JP2010059236A - Antistatic and anti-glaring coating composition, antistatic and anti-glaring film, and method for producing the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic and anti-glaring coating composition that excels in hard coat characteristics, and can easily form an antistatic and anti-glaring layer having both of excellent anti-glaring and antistatic performance. <P>SOLUTION: This coating composition forms the antistatic and anti-glaring layer by coating the composition on a transparent substrate, in which the composition includes a first, second and third components. The first component is an acrylic copolymer which contains an unsaturated double bond, the second component is a monomer which contains a polyfunctional unsaturated double bond, and the third component is a monomer, oligomer or resin that has surface resistivity of ≤1.0×10<SP>12</SP>Ω/sq. and a solubility parameter (SP<SB>3</SB>) of ≥12.8, and the third component is another one different from the first and second components. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antistatic antiglare coating composition capable of forming an antistatic antiglare layer on various transparent plastic films, transparent plastic plates, and transparent substrates such as glass, and the antistatic properties thereof. The present invention relates to an antistatic antiglare film having an antistatic antiglare layer formed from an antiglare 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 liquid crystal display devices, an anti-glare (AG) film that roughens the surface is often provided on the display surface. By providing an anti-glare film on the display surface, external light is irregularly reflected by the irregularities on the surface of the anti-glare film, and thereby the outline of the image reflected on the display surface can be blurred. As a result, it is possible to eliminate an obstacle to screen visibility caused by reflection of a reflected image when the display is used.

  By the way, on the display surface, it is required to eliminate the obstacle to screen visibility by providing an antiglare film as described above, and at the same time, antistatic performance to prevent adhesion of dust and the like is also required. This is because a transparent base material such as a glass base material or a plastic base material on the display surface has a high insulating property, and thus has a property that it is easily charged and dust and the like are easily attached. Problems caused by the fact that the display surface is easily charged and dust is likely to adhere to it include not only a decrease in the screen visibility of the display due to the adhesion of dust, but also the risk of failure of electronic components due to the discharge of charges accumulated by charging. For this reason, both excellent anti-glare performance and excellent antistatic performance are required on the display surface.

  As a method for producing an antiglare film for improving the display performance of a liquid crystal display device, generally, a method for roughening the surface by processing such as cutting, embossing, and bonding at the time of film production, or a layer containing particles And a method of roughening the surface of the film. At present, a method of providing the latter layer containing particles on a film is widely used.

  JP 2001-323206 A (Patent Document 1) discloses a compound (A) having a (meth) acryloyl group in the molecule, and a compound (B) having a quaternary ammonium base and a (meth) acryloyl group in the molecule. And an antiglare antistatic hard coat resin composition comprising a compound (C) having a tricyclodecane skeleton and a (meth) acryloyl group in the molecule, and spherical particles (D) having an average particle diameter of 1 to 20 μm Has been. In this composition, expression of anti-glare performance is achieved by using spherical particles (D) having an average particle diameter of 1 to 20 μm. However, when anti-glare performance is expressed using such spherical particles, for example, there is a problem that the particles to be used are not uniformly dispersed. In order to uniformly disperse the particles in the composition, for example, care must be taken such as controlling and adjusting the viscosity of the composition. If the particles are aggregated without being uniformly dispersed, the uneven shape on the surface may be out of the desired range, resulting in problems such as reduced transmitted image clarity and so-called white blurring.

  Japanese Patent Laid-Open No. 2006-218461 (Patent Document 2) discloses an antiglare hard coat transfer material in which a hard coat layer, a primer layer, and an adhesive layer are sequentially formed on an uneven layer made of a resin and fine particles. An antistatic antiglare hard coat transfer material is described in which the coating layer is composed of an antistatic agent and a resin, and the primer layer is composed of an amino-modified acrylic resin. Also in this antistatic antiglare hard coat transfer material, the antiglare performance is derived from the shape of the concavo-convex layer made of resin and fine particles. Therefore, for example, the same problem as described above that the particles to be used are not uniformly dispersed may occur. The antistatic antiglare hard coat transfer material described in the cited document 2 is also such that an antistatic antiglare hard coat is formed by transferring the transfer material. Therefore, transfer work is essential for forming an antistatic antiglare hard coat, and the procedure is complicated.

  On the other hand, examples of a method for forming a concavo-convex shape without using particles include a processing method such as cutting and embossing. However, when the surface is roughened by processing such as cutting or embossing at the time of film production, it is difficult to randomly provide the uneven shape of the rough surface, and the uneven shape may be followed by rules. . If the irregular shape conforms to a certain rule, the light reflected by the irregular surface may interfere with each other, causing a problem in the display on the 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 uneven structure of the antiglare layer overlapping the arrangement direction of the pixels of the display device. This tends to occur when the 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.

  International Publication No. 2005/073763 (Patent Document 3) is an application by the present applicant. In Patent Document 3, after applying an antiglare coating composition on a substrate, the first component and the second component are phase-separated on the surface based on the difference in physical properties of the first component and the second component. An antiglare coating composition is described in which a resin layer having random irregularities is formed. With this antiglare coating composition, an antiglare layer can be easily formed on the surface of a display or the like. However, antistatic properties such as antiglare and antistatic properties can be easily formed due to demands for antistatic properties due to the recent complication of display technology. There has been a need to study antiglare coating compositions.

JP 2001-323206 A Japanese Patent Laid-Open No. 2006-218641 International Publication No. 2005/073763

  The present invention solves the above-mentioned conventional problems. The object of the present invention is to provide an antistatic antiglare layer having excellent hard coat properties and having both excellent antiglare performance and excellent antistatic performance. Is to provide an antistatic antiglare coating composition that can be more easily formed.

The present invention
An antistatic antiglare coating composition that is applied on a transparent substrate to form an antistatic antiglare layer,
The antistatic antiglare coating composition includes a first component, a second component, and a third component. After applying the antistatic antiglare coating composition on a substrate, the first component, Based on the difference between the solubility parameters of the second component and the third component, the antistatic antiglare layer having the first component, the second component, and the third component phase-separated and having random irregularities on the surface. An antistatic antiglare coating composition formed, and the first component is an unsaturated double bond-containing acrylic copolymer;
The second component is a polyfunctional unsaturated double bond-containing monomer, and the third component has a single film surface resistivity of 1.0 × 10 ¹² Ω / □ or less and a solubility parameter. (SP ₃ ) is 12.8 or more, which is a monomer, oligomer or resin that is a component different from the first component and the second component, and
The solubility parameter (SP ₁ ) of the first component, the solubility parameter (SP ₂ ) of the second component, and the solubility parameter (SP ₃ ) of the third component are the following conditions:
SP ₁ <SP ₂
SP ₁ <SP ₃
SP ₂ -SP ₁ is 0.5 or more SP ₃ -SP ₁ is 2.7 or more;
An antistatic antiglare coating composition that satisfies the above condition is provided, whereby the above object is achieved.

