KR20100095384A - Anti-glare coating composition, anti-glare film and method of producing the same - Google Patents

Abstract

[Problem] In the antiglare film which solves the problem of the prior art and is further imparted to the antiglare film, and more specifically, can be applied to a display device such as a liquid crystal television, under an external light. Not only improves whiteness, etc., but also provides excellent contrast performance, in particular, black distinctive feeling (i.e., clean black with strong glossiness), and in addition, anti-glare film which can easily produce an anti-glare film having excellent anti-fingerprint property. Provision of a coating composition.
Means for Solving the Problems A composition for forming an antiglare layer on a transparent substrate, the composition comprising a first component and a second component, wherein the first component is an unsaturated double bond-containing acrylic copolymer, and the second component is It is a polyfunctional unsaturated double bond containing component containing a bifunctional or more than unsaturated double bond containing monomer, The said composition further contains a polyether skeleton containing urethane (meth) acrylate (A) as a 3rd component, and And / or (meth) acrylate (B) having a refractive index of 1.52 or more, having a cyclic structure and containing at least one reactive unsaturated double bond, wherein the composition is applied onto the transparent substrate. Later, according to the difference of the physical properties of a 1st component and a 2nd component, a 1st component and a 2nd component phase-separate, and the anti-glare layer which has random unevenness | corrugation on the surface is formed.

Description

Anti-glare coating composition, anti-glare film, and manufacturing method thereof {ANTI-GLARE COATING COMPOSITION, ANTI-GLARE FILM AND METHOD OF PRODUCING THE SAME}

INDUSTRIAL APPLICABILITY The present invention can impart not only anti-glare properties, but also contrast performance, particularly a clear feeling of black and anti-fingerprint, on transparent substrates such as various transparent plastic films, transparent plastic plates and glass. An antiglare film having a composition for forming an antiglare layer (hereinafter referred to as an antiglare coating composition) and an antiglare layer formed from the antiglare coating composition.

Liquid crystal displays, such as liquid crystal displays and liquid crystal televisions, have advantages such as thin, light weight, low power consumption, and the like, and are used in various fields such as computers, word processors, televisions, cellular phones, and portable information terminal devices. In these liquid crystal displays, on the display surface, anti-glare (AG) films for roughening the surface, low reflection (LR) films for adjusting the refractive index, anti-reflection (AR) films, and the like are used. It is installed. These attempts have been made to solve the defects such as the decrease in contrast caused by the reflection of external light and the reflection of the background reflected on the display surface.

As a manufacturing method of the anti-glare film which improves the display performance of a liquid crystal display device, generally, the method of roughening the surface by processing, such as cutting, shaping | molding, shaping | molding, etc. at the time of film manufacture, or resin The method of roughening the surface of a film by providing the layer containing particle | grains on a film, etc. are mentioned. At present, the method of providing the layer containing the latter resin particle 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 comprising a light transmissive resin and translucent microparticles is laminated. The anti-glare film which protrudes 0.1-0.3 micrometer from the surface is described. In the production of such an antiglare film, for example, there is a problem that the fine particles to be used do not uniformly disperse. In order to disperse | distribute resin uniformly in a solution, attention, such as controlling and adjusting a solution viscosity, is needed. If the fine particles are not uniformly dispersed and aggregated, the irregularities on the surface may deviate from a desired range, resulting in a decrease in transmission image clarity or so-called white clouding.

On the other hand, when roughening a surface by processing, such as cutting, mold forming, and joining at the time of film manufacture, it is difficult to install the unevenness of the roughness at random, and unevenness may follow a certain rule. If the unevenness conforms to a certain rule, the light reflected from the uneven surface may interfere with each other, thereby reinforcing the reflected light, causing a moire shape, or causing a defect in the display of the display. That is, the generation of moire pattern is caused by the arrangement direction of the fine uneven structure of the antiglare layer overlapping with the arrangement direction of the pixels of the display device. While the pixels are regularly arranged, they tend to occur when the fine uneven structure is located so as to overlap the rule. Moreover, when forming an anti-glare layer by mold pressure shaping | molding, processes, such as the shaping | molding process of a glare-proof layer and the mold used for this shaping | molding pressure, are cumbersome. In addition, it is also necessary to be careful that foreign matter does not adhere to the molding surface of the mold used for the mold pressure.

Japanese Patent Laid-Open No. 2003-004917 (Patent Document 2) discloses a polarizing plate with an antiglare layer having an antiglare film and a polarizer, wherein an arrangement direction of the fine concavo-convex structure of the antiglare layer is in the absorption axis direction or the transmission axis direction of the polarizer. A polarizing plate with an antiglare layer is described, which is 22.5 ° ± 12.5 °. As described herein, in the case of providing the fine concavo-convex structure by processing, the angle in the arrangement direction or the like must be finely adjusted, which makes the manufacturing process complicated. In addition, when the pixels of the display element become smaller due to high resolution and colorization of the display screen, the occurrence probability of the moire pattern is considered to be higher. Therefore, a technique for solving this problem is required.

Japanese Patent Application Laid-Open No. 2000-267086 (Patent Document 3) discloses a method for manufacturing an electrode substrate for a reflective liquid crystal display device, including a step of applying a mixed resin solution obtained by mixing a plurality of resins which are easily phase separated from each other. It is described. In addition, Japanese Patent Laid-Open No. 2001-305316 (Patent Document 4) describes a reflecting plate having a resin layer in which irregularities are formed by a structure in which at least two types of resin parts are dispersed and held with each other. However, these substrates or reflecting plates are different from the anti-glare film in which these performances are important because they do not need to consider the performance of the reflection of the background reflected on the display surface, the transparency of the transparent image, and the cloudiness.

Moreover, as a technique which solves the problem of the said prior art, Unexamined-Japanese-Patent No. 2008-197320 (patent document 5) discloses the anti-glare coating composition which can form the anti-glare layer apply | coated on a transparent base material, The anti-glare coating composition is not deliberately blended with resin particles in order to form fine irregularities. The anti-glare coating composition comprises a first component, a second component, and a fluorine compound and / or a siloxane compound. According to the difference of the physical property of a 2nd component, a 1st component and a 2nd component phase-separate, and can easily form the resin layer which has random fine dense unevenness | corrugation on the surface. In addition, Japanese Patent No. 3998697 (Patent Document 6) discloses an antiglare coating composition characterized by containing no resin particles as a coating composition for forming an antiglare layer applied on a transparent substrate. The coating coating composition comprises a first component and a second component, and in accordance with the difference in physical properties of the first component and the second component, more specifically, by using a difference in SP values, the first component and the second component. By this phase separation, a resin layer having random irregularities on the surface can be formed on the transparent substrate. By these anti-glare coating compositions, an anti-glare film having improved reflection, cloudiness and the like can be easily formed.

However, recently, in liquid crystal display devices such as liquid crystal televisions and liquid crystal displays, it is strongly desired to display a clear black with strong contrast performance, particularly a clear sense of black, that is, a glossiness. In addition to the correspondence on the driving method and the circuit side, the correspondence on the outermost surface of a display device, especially an anti-glare film, is demanded. In addition, in these display devices, excellent anti-fingerprint is also strongly desired.

Japanese Patent Publication No. 2002-221610 Japanese Patent Publication No. 2003-004917 Japanese Patent Laid-Open No. 2000-267086 Japanese Patent Laid-Open No. 2001-305316 Japanese Patent Publication No. 2008-197320 Japanese Patent No. 3998697

MEANS TO SOLVE THE PROBLEM This invention makes it a subject to solve the problem of the said prior art, and to provide a further function to an anti-glare film, and more specifically, this invention is an anti-glare applicable to display apparatuses, such as a liquid crystal television, etc. In the film, the antiglare film which not only improves the appearance of light, turbidity, etc. under external light, but also provides excellent contrast performance, in particular, a clear feeling of black (i.e., a clean black with a strong gloss), and also has an excellent anti-fingerprint property. An object of the present invention is to provide an anti-glare coating composition which can be easily produced.

The present inventors have diligently studied that the anti-glare coating composition contains, as a first component, an unsaturated double bond-containing acrylic copolymer, and as a second component contains a specific multifunctional unsaturated double bond-containing component. After the composition is applied onto the transparent substrate, the first component and the second component are phase-separated according to the difference in the physical properties of the first component and the second component, in particular, the difference in the SP value, thereby providing random fine irregularities on the surface. When the resin layer which has is formed, and a composition contains a polyether skeleton containing urethane (meth) acrylate, it not only improves glare, cloudiness, etc. in an anti-glare film, but also excellent contrast performance, especially black It has been found that clear black, which has a strong sense of gloss, is obtained, and excellent anti-fingerprint is obtained. Moreover, the present inventors discovered that the black feeling in an anti-glare film improves also by mix | blending the specific (meth) acrylate of refractive index 1.52 or more to a composition, and came to complete this invention. Accordingly, the present invention provides the following.

A composition for forming an antiglare layer on a transparent substrate, the composition comprising a first component and a second component, wherein the first component is an unsaturated double bond-containing acrylic copolymer, and the second component contains a bifunctional or higher unsaturated double bond It is a polyfunctional unsaturated double bond containing component containing a monomer, The said composition further has a cyclic structure as a 3rd component as polyether skeleton containing urethane (meth) acrylate (A), and / or a 4th component. A (meth) acrylate (B) having a refractive index of 1.52 or more, comprising at least one reactive unsaturated double bond, and after applying the composition onto the transparent substrate, the first component and the second component According to the difference in the physical properties of the composition, the first component and the second component phase-separated, so that the antiglare layer having random irregularities on the surface is formed.

In the composition of the present invention, preferably, the (meth) acrylate (A) includes a structure represented by the following formula (1), and has a water tolerance of 6.0 mL or less and a solubility parameter of 12 or less. (SPA).

[Wherein X represents a residue excluding the hydroxyl group of the sock end of the polyol compound having a polyether skeleton]

In the composition of the present invention, Preferably, the (meth) acrylate (A) is a polyol compound (a) having a polyether skeleton, a polyisocyanate (b), and a hydroxyl group-containing (meth) It is obtained by making an acrylate monomer (c) react.

