JP5237745B2 - Weather-resistant anti-glare coating composition, weather-resistant anti-glare film and method for producing the same - Google Patents

Description

  The present invention relates to a weather-resistant anti-glare coating composition capable of forming a weather-resistant anti-glare layer on transparent substrates such as various transparent plastic films, transparent plastic plates and glass, and the weather-resistant anti-glare property The present invention relates to a weather-resistant anti-glare film having an anti-glare layer formed from a coating composition.

  In recent years, applications of flat panel displays such as liquid crystal display devices (liquid crystal displays), LEDs (light emitting diode displays), ELDs (electroluminescence displays), VFDs (fluorescent displays), PDPs (plasma display panels), etc. are expanding. . For example, liquid crystal display devices have advantages such as thinness, light weight, and low power consumption, and are used in various fields such as computers, word processors, televisions, mobile phones, and portable information terminal devices. In these flat panel displays, cases of being installed outdoors or semi-outdoors are also increasing. For example, flat panel displays that are installed outdoors or semi-outdoors for the purpose of posting information such as advertisements are increasing. Further, in a liquid crystal display device, a so-called touch panel having a mechanism for operating a device by pressing a display on a screen has a superior operability, for example, a bank ATM, a vending machine, a personal digital assistant (PDA), a copying machine. As a guidance display device installed in facilities such as facsimiles, game machines, museums and department stores, car navigation, multimedia stations (multifunctional terminals installed in convenience stores), mobile phones, railway vehicle monitoring devices, etc. It is widely used not only indoors but also outdoors or semi-outdoors.

  In flat panel displays such as liquid crystal display devices, an anti-glare (AG) layer or film that roughens the surface, or a low reflection (LR) layer or film that adjusts the refractive index on the display surface. Further, an anti-reflection film (AR) is provided. As a result, problems such as a decrease in contrast due to reflection of external light and reflection of the background reflected on the display surface are solved.

  As a method for producing an antiglare film for improving the display performance of a liquid crystal display device, in general, a method of roughening the surface by processing such as cutting, embossing molding, bonding or the like at the time of film production, or including resin particles And a method of roughening the surface of the film by providing a layer on the film. Currently, the latter method of providing a layer containing resin particles on a film is widely used.

  Japanese Patent Application Laid-Open No. 2002-221610 (Patent Document 1) discloses an antiglare film in which an antiglare layer including a translucent resin and a translucent fine particle is laminated, the translucent resin and the translucent fine particle. The difference between the refractive index and the antiglare film is 0.3 or less and the translucent resin protrudes from the surface of the antiglare layer by 0.1 to 0.3 μm. In the production of such an antiglare film, for example, there is a problem that the fine particles used are not uniformly dispersed. In order to uniformly disperse the resin in the solution, it is necessary to take care such as controlling and adjusting the solution viscosity. If the fine particles are aggregated without being uniformly dispersed, the uneven shape on the surface may deviate from a desired range, resulting in a decrease in transmitted image sharpness or a so-called glare or white blur.

  On the other hand, when the surface is roughened by processing such as cutting, embossing, and bonding at the time of film production, it is difficult to provide irregularities on the rough surface at random, and the irregularities may be followed. is there. When the irregularity is followed, the light reflected by the irregular surface may interfere with each other, causing a problem in display display such as an increase in reflected light or a moire pattern. That is, the occurrence of the moire pattern is caused by the arrangement direction of the fine concavo-convex structure of the antiglare layer overlapping the arrangement direction of the pixels of the display device. This tends to occur when the fine concavo-convex structure is positioned so as to overlap the rule, while the pixels are regularly arranged. Further, when the antiglare layer is formed by stamping, a step of pressing the antiglare layer and a step of cleaning the mold used for the stamping are necessary, which is complicated. Furthermore, it is necessary to pay attention so that foreign matter does not adhere to the molding surface of the mold used for embossing.

  Japanese Patent Laid-Open No. 2003-004917 (Patent Document 2) discloses a polarizing plate with an antiglare layer comprising an antiglare film and a polarizer, wherein the arrangement direction of the fine uneven structure of the antiglare layer is that of the polarizer. A polarizing plate with an antiglare layer, which is 22.5 ° ± 12.5 ° with respect to the absorption axis direction or the transmission axis direction, is described. As described herein, in the case of providing a fine concavo-convex structure by processing, it is necessary to finely adjust the angle in the arrangement direction and the manufacturing process becomes complicated. In addition, it is considered that the probability of the occurrence of a moire pattern increases as the pixels of the display element become smaller due to the higher definition and colorization of the display screen. Therefore, a technology for solving this problem is required.

  International Publication WO 2005/073763 (Patent Document 3) discloses an antiglare coating composition containing a first component and a second component, which is applied on a substrate, and then the first component and the second component. An antiglare coating composition is described in which a first component and a second component are phase-separated based on a difference in physical properties of components, and a resin layer having random irregularities is formed on the surface. By using this antiglare coating composition, it is possible to obtain an antiglare layer having an irregular uneven shape and generating no moire. However, with the recent expansion of applications of flat panel displays, there is an increasing demand for having excellent weather resistance in addition to excellent antiglare properties. Therefore, there has been room for research on a weather-resistant anti-glare coating composition capable of forming an anti-glare layer having excellent weather resistance.

JP 2002-221610 A JP 2003-004917 A International Publication WO 2005/073763 Specification

  The present invention solves the above-mentioned conventional problems. The object of the present invention is to provide a weather-resistant anti-glare coating composition capable of forming an anti-glare layer having better weather resistance, and the weather resistance. An object of the present invention is to provide a weatherproof antiglare film having an antiglare layer formed from an antiglare coating composition.

The present invention
A weather resistant anti-glare coating composition that is coated on a transparent substrate to form a weather resistant anti-glare layer,
The weather-resistant anti-glare coating composition includes a first component and a second component. After the weather-resistant anti-glare coating composition is applied on a substrate, the SP value of the first component and the second component is determined. A weather resistant antiglare coating composition in which a first component and a second component are phase-separated based on the difference, and a resin layer having random irregularities is formed on the surface, and the first component is unsaturated A double bond-containing acrylic copolymer,
This second component contains a polyfunctional unsaturated double bond containing a trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in a monomer molecule. Monomer,
A weather-resistant and anti-glare coating composition is provided, whereby the above object is achieved.

