JP3494195B2 - Anti-reflection filter - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a CRT display, a projection television, a plasma display,
The present invention relates to a translucent antireflection filter which is used by being attached to the surface of a VDT such as an EL display or a liquid crystal display or used as a front plate.

[0002]

2. Description of the Related Art Display screens such as various displays use translucent antireflection filters in order to prevent reflection of illumination light and blurring of the image due to the background being reflected. On the other hand, the display screen shows
There is adherence of hand dust, fingerprints, sweat, cosmetics, etc.If an antireflection film is formed, stains due to the adherence will be conspicuous,
In addition, it becomes difficult to remove the dirt. So it ’s hard to get dirty,
Alternatively, in order to make it easier to wipe off stains, a scheme has been made to further provide an antifouling layer on the surface of the antireflection film. For example, in JP-A-64-86101, on the surface of the base material,
There has been proposed an antireflection article having a stain resistance and a scratch resistance, which is provided with an antireflection film mainly composed of silicon dioxide and further treated with a compound containing an organic silicon substituent on the surface thereof. Further, Japanese Patent Application Laid-Open No. 4-338901 proposes a CRT filter having a stain-resistant and scratch-resistant CRT filter in which a terminal silanol organopolysiloxane is similarly coated on the antireflection film. Further, in Japanese Patent Publication No. 6-29332, a low reflection property and an anti-reflection property are obtained by laminating an antireflection film made of a mono- or disilane compound containing a polyfluoroalkyl group and a silane compound having a halogen atom, an alkyl group or an alkoxy group on a plastic surface. A low-reflection plastic having stain resistance has been proposed.

[0003]

The anti-reflection filter proposed up to this point has some stain resistance, but it is still insufficient. In particular, since the adhered contaminants are difficult to wipe off, it is necessary to use water and / or an organic solvent for wiping off, and the substance exhibiting the stain resistance is easily removed by this wipe off, and the stain resistance,
Its permanence is poor. Therefore, it is an object of the present invention to provide an antireflection filter that not only has a higher anti-staining property, but also can easily remove a contaminant and its effect is long-lasting.

[0004]

The present invention is directed to an antireflection film comprising a layer of an inorganic compound on one or both sides of a film or sheet comprising a transparent substrate, and the following general formula:
Is an antireflection filter in which a layer made of a silane compound having a number average molecular weight of 5 × 10 ² to 1 × 10 ⁵ is formed.

[0005]

[Chemical 3] (In the formula, R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or a trifluoromethyl group. , R ¹ is a hydrolyzable group, R ² is hydrogen or an inert monovalent organic group, a, b,
c and d represent an integer of 0 to 200, e represents 0 or 1, m and n represent an integer of 0 to 2, and p represents an integer of 1 to 10. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the transparent substrate in the present invention include glass and transparent plastics,
Its shape is a film or sheet. Examples of transparent plastics include acrylic resins, polycarbonate resins, polyester resins, cellulose resins such as triacetyl cellulose and diacetyl cellulose, and styrene resins. Among them, acrylic resin is suitable from the viewpoint of light transmission and weather resistance. Among the acrylic resins, an acrylic resin in which acrylic rubber is dispersed is preferable in terms of impact strength, and an acrylic resin containing a glutaric anhydride unit or a glutarimide unit is preferable in terms of heat resistance.
Further, as these transparent substrates, an optical film or sheet having polarization characteristics, for example, an iodine-based or dye-based polarizing film or sheet made of polyvinyl alcohol resin, or a film in which the polarizing film or sheet and a cellulose-based resin or the like are laminated, or Sheets and the like can be mentioned in the same manner.

The film or sheet made of a transparent substrate may be a single layer or a laminated layer. Its thickness is
Although it can be arbitrarily selected depending on the usage, it is usually 0.01 to 1
It is about 0 mm.

A direct antireflection film is formed on one or both surfaces of a film or sheet made of a transparent substrate (hereinafter, this "film or sheet made of a transparent substrate" may be simply referred to as "transparent substrate"). Alternatively, a hard coat layer may be formed on one or both surfaces of the transparent substrate in advance, and an antireflection film may be formed on the hard coat layer. By forming this hard coat layer on the surface of a transparent base material and coating the surface of the base material, not only the surface hardness is increased, but also the surface in contact with the antireflection film is smoothed and the adhesion of the antireflection film is improved. To do.

