JP2010144009A - Coating composition, laminate, and method of producing laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition that improves a production efficiency by forming a multilayer structure by one coating process, a laminate having a multilayer structure formed by using the coating composition, and a method of producing the laminate. <P>SOLUTION: The coating composition comprises: first inorganic fine particles that is surface-modified with a polymer having a polydialkylsiloxane group-containing unit and a unit containing a reactive group for surface-modifying an inorganic fine particle; a curable binder; a solvent; and an initiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides a coating composition capable of forming a multilayer structure in one coating step and having high production efficiency, a laminate in which a multilayer structure of two or more layers is formed using the coating composition, and the laminate The present invention relates to a manufacturing method for forming.

Antireflection laminates, particularly antireflection films, are used in various image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), cathode ray tube display devices (CRT), etc. Located on the surface of the display, low reflectance is required to prevent deterioration of contrast due to reflection of external light and image reflection, and high physical strength (such as scratch resistance) and transparency are also required. Yes.
Among them, as an antireflection film showing an extremely low reflectance with an average reflectance of 1% or less, for example, a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer have different refractive indexes on a substrate. It is known to be obtained by laminating four layers of thin films (see, for example, Patent Documents 1 and 2).

These antireflection films are usually manufactured by a coating method, but laminating a plurality of thin films having different refractive indexes requires a film forming process including at least a plurality of coating processes. In addition, it is necessary to provide facilities associated with a plurality of film forming processes, and there is a problem in productivity because a process time for operating them is necessary.
Regarding this problem, a technique capable of forming two or more layers from one coating film has been disclosed (see, for example, Patent Documents 3 and 4). However, this technology is excellent in that an antireflection film can be produced with a small number of coating processes, but there is no freedom in the choice of coating solvent, and it is difficult to control the drying process after coating. It is difficult to obtain an antireflection film having high antireflection performance obtained by precise film thickness control due to nonuniformity.

JP 2003-121606 A JP 2003-262702 A JP 2006-206932 A JP 2007-038199 A

  The present invention relates to a coating composition that improves production efficiency by forming a multilayer structure in a single coating step, a laminate in which a multilayer structure is formed using the coating composition, and a method for forming the laminate. An object is to provide a manufacturing method.

The present invention relates to a coating composition that improves the production efficiency capable of forming a multilayer structure in a single coating step, and is a specific compound that has a particularly low surface energy and excellent binding power to particles. In this technique, the surface of one inorganic fine particle is modified so that it is spontaneously distributed in the coating film coated with the inorganic fine particle.
In particular, the first inorganic fine particles having a reduced surface energy as described above can be unevenly distributed in the upper layer on the air interface side, and a multilayer structure can be formed in the coating film. At this time, if the second inorganic fine particles are present at the same time, the second inorganic fine particles can occupy the lower layer together with the uneven distribution of the first inorganic fine particles, and as a result, the particles are separated from each other. Is possible. Furthermore, when at least one of the binders is a fluorine-containing curable resin compound, in addition to separating the particles, the binders can be separated, and a multilayer structure having a large refractive index difference can be formed.
In the present invention, the specific compound for reducing the surface energy by modifying the surface of the inorganic fine particles is a polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles.
The object of the present invention is achieved by the following configuration.

1. A coating composition comprising first inorganic fine particles surface-modified with a polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles, a curable binder, a solvent, and an initiator.
2. 2. The coating composition according to 1 above, wherein the polymer having a unit having the polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles has a polydialkylsiloxane group in the side chain.
3. 3. The coating composition according to 1 or 2 above, wherein the polymer having a unit having the polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles has a structure represented by the following general formula [I].

(In the formula, R 1 and R 2 represent a hydrogen atom or an alkyl group. L 2 represents a divalent linking group having 10 or less carbon atoms, n 2 represents 0 or 1, and R 11 to R 15 each independently represent 1 to 1 carbon atoms. 5 represents an alkyl group or an aryl group, q is an integer of 10 to 500, L represents a divalent linking group having 10 or less carbon atoms, m represents 0 or 1, and A represents a hydroxyl group or a hydrolysis. Represents a possible group, y represents a number 0 <y <100.)
4). The first inorganic fine particles are surface-modified with a polymer having a unit having the polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles, and an organosilicon compound having a polymerizable functional group. 4. Coating composition in any one of said 1-3 which is microparticles | fine-particles.
5). 5. The coating composition according to any one of 1 to 4 above, wherein the first inorganic fine particles are silica particles.
6). 6. The coating composition according to any one of 1 to 5, wherein the curable binder is a fluorine-containing curable compound.
7). The coating composition according to any one of 1 to 6, further comprising second inorganic fine particles.
8). 8. The coating composition according to 7 above, wherein the second inorganic fine particles are fine particles of titanium oxide or zirconium oxide.
9. The manufacturing method of the laminated body which forms the multilayer structure of 2 or more layers by the process of apply | coating the coating composition in any one of said 1-8 on a base material, the process of drying, and the process of hardening.
10. A laminate having a particle-containing layer produced using the production method according to 9 above.
11. 11. The laminate according to 10 above, wherein the laminate has an antireflection function.

  ADVANTAGE OF THE INVENTION According to this invention, the coating composition which can form a multilayer structure by one application | coating process can be provided. Also, by applying and curing the coating composition to form a laminate, the manufacturing process can be simplified, and a laminate with low reflectance, good scratch resistance, and excellent adhesion can be produced. Furthermore, a manufacturing method for forming a laminate having such characteristics can also be provided.

  The coating composition of the present invention comprises a first inorganic fine particle surface-modified by a polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particle, a curable binder, a solvent, and an initiator. Contains agents. A multilayer structure can be formed by applying and curing the coating composition.

  In addition, although the description of “layer” generally refers to those having a clear interface, in the present invention, even if the interface is not clear, a portion where fine particles are unevenly distributed or a plurality of curable binders are substantially separated. For the sake of convenience, the portion that is clearly shown is described as a “layer”.

  Furthermore, a layer having inorganic fine particles and a binder having a high refractive index in one coating step by containing the second inorganic fine particles, an organosilicon compound having a polymerizable functional group, a fluorine-containing curable resin compound, etc. A multilayer structure consisting of a (high refractive index layer) and a layer having a low refractive index inorganic fine particles and a binder (low refractive index layer) can be formed, has low reflectivity, good scratch resistance, and adhesion. It becomes possible to produce a laminate excellent in the above.

[Coating composition]
(Polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of inorganic fine particles)
The mass average molecular weight of the polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of inorganic fine particles in the present invention is preferably from 1,000 to 200,000, more preferably from 3,000 to 150,000, most preferably from 10,000 to 100,000. preferable.
Here, the mass average molecular weight is expressed in terms of polystyrene by solvent THF and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). Molecular weight.

  The polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of inorganic fine particles preferably has a polydialkylsiloxane group in the side chain.

  The polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of inorganic fine particles preferably has a structure represented by the following general formula [I].

In the formula, R1 and R2 represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
L2 represents a divalent linking group having 10 or less carbon atoms, preferably a linking group represented by -COO-L'- or -OL- (wherein L 'is an alkylene group), and n2 is 0 or 1 is represented, preferably 1.
R11 to R15 may be the same or different and each represents an alkyl or aryl group having 1 to 5 carbon atoms, preferably all are methyl groups, and q is an integer of 10 to 500, preferably 10-200.
L represents a divalent linking group having 10 or less carbon atoms, and is preferably a linking group represented by —COO-L′— or —O—L′— (L ′ is an alkylene group), and m is 0 or 1 is represented.
A represents a hydroxyl group or a hydrolyzable group, preferably a methoxy group or an ethoxy group.
y represents mol%, preferably 10 to 90, and particularly preferably 30 to 90.

  The polymer represented by the general formula [I] and having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of inorganic fine particles is a unit having a polydialkylsiloxane group having an effect of unevenly distributing particles. The structure is divided into units for chemically bonding to the particle surface. That is, it is a graft polymer in which a polydialkylsiloxane group is introduced into the side chain, and has a structure capable of bonding to inorganic fine particles only at one end of the polydialkylsiloxane. Therefore, the polymer having the structure represented by the general formula [I] is considered to have a structure in which each unit is oriented and separated in the molecule due to the surface energy difference, and the bond to the inorganic fine particles is stronger. Thus, the modified inorganic fine particles can be effectively unevenly distributed on the surface.

  Specific examples of the polymer having the structure represented by the general formula [I] are shown in Table 1 below, but are not limited thereto.

  For example, in Example I-1, one-end silaplane “FM-0711” manufactured by Chisso Corporation and 3- (trimethoxysilyl) propyl acrylate are mixed in an organic solvent so as to have a desired molar ratio. It can synthesize | combine by adding the radical polymerization initiator of and polymerizing.

