JPH01256576A - Nonglare hard coating film - Google Patents

Abstract

PURPOSE:To obtain a nonglare hard coating film improved in nonglare property, hardness, abrasion resistance and scratch resistance, by coating a desired base material with a composition comprising a specified silica sol, a fine silica powder and a vehicle and curing it. CONSTITUTION:A silica sol (A) is obtained by dispersing silica of a mean particle diameter of 5-200nm in an organic solvent such as a high-MW silicic anhydride or an alcohol. A desired base material is coated with a composition obtained by mixing 50-35pts.wt. component A with 0.1-20pts.wt., per 100pts.wt. mixture of component A with a vehicle, fine silica powder (B) which is a secondary agglomerate comprising primary particles of a particle diameter of 5-50nm and 100pts.wt. vehicle (C) comprising an organosilicon compound of the formula [wherein R<1-2> are each an alkyl, an alkenyl, an aryl or a hydrocarbon group substituted by halogen, epoxy, glycidoxy, amino, mercapto, methacryloxy or cyano, R<3> is a 1-8C alkyl, an alkoxyalkyl, an acyl or a phenyl, and (a) and (b) are each 0-1] and/or its hydrolyzate (C), and this composition is cured to obtain the title film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a hard coat film having a surface with excellent non-glare and antireflection properties, abrasion resistance, and scratch resistance.

The hard coat film of the present invention is particularly suitable for various display front panels such as CRT front panels, touch panels, showcases, and meter covers, and various glossy molded products.
used.

[Prior Art] Today, the number of devices that use displays, such as large computer terminals, has increased rapidly, and problems such as eye strain, discomfort, and decreased work efficiency have emerged, especially due to the presence of reflected light in front of the display. . In order to eliminate this problem, we added non-glare properties to the front of the display.
There is a strong demand for hard coat films that can suppress glare, and various developments are underway. As for the types of coatings, coatings have been developed for synthetic resin molded products mainly made of acrylic resin, polyester resin, melamine resin, etc., zinc steel plates, aluminum steel plates, stainless steel plates, etc.
JP-A-62-7768, JP-A-62-18388
6, Japanese Patent Application Laid-open No. 62-243662, etc.

Further, JP-A-62-1923/15 discloses a compound consisting of epoxysilane, alkoxysilane and silica fine particles, which has excellent surface hardness, abrasion resistance, flexibility, etc.

[Problems to be Solved by the Invention] Methods such as those disclosed in JP-A-62-7768 require special molding equipment such as an ultraviolet irradiation device, an ionizing radiation irradiation device, and a mold. The surface had low hardness and was not durable enough for practical use.

In addition, the compound of JP-A-82-19023/I@publication is
Non-glare properties were not considered.

The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to provide a film that has excellent non-glare properties and has improved film hardness, abrasion resistance, and scratch resistance. Our objective is to provide a durable hard coat film.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have completed the present invention having the following configuration.

"It is a secondary aggregate consisting of silica sol with an average particle size of 5 nm to 200 nm, primary particles with a particle size of 5 nm to 5 Qnm, and the main components are silica fine powder with a particle size of 1 μm to 100 μm and a vehicle. A non-glare hard coat film characterized by the following." The silica sol in the present invention is a colloidal dispersion in an organic solvent such as high molecular weight silicic anhydride and/or alcohol. The average particle size is approximately 5 to 200n.
m is preferably used, and those with a diameter of about 7 to 5 Q nm are more preferred.

If the average particle size is less than about 5 nm, the stability of the dispersion state is poor, and it tends to be difficult to obtain products of consistent quality.If the average particle size is more than 200 nm, the resulting coating film may have insufficient transparency. Yes, cloudiness may appear. It is also possible to use two or more types of silica sols having different average particle diameters.

The silica fine powder of the present invention has a primary particle size of 5 nm to 50 nm.
nm, and the particle size of its secondary aggregates is 1 μm ~”
tooLtn, and may be synthesized by either a wet method or a dry method for producing silica. Since fine silica powder has good dispersibility and dispersion stability, it is preferable to use a powder that is porous and has an internal surface area. Among them, hydrophobic silica is most preferred in terms of dispersibility.