The antistatic antiglare coating composition further contains an organic solvent, and the solubility parameter (SP ₁ ) of the first component and the solubility parameter (SP _sol ) of the organic solvent _{satisfy the following} conditions:
The difference between SP ₁ and SP _sol is 1.7 or less;
It is more preferable that the relationship is satisfied.

  The third component is a monomer, oligomer or resin having at least one polar group selected from the group consisting of an acid-base ion pair, a betaine structure, a quaternary ammonium salt, and an imidazolium salt. Is more preferable.

  The third component is a urethane (meth) acrylate having at least one polar group selected from the group consisting of an acid-base ion pair, a betaine structure, a quaternary ammonium salt, and an imidazolium salt. More preferred.

The weight ratio of the first component, the second component and the third component of the antistatic antiglare coating composition is as follows:
First component: (second component + third component) = 0.1: 99.9 to 30:70
Second component: Third component = 1: 99 to 99: 1
It is more preferable that the relationship is satisfied.

  The present invention is further an antistatic antiglare film having a transparent substrate and an antistatic antiglare layer, wherein the antistatic antiglare layer is formed from the antistatic antiglare coating composition. An antistatic antiglare film is also provided.

The present invention further includes
An application step of applying the antistatic antiglare coating composition to a transparent substrate, and a light irradiation step of irradiating the obtained coating film with light to separate and harden it;
Including
A method for producing an antistatic antiglare film is also provided.

  The present invention also provides an antistatic antiglare film obtained by the method for producing the antistatic antiglare film.

  The present invention further provides a display device in which an antistatic antiglare layer obtained by applying and curing the antistatic antiglare coating composition is used as an outermost layer of a display.

  By using the antistatic antiglare coating composition of the present invention, an antistatic antiglare layer having excellent hard coat properties and having both excellent antiglare performance and excellent antistatic performance can be more easily obtained. Can be formed. The antistatic antiglare layer obtained by the antistatic antiglare coating composition of the present invention has an irregular concavo-convex shape in which the concavo-convex arrangement is naturally determined. And by this uneven | corrugated shape, the performance that transparency etc. is high, is excellent in visibility, and is excellent in anti-glare property will be achieved.

Background to the Present Invention First, the background to the present invention will be described. As described in detail below, the coating composition of the present invention is a layer having random irregularities on the surface due to phase separation based on the difference in solubility parameter of each component after coating on a substrate. Is a coating composition characterized in that is formed. And in such a coating composition, as a method of imparting antistatic properties,
1. 1. a method of imparting antistatic performance by applying a surfactant or the like on the obtained uneven layer, and A method of including an antistatic agent in the coating composition;
And so on. However, However, this method of applying a surfactant has a drawback that it is inferior in stability over time with respect to the development of antistatic performance because the surfactant is only adhered to the surface.

  1. An antistatic agent is included in the coating composition. Examples of the antistatic agent in this method include metals such as nickel, silver and copper, or conductive materials such as conductive carbon such as graphite. However, when these conductive materials are used, there is a problem that the obtained uneven layer is colored. Therefore, when these conductive materials are used in the antiglare coating composition, the screen visibility of the display is significantly reduced due to coloring. Therefore, it is very difficult to use these conductive materials.

  2. As another antistatic agent in this method, for example, a method using an antistatic agent such as urethane (meth) acrylate having an alkali metal salt is also conceivable. However, it has been experimentally found that the inclusion of these antistatic agents in the coating composition causes a problem that phase separation does not occur and uneven shapes are not formed. The reason why the uneven shape is not formed by using such an antistatic agent is that the balance of the phase separation mechanism due to the difference in solubility parameter of each component due to the inclusion of an antistatic functional group such as an alkali metal salt. It is considered that phase separation did not occur and this caused phase separation.

  In response to such a problem, the present inventors searched for a third component that can impart antistatic properties and can ensure the phase separation of the coating composition. As a result, it has been found by experiments that two performances of antistatic performance and phase separation mechanism can be ensured by using the third component shown below, thereby completing the present invention. Hereinafter, the antistatic antiglare coating composition of the present invention will be sequentially described.

Antistatic antiglare coating composition The antistatic antiglare coating composition of the present invention forms an antiglare layer having excellent antistatic properties when applied on a transparent substrate. This antistatic antiglare coating composition contains at least three kinds of components, a first component, a second component, and a third component. The first component, the second component, and the third component are based on the difference in physical properties between the first component, the second component, and the third component when the antiglare coating composition is applied onto the substrate. The first component, the second component, and the third component are characterized by phase separation.

First Component The antistatic antiglare coating composition of the present invention contains an unsaturated double bond-containing acrylic copolymer as the first component. In the antistatic antiglare coating composition of the present invention, the first component, and the second component and the third component described in detail below both contain an unsaturated double bond that is a photocurable group. ing. As a result, an antistatic antiglare layer having excellent hard coat properties and hardly causing scratches or the like is obtained.

  As the unsaturated double bond-containing acrylic copolymer as the first component, for example, a resin obtained by polymerizing or copolymerizing a polymerizable unsaturated monomer having an acid group such as a (meth) acrylic monomer or a polymerization having this acid group A copolymer obtained by reacting a monomer having an ethylenically unsaturated double bond and an epoxy group with a resin obtained by copolymerizing an ethylenically unsaturated monomer and another monomer having an ethylenically unsaturated double bond; A copolymer obtained by reacting a polymerizable unsaturated monomer having a monomer with another ethylenically unsaturated double bond and a monomer having an epoxy group; a polymerizable unsaturated monomer having this acid group and another ethylenically unsaturated double And a copolymer obtained by reacting a monomer having a bond and an isocyanate group.

  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, tert-methacrylic acid or acrylic acid Spotted , 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 Nilidene, 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.

Second Component A polyfunctional unsaturated double bond-containing monomer is used as the second component in the antistatic antiglare coating composition of the present invention. This second component and the third component described below are phase-separated from the first component to form an antiglare layer having random irregularities on the surface. As the polyfunctional unsaturated double bond-containing monomer preferably used as the second component, for example, a dealcoholization reaction product of polyhydric alcohol and (meth) acrylate, specifically, dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) Acrylate or the like can be used. In addition, an acrylate monomer having a polyethylene glycol skeleton such as polyethylene glycol # 200 diacrylate and light acrylate 4EGA (both manufactured by Kyoeisha Chemical Co., Ltd.) can also be used. Among these polyfunctional unsaturated double bond-containing monomers, pentaerythritol triacrylate, pentaerythritol tetraacrylate, light acrylate 4EGA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), dipentaerythritol pentaacrylate and hexaacrylate It is particularly preferable to use One of these polyfunctional unsaturated double bond-containing monomers may be used alone, or two or more thereof may be mixed and used.