  As another method for synthesizing the polymer having the structure represented by the general formula [I], a copolymer of a polydimethylsiloxane compound having an unsaturated double bond and a hydroxyl group-containing compound having an unsaturated double bond is used. Examples thereof include a method of modifying the hydroxyl group of the hydroxyl group-containing copolymer with a compound having an alkoxysilyl group after the formation. As polydimethylsiloxane compounds having an unsaturated double bond, commercially available silaplanes “FM-0711” and silaplanes “FM-0721” and “FM-0725” (manufactured by Chisso Corporation) are commercially available. Is mentioned. Examples of the hydroxyl group-containing compound having an unsaturated double bond include hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether and the like. In addition, it is preferable to use a compound having one isocyanate group and at least one alkoxysilyl group in the molecule for introducing an alkoxysilyl group into the hydroxyl group-containing copolymer. For example, 3-isocyanatopropyl Examples include trimethoxysilane and 3-isocyanatopropyltriethoxysilane.

  The polymer having the structure represented by the general formula [I] is preferably used in an amount of 1% by mass to 100% by mass with respect to the inorganic fine particles, more preferably 5% by mass to 80% by mass, and still more preferably. It is 10 mass%-50 mass%.

  Further, in addition to a polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles, an organic silicon compound having a polymerizable functional group is further used in combination to form the first inorganic fine particles. Surface modification is also suitable. The organosilicon compound having a polymerizable functional group has a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles in order to bind the first inorganic fine particles and the binder by a polymerization reaction. By using in combination with the polymer, it is possible to achieve good separation from the second inorganic fine particles, and it is possible to improve the scratch resistance due to the strong bonding force between the first inorganic fine particles and the binder.

Examples of the polymerizable functional group include an ethylenically unsaturated group (for example, (meth) acryl group, allyl group, styryl group, vinyloxy group, etc.) capable of addition reaction / polymerization reaction with radical species, and cationic polymerizable group (epoxy group). , An oxatanyl group, a vinyloxy group, etc.), a polycondensation reactive group (hydrolyzable silyl group, etc., N-methylol group) and the like, and a group having an ethylenically unsaturated group is preferable.
Among organosilicon compounds having an ethylenically unsaturated group, organosilicon compounds having a (meth) acryl group can be particularly preferably used in the present invention. The compounds include γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltri Examples thereof include, but are not limited to, ethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and the like.

(First inorganic fine particles)
The first inorganic fine particles in the present invention are preferably metal oxide fine particles, and more preferably silica fine particles. The silica fine particles may be general silica fine particles (solid silica fine particles), but it is preferable to use hollow silica fine particles in order to further lower the refractive index.

The hollow silica fine particles have a refractive index of 1.15 to 1.40, more preferably 1.15 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the whole particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica fine particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is calculated by the following formula (VIII).
(Formula ^{VIII) x = (4πa 3/} 3) / (4πb 3/3) × 100
The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. Increasing the porosity of the hollow silica fine particles can lower the refractive index of the particles. However, if the refractive index is to be made smaller than 1.15, the thickness of the outer shell becomes too thin and the strength of the particles is insufficient. . The refractive index of these hollow silica fine particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

The average particle size of the first inorganic fine particles is preferably 1 nm to 100 nm, more preferably 30 nm to 80 nm, and particularly preferably 50 nm to 80 nm.
The average particle size distribution is preferably monodisperse. The average particle diameter of the inorganic fine particles can be measured with a Coulter counter.

The content of the first inorganic fine particles in the coating composition is preferably 10 to 45 mass%, more preferably 15 to 40 mass%, and most preferably 15 to 35 mass% with respect to 100 mass% of the total solid content. When the content is less than 10% by mass, the difference in reflectance between the unevenly distributed portion and the non-distributed portion of the first inorganic fine particles is small, and the reflectance as a laminate tends to be high. When there is more content of than 45 mass%, there exists a tendency for film | membrane intensity | strength to fall.
The first inorganic fine particles may be one type or two or more types.

The first inorganic fine particles surface-modified with a polymer having a unit having a polydialkylsiloxane group of the present invention and a unit having a reactive group for modifying the surface of inorganic fine particles have low surface free energy from the viewpoint of good layer separation. It is preferable. The surface free energy of the surface-modified first inorganic fine particles is preferably 35 mN / m or less, and more preferably 24 mN / m to 30 mN / m. The surface free energy of the surface-modified first inorganic fine particles can be calculated by measuring the contact angle between water and methylene iodide after applying the particle dispersion on the substrate.
Moreover, as a surface free energy difference with a curable binder, it is preferable that it is 10 mN / m or more, and it is more preferable that it is 20 mN / m or more. When the surface free energy difference is smaller than 10 mN / m, the separability tends to be deteriorated.

(Curable binder)
The curable binder contained in the coating composition of the present invention may be a monomer or a curable polymer. Monomers or polymers that are cured mainly by ultraviolet rays and electron beams, that is, ionizing radiation curable resins, ionizing radiation curable resins in which a thermoplastic resin and a solvent are mixed, and thermosetting resins are exemplified. A preferable curable binder preferably has a surface free energy larger than that of the surface-modified first inorganic fine particles, preferably a surface free energy of 35 mN / m or more, and 35 mN / m to 70 mN / m. m is more preferable, and 35 mN / m to 60 mN / m is particularly preferable. The surface free energy difference from the surface-modified first inorganic fine particles is as described above. The surface free energy of the curable binder can be calculated by measuring the contact angle between water and methylene iodide after coating the binder on the substrate.

  At least one of the curable binders is preferably a polymer having a saturated hydrocarbon or polyether as a main chain after curing, and more preferably a polymer having a saturated hydrocarbon as a main chain. The curable resin compound is preferably crosslinked after forming the layer structure. These polymers having a saturated hydrocarbon as the main chain can be obtained, for example, by a polymerization reaction of an ethylenically unsaturated monomer, and have two or more ethylenically unsaturated groups in order to obtain a crosslinked binder. It is preferable to use a monomer.

  Examples of monomers having two or more ethylenically unsaturated groups include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene Glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- ( (Meth) acryloyloxypropionate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( Acrylate), tri (2-hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1 2-butadiene di (meth) acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 3,8-bis (meth) acryloyloxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane 1,4-bis ((Meth) acryloyloxymethyl) cyclohexane, hydroxypivalin sun ester neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, epoxy-modified bisphenol A di (meth) acrylate, and the like. Only one type of polyfunctional monomer may be used, or two or more types may be used in combination.

  These monomers having an ethylenically unsaturated group can be cured by a polymerization reaction by ionizing radiation or heat after being dissolved in a solvent, coated and dried together with various polymerization initiators and other additives.

  Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder by a reaction of a crosslinkable group. Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. The binder having these crosslinkable functional groups can form a crosslinked structure by heating after coating.

In the present invention, the content of the curable binder in the coating composition is preferably 1 to 50% by mass, more preferably 1 to 40% by mass with respect to 100% by mass of the total solid content of the coating composition. 30% by mass is most preferred.
One type of curable binder may be used, or two or more types may be used.

(solvent)
As the solvent used in the coating composition of the present invention, it is possible to dissolve or disperse each component, it is easy to form a uniform surface in the coating process and the drying process, liquid preservation can be ensured, and an appropriate saturated vapor pressure. It is possible to use various solvents selected from the viewpoints of having
One type of solvent may be used, or two or more types of solvents may be mixed and used. In particular, from the viewpoint of drying load, the main component is a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature, and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed (100 mass of solvent having a boiling point of 100 ° C. or lower). 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and particularly preferably 3 to 30 parts by mass) of a solvent having a boiling point of 100 ° C. or higher. By using at least two kinds of organic solvents having different boiling points, it is easy to form a multilayer structure, and effects such as easy separation of the binder when using plural kinds of binders are obtained.

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichlorethylene (87.2 ° C), etc. Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C) and other ethers, ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl ketone) The same, ketones such as 79.6 ° C., alcohols such as methanol (64.5 ° C.), ethanol (78.3 ° C.), 2-propanol (82.4 ° C.), 1-propanol (97.2 ° C.) , Cyano compounds such as acetonitrile (81.6 ° C.) and propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.) and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C or higher include, for example, octane (125.7 ° C), toluene (110.6 ° C), xylene (138 ° C), tetrachloroethylene (121.2 ° C), chlorobenzene (131.7 ° C), Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.), Examples include 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.), and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

  Another preferred example of using two or more solvents is to use two solvents having a boiling point difference greater than a specific value. The difference between the two solvent boiling points is preferably 25 ° C. or more, particularly preferably 35 ° C. or more, and further preferably 50 ° C. or more.

  The mixing ratio of the solvent is preferably added so that the solid content concentration of the coating composition is 2 to 30% by mass, more preferably 3 to 20% by mass, and more preferably 5 to 15% by mass. It is particularly preferable to add so as to be%. If the solid content concentration is too low, there is a concern that drying takes time and film thickness unevenness due to drying is likely to occur, and if the solid content concentration is too high, it becomes difficult to form a multilayer structure, and the coating amount is reduced and applied. There is concern that unevenness is likely to occur.

