve by containing -30% by mass. In particular, it is desirable to achieve the two-dimensional surface roughness only by blending non-porous silica fine particles. In addition to blending non-porous silica fine particles, dry blending such as porous silica blending, plasma etching, and mechanical polishing is possible. The two-dimensional surface roughness may be achieved by using etching or wet etching with NaOH aqueous solution in combination.

  Next, the anti-fingerprint coating material composition for forming the coating film of this anti-fingerprint coating product will be described in detail. The anti-fingerprint coating material composition comprises a matrix-forming material containing a tetrafunctional alkoxysilane (A) and a hydrolyzable silane compound (B) having a phenyl group, and non-porous silica fine particles as an essential component. It is prepared by blending.

  The tetrafunctional alkoxysilane (A) used in the present invention is represented by the following formula (1).

Si (OR) ₄ (1)
“R” in the alkoxyl group “OR” in the formula (1) is not particularly limited as long as it is a monovalent hydrocarbon group, and may be the same or different. “R” is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples include groups. Among the alkyl groups contained in the alkoxide group, those having 3 or more carbon atoms may be linear such as n-propyl group, n-butyl group, isopropyl group, It may have a branch such as an isobutyl group or a t-butyl group. Among these, a methyl group having 1 to 4 carbon atoms, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group are preferable. For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetra-i-propoxysilane, tetra-n-butoxysilane and the like can be preferably used.

  The hydrolyzable silane compound (B) having a phenyl group used in the present invention has a silicon atom having a phenyl group and a hydrolyzable group bonded to the molecule, and is compatible with a tetrafunctional alkoxysilane. Anything is possible. One having one or more silicon atoms can be used in the molecule, and one or more phenyl groups may be contained in the molecule. The phenyl group may or may not have a substituent. It is preferable to have two or more hydrolyzable groups in the molecule. The hydrolyzable silane compound (B) having a phenyl group only needs to contain a phenyl group. Even if the phenyl group is bonded directly to the silicon atom, the phenyl group is bonded to the silicon atom via an alkyl group. Also good.

The hydrolyzable silane compound (B) having a phenyl group is preferably a phenyl group-containing alkoxysilane compound. Examples of the phenyl group-containing alkoxysilane compound include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and phenylphenylsilane exemplified by triphenylethoxysilane;
An alkyl-substituted phenylalkoxysilane in which a phenyl group to which an alkyl substituent is bonded, as exemplified in di (p-tolyl) dimethoxysilane and di (p-tolyl) diethoxysilane, is bonded to a silicon atom;
Bisalkoxysilylbenzene in which two silicon elements are bonded via a phenyl group, as exemplified by 1,4-bis (triethoxysilyl) benzene;
An alkylphenylalkoxysilane in which a phenyl group and an alkyl group are directly bonded to a silicon atom as exemplified by methylphenyldimethoxysilane;
Examples thereof include phenealkylalkoxysilanes in which a phenyl group is bonded to a silicon atom via a linear or branched alkyl group having 2 to 5 carbon atoms as exemplified by phenethyltrimethoxysilane. it can.

  As the hydrolyzable group, in addition to the alkoxyl group described above, an acetoxy group, an oxime group (—O—N═C—R (R ′)), an enoxy group (—O—C (R) ═C (R ′) R ”), Amino group, aminoxy group (—O—N (R) R ′), amide group (—N (R) —C (═O) —R ′) (in these groups, R, R ′, R ″) May be, for example, independently a hydrogen atom or a monovalent hydrocarbon group) or halogen.

  The above-mentioned tetrafunctional alkoxysilane (A) and the hydrolyzable silane compound (B) having a phenyl group are obtained by converting at least the tetrafunctional alkoxysilane (A) into a hydrolyzate or partially hydrolyzed in the anti-fingerprint coating material composition. It is regarded as a decomposition product.