The second component is a component different from the third component described below. Specifically, the polyfunctional unsaturated double bond-containing monomer in which the surface resistivity of the single film formed from the third component and the photopolymerization initiator is 1.0 × 10 ¹² Ω / □ or less is Not included in the two components. Thus, for example, a polyfunctional unsaturated double bond-containing monomer having at least one polar group selected from the group consisting of an acid-base ion pair, a betaine structure, a quaternary ammonium salt, and an imidazolium salt Not included in the two components.

In the antistatic antiglare coating composition of the present invention, the solubility parameter (SP value) of the first component, the second component, and the third component contained in the composition when the composition is applied. Based on the difference, the first component, the second component, and the third component are phase-separated, and a resin layer having random irregularities on the surface is formed. In the antistatic antiglare coating composition of the present invention, the solubility parameter (SP ₁ ) of the first component which is an unsaturated double bond-containing acrylic copolymer, and the polyfunctional unsaturated double bond are contained. In the solubility parameter (SP ₂ ) of the second component that is a monomer,
SP ₁ <SP ₂ and
It is required that SP ₂ -SP ₁ satisfies the relationship of 0.5 or more. The difference (SP ₂ −SP ₁ ) between the solubility parameter of the first component and the solubility parameter of the second component is more preferably 0.8 or more. The upper limit of the difference in solubility parameter is not particularly limited, but is generally 15 or less, preferably 5 or less. When SP ₁ and SP ₂ satisfy the above relationship, phase separation occurs based on the difference in solubility parameter (SP value). Specifically, when the difference between the solubility parameter of the first component and the solubility parameter of the second component is 0.5 or more, the compatibility of the resins with each other is low, so that the first after coating of the coating composition. It is believed that phase separation between the component and the second component results.

Here, the solubility parameter (sometimes abbreviated as SP value) 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. Note that SP ₁ , SP ₂ and SP ₃ in the case where the first component, the second component or the third component is a mixture of two or more are the average values of the solubility parameters of the respective resins or compounds as SP ₁ , SP and _2, SP _3.

  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 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

Third Component As the third component in the antistatic antiglare coating composition of the present invention, the surface resistivity of the single film is 1.0 × 10 ¹² Ω / □ or less, and the solubility parameter is 12.8. A monomer, oligomer, or resin that is a component different from the second component is used. The third component and the second component are phase-separated from the first component to form an antiglare layer having random irregularities on the surface.

As described above, the third component has a surface resistivity of not more than 1.0 × 10 ¹² Ω / □ (sometimes described as ohm per square, Ω / sq.), And the surface resistivity is low. It is an ingredient. The monomer, oligomer or resin, which is a component having a low surface resistivity used as the third component, contributes particularly to the reduction of the surface resistance of the antistatic antiglare layer, and functions as a so-called antistatic agent, oligomer or oligomer. Resin. In this specification, the surface resistivity of the third film of the third component is determined by using a test piece of a film obtained by curing the third component using a photopolymerization initiator, if necessary, at a temperature of 23 ° C., The surface resistivity was measured at an applied voltage of 100 V with a “super insulation meter SM-8220” manufactured by Toa Denpa Kogyo Co., Ltd. in an environment of 50% humidity.

The third component further has a solubility parameter (SP ₃ ) of 12.8 or more, and the solubility parameter of the first component and the solubility parameter of the third component:
SP ₁ <SP ₃ and
It is required that SP ₃ -SP ₁ satisfies the relationship of 2.7 or more.

More preferably, the difference (SP ₃ −SP ₁ ) between the solubility parameter of the first component and the solubility parameter of the third component is 2.8 or more. The upper limit of the difference in solubility parameter is not particularly limited, but is generally 10 or less, preferably 5 or less, and more preferably 3.4 or less.

Similar to the second component, the third component is phase-separated from the first component to form an antiglare layer having random irregularities on the surface. Here, in the second component, phase separation occurs in a range where the difference in solubility parameter from the first component is larger than 0.5. In contrast, the third component needs to have a solubility parameter (SP ₃ ) of 12.8 or more and a difference in solubility parameter from the first component of 2.7 or more. As described above, the reason why the difference in solubility parameter between the third component and the first component needs to be larger than the difference between the solubility parameter between the second component and the first component is bound by theory. However, the third component has a low surface resistivity, that is, the third component has a polar group for lowering the surface resistivity, so that the solubility parameter (SP ₃ ) is measured to be high. it is conceivable that.

  The third component is more preferably a monomer, oligomer or resin having a urethane structure. The case where the third component has a urethane structure is also considered to contribute to the phase separation performance with the first component. The urethane structure is a highly polar skeleton in the polymer skeleton. And when a 3rd component has a urethane structure, polarity performance will be provided to the 3rd component considered to contribute to expression of uneven | corrugated formation. Thus, it is thought that the phase separation function of the 3rd component and the 1st component will be favorably secured because the 3rd component has a urethane structure.

  More preferably, the third component is a monomer, oligomer or resin containing at least one polar group selected from the group consisting of an acid-base ion pair, a betaine structure, a quaternary ammonium salt, and an imidazolium salt. preferable. These acid-base ion pairs, betaine structures, quaternary ammonium salts, and imidazolium salts are all polar groups and have a role of reducing surface resistivity.

  Examples of a preferable third component include urethane (meth) acrylates having at least one polar group selected from the group consisting of quaternary ammonium salts and imidazolium salts. Since these urethane (meth) acrylates have a (meth) acrylate group that is photopolymerizable, they can undergo a crosslinking reaction with the first component and the second component, so that the resulting antistatic antiglare layer is excellent. There is an advantage that it has a high physical strength.

  Examples of urethane (meth) acrylates having a quaternary ammonium salt include reaction products of a polyisocyanate compound (a), a hydroxyl group-containing (meth) acrylate compound (b), and a hydroxyl group-containing quaternary ammonium salt (c-1). Can be mentioned.

  Moreover, as urethane (meth) acrylate which has an imidazolium salt, the reaction product of a polyisocyanate compound (a), a hydroxyl-containing (meth) acrylate compound (b), and an active hydrogen containing imidazolium salt (c-2) is mentioned. It is done.