(Initiator)
As the initiator used in the coating composition of the present invention, a radical polymerization initiator such as a photo radical initiator or a thermal radical initiator, a photo cationic polymerization initiator, or the like can be preferably used. Among these, a photo radical polymerization initiator or a photo cation polymerization initiator is preferable, and a photo radical polymerization initiator is particularly preferable. One or more initiators may be used.

Photo radical (polymerization) initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides Examples include compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (p.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), and are useful for the present invention.
Preferable examples of commercially available photocleavable photoradical (polymerization) initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.
The photo radical (polymerization) initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the curable binder.
In addition to the photoradical (polymerization) initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

(Second inorganic fine particles)
The coating composition of the present invention can contain second inorganic fine particles in addition to the first inorganic fine particles so that each fine particle forms a multilayer structure. As the second inorganic fine particles, metal oxide fine particles are preferably used from the viewpoint of refractive index. As the metal oxide fine particles, oxide fine particles containing at least one element selected from the group consisting of aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium are preferably used. In particular, in order to enhance the antireflection function, it is necessary to increase the refractive index difference in the multilayer structure. As the metal oxide fine particles used for this purpose, at least one metal oxide selected from titanium oxide and zirconium oxide is used. Things are preferred. From the viewpoint of light resistance, it is preferable to use a metal oxide selected from zirconium having no photocatalytic action or titanium having suppressed photocatalytic action.
In addition, when the antistatic property is imparted to the laminated film using the second inorganic fine particles, it is preferable to use conductive inorganic fine particles, and among the above-described metal group, among indium, zinc, tin, and antimony. It is preferable to use at least one metal oxide selected from inorganic fine particles mainly composed of at least one metal oxide selected.

  The surface free energy of the second inorganic fine particles is preferably 35 mN / m or more, and more preferably 40 mN / m to 70 mN / m. As in the case of the curable binder, it is preferable to increase the difference in surface free energy from the surface-modified first inorganic fine particles because the separability can be improved. The surface free energy difference is preferably 10 mN / m or more, and more preferably 15 mN / m or more. When the surface free energy difference is smaller than 10 mN / m, it is not preferable because the separation from the first inorganic fine particles is deteriorated or the separation takes time. The surface free energy of the second inorganic fine particles can be calculated by the same method as that for the first inorganic fine particles.

  The average particle size of the second inorganic fine particles is preferably a particle size that is sufficiently smaller than the wavelength of visible light and does not scatter light in the wavelength region of visible light. The preferred average particle diameter of the second inorganic fine particles is preferably 1 to 100 nm, preferably 2 to 50 nm, and most preferably 3 to 30 nm. The shape of the fine particles is not particularly limited, but generally spherical particles are preferably used.

  The content of the second inorganic fine particles in the coating composition is preferably 10 to 60% by mass and more preferably 15 to 50% by mass with respect to the total solid content. The second inorganic fine particles may be used alone or in combination of two or more.

(Fluorine-containing curable compound)
The coating composition of the present invention can contain a fluorine-containing curable compound as at least one kind of curable binder. If the fluorine-containing curable compound can form a layer integrated with the surface-modified first inorganic fine particles of the present invention, it is preferable because a layer having a lower refractive index can be formed. From such a viewpoint, the fluorine-containing curable resin compound that can be used in the present invention preferably has a small surface free energy difference from the surface-modified first inorganic fine particles, and the surface free energy difference is less than 10 mN / m. Preferably, it is 5 mN / m or less.

  Examples of the fluorine-containing curable compound include a fluorine-containing vinyl monomer mainly constituting a fluorine-containing copolymer, and fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meta ) Acrylic acid partial or fully fluorinated alkyl ester derivatives {for example, “Biscoat 6FM” (trade name), Osaka Organic Chemical Industry Co., Ltd., “R-2020” (trade name), Daikin Industries, Ltd., etc.} And fully or partially fluorinated vinyl ethers, and the like, preferably perfluoroolefins, and particularly preferably hexafluoropropylene from the viewpoint of refractive index, solubility, transparency, availability, and the like.

Examples of the structural unit for imparting crosslinking reactivity include units represented by the following (A), (B), and (C).
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether,
(B): a monomer having a carboxyl group, a hydroxy group, an amino group, a sulfo group or the like {for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether , Maleic acid, crotonic acid, etc.}
(C): A group having a crosslinkable functional group separately from a group that reacts with the functional groups (A) and (B) in the molecule and a structural unit of the above (A) and (B). Examples thereof include structural units obtained (for example, structural units that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

  In the structural unit (C), the crosslinkable functional group is preferably a photopolymerizable group. Examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide group, Carbonyl azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclopropene group And azadioxabicyclo group. These may be not only one type but also two or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting a (meth) acrylic acid ester containing an isocyanate group with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.

The amount of the photopolymerizable group introduced can be arbitrarily adjusted, and the carboxyl group, hydroxyl group, etc. can be controlled from the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength. You may leave.
In the present invention, the introduction amount of the structural unit for imparting crosslinkability in the copolymer is preferably 10 to 50 mol%, more preferably 15 to 45 mol%, particularly preferably 20 to 40 mol%. This is the case of mol%.

  In the copolymer useful in the present invention, in addition to the repeating unit derived from the fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain of the structural unit for imparting crosslinkability, adhesion to the substrate Other vinyl monomers can be appropriately copolymerized from various viewpoints such as properties, polymer Tg (contributing to film hardness), solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, and the like. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. Is more preferable, and the range of 0 to 30 mol% is particularly preferable.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic) 2-ethylhexyl acid, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p-methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate) , Vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  The fluorine-containing curable compound particularly useful in the present invention is a random copolymer of a perfluoroolefin and a vinyl ether or vinyl ester. In particular, it preferably has a group capable of undergoing crosslinking reaction alone {a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group}. These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol%, of the total polymerized units of the polymer. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP-A-2004-45462.

  In addition, a polysiloxane structure may be introduced into the fluorine-containing curable compound useful in the present invention for the purpose of imparting antifouling properties. The method for introducing the polysiloxane structure is not limited. For example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631, and JP-A-2000-313709, silicone macroazo A method for introducing a polysiloxane block copolymer component using an initiator; a method for introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. Is preferred. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and copolymers A-2 and A-3 of JP-A-2-251555. It is preferable that these polysiloxane components are 0.5-10 mass% in a polymer, Most preferably, it is 1-5 mass%.

  The preferred molecular weight of the fluorine-containing curable compound that can be preferably used in the present invention is a mass average molecular weight of 5000 or more, preferably 10,000 to 500,000, and most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

  As described in JP-A-10-25388 and JP-A-2000-17028, a curing agent having a polymerizable unsaturated group may be used in combination with the fluorine-containing curable compound as described above. Further, as described in JP-A-2002-145952, combined use with a compound having a fluorine-containing polyfunctional polymerizable unsaturated group is also preferable.

  In the present invention, the content of these fluorine-containing curable compounds is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and more preferably 3 to 30% by mass with respect to 100% by mass of the total solid content of the coating composition. Is most preferred.

[Laminate]
(Structure of laminate)
The laminate of the present invention is a laminate in which a multilayer structure of two or more layers is formed by applying at least the coating composition of the present invention on a substrate, and this multilayer structure includes the following structures.
(A) Layer in which the first inorganic fine particles are present at a high density / Layer substantially free of the first inorganic fine particles (B) Layer in which the first inorganic fine particles are present at a high density / Second inorganic fine particles Layer with high density (C) Layer with first inorganic fine particles and fluorine-containing curable compound present at high density / Layer with high density curable binder other than fluorine-containing curable compound (D) First Layer with high density of inorganic fine particles and fluorine-containing curable compound (low refractive index layer) / layer with high density of curable binder other than second inorganic fine particles and fluorine-containing curable compound (high refractive index) layer)

  When applying the coating composition on the substrate, it is of course designed to optimize the refractive index and film thickness of the layer having the above multilayer structure, but the intermediate refractive index for further reducing the reflectance. A layer, an antistatic functional layer for preventing dust, a hard coat layer for imparting physical strength, an antiglare layer for imparting antiglare properties, and the like can be provided depending on the purpose.

  In the case of producing an antireflection film using the laminate production method of the present invention, the coating composition of the present invention may be applied using the substrate as a transparent film substrate. In that case, as a preferable embodiment having good optical characteristics, physical characteristics, and the like, a configuration of a film substrate / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer can be exemplified.

〔Base material〕
The substrate that can be used in the present invention may be any substrate as long as various layers can be laminated, but a film substrate is preferable from the viewpoint of high productivity by continuous conveyance.
The film substrate is not particularly limited as long as it has an excellent visible light transmittance (preferably a light transmittance of 90% or more) and excellent transparency (preferably a haze value of 1% or less). Specifically, for example, a film made of a transparent polymer such as a polyester polymer such as polyethylene terephthalate and polyethylene naphthalate, a cellulose polymer such as diacetyl cellulose and triacetyl cellulose, a polycarbonate polymer, and an acrylic polymer such as polymethyl methacrylate. Is mentioned. In addition, styrene polymers such as polystyrene and acrylonitrile / styrene copolymer, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, olefin polymers such as ethylene / propylene copolymer, vinyl chloride polymers, nylon and aromatic polyamides. Examples thereof include a film made of a transparent polymer such as an amide polymer. Furthermore, imide polymers, sulfone polymers, polyether sulfone polymers, polyether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers Examples thereof include a film made of a transparent polymer such as a polymer, an epoxy-based polymer, and a blend of the aforementioned polymers. In particular, those having a small optical birefringence are preferably used.