In the composition of this invention, Preferably, the said (meth) acrylate (B) is an acrylate monomer which has a structure represented by following formula (2).

[Wherein n is 2 or more]

The composition of the present invention preferably further comprises an organic solvent, wherein the SP value (SP ₁ ) of the first component, the SP value (SP ₂ ) of the second component and the SP value (SP _sol ) of the organic solvent are , The condition that SP ₁ <SP ₂ , and the condition that the difference between SP ₁ and SP _sol is equal to or less than 1.7, and the difference between the SP value SP ₁ of the first component and the SP value SP ₂ of the second component 0.8 to 3.6.

In the composition of the present invention, preferably, the SP ₁ is 10.5 or less, and the SP ₂ is 11.3 or more.

The composition of the present invention preferably further comprises at least one component selected from the group consisting of a polymerization initiator, a curing agent, a catalyst and a photosensitizer.

The composition of the present invention is preferably characterized by not containing resin particles.

Moreover, this invention relates to the anti-glare film in which the said anti-glare layer is formed from the said composition as an anti-glare film which has a transparent base material and an anti-glare layer.

This invention also relates to the manufacturing method of an anti-glare film containing the coating process which apply | coats said composition to a transparent base material, and the hardening process which hardens the obtained coating film.

Moreover, this invention relates to the manufacturing method of the anti-glare film containing the coating process of apply | coating said composition to a transparent base material, the drying process of drying and phase-separating the obtained coating film, and the hardening process of hardening a dried coating film. will be.

The present invention further relates to a method for producing an antiglare film, which includes a coating step of applying the composition to a transparent substrate, and a light irradiation step of irradiating light onto the obtained coating film to perform phase separation and curing.

This invention relates to the antiglare film obtained further by the manufacturing method of said anti-glare film.

Moreover, this invention relates to the polarizing plate which is the said anti-glare film and the polarizing plate which has a polarizing element, and is laminated | stacked facing the anti-glare film surface which is a surface opposite to the anti-glare layer provided in the transparent base material, and a polarizing element surface.

The present invention further relates to a transmissive display device having a planar transmissive display, a light source device for irradiating the translucent display from the back, and the anti-glare film laminated on the surface of the transmissive display.

Moreover, this invention relates to the liquid crystal display device in which said anti-glare film was used for the outermost layer of a display.

The anti-glare coating composition of this invention can be provided on the base material, and if necessary, after drying, it can harden | cure, and can install the anti-glare layer which is a resin layer which has an unevenness | corrugation on the surface. Therefore, the glare-proof layer which has unevenness | corrugation on the surface can be formed by a simpler process compared with the method of going through two processes, such as forming a resin layer and forming the protrusion used as a base of unevenness | corrugation.

In addition, when the irregularities are formed on the surface of the antiglare layer according to the present invention, since the irregularities are naturally determined, irregular irregularities can be formed on the surface of the antiglare layer. For this reason, the moire due to the regularity of the irregularities arrangement does not occur. By using the anti-glare coating composition of this invention, the anti-glare layer which has an unevenness | corrugation on the surface can be formed easily, and an anti-glare film can be manufactured easily using this. The obtained anti-glare film has the outstanding performance that there is little shine and turbidity, and low haze is low, and high total light transmittance is high. Here, haze means the ratio of the scattered light transmission amount to the total light transmission amount.

In addition, the present invention further provides a function in the antiglare film that can be applied to a display device such as a liquid crystal television without particularly improving the problems of the prior art such as the reflection of the antiglare film and the cloudiness. It is possible to provide excellent contrast performance under external light, in particular, a clear sense of black (i.e., clean black with a strong glossiness), and further, an antiglare film having excellent anti-fingerprint can be produced simply. Moreover, since the resin layer formed from the composition of this invention has random fine unevenness | corrugation on the surface, when laminating, it can exhibit not only anti blocking property but also anti-Newton's ring property.

1 is a schematic cross-sectional view of an antiglare film of the present invention.
2 is a schematic explanatory diagram of total light transmittance.
It is a cross-sectional schematic of the polarizing plate using the anti-glare film of this invention.
4 is a schematic cross-sectional view of a transmissive display device using the anti-glare film of the present invention.

Anti-glare Coating Composition

The anti-glare coating composition of this invention is apply | coated on a transparent base material, and forms an anti-glare layer. This anti-glare coating composition contains at least two kinds of components, a first component and a second component. When the anti-glare coating composition is applied on the transparent substrate, these first component and the second component are phase-separated from the first component and the second component according to the difference in the physical properties of each of the first component and the second component. And a resin layer having random fine irregularities on its surface, that is, an antiglare layer is formed.

1st component

As a 1st component, (meth) acrylic resin is preferable and especially, an unsaturated double bond containing acrylic copolymer is especially preferable. The unsaturated double bond-containing acrylic copolymer is not particularly limited as long as it is an acrylic copolymer having an unsaturated double bond group exhibiting polymerization reactivity, and may be an oligomer or a resin, for example, a resin polymerized or copolymerized with a (meth) acryl monomer. A resin obtained by copolymerizing a (meth) acrylic monomer with another copolymerizable monomer or a monomer having another ethylenically unsaturated double bond, a resin obtained by reacting a (meth) acryl monomer with a monomer having another ethylenically unsaturated double bond and an epoxy group, The resin etc. which made the (meth) acryl monomer, the monomer which has another ethylenically unsaturated double bond, and the isocyanate group react are mentioned. As resin which contains a (meth) acrylic resin in skeletal structure, Resin which superposed | polymerized or copolymerized the (meth) acryl monomer, Resin which copolymerized the monomer which has a (meth) acryl monomer and another ethylenically unsaturated double bond, (meth) A resin obtained by reacting an acrylic monomer with another copolymerizable monomer or another ethylenically unsaturated double bond and a monomer having an epoxy group, a resin obtained by reacting a (meth) acryl monomer with a monomer having another ethylenically unsaturated double bond and an isocyanate group. Etc. can be mentioned. These unsaturated double bond containing acrylic copolymers may be used individually by 1 type, and may mix and use 2 or more types. In addition, in this specification, an "oligomer" is a polymer which has a repeating unit, and means that the number of this repeating unit is 3-10. The SP value of the first component (SP ₁₎ is preferably not more than 10.5. If the SP value SP ₁ of the first component exceeds the above preferable value, random unevenness may not be formed, which is not preferable.

The compounding quantity of a 1st component is 0.1 to 10 weight%, Preferably it is 0.5 to 5 weight% with respect to the weight of the total solid of a 1st component and a 2nd component. If the blending amount of the first component is less than 0.1% by weight, it is too small compared to the second component, so that phase separation is not performed so that fine irregularities are not formed, and thus there is a fear of problems such as difficulty in expressing anti-glare properties. If it exceeds 10% by weight, phase separation may occur excessively large, the surface irregularities become rough, high haze, and turbidity may become remarkable.

2nd component

The composition of this invention contains a 2nd component, As a 2nd component, It is a compound which has a unsaturated double bond group which shows several polymerizability in one molecule as a polyfunctional unsaturated double bond containing component, and is monomer, an oligomer, resin Or a mixture thereof may be used. As an essential component, any one containing two or more unsaturated double bond-containing monomers is not particularly limited, but a different one from the above first component is used. The SP value of the second component (SP ₂₎ is preferably not less than 11.3. If the SP value SP ₂ of the second component is less than the above preferable value, random unevenness may not be formed, which is not preferable.

The unsaturated double bond-containing monomer having a bifunctional or higher function is not particularly limited as long as it is a monomer having at least two double bonds, and has, for example, a bifunctional or higher functionality which is a dealcohol reactant of a polyhydric alcohol and a (meth) acrylate. An unsaturated double bond containing monomer can be mentioned. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylol pro Payne tri (meth) acrylate, tripropylene glycol di (meth) acrylate, nanoethylene glycol di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) acrylate Etc. can be mentioned. In addition, an acrylate monomer having a polyethylene glycol skeleton such as polyethylene glycol # 200 diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) may be used as the unsaturated double bond-containing monomer having two or more functions. The monofunctional or higher unsaturated double bond-containing monomer may be used alone or in combination of two or more kinds thereof.

The compounding quantity of a bifunctional or more than unsaturated double bond containing monomer does not have limitation in particular, For example, it is 50-100 weight% in the total weight of a 2nd component, Preferably it is 60-100 weight%. When the compounding quantity of the bifunctional or more than unsaturated double bond containing monomer is less than 50 weight%, the pencil hardness of a coating film will become lower than 2H, and there exists a possibility of the problem that hard-coating property falls and also a scratch resistance falls. .

When the composition of this invention further abbreviates as "polyether frame | skeleton containing urethane (meth) acrylate (A)" (hereinafter as (meth) acrylate (A) or a component (A)) as a 3rd component. May be included).

(Meth) acrylate (A) has the shape control effect mentioned later, and can make the shape of the unevenness | corrugation formed in the surface of an anti-glare layer into a smooth shape. As a result, when the anti-glare layer formed from the composition of the present invention is applied to a liquid crystal display device or the like as an anti-glare film, not only the improvement of light reflecting, cloudiness, etc., but also excellent contrast performance, in particular, a clear sense of black, that is, a clean black with strong glossiness Can be seen. In addition, (meth) acrylate (A) may be oligomer or resin, and in this specification, an "oligomer" is a polymer which has a repeating unit, and says that the number of this repeating unit is 3-10.

The (meth) acrylate (A) that can be used in the present invention is not particularly limited as long as it is a polyether skeleton-containing urethane (meth) acrylate, but preferably,

(i) each end of the molecule has at least one (meth) acrylate group,

(ii) having a structure represented by the following formula (1):

[Wherein, X represents a moiety excluding the hydroxyl group of the sock end of the polyol compound having a polyether skeleton], and

(iii) the tolerance is 6.0 mL or less, and the solubility parameter (SP value (SP _A )) is 12 or less,

It is urethane (meth) acrylate on condition of.