  The polyisocyanate compound (a) is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates. Specifically, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethyl Polyisocyanates such as xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate, naphthalene diisocyanate, or trimer compounds or multimers of these polyisocyanates Compound, A uret type polyisocyanate, a water dispersion type polyisocyanate (for example, “Aquanate 100”, “Aquanate 110”, “Aquanate 200”, “Aquanate 210”, etc., manufactured by Nippon Polyurethane Industry Co., Ltd.), or these A reaction product of polyisocyanate and polyol is exemplified. These may be used alone or in combination of two or more.

  Examples of such polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, 1,6 -Hexanediol, neopentyl glycol, cyclohexane dimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, poly Polyhydric alcohols such as tetramethylene glycol and polyethylene oxide Polyether polyol having at least one structure of polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization, polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itacone Examples include polyester polyols that are condensates with polybasic acids such as acids, adipic acid, and isophthalic acid, caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, and polybutadiene-based polyols such as polyolefin-based polyols and hydrogenated polybutadiene polyols. .

  Furthermore, as such polyol, for example, 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid Also included are carboxyl group-containing polyols such as homogentisic acid, and sulfonic acid group or sulfonate group-containing polyols such as sodium 1,4-butanediolsulfonate.

  When a reaction product of polyisocyanate and polyol is used as the polyisocyanate compound (a), for example, it may be used as a terminal isocyanate group-containing polyisocyanate obtained by reacting the polyol with the polyisocyanate. In the reaction between the polyisocyanate and the polyol, a metal catalyst such as dibutyltin dilaurate or bismuth neodecanoate or an amine system such as 1,8-diazabicyclo [5.4.0] undecene-7 is used for the purpose of promoting the reaction. It is also preferable to use a catalyst or the like.

  As the polyisocyanate compound (a), diisocyanates such as tolylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate are preferable because the viscosity of the obtained urethane (meth) acrylate can be lowered.

The hydroxyl group-containing (meth) acrylate compound (b) is not particularly limited as long as it is a (meth) acrylic acid partial ester of a polyhydric alcohol. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone modified 2-hydroxyethyl A hydroxyl group-containing (meth) acrylate compound having one (meth) acryloyl group such as (meth) acrylate,
2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified pentaerythritol Hydroxyl-containing (meth) acrylate compounds having two or more (meth) acryloyl groups such as tri (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate can give. These may be used alone or in combination of two or more.

  Among these, as the hydroxyl group-containing (meth) acrylate compound (b), 2-hydroxyethyl acrylate, pentaerythritol tri (meth) acrylate are used from the viewpoint of high crosslinking density and surface hardness of the resulting cured coating film. Dipentaerythritol penta (meth) acrylate and the like are preferable.

  As the hydroxyl group-containing quaternary ammonium salt (c-1) used for the preparation of urethane (meth) acrylate having a quaternary ammonium salt, a quaternary ammonium salt represented by the following formula can be used.

  In the formula, R and R ′ are alkyl groups having 1 to 20 carbon atoms, Y is chlorine or bromine, m and n are each independently an integer of 1 to 49, and m + n is 2 to 50. .

  Preferable specific examples of the hydroxyl group-containing quaternary ammonium salt (c-1) represented by the above formula include polyoxyethylene dimethyl ammonium chloride, polyoxyethylene diethyl ammonium chloride, polyoxyethylene lauryl methyl ammonium chloride, polyoxyethylene cetyl. Examples include methylammonium chloride, polyoxyethylene stearylmethylammonium chloride, and those in which these chlorines are replaced by bromine.

  As the active hydrogen-containing imidazolium salt (c-2) used for the preparation of urethane (meth) acrylate having an imidazolium salt, an imidazolium salt represented by the following formula can be used.

In the formula, R ^{1 to} R ⁵ may be the same or different from each other, and may have a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, an aldehyde group, or an ether-bonded oxygen atom. 1 to 20 hydrocarbon groups or hydrogen atoms, and at least one of R ^{1 to} R ⁵ contains an active hydrogen reactive with an isocyanate group. Among these, at least one of R ^{1 to} R ⁵ is a hydroxyalkyl group, particularly a hydroxyalkyl group having 1 to 6 carbon atoms, and more preferably 1 to 1 carbon atoms from the viewpoint of easy control of the reaction with an isocyanate group. 3 hydroxyalkyl groups are preferred, and of these, the hydroxyethyl group is most preferred.

X is chlorine, bromine, iodine, BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , AlCl ₄ , HSO ₄ , ClO ₄ , CF ₃ SO ₃ , CH ₃ SO ₃ , CF ₃ SO ₄ , CH ₃ SO ₄ , CF ₃ CO ₂ , CH ₃ CO ₂ , CF ₃ C ₆ F ₄ SO ₃ , CF ₃ C ₆ H ₄ SO ₃ , CH ₃ C ₆ H ₄ SO ₃ , (C ₂ F ₅ SO ₂ ) ₂ N, (C _{2 F 5 SO 2) (CF} 3 SO 2) N, and the like _{(CF 3 SO 2) 2 N} . X is preferably bromine, (C ₂ F ₅ SO ₂ ) ₂ N or (CF ₃ SO ₂ ) ₂ N from the viewpoint of lowering the melting point of the active hydrogen-containing imidazolim salt.

  Preferred specific examples of the active hydrogen-containing imidazolium salt (c-2) represented by the above formula include 1-hydroxyethyl-3-octylimidazolium bromide, 1-hydroxyethyl-3-methylimidazolium bistrifluoromethanesulfonimide 1-hydroxyethyl-3-octylimidazolium bistrifluoromethanesulfonimide and the like.

  These polyisocyanate compounds (a), hydroxyl group-containing (meth) acrylate compounds (b), and hydroxyl group-containing quaternary ammonium salts (c-1) or active hydrogen-containing imidazolium salts (c-2) The blending amount in the reaction is not particularly limited, but the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (b) and the hydroxyl group-containing group are contained in 1 mol of the isocyanate group of the polyisocyanate compound (a). The quaternary ammonium salt (c-1) or the active hydrogen-containing imidazolium salt (c-2) is preferably added so that the total number of moles of the active hydrogen is 0.5 to 2 mol, 0.8 to 1 It is more preferable to add so that it may become 2 mol. If the total number of moles is less than the lower limit, the storage stability tends to be reduced by the isocyanate groups remaining when the paint is formed. When the upper limit is exceeded, unreacted hydroxyl group-containing quaternary ammonium salt (c-1) or active hydrogen-containing imidazolium salt (c-2) tends to bleed out from the resulting cured coating film.