  Among them, the tetrafunctional alkoxysilane (A) and the hydrolyzable silane compound (B) having a phenyl group are hydrolyzed in the coexistence to be adjusted to a cohydrolyzate or a copartial hydrolyzate. preferable. In this case, a phenyl group-containing alkoxysilane compound is preferably used as the hydrolyzable silane compound (B) having a phenyl group. The “co-hydrolyzate or co-hydrolyzate” includes those containing either one or both of a co-complete hydrolyzate and a co-partial hydrolysate.

  Further, in the co-hydrolyzate or co-hydrolyzate of the tetrafunctional alkoxysilane (A) and the hydrolyzable silane compound (B) having a phenyl group, the tetrafunctional alkoxysilane (A) and the phenyl group The mixing ratio with the phenyl group-containing alkoxysilane compound, which is the hydrolyzable silane compound (B), is preferably set in the range of 95: 5 to 20:80 as the solid content mass ratio. This is because if the content ratio of the phenyl group-containing alkoxysilane compound is less than 5% by mass, the fingerprint resistance may not be sufficient depending on the application, and if it exceeds 80% by mass, the film strength may not be sufficient. . More preferably, the content ratio of the phenyl group-containing alkoxysilane compound is 10% by mass or more and 50% by mass or less.

  Here, as described above, the tetrafunctional alkoxysilane (A) and the hydrolyzable silane compound (B) having a phenyl group are hydrolyzed to prepare a co-hydrolyzate or co-partial hydrolyzate. Is not particularly limited. In the present invention, the non-porous silica fine particles and the porous silica fine particles (hereinafter referred to as “non-porous silica fine particles”) blended as desired are mixed at the stage of forming the co-hydrolyzate or co-partial hydrolyzate. It is preferable. By setting it as such a mixing | blending order, the coating material composition excellent in the film formation ability and the film strength can be formed. In addition, after forming a cohydrolyzate or a copartial hydrolyzate, when mix | blending nonporous silica microparticles | fine-particles etc., you may make it hydrolyze after mixing nonporous silica microparticles | fine-particles.

  Although the weight average molecular weight of a cohydrolyzate or a copartial hydrolyzate is not specifically limited, The range of 1000-5000 is preferable. If it is less than 1000, the film-forming ability is inferior. Conversely, if it exceeds 5000, the film strength may decrease. The temperature condition during the hydrolysis is preferably about 20 ° C to 60 ° C. If the temperature is lower than this range, the reaction does not proceed. On the other hand, if the temperature is higher than this range, the reaction proceeds too quickly and it is difficult to secure a certain molecular weight, and the molecular weight becomes too large and the film strength may decrease. There is.

  As non-porous silica fine particles, voids other than defects are not observed when the particles are observed with a scanning electron microscope. For example, silica fine particles having a porosity of less than 10% are preferable. As the non-porous silica fine particles, for example, a powdery one or a sol-like one may be used. When the non-porous silica fine particles are used in a sol form, that is, as colloidal silica, there is no particular limitation. For example, water-dispersible colloidal silica or a hydrophilic organic solvent-dispersible colloid such as alcohol is used. be able to. Generally, such colloidal silica contains 20% by mass to 50% by mass of silica as a solid content, and the silica compounding amount can be determined from this value. Non-porous silica fine particles are included for the so-called filler effect, and have the effect of improving the strength of the cured film or preventing cracks.

  The blending amount of the non-porous silica fine particles is set so as to be 5% by mass to 30% by mass in the total solid content in the anti-fingerprint coating material composition. If it is less than 5% by mass, the effect of wetting and spreading due to the unevenness of the coating film surface due to the blending of the nonporous silica fine particles cannot be obtained, and if it exceeds 30% by mass, haze may be increased. In particular, those containing non-porous silica fine particles in a proportion of 5% by mass or more and 25% by mass or less, and more preferably 10% by mass or more and 25% by mass or less in the total solid content have a high wetting and spreading effect due to coating film surface irregularities, Haze generation is also small.