When the composition of the present invention has a polyether structure with a urethane bond represented by the formula (1), not only excellent black feeling, but also excellent anti-fingerprint property, in particular, excellent fingerprint wiping property can be obtained. You lose. In addition, when the component (A) has at least one (meth) acrylate group in each of the sock ends, good scratch resistance can be obtained.

In addition, the urethane (meth) acrylate of component (A) may have a branched structure. In this case, the term "both ends" means both ends in the state where the molecular chain is the longest. And when it has such a branched structure, you may have at least 1 (meth) acrylate group also in the terminal of a molecular chain.

As a polyether skeleton containing urethane (meth) acrylate (A) which has the structure represented by said Formula (1), and each has at least 1 (meth) acrylate group, for example, the polyol compound which has a polyether skeleton ( The reactant of a), a polyisocyanate (b), and a hydroxyl group containing (meth) acrylate monomer (c) is mentioned.

Examples of the polyol compound (a) having a polyether skeleton include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, 1,6 Polyether polyols having one or more structures of hexanediol, bisphenol A polyethoxydiol, polycaprolactone, and polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide or random copolymerization; Polyether-modified polyhydric alcohols, such as trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerol and polytetramethylene glycol, Polyhydric alcohols including polyether skeletons; Polyester polyols which are condensates of the polyether polyols and polybasic acids such as maleic anhydride, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, adipic acid and isophthalic acid; Caprolactone-modified polyols obtained by caprolactone-modified polyether polyols; Etc. can be mentioned.

Examples of the polyisocyanate (b) include polyisocyanates such as aromatics, aliphatics, and alicyclic systems, among which tolylene diisocyanate and diphenylmethane diisocyanate. Nate, Hydrogenated Diphenylmethane Diisocyanate, Polyphenylmethane Polyisocyanate, Modified Diphenylmethane Diisocyanate, Hydrogenated Xylene Diisocyanate, Xylene Diisocyanate Anate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3 Bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine Polyisocyanates such as shin triisocyanate, naphthalene diisocyanate or trimer compounds of these polyisocyanates, biuret polyisocyanates, water dispersion polyisocyanates, or these And reaction products of polyisocyanates and polyols.

The hydroxyl group-containing (meth) acrylate monomer (c) may be a monofunctional monomer having one (meth) acrylate group or may be a polyfunctional monomer having two or more (meth) acrylate groups. As the monofunctional monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 2-hydroxyethyl acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone modified 2-hydroxyethyl (meth) acrylate, and the like. As the polyfunctional monomer, for example, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified Dipentaerythritol penta (meth) acrylate, an ethylene oxide modified pentaerythritol tri (meth) acrylate, etc. are mentioned.

Polyether frame | skeleton containing urethane (meth) acrylate (A) which has at least one (meth) acrylate group each at the both ends has the polyol compound (a), polyisocyanate (b), and hydride which have a polyether frame | skeleton. It can prepare by making a hydroxyl group containing (meth) acrylate monomer (c) react. In this preparation, for example, a polyol compound (a) having a polyether skeleton, a polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate monomer (c) may be reacted at once, or for example, poly After the polyol compound (a) having an ether skeleton is reacted with the polyisocyanate (b), the hydroxyl group-containing (meth) acrylate monomer (c) may be reacted.

Reaction of the polyol compound (a) and polyisocyanate (b) which have a polyether backbone is isocyanate of polyisocyanate (b) with respect to 1 equivalent of hydroxyl groups of a polyol compound (a). It is preferable to react 1.1-2.5 equivalents of groups, and it is especially preferable to react 1.3-2.0 equivalents. 70-100 degreeC is preferable and, as for reaction temperature, about 1 to 20 hours are preferable. In the reaction of the polyol compound (a) and polyisocyanate (b), a metal catalyst such as butyl tin dilaurate or an amine system such as 1,8-diazabicyclo [5.4.0] undecene-7 It is more preferable to promote the reaction using a catalyst or the like.

In the case of reacting a polyol compound (a) having a polyether skeleton, a polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate monomer (c) at once, a hydroxyl group-containing (meth) acrylate It is preferable to use 1.0-1.5 equivalent with respect to 1 equivalent of polyisocyanate (b), and, as for the quantity of monomer (c), it is more preferable to use 1.0-1.3 equivalent. As for reaction temperature, 60-100 degreeC is preferable, and it is preferable that reaction time is 1 to 20 hours.

Moreover, when making a hydroxyl group containing (meth) acrylate monomer (c) react, after making polyol compound (a) and polyisocyanate (b) which have a polyether skeleton react, a polyol compound (a ) And 0.95 to 1.5 equivalents of hydroxyl groups of the hydroxyl group-containing (meth) acrylate monomer (c) with respect to 1 equivalent of isocyanate groups of the reactants of the polyisocyanate (b), , 1.0 to 1.1 equivalents is particularly preferred. 60-100 degreeC is preferable and, as for reaction temperature, it is preferable that reaction time is 1 to 20 hours.

It is more preferable that the weight average molecular weights of the polyether skeleton containing urethane (meth) acrylate (A) which have each at least one (meth) acrylate group each at the socks end are 3000-50000. In addition, the average molecular weight here is a weight average molecular weight and can be computed from the measurement result of gel permeation chromatography (GPC) using polystyrene as a standard.

In the present invention, as the polyether skeleton-containing urethane (meth) acrylate (A), the tolerance is 6.0 mL or less, preferably 5.0 mL or less, more preferably 4.0 mL or less, and the solubility parameter (SP value) ( SP _A ) is 12 or less, Preferably it is 11.5 or less, More preferably, it is 11.0 or less. When the tolerance of the (meth) acrylate (A) is 6.0 mL or less and the solubility parameter is 12 or less, good fingerprint resistance is obtained. In addition, when the tolerance of the (meth) acrylate (A) is higher than 6.0 mL or the solubility parameter is higher than 12, the distinct blackness and fingerprints of black are significantly reduced, and phase separation of the first component and the second component is performed. It is unpreferable because anti-glare property may not be obtained in the resin layer obtained by inhibiting the stiffness.

The tolerance is to evaluate the degree of hydrophilicity, and the higher the value, the higher the hydrophilicity. In the method for measuring the tolerance, 0.5 g of the urethane-modified polyester resin is mixed with 10 ml of tetrahydrofuran in a 100 ml beaker under 23 ° C, and ion-exchanged water is gradually added to the mixture using a burette. The amount of ion-exchanged water required (ml) until turbidity occurs in the mixture is measured. The amount (ml) of this ion-exchange water is defined by the tolerance.

The solubility parameter (sometimes abbreviated as SP value) is a measure of solubility. The larger the value, the higher the polarity. The smaller the value, the lower the polarity. In addition, the SP value in the case where a component (A) is a mixture of 2 or more types makes SP the weighted average value of the solubility parameter of each component. SP value can be actually measured by the method demonstrated concretely below. (Reference: SUH, CLARKE, J. P. S. A-1, 5, 1671-1168 (1967)).

When the tolerance of the component (A) is 6.0 mL or less and the solubility parameter (SP value) (SPA) is 12 or less, the reason why a good anti-fingerprint is obtained is not limited to the theory but is considered as follows. Since component (A) has a urethane group, it has a locally polar partial structure in a molecule | numerator. On the other hand, component (A) is said to be a compound with low polarity as a whole molecule | numerator because a tolerance is 6.0 mL or less. Here, the lipid component constituting the fingerprint mark is made of long chain fatty acid, and the long chain fatty acid is composed of a low polarity portion by an alkyl group and a high carboxyl group. In order to improve the anti-fingerprint, it is thought that the affinity to the lipid component constituting the fingerprint mark may be increased. Therefore, as described above, a highly polarized site (urethane group) in the molecule and a low polarity as a whole molecule It is thought that favorable anti-fingerprint could be provided by using the component (A) which has a. The same applies to the solubility parameter. By solubility parameter being 12 or less, the component (A) which has a highly polar urethane group turns into a compound with low polarity as a whole molecule. And it is thought that affinity to the lipid component which comprises a fingerprint mark becomes high by this, and it becomes difficult to show the said lipid component which adhered, and fingerprint resistance is considered to improve. In particular, it is considered that the effect of becoming difficult to see when wiping the lipid component becomes remarkable, and it is considered that particularly excellent fingerprint wiping property can be obtained. On the other hand, any of those having a tolerance of 6.0 mL or less and a solubility parameter of 12 or less exhibits low polarity as a whole molecule. On the other hand, the present invention is not all that can be elucidated by the above theory, and has a locally polarized structure having a tolerance of 6.0 mL or less, a solubility parameter of 12 or less, and having a urethane group. By using the component (A) which has all the properties, the improvement of an anti-fingerprint is achieved. And the present inventor has found the said fact by experiment and came to complete this invention.

On the other hand, as a more preferable example of the component (A) in this invention, the polyether skeleton containing urethane (meth) acrylate represented by following formula is mentioned, for example.

[In formula, R <^1> is the residue remove | excluding the hydroxyl group of the sock end of the polyol compound (a) which has a polyether skeleton, and R <^2> removes the isocyanate group of the sock end of polyisocyanate (b). It is a residue and R <^3> and R <^4> may be same or different, and are residues except the hydroxyl group of the hydroxyl group containing (meth) acrylate monomer (c), and n is an integer of 1-60.]

As for this polyether skeleton containing urethane (meth) acrylate (A), it is more preferable that weight average molecular weights are 3000-50000. Moreover, it is more preferable that said n is an integer of 1-60, and it is more preferable that it is an integer of 1-30.

The compounding quantity of (meth) acrylate (A) does not have limitation in particular, For example, it is 0-20 weight% with respect to the total solid weight of 1st and 2nd component, More preferably, it is 2-20 weight%. If the blending amount exceeds 20% by weight, the smooth uneven shape cannot be maintained; (Meth) acrylate (A) becomes difficult to melt | dissolve, and it becomes difficult to become a homogeneous solution; Inhibits phase separation between the first component and the second component; There exists a possibility of the problem that the round of the formed film becomes large too much.