The hard coat layer may be a known one used for this purpose. For example, a cured film obtained by polymerizing and curing a raw material containing a polyfunctional monomer as a main component can be mentioned. Specifically, a urethane-modified (meth) acrylic oligomer, an esterified product of a polyhydric alcohol and (meth) acrylic acid, and a polyfunctional polymerizable compound containing two or more acryloyl groups and methacryloyl groups such as polyether (meth) acrylate. UV compound,
Examples include a layer polymerized and cured by an activation energy ray such as an electron beam; or a material obtained by crosslinking and curing a silicon-based, melamine-based, or epoxy-based crosslinkable resin raw material with heat. Above all, in terms of durability and ease of handling, a layer obtained by curing a resin raw material made of a urethane-modified acrylic oligomer with ultraviolet rays or electron beams, and a resin raw material made of a silicon-based polyfunctional polymerizable compound were cured by heat. The layers are excellent.

The urethane-modified (meth) acrylate can be obtained by a urethanization reaction between a terminal isocyanate polyurethane and a (meth) acrylic acid derivative having a hydroxyl group. The terminal isocyanate polyurethane is produced by reacting a polyisocyanate such as hexamethylene diisocyanate and isophorone diisocyanate with an oligomer having a plurality of hydroxyl groups such as polycaprolactone diol and polytetramethylene diol. Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate,
Examples thereof include 2-hydroxypropyl (meth) acrylate.

Examples of the polyhydric alcohol in the esterified product of polyhydric alcohol and (meth) acrylic acid include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, hexanediol and neopentyl. Glycol, 2-ethyl-
Dihydric alcohols such as 1,3-hexanediol, 2,2′-thiodiethanol and 1,4-cyclohexanedimethanol, and 3 such as trimethylolpropane, pentaglycerol, glycerol, pentaerythritol, diglycerol and dipentaglycerol. An alcohol having a valency or more can be mentioned. Further, in order to impart flexibility to the obtained cured film and prevent cracking, in the formation of an esterified product of a polyhydric alcohol and (meth) acrylic acid, a polyunsaturated carboxylic acid is further added in addition to (meth) acrylic acid. May be added in a small amount to form a mixed ester. Examples of the polyunsaturated carboxylic acid include succinic acid, tetrahydrophthalic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid and the like.

As a method for forming the hard coat layer, first, a method is used in which a raw material is used in a usual coating operation, for example, a substrate is rotated and a coating agent is dropped on the base material to form a coating film with the coating agent. Coating by which the base material is uniformly formed; immersion coating in which the base material is dipped in a coating agent solution and pulled up at a constant speed to form a coating; formation of the coating material film on rolls, and movement of the base material between rolls Roll coating or gravure coating that transfers the coating agent of the roll onto the base material by means of curtain flow coating or the like, in which the coating material is cast in a waterfall shape and the base material passes underneath to form a coating film of the coating material. Coating (eg "Coating method" (Yuji Harasaki, Maki Shoten, issued October 30, 1979) and "Coating machine and peripherals" (Aoyama et al. Company polymer industry Institute, the method described in Technical Institute, 1979 February issue)), followed by, as described above, by the method according to the raw materials used,
The method of hardening can be mentioned.

The thickness of the hard coat layer is preferably 1 to 20 μm from the viewpoint of coating film strength, surface strength and optical characteristics.