Fine silica powder is an ingredient for achieving non-glare properties.
Since non-glare properties vary significantly depending on differences in average particle diameter, degree of dispersion, adjustment of amount added, etc., they are used under conditions depending on the purpose of use. It is also possible to use two or more kinds of silica fine powders having different average particle diameters.

The vehicle component of the present invention is used for the purpose of dispersing silica sol and fine silica powder, and may be any component as long as it can be dispersed. A silicon compound and/or its hydrolyzate is used. Among these, an organosilicon compound represented by the following general formula (A>) and/or a hydrolyzate thereof are preferably used.

RlaR”bs! (OR3)4-a-b (△)
(In the formula, R1 and R2 are each an alkyl group, an alkenyl group, an aryl group, or a hydrocarbon group having a halogen, an epoxy group, a glycidoxy group, an amino group, a mercapto group, a methacryloxy group, or a cyano group, and R3 is the number of carbon atoms. is an alkyl group, an alkoxyalkyl group, an acyl group, or a phenyl group of 1 to 8, and a and b are O or 1.) Specific representative examples include methyl silicate, ethyl silicate, n-propyl silicate, Tetraalkoxysilanes such as i-propyl silicate, n-butyl silicate, 5ec-butyl silicate and t-butyl silicate, and their hydrolysates, as well as methyl 1-lime 1-xysilane, methyl 1-ethoxysilane, methyl 1 ~Rimethoxyel 1~xysilane, methyltrimethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltrier 1~xysilane, vinyltrimethoxysilane, vinyltriacetoxysilane,
Vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ
-Chloropropyltrimethoxysilane, T-chloropropyltriethoxysilane, γ-chloropropyl1-lyacetoxysilane, 3.3.3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyl!・Rimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane rutrier 1-xysilane, N-β-(aminoethyl)-
γ-aminopropyltrimethoxysilane, β-cyanethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltrimethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyedyltrimethoxysilane, α-glycidoxyedyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltri-oxysilane,
β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriproboxy Silane, T-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyl triethoxysilane,
β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, T-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane , δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyl 1-ethoxysilane, β-(3.

4-Epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrier 1-xysilane, β-(3,4-epoxycyclohexyl)ethyl 1-liproboxysilane, β-(3.4)
-Epoxycyclohexyl)ethyl rib 1~xysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3
, 4-epoxycyclohexyl)propyltriethoxysilane, '7''-(3.4-epoxycyclohexyl)
Propyltriethoxysilane, β-(3,4-epoxycyclohexyl)butyltrimethoxysilane, β-(3
．． Trialkoxysilanes such as 4-epoxycyclohexyl)butyltrimethoxysilane, triazyloxysilane, or triphenoxysilanes or their hydrolysates, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxy Silane, γ-chloropropylmethyldimethoxysilane, T-chloropropylmethyldiethoxysilane, dimethyljethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilamptopropylmethyldimethoxysilane, γ- Mercaptopropylmethyljethoxysilane Minopropylmethyldimethoxysilane, T-aminopropylmethyljethoxysilane, Methylvinyldimethoxysilane, Methylvinyljethoxysilane, Glycidoxymethylmethyldimethoxysilane, Glycidoxymethylmethyldimethoxysilane, , α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane, β
-Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane, β-glycidoxypropylmethyldimethoxy Silane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, T-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldiproboxysilane, γ-glycidoxypropylmethyldimethoxysilane, Sidoxypropylmethyldibu 1 - xysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyl ethyldimethoxysilane, T-glycidoxypropyl Ethyljethoxysilane, γ-glycidoxypropylethyldiproboxysilane, T-glycidoxypropylvinyldimethoxysilane, T-glycidoxypropylvinyljethoxysilane, γ-glycidoxypropylphenyldimer-1-xysilane, Examples include sial]oxysilanes or diacyloxysilanes such as γ-glycidoxyprobylnoenyldiethoxysilane, or hydrolysates thereof.