  The thickness and width of the film substrate can be appropriately determined. The thickness of the film substrate is generally about 10 to 500 μm in consideration of workability such as strength and handleability, and thin layer properties. 20-300 micrometers is especially preferable, and 30-200 micrometers is more preferable. As a width | variety of a film base material, the thing of 100-5000 mm is used suitably, It is preferable that it is 800-3000 mm, and it is more preferable that it is 1000-2000 mm. Furthermore, it does not restrict | limit especially as a refractive index of a film base material, It is usually about 1.30-1.80, It is especially preferable that it is 1.40-1.70.

  The surface of the substrate is preferably smooth, and the average roughness Ra is preferably 1 μm or less, preferably 0.0001 to 0.5 μm, and 0.001 to 0.1 μm. Is more preferable.

[Method for producing laminate]
The laminate of the present invention can be produced by a step of applying a coating composition, a step of drying, and a step of curing, and is continuously applied, dried and cured by using a film substrate as described above. The process can be performed and high productivity can be realized. At this time, the laminate is a film-like laminate, that is, an antireflection film. Each process will be described below. In addition, the manufacturing method of this invention may have another process other than the said process.

(Coating process)
Examples of the coating method in the production method of the present invention include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and an extrusion coating method (die coating method) (US Patent). No. 2,681,294), and a known method such as a micro gravure coating method is used. Among them, a micro gravure coating method and a die coating method are preferably used from the viewpoint of high productivity and coating film uniformity.

  Here, the micro gravure coating method refers to a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and having a gravure pattern engraved on the entire circumference, below the support and in the transport direction of the support. While rotating the gravure roll in a reverse direction, the surplus coating liquid is scraped off from the surface of the gravure roll by a doctor blade, and a predetermined amount of coating liquid is applied to the lower surface of the support at a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating is performed by transferring the liquid. A roll-shaped transparent support can be continuously unwound, and at least one layer can be coated on one side of the unwound support by a microgravure coating method.

  As coating conditions by the micro gravure coating method, the number of gravure patterns imprinted on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. It is preferably 1 to 50 m / min.

(Drying process)
In the production method of the present invention, the coating composition of the present invention is coated on a substrate and then conveyed by a web to a heated zone to dry the solvent. The temperature of the drying zone at that time is preferably 25 ° C. to 140 ° C., and it is also suitable to adjust the first half of the drying zone to a relatively low temperature and the second half to a relatively high temperature. However, it is essential to set the temperature below the temperature at which components other than the solvent contained in the coating composition start to volatilize. There is no restriction | limiting of a drying process other than these preferable drying conditions, The method which can be used for drying after normal application | coating can be used.

(Curing method)
In the present invention, the coated and dried laminate can be cured by ultraviolet irradiation and / or heat. Here, curing by ultraviolet irradiation means low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, etc., ArF excimer laser, KrF excimer laser, excimer lamp or synchrotron radiation. This refers to curing the film by irradiating the dried film with ultraviolet light using a light source such as light.
The irradiation conditions vary depending on individual lamps, but the amount of light irradiated is preferably 20~10000mJ / cm ^2, more preferably from 100 to 2000 mJ / cm ^2, particularly preferably 400~2000mJ / cm ^2.
In the case of curing with ultraviolet rays, each layer may be irradiated one by one, or may be irradiated after lamination. For the purpose of accelerating the curing of the surface during ultraviolet irradiation, the oxygen concentration can be lowered by purging with nitrogen gas or the like. The oxygen concentration in the environment for curing is preferably 5% or less. When the outermost layer forms a low refractive index layer as in the antireflection film of the present invention, the oxygen concentration is preferably 0.1% or less, more preferably 0.05% or less, and most preferably 0.02% or less. preferable.
The laminate obtained by the production method of the present invention preferably has a particle-containing layer. The laminate preferably has an antireflection function.

[Hard coat layer]
In the laminate of the present invention, a hard coat layer can be provided on one surface of the substrate in order to impart physical strength.

The thickness of the hard coat layer is generally about 0.5 μm to 50 μm from the viewpoint of imparting sufficient durability or impact resistance, curling, productivity, and cost. The preferred film thickness is 1 μm to 30 μm, more preferably 2 μm to 20 μm, and most preferably 3 μm to 15 μm.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, further preferably 3H or more, and most preferably 5H or more in the pencil hardness test.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  The refractive index of the hard coat layer is preferably in the range of 1.48 to 1.75, more preferably 1.49 to 1 in terms of optical design, reflectance, color, unevenness, and cost. .65, and more preferably 1.50 to 1.55.

  When the anti-glare function is imparted by surface scattering of the hard coat layer, the surface haze (the value obtained by subtracting the internal haze value from the total haze value. 0.1% to 20% is preferable, 0.2% to 5% is more preferable, and 0.2% to 2% is particularly preferable. When the surface haze is too large, the bright room contrast is deteriorated, and when it is too small, the reflection is deteriorated.

  In addition, when the hard coat layer contains translucent particles to give internal scattering, the preferred range of internal haze varies depending on the purpose, but due to internal scattering, liquid crystal panel patterns, color unevenness, luminance unevenness, glare, etc. are observed. When making it difficult or providing the function of expanding the viewing angle by scattering, the internal haze value is preferably 0% to 60%, more preferably 1% to 40%, and more preferably 10% to 35%. It is particularly preferred that If the internal haze is too large, the front contrast is lowered and the brownishness is increased. If it is too small, the combination of materials that can be used is limited, and it becomes difficult to match antiglare and other characteristic values, and the cost is high. On the other hand, when importance is attached to the front contrast, 0% to 30% is preferable, more preferably 1% to 20%, and most preferably 1% to 10%.

  Moreover, about the surface uneven | corrugated shape of a hard-coat layer, it is preferable that centerline average roughness (Ra) shall be 0.30 micrometer or less. Ra is more preferably 0.01 to 0.20 μm, and still more preferably 0.01 to 0.12 μm. When Ra is large, problems such as white blurring due to surface scattering and difficulty in obtaining uniformity of the layer formed on the hard coat layer may occur.

[Conductive layer]
In the laminated body of the present invention, a conductive layer can be provided for the purpose of preventing static charge, thereby preventing dust on the surface of the laminated body. The conductive layer may be provided as a separate layer from each layer, or any of the stacked layers may be provided as a dual-purpose layer that also serves as the conductive layer.

The thickness of the conductive layer is preferably 0.01 μm to 10 μm, more preferably 0.03 μm to 7 μm, and most preferably 0.05 μm to 5 μm. Preferably the surface resistivity of the conductive layer is ¹⁰ 5 ^{~10 12 Ω} / ^sq, more preferably 10 5 ~10 ⁹ Ω / ^sqμm, and most preferably 10 5 ~10 ⁸ Ω / sqμm . The surface resistance of the conductive layer can be measured by a known measuring method, for example, it can be measured by a four-probe method.

[Protective film for polarizing plate]
When using the antireflection film of the present invention formed on a film substrate for a liquid crystal display device, in order to use the antireflection film as a surface protective film for a polarizing film (protective film for a polarizing plate) in preparing a polarizing plate. The surface of the transparent support opposite to the side having the low refractive index layer, that is, the surface to be bonded to the polarizing film is hydrophilized to improve the adhesion to the polarizing film mainly composed of polyvinyl alcohol. It is preferable to do.

  As the film substrate, it is particularly preferable to use a triacetyl cellulose film. As a method for producing a protective film for polarizing plate in the present invention, (1) each of the above-mentioned layers (eg, hard coat layer, medium refractive index layer, two surface layers, etc.) on one surface of a previously saponified transparent support. There are two methods: (2) a method of coating each layer on one side of the transparent support, and then a saponification treatment on the side to be bonded to the polarizing film. Since the surface to which the coat is to be applied is hydrophilized, it may be difficult to ensure the adhesion between the support and the hard coat layer, and the method (2) is preferred.