  The trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 mole equivalents of the above-mentioned alkylene oxide unit having 2 to 4 carbon atoms in the monomer molecule is added to the weight of the resin solid content of the weather resistant antiglare coating composition. The content is preferably 2 to 50% by weight.

In addition, the SP value (SP ₁ ) of the first component and the SP value (SP ₂ ) of the second component are the conditions of the following formula:

It is preferable that the relationship is satisfied.

Further, a weather resistant antiglare coating composition containing an organic solvent,
The SP value of the first component (SP ₁ ), the SP value of the second component (SP ₂ ), and the SP value of the organic solvent (SP _sol ) are as _follows :
The difference between SP ₁ and SP _sol is 2 or less;
It is preferable that the relationship is satisfied.

  In addition, the trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 mole equivalents of the above-described alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule is added to a trifunctional or higher polyhydric alcohol with 2 to 2 carbon atoms. More preferably, it is a (meth) acrylate monomer obtained by introducing 4 alkylene oxide skeletons and then reacting with (meth) acrylates.

  Further, the trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of the above-described alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule is represented by the following formula 1

[In Formula 1,
n, m and p are each independently an integer of 2 to 4,
x, y and z are each independently an integer of 0 to 3, provided that the sum of x, y and z is 3 to 6, and R ¹ has a hydroxyl group. Or an alkyl group having 1 to 3 carbon atoms,
R ² , R ³ and R ⁴ are each independently hydrogen or a methyl group. ]
It is preferable that it is a monomer shown by these.

  The weather-resistant and anti-glare coating composition does not contain an inorganic filler and resin particles.

  The weather-resistant and anti-glare coating composition is also characterized by not containing an ultraviolet absorber.

  The present invention further provides a weather-resistant anti-glare film having a transparent substrate and an anti-glare layer, wherein the anti-glare layer is formed from the weather-resistant anti-glare coating composition. To do.

  The haze of this weather resistant antiglare film is preferably less than 20%.

  Moreover, Ra (arithmetic mean roughness of the roughness curve) and Rz (maximum height roughness of the roughness curve) of the weatherproof antiglare film are the following conditions:

It is preferable that the relationship is satisfied.

  Furthermore, it is preferable that the average length (Sm) of the roughness curve element on the surface of the antiglare film of the weather resistant antiglare film is 200 μm or less.

The present invention further includes
An application step of applying the weatherproof antiglare coating composition to the transparent substrate, and a curing step of curing the obtained coating film;
A method for producing a weather-resistant antiglare film is also provided.

The present invention further includes
An application step of applying the weather-resistant anti-glare coating composition to the transparent substrate, and a light irradiation step of irradiating the obtained coating film with light to separate and harden the phase;
A method for producing a weather-resistant antiglare film is also provided.

  The present invention also provides a weather-resistant antiglare film obtained by the method for producing an antiglare film.

  The weather-resistant anti-glare coating composition of the present invention can be provided with an anti-glare layer, which is a resin layer having irregularities on the surface, only by curing after coating on a substrate and drying as necessary. . Further, when irregularities are formed on the surface of the antiglare layer according to the present invention, the irregular arrangement is spontaneously determined, so that irregular irregular shapes can be formed on the surface of the antiglare layer. For this reason, it has the feature that the moire resulting from the regularity of uneven | corrugated arrangement | positioning does not generate | occur | produce. And the anti-glare layer obtained from the weather-resistant anti-glare coating composition of the present invention has a feature that yellowing due to aging or the like is reduced and the weather resistance is excellent. In the weather-resistant antiglare coating composition of the present invention, a trifunctional or higher functional unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in a monomer molecule as a second component Is contained, it has the characteristic that an excellent weather resistance can be obtained without using a weather resistance stabilizer such as an ultraviolet absorber.

  By using the weather-resistant anti-glare coating composition of the present invention, it is possible to easily form an anti-glare layer having irregularities on the surface and excellent weather resistance, and using this, a weather-resistant anti-glare film can be easily formed. Can be manufactured. And, the obtained weather-resistant anti-glare film has no reflection, has a high haze (cloudiness value) and a high total light transmittance, is excellent in weather resistance, and has an excellent surface hardness. It has excellent performance.

Weather-resistant anti-glare coating composition The weather-resistant anti-glare coating composition of the present invention forms an anti-glare layer having excellent weather resistance when applied on a transparent substrate. This weather resistant antiglare coating composition contains at least two components, a first component and a second component. When the anti-glare coating composition is applied onto a substrate, the first component and the second component are based on the difference in SP value between the first component and the second component. It has the feature that the components are phase separated.

  The weather-resistant antiglare coating composition of the present invention contains an unsaturated double bond-containing acrylic copolymer as a first component. Examples of the unsaturated double bond-containing acrylic copolymer include a resin obtained by polymerizing or copolymerizing a polymerizable unsaturated monomer having an acid group such as a (meth) acrylic monomer, or a polymerizable unsaturated monomer having this acid group. A copolymer obtained by reacting a monomer copolymerized with another ethylenically unsaturated double bond monomer with a monomer having an ethylenically unsaturated double bond and an epoxy group; polymerizable unsaturation having this acid group A copolymer obtained by reacting a monomer with a monomer having another ethylenically unsaturated double bond and an epoxy group; a polymerizable unsaturated monomer having this acid group and another ethylenically unsaturated double bond and an isocyanate group And a copolymer obtained by reacting a monomer having the same.

  As an example of a specific method for preparing an unsaturated double bond-containing acrylic copolymer, for example, a polymerizable unsaturated monomer having an acid group was copolymerized with another polymerizable unsaturated monomer, and then obtained. The method of making the acid group of a copolymer react with the epoxy group of an epoxy-group-containing ethylenically unsaturated monomer is mentioned.

  Examples of the polymerizable unsaturated monomer having an acid group include acrylic acid, methacrylic acid, crotonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, and 2- (meth). Monocarboxylic acids such as acryloyloxyethyl hexahydrophthalic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; and malee Monoesters of dicarboxylic acids such as monoethyl acid, monoethyl fumarate and monoethyl itaconate; or substituted derivatives thereof substituted by α-position haloalkyl, alkoxy, halogen, nitro or cyano; o-, m-, p- Vinyl benzoic acid or their alkyl And the like; alkoxy, halogen, nitro, cyano, substituted derivatives substituted by an amide or ester. These may use only 1 type and may use 2 or more types together.