When the composition of this invention contains the above-mentioned (meth) acrylate (A) as a 3rd component, not only does not inhibit phase separation of a 1st component and a 2nd component, but also a 1st component and agent It is thought that the two components have a function of maintaining a random uneven shape formed by phase separation. That is, since the uneven shape is caused only by the difference between the physical properties of the first component and the second component, the shape may collapse until the curing reaction and the smooth uneven surface shape may collapse. On the other hand, by the hydrogen bonding of the urethane groups which the said (meth) acrylate (A) has, the effect which can reduce the possibility of the above-mentioned uneven | corrugated surface shape fall can be anticipated. Thereby, a more preferable smooth uneven surface shape can be formed. When such a smooth uneven shape is formed on the surface of the antiglare layer, scattering of light on the surface is suppressed, and when the antiglare layer is formed or provided on a liquid crystal display device or the like, the black display is displayed as a more beautiful gloss black. can do. In addition, since the (meth) acrylate (A) has a locally polar partial structure in the molecule and a low polar compound as the whole molecule, the (meth) acrylate (A) is the same as the lipid component constituting the fingerprint marks. Since it has a structure, affinity with a lipid component becomes high and it can improve not only the expression of a clear feeling of black by the surface shape control mentioned above, but also the fingerprint property, such as the wiping property of a fingerprint.

In the present invention, for the purpose of imparting excellent black feeling and anti-fingerprint to the antiglare film, the composition of the present invention further has, as a fourth component, a "cyclic structure and at least one reactive unsaturated 2 It may contain (meth) acrylate (B) "(hereinafter abbreviated as (meth) acrylate (B) or component (B) below) which has a refractive index of 1.52 or more including a middle bond.

As (meth) acrylate (B) which can be used by this invention, if there is a (meth) acrylate which has a cyclic structure and the refractive index which contains at least 1 reactive unsaturated double bond is 1.52 or more, there will be no limitation in particular.

As an "cyclic structure" which (meth) acrylate (B) has, an aromatic ring, a saturated hydrocarbon ring, a non-aromatic unsaturated hydrocarbon ring, etc. are mentioned, for example. As an "aromatic ring", a C6-C30 aromatic ring (for example, a benzene ring, a naphthalene ring group, etc.) etc. are mentioned, for example. As a "saturated hydrocarbon ring", a C3-C30 saturated hydrocarbon ring (for example, a cyclopentane ring, a cyclohexane ring, etc.) etc. are mentioned, for example. As a "non-aromatic unsaturated hydrocarbon ring", a C3-C30 non-aromatic unsaturated hydrocarbon ring (for example, cyclopentadiene ring, dicyclopentadiene ring, etc.) etc. are mentioned, for example.

The "reactive unsaturated double bond" contained in the (meth) acrylate (B) is a monomer having an unsaturated double bond group exhibiting polymerizability, for example, a polymerizable unsaturated double bond (eg, vinyl group, allyl group, ( Carbon-carbon double bonds contained in a meth) acryloyl group or the like), and generally does not mean an aromatic double bond or the like that is not polymerizable.

In addition, in this invention, "refractive index" can be determined according to a conventionally well-known measuring method, for example, the measuring method mentioned later. The refractive index of (meth) acrylate (B) becomes like this. Preferably it is 1.52 or more, More preferably, it is 1.55-1.60. When the refractive index of the (meth) acrylate (B) is 1.52 or more, scattering of light can be suppressed by the high refractive index without changing the surface irregularities of the formed antiglare layer, and a clear feeling of black can be enhanced. have. In addition, when the refractive index of the (meth) acrylate (B) is less than 1.52, not only the whiteness of the anti-glare layer may become remarkable depending on the viewing angle, but also the effect of suppressing the scattering of the light described above becomes small, and thus black. It is not desirable to increase the apparent feeling of. By mix | blending (meth) acrylate (B), it can be expected to maintain the random uneven | corrugated shape formed by phase-separation of a 1st component and a 2nd component. Since (meth) acrylate (B) has a cyclic structure in a molecule | numerator, it can be expected to become a material which has a high glass transition temperature. Since high glass transition temperature can be provided to the composition before hardening apply | coated on the transparent base material, it can expect to maintain the said uneven | corrugated shape.

Moreover, the film obtained by hardening | curing the composition containing (meth) acrylate (B) can be expected to have high refractive index. By this high refractive index, the effect of suppressing the occurrence of unexpected diffuse reflection or scattering of light on the uneven surface can be expected. For example, the light incident from the upper surface direction of the film having the uneven shape increases the amount of light guided into the film due to the high refractive index of the (meth) acrylate (B). As a result, the diffuse reflection and scattering are suppressed. You can expect to be.

As (meth) acrylate (B), the acrylate monomer which has an aromatic ring in the molecule | numerator of a structure represented by a following formula is especially preferable:

[Wherein n is 2 or more]

(Meth) acrylate (B) can be suitably synthesize | combined according to the method known to a person skilled in the art, and a commercial item can also be used.

The compounding quantity of (meth) acrylate (B) is not specifically limited, For example, it is 0-30 weight% with respect to the total solid weight of 1st component and 2nd component, Preferably it is 0-20 weight%. When the compounding quantity of (meth) acrylate (B) exceeds 30 weight%, there exists a possibility of the problem that (meth) acrylate (B) becomes difficult to melt | dissolve and becomes difficult to become a homogeneous solution.

As mentioned above, a black clear feeling can be provided by mix | blending (meth) acrylate (B) with a composition.

Moreover, it is preferable that the 1st component and 2nd component in this invention have functional groups which mutually react, respectively. By making these functional groups react with each other, the tolerance of the anti-glare layer obtained by the anti-glare coating composition of the present invention can be enhanced. As a combination of such functional groups, for example, functional groups (active group, amino group, thiol group, carboxyl group, etc.) having an active hydrogen, an epoxy group, a functional group having an active hydrogen, an isocyanate group, an ethylenically unsaturated group and an ethylenically unsaturated group (Polymerization of ethylenically unsaturated groups occurs), silanol groups and silanol groups (condensation polymerization of silanol groups occurs), silanol groups and epoxy groups, functional groups having active hydrogens and functional groups having active hydrogens, active methylene and acryloyl groups, An oxazoline group, a carboxyl group, etc. are mentioned. As the "functional groups reacting with each other" herein, the reaction does not proceed only by mixing only the first component and the second component, but reacts with each other by mixing a polymerization initiator, a curing agent, a catalyst, a photosensitizer, and the like together. Included. As a polymerization initiator which can be used here, a photoinitiator, a thermal polymerization initiator, a radical initiator, etc. are mentioned. For example, as a photoinitiator, 2-hydroxy-2 methyl-1- phenyl- propane- 1-one, 1-hydroxy cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl, for example. ] -2-morpholinopropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Nophenyl) -butanone-1, alpha-hydroxy- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl-1-phenyl]} propan-1-one, etc. are mentioned. have. Examples of the thermal polymerization initiator include azo-based polymerization initiators such as azobisisobutyronitrile and peroxide-based polymerization initiators such as benzoyl peroxide. As a catalyst, an acid, a base catalyst, a metal catalyst, etc. are mentioned, As a photosensitizer, benzophenone and its derivative (s), thioxanthone and its derivative (s), anthraquinone and its derivative (s), coumarin and its derivative (s), etc. are mentioned. As a hardening | curing agent, a melamine hardening | curing agent, a (block) isocyanate hardening | curing agent, an epoxy hardening | curing agent, etc. are mentioned, for example.

When each of the first component and the second component has a functional group reacting with each other, the mixture of the first component and the second component has a curability of thermosetting and photocurable (ultraviolet curing, visible curing, infrared curing, etc.). do. Since thermosetting can affect the thermoplastic resin etc. which can become a base material, it is preferable to perform hardening reaction which does not use heat, especially photocuring reaction.

Moreover, the molecular weight (weight average molecular weight (Mw) when 1st component and 2nd component are resin) of a 1st component and a 2nd component becomes like this. Preferably it is 1000-100000, More preferably, it is 5000-100000. In this invention, molecular weight and a weight average molecular weight can be determined as a conversion value by a polystyrene standard using GPC measurement.

As physical properties of the first component and the second component, which cause phase separation of the first component and the second component, for example, SP value, glass transition temperature (Tg), surface tension, weight average molecular weight, number average molecular weight, etc. may be mentioned. In particular, in the present invention, the difference in SP value is particularly important as the difference between the physical properties of the first component and the second component.

SP value is an abbreviation of Solubility Parameter and it becomes a measure of solubility. The larger the value, the higher the polarity. On the contrary, the smaller the value, the lower the polarity.

For example, SP value can be measured by the following method (refer to SUH, CLARKE, J. P. S. A-1, 5, 1671-1168 (1967)).

Measuring temperature: 20 ℃

Sample: 0.5 g of resin is weighed into a 100 ml beaker, 10 ml of a good solvent is added using a hole pipette, and dissolved by a magnetic stirrer.

menstruum:

Good solvent… Dioxane, acetone, etc.

Empty solvent… n-hexane, ion-exchanged water, etc.

Turbidity measurement: The poor solvent is dripped using a 50 ml burette, and the cloudy point is taken as a drop amount.