  The average primary particle diameter of the non-porous silica fine particles is 50 nm to 200 nm as described above, and is preferably 80 nm to 120 nm. If it is within this range, the effect of wetting and spreading due to the coating surface unevenness can be obtained, and an appropriate surface unevenness structure in which haze does not increase can be obtained. In the present specification, the average primary particle size is determined by a dynamic light scattering method.

  The fingerprint-resistant coating material composition of the present invention may contain porous silica fine particles in addition to non-porous silica fine particles. In order to obtain low reflectivity with a single-layer coating film, it is preferable to use non-porous silica fine particles and porous silica fine particles in combination. In this case, the non-porous silica fine particles are preferably contained in an amount of 5 to 25% by mass in the total solid content, and the porous silica fine particles are preferably contained in an amount of 5 to 30% by mass in the total solid content. If the blending amount of the porous silica fine particles is less than 5% by mass, the effect of improving the low refractive index of the coating film due to the blending of the porous silica fine particles may not be obtained. May cause. Those containing porous silica fine particles in a proportion of 15% by mass or more and 25% by mass or less in the total solid content are excellent as an antireflection coating-forming material and are preferable.

  The total amount of the porous silica fine particles and the non-porous silica fine particles is particularly preferably in the range of 10% by mass to 30% by mass with respect to the total solid content in the fingerprint-resistant coating material composition. When it is within this range, a fingerprint-resistant coated film-formed product having both low reflectivity and mechanical strength can be obtained.

  The porous silica fine particles having an average primary particle diameter of 30 nm to 100 nm are preferably used regardless of the kind. When the average primary particle diameter is within this range, an effect of wetting and spreading due to the coating surface unevenness is obtained, an appropriate surface unevenness structure in which haze does not increase is obtained, and mechanical strength is also excellent. The porous silica fine particles have a porosity of 20% or more, and hollow silica fine particles, mesoporous fine particles and the like are preferably used.

  The hollow silica fine particles have an outer shell composed of a silica-based inorganic oxide. For example, the outer shell has a silica single layer, a single layer of a composite oxide composed of silica and an inorganic oxide other than silica, Examples thereof include a laminated layer having two or more layers. At this time, the thickness of the outer shell can be, for example, in the range of 1 nm to 50 nm, preferably 5 nm to 20 nm, and this thickness is in the range of 1/50 to 1/5 of the average particle diameter of the hollow fine particles. Things can be used. The average particle diameter of the hollow silica fine particles can be set in the range of 5 nm to 2 μm, for example. If the average particle size is smaller than 5 nm, the effect of lowering the refractive index due to hollowness is small. Conversely, if the average particle size is larger than 2 μm, the transparency becomes extremely poor and diffuse reflection (Anti-Glare ) Will contribute greatly. As an application in which high transparency is required for the coating film, for example, in order to prevent reflection of a display or the like, the average particle diameter of the hollow silica fine particles is preferably in the range of 30 nm to 100 nm. The average particle diameter can be determined by a dynamic light scattering method.

  The porous silica fine particles may be in the form of a powder or those prepared in a sol form. When the porous silica fine particles are used in a sol form, that is, as colloidal silica, it is not particularly limited. For example, water-dispersible colloidal silica or organic solvent-dispersible colloid such as alcohol can be used. Generally, such colloidal silica contains 20% by mass to 50% by mass of silica as a solid content, and the silica compounding amount can be determined from this value.

  For example, the anti-fingerprint coating material composition of the present invention can be obtained by blending the above-described components as follows.