The antireflection film is laminated directly on one side or both sides of the transparent substrate or on the surface of the hard coat layer formed on one side or both sides of the transparent substrate. The antireflection film may be a known film composed of a single-layered or multi-layered thin film of an inorganic compound, and can be formed by a known method such as a vacuum vapor deposition method, an ion plating method and a sputtering method.
For example, in the vacuum vapor deposition method, the substrate to be coated is placed in a vacuum tank, the degree of vacuum is usually set to 10 ⁻⁴ Torr or less, and the substance to be vapor deposited is heated and vaporized by resistance heating, electron beam heating, etc. A thin film can be formed by condensing the substance on the surface of the substrate. In the sputtering method, glow discharge is usually performed between two electrodes under a low pressure of about 10 ⁻³ Torr, and the cathode substance released by the glow discharge can be attached to the substrate. More specifically, the above-mentioned JP-A-4-338901 and JP-A-64-861.
No. 01, further, the method described in JP-A-56-113101. Regarding the structure of the antireflection film, U.S. Pat. No. 3,185,020 and U.S. Pat.
Those described in Japanese Patent Publications and the like can be mentioned. As the antireflection film, there is an organic antireflection film such as an antireflection film in which a polystyrene layer or the like is laminated (Japanese Patent Laid-Open No. 6-344487), but the antireflection film used in the present invention is a reflection formed of an inorganic compound layer. An organic antireflection film, which is an antireflection film, is difficult to obtain a silane compound layer having good durability.

Examples of the inorganic compound used include silicon dioxide, silicon oxide such as silicon monoxide, yttrium oxide, aluminum oxide, magnesium oxide, thorium oxide, tin oxide, lanthanum oxide, indium oxide, neodymium oxide, antimony oxide, and oxide. Metal oxides such as zirconium, cerium oxide, titanium oxide, bismuth oxide,
Metal halides such as calcium fluoride, sodium fluoride, lithium fluoride, magnesium fluoride, lanthanum fluoride, neodymium fluoride, cerium fluoride and lead fluoride, metal sulfides such as zinc sulfide, cadmium sulfide and antimony trisulfide. Compounds, metal selenides such as zinc selenide, cadmium telluride, metal tellurides such as lead telluride, silicon, germanium, tellurium, and the like.

The layer composed of the silane compound is formed on the antireflection film.
Is a coating film that functions as an antifouling layer.
The orchid compound is represented by the above general formula 3 and its number
Average molecular weight is 5 × 10²~ 1 x 10^FiveIs. Above all
R in the general formula_fIs usually a straight chain having 1 to 16 carbon atoms
A branched or branched perfluoroalkyl group, which is preferred
Ku CF₃ Base, C₂ F_Five Base, C₃ F ₇ It is a base. To Y
In general, the lower alkyl group in the formula has 1 to 5 carbon atoms.
One of them is. R¹ The hydrolyzable group of is a salt
Halogen atom such as elementary atom, bromine atom, iodine atom, R³ 
O group, R³ COO group, (R^Four )₂ C = C (R³ ) CO
Group, (R³)₂ C = NO group, R^Five C = NO group, (R^Four )₂
 N group, and R³ CONR^Four Groups are preferred. (here,
R³ Is an aliphatic carbon such as an alkyl group usually having 1 to 10 carbon atoms
Usually a hydrogen atom group or a phenyl group having 6 to 20 carbon atoms
Aromatic hydrocarbon group, R^Four Is a hydrogen atom or an alkyl group, etc.
Usually a lower aliphatic hydrocarbon group having 1 to 5 carbon atoms, R^FiveIs
Usually divalent aliphatic having 3 to 6 carbon atoms such as alkylidene group
It is a hydrocarbon group. ) More preferably, chlorine atom, CH₃ O group, C₂ H_Five O
It is a base. R² Is a hydrogen atom or an inert monovalent organic group
And preferably has usually 1 to 1 carbon atoms such as an alkyl group.
4 monovalent hydrocarbon groups. a, b, c, d are 0-2
It is an integer of 00, and preferably 1 to 50. m and
And n are integers of 0 to 2, and preferably 0. p
Is an integer of 1 or 2 or more, preferably 1 to 10
It is an integer, and more preferably an integer of 1 to 5. Well
Also, the number average molecular weight is 5 × 10² ~ 1 x 10^Five And is good
1x10 is better³~ 1 x 10^Four Is.

As a preferred structure of the silane compound represented by the above general formula 3, R _f is C ₃ F ₇
A compound in which a is an integer of 1 to 50, b, c and d are 0, e is 1, Z is a fluorine atom, and n is 0, that is, the following general formula: There is a compound represented by 4.