[Saponification]
(1) Immersion method This is a technique in which the antireflection film as described above is immersed in an alkaline solution under appropriate conditions to saponify all surfaces reactive with alkali on the entire surface of the film. Is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / l, particularly preferably 1 to 2 mol / l. The liquid temperature of a preferable alkali liquid is 30-70 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the above saponification conditions is preferably a combination of relatively mild conditions, but can be set according to the material and configuration of the antireflection film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface of the transparent support opposite to the surface having the antireflection layer is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle with water on the surface of the transparent support opposite to the side having the low refractive index layer, the better from the viewpoint of adhesion to the polarizing film, while the dipping method simultaneously reduces the low refractive index. Since the surface having the rate layer is damaged by alkali, it is important to set the reaction conditions to the minimum necessary. As an index of the damage received by the antireflection layer due to alkali, particularly when the surface of the transparent support opposite to the side having the antireflection structure layer, that is, the bonding angle of the antireflection film, the contact angle with water is used. When the support is triacetylcellulose, the contact angle is preferably 20 to 50 degrees, preferably 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or more, there is a problem in the adhesion to the polarizing film, which is not preferable. On the other hand, if it is less than 20 degrees, the damage received by the antireflection layer is so great that physical strength and light resistance are impaired, which is not preferable.

(2) Alkaline liquid application method As a means for avoiding damage to the antireflection film in the above-described immersion method, the alkaline liquid is applied only on the surface opposite to the surface having the antireflection film under appropriate conditions, heated, washed with water, A drying alkaline solution coating method is preferably used. The application in this case means that an alkali solution or the like is brought into contact only with the surface to be saponified, and at this time, the contact angle with respect to water of the bonded surface of the antireflection film is 10 to 50 degrees. It is preferable to perform a saponification treatment. In addition to the application, it may include spraying, contact with a belt containing liquid, or the like. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, it is possible to have a layer using a material weak against the alkali solution on the opposite surface. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, peeling, etc. caused by alkali solution, so it is not desirable to use the immersion method. Is possible.

  In any of the above saponification methods (1) and (2), for example, each layer can be unwound from a roll-shaped support and formed after each production step. Also good. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

〔Polarizer〕
The polarizing plate is a laminate having a polarizing film and two protective films for protecting both the front side and the back side of the polarizing film, and includes an embodiment in which at least one of the protective films is an antireflection film. It is out. Hereinafter, the case of an antireflection film will be described as an example.
The polarizing plate has an antireflection film on at least one of the polarizing film protective film (polarizing plate protective film). The transparent support of the antireflection film is adhered to the polarizing film through an adhesive layer made of polyvinyl alcohol, and the protective film of the other polarizing film is adhered to the antireflective film of the polarizing film through the adhesive layer. It adheres to the main surface opposite to the main surface. The main surface opposite to the main surface bonded to the polarizing film of the other protective film has an adhesive layer.
By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having physical strength and an excellent antireflection function can be produced, and the cost can be greatly reduced.
Further, by preparing a polarizing plate using the antireflection film of the present invention as one of the protective films for polarizing plates and an optical compensation film having optical anisotropy described later as the other protective film of the polarizing film, Thus, it is possible to produce a polarizing plate that improves the contrast in the bright room of the liquid crystal display device and can greatly widen the viewing angle in the vertical and horizontal directions and in the oblique direction.

[Optical compensation film]
The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film, but it has optical anisotropy made of a compound having a discotic structural unit described in JP-A-2001-100042 in terms of widening the viewing angle. An optical compensation film having a layer, wherein the angle formed by the discotic compound and the support varies with the distance from the transparent support, is preferable.
The angle preferably increases as the distance from the support surface side of the optically anisotropic layer increases.
When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.
Also, an aspect in which the optically anisotropic layer further contains a cellulose ester, an aspect in which an alignment layer is formed between the optically anisotropic layer and the transparent support, and an optical compensation film having the optically anisotropic layer It is also preferable that the transparent support has an optically negative uniaxial property and has an optical axis in the normal direction of the surface of the transparent support and further satisfies the following conditions.
20 ≦ {(nx + ny) / 2−nz} × d ≦ 400
In the above conditional expression, nx is the refractive index in the slow axis direction (direction in which the refractive index is maximum) in the film plane, and ny is the fast axis direction in the film plane (direction in which the refractive index is minimum). Where nz is the refractive index in the thickness direction of the film, and d is the thickness of the optical compensation layer.

[Image display device]
As an image display device having the laminate of the present invention, particularly an antireflection film, a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (OLED), a cathode ray tube display device (CRT), a field emission display (FED), a surface electric field display (SED), etc. are mentioned, Especially, it is preferable to use the antireflection film of this invention as a surface film of a liquid crystal panel screen. Examples of the image display device having a polarizing plate having the antireflection film of the present invention include an image display device such as a liquid crystal display device (LCD) and an electroluminescence display (OLED). In the image display device of the present invention, the polarizing plate having the antireflection film of the present invention is used by bonding directly to the glass of the liquid crystal cell of the liquid crystal display device or through another layer.

The polarizing plate using the antireflection film used in the present invention includes twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell ( It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device in a mode such as OCB).
Further, when used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained.
Further, when combined with a λ / 4 plate, it can be used to reduce reflected light from the surface and the inside as a polarizing plate for reflective liquid crystal or a surface protective plate for OLED.

  Hereinafter, the present invention will be described in detail by examples in the production of an antireflection film, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are mass-based values.

[Comparative Example 1: Antireflection film 101]
(Preparation of coating liquid A for hard coat layer)
306 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in a mixed solvent of 16 parts by mass of methyl ethyl ketone and 220 parts by mass of cyclohexanone. After adding 7.5 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) to the resulting solution and stirring until dissolved, 450 parts by mass of MEK-ST (average particle size) (Methyl ethyl ketone dispersion of SiO ₂ sol having a solid content concentration of 30% by mass) was added and stirred to obtain a uniform solution. This solution was filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm to prepare a coating liquid A for hard coat layer.

(Preparation of coating solution B)
5.4 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 0.2 parts by mass of a photopolymerization initiator (Irgacure 184), 85 parts by mass of methyl ethyl ketone and 9.4 parts by mass of cyclohexanone were added. And stirred to prepare coating solution B.

(Preparation of coating solution C)
(Preparation of hollow silica particle dispersion S-1)
Hollow silica particle fine particle sol A (isopropyl alcohol silica sol, average particle diameter 60 nm, silica concentration 20%), 30.5 parts by mass of γ-acryloyloxypropyltrimethoxysilane and 1.51 parts by mass of diisopropoxyaluminum ethyl acetate After adding 500 parts by mass of methyl ethyl ketone and mixing, 9 parts by mass of ion-exchanged water was added. The mixture was reacted at 60 ° C. for 8 hours and then cooled to room temperature, and 1.8 parts by mass of acetylacetone was added to obtain a dispersion. Thereafter, while adding cyclohexanone so that the silica content is substantially constant, solvent replacement is performed by distillation under reduced pressure at a pressure of 30 Torr. Finally, organic compounds having a polymerizable functional group with a solid content concentration of 18.2% are obtained by adjusting the concentration. A hollow silica particle dispersion S-1 whose surface was modified with a silicon compound was obtained.

  A composition having the following composition was mixed using the obtained hollow silica particle dispersion S-1, and the resulting solution was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution C.

(Composition of coating liquid C)
Pentaerythritol triacrylate (PETA) 2.4 parts by weight Hollow silica particle dispersion S-1 (18.2%) 17.5 parts by weight Irgacure 907 0.1 parts by weight Methyl ethyl ketone 77.1 parts by weight Cyclohexanone 2.9 parts by weight

(Preparation of hard coat layer)
On a triacetyl cellulose film (TD80UF, manufactured by Fuji Film Co., Ltd., refractive index 1.48) as a transparent support having a layer thickness of 80 μm, the hard coat layer coating solution A having the above composition was applied using a gravure coater. . After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^{2. The} coating layer was cured by irradiating ultraviolet rays with an irradiation amount of 300 mJ / cm ² to form a hard coat layer A having a thickness of 8 μm.

(Preparation of coating film using coating liquid B)
On the hard coat layer A, the coating liquid B was applied using a gravure coater. The coating film was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was a 180 W / cm air-cooled metal halide lamp (I Graphics Co., Ltd.) purged with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. The irradiance was 400 mW / cm ² and the irradiation amount was 400 mJ / cm ² .

(Preparation of coating film using coating film C)
On the coating film coated with the coating liquid B, the coating liquid C was coated using a gravure coater. The coating film was dried at 60 ° C. for 75 seconds, and the ultraviolet curing condition was as follows: using a 240 W / cm air-cooled metal halide lamp while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less, and an illuminance of 400 mW / The irradiation dose was cm ² and the irradiation dose was 600 mJ / cm ² .

  When the cross section of the antireflection film 101 was observed with a transmission electron microscope, the coating film formed with the coating liquid B had a thickness of 100 nm, and the coating film formed with the coating liquid C had a thickness of 100 nm. At this time, the hollow silica particles were uniformly distributed over 100 nm above the coating film, and it was confirmed that the particle thickness was uniform and there was no unevenness.

[Comparative Example 2: Antireflection film 102]
The coating liquid B and the coating liquid C in the method for producing the antireflection film 101 shown in Comparative Example 1 are changed to the following one-liquid two-layer coating liquid W-0 to be one-component, and the coating method is the following coating An antireflection film 102 was produced in the same manner as in Comparative Example 1 except that the method was changed.