  First, a tetrafunctional alkoxysilane (A), a hydrolyzable silane compound (B) having a phenyl group, an alcohol solvent, water, and an acid catalyst are mixed to have the above-described weight average molecular weight 4. A cohydrolyzed product or a cohydrolyzed product of the functional alkoxysilane (A) and the hydrolyzable silane compound (B) having a phenyl group is prepared. The obtained co-hydrolyzate or co-partial hydrolyzate is blended with non-porous silica fine particles having an average primary particle diameter of 50 nm to 200 nm in an amount of 5% by mass to 30% by mass in the total solid content. By diluting with a solvent, the anti-fingerprint coating material composition of the present invention can be obtained. When blending the non-porous silica fine particles, the porous silica fine particles having an average primary particle diameter of 30 nm to 100 nm may be blended in an amount of 5% by mass to 30% by mass in the total solid content if desired.

  In the anti-fingerprint coating material composition of this embodiment, the tetrafunctional alkoxysilane (A) and the hydrolyzable silane compound (B) having a phenyl group have a water ratio (water molar ratio) to alkoxy group of 1. It is desirable to have made it react by 0.0-3.0. The water ratio here is included in the number of moles of water added to the anti-fingerprint coating material composition, the tetrafunctional alkoxysilane (A), and the hydrolyzable silane compound (B) having a phenyl group. The number of moles of an alkoxy group (for example, if it is a tetrafunctional alkoxysilane, it is a value obtained by multiplying the number of moles of the tetrafunctional alkoxysilane by the number of alkoxy groups “4”. It is a ratio to the total sum of the number of moles of trifunctional alkoxysilane multiplied by the number of alkoxy groups “3”. When the water ratio is 1.0 or less, particularly 0.5 or less, the hydrolysis reaction is insufficient and the coating film forming ability is lowered, and when it is 3.0 or more, particularly 5.0, the scratch resistance is lowered.

  As the solvent, an appropriate one that can be easily volatilized by heating or the like can be used. For example, methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t- Alcohols such as butyl alcohol and diacetone alcohol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and 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, toluene and the like can be used.

  The blending of the solvent can be set as appropriate. However, considering the ease of application of the fingerprint-resistant coating material composition, the ease of controlling the film thickness of the coating film, and the stability of the fingerprint-resistant coating material composition, the content of the solvent in the paint is 50 It is preferable to be adjusted in the range of mass% to 99.8 mass%, and more preferably in the range of 70 mass% to 99 mass%.

  By coating the surface of the base material with the anti-fingerprint coating material composition prepared as described above to form a film and drying and curing the film, a film-formed product having a film formed on the outermost surface is obtained. Obtainable. The base material to which the anti-fingerprint coating material composition is applied is not particularly limited. For example, inorganic base materials such as glass, metal base materials, polycarbonate and polyethylene terephthalate are representative. Examples of the shape of the substrate include a plate shape and a film shape. Furthermore, one or more layers may be formed on the surface of the substrate.

  The method of coating the fingerprint-resistant coating material composition on the surface of the substrate is not particularly limited. For example, brush coating, spray coating, dipping (dipping, dip coating), roll coating, flow coating Various ordinary coating methods such as curtain coating, knife coating, spin coating, table coating, sheet coating, single wafer coating, die coating, and bar coating can be selected.

  Moreover, it is preferable to heat-treat this after drying the coating formed on the surface of the substrate. By this heat treatment, the mechanical strength of the coating film can be further improved. The temperature during the heat treatment is not particularly limited, but it is preferable to perform the treatment at a relatively low temperature of 60 ° C. to 300 ° C. for 5 minutes to 120 minutes. When the treatment is performed at a temperature higher than 300 ° C., the phenyl group may be thermally decomposed, which may reduce the wettability of the fingerprint component. Even if heat treatment is performed at such a low temperature, the same mechanical strength as when heat treatment is performed at a high temperature can be obtained, so that the film forming cost can be reduced, and as in the case of heat treatment at a high temperature. The type of the base material is not limited. In addition, for example, in the case of a glass substrate, since the thermal conductivity is low, it takes time for temperature rise and cooling, and the heat treatment at a high temperature slows down the processing speed, whereas the heat treatment at a low temperature conversely increases the processing speed. It is something that can be done. The film thickness of the coating film formed on the surface of the substrate can be appropriately selected according to the intended use and purpose, and is not particularly limited, but is preferably in the range of 50 nm to 5 μm. In particular, in the case of antireflection applications, 50 nm to 100 nm is preferable.