  Other polymerizable unsaturated monomers include, for example, styrene or substituted derivatives substituted with α-, o-, m-, p-alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester of styrene; butadiene, Olefins such as isoprene and neoprene; o-, m-, p-hydroxystyrene or substituted derivatives thereof substituted by alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester or carboxy; vinylhydroquinone, 5- Polyhydroxyvinylphenols such as vinyl pyrogallol, 6-vinyl pyrogallol, 1-vinyl phloroglicinol; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, ter- of methacrylic acid or acrylic acid Butyl Pentyl, neopentyl, isoamylhexyl, cyclohexyl, adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenesyl, cresyl, glycidyl, isobornyl, triphenylmethyl, dicyclopentanyl, cumyl, 3- (N, N-dimethylamino) propyl, 3- (N, N-dimethylamino) ethyl, furyl or furfuryl ester; anilide or amide of methacrylic acid or acrylic acid, or N, N-dimethyl, N, N -Diethyl, N, N-dipropyl, N, N-diisopropyl or anthranilamide; acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl fluoride Redene, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N-methacryloylphthalimide, N-acryloylphthalimide and the like can be used.

  Examples of the epoxy group-containing ethylenically unsaturated monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexanyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and the like. It is done. In order to prepare a coating composition exhibiting balanced curability and storage stability, it is preferable to use glycidyl (meth) acrylate.

  As described above, the unsaturated double bond-containing acrylic copolymer is prepared by dissolving a polymerizable unsaturated monomer having an acid group and other polymerizable unsaturated monomers in a solvent and heating as necessary. In addition, it can be obtained by a method of copolymerizing and then reacting the obtained acid group of the copolymer and the epoxy group of the epoxy group-containing ethylenically unsaturated monomer. In the copolymerization reaction, it is preferable that a chain transfer agent is present if necessary. You may add a monomer component, a polymerization initiator, a solvent, and a chain transfer agent continuously.

  Examples of the solvent that can be used in the copolymerization of the unsaturated double bond-containing acrylic copolymer include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol, acetone, methyl isobutyl ketone, and cyclohexanone. Ketones such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc., 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxy) Ethoxy) ethanol and other carbitols, methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate DOO, ethylene glycol diacetate, esters such as glycerol triacetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether. The amount of these solvents used is preferably 20 to 1000 parts by weight per 100 parts by weight of the total amount of monomers as the reaction raw material.

  As the polymerization initiator that can be used in the copolymerization of the unsaturated double bond-containing acrylic copolymer, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisiso Azo compounds such as butyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl Organic peroxides such as peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane, tertiary butylperoxy-2-ethylhexanoate; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be used as a redox initiator using a peroxide together with a reducing agent.

  Examples of chain transfer agents that can be used in the copolymerization include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, and chloroform. And alkyl halides such as carbon tetrachloride and carbon tetrabromide.

  Copolymerization can be carried out, for example, by stirring at 60 to 150 ° C. for 3 to 48 hours.

  Next, the acid group of the obtained copolymer is reacted with an epoxy group-containing ethylenically unsaturated monomer. This reaction causes the acid group of the copolymer to react with the epoxy group of the epoxy group-containing ethylenically unsaturated monomer, and thereby the unsaturated double bond (ethylenically unsaturated double bond) in the copolymer. Will be introduced. In this way, an unsaturated double bond-containing acrylic copolymer can be obtained. As this introduction reaction method, it can carry out by stirring for 3-48 hours, for example at 60-150 degreeC.

  Further, as another example of a specific method for preparing the unsaturated double bond-containing acrylic copolymer, for example, an epoxy group-containing ethylenically unsaturated monomer and another polymerizable unsaturated monomer are copolymerized, The method of making the epoxy group of the obtained copolymer react with the acid group of the polymerizable unsaturated monomer which has an acid group is mentioned. The reaction method such as the polymerization method in this method is the same as described above.

  The weight average molecular weight of the unsaturated double bond-containing acrylic copolymer used as the first component in the present invention is preferably 500 to 100,000, more preferably 1,000 to 50,000. The weight average molecular weight in this specification means the weight average molecular weight by polystyrene conversion. Moreover, the unsaturated double bond containing acrylic copolymer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The weather resistant antiglare coating composition of the present invention contains a polyfunctional unsaturated double bond-containing monomer as a second component. In the present invention, the polyfunctional unsaturated double bond-containing monomer as the second component is a trifunctional or higher functional unsaturated monomer having 3 to 6 mole equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule. It contains a double bond-containing monomer.

  A trifunctional or higher functional unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in a monomer molecule is, for example, a trifunctional or higher polyhydric alcohol having 2 to 4 carbon atoms. It can prepare by introduce | transducing the alkylene oxide frame | skeleton of this, and making this react with (meth) acrylate.

  Examples of the trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule include a monomer represented by the following formula 1.

In the above formula 1,
n, m and p are each independently an integer of 2 to 4,
x, y and z are each independently an integer of 0 to 3, provided that the sum of x, y and z is 3 to 6, and R ¹ has a hydroxyl group. Or an alkyl group having 1 to 3 carbon atoms,
R ² , R ³ and R ⁴ are each independently hydrogen or a methyl group.

  Examples of the trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule include, for example, triethylene glycol-trimethylolpropane tri (meth) acrylate, Examples include propylene glycol-trimethylolpropane tri (meth) acrylate, hexaethylene glycol-trimethylolpropane tri (meth) acrylate, hexapropylene glycol-trimethylolpropane tri (meth) acrylate, and the like.

  In the present invention, a polyfunctional unsaturated double bond-containing monomer containing a trifunctional or higher functional unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in a monomer molecule. By using the second component as a weather resistant antiglare coating composition, the effect of improving the weather resistance of the antiglare layer formed by the coating composition can be obtained.