(Preparation of 1-component 2-layer coating solution W-0)
2.7 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 1.2 parts by mass of pentaerythritol triacrylate, 8.7 parts by mass of the hollow silica particle dispersion S-1 and light 0.2 parts by mass of a polymerization initiator (Irgacure 184), 84.3 parts by mass of methyl ethyl ketone and 2.9 parts by mass of cyclohexanone were added and stirred to prepare a one-part / two-layer coating liquid W-0.

(Coating method of 1 liquid 2 layer coating liquid W-0)
A hard coat layer A was produced on a triacetyl cellulose film having a layer thickness of 80 μm in the same manner as in Comparative Example 1, and a one-component / two-layer coating solution W-0 was applied onto the layer using a gravure coater. The film thickness was adjusted to 200 nm.
After coating, it is allowed to stand at 25 ° C. for 90 seconds, and then dried at 90 ° C. for 60 seconds. The UV curing condition is 240 W / cm air-cooled metal halide lamp while purging with nitrogen so that the oxygen concentration is 0.1 vol% or less. Was used to produce an antireflection film 102 with an illuminance of 400 mW / cm ² and an irradiation amount of 600 mJ / cm ² .

[Example 1: Antireflection film 103]
The anti-reflection was performed in the same manner as in Comparative Example 2 except that the one-component / two-layer coating solution W-0 in the method for producing the anti-reflection film 102 shown in Comparative Example 2 was changed to the following one-component / two-layer coating solution W-1. A film 103 was produced.

(Preparation of hollow silica particle dispersion S-2)
Hollow silica particle fine particle sol A (isopropyl alcohol silica sol, average particle diameter 60 nm, silica concentration 20%), 30 parts by mass of Example I-1 of general formula [I], and diisopropoxyaluminum ethyl acetoacetate 1 After adding 0.5 parts by mass and 500 parts by mass of methyl ethyl ketone and mixing, 9 parts by mass of ion-exchanged water was added. The mixture was reacted at 60 ° C. for 8 hours and then cooled to room temperature, and 1.8 parts by mass of acetylacetone was added to obtain a dispersion. Then, while adding cyclohexanone so that the silica content is substantially constant, solvent replacement is performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a polymer having a polydialkylsiloxane group having a solid content concentration of 18.2% by adjusting the concentration. The surface-modified hollow silica particle dispersion S-2 was obtained.

(Preparation of 1-component 2-layer coating solution W-1)
2.7 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 1.2 parts by mass of pentaerythritol triacrylate, 8.7 parts by mass of the hollow silica particle dispersion S-2, light 0.2 parts by mass of a polymerization initiator (Irgacure 184), 84.3 parts by mass of methyl ethyl ketone and 2.9 parts by mass of cyclohexanone were added and stirred to prepare a one-part / two-layer coating liquid W-1.

(Coating method of 1 liquid 2 layer coating liquid W-1)
On the hard coat layer A, a one-component two-layer coating solution W-1 was applied and cured using a gravure coater in the same manner as in Comparative Example 1 so that the film thickness was 200 nm.

〔Evaluation methods〕
The antireflection films 101 to 103 were evaluated by the following methods.

(Partial distribution of particles)
The cured antireflection film sample was cut perpendicular to the thickness direction, and the cross section was observed with a transmission electron microscope to evaluate the thickness of each particle and the amount of different particles mixed in the cross-sectional image. The case where there is no unevenness in the thickness of each particle and there is no mixing of different kinds of particles, ○, the case where the unevenness of each particle thickness or the mixing amount of different kinds of particles is within 10%, Δ, the unevenness of each particle thickness or different kinds The case where the mixing amount of particles was larger than 10% and within 30% was evaluated as x, and the case where the unevenness of each particle thickness or the mixing amount of different kinds of particles was larger than 30% was evaluated as xx.

(Integral reflectance)
Using a spectrophotometer (manufactured by JASCO Corporation) with the back side of the antireflection film sample roughened with sandpaper and then treated with black ink to eliminate backside reflection. In the wavelength region of 380 to 780 nm, the integrated spectral reflectance at an incident angle of 5 ° was measured. The arithmetic average value of the integrated reflectance of 450 to 650 nm was used for the result.

(Steel wool scratch resistance)
After the antireflection film sample was placed at 25 ° C. and 60% RH for 1 hour, the surface of the sample was subjected to a rubbing test with a rubbing tester using steel wool as a rubbing material to evaluate scratch resistance. The back surface of the sample after the rubbing test was treated with black ink, and scratches on the rubbing portion of the sample surface were observed. Samples that do not have any scratches on the sample surface and cannot be seen by visual evaluation of reflected light ◎, those that can not be seen by visual evaluation of reflected light ○, those that can be seen by visual evaluation of reflected light, but are of little concern Δ, scratches were observed by visual evaluation of reflected light, and scratches were anxious.
Evaluation conditions Rub: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade No. 0000)
The sample was wound around the tip (1 cm × 1 cm) of a tester that was in contact with the sample and fixed with a band.
Travel distance (one way): 13cm
Rubbing speed: 13 cm / sec Load: 300 g / cm ²
Tip contact area: 1 cm x 1 cm
Number of rubs: 10 round trips

(Adhesion)
The surface of the antireflection film sample having the low refractive index layer is cut into 11 squares and 11 horizontal grids with a cutter knife, and a total of 100 square squares are engraved, made by Nitto Denko Corporation. The polyester adhesive tape (NO. 31B) was pressed and the adhesion test was repeated 5 times at the same place. The degree of peeling was evaluated according to the following four levels.
A: No peeling was observed in 100 squares.
○: Within 100 squares, peeling was observed within 2 squares.
(Triangle | delta): The thing by which peeling was recognized in 100 squares is a thing of 3-10cm.
X: A thing in which peeling was recognized in 100 squares exceeded 10 squares.

As can be seen from Table 2, in Comparative Example 1, the production efficiency is low because each layer is sequentially applied by layer, but it can be seen that the particles are unevenly distributed by layer by sequential application. On the other hand, in Comparative Example 2, since the first and second coating layers are separated into two layers by one-layer coating, the production efficiency is high, but the uneven distribution of particles is poor and the integrated reflectance increases compared to Comparative Example 1. ing.
On the other hand, in Example 1, since the first and second coating layers are separated into two layers by one-layer coating, the production efficiency is high, and the uneven distribution of particles, the integral reflectance, and the scratch resistance are Comparative Example 1. As a result, the adhesion was excellent. The reason why the adhesion of the antireflection film 102 of Example 1 is excellent is considered to be that the interface bonding of the layers is good because two layers are separated by one-layer coating.

[Comparative Example 3: Antireflection film 201]
The antireflection film 201 was produced by changing the coating liquid B and the coating liquid C in the method for producing the antireflection film 101 shown in Comparative Example 1 to the coating liquid D and the coating liquid E.

(Preparation of coating solution D)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in 21.0 parts by mass of zirconium oxide fine particle sol (methyl ethyl ketone zirconium sol, average particle diameter 10 nm, zirconium oxide mass concentration 30%, manufactured by Sumitomo Osaka Cement Co., Ltd.) DPHA) 2.7 parts by mass, photopolymerization initiator (Irgacure 184) 0.1 parts by mass, methyl ethyl ketone 73.7 parts by mass and cyclohexanone 2.5 parts by mass were added and stirred to prepare coating solution D.

(Preparation of coating solution E)
2.2 parts by mass of pentaerythritol triacrylate, 15.8 parts by mass of the hollow silica particle dispersion S-1 (18.2%), 0.1 parts by mass of the photopolymerization initiator (Irgacure 184), and 78 of methyl ethyl ketone .9 parts by mass and 3 parts by mass of cyclohexanone were added and stirred to prepare coating solution E.

In the same manner as for the antireflection film 101, the hard coat layer A is applied and cured on the triacetylcellulose film using the hard coat layer coating liquid A, and then the coating liquid D and the coating liquid are sequentially applied on the hard coat layer A. A coating film was formed using E and cured.
When the cross section of the antireflection film 201 was observed with a transmission electron microscope, the coating film formed with the coating liquid D was 110 nm thick, and the coating film formed with the coating liquid E was 90 nm thick. At this time, the hollow silica particles are uniformly distributed at 90 nm at the upper part of the coating film, and the zirconium oxide particles are uniformly distributed at 110 nm at the lower part of the coating film. It could be confirmed.

[Comparative Example 4: Antireflection film 202]
The antireflection film 202 was produced by changing the coating liquids D and E in the production method of the antireflection film 201 to the following one-liquid / two-layer coating liquid W-2.

(Preparation of 1-component 2-layer coating solution W-2)
Zirconium oxide fine particle sol (zirconium oxide mass concentration 30%) 10.5 parts by mass, hollow silica particle dispersion S-1 8.7 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 1.3 parts by mass, 1.1 parts by mass of pentaerythritol triacrylate, 0.1 parts by mass of photopolymerization initiator (Irgacure 184), 75.7 parts by mass of methyl ethyl ketone, and 2.5 parts by mass of cyclohexanone are added. And stirred to prepare a one-component two-layer coating solution W-2.