[0018]

[Chemical 4] (In the formula, Y, m, R ¹ and p have the same meanings as described above,
q represents an integer of 1 to 50. )

These silane compounds can be obtained by silane treatment of commercially available perfluoropolyether. For example, as disclosed in Japanese Patent Laid-Open No. 1-294709.

The layer made of the silane compound may be formed on the antireflection film by the same coating method as the coating of the raw material for forming the hard coat layer. That is, spin coating, dip coating, roll coating, gravure coating, curtain flow coating and the like are used. It is preferable that the coating is performed by diluting with a solvent from the viewpoint of controlling the thickness of the layer made of the silane compound and from the viewpoint of workability. Examples of the solvent include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,
Usually has 5 to 12 carbon atoms such as 3-dimethylcyclohexane
And perfluorinated aliphatic hydrocarbons, polyfluorinated aromatic hydrocarbons such as bis (trifluoromethyl) benzene, and polyfluorinated aliphatic hydrocarbons. The concentration of the silane compound in the coating solution is 0.05 to 0.5 in the dip coating method.
wt% is preferred.

The thickness of the silane compound layer is preferably 0.001 to 0.03 μm from the viewpoint of anti-contamination effect and anti-reflection effect.

[0022]

The antireflection filter of the present invention is less likely to be stained than the conventional one. Moreover, it is easy to remove stains once attached and has excellent durability. Therefore, CR
As an anti-reflection filter for VDT such as T-display, projection TV, plasma display, EL display, liquid crystal display, etc., by sticking or arranging it on the front surface of VDT and using it, not only the anti-reflection function but also an excellent anti-pollution effect can be achieved. Demonstrate.

[0023]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the examples.
In the examples, evaluation test methods for various physical properties are as follows. (1) Reflectance measurement; using a self-recording spectrophotometer (MPS-2000: Shimadzu Corporation), incidence angle 1 at wavelength 300 nm to 800 nm
The average reflectance at 5 ° was measured. (2) Contact angle with water: Using a contact angle meter (CA-A type: Kyowa Interface Science Co., Ltd.), make a water drop with a diameter of 1.0 mm at the tip of the needle at room temperature and use it on the surface of the substrate. Drops were made by touching. The angle between the droplet and the surface generated at this time was measured and used as the contact angle. (3) Durability: A durability test was conducted by wiping the surface of the base material 20 times with a cellulose nonwoven fabric (Bencot: Asahi Kasei), and then measuring the contact angle with water by the method described above. (4) Adhesion of fingerprints: The thumb of the right hand was pressed against the surface of the base material for 3 seconds to adhere the fingerprints, and the easiness of sticking or the conspicuousness was visually determined. The judgment criteria are as follows. ◯: The amount of fingerprints attached is small, and the attached fingerprints are inconspicuous. X: Fingerprints can be clearly recognized as attached. (5) Wipeability of fingerprints: The adhered fingerprints were wiped off with a cellulose nonwoven fabric, and the ease of removing the fingerprints was visually evaluated. The criteria for judgment are as follows. ◯: Fingerprints can be completely wiped off. Δ: A fingerprint is wiped off. X: The fingerprint is extracted and the trace is widened, and it is difficult to remove it.

Example 1 (1) Preparation of acrylic sheet with antireflection film 200 mm × 300 m with a mask film attached on one side
mx 0.25 mm impact-resistant acrylic sheet (Technoloy:
Sumitomo Chemical Co., Ltd.) was dipped in a urethane acrylate hard coat agent (Unidick 17-806: Dainippon Ink Co., Ltd., solid content in toluene is 30%), and 45 cm /
It was pulled up at a speed of a minute and applied. After evaporating the solvent, the mask film was removed, and a 120 W metal halide lamp (UB0451 made by Eye Graphics Co., Ltd.) was used.
A hard coat layer was formed on one side of the acrylic sheet by irradiating from a distance of cm for 10 seconds. The acrylic sheet provided with this hard coat layer was placed in a vacuum vapor deposition tank of a vacuum vapor deposition apparatus (Shincron BMC-700 Co., Ltd.), and the degree of vacuum was set to 2 × 10 ⁻⁵ Torr, and then silicon dioxide, titanium dioxide, silicon dioxide, By EB (electron beam) in the order of titanium and silicon dioxide, the thickness of each layer is 15, 15,
It vapor-deposited so that it might become 28,107,90 nm, and obtained the acrylic sheet with an antireflection film.