  The trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of this alkylene oxide unit of 2 to 4 carbon atoms in the monomer molecule is added to the weight of resin solids of the weather resistant antiglare coating composition. The content is preferably 2 to 50% by weight. If the amount of the trifunctional or higher unsaturated double bond-containing monomer exceeds 50% by weight, the initial adhesion to the substrate of the resulting weatherproof antiglare coating composition may be lowered. Furthermore, the pencil hardness of the resulting antiglare layer may be lowered and the steel wool resistance may be lowered. On the other hand, when the amount of the trifunctional or higher unsaturated double bond-containing monomer is less than 2% by weight, the effect of improving the weather resistance of the resulting antiglare layer may not be obtained.

  By using the weather-resistant anti-glare coating composition of the present invention, the weather resistance of the resulting anti-glare layer can be improved without using a weather-resistant stabilizer such as an ultraviolet absorber. As the ultraviolet absorber, for example, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzoate ultraviolet absorber, a hindered amine ultraviolet absorber and the like are generally used in the resin field and the like. Yes. However, many of these ultraviolet absorbers are colored by absorbing ultraviolet rays, such as hindered amine ultraviolet absorbers. Therefore, in an antiglare coating composition used for forming an antiglare layer of a liquid crystal display device that requires high visibility, the use of these ultraviolet absorbers is very limited. And according to this invention, it became possible to improve the weather resistance of a glare-proof layer, without using weathering stabilizers, such as such an ultraviolet absorber.

  In the present invention, as the polyfunctional unsaturated double bond-containing monomer, a trifunctional or higher functional unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule. It is preferable to use the polyfunctional unsaturated double bond-containing monomer to be contained in combination with other polyfunctional unsaturated double bond-containing monomers. The surface hardness of the resulting antiglare layer can be ensured by using other polyfunctional unsaturated double bond-containing monomers in combination.

  Examples of the polyfunctional unsaturated double bond-containing monomer other than the trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of the alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule include, for example, And a bifunctional or higher polyfunctional unsaturated double bond-containing monomer which is a dealcoholization reaction product of a monohydric alcohol and (meth) acrylate, more preferably a trifunctional or higher polyfunctional unsaturated. And double bond-containing monomers. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylol Examples thereof include propanetetra (meth) acrylate and neopentyl glycol di (meth) acrylate.

  A polyfunctional unsaturated double bond-containing monomer containing a trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule The ratio of the unsaturated double bond-containing monomer (a) to the other polyfunctional unsaturated double bond-containing monomer (b) is (a) :( b) = 3: 97 to 50:50. Is preferred. When the ratio of (a) is lower than 3, sufficient weather resistance improvement effects may not be obtained. Moreover, when the ratio of (a) exceeds 50, there exists a possibility that the surface hardness of the glare-proof layer obtained may become low.

In the weather-resistant antiglare coating composition of the present invention, when the composition is applied, the first component and the second component are based on the difference in SP value between the first component and the second component contained in the composition. Phase-separate and a resin layer having random irregularities on the surface is formed. In the weather-resistant antiglare coating composition of the present invention, the SP value (SP ₁ ) of the first component which is an unsaturated double bond-containing acrylic copolymer is a polyfunctional unsaturated double bond-containing monomer. A value lower than the SP value (SP ₂ ) of the second component is preferable.

  The SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility. The SP value indicates that the larger the value, the higher the polarity, and the smaller the value, the lower the polarity.

  For example, the SP value can be measured by the following method [references: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].

Measurement temperature: 20 ° C
Sample: Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
solvent:
Good solvent: poor solvent such as dioxane, acetone, etc. n-hexane, ion-exchanged water, etc. Muddy point measurement: The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.

  The SP value δ of the resin is given by the following equation.

Vi: Molecular volume of the solvent (ml / mol)
φi: Volume fraction of each solvent at cloud point δi: SP value of solvent ml: Low SP poor solvent mixed system mh: High SP poor solvent mixed system

The weather-resistant anti-glare coating composition of the present invention is such that the SP value (SP ₁ ) of the first component and the SP value (SP ₂ ) of the second component are the following mathematical conditions:

It is preferable that the relationship is satisfied. The difference (SP ₂ −SP ₁ ) between the SP value of the first component and the SP value of the second component is preferably 0.5 or more, and more preferably 0.8 or more. The upper limit of the difference in SP value is not particularly limited, but is generally 15 or less, preferably 5 or less. When the difference between the SP value of the first component and the SP value of the second component is 0.5 or more, the compatibility of the resins with each other is low, thereby the first component and the second component after the coating composition is applied. It is thought that phase separation is brought about. Incidentally SP ₁ and SP ₂ if the first component or the second component is a mixture of more than two species, the average value of the SP value of each resin or compound and _SP 1, SP _two.

The weather resistant antiglare coating composition of the present invention may further contain an organic solvent. In this case, the SP value (SP _sol ) of the organic solvent contained in the weatherproof and antiglare coating composition is as follows:
The difference between SP ₁ and SP _sol is 2 or less;
It is more preferable that the relationship is satisfied. When the difference between SP ₁ and SP _sol is 2 or less, an antiglare layer having low haze and excellent antiglare performance can be prepared. The difference between SP ₁ and SP _sol is more preferably 1 or less, that is, in the range of 0 to 1. Note that SP ₁ and SP _sol need only have a difference of 2 or less. It may be SP ₁ <SP _sol , or SP ₁ > SP _sol .

  In addition to the first component and the second component, the weather-resistant anti-glare coating composition of the present invention may contain a commonly used resin. By using the first component and the second component as described above, the weather-resistant anti-glare coating composition of the present invention can form a resin layer having irregularities without including resin particles or the like. There is a feature.

  The weather resistant antiglare coating composition of the present invention is prepared by mixing the first component and the second component together with a solvent, a polymerization initiator, an additive and the like as required. The ratio of the first component to the second component in the weather resistant antiglare coating composition of the present invention is preferably 1:99 to 99: 1, more preferably 1:99 to 50:50, and 1:99 to 20:80 is more preferable.

  The weather resistant antiglare coating composition of the present invention preferably contains a photopolymerization initiator. Due to the presence of the photopolymerization initiator, the first component and the second component are polymerized by light irradiation. Examples of photopolymerization initiators include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and oxime ester polymerization initiators. Examples of alkylphenone photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl 1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Examples of titanocene-based photopolymerization initiators include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Is mentioned. Examples of the oxime ester polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy And ethoxy) ethyl ester. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

  Among the photopolymerization initiators, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2,2-dimethoxy-1,2-diphenylethane-1-one and the like More preferably used.