The method for preparing urethane (meth) acrylate having a quaternary ammonium salt or urethane (meth) acrylate having an imidazolium salt is not particularly limited,
(A) Polyisocyanate compound (a), hydroxyl group-containing (meth) acrylate compound (b), and hydroxyl group-containing quaternary ammonium salt (c-1) or active hydrogen-containing imidazolium salt (c-2) A method of charging and reacting with
(B) After reacting the polyisocyanate compound (a) with the hydroxyl group-containing (meth) acrylate compound (b), the hydroxyl group-containing quaternary ammonium salt (c-1) or the active hydrogen-containing imidazolium salt (c -2) and a reaction method,
(C) After reacting the polyisocyanate compound (a) with the hydroxyl group-containing quaternary ammonium salt (c-1) or active hydrogen-containing imidazolium salt (c-2), the hydroxyl group-containing (meth) acrylate group A method of reacting compound (b),
Etc. Among these, the method (c) is preferable from the viewpoint of stability of reaction control and shortening of production time.

  In this reaction, for the purpose of accelerating the reaction, a metal catalyst such as dibutyltin dilaurate or bismuth neodecanoate or an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7 is used. It is also preferable to use it, and the reaction temperature is preferably in the range of 30 to 90 ° C, particularly 40 to 70 ° C.

  Other examples of the preferred third component include resins having an acid-base ion pair and / or a betaine structure.

  Resins having an acid-base ion pair and / or a betaine structure in the molecule include an acid-base ion pair such as a salt which is an ion pair consisting of a sulfonic acid or a carboxylic acid and a base, and / or a tertiary amine and a halogen. Ammonium salts obtained from alkyl halides, phosphonium salts obtained from trivalent phosphine compounds and alkyl halides, radical-reactive unsaturated group-containing monomers and acids having a betaine structure such as a reaction product of a carboxylic acid and a tertiary amine A polymer obtained by polymerizing a compound having a radical reactive unsaturated group that does not have a base ion pair and a betaine structure, or a radical reaction obtained by reacting this polymer with a monomer containing a radical reactive unsaturated group. An unsaturated group-containing polymer is preferred.

  Examples of the radical-reactive unsaturated group-containing monomer having an acid-base ion pair include an amine salt of (meth) acryloylaminoalkylsulfonic acid and an amine salt of phosphoric anhydride adduct of (meth) acryloyloxyalkyl alcohol. Examples of the radical reactive unsaturated group-containing monomer having a betaine structure include phosphonium salts of halogenated alkyl vinyl ethers and trivalent organic phosphorus compounds, and quaternary compounds of dialkylaminoalkyl (meth) acrylates and alkyl halides. An ammonium salt is mentioned.

  Examples of monomers having an acid-base ion pair and a radical-reactive unsaturated group having no betaine structure include monofunctional polyalkyl (meth) acrylate, monofunctional polyoxyalkylene (meth) acrylate, and monofunctional polyester (meth). Acrylate, monofunctional polycaprolactone (meth) acrylate, reaction adduct of m-isopropenyl-α, α'-dimethylbenzyl isocyanate and butyroxypoly-ε-caprolactone adduct, methacrylate of polycaprolactone monoalcohol, aliphatic group or fragrance One terminal (meth) acrylate of a polymer of a radical reactive unsaturated group-containing monomer having a group.

  In addition, as a radical reactive unsaturated group-containing monomer that further modifies this polymer into a radical reactive unsaturated group-containing polymer, a part of the radical reactive unsaturated group-containing compound having an oxirane ring in the molecule is copolymerized, Thereafter, a radical reactive unsaturated group-containing compound having a carboxyl group in the molecule is added and reacted, or a part of the radical reactive unsaturated group-containing compound having a carboxyl group in the molecule is copolymerized, Thereafter, it is obtained by adding and reacting a radical reactive unsaturated group-containing compound having an oxirane ring in the molecule.

  Examples of the radical-reactive unsaturated group-containing compound having an oxirane ring in the molecule include glycidyl (meth) acrylate, glycidyloxylalkyl (meth) acrylate, and cyclohexyloxirane skeleton-containing (meth) acrylate.

  Examples of the radical-reactive unsaturated group-containing compound having a carboxyl group in the molecule include an addition reaction product of (meth) acrylic acid, alkylene glycol mono (meth) acrylates and carboxylic acid anhydride, epoxy compound An addition reaction product of a compound obtained by reacting an acid and a carboxylic anhydride may be mentioned. Examples of mono (meth) acrylates of alkylene glycol include hydroxyethyl (meth) acrylate and polyethylene glycol mono (meth) acrylate, and examples of carboxylic acid anhydride include succinic anhydride, (hydrogenated) phthalic anhydride, and anhydrous A maleic acid is mentioned, A phenyl glycidyl ether is mentioned as an epoxy compound, A (meth) acrylic acid is mentioned as a carboxylic acid.

  The resin having an acid-base ion pair or betaine structure may be a resin having a fluorocarbon group. For example, a resin having an acid-base ion pair or betaine structure and a fluorocarbon group is obtained by, for example, obtaining a block polymer of halogenated alkylstyrene having 2-mercaptoethanol introduced at the terminal, and then 2- (meth) acryloyl at the hydroxyl group. By adding oxyethyl isocyanate, a halogenated alkyl group-containing unsaturated macromonomer having an unsaturated group introduced at the terminal is synthesized.

  For this unsaturated macromonomer containing an alkyl halide group into which an unsaturated group is introduced at the end, a chain transfer agent having a carboxylic acid in the molecule such as 2-mercaptopropionic acid is used instead of 2-mercaptoethanol. Thus, after obtaining a block polymer of halogenated alkylstyrene, it can also be obtained by adding a vinyl compound having a glycidyl group in its molecule, such as glycidyl methacrylate, to the carboxylic acid group.

  The halogenated alkyl group-containing unsaturated macromonomer, the fluorocarbon group-containing unsaturated monomer, and the (meth) acrylic acid monoester monomer are copolymerized at a weight ratio of 5 to 90: 5 to 90: 0 to 80. A high molecular compound in which a halogenated alkyl group in the copolymer is reacted with a tertiary amine or a tertiary phosphine to form a repeating unit of a halogenated quaternary ammonium group or a halogenated quaternary phosphonium group is synthesized. .