(2) Preparation of Antifouling Solution Using a fluorine-containing polyether represented by the following formula 5 as the raw material of Example 6 of JP-A-1-294709, CH ₂ was used according to Example 4 of the publication. = CHSiCl ₃ was reacted with vinyltrichlorosilane, and the obtained iodine-containing silane compound was treated with zinc powder and methanol to obtain a silane compound represented by the following formula 6 and having a number average molecular weight of about 5,000.

[0026]

Embedded image _{C 3 F 7 - (OCF 2} CF 2 CF 2) 24 -O (CF 2) 2 I

[0027]

[Chemical 6]

Specifically, in a 200 ml four-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a thermometer, 40 g of the ω-fluoropolyperfluorooxetane iodine compound represented by the chemical formula 5 was added to hexafluorotetrahydrofuran. What was dissolved in 80 g of chlorobutane and 1.5 g (1 × 10 ^-2 mol) of di-t-butyl peroxide were charged, and after the system was sufficiently replaced with nitrogen, vinyltrichlorosilane was added from a dropping funnel under a nitrogen stream. 16.1 g (0.1 mol) was added dropwise. After completion of the dropping, the temperature in the system was raised to 120 ° C. and the reaction was carried out for 4 hours. After completion of the reaction, volatile matter was completely distilled off under reduced pressure to obtain 38.7 g of a silane compound having iodine at the terminal. Then, in a flask similar to the above, a solution prepared by dissolving 34.4 g of the silane compound in 50 g of perfluorohexane was charged, and 2.1 g of zinc was added.
(3.2 × 10 ^-2 mol) was dispersed by vigorous stirring. The system was cooled in an ice water bath, and 10 g of anhydrous methanol was added dropwise under a nitrogen stream. After completion of dropping, the ice-water bath was removed, and the mixture was reacted under heating under reflux for 2 hours. After the reaction was completed, the insoluble matter was filtered off, and the lower layer was separated from the liquid phase separated into two layers using a separating funnel. After the obtained solution was washed with anhydrous methanol three times,
By completely distilling off the volatile matter under reduced pressure, 31.6 g of a hydrogenated silane compound represented by Chemical formula 6 was obtained.

From ¹ H-NMR, 1.2 to 3.0 ppm
A wide range of absorbers derived from each hydrogen atom of the following formula 7 appeared. As the internal standard, 5.0 mol% of ω-fluoropolyperfluorooxetane hydride was added, and the degree of polymerization P (average value of p in Chemical formula 4) was calculated from the following formula 1 to be 2.0.

[0030]

[Chemical 7]

[0031]

## EQU1 ## I / I _s = [0.95 (3P + 1)] / 0.05 I: integrated absorption intensity I _{s of} 1.2 to 3.0 ppm: integrated absorption intensity P of internal standard substance P: polymerization degree Average value of p in 4)

Then, the obtained silane compound was diluted with tetradecafluorohexane to prepare a pollution preventing liquid having a concentration of 0.1% by weight.

(3) Coating of Acrylic Sheet with Antireflection Film by Antifouling Layer (Layer Made of Silane Compound) The surface of the acrylic sheet with antireflection film prepared in (1) above, on which the antireflection film is not laminated, is masked. After covering with a film, this sheet was dipped in the antifouling solution prepared in (2) and pulled up at a speed of 15 cm / min to apply. After coating, the solution was left standing overnight at room temperature to volatilize the solvent to form a pollution prevention layer on the surface of the antireflection film, remove the mask film, and obtain an antireflection filter. Various physical properties were evaluated. The results are shown in Table 1.