  A preferable amount of the photopolymerization initiator is 0.01 to 20 parts by weight with respect to 100 parts by weight of the first component, the second component and other resin as necessary (collectively referred to as “resin component”). And more preferably 1 to 10 parts by weight.

  The solvent in the coating composition used in the present invention is not particularly limited, and is appropriately selected in consideration of the first component and the second component, the material of the portion that is the base of the coating, the coating method of the composition, and the like. Is done. Specific examples of the solvent used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Ether solvents such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide Amide solvents such as N-methylpyrrolidone; methyl cellosol , Ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, alcohol solvents such as propanol; and the like; dichloromethane, halogenated solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  Various additives can be added to the weather-resistant antiglare coating composition of the present invention as necessary. Examples of such additives include conventional additives such as antistatic agents, plasticizers, surfactants, and antioxidants.

  The weather resistant anti-glare coating composition of the present invention can easily form an anti-glare layer having irregularities on the surface and excellent weather resistance without using resin particles. The weather-resistant anti-glare coating composition of the present invention is a flat panel display such as a liquid crystal display device, a light emitting diode display, an electroluminescence display, a fluorescent display, a plasma display panel, a CRT display, etc. It can use suitably, when providing a glare-proof layer on the surface of this film.

  The weather-resistant anti-glare coating composition of the present invention can be particularly suitably used for providing an anti-glare layer on both surfaces of the upper film of a flat panel display installed outdoors or semi-outdoors. . The weather resistant antiglare coating composition of the present invention does not contain resin particles. Therefore, by providing the antiglare layer on the film using the weather resistant antiglare coating composition of the present invention, it is possible to eliminate the optical problem of glare of the antiglare layer caused by aggregation of resin particles. . Moreover, since the weather-resistant antiglare coating composition of the present invention does not contain resin particles, there is no problem that the resin particles are peeled off due to pressure and film deformation when contacting the film or wiping the film. There is also an advantage. Furthermore, the antiglare layer formed by the weather-resistant antiglare coating composition of the present invention also has an advantage of having a good surface hardness.

  And the weather resistance of an anti-glare layer is improving the weather resistance anti-glare coating composition of this invention, without using weather resistance stabilizers, such as a ultraviolet absorber. Therefore, excellent antiglare properties, visibility, and weather resistance are achieved without causing problems such as a decrease in scratch resistance or a decrease in hard coat properties due to the incorporation of a weather resistance stabilizer. Therefore, the weather-resistant antiglare coating composition of the present invention can be suitably used for flat panel displays installed outdoors or semi-outdoors.

Antiglare film with weatherability antiglare coating composition of the present invention, it is possible to form a weather-resistant anti-glare film having excellent antiglare property, visibility and weather resistance. Such a weather-resistant anti-glare film has a transparent substrate and an anti-glare layer excellent in weather resistance.

  Various transparent plastic films, transparent plastic plates, glass and the like can be used as the transparent substrate. Examples of transparent plastic films include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester A film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth) acrylonitrile film, or the like can be used. It is preferable to use a PET film as the transparent substrate from the viewpoint of strength and the like. In addition, although the thickness of a transparent base material can be selected timely according to a use, generally it is used at about 25-1000 micrometers.

  The antiglare layer is formed by applying the weather-resistant antiglare coating composition on a transparent substrate. The application method of the coating composition can be selected as appropriate according to the coating composition and the state of the painting process. For example, the dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure method It can be applied by a coating method or an extrusion coating method (US Pat. No. 2,681,294).

  The thickness of the antiglare layer is not particularly limited, and can be set as appropriate in consideration of various factors. For example, the coating composition can be applied so that the dry film thickness is 0.01 to 20 μm.

  The coating film applied to the transparent substrate may be cured as it is, or the coating film may be dried before curing and phase-separated in advance before curing. When drying before hardening a coating film, it is 30-200 degreeC, More preferably, it is dried at 40-150 degreeC for 0.1-60 minutes, More preferably, it is 1-30 minutes, A solvent is removed, Phase separation can be achieved. Drying before curing and phase separation in advance has the advantage that the solvent in the antiglare layer can be effectively removed and irregularities of a desired size can be provided.

The antiglare layer is formed by curing the coating film obtained by applying the coating composition or the dried coating film. This curing can be performed by irradiating light using a light source that emits light having a wavelength as required. As light to irradiate, for example, light having an exposure amount of 0.1 to 1.5 J / cm ² , preferably 0.3 to 1.5 J / cm ² can be used. The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. Thus, an anti-glare layer can be hardened by irradiating light. Further, such light irradiation can also promote phase separation, and thereby has an advantage that unevenness of the surface shape caused by uneven drying of the solvent contained in the coating composition can be avoided.

  The weather-resistant anti-glare film of the present invention thus formed has an irregular uneven-shaped anti-glare layer in which the uneven arrangement is naturally determined.

を満たす関係にあるのが好ましい。ここで、粗さ曲線の算術平均粗さ（Ｒａ）および粗さ曲線の最大高さ粗さ（Ｒｚ）とは、ＪＩＳ Ｂ ０６０１−２００１において規定されるパラメーターである。 The weather-resistant anti-glare film of the present invention has the following conditions for Ra (arithmetic mean roughness of the roughness curve) and Rz (maximum height roughness of the roughness curve) of the weather-resistant anti-glare film:

It is preferable that the relationship is satisfied. Here, the arithmetic mean roughness (Ra) of the roughness curve and the maximum height roughness (Rz) of the roughness curve are parameters defined in JIS B 0601-2001.

  When the Ra (arithmetic mean roughness of the roughness curve) of the weather-resistant anti-glare film is 0.05 μm or more and 0.5 μm or less, excellent anti-glare property, no occurrence of moire, excellent scratch resistance, etc. There are advantages. In addition, since the Rz (maximum roughness of the roughness curve) of the weather-resistant anti-glare film is 0.5 μm or more and 2.0 μm or less, excellent anti-glare property, no moire occurs, and scratch resistance There are advantages such as excellent.