  In the synthesis of a halogenated alkyl group-containing unsaturated macromonomer used for synthesizing a polymer compound in which a repeating unit of a halogenated quaternary ammonium group or a halogenated quaternary phosphonium group is formed, Instead, for example, a vinyl compound having a tertiary amine in the molecule such as dimethylaminoethyl methacrylate is used, and carbon and halogen in the molecule such as benzyl chloride are used instead of the tertiary amine or tertiary phosphine used later. It can also be obtained by using a halogenated alkyl, aryl halide, or halogenated aralkyl having a bond with. In addition, by using phosphate esters or sulfate esters such as trimethyl phosphate, dimethyl sulfate or methyl p-toluenesulfonate instead of benzyl chloride, halogen-free ion pairs can be used as polar structural repeating units. A polymer compound having a fluorocarbon group can be obtained.

The antistatic antiglare coating composition of the present invention such as other components preferably contains a photopolymerization initiator. Due to the presence of the photopolymerization initiator, the first component, the second component, and the third 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 with respect to 100 parts by weight of the first component, the second component, the third component, and other resin as necessary (collectively referred to as “coating layer forming component”). 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight.

The antistatic 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 antistatic antiglare coating composition is as follows:
The difference between the SP ₁ and _{SP sol} is 1.7 or less;
It is more preferable that the relationship is satisfied. When the difference between SP ₁ and SP _sol is 1.7 or less, an anti-glare layer that is suitable for use in a display device or the like and has excellent anti-glare performance can be prepared. Note that SP ₁ and SP _sol need only have a difference of 1.7 or less. Accordingly, SP ₁ <SP _sol may be satisfied, and SP ₁ > SP _sol may be satisfied.

  In addition to the first component, the second component, and the third component, the antistatic antiglare coating composition of the present invention contains a resin that is usually used (that is, another resin) as necessary. May be. However, the types and contents of the other resins are on condition that they do not adversely affect the phase separation performance of the first component, the second component, and the third component.

  The antistatic antiglare coating composition of the present invention may contain a filler that imparts antistatic properties, if necessary. However, the types and contents of the other resins are on condition that they do not adversely affect the phase separation performance of the first component, the second component, and the third component. Examples of the filler that imparts antistatic properties that can be used as necessary in the antistatic antiglare coating composition of the present invention include conductive fillers such as various metal alkoxides, zinc antimonate sol, and ITO powder. . These conductive fillers have the advantage of high transparency and do not hinder the visibility of the resulting antistatic antiglare layer.

Preparation of antistatic antiglare coating composition The antistatic antiglare coating composition of the present invention comprises a first component, a second component and a third component, a solvent, a polymerization initiator and an additive as required. It is prepared by mixing together.

In the antistatic antiglare coating composition, the weight ratio of the first component, the second component and the third component is:
First component: (second component + third component) = 0.1: 99.9 to 30:70
Second component: Third component = 1: 99 to 99: 1
It is preferable that the relationship is satisfied. The weight ratio of the first component: (second component + third component) is more preferably 1:99 to 15:85. The weight ratio of the second component to the third component is more preferably 10:90 to 30:70.
In the weight ratio of the first component, the second component, and the third component, when the ratio of the first component is below the above-mentioned preferable lower limit, unevenness due to phase separation between the first component, the second component, and the third component is generated. It may not be formed sufficiently, and good antiglare performance may not be exhibited.
On the other hand, when the ratio of the first component exceeds the above preferable upper limit, the unevenness becomes too large and the contrast is lowered, the sharpness of the image is lowered, or the glare phenomenon becomes obvious, for example, the visibility of the display screen There is a risk of lowering.

  The solvent in the antistatic antiglare coating composition used in the present invention is composed of the first component, the second component and the third component, the material of the part serving as the base of the coating, the solubility parameter of the solvent, and the coating of the composition. The method is appropriately selected in consideration of the method and the like. 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.

  A preferable amount of the solvent is 1 to 10000 parts by weight, more preferably 50 parts, based on 100 parts by weight of the film forming component including the first component, the second component, the third component, and other resins as necessary. -500 parts by weight.

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

  The antistatic antiglare coating composition of the present invention is excellent in hard coat properties and is applied and cured with an antistatic antiglare layer having both excellent antiglare performance and excellent antistatic performance. It can be formed by a simpler procedure. The antistatic antiglare coating composition of the present invention is charged on the outermost layer of a display device such as 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, and a CRT display. It can be particularly suitably used for providing a preventive antiglare layer.

  The antistatic antiglare coating composition of the present invention does not contain resin particles. Therefore, by using the antistatic antiglare coating composition of the present invention and providing an antiglare layer on the film, it is possible to eliminate the optical problem of glare of the antiglare layer caused by aggregation of resin particles. it can. In addition, since the antistatic antiglare coating composition of the present invention does not contain resin particles, there is a 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 of not. Furthermore, the antiglare layer formed by the antistatic antiglare coating composition of the present invention also has an advantage of having a good surface hardness.

  The antistatic antiglare layer formed by the antistatic antiglare coating composition of the present invention can be used, for example, for the internal structure of a liquid crystal display device. The antistatic antiglare layer formed according to the present invention is excellent in antistatic performance, has an excellent surface hardness, and has an advantage that there is no inconvenience such as peeling off of resin particles. Therefore, it can be used well in the internal structure of a liquid crystal display device that is a precision instrument and requires antistatic performance. Examples of the use of the antistatic antiglare layer in the present invention in the internal structure of a liquid crystal display device include, for example, a Newton ring prevention layer that prevents sticking of a light transmissive member.

  The antistatic antiglare layer formed by the antistatic antiglare coating composition of the present invention can be suitably used for articles other than display devices because it further has excellent transparency and antistatic properties. it can. By providing the antistatic antiglare layer in the present invention on a transparent member such as a display, for example, it is possible to impart excellent antistatic properties without impairing the transparency, and thereby dust on the transparent member. Can be prevented. By providing the antistatic antiglare layer in the present invention as a protective layer for home appliances, for example, a matte appearance due to the antiglare effect can be provided, and adhesion of dust and the like can also be prevented.

Antistatic antiglare film Using the antistatic antiglare coating composition of the present invention, an antistatic antiglare film having excellent hard coat properties, antiglare properties, visibility and antistatic properties is formed. Can do. Such an antistatic antiglare film has a transparent substrate and an antistatic antiglare layer.

  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 suitably selected according to a use, it is generally used at about 25-1000 micrometers.

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

  The thickness of the antistatic antiglare layer is not particularly limited, and can be appropriately set in consideration of various factors. For example, the coating composition can be applied so that the dry film thickness is 0.1 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 the coating film, the solvent is removed by drying at 30 to 200 ° C., more preferably 40 to 150 ° C. for 0.1 to 60 minutes, more preferably 0.5 to 30 minutes. , Phase separation can be performed in advance. Drying before curing and phase separation in advance has the advantage that the solvent in the antistatic antiglare layer can be effectively removed and irregularities of a desired size can be provided.