Comparative Example 1 The acrylic sheet with antireflection film obtained in (1) of Example 1 was evaluated as it was. The evaluation results are shown in Table 1.

Comparative Example 2 C ₈ F ₁₇ C ₂ H ₄ Si (OCH ₃ ) ₃ (manufactured by Toshiba Silicone Co., Ltd., trade name XC98-A5382) was diluted with isobutanol to prepare a 1.6 g / L solution as an antifouling solution. An antireflection filter was prepared in the same manner as in Example 1 except that the above-mentioned one was used. The evaluation results are shown in Table 1.

Comparative Example 3 A dimethylpolysiloxane having silanol groups at both ends (trade name: XF, manufactured by Toshiba Silicone Co., Ltd.) was used as an antifouling liquid.
3905) was dissolved in a methyl isobutyl ketone / cyclohexanone (6/4) mixed solvent to prepare a 1 g / L solution, and an antireflection filter was prepared in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 2 200 mm × 300 mm instead of the impact resistant acrylic sheet
Examples except that a 0.3 mm polarizing film (Sumikaran: manufactured by Sumitomo Chemical Co., Ltd., structure (three-layer structure): iodine-based polarizing film consisting of triacetyl cellulose / polyvinyl alcohol / triacetyl cellulose) was used. An antireflection filter was produced in the same manner as in 1. Table 1 shows the evaluation results
Shown in.

[0038]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G09F 9/00 321 C08G 65/32 (72) Inventor Yuji Tanaka Nishiichitsuya 1-1, Settsu-shi, Osaka Daikin Industry Co., Ltd. Yodogawa In-house (72) Inventor Jinji Hachisuka No. 1-1 Nishiichitsuya, Settsu-shi, Osaka Daikin Industry Co., Ltd. Yodogawa Manufacturing (56) Reference JP-A-7-40457 (JP, A) JP-A-5-311149 ( JP, A, JP 61-130902 (JP, A), JP 2-55781 (JP, A) JP 1-130101 (JP, A) JP 4-296336 (JP, A) JP 5-186761 (JP, A) JP 6-172446 (JP, A) JP 1-294709 (JP, A) Japanese Patent 6-29332 (JP, B2) (58) Fields investigated (Int .Cl. ⁷ , DB name) G02B 1/10

Claims (7)

(57) [Claims] 1. A film or sheet comprising a transparent substrate
Anti-reflection consisting of a layer of inorganic compound on at least one side
Membrane, and number average molecular weight 5 represented by the following general formula 1
× 10 ² ~ 1 x 10^Five A layer consisting of the silane compound of
Anti-reflection filter. [Chemical 1] (In the formula, R_fIs a linear or branched chain having 1 to 16 carbon atoms.
-Fluoroalkyl group, X is iodine atom or hydrogen atom
Child, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom
Child or trifluoromethyl group, R¹ Is hydrolyzable
Group, R² Is hydrogen or an inert monovalent organic group, a, b,
c and d are integers of 0 to 200, e is 0 or 1, m and
n represents an integer of 0 to 2 and p represents an integer of 1 to 10. ) 2. The antireflection filter according to claim 1, wherein the silane compound is a compound represented by the following general formula 2. [Chemical 2] (In the formula, Y represents a hydrogen atom or a lower alkyl group, R ¹ represents a hydrolyzable group, q represents an integer of 1 to 50, m represents an integer of 0 to 2, and p represents an integer of 1 to 10.) 3. The antireflection filter according to claim 1, wherein p of the silane compound represented by the general formula 2 is 1. 4. The antireflection filter according to claim 1, further comprising a hard coat layer formed between the film or sheet made of a transparent substrate and the antireflection film. 5. The antireflection filter according to claim 1, wherein the film or sheet made of a transparent substrate has a thickness of 0.01 to 10 mm. 6. The antireflection film comprises at least two layers, and among the layers of the antireflection film, the layer farthest from the film or sheet made of a transparent substrate is a layer made of silicon oxide or a metal oxide. Item 1. The antireflection filter according to item 1. 7. A silane compound layer having a thickness of 0.001 to
The antireflection filter according to claim 1, which has a thickness of 0.03 μm.