  The arithmetic mean roughness (Ra) of the roughness curve is obtained by extracting only the reference length from the roughness curve in the direction of the average line, the X axis in the direction of the average line of the extracted portion, and the Y axis in the direction of the vertical magnification. When the roughness curve is expressed by y = f (x), the value obtained by the following formula is expressed in micrometers (μm).

  The arithmetic average roughness (Ra) of the surface roughness curve of the antiglare layer should be measured according to JIS B 0601-2001 using, for example, an evaluation type surface roughness measuring machine manufactured by Mitutoyo Corporation. Can do.

  For the maximum height roughness (Rz) of the roughness curve, only the reference length is extracted from the roughness curve in the direction of the average line, and the interval between the peak line and the valley bottom line of this extracted part is the vertical magnification of the roughness curve. Measured in the direction of, and this value is expressed in micrometers (μm). The maximum height roughness (Rz) of the surface roughness curve of the antiglare layer is measured according to JIS B 0601-2001 using, for example, an evaluation type surface roughness measuring machine manufactured by Mitutoyo Corporation. be able to.

  In the weather resistant antiglare film of the present invention, Sm is preferably 200 μm or less, and more preferably 150 μm or less. The lower limit is preferably 5 μm. Here, Sm is the average length of the roughness curve elements on the surface, and is generally referred to as the average interval between the peaks and valleys of the roughness curve or the average interval between the irregularities. Sm can be measured according to JIS B0633 using, for example, an ultra-deep shape measuring microscope manufactured by Keyence Corporation. Note that JIS B0633 is a Japanese industrial standard created by translating ISO 4288 without changing the technical contents and the format of the standard form.

The antiglare film of the present invention preferably has a total light transmittance of 80% or more, and more preferably 85% or more. In particular, since the present invention does not contain resin particles, it is possible to achieve a high total light transmittance as described above. The total light transmittance (T _t (%)) is calculated by the following equation by measuring the incident light intensity (T ₀ ) with respect to the antiglare film and the total transmitted light intensity (T ₁ ) transmitted through the antiglare film. .

  The total light transmittance can be measured using, for example, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).

  The antiglare film of the present invention preferably has a haze of 20% or less, and more preferably 10% or less. According to the present invention, it is possible to prepare an antiglare film having excellent performance such as low haze and excellent antiglare property as described above. Advantages of low haze include that when an antiglare film is provided in a liquid crystal display device, the sharpness of the displayed image is not impaired and white blurring is less likely to occur. Such an antiglare film having a low haze has an advantage that the sharpness of an image displayed on a high-detail liquid crystal display device is not particularly impaired.

Ｈ：ヘイズ（曇価）（％）
Ｔ_ｄ：拡散透光率（％）
Ｔ_ｔ：全光線透過率（％） The haze can be calculated from the following formula in accordance with JIS K7105.

H: Haze (cloudiness value) (%)
T _d : Diffuse transmittance (%)
T _t : Total light transmittance (%)

  The haze can be measured using, for example, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).

  The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on weight unless otherwise specified.

Preparation Example 1 Preparation of Unsaturated Double Bond-Containing Acrylic Copolymer A mixture consisting of 171.6 g of isobornyl methacrylate, 2.6 g of methyl methacrylate, and 9.2 g of methacrylic acid was mixed. This mixed solution was added to 330.0 g of methyl isobutyl ketone heated to 110 ° C. under a nitrogen atmosphere in a 1000 ml reaction vessel equipped with a stirring blade, a nitrogen introducing tube, a cooling tube and a dropping funnel. -Propylene glycol monomethyl ether solution containing 1.8 g of ethylhexanoate was added dropwise at a constant rate over 3 hours at the same time as a solution of 80.0 g of propylene glycol monomethyl ether, and then reacted at 110 ° C for 30 minutes. Thereafter, 0.2 g of tertiary butyl peroxy-2-ethylhexanoate was added dropwise to a solution of 17.0 g of propylene glycol monomethyl ether, and 5.0 g of propylene glycol containing 1.4 g of tetrabutylammonium bromide and 0.1 g of hydroquinone. A monomethyl ether solution was added, and a solution of 22.4 g of 4-hydroxybutyl acrylate glycidyl ether and 5.0 g of propylene glycol monomethyl ether was added dropwise over 2 hours with air bubbling, followed by further reaction over 5 hours. An unsaturated double bond-containing acrylic copolymer having a number average molecular weight of 5,500 and a weight average molecular weight of 18,000 was obtained. This resin had an Sp value of 10.0.

Example 1
48 parts by weight of dipentaerythritol hexaacrylate (SP value: 12.1) which is a functional unsaturated double bond-containing monomer, 24 parts by weight of pentaerythritol triacrylate (SP value: 12.7), triethylene glycol-trimethylol 24 parts by weight of propane triacrylate (SP value: 11.6), 4 parts by weight of the acrylic copolymer (SP value: 10.0) of Preparation Example 1, and 5 parts by weight of a photopolymerization initiator α-hydroxycyclohexyl phenyl ketone , Isopropyl alcohol (SP value: 11.5) and methyl isobutyl ketone (SP value: 8.3) were used as solvents and the amounts shown in the table were used to prepare a non-volatile content of 45%.
This solution was bar-coated with a bar coater (No. 7) on a polyethylene terephthalate film substrate having a thickness of 100 μm at an environmental temperature of 23 ° C., and dried at 80 ° C. for 1 minute so that the film thickness was 4 μm. . Thereafter, the coating film was irradiated with an 80 W high-pressure mercury lamp so as to have an energy of 500 mJ / cm ² to form a weather-resistant anti-glare layer to obtain a weather-resistant anti-glare film.

Example 2
In Example 1, except that dipentaerythritol hexaacrylate is 24 parts by weight and triethylene glycol trimethylolpropane triacrylate is 48 parts by weight, the same anti-glare layer is formed by the same preparation method. A weather resistant antiglare film was obtained.

Example 3
In Example 1, a weather-resistant antiglare layer was formed by the same preparation method except that 66 parts by weight of dipentaerythritol hexaacrylate and 6 parts by weight of triethylene glycol trimethylolpropane triacrylate were used. A weather resistant antiglare film was obtained.

Example 4
In Example 1, all preparations were the same except that 24 parts by weight of tripropylene glycol trimethylolpropane triacrylate (SP value: 11.2) was used instead of 24 parts by weight of triethylene glycol trimethylolpropane triacrylate. The weather resistant anti-glare layer was formed by the above method to obtain a weather resistant anti-glare film.