  Since the anti-fingerprint coating material composition according to the present invention can easily form a coating film having a low refractive index, it is suitable for antireflection applications. For example, when the refractive index of the base material is less than 1.55, a coating film having a refractive index of 1.55 or more is formed on the surface of the base material, and this is used as an intermediate layer. It is effective to form a coating film from the fingerprint-resistant coating material composition according to the present invention. The coating film for forming the intermediate layer can be formed using a known high refractive index material, and if the refractive index of the intermediate layer is 1.55 or more, the anti-fingerprint coating according to the present invention The difference in refractive index from the coating film due to the material composition becomes large, and an antireflection substrate excellent in antireflection performance can be obtained. In particular, when the anti-fingerprint coating film contains non-porous silica fine particles and does not contain porous silica fine particles, since the refractive index of the anti-fingerprint coating film is not so low, an intermediate layer having a refractive index of 1.55 or more is used. It is preferable to provide the antireflection performance.

  From the viewpoint of improving fingerprint visibility, the anti-fingerprint film-formed product of the present invention preferably has a reflectance of 1.5 to 3%. In particular, when the reflectance is adjusted to 2% to 3%, the color tone change of the fingerprint trace is small, and the fingerprint visibility can be made particularly excellent. Moreover, it is preferable that a haze is 1% or less.

  Examples of the use for antireflection include, for example, the surface of the display, the outermost surface of the touch panel display, and parts where fingerprints are easily attached, such as protective covers for various display displays.

  The above-described fingerprint-resistant coating material composition of the present invention has a two-dimensional surface roughness (Ra) of 5 nm to 20 nm, and can obtain the effect of spreading and spreading fingerprint stains by increasing the surface area without increasing haze, It is possible to form a coating film having so-called fingerprint resistance, in which attached fingerprint stains are not noticeable. Furthermore, it contains a hydrolyzable silane compound having a phenyl group as a matrix resin, and the phenyl group is present on the surface of the coating film, so that neutral fats (triglycerides, etc.) and neutral fats, which are the main oil components of fingerprints The free fatty acid decomposed by is excellent in wet spreadability and has the effect of making the attached fingerprints less noticeable. In addition, the anti-fingerprint coating material composition contains non-porous silica fine particles and contains hydrolyzate or partial hydrolyzate of tetrafunctional alkoxysilane, thereby achieving mechanical strength while maintaining fingerprint resistance. can do.

  Next, the present invention will be specifically described with reference to examples. The weight average molecular weight was measured as a converted value by preparing a calibration curve with standard polystyrene by gel permeation chromatography (GPC).

Example 1
Phenethyltrimethoxysilane (manufactured by Gelest Co., Ltd.) as a hydrolyzable silane compound (B) having a phenyl group is added to 166.4 parts by mass of tetraethoxysilane (A) as tetrafunctional alkoxysilane (A). SIP67222.6 (trade name) ") 76.6 parts by mass, 54 parts by mass of water and 18 parts by mass of 0.4N hydrochloric acid aqueous solution were added and mixed well using a disper to obtain a mixture. This mixed liquid was allowed to stand at room temperature for 96 hours, and a copolymerized hydrolyzate (hereinafter referred to as a tetrafunctional alkoxysilane (A) having a weight average molecular weight of 1180 and a hydrolyzable silane compound (B) having a phenyl group. (Referred to as “phenyl-silicone cohydrolyzate”) as a matrix forming material of the coating film.