(Coating method of 1 liquid 2 layer coating liquid W-2)
Similarly to the antireflection film 102, the one-component / two-layer coating solution W-2 was applied onto the hard coat layer A by using a gravure coater so that the film thickness was adjusted to 200 nm.
After coating, it is allowed to stand at 25 ° C. for 90 seconds, and then dried at 90 ° C. for 60 seconds. The UV curing condition is 240 W / cm air-cooled metal halide lamp while purging with nitrogen so that the oxygen concentration is 0.1 vol% or less. Was used to produce an antireflection film 202 with an illuminance of 400 mW / cm ² and an irradiation amount of 600 mJ / cm ² .

[Example 2: Antireflection film 203]
An antireflection film 203 was produced in the same manner except that the one-component / two-layer coating solution W-2 in the method for producing the antireflection film 202 was changed to the following one-component / two-layer coating solution W-3.

(Preparation of 1-component 2-layer coating solution W-3)
Zirconium oxide fine particle sol (zirconium oxide mass concentration 30%) 10.5 parts by mass, hollow silica particle dispersion S-2 8.7 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 1.3 parts by mass, 1.1 parts by mass of pentaerythritol triacrylate, 0.1 parts by mass of photopolymerization initiator (Irgacure 184), 75.7 parts by mass of methyl ethyl ketone, and 2.5 parts by mass of cyclohexanone are added. And stirred to prepare a one-component two-layer coating solution W-3.

  The obtained antireflection films 201 to 203 were evaluated in the same manner as the antireflection films 101 to 103. The evaluation results are shown in Table 3 below.

  As can be seen from Table 3, in Example 2, each layer was separated into two layers by one-layer coating, so that the production efficiency was high, and the uneven distribution of particles, the integral reflectance, and the scratch resistance were the same as in Comparative Example 3. There was also a result of excellent adhesion. In Comparative Example 4, since the uneven distribution of particles was poor, the integrated reflectance was high and the adhesion was poor.

  Antireflection films 301 to 304 were produced by the following method.

[Comparative Example 5: Antireflection film 301]
(Preparation of coating solution F)
(Preparation of aluminum-containing zinc oxide fine particle dispersion A-1)
Aluminum-containing zinc oxide fine particles (manufactured by Hakusuitec Co., Ltd., passet CK (trade name), primary particle size 30 nm), dispersant (manufactured by Enomoto Kasei Co., Ltd., PLAAD ED211 (trade name), high number average molecular weight 40,000 Molecular polycarboxylic acid amidoamine salt, solid content 50%) and methyl ethyl ketone were mixed in a blending amount of 30/3/67 (mass ratio). 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 33%. Also, 2 g of this dispersion was weighed into a magnetic crucible, pre-dried on a hot plate at 80 ° C. for 30 minutes, and baked in a muffle furnace at 750 ° C. for 1 hour. When calculated, it was 30%.
In a 50 ml plastic bottle of a paint shaker, 40 g of glass beads (manufactured by TOSHINRIKO, BZ-01, bead diameter 0.1 mm, volume of about 16 ml) and the above mixed solution (30 g) are dispersed for 8 hours, and aluminum-containing zinc oxide fine particles are dispersed. A liquid A-1 was obtained.

  21.0 parts by mass of the aluminum-containing zinc oxide fine particle dispersion A-1, 2.7 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), and 0 of the photopolymerization initiator (Irgacure 184) .1 part by mass, 73.7 parts by mass of methyl ethyl ketone and 2.5 parts by mass of cyclohexanone were added and stirred to prepare coating solution F.

(Synthesis of perfluoroolefin copolymer P-1)
Into a stainless steel autoclave with a stirrer of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 0.53 MPa (5.4 kg / cm ² ). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa (3.2 kg / cm ² ), the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer P-1.

  In the above structural formula, 50:50 represents a molar ratio.

(Preparation of 1-component 2-layer coating solution W-4)
Zirconium oxide fine particle sol (zirconium oxide mass concentration 30%) 10.5 parts by mass and hollow silica particle fine particle sol A 7.8 parts by mass, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 1.3 parts by mass, 0.3 parts by mass of pentaerythritol triacrylate, 0.9 parts by mass of perfluoroolefin copolymer P-1, 0.1 parts by mass of photopolymerization initiator (Irgacure 184), and methyl ethyl ketone After adding 76.6 parts by mass and 2.5 parts by mass of cyclohexanone and stirring, the mixture is filtered through a polypropylene filter having a pore size of 1 μm to obtain a one-part / two-layer coating liquid W-4 of a high refractive index layer and a low refractive index layer. Prepared.

(Coating method of 1 liquid 2 layer coating liquid W-4)
On a triacetyl cellulose film (TD80UF, manufactured by Fuji Film Co., Ltd., refractive index 1.48), the coating liquid A for the hard coat layer having the above composition is used, and then the coating liquid F is formed to a thickness of 60 nm using a gravure coater. It applied so that it might become. The drying and curing conditions of the hard coat layer are the same as those of the antireflection film 101, the drying condition of the coating solution F is 90 ° C. for 30 seconds, and the ultraviolet curing condition is nitrogen so that the oxygen concentration is 1.0% by volume or less. While purging, a 180 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiation amount of 400 mW / cm ² and an irradiation amount of 400 mJ / cm ² .
Thereafter, the one-component two-layer coating solution W-4 was applied so as to have a film thickness of 200 nm. After coating, the coating solution was allowed to stand at 25 ° C. for 90 seconds and then dried at 90 ° C. for 60 seconds. An anti-reflective film 301 having an irradiance of 400 mW / cm ² and an irradiation amount of 600 mJ / cm ² using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with a nitrogen purge. Was made.

[Comparative Example 6: Antireflection film 302]
(Preparation and application method of 1-component 2-layer coating solution W-5)
Zirconium oxide fine particle sol (zirconium oxide mass concentration 30%) 10.5 parts by mass and hollow silica particle dispersion S-1 8.7 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA ) 1.3 mass parts, pentaerythritol triacrylate 0.3 mass parts, perfluoroolefin copolymer P-1 0.9 mass parts, photopolymerization initiator (Irgacure 184) 0.1 mass parts, After adding 75.7 parts by mass of methyl ethyl ketone and 2.5 parts by mass of cyclohexanone, the mixture is stirred and then filtered through a polypropylene filter having a pore size of 1 μm to form a one- and two-layer coating solution W having a high refractive index layer and a low refractive index layer. -5 was prepared.
An antireflection film 302 was produced in the same manner except that the prepared one-component / two-layer coating solution W-5 was used instead of the one-component / two-layer coating solution W-4 in the production method of the antireflection film 301.

[Example 3: Antireflection film 303]
(Preparation of hollow silica particle dispersion S-3)
After the hollow silica particle fine particle sol A was added to 500 parts by mass, 30 parts by mass of Example I-2 of the general formula [I], 500 parts by mass of methyl ethyl ketone and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. 9 parts of ion exchange water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added to obtain a dispersion. Then, while adding cyclohexanone so that the silica content is substantially constant, solvent replacement is performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a polymer having a polydialkylsiloxane group having a solid content concentration of 18.2% by adjusting the concentration. The hollow silica particle fine particle sol S-3 whose surface was modified with When the amount of IPA remaining in the obtained dispersion was analyzed by gas chromatography, it was 0.5% or less.

(Preparation and application method of 1-component 2-layer coating solution W-6)
In the same manner except that the obtained hollow silica particle dispersion S-3 is used in place of the hollow silica particle dispersion S-1 in the production method of the antireflection film 302, a one-component two-layer coating solution W-6 is prepared. Prepared.
An antireflection film 303 was produced in the same manner except that W-6 was used instead of W-5 in the production method of the antireflection film 302.

[Example 4: Antireflection film 304]
(Preparation of hollow silica particle dispersion S-4)
30 parts by mass of Example I-2 of the general formula [I], 10 parts by mass of γ-acryloyloxypropyltrimethoxysilane, 500 parts by mass of methyl ethyl ketone, and diisopropoxyaluminum ethyl acetoacetate 1 After adding 5 parts by mass and mixing, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone, and obtained the dispersion liquid. Then, while adding cyclohexanone so that the silica content is substantially constant, solvent replacement is performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a polymer having a polydialkylsiloxane group having a solid content concentration of 18.2% by adjusting the concentration. The surface-modified hollow silica particle fine particle sol S-4 was obtained. When the amount of IPA remaining in the obtained dispersion was analyzed by gas chromatography, it was 0.5% or less.

(Preparation and application method of 1-liquid 2-layer coating liquid W-7)
In the same manner except that the obtained hollow silica particle dispersion S-4 is used in place of the hollow silica particle dispersion S-1 in the production method of the antireflection film 302, a one-component two-layer coating solution W-7 is prepared. Prepared. An antireflection film 304 was produced in the same manner except that the one-component / two-layer coating solution W-7 prepared in place of the one-component / two-layer coating solution W-5 in the production method of the antireflection film 302 was used.