Example 5
In Example 1, 24 parts by weight of hexaethylene glycol trimethylolpropane triacrylate (M-360) (SP value: 12.3) was used instead of 24 parts by weight of triethylene glycol trimethylolpropane triacrylate. In all, the same preparation method was used to form a weather-resistant anti-glare layer to obtain a weather-resistant anti-glare film.

Example 6
In Example 1, 24 parts by weight of hexapropylene glycol trimethylolpropane triacrylate (M-320) (SP value: 11.6) was used instead of 24 parts by weight of triethylene glycol trimethylolpropane triacrylate. In all, the same preparation method was used to form a weather-resistant anti-glare layer to obtain a weather-resistant anti-glare film.

Comparative Example 1
In Example 1, an antiglare layer was formed by the same preparation method except that triethylene glycol trimethylolpropane triacrylate was not used and 72 parts by weight of dipentaerythritol hexaacrylate was used. A film was obtained.

Comparative Example 2
In Example 1, the same preparation method was used except that triethylene glycol trimethylolpropane triacrylate was not used, and 48 parts by weight of dipentaerythritol hexaacrylate and 48 parts by weight of pentaerythritol triacrylate were used. A layer was formed to obtain an antiglare film.

Comparative Example 3
In Example 1, an antiglare layer was formed by the same preparation method except that 24 parts by weight of trimethylolpropane triacrylate was used instead of 24 parts by weight of triethylene glycol trimethylolpropane triacrylate. A dazzling film was obtained.

Comparative Example 4
In Example 1, an antiglare layer was formed by the same preparation method except that 24 parts by weight of tripropylene glycol diacrylate was used instead of 24 parts by weight of triethylene glycol trimethylolpropane triacrylate. A dazzling film was obtained.

Comparative Example 5
In Example 1, instead of using 24 parts by weight of triethylene glycol trimethylolpropane triacrylate, all except that 24 parts by weight of tricyclodecane dimethanol acrylate was used to form an antiglare layer, An antiglare film was obtained.

Comparative Example 6
In Example 1, an antiglare layer was formed by the same preparation method except that 24 parts by weight of nanoethylene glycol diacrylate was used instead of 24 parts by weight of triethylene glycol trimethylolpropane triacrylate. A dazzling film was obtained.

Comparative Example 7
In Comparative Example 1, an antiglare layer was formed by the same preparation method except that 3 parts by weight of tinuvin 384-2 as an ultraviolet absorber and 2 parts by weight of tinuvin 292 as a light stabilizer were further added. An antiglare film was obtained.

  The following evaluation tests were conducted on the weather resistant anti-glare film having the weather resistant anti-glare layer obtained in the above examples and comparative examples. The results obtained are shown in the table below.

Initial appearance About the weather-proof anti-glare layer obtained by the said Example and comparative example, the coating-film external appearance before performing the following ASTM G154 weathering test was evaluated visually based on the following reference | standard.
○: Defects such as peeling or cracking of the coating film are not observed ×: Defects such as peeling or cracking of the coating film are observed

State of coating after weathering test Weathering test according to ASTM (American Standards Testing Material) G154 (1 cycle: irradiating light at a wavelength of 313 nm for 4 hours at 60 ° C. and then maintaining for 4 hours in a dark room at 50 ° C. for 25 cycles Repeatedly)), the appearance of the coating film was visually evaluated based on the following criteria.
○: There is no significant change in the appearance of the coating film before and after the weather resistance test. Δ: Partial peeling or cracking of the coating film occurs. ×: Many peeling or cracking of the coating film occurs.

Anti-glare property A fluorescent lamp was reflected on the surface of the anti-glare layer of the obtained weather-resistant anti-glare film, and the anti-glare property was visually evaluated according to the appearance of the reflected fluorescent lamp end.
○: The end of the fluorescent lamp appears blurred Δ: The end of the fluorescent lamp appears blurred *: The end of the fluorescent lamp is clearly visible

Total light transmittance The total light transmittance (%) of the obtained weather-resistant anti-glare film was measured based on a model NDH-2000 “Houhou 3” manufactured by Nippon Denshoku Industries Co., Ltd.

Adhesion test The surface of the antiglare layer of the obtained weatherproof antiglare film was placed with 11 scratches at an interval of 1 mm with a cutter knife to make a total of 100 squares. Next, Nichibansello tape ^{(registered trademark)} was completely adhered from above, peeled off in a 45-degree direction with respect to the film, and evaluated by the number of squares completely remaining on the film.

Pencil hardness About the anti-glare layer of the obtained weather-resistant anti-glare film, the pencil hardness of the anti-glare layer was measured according to JIS K5600-5-4 (1999) and scratch hardness (pencil method).

Steel Wool Resistance On the surface of the anti-glare layer of the obtained weather-resistant anti-glare film, the degree of scars on the surface produced after steel wool # 1000 was reciprocated 10 times with a load of 1000 g / cm ² was visually evaluated.
○: No scars are confirmed Δ: Some scars are confirmed ×: Many scars are confirmed

Arithmetic mean roughness of roughness curve (Ra)
The arithmetic mean roughness (Ra) of the roughness curve of the unevenness on the surface of the antiglare layer of the obtained weather resistant antiglare film was measured according to JIS-B0601 using an ultra-deep shape measuring microscope manufactured by Keyence. Ra values were obtained.

Maximum height of roughness curve (Rz)
The maximum height roughness (Rz) of the roughness curve of the unevenness on the surface of the anti-glare layer of the obtained weather-resistant anti-glare film was measured according to JIS-B0601 using an ultra-deep shape measuring microscope manufactured by Keyence. Rz value was obtained.

Average length of surface roughness curve element (Sm)
The average length (Sm) of the roughness curve element on the surface of the antiglare layer of the obtained weather resistant antiglare film was measured according to JIS-B0633 using an ultra-deep shape measuring microscope manufactured by Keyence, and the Sm value. Got.