  Next, isopropanol-dispersed non-porous silica fine particles (“IPA-ST-ZL (product name)” manufactured by Nissan Chemical Industries, solid content 30 mass%, average primary particle size 100 nm) and isopropanol-dispersed porous silica fine particles (catalyst conversion) “Suriria CS60-IPA (product name)” manufactured by Kogyo Co., Ltd., solid content 20% by mass, average primary particle size 60 nm, outer shell thickness of about 10 nm) on the basis of solid content, non-porous silica fine particles / porous silica fine particles / phenyl -Blended so that the silicone cohydrolyzate (condensed compound equivalent) is 10/15/75 by mass ratio, and then IPA / butyl acetate / butyl cellosolve mixed solution (diluted) so that the total solid content is 3% by mass Example 5: Dilution with a premixed solution so that 5% by mass in the total amount of the later solution is butyl acetate and 2% by mass in the total amount is butyl cellosolve. To obtain a coating material composition.

  And after leaving this coating material composition to stand for 1 hour, PET substrate (single-sided hard coat treatment, hard coat refractive index 1) was previously surface-washed with a UV-ozone cleaner (excimer lamp, manufactured by USHIO INC., Model H0011). .77) a hard coat surface coated with a wire bar coater to form a coating film having a thickness of about 100 nm, and heat-treated at 120 ° C. for 5 minutes in an oxygen atmosphere to provide a coating film-formed product provided with the coating film Got.

(Example 2)
A coating film-formed product having a coating film was obtained in the same manner as in Example 1 except that the PET substrate was changed to one having a hard coat refractive index of 1.57.

(Example 3)
Coating material in the same manner as in Example 1 except that the non-porous silica fine particles / porous silica fine particles / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 10/0/90 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 1.

Example 4
A coating film-formed product having a coating film was obtained in the same manner as in Example 3 except that the PET substrate was changed to one having a hard coat refractive index of 1.57.

(Example 5)
356 parts by mass of methanol is added to 138.6 parts by mass of tetraethoxysilane as tetrafunctional alkoxysilane (A), and further phenylmethyldimethoxysilane (manufactured by Gelest Co., Ltd.) as hydrolyzable silane compound (B) having a phenyl group. SIP6740.0 (trade name) ") is added to 60.7 parts by mass, and the weight-average molecular weight of the resulting phenyl-silicone cohydrolyzate is adjusted to 1150 to obtain non-porous silica fine particles / porous silica fine particles / phenyl Example 1 except that the silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 25/0/75 on a solid basis, and the PET base material was changed to a hard coat refractive index of 1.57. After obtaining a coating material composition in the same manner, a film-formed product having a paint film was obtained in the same manner as in Example 1.

(Example 6)
Coating material in the same manner as in Example 5 except that the non-porous silica fine particle / porous silica fine particle / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 5/15/80 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 5.

(Example 7)
Coating material in the same manner as in Example 5 except that the non-porous silica fine particles / porous silica fine particles / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 10/25/65 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 5.

(Example 8)
Coating material in the same manner as in Example 5 except that the non-porous silica fine particles / porous silica fine particles / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 10/30/60 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 5.

(Comparative Example 1)
Coating material in the same manner as in Example 1 except that the non-porous silica fine particles / porous silica fine particles / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 0/40/60 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 5.

(Comparative Example 2)
A film-formed product having a coating film was obtained in the same manner as in Comparative Example 1 except that the PET substrate was changed to one having a hard coat refractive index of 1.57.

(Comparative Example 3)
Coating material in the same manner as in Example 5 except that the non-porous silica fine particles / porous silica fine particles / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 0/20/80 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 5.

(Comparative Example 4)
Coating material in the same manner as in Example 5 except that the non-porous silica fine particles / porous silica fine particles / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 0/0/100 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 5.

(Comparative Example 5)
Coating material in the same manner as in Example 5 except that the non-porous silica fine particles / porous silica fine particles / phenyl silicone cohydrolyzate (condensed compound equivalent) was changed to a mass ratio of 25/30/45 on a solid basis. After obtaining the composition, a film-formed product having a coating film was obtained in the same manner as in Example 5.