An antistatic antiglare layer is formed by curing a coating film obtained by applying the coating composition or a 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 antistatic glare-proof layer can be hardened by irradiating light. Moreover, such light irradiation can also promote phase separation, and thereby has an advantage that unevenness of the surface shape due to drying unevenness of the solvent contained in the coating composition can be avoided.

  The antistatic antiglare film of the present invention formed in this way has an irregularly shaped antistatic antiglare layer having irregular irregularities, where the uneven arrangement is naturally determined. A cross-sectional schematic view of the resulting antistatic antiglare film is shown in FIG. The antistatic antiglare film 1 has an antistatic antiglare layer 3 and a transparent substrate 5. Since the unevenness on the surface of the antistatic antiglare film of the present invention is determined spontaneously, an irregular uneven shape can be formed on the surface of the resin layer.

The antistatic 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 measured by measuring the incident light intensity (T ₀ ) with respect to the antistatic antiglare film and the total transmitted light intensity (T ₁ ) transmitted through the antistatic antiglare film, Calculated by the following formula.

  The total light transmittance can be measured using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

  The antistatic antiglare film of the present invention preferably has a haze of 1.5 to 10%. According to the present invention, as described above, an antistatic antiglare film having excellent performance such as low haze and excellent antiglare property can be prepared. Advantages of having a haze of 10% or less include that when an antistatic antiglare film is provided on a liquid crystal display device, the sharpness of a displayed image is not impaired and white blurring is less likely to occur. It is done. Such an antistatic antiglare film having a low haze has an advantage of not impairing the sharpness of an image displayed on a display device.

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: diffusion light 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 (1) Mixing a mixture of 187.2 g isobornyl methacrylate, 2.8 g methyl methacrylate, 10.0 g methacrylic acid and 160.0 g propylene glycol monomethyl ether did. This mixed solution was added to 200.0 g of propylene glycol monomethyl ether heated to 100 ° 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. The solution was added dropwise at a constant rate over 3 hours at the same time with an 80.0 g solution of propylene glycol monomethyl ether containing 2.0 g of 2-ethylhexanoate, and then reacted at 100 ° C. for 1 hour. Thereafter, a propylene glycol monomethyl ether solution containing 0.2 g of tertiary butyl peroxy-2-ethylhexanoate was added dropwise and reacted at 100 ° C. for 1 hour. To the reaction solution, 5.0 g of propylene glycol monomethyl ether solution containing 1.5 g of tetrabutylammonium bromide and 0.2 g of hydroquinone was added. While air bubbling, 173.0 g of glycidyl methacrylate and 5.0 g of propylene glycol monomethyl ether were added. The solution was added dropwise over 1 hour and then further reacted over 5 hours. An unsaturated double bond-containing acrylic copolymer having a number average molecular weight of 8800 and a weight average molecular weight of 18,000 was obtained. This resin had an Sp value of 9.8.

Preparation Example 2 Preparation of unsaturated double bond-containing acrylic copolymer (2) A mixture comprising 187.2 g of isobornyl methacrylate, 2.8 g of methyl methacrylate, 10.0 g of methacrylic acid and 160.0 g of propylene glycol monomethyl ether was mixed. did. This mixed solution was added to 200.0 g of propylene glycol monomethyl ether heated to 100 ° 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, and then tert-butylperoxy-2- The solution was added dropwise at a constant rate over 3 hours at the same time with an 80.0 g solution of propylene glycol monomethyl ether containing 4.0 g of ethylhexanoate, and then reacted at 100 ° C. for 1 hour. Thereafter, a propylene glycol monomethyl ether solution containing 0.4 g of tertiary butyl peroxy-2-ethylhexanoate was added dropwise and reacted at 100 ° C. for 1 hour. Add 5.0 g of propylene glycol monomethyl ether solution containing 1.5 g of tetrabutylammonium bromide and 0.2 g of hydroquinone to the reaction solution, and further add 173 g of glycidyl methacrylate and 5.0 g of propylene glycol monomethyl ether while bubbling air. The solution was added dropwise over 1 hour, and then further reacted over 5 hours. An unsaturated double bond-containing acrylic copolymer having a number average molecular weight of 4000 and a weight average molecular weight of 12,000 was obtained. The Sp value of this resin was 10.0.

Example 1
3.0 parts by weight of an unsaturated double bond-containing acrylic copolymer of Preparation Example 2 (first component, Sp value of this resin: 10.0), Aronix M402 (polyfunctional unsaturated double bond-containing monomer) Second component, Sp value of this monomer: 12.1) 27 parts by weight, purple light UV-AS102 (third component, SP value: 12.8, surface resistivity 1.0 × 10 ¹⁰ Ω / □) 70 parts by weight 7.0 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone which is a photoinitiator, and isobutyl alcohol (SP value: 11.3) as a solvent are mixed to obtain an antistatic antiglare coating composition. Got. The obtained antistatic antiglare coating composition was applied to a triacetyl cellulose film having a thickness of 80 μm at an environmental temperature of 23 ° C. with a bar coater and 60 ° C. at 80 ° C. so that the dry film thickness was 10 μm. The solvent was removed by heating for 2 seconds to dry. Thereafter, this film was irradiated with ultraviolet rays with a 120 W / cm high-pressure mercury lamp so that the ultraviolet rays were 300 mJ / cm ² to form an antistatic antiglare film.

Examples 2 to 4 and Comparative Examples 1 to 4
An antistatic antiglare film was formed in the same manner as in Example 1 except that the components and amounts described in Table 1 or 2 were used.

  The obtained antistatic antiglare film was evaluated according to the following.

Place the antistatic antiglare films obtained antiglare evaluated under fluorescent lamp, to confirm the presence or absence of glare of the fluorescent lamp visually. The evaluation criteria are as follows.
○: Fluorescent light is not reflected △: Fluorescent light is reflected a little ×: Fluorescent light is reflected

Ｈ：ヘイズ（曇価）（％）
Ｔ_ｄ：拡散透光率（％）
Ｔ_ｔ：全光線透過率（％） Haze (cloudiness value)
Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the diffusion light transmittance (T _d (%)) and the total light transmittance (T _t (%)) of the antistatic antiglare film are measured, and the haze is measured. Calculated.

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

Measurement of 60 ° Gloss Value Using a GM-268 gloss meter (manufactured by Konica Minolta Sensing), 60 ° gloss of the antistatic antiglare film was measured three times, and an average value was calculated from these measured values. The results are shown in the table below. The lower the 60 ° gloss value, the lower the specular gloss in human visual evaluation, and the better the antiglare film with better antiglare properties.