＊ＩＲ＃１８４：長瀬産業社イルガキュア＃１８４、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン（光重合開始剤）
チヌビン＃３８４−２：チバスペシャルティケミカル社、ベンゾトリアゾール系紫外線吸収剤
チヌビン＃１２３：チバスペシャルティケミカル社、ヒンダードアミン系光安定剤

* IR # 184: Nagase Sangyo Irgacure # 184, 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator)
Tinuvin # 384-2: Ciba Specialty Chemicals, benzotriazole UV absorber Tinuvin # 123: Ciba Specialty Chemicals, hindered amine light stabilizer

As shown in the above table, it was confirmed that the antiglare film formed by the weather resistant antiglare coating composition of the example was excellent in weather resistance because of excellent weather appearance. The anti-glare films of the examples also had high initial adhesion, and it was confirmed that they had a hardness (pencil hardness) sufficient for practical use. The antiglare films of the examples further had a feature of little yellowing in visual evaluation after the weather resistance test, although neither the ultraviolet absorber nor the light stabilizer was contained. On the other hand, it was confirmed that the antiglare films obtained from Comparative Examples 1 to 3 and 5 were inferior in the coating state after the weather resistance test and did not have sufficient weather resistance. In addition, the antiglare films obtained from Comparative Examples 1 to 3 and 5 have higher haze values after the weather resistance test than those of Examples, and the visibility may deteriorate with time. It could be confirmed.
The antiglare film obtained from Comparative Example 4 was inferior in antiglare property, adhesion and steel wool resistance. It was confirmed that the antiglare film obtained in Comparative Example 6 was inferior in adhesion and steel wool resistance. Comparative Example 7 includes Comparative Example 1 containing an ultraviolet absorber and a light stabilizer as additives. In Comparative Example 7, it was confirmed that the coating state after the weather resistance test was improved compared to Comparative Example 1, but the adhesion and steel wool resistance were poor.

  The weather-resistant anti-glare coating composition of the present invention can be coated on a substrate, dried as necessary, and then cured to provide an anti-glare layer having unevenness on the surface and having excellent weather resistance. it can. The anti-glare layer obtained from the weather-resistant anti-glare coating composition of the present invention has excellent weather resistance, reduced yellowing due to aging, etc., and further has excellent surface hardness. . And the weather-resistant anti-glare coating composition of the present invention has the characteristic that excellent weather resistance can be obtained without using a weather-resistant stabilizer such as an ultraviolet absorber, so that excellent optical properties are required. It can be suitably used in flat panel displays.

Claims (15)

A weather resistant anti-glare coating composition that is coated on a transparent substrate to form a weather resistant anti-glare layer,
The weather resistant anti-glare coating composition includes a first component and a second component, and after applying the weather resistant anti-glare coating composition on a substrate, the SP value of the first component and the second component A weather resistant antiglare coating composition in which a first component and a second component are phase-separated based on a difference, and a resin layer having random irregularities is formed on the surface, and the first component is unsaturated A double bond-containing acrylic copolymer,
The second component contains a polyfunctional unsaturated double bond containing a tri- or higher functional unsaturated double bond-containing monomer having 3 to 6 molar equivalents of an alkylene oxide unit having 2 to 4 carbon atoms in a monomer molecule. Monomer,
Weatherproof and antiglare coating composition.   The trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of the alkylene oxide unit having 2 to 4 carbon atoms in the monomer molecule is added to the weight of the resin solid content of the weather resistant antiglare coating composition. The weather-resistant antiglare coating composition according to claim 1, which is contained in an amount of 2 to 50% by weight. The SP value (SP ₁ ) of the first component and the SP value (SP ₂ ) of the second component are the conditions of the following formula:

The weather-resistant antiglare coating composition according to claim 1 or 2, wherein Further, a weather resistant antiglare coating composition containing an organic solvent,
The SP value of the first component (SP ₁ ), the SP value of the second component (SP ₂ ), and the SP value of the organic solvent (SP _sol ) are as _follows :
The difference between SP ₁ and SP _sol is 2 or less;
The weather-resistant antiglare coating composition according to claim 3, wherein   The trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of the alkylene oxide unit having 2 to 4 carbon atoms in one monomer molecule is added to a trihydric or higher polyhydric alcohol having 2 to 4 carbon atoms. The weather resistant antiglare coating composition according to any one of claims 1 to 4, which is a (meth) acrylate monomer obtained by introducing an alkylene oxide skeleton and then reacting with (meth) acrylate. The trifunctional or higher unsaturated double bond-containing monomer having 3 to 6 molar equivalents of the alkylene oxide unit having 2 to 4 carbon atoms in the monomer molecule is represented by the following formula 1

[In Formula 1,
n, m and p are each independently an integer of 2 to 4,
x, y and z are each independently an integer of 0 to 3, provided that the sum of x, y and z is 3 to 6, and R ¹ has a hydroxyl group. Or an alkyl group having 1 to 3 carbon atoms,
R ² , R ³ and R ⁴ are each independently hydrogen or a methyl group. ]
The weather-resistant antiglare coating composition according to claim 1, which is a monomer represented by:   The weather-resistant antiglare coating composition according to claim 1, which does not contain an inorganic filler and resin particles.   The weather resistant antiglare coating composition according to any one of claims 1 to 7, which does not contain an ultraviolet absorber.   A weather-resistant anti-glare film having a transparent substrate and an anti-glare layer, wherein the anti-glare layer is formed from the weather-resistant anti-glare coating composition according to claim 1. the film.   The weather resistant anti-glare film according to claim 9, wherein the weather resistant anti-glare film has a haze of less than 20%. The Ra (arithmetic mean roughness of the roughness curve) and Rz (maximum height roughness of the roughness curve) of the weatherproof antiglare film are as follows:

The weather-resistant antiglare film according to claim 9, wherein   The weather resistant anti-glare film according to claim 9, wherein the average length (Sm) of the roughness curve element on the surface of the anti-glare film is 200 µm or less. An application step of applying the weather resistant antiglare coating composition according to any one of claims 1 to 8 to a transparent substrate, and a curing step of curing the obtained coating film,
A method for producing a weather-resistant antiglare film. An application step of applying the weather-resistant antiglare coating composition according to any one of claims 1 to 8 to a transparent substrate, and a light irradiation step of irradiating the obtained coating film with light to separate and harden the phase. ,
A method for producing a weather-resistant antiglare film.   The weather-resistant anti-glare film obtained by the manufacturing method of the anti-glare film of Claim 13 or 14.