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

Vi: molecular volume of solvent (ml / mol)

φi: volume fraction of each solvent in the turbidity point

δi: SP value of the solvent

ml: Low SP poor solvent mixture system

mh: High SP poor solvent mixture

When the difference in the physical properties of each of the first component and the second component that causes phase separation between the first component and the second component is a difference between the SP values, the SP value SP ₁ of the first component is equal to the SP value of the second component ( It is preferable that it is lower than SP ₂ ) and satisfies SP ₁ <SP ₂ . Of the first component of the SP value (SP ₁₎ and a second component of the SP value (SP ₂₎ SP value is preferred, and greater than the difference, and 0.8 of the difference upper limit is not particularly limited, in general, is 15 or less. The difference between the SP value SP ₁ of the first component and the SP value SP ₂ of the second component is more preferably 0.8 to 3.6. In addition, as above-mentioned, when a 1st component and a 2nd component are a mixture, respectively, the SP value of a 1st component and a 2nd component is represented by the weighted average value of the individual SP value of each component, respectively. When the difference between the SP value SP ₁ of the first component and the SP value SP ₂ of the second component is 0.8 or more, the compatibility of the resins with each other is low, whereby the first component and the agent are applied after application of the coating composition. It is thought that the phase separation of two components is brought about. If the difference between the SP value SP ₁ of the first component and the SP value SP ₂ of the second component is less than 0.8, formation of irregularities due to phase separation becomes difficult, and thus the anti-glare property tends to be lowered. Further, when the difference between the SP value SP ₁ of the first component and the SP value SP ₂ of the second component exceeds 3.6, the compatibility between the unsaturated double bond-containing acrylic copolymer of the first component and the second component This becomes extremely bad, and there is a possibility that the first component and the second component can be separated, and there is a possibility that the uniformity as the coating composition may be lost, which is not preferable.

The anti-glare coating composition of the present invention may further contain an organic solvent. Then, the room, the first component, first with respect to the second component and the organic solvent, SP value of the first component (SP _1), SP value of the second component (SP ₂₎ and the SP value of the organic solvent contained in overt coating composition (SP _sol ) under the following conditions;

SP ₁ <SP ₂ , and

The difference between SP ₁ and SP _sol is 1.7 or less, preferably 1.5 or less;

It is more preferable to be in a relationship that satisfies. When the difference between SP ₁ and SP _sol is 1.7 or less, an anti-glare film having low haze and excellent anti-glare performance can be prepared. On the other hand, when the difference between SP ₁ and SP _sol exceeds 1.7, it becomes difficult to sufficiently dissolve the unsaturated double bond-containing acrylic copolymer of the first component, the shape of the unevenness becomes rough, and the anti-glare property may be lowered. In addition, there is a possibility that the uniformity of the antiglare layer to be formed is lowered. It is more preferable that the difference between SP ₁ and SP _sol is 1 or less, that is, in the range of 0-1.

On the other hand, SP ₁ and SP _sol is good if their difference is 1.7 or less. In addition, SP ₁ <SP _sol may be sufficient, and SP ₁ > SP _sol may be sufficient.

As a preferable organic solvent, when a 1st component and a 2nd component are the said combination, For example, Ketone solvents, such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; Ether solvents such as anisole, phentolpropylene propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like. These solvent may be used individually by 1 type, and may mix and use 2 or more types of organic solvent. In addition, the, at least one kind of organic solvent used, the is satisfies the condition of "SP ₁ and the difference between the SP _sol is not more than 1.7", the above-mentioned conditions all the organic solvent used in the case of using the organic solvents of two or more There is no need to satisfy.

The coating composition of the present invention may contain monomers, oligomers, resins or mixtures thereof which are usually used in addition to the first component and the second component. The coating composition of this invention is characterized by being able to form the anti-glare layer which has unevenness | corrugation, even if it does not contain an inorganic particle, resin particle, etc. by using the above-mentioned 1st component and 2nd component. Therefore, it is preferable that the composition of this invention does not contain an inorganic particle and / or resin particle.

The coating composition of this invention is prepared by mixing a 1st component and a 2nd component with the solvent, a catalyst, and a hardening | curing agent as needed. As for the ratio of a 1st component and a 2nd component in a coating composition, 0.1: 99.9-10: 90 are preferable, and 0.5: 99.5-5: 95 are more preferable. When using a catalyst, 0.01-20 mass parts, Preferably it is with respect to 100 mass parts of a 1st component, a 2nd component, and another monomer, oligomer, resin, or mixture thereof (together called "resin component") as needed. Can add 1-10 mass parts. When using a hardening | curing agent, 0.1-50 mass parts with respect to 100 mass parts of said resin components, Preferably 1-30 mass parts can be added. When using a solvent, 1-9900 mass parts, Preferably 100-900 mass parts can be added with respect to 100 mass parts of said resin components.

The solvent in the coating composition used by this invention is not specifically limited, It selects timely in consideration of the 1st component and the 2nd component, the material of the part used as a base of coating, the coating method of a composition, etc. As a specific example of the solvent used, For example, 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, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, Ether solvents such as phentol; Ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; Amide solvents such as dimethylformamide, diethylformamide and N-methylpyrrolidone; Cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Alcohol solvents such as methanol, ethanol, propanol and isopropanol; And halogen-based solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more thereof. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

The anti-glare coating composition of this invention can add various additives as needed. As such an additive, commercial additives, such as an antistatic agent, a plasticizer, surfactant, antioxidant, and a ultraviolet absorber, are mentioned.

As described above, the composition of the present invention, in addition to the first component and the second component, further comprises (meth) acrylate (A) and / or (meth) acrylate (B). When the anti-glare layer formed from the composition of the present invention is applied to the anti-glare film described in detail below, the anti-glare film can exhibit excellent contrast performance, in particular, a clear black with a strong sense of black, ie, a glossiness, and furthermore, prevention It can also provide moonshine.

The reason why excellent contrast performance, in particular, a clear sense of black is obtained, is not limited by theory, but is considered as follows. By the composition containing the above-mentioned (meth) acrylate (A) as a 3rd component, in the unevenness | corrugation which arises by phase separation of a 1st component and a 2nd component, by the effect of the hydrogen bond of urethane groups, The effect of preventing the uneven shape from collapsing until the curing reaction can be expected. Thereby, the uneven | corrugated shape produced | generated by the difference of SP value of a 1st component and a 2nd component can maintain a smooth uneven | corrugated surface shape, without damaging an original shape. When such a smooth uneven shape is formed on the surface of the antiglare layer, scattering of light on the surface is suppressed as compared with the case where the conventional (meth) acrylate (A) is not included, and the antiglare layer is applied to the liquid crystal display device. If it is formed or provided on the back, the black display can be displayed as a clean black with strong glossiness.

Moreover, when a composition contains (meth) acrylate (B) which the above-mentioned refractive index contains 1.52 or more as a 4th component, the scattering of light is suppressed by the high refractive index, without changing a surface asperity shape. I can do it and can raise a clear feeling of black.

Moreover, when the composition of this invention contains both (meth) acrylate (A) and (B), the anti-glare layer and anti-glare film which have a strong black distinctive feeling by the synergistic effect of both are made. Can be formed.

Moreover, according to this invention, as a film containing the anti-glare layer formed of the composition containing (meth) acrylate (A), the outstanding anti-fingerprint is obtained as mentioned above. The reason for this is not bound by theory, but is considered as follows. In general, the lipid component constituting the fingerprint mark is mainly composed of a high polarity portion and a low polarity portion. Therefore, as a compound having a structure similar to such a lipid component, (meth) acrylate (A) [this component (A) has a locally polar partial structure in the molecule and has a low polarity as a whole molecule. Compound] into the composition, which increases the affinity to the lipid component and significantly improves the fingerprint properties such as fingerprint wiping and the like, as well as the appearance of a distinct black feeling by the above-described surface shape control. Therefore, the composition of this invention contains (meth) acrylate (A), and the anti-glare layer and anti-glare which have further improved anti-fingerprint compared with the prior art which does not contain (meth) acrylate (A) are included. A manifest film can be provided.

Moreover, since the resin layer formed from the composition of this invention has fine unevenness | corrugation on the surface as mentioned above, when it is set as a laminated body, not only anti-blocking property but also anti-newtoning property can be exhibited.

Antiglare film

The anti-glare film of this invention has a transparent base material and an anti-glare layer. This anti-glare layer is formed from said anti-glare coating composition.

As a transparent base material, various transparent plastic films, a transparent plastic plate, glass, etc. can be used. As a transparent plastic film, For example, a triacetyl cellulose (TAC) film, a polyethylene terephthalate (PET) film, a diacetylene cellulose film, an acetate butylate cellulose film, a polyether sulfone film, a polyacrylic resin film, a polyurethane resin film, polyester A film, a polycarbonate film, a polysulfone film, a polyether film, a polymethyl pentene film, a polyether ketone film, a (meth) acrylonitrile film, etc. can be used. As the transparent substrate, it is preferable to use triacetyl cellulose. The refractive index of triacetyl cellulose is about 1.48. Since triacetyl cellulose is widely used as a protective film which protects the polarizing layer of a polarizing plate, the anti-glare film obtained by using it as a transparent base material can be used as a protective film as it is. In addition, although the thickness of a transparent base material can be selected timely according to a use, it is generally used in about 25-1000 micrometers.

An anti-glare layer is formed by apply | coating the said anti-glare coating composition on a transparent base material. The coating method of the coating composition can be selected in a timely manner according to the conditions of the coating composition and the coating process, for example, bar coating method, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure It can apply | coat by a coating method, the extrusion coating method (the US patent 2681294 specification), etc.

The thickness of the antiglare layer is not particularly limited and can be set in time in consideration of various factors. For example, the coating composition may be applied such 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 may be subjected to phase separation before curing. When drying before hardening a coating film, it can dry for 0.1 to 60 minutes, More preferably, for 1 to 30 minutes at 30-200 degreeC, More preferably, 40-150 degreeC, The solvent can be removed and phase-separation can be carried out beforehand. . In the case where the mixture of the first component and the second component is photocurable, drying before phase hardening and preliminarily separating the solvent has an advantage that the solvent in the antiglare layer can be effectively removed and unevenness of a desired size can be provided.

As another method of phase-separating before hardening, you may use the method of phase-separating by irradiating light to a coating film. As the light to be irradiated, for example, light having an exposure amount of 0.1 to 1.5 J / cm ² , preferably light having 0.5 to 1.5 J / cm ² can be used. Although the wavelength of this irradiation light is not specifically limited, For example, irradiation light etc. which have a wavelength of 360 nm or less can be used. For example, when 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one or the like is used as the photoinitiator, the irradiation light is preferably irradiated with light having a wavelength around 310 nm. And it is more preferable to irradiate light which has a wavelength of 360 nm vicinity further. Such light can be obtained using a high pressure mercury lamp, an ultra high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and hardening occur. By irradiating light and phase-separating, there exists an advantage that the nonuniformity of the surface shape resulting from the dry nonuniformity of the solvent contained in a coating composition can be avoided.