Surface resistivity measurement Using a surface resistance measuring device (manufactured by Toa Denpa Kogyo Co., Ltd., super insulation meter SM-8220), an antistatic anti-glare film was applied at 23 ° C. and 50% environment with an applied voltage of 100 V and the surface The resistivity was measured. If the value of this surface resistivity is 1 × 10 ¹² or less, it can be evaluated that the antistatic performance is excellent.

Steel wool rating # 0000 steel wool resistance (SW resistance) under a load of 1 kg / cm ^s, After 10 reciprocate with the resulting antistatic antiglare film on, antistatic antiglare The presence or absence of scratches on the film was confirmed visually.
A: 0 to 5 scratches are confirmed.
Δ: 6 to 10 scratches are confirmed.
X: 11 or more scratches are confirmed.

The composition and evaluation results of Examples 1 to 4 and Comparative Examples 1 to 4 are summarized in the following table. The symbols in the table indicate the following contents.
Aronix M305: manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate and pentaerythritol tetraacrylate, SP value 12.7
Light acrylate 4EGA: manufactured by Kyoeisha Chemical Co., Ltd., PEG # 200 diacrylate, SP value 13.6
Aronix M402: manufactured by Toagosei Co., Ltd., dipentaerythritol pentaacrylate and hexaacrylate, SP value 12.1
Light Procoat ASC-G: manufactured by Kyoeisha Chemical Co., Ltd., SP value 13.0, surface resistivity of single film 1.8 × 10 ¹¹ Ω / □
Purple light UV-AS102: manufactured by Nippon Synthetic Chemical Co., Ltd., SP value 12.8, surface resistivity 1.0 × 10 ¹⁰ Ω / □
-Full cure UEN-001: manufactured by Soken Chemical Co., Ltd., SP value 12.4, surface resistivity 1.0 × 10 ⁹ Ω / □
NK oligo U-201 PA-60: manufactured by Shin-Nakamura Chemical Co., Ltd., SP value 11.5, surface resistivity 1.8 × 10 ¹⁰ Ω / □
Irgacure 184D: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by Ciba Specialty Chemicals Co., Ltd.

As shown in the above table, all of the antistatic antiglare films obtained from the antistatic antiglare coating compositions of the examples have good antiglare performance (antiglare evaluation and 60 ° gloss value evaluation). ) And excellent antistatic performance.
On the other hand, although the film obtained by Comparative Example 1 not containing the third component had good antiglare performance, it had poor antistatic performance.
Although it is a polyfunctional unsaturated double bond-containing monomer, the film obtained by Comparative Examples 3 and 4 containing a component whose solubility parameter is outside the range of the third component of the present invention has good antistatic performance. However, the uneven shape was not formed, and the antiglare performance was poor.
The film obtained by Comparative Example 2 not containing the first component also had no anti-glare shape and poor antiglare performance.

  The antistatic antiglare coating composition of the present invention is applied on a substrate, dried as necessary, and then cured to provide an antistatic antiglare layer having random irregularities on the surface. Can do. By using the antistatic antiglare coating composition of the present invention, an antistatic antiglare layer having irregularities on the surface can be formed by a simpler process of application. For this reason, the antistatic antiglare coating composition of the present invention can be suitably used for large-screen liquid crystal displays that have been mass-produced in recent years. And the anti-glare film obtained by the antistatic anti-glare coating composition of the present invention is excellent in anti-static properties, and further has the advantage of excellent anti-static durability.

1 is a cross-sectional schematic view of an antiglare film of the present invention.

Explanation of symbols

  1: Antiglare film, 3: Antiglare layer, 5: Transparent substrate.

Claims (9)

An antistatic antiglare coating composition that is applied on a transparent substrate to form an antistatic antiglare layer,
The antistatic antiglare coating composition comprises a first component, a second component and a third component, and after the antistatic antiglare coating composition is applied on a substrate, the first component, Based on the difference in solubility parameter between the second component and the third component, the first component, the second component and the third component are phase-separated, and an antistatic antiglare layer having random irregularities on the surface is provided. An antistatic antiglare coating composition formed, and the first component is an unsaturated double bond-containing acrylic copolymer;
The second component is a polyfunctional unsaturated double bond-containing monomer, and the third component has a surface resistivity of a single film of 1.0 × 10 ¹² Ω / □ or less, and a solubility parameter (SP ₃ ) is 12.8 or more, is a monomer, oligomer or resin that is a component different from the first component and the second component, and
The solubility parameter (SP ₁ ) of the first component, the solubility parameter (SP ₂ ) of the second component, and the solubility parameter (SP ₃ ) of the third component are the following conditions:
SP ₁ <SP ₂
SP ₁ <SP ₃
SP ₂ -SP ₁ is 0.5 or more SP ₃ -SP ₁ is 2.7 or more;
An antistatic antiglare coating composition that satisfies the following conditions. Furthermore, it is an antistatic antiglare coating composition containing an organic solvent, wherein the solubility parameter (SP ₁ ) of the first component and the solubility parameter (SP _sol ) of the organic solvent are the following conditions:
The difference between SP ₁ and SP _sol is 1.7 or less;
The antistatic antiglare coating composition according to claim 1, wherein   The third component is a monomer, oligomer, or resin having at least one polar group selected from the group consisting of an acid-base ion pair, a betaine structure, a quaternary ammonium salt, and an imidazolium salt. 3. The antistatic antiglare coating composition according to 1 or 2.   The third component is a urethane (meth) acrylate having at least one polar group selected from the group consisting of an acid-base ion pair, a betaine structure, a quaternary ammonium salt, and an imidazolium salt. The antistatic antiglare coating composition according to any one of -3. The weight ratio of the first component, the second component and the third component of the antistatic antiglare coating composition is as follows:
First component: (second component + third component) = 0.1: 99.9 to 30:70
Second component: Third component = 1: 99 to 99: 1
The antistatic antiglare coating composition according to any one of claims 1 to 4, which has a relationship satisfying   An antistatic antiglare film having a transparent substrate and an antistatic antiglare layer, wherein the antistatic antiglare layer comprises the antistatic antiglare coating composition according to any one of claims 1 to 5. An antistatic antiglare film formed. An application process for applying the antistatic antiglare coating composition according to any one of claims 1 to 5 to a transparent substrate, and light irradiation for irradiating the obtained coating film with light to cause phase separation and curing. Process,
Including
A method for producing an antistatic antiglare film.   An antistatic antiglare film obtained by the method for producing an antistatic antiglare film according to claim 7.   A display device in which an antistatic antiglare layer obtained by applying and curing the antistatic antiglare coating composition according to claim 1 is used as an outermost layer of a display.

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