  The coating films obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated by measuring two-dimensional surface roughness, haze, fingerprint visibility, reflectance, and mechanical strength by the following methods. . The results are shown in Table 1. Moreover, the atomic force microscope image of Examples 1-4 is shown in FIG.

[Surface roughness of coating film]
The surface roughness of the coating film was measured using an atomic force microscope (“SPM-9500” manufactured by Shimadzu Corporation) with a visual field of 10 μm × 10 μm. The measurement place was changed, the measurement was performed three times, and the average value was calculated.

[Haze (Transparency)]
Using a haze meter (“NDH2000 (product name)” manufactured by Nippon Denshoku Industries Co., Ltd.), the haze value was measured and the transparency was evaluated.

[Fingerprint visibility]
The abdominal surface of the finger end was pressed against the surface of the coating film to adhere fingerprint stains, and the five-step evaluation was performed visually as follows.
1. 1. Fingerprint marks can be clearly seen. 2. A fingerprint mark can be visually recognized. Although it cannot be visually recognized as a fingerprint mark, the distinction between a fingerprint smeared portion and a non-sticky portion can be clearly seen. 4. The distinction between the fingerprint smudged part and the non-sticky part is not clearly visible. Almost no visible part of fingerprint stains [Reflectance]
Matte black coating is applied to the side of the acrylic plate where the coating film is not formed (back side) to suppress back side reflection, and the 5 ° relative reflectance (minimum reflectance) on the coating side is measured with a spectrophotometer (manufactured by Hitachi, Ltd.) "U-4100 (product name)").

[Mechanical strength]
Steel wool # 0000 was slid 10 times (speed: 1 cm / sec) with a load of 250 g / cm ^{2 on} the surface of the cured coating, and the mechanical strength was determined as follows based on the level of scratches generated in the cured coating.
1. Full surface peeling 2. Full scratch 3. Full-faced light wound 4. 4. There is no wound and there is a dent. No scratches, no bumps As shown in Table 1, Examples 1 to 8 were all excellent in mechanical strength with no scratches caused by the steel wool test, and good fingerprint visibility of 3 or more. The result was shown. In particular, in Examples 2, 4, 5 and 6, since the reflectance exceeded 2%, the color change of the fingerprint mark was small and the fingerprint visibility was particularly excellent. On the other hand, those of Comparative Examples 1 to 3 containing porous silica but not containing non-porous silica fine particles were inferior in mechanical strength. Furthermore, those of Comparative Examples 3 to 5 having a two-dimensional surface roughness Ra outside the range of 5 nm to 20 nm were inferior in fingerprint visibility.

Claims (4)

  A coating film containing a non-porous silica fine particle, a hydrolyzate or partial hydrolyzate of a tetrafunctional alkoxysilane, and a hydrolyzate or partial hydrolyzate of a hydrolyzable silane compound having a phenyl group is used as a base material. An anti-fingerprint film-formed product comprising an outermost surface and a two-dimensional surface roughness Ra of the outermost surface of the coating film of 5 nm to 20 nm.   A fingerprint-resistant coating material composition for forming a coating film of the fingerprint-resistant coating film-formed product according to claim 1, comprising a non-porous silica fine particle, a tetrafunctional alkoxysilane, and a phenyl group The non-porous silica fine particles have an average primary particle diameter of 50 nm to 200 nm and are contained in a total solid content of 5% by mass to 30% by mass. A fingerprint-resistant coating material composition.   3. The non-porous silica fine particles are contained in a total solid content of 5% by mass to 25% by mass, and the porous silica fine particles are contained in a total solid content of 5% by mass to 30% by mass. The anti-fingerprint coating material composition described in 1.   The fingerprint-resistant coating material composition according to claim 3, wherein the porous silica fine particles have an average primary particle size of 30 nm to 100 nm.

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