An anti-glare layer is formed by hardening the coating film obtained by application | coating of a coating composition, or the dried coating film. When the mixture of a 1st component and a 2nd component is thermosetting, it can harden by heating at 40-280 degreeC, More preferably, 80-250 degreeC for 0.1 to 180 minutes, More preferably, 1 to 60 minutes. When the mixture of a 1st component and a 2nd component is photocurable, it can harden | cure by irradiating light using the light source which emits light of a wavelength as needed. In addition, light irradiation can also be used for the purpose of phase-separating as mentioned above.

The cross-sectional schematic of the anti-glare film formed in this way is shown in FIG. The antiglare film 1 has an antiglare layer 3 and a transparent base material 5. Since the unevenness | corrugation of the surface of the anti-glare film of this invention naturally determines an uneven | corrugated arrangement, an irregular uneven | corrugated shape can be formed in the surface of a resin layer.

As for the anti-glare film of this invention, arrangement | positioning of the uneven | corrugated shape in which the surface of an anti-glare layer is irregular is naturally determined. And it is preferable that the anti-glare film of this invention does not have the maximum of the scattered light intensity with respect to a scattering angle. When light is irradiated in the normal direction with respect to the surface of an anti-glare film, ie, at right angles with respect to the film surface, the transmitted light has a maximum direction in which the irradiation light proceeds as it is, that is, a direction where the scattering angle is 0 °. And since irradiation light scatters by an anti-glare film, light will permeate | transmit also in the direction which shifted the angle from this normal line direction. This scattered light is scattered light (transmission scattered light). It is preferable that the anti-glare film of this invention does not have the maximum of the scattered light intensity with respect to this scattering angle. In the case where the scattered light has a maximum value, scattered light may be collected at a specific angle, whereby interference of light may occur. The generation of interference of light is not preferable because there is a possibility that the sharpness of the image passing through the antiglare film may be reduced.

It is preferable that the total light transmittance is 90% or more, and, as for the anti-glare film of this invention, it is more preferable that it is 95% or more. Especially in this invention, since it does not contain resin particle, it becomes possible to achieve high total light transmittance as mentioned above. The total light transmittance (T _t (%)) measures the incident light intensity (T ₀ ) with respect to the antiglare film and the combat light intensity (T ₁ ) transmitted through the antiglare film, and is calculated by the following equation. 2 is a schematic explanatory diagram of the total light transmittance.

The measurement of total light transmittance can be measured, for example using a haze meter (made by Nihon Denshoku Industries Co., Ltd.).

It is preferable that haze is less than 20%, as for the anti-glare film of this invention, it is more preferable that it is 18% or less, It is more preferable that it is 15% or less, It is especially preferable that it is 10% or less. ADVANTAGE OF THE INVENTION According to this invention, the anti-glare film which has the outstanding performance that haze is low and is excellent in anti-glare property as mentioned above can be prepared. As an advantage of having a low haze, when the antiglare film is provided in a liquid crystal display device, one that does not impair the clarity of the image to be displayed, and that cloudiness is unlikely to occur. The anti-glare film having such a low haze has an advantage of not particularly impairing the sharpness of the image displayed on the high-definition liquid crystal display device.

The haze can be calculated by the following formula in accordance with JIS K 7105.

H: haze (% litter)

T _d : diffusion transmittance (%)

T _t : Total light transmittance (%)

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

The antiglare film of the present invention may further have a low refractive index layer. The low refractive index layer is made of a low refractive index resin. When the low refractive index layer is laminated on at least one surface of the antiglare layer so as to reflect the light from the outside (external light source) on the surface of the antiglare film, for example, when the low refractive index layer is provided to the outermost surface in the optical member or the like. It can prevent effectively. Moreover, the haze of an anti-glare film can be further lowered by arrange | positioning so that a low refractive index layer may become an outermost surface. By arranging the low refractive index layer to be the outermost surface, that is, forming an antiglare layer on the transparent substrate and further forming a low refractive index layer on the antiglare layer, the haze of the obtained antiglare film can be further lowered.

The refractive index of the low refractive index resin is, for example, 1.35 to 1.39, preferably 1.36 to 1.39, and more preferably about 1.38 to 1.39.

The thickness of the low refractive index layer is, for example, 0.05 to 2 µm, preferably 0.1 to 1 µm (for example, 0.1 to 0.5 µm), and more preferably about 0.1 to 0.3 µm.

As low refractive index resin, fluororesins, such as a methylpentene resin, diethylene glycol bis (allylcarbonate) resin, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), etc. are mentioned, for example. In addition, it is preferable that a low refractive index layer contains a fluorine-containing compound normally. By using a fluorine-containing compound, the refractive index of the low refractive index layer can be reduced as desired.

The fluorine-containing compound has a functional group (such as a crosslinkable group or a curable group such as a crosslinkable group or a polymerizable group) that reacts with a fluorine atom by heat or an active energy ray (such as an ultraviolet ray or an electron beam), and is cured or crosslinked by heat or an active energy ray. And fluorine-containing resin precursors capable of forming fluorine-containing resins (particularly cured or crosslinked resins). As such a fluorine-containing resin precursor, for example, a fluorine atom-containing thermosetting compound or resin (with a fluorine atom, a reactive group (epoxy group, isocyanate group, carboxyl group, hydroxyl group, etc.), polymerizable group (vinyl group, allyl group) , Low molecular weight compounds having a (meth) acryloyl group, etc.), fluorine atom-containing photocurable compounds or resins curable by active light (such as ultraviolet rays) or resins (such as ultraviolet curable compounds such as photocurable fluorine-containing monomers or oligomers) Etc. can be mentioned.

As the fluorine atom-containing thermosetting compound or resin, for example, a low molecular weight resin obtained by using at least a fluorine-containing monomer, for example, an epoxy obtained by using a fluorine-containing polyol (particularly a diol) in place of part or all of the polyol component as a constituent monomer. Fluorine-containing resins; Similarly, unsaturated polyester-based fluorine-containing resins obtained using fluorine atom-containing polyols and / or fluorine atom-containing polycarboxylic acid components in place of some or all of the polyol and / or polycarboxylic acid components; Instead of some or all of the polyol and / or polyisocyanate component, a urethane-based fluorine-containing resin or the like obtained by using a fluorine atom-containing polyol and / or polyisocyanate component can be exemplified. These thermosetting compounds or resins can be used individually or in combination of 2 or more types.

The fluorine atom-containing photocurable compound includes, for example, a monomer and an oligomer (or a resin, particularly a low molecular weight resin), and as the monomer, for example, fluorine corresponding to the monofunctional monomer and the polyfunctional monomer exemplified in the above-mentioned antiglare layer. Monofunctional monomers such as vinyl monomers such as fluorine atom-containing (meth) acrylic monomers such as fluorinated alkyl esters of (meth) acrylic acid and fluoroolefins; And di (meth) acrylates of fluorinated alkylene glycols such as 1-fluoro-1,2-di (meth) acryloyloxyethylene and the like]. In addition, as an oligomer or resin, the fluorine atom containing oligomer or resin corresponding to the oligomer or resin which were illustrated by the term of the said glare-proof layer can be used. These photocurable compounds can be used individually or in combination of 2 or more types.

The curable precursor of a fluorine-containing resin can be obtained, for example in the form of a solution (coating liquid), and such a coating liquid is, for example, "TT1006A" and "JN7215" manufactured by Nippon Synthetic Rubber Co., Ltd. Note) It can obtain as "defencer TR-330" etc. made.

The anti-glare film of this invention can also be comprised from an anti-glare layer and a low refractive index layer using a low refractive index layer as a transparent base material. The anti-glare film of the present invention may also be composed of a transparent base material, an anti-glare layer and a low refractive index layer sequentially formed on the transparent base material.

Polarizer

The anti-glare antireflection film of this invention can be used for the polarizing plate of a liquid crystal display device (liquid crystal display). The cross-sectional schematic of the polarizing plate using the anti-glare film of this invention is shown in FIG. The polarizing plate 10 illustrated in FIG. 3 is a structure in which the anti-glare film 1 is provided on one surface (upper surface side in FIG. 3) of the polarizing layer (polarizing element) 12.

The polarizing layer 12 is laminated between two transparent substrates 5 and 14. TAC films can be used as the transparent substrates 5 and 14. This polarizing layer 12 has a three-layer structure, a film in which iodine is applied to polyvinyl alcohol (PVA) in the first layer and the third layer, and a second layer in the middle are made of PVA film. This anti-glare film 1 is the structure which laminated | stacked the anti-glare layer 3 on the transparent base material 5.

When using a TAC film as a transparent base material provided in the both sides of the said polarizing layer 12, since there is no birefringence and polarization is not scattered, even if it laminates with PVA and PVA + iodine film which become a polarizing element, polarization will be scattered. It is not broken. Therefore, a liquid crystal display device excellent in display quality can be obtained using such a polarizing plate 10.

As a polarizing element which comprises the polarizing layer 12 in the above-mentioned polarizing plate 10, it is a polyvinyl formal film, a polyvinyl acetal film, ethylene-acetic acid to the PVA film which is dyed with iodine or dye, and is extended | stretched. Vinyl copolymer-based saponification films.

In addition, in laminating | stacking each film which comprises the polarizing layer 12, saponification process may be given to the said transparent base material in order to increase adhesiveness and to prevent electrostatic discharge.

Liquid crystal display

The anti-glare antireflection film of this invention can be used for a liquid crystal display device (liquid crystal display). 4 is a schematic cross-sectional view of a transmissive display device using the anti-glare film of the present invention.

The liquid crystal display device 20 shown in FIG. 4 laminates the polarizing plate 22 similar to the said polarizing plate 10, the liquid crystal panel 24, and the polarizing plate 26 in this order, and polarizing plate 26 It is a transparent liquid crystal display device in which the backlight 28 is disposed on the rear surface on the () side.