It is also possible to add one type or two or more types of these organosilicon compounds. Particularly for the purpose of imparting dyeability, it is suitable to use organosilicon compounds containing epoxy groups and glycidoxy groups.

These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and further promote curing.

Hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid and stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. During hydrolysis, - of the general formula (A>)
Addition of pure water or acidic aqueous solution in an amount equal to or more than 3 times the mole of OR3 group is particularly preferred from the viewpoint of accelerating curing.

During hydrolysis, alcohol and other substances are produced, so it is possible to carry out the hydrolysis without a solvent.However, in order to perform the hydrolysis roughly and uniformly, it is possible to mix the organosilicon compound and a solvent and then carry out the hydrolysis. It is also possible to do so. Further, depending on the purpose, it is possible to remove an appropriate amount of the hydrolyzed alcohol etc. under heating and/or reduced pressure before use, and it is also possible to use a suitable solvent after that.

Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as toluene and xylene.

Moreover, these solvents can also be used as a mixed solvent of two or more types as required. Also, depending on the purpose, it is possible to accelerate the hydrolysis reaction and heat it above room temperature to roughly advance reactions such as precondensation, or to lower the hydrolysis temperature to below room temperature to suppress precondensation. Needless to say, it is also possible to do so.

The mixing ratio of these silica sol, fine silica powder, and vehicle should be adjusted depending on the required performance, but it is preferable that the ratio of addition in the resulting film is within the following range. That is, the silica sol is preferably used in an amount of 50 to 350 parts by weight per 100 parts by weight of the vehicle. If it exceeds this range, a decrease in surface hardness, whitening of the coating film, cracks, etc. are likely to occur. It is preferably used in a range of 65 to 250 parts by weight. The mixing ratio of fine silica powder is determined depending on the required non-glare property, but from the viewpoint of paint stability, applicability, and adhesion (
vehicle + silica sol) 0.1 to 100 parts by weight
It is preferable to use the V1 joint with a 20-fold foot section. 0.
If it is less than 1 single part, sufficient non-glare properties cannot be obtained, and if it exceeds 20 folds, transparency tends to decrease.

The coated substrate used in the present invention is not limited in any way, and various plastic substrates, inorganic glass substrates, aluminum substrates, and ceramic substrates can be used. Typical examples include transparent substrates such as poly(diethylene glycol bisallyl carbonate (meth)acrylate resin, polyester, polypropylene, cellulose resin, and glass), as well as aluminum steel plates, stainless steel plates, and zinc steel plates. Depending on the use and purpose, these substrates are preferably subjected to surface treatment with a coupling agent, coating with a primer, chemical treatment with acid or alkali, or various physical treatments.

Various curing agents can be used in combination with the coating composition used in forming the film of the present invention for the purpose of accelerating curing and enabling low-temperature curing. As the curing agent, various epoxy resin curing agents or various organosilicon resin curing agents are used.

Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds, metal alkoxides, and alkali metal organic carboxylates and carbonates. Examples include various salts. It is also possible to use a mixture of two or more of these curing agents. Among these curing agents, the aluminum chelate compounds shown below are particularly useful for the purpose of the present invention from the viewpoints of stability of the coating material, coloring of the coating film after coating, and the like.

The aluminum chelate compound referred to herein is, for example, an aluminum chelate compound represented by the general formula AαXn Y3-n.

However, in the formula, X is OL (L is a lower alkyl group), Y is a single formula M'
At least one ligand derived from a compound represented by CCOCH2C0M2 (', M'' are both lower alkyl groups) and a ligand derived from a compound represented by the general formula (% lower alkyl group) Yes, n is Oll or 2
It is.

The general formula AQXoY3- is particularly useful as a curing agent in the present invention.
As the aluminum chelate compound represented by 0, various compounds can be mentioned, but the solubility in the composition, stability,
Particularly preferred from the viewpoint of effectiveness as a curing catalyst are aluminum acedelacetonate, aluminum bisethyl acetoacetate monoacetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, and aluminum chelate 1so-propoxide. Monomethyl acetoacetate, etc. It is also possible to use a mixture of two or more of these.