Examples of the liquid crystal mode used in the liquid crystal panel 24 in the liquid crystal display device 20 include a twist nematic type (TN), a super twisted nematic type (STN), a phase transition type (PC), and a polymer dispersion type (PDLC). ) May be used.

As the driving mode of the liquid crystal, either a simple matrix type or an active matrix type may be used. In the case of the active matrix type, a driving method such as TFT (Thin Film Transistor), MIM (Metal In Metal Liquid Crystal) or the like is adopted. The liquid crystal panel 24 may be either a color type or a black and white photograph type.

In addition to the liquid crystal display device, the anti-glare antireflection film of the present invention can be used for an image display device such as a plasma display panel (PDP), an electroluminescent display (ELD), or a cathode ray tube display device (CRT). When using the anti-glare film of this invention for a liquid crystal display device, it can arrange | position on the outermost surface of a display, such as providing an adhesion layer on the transparent base material surface in which the anti-glare layer is not provided. On the antiglare layer of the antiglare film according to the present invention, an antireflection treatment may be further performed.

The resin layer formed of the composition of the present invention can also be used for the internal structure of a liquid crystal display device, for example. The resin layer formed by this invention has the advantage that it has favorable surface hardness and there is no defect, such as peeling of a resin particle. Therefore, it can utilize favorably also in the internal structure of a precision instrument, especially a liquid crystal display device. As an example of using the resin layer formed from the composition of this invention in the internal structure of a liquid crystal display device, the Newton ring prevention layer etc. which prevent adhesion of a light transmissive member, etc. are mentioned, for example.

In addition, the resin layer formed of the composition of the present invention can be suitably used for articles other than display devices in view of excellent transparency and anti-glare properties. By providing the resin layer formed from the composition of this invention on transparent members, such as a display, for example, the reflection of external light can be prevented without compromising transparency. The resin layer formed from the composition of this invention can provide the matt appearance by an anti-glare effect, for example, by providing it as a protective layer, such as household electrical appliances.

Example

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto. In addition, "part" shows a mass part, unless it notices previously.

Production Example 1: Preparation of unsaturated double bond-containing acrylic copolymer (first component)

190 mass parts of propylene glycol monomethyl ethers were thrown into the reaction container provided with the stirring apparatus, the nitrogen inlet tube, the heating and temperature control apparatus, the dropping port, and the cooling tube, and the internal temperature was heated to 100 degreeC, stirring in nitrogen atmosphere. Next, the polymerizable monomer mixed solution which consists of 187 mass parts of isobornyl methacrylates, 3 mass parts of methyl methacrylates, 10 mass parts of methacrylic acid, and 200 mass parts of propylene glycol monomethyl ethers, and t-butylperoxy-2 -The polymerization initiator solution which consists of 2 mass parts of ethylhexanoate and 80 mass parts of propylene glycol monomethyl ethers was dripped at the same speed over two hours simultaneously from two dripping funnels using two dripping funnels. The reaction temperature was maintained at 100 ° C. while stirring. Next, reaction was further performed at 100 degreeC for 1 hour. Subsequently, a liquid solution was prepared by heating a 100-shot polymerization initiator solution containing 0.2 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and 27 parts by mass of propylene glycol monomethyl ether over 1 hour. The mixture was kept at 占 폚 and added dropwise to carry out a polymerization reaction. Subsequently, a mixed solution of 1.5 parts by mass of tetrabutylammonium bromide, 0.2 parts by mass of hydroquinone and 5 parts by mass of propylene glycol monomethyl ether was added to the solution, changed from nitrogen atmosphere to air bubbling, and glycidyl methacrylate 17. The solution which consists of a mass part and 5 mass parts of propylene glycol monomethyl ethers was dripped over 1 hour, Then, addition reaction was performed over 5 hours, and the unsaturated double bond containing acrylic copolymer was produced. The weight average molecular weight of the obtained unsaturated double bond containing acrylic copolymer was 17000 by GPC (gel permeation chromatography: polystyrene conversion) measurement. In addition, the SP value of the unsaturated double bond-containing acrylic copolymer was 10.0, the tolerance value was 3.3 mL, the refractive index was 1.486, and the nonvolatile content (NV) was 30%.

Preparation Example 2 Preparation of Polyether Skeleton-Containing Urethaneacrylate (Third Component)

666 parts by weight of isophorone diisocyanate (IPDI), 2000 parts by weight of polypropylene glycol (polypropylene glycol 1000, manufactured by Kishida Chemical Co., Ltd.), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Mixed weight ratio 60:40) 900 parts by weight were added to the reaction vessel, and 1000 ppm of dibutyltin dilaurate as a catalyst, 1000 ppm of hydroquinone as a polymerization inhibitor, and methyl isobutyl ketone (MIBK, 40 as solids) were used. Used in an amount of%), and mixed at 80 ° C for 3 hours while blowing air.

In this way, the polyether skeleton containing urethane acrylate which has an acrylate group at the sock end was obtained. The SP value, the tolerance value, and the refractive index of the obtained polyether skeleton containing urethane acrylate were measured, and the SP value was 10.8, the tolerance value was 3.5 mL, and the refractive index was 1.483. In addition, the weight average molecular weight was 7000. In addition, the weight average molecular weight was shown by the polystyrene conversion value by GPC measurement.

Example 1 Preparation of Antiglare Film

In a container equipped with a stirring device, 4.0 parts by mass of the unsaturated double bond-containing acrylic copolymer (SP value: 10.0) of Production Example 1 as the first component, and 50.0 parts by mass of methyl isobutyl ketone (SP value: 8.3) as the organic solvent 75.0 parts by mass of a mixture of dipentaerythritol hexaacrylate and pentaacrylate (SP value: 12.1) and a mixture of pentaerythritol triacrylate and tetraacrylate (SP value) as a second component : 12.7) 2.0 parts by mass of the polyether skeleton-containing urethane acrylate of the Preparation Example 2 (water tolerance: 3.5 mL, SP value: 10.8) as 25.0 parts by mass and the third component, and isopropyl alcohol (SP value) : 11.5) 118.0 parts by mass, 5.0 parts by mass of 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator, and α-hydroxy- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl-1 -Phenyl)]} propan-1-one by adding 1.0 parts by mass A wise coating composition (nonvolatile content: 42.6%) was obtained.

A non volatile matter means the non volatile matter% at the time of heating at 105 degreeC for 3 hours measured according to "JIS K 5601 1 2". In addition, the refractive index was measured at 20 degreeC using the monobromonaphthalene in the state as it is about a liquid substance, and the film state about a solid substance with an Abbe refractometer (made by Atago Co., 2T type), respectively.

At room temperature (20 ° C.), using a bar coater No. 9, the anti-glare coating composition was coated on a triacetyl cellulose film so that the dry film thickness was 6 μm, and heated at 80 ° C. for 1 minute to dry the solvent in the coating film. Removed. Thereafter, an ultra-high pressure mercury lamp (manufactured by Fusion, H-valve type) was irradiated and cured in an air environment at an energy of 500 mJ / cm ² to form an anti-glare layer having fine and dense irregularities to obtain an anti-glare film.

In the same manner as in Example 1, the compositions of Examples 2 to 7 and Comparative Examples 1 to 4 were prepared according to the formulation (solid content mass basis) shown in the following table.

Each component used by the Example and the comparative example is as follows.

2nd component

Mixture of dipentaerythritol hexaacrylate and pentaacrylate (made by Doa Synthetic Co., Ltd., brand name: Aronix M402): SP value = 12.1, tolerance value = 7.4 mL, refractive index = 1.491

Mixture of pentaerythritol triacrylate and tetraacrylate (made by Toa Synthetic Co., Ltd., brand name: Aronix M305): SP value = 12.7, Tolerance value = 7.7 mL, Refractive index = 1.481

Third ingredient (comparison)

Polyether skeleton-free urethane acrylate (made by Shin-Nakamura Chemical Co., Ltd., brand name: U-324A): SP value = 12.0, tolerance value = 7.3 mL, refractive index = 1.498 (calculated value)

Polyether skeleton-free urethane acrylate (made by Nippon Kayaku Co., Ltd., brand name: DPHA-40H): SP value = 11.9, tolerance value = 6.3 mL, refractive index = 1.485

Polyether frame | skeleton free urethane acrylate (made by Negami Corporation, brand name: UN-904): SP value = 12.7, tolerance value = 7.5 mL, refractive index = 1.472

4th ingredient

Bisphenol A EO modified diacrylate (Doa Synthetic agent, brand name: M-211B): SP value = 11.3, tolerance value = 3.8 mL, refractive index = 1.538

Phenolic novolac-type epoxy acrylate (made by Hitachi Kasei Kogyo Co., Ltd., brand name: Hitaroid 7660-0): SP value = 12.7, tolerance value = 7.5 mL, refractive index = 1.567

Bisaryl fluorene acrylate (made by Osaka Gas Chemical, brand name: Ogsol EA-0200): SP value = 9.8, tolerance value = 3.2 mL, refractive index = 1.617

Organic solvent

Isopropyl alcohol (made by Shoei Chemical Co., Ltd.): SP value = 11.5

Methyl isobutyl ketone (made by Shoei Chemical Co., Ltd.): SP value = 8.3

In the antiglare films produced in Examples and Comparative Examples, black distinctive perception (visual), anti-fingerprint (fingerprint wiping), anti-glare, haze (H (%)), and total light transmittance (Tt (%)) were respectively measured. It evaluates or measures and shows a result in the following table | surfaces.

Evaluation of distinct black color (visual)

The clear feeling of black was evaluated by visual observation according to the following evaluation criteria.

◎: no turbidity

○: very little turbidity

△: slightly cloudy

×: Turbidity is clearly confirmed

Evaluation of fingerprint (fingerprint wiping)

Fingerprints were affixed to the obtained anti-glare film, and then wiped off 10 times using a clean wiper, and the subsequent fingerprint adhesion state was visually confirmed.

 (Double-circle): Oil of a fingerprint is not seen at all.

 (Circle): The oil of a fingerprint is seen a little.

 (Triangle | delta): The oil of a fingerprint is seen a little.

 X: The oil of a fingerprint looks like a tendon form.

Antiglare Evaluation

The obtained anti-glare film was placed under a fluorescent lamp, and the degree of reflection of the fluorescent lamp was visually confirmed. Evaluation criteria are as follows.

(Circle): The outline of the fluorescent lamp which shined in was remarkably skewed.

(Triangle | delta): The outline of the fluorescent lamp which shined in is slightly skewed.

X: The outline of the fluorescent lamp which shined in is clearly understood

Measurement of haze (H (%)) and total light transmittance (Tt (%))

Using a haze meter (manufactured by Nihon Denshoku Industries Co., Ltd.), the diffusive transmittance (T _d (%)) of the antiglare film and the following total light transmittance (T _t (%)) were measured, and haze (H (% ))

H: haze (% litter)

T _d : Diffuse light transmittance (%)

T _t : Total light transmittance (%)

The total light transmittance (Tt (%)) is determined by using a haze meter (manufactured by Nihon Denshoku Industries Co., Ltd.) to determine incident light intensity (T ₀ ) and anti-glare film (T ₁ ) transmitted through the anti-glare film. It measured and computed the total light transmittance (Tt (%)) by following Formula.

The composition of the comparative example 1 is a composition containing a 1st component and a 2nd component, As a result, in the coating film formed from the composition of the comparative example 1, it is fine due to the difference of the physical property of a 1st component and a 2nd component. Dense random unevenness | corrugation could be formed and favorable anti-glare property was obtained. Moreover, the coating film formed from the composition of Comparative Example 1 had excellent haze (5%) and total light transmittance (91%). However, since the composition of Comparative Example 1 did not contain any of the third component and the fourth component, the distinct black feeling and the fingerprint resistance were not excellent together.

In contrast, the compositions of Examples 1 to 3 of the present invention, like Comparative Example 1, contain the first component and the second component, and further, as the third component, the polyether skeleton-containing urethane acrylate of Preparation Example 2 ( It is a composition containing a tolerance value: 3.5 mL, SP value: 10.8), As a result, in the coating film formed from the composition of Examples 1-3, compared with the comparative example 1, both black distinct feeling and an anti-fingerprint are carried out. This has improved significantly. In addition, in the composition of Examples 1-3, although the 3rd component was mix | blended, the outstanding anti-glare property was obtained, without inhibiting formation of fine and dense unevenness | corrugation. In addition, in the composition of Examples 1-3, although haze was mix | blended with the 3rd component, haze fell surprisingly and it was able to maintain the outstanding total light transmittance.

The composition of Examples 4-6 is a composition containing the 1st component and 2nd component similarly to the comparative example 1, and containing the acrylate whose refractive index is 1.52 or more as a 4th component, As a result, Example 4 In the coating film formed from the composition of the said-6, compared with the comparative example 1, the distinct black feeling improved remarkably. Moreover, in the composition of Examples 4-6, although the 4th component was mix | blended, the outstanding anti-glare property was obtained, without inhibiting formation of fine and dense unevenness | corrugation. In addition, in the composition of Examples 4-6, although haze was mix | blended with the 4th component, the haze fell surprisingly and it was able to maintain the outstanding total light transmittance.

The composition of Example 7 contains the 1st component and the 2nd component similarly to the comparative example 1, and further, as a 3rd component, the polyether skeleton containing urethane acrylate of the manufacture example 2 (tolerance value: 3.5 mL, SP Value: 10.8) and a acrylate having a refractive index of 1.567 as the fourth component, and as a result, surprisingly, in the coating film formed from the composition of Example 7, by the synergistic effect of the third component and the fourth component, Compared with the comparative example 1, both the black distinctive feeling and the fingerprint were remarkably improved. In the composition of Example 7, surprisingly, despite blending the third component and the fourth component, excellent anti-glare properties were obtained without inhibiting the formation of fine and dense irregularities. In addition, in the composition of Example 7, despite mixing the third component and the fourth component, the haze was remarkably lowered, and the excellent total light transmittance could be maintained.

In contrast, in the composition of Comparative Example 2, in addition to the first component and the second component, UN-904 was blended as the third component, but UN-904 is a urethane acrylate that does not contain a polyether skeleton. The tolerance value is 7.5 mL, which deviates from the prescribed amount (6.0 mL or less) of the present invention. Furthermore, the SP value is 12.7, deviating from the prescribed amount (12 or less) of the present invention. As a result, in the coating film formed from the composition of the comparative example 2, the distinct black feeling fell remarkably.

In the composition of the comparative example 3, although U-324A was mix | blended as a 3rd component in addition to a 1st component and a 2nd component, U-324A is a urethane acrylate which does not contain a polyether skeleton, Furthermore, a tolerance value Is 7.3 mL, which deviates from the prescribed amount (6.0 mL or less) of the present invention. As a result, in the coating film formed from the composition of the comparative example 3, the distinct black feeling fell remarkably.

In the composition of the comparative example 4, in addition to the 1st component and the 2nd component, although DPHA-40H was mix | blended as a 3rd component, DPHA-40H is urethane acrylate which does not contain a polyether skeleton, Furthermore, a tolerance value Is 6.3 mL, which deviates from the prescribed amount (6.0 mL or less) of the present invention. As a result, in the coating film formed from the composition of the comparative example 4, the distinct black feeling fell remarkably.

The composition of the present invention, as shown in the Examples and Comparative Examples, includes the third component or the fourth component in addition to the first component and the second component, thereby providing not only anti-glare property but also excellent black distinctive feeling. A function can be provided further to an anti-glare film. Moreover, by mix | blending a 3rd component with a composition, by the synergistic effect of a 3rd component and a 4th component, both the outstanding outstanding black distinctive feeling and a fingerprint-proof property are obtained further.

As described above, the present invention can impart even more functions such as excellent black distinctive feeling and anti-fingerprint to the antiglare film, and when applied to a display device such as a liquid crystal television, improves reflection, haze and the like under external light. In addition, it is possible to provide excellent contrast performance, in particular, a clear sense of black (i.e., clean black with a strong glossiness), and in addition, excellent anti-fingerprint property, which is very advantageous.

One… Anti-glare film, 3... Anti-glare layer, 5... Transparent substrate, 10... Polarizer, 12... Polarizing layer, 14... Transparent substrate, 20... Liquid crystal display; Polarizing plate, 24... Liquid crystal panel, 26... Polarizing plate, 28... Backlight.

Claims (16)

A composition for forming an antiglare layer on a transparent substrate, comprising a first component and a second component,
The first component is an unsaturated double bond-containing acrylic copolymer,
The second component is a multifunctional unsaturated double bond containing component comprising a bifunctional or higher unsaturated double bond containing monomer,
The composition further,
The polyether skeleton-containing urethane (meth) acrylate (A) as the third component, and / or the fourth component, having a cyclic structure and containing at least one reactive unsaturated double bond, has a refractive index of 1.52 or more (meth ) Acrylate (B),
After apply | coating the said composition on the said transparent base material, according to the difference of the physical property of a 1st component and a 2nd component, a 1st component and a 2nd component phase-separate, and the anti-glare layer which has random unevenness | corrugation on the surface is formed, Composition. The method of claim 1,
The said (meth) acrylate (A) contains the structure represented by following General formula (1), and has 6.0 mL or less of tolerance and 12 or less solubility parameter (SPA).
[Formula 1]

[Wherein X represents a residue excluding the hydroxyl group of the sock end of the polyol compound having a polyether skeleton] The method according to claim 1 or 2,
The (meth) acrylate (A) is,
Polyol compound (a) having a polyether skeleton,
Polyisocyanate (b), and
The composition obtained by making a hydroxyl group containing (meth) acrylate monomer (c) react. The method according to any one of claims 1 to 3,
The said (meth) acrylate (B) is a composition which is an acrylate monomer which has a structure represented by following formula (2).
(2)

[Wherein n is 2 or more] The method according to any one of claims 1 to 4,
Furthermore, the organic solvent contains SP value SP ₁ of the first component, SP value SP ₂ of the second component, and SP value SP _sol of the organic solvent.
The condition that SP ₁ <SP ₂ , and
The difference between SP ₁ and SP _sol is 1.7 or less
In a relationship that satisfies
The difference between the SP value SP ₁ of the first component and the SP value SP ₂ of the second component is 0.8 to 3.6,
Composition. 6. The method according to any one of claims 1 to 5,
Said SP ₁ is 10.5 or less, and said SP ₂ is 11.3 or more composition. The method according to any one of claims 1 to 6,
A composition further comprising at least one component selected from the group consisting of a polymerization initiator, a curing agent, a catalyst and a photosensitizer. The method according to any one of claims 1 to 7,
A composition comprising no resin particles. An antiglare film having a transparent base material and an antiglare layer, wherein the antiglare layer is formed from the composition according to any one of claims 1 to 8. The coating process of apply | coating the composition of any one of Claims 1-8 to a transparent base material, and
Curing process of hardening obtained coating film
A manufacturing method of an anti-glare film comprising a. The coating process of apply | coating the composition of any one of Claims 1-8 to a transparent base material,
A drying step of drying and drying the obtained coating film, and
Hardening process to harden dried coating film
A manufacturing method of an anti-glare film comprising a. The coating process of apply | coating the composition of any one of Claims 1-8 to a transparent base material, and
Light irradiation process which irradiates light to the obtained coating film, phase-separates, and hardens
A manufacturing method of an anti-glare film comprising a. Antiglare film obtained by the manufacturing method of the antiglare film in any one of Claims 10-12. As a polarizing plate which has the anti-glare film of Claim 13 and a polarizing element,
The polarizing plate in which the anti-glare film surface which is an opposite surface to the anti-glare layer provided in the transparent base material, and the polarizing element surface are laminated | stacked and opposed. A transmissive display device having a planar transmissive display, a light source device for irradiating the transmissive display from the back, and an antiglare film according to claim 13 laminated on a surface of the transmissive display. A liquid crystal display device wherein the antiglare film according to claim 13 is used for the outermost layer of a display.

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