Coating means for coating the transparent substrate of the present invention include brush coating, dip coating, roll coating, spray coating,
Common coating methods such as spin coating and flow coating can be easily used.

Particularly in the present invention, it is preferable to add a coating composition to the coating composition in advance of application in order to prevent the settling of fine silica powder, which is a non-glare imparting component. As for the stirring method, stirring with a simple stirring rod is possible, and a method of stirring while performing circulation and filtration is also preferable for the present invention.

The thickness of the coating in the present invention is not particularly limited. However, from the point of view of adhesive strength retention, hardness, etc.
It is preferably used between 5 μm and 20 μm. Particularly preferably, the thickness is 0.7 μm to 15 μm. In addition, when applying the coating composition, it is used after being diluted with various solvents for reasons such as workability and film thickness control. Examples of diluting solvents include water, alcohol, ester, ether, ketone, halogenated hydrocarbon, or toluene. A variety of aromatic solvents can be used depending on the purpose, and a mixed solvent can also be used if necessary.

As a method for dispersing each component in the present invention, stirring using a simple stirring blade is also possible, but from the standpoint of further improving the dispersion state, paint conditioners, sand mills, three-roll mills, ball mills, homo mixers, and homogenizers can be used. etc. are preferably used. From the viewpoint of reproducibility, homomixers and homogenizers are most preferably used.

In addition, in order to maintain a stable dispersion state and improve the uniformity of coating film adhesion, various surfactants are preferably added, such as silicone surfactants, foot nail surfactants, organic surfactants, etc. is used.

To form a film from these compositions, a coating composition containing these compositions is coated and then dried and cured by heating.

The curing temperature varies depending on the compound selected and working conditions, but is 60'C to 300C, preferably 80C to 200C.
is used. If the temperature is lower than this, curing will be insufficient, and if the temperature is higher than this, problems such as cracks and decomposition of the film will occur.

The transparent molded product according to the present invention (q) provides non-glare properties due to the aggregates on the outermost surface, and the coating itself maintains transparency, has a high hardness surface, has excellent wear resistance, and is suitable for CRTs. It can be preferably used for various display front panels such as front panels, touch panels, showcases, and meter covers.

EXAMPLES In order to clarify the characteristics of the present invention, Examples are given below, but the present invention is not limited to these Examples.

"Example" Example 1 <1) Preparation of silane hydrolyzate γ-glycidoxypropyl 1 to rimethoxysilane 233
．． 0.09 was cooled to 10° C., 53.3 g of a 0.01N hydrochloric acid aqueous solution was gradually added dropwise to the mixture while stirring, and after the stirring was completed, stirring was continued for an additional 30 minutes at room temperature to obtain a silane hydrolyzate.

(2> Preparation of coating agent 11 Add acetylacetene 33 to the silane hydrolyzate described above.
．． 6q, methanol silica sol (manufactured by Catalyst Kasei Co., Ltd., 08C)
AI-1132 solid content 30% > 660゜0g was mixed, and 3.8% of fluorine-based nonionic surfactant was added as a surfactant.
1 to 18 g of aluminum acetylacetate were added and thoroughly stirred. Further, 30 g of fine silica powder (AERO3IL 380, manufactured by Nippon Aerosil Co., Ltd.) was added and dispersed in a homogenizer to obtain a coating composition.

(3) Preparation of molded product with non-glare hard coat film Diethylene glycol bisallyl carbonate polymer (2 x 100 x 1
00 mm) using the coating composition prepared in the previous section (2) under the following conditions (pulling speed t
W10cm/m1n) L/ta. 80'C/12 soon
The molded product was pre-cured for 20 minutes and then heated at 130'C for 2 hours to obtain a molded article having a non-glare hard coat film. The solid proportions of the silica sol, vehicle, and silica fine powder in the resulting coating were 60 parts: 50 parts: 8 parts, respectively.
Adjusted by department. Moreover, the film thickness was 2.5 μm.

(4) Evaluation When the molded product prepared in (3) above was attached to the front of a CRT, characters and figures on the CRT screen could be clearly seen. Also, when I reflected the 37 watts (-) of indoor fluorescent lights on the front of the molded product, the reflection was much suppressed compared to the base material before the lighting, and I did not feel any glare. In addition, use a steel knife to insert 100 gongs that reach the 1 mm square substrate on the coating surface, and use a steel knife to insert cellophane adhesive tape (trade name: "Cello Tape" Nichiban product) into the film in a 90-degree direction. When the film was rapidly peeled off and the presence of peeling of the paint film was examined, no peeling of the paint film was observed, indicating that it had good adhesion. Pencil hardness test (
JIS K5400) was performed to obtain 9F-1. Further, even though the coating film was strongly rubbed with steel wool (#1), it did not show any scratches and had good surface hardness. The average diameter of secondary aggregates of fine silica powder on the outermost surface of the coating was 0.9 μm as measured by JISBO651.

Comparative Example 1 Example 1 except that the fine silica powder was removed from Example 1.
I did it in the same way.

Non-glare properties were not obtained, or the transparent molded product had physical properties such as surface hardness and adhesion that were equivalent to those of Example 1.
9.

Example 2 In Example 1, the amount of methanol silica sol added was 4.
The process was carried out in the same manner as in Example 1 except that the amount was reduced to 1/2.

No scratches were observed in the steel wool (#0000) hardness test, and the surface had good surface hardness. Regarding other performances, the evaluation results were similar to those of Example 1.

Example 3 The coating composition prepared in Example 1 was coated and evaluated on the substrate shown in (a) below in the same manner as in Example 1.

(a) Dip coat the paint of (b) below on the Nesa glass substrate (pulling speed 20 cm/min) and apply the coating at 80°C/12
After preliminary curing for 30 minutes, heat curing was performed at 140'C for 2 hours, and the surface of the formed film was etched by plasma treatment with oxygen.

(b) Preparation of paint Add bisphenol A type epoxy resin (trade name: Epicoat 827, manufactured by Shell Chemical Co., Ltd.) 7 to the silane hydrolyzate.
1.3g, N,N-dimethylborumamide 221Q, benzyl alcohol 99.9g, methyl alcohol 171
．． 2g of silicone surfactant and 1.5g of silicone surfactant were added and mixed, and further colloidal antimony pentoxide sol (manufactured by Nissan Chemical Co., Ltd., trade name: Antimony Sol A-2550>297.2C) was added.
], 14.3 g of aluminum acetylacetonate was added thereto, and after thorough stirring, a coating composition was prepared.

(C) Evaluation The obtained molded product having two layers of coating on the Nesa glass substrate exhibited the same appearance and physical properties as in Example 1. Also, 2
The total layer thickness was about 6 μm, and the film capacitance was about 900 PF/cnf.

[Effects of the Invention] According to the present invention, a hard coat film having excellent non-glare properties can be obtained, which has the following effects.

(1) Surface #! It has high wear resistance, frostbite resistance, and durability.

(2) Non-glare properties can be obtained by applying paint, and it can be used for various shapes and articles.

Claims (2)

[Claims] (1) A silica sol with an average particle size of 5 nm to 200 nm, a secondary aggregate consisting of primary particles with a particle size of 5 nm to 50 nm, and the main components are silica fine powder with a particle size of 1 μm to 100 μm and a vehicle. A non-glare hard coat film characterized by: (2) The non-glare hard coat film according to claim (1), wherein the vehicle contains an organosilicon compound represented by the following general formula (A) and/or a hydrolyzate thereof. R^1_aR^2_bSi(OR^3)_4_-_a_
-_b(A) (In the formula, R^1 and R^2 each represent an alkyl group, an alkenyl group, an aryl group, or a halogen, an epoxy group, a glycidoxy group, an amino group, a mercapto group, a methacryloxy group, or a cyano group. a hydrocarbon group, R^3 is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group,
Acyl group, phenyl group, a and b are 0 or 1
It is. )