  The obtained antireflection films 301 to 304 were evaluated in the same manner as the antireflection film. The evaluation results are shown in Table 4 below.

  As can be seen from Table 4, the antireflection films 303 and 304 of the present invention have good uneven distribution of particles, low integrated reflectance, and good scratch resistance. In particular, the antireflection film 304 has better scratch resistance than the antireflection film 303, which is a polymer having a unit having a polydialkylsiloxane group of the present invention and a unit having a reactive group for surface modification of inorganic fine particles. It can be seen that this is due to the combined use of an organosilicon compound having a polymerizable functional group. In contrast, the antireflection films 301 and 302 increase the integrated reflectance by mixing particles. Further, it can be seen that the scratch resistance is inferior to the antireflection films 303 and 304.

[Comparative Example 7: Antireflection film 401]
An antireflection film 401 was produced by the following method.

(Preparation of coating solution G)
21.0 parts by mass of titanium oxide fine particle sol (average particle diameter 30 nm, methyl ethyl ketone dispersion with 30% titanium oxide concentration), 2.7 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), light A polymerization initiator (Irgacure 184) 0.1 part by mass, methyl ethyl ketone 73.7 parts by mass, and cyclohexanone 2.5 parts by mass were added and stirred to prepare a coating solution H.

(Preparation of silica particle dispersion SS-1)
Silica particle fine particle sol B (isopropyl alcohol silica sol, average particle diameter 45 nm, silica concentration 30%) 333 parts by mass, γ-acryloyloxypropyltrimethoxysilane 30.5 parts by mass, methyl ethyl ketone 333 parts by mass and diisopropoxyaluminum ethylacetate After adding 1.5 parts by mass of acetate and mixing, 9 parts by mass of ion-exchanged water was added. The mixture was reacted at 60 ° C. for 8 hours and then cooled to room temperature, and 1.8 parts by mass of acetylacetone was added to obtain a dispersion. Thereafter, while adding cyclohexanone so that the silica content is substantially constant, solvent replacement is performed by distillation under reduced pressure at a pressure of 30 Torr. Finally, organic compounds having a polymerizable functional group with a solid content concentration of 18.2% are obtained by adjusting the concentration. A hollow silica particle dispersion SS-1 whose surface was modified with a silicon compound was obtained.

(Preparation of coating solution H)
Pentaerythritol triacrylate 2.2 parts by mass, silica particle dispersion SS-1 (18.2%) 15.8 parts by mass, photopolymerization initiator (Irgacure 184) 0.1 parts by mass, methyl ethyl ketone 78.9 parts by mass, 3 parts by mass of cyclohexanone was added and stirred to prepare a coating solution. Thereafter, the obtained solution was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution H.

On the triacetyl cellulose film having a layer thickness of 80 μm, the coating liquid A for hard coat layer having the above composition was applied using a gravure coater, dried, and then cured by ultraviolet rays.
On the hard coat layer A, the coating liquid F, the coating liquid G, and the coating liquid H were sequentially applied using a gravure coater, dried, and UV-cured to produce an antireflection film 401.
When a cross section of the antireflection film 401 was observed with a transmission electron microscope, the layer formed with the coating liquid F was formed with a film thickness of 60 nm, and the layer formed with the coating liquid G was formed with a film thickness of 110 nm and the coating liquid H. The layer was 90 nm thick. At this time, the silica particles are uniformly distributed in 90 nm of the uppermost layer of the coating film formed by the coating liquid H, and the titanium oxide particles are uniformly distributed in the 110 nm film formed by the coating liquid G. It was confirmed that the particle thickness was uniform, non-uniformity, and there were no different kinds of particles.

[Example 5: Antireflection film 402]
An antireflection film 402 was produced in the same manner except that the coating solution G and coating solution H of the antireflection film 401 were changed to the following one-component / two-layer coating solution W-8.

(Preparation of silica particle dispersion SS-2)
Silica particle fine particle sol (isopropyl alcohol silica sol, average particle diameter 45 nm, silica concentration 30%), 333 parts by mass, Example I-1 of general formula [I] is 30 parts by mass, methyl ethyl ketone 333 parts by mass and diisopropoxyaluminum ethylacetate After adding 1.5 parts by mass of acetate and mixing, 9 parts by mass of ion-exchanged water was added. The mixture was reacted at 60 ° C. for 8 hours and then cooled to room temperature, and 1.8 parts by mass of acetylacetone was added to obtain a dispersion. Then, while adding cyclohexanone so that the silica content is substantially constant, solvent replacement is performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a polymer having a polydialkylsiloxane group having a solid content concentration of 18.2% by adjusting the concentration. The surface-modified hollow silica particle dispersion SS-2 was obtained.

(Preparation of 1-component 2-layer coating solution W-8)
10.5 parts by mass of titanium oxide fine particle sol (titanium dioxide mass concentration 30%) and 8.7 parts by mass of silica particle dispersion SS-2, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 1 .3 parts by weight, 0.3 parts by weight of pentaerythritol triacrylate, 0.9 parts by weight of perfluoroolefin copolymer P-1, 0.1 parts by weight of photopolymerization initiator (Irgacure 184), 75.7 parts by weight of methyl ethyl ketone And 2.5 parts by mass of cyclohexanone were added and stirred to prepare a one-component two-layer coating solution W-8.

(Coating method of 1 liquid 2 layer coating liquid W-8)
On the triacetyl cellulose film (TD80UF, manufactured by Fuji Film Co., Ltd., refractive index 1.48), the hard coat layer coating solution A having the above composition is applied, and then the previous coating solution F is formed into a film using a gravure coater. The coating was applied so that the thickness was 60 nm.
Thereafter, the one-component two-layer coating solution W-8 was applied so as to have a film thickness of 200 nm, and after coating, left at 25 ° C. for 90 seconds and then dried at 90 ° C. for 60 seconds, with an oxygen concentration of 0.1% by volume or less An anti-reflective film 402 with an irradiation intensity of 400 mW / cm ² and an irradiation amount of 600 mJ / cm ² using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with a nitrogen purge. Was made.

[Example 6: Antireflection film 403]
An antireflection film 403 was produced in the same manner except that the one-component / two-layer coating solution W-8 of the antireflection film 402 was changed to the following one-component / two-layer coating solution W-9.

(Preparation of silica particle dispersion SS-3)
Silica particle fine particle sol (isopropyl alcohol silica sol, average particle diameter 45 nm, silica concentration 30%) 333 parts by mass, Example I-1 of general formula [I] 30 parts by mass, γ-acryloyloxypropyltrimethoxysilane 10 parts by mass After adding and mixing 333 parts by mass of methyl ethyl ketone and 1.5 parts by mass of diisopropoxyaluminum ethyl acetoacetate, 9 parts by mass of ion-exchanged water was added. The mixture was reacted at 60 ° C. for 8 hours and then cooled to room temperature, and 1.8 parts by mass of acetylacetone was added to obtain a dispersion. Then, while adding cyclohexanone so that the silica content is substantially constant, solvent replacement is performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a polymer having a polydialkylsiloxane group having a solid content concentration of 18.2% by adjusting the concentration. And a hollow silica particle dispersion SS-3 surface-modified with an organosilicon compound having a polymerizable functional group was obtained.

(Preparation of 1-component 2-layer coating solution W-9)
10.5 parts by mass of titanium oxide fine particle sol (titanium dioxide mass concentration 30%) and 8.7 parts by mass of silica particle dispersion SS-3, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 1 .3 parts by weight, 0.3 parts by weight of pentaerythritol triacrylate, 0.9 parts by weight of perfluoroolefin copolymer P-1, 0.1 parts by weight of photopolymerization initiator (Irgacure 184), 75.7 parts by weight of methyl ethyl ketone And 2.5 parts by mass of cyclohexanone were added and stirred to prepare a one-component two-layer coating solution W-9.
An antireflection film 403 was produced in the same manner except that the one-component / two-layer coating solution W-8 of the antireflection film 402 was changed to the one-component / two-layer coating solution W-9.

  The antireflection films 401 to 403 were evaluated by the same method as described above. The obtained results are shown in Table 5 below.

  As can be seen from Table 5, the integrated reflectance of the antireflection films 402 and 403 is equivalent to that of the antireflection film 401, and it can be seen that two layers can be separated by one-layer coating. Further, the antireflection films 402 and 403 use different types of particles from the two types of inorganic fine particles used in Examples 1 to 4, and even in such a case, two layers can be separated by one-layer coating. I understand that there is. It can also be seen that the antireflection film 403 has better scratch resistance than the antireflection film 402 for the same reason as the antireflection film 304.

  From the results of these Examples and Comparative Examples, the coating composition of the present invention can form a high refractive index layer and a low refractive index layer in a single coating process, has high productivity and good optical properties. It is proved to be an antireflection film having good scratch resistance and excellent adhesion.

Claims (11)

  A coating composition comprising first inorganic fine particles surface-modified with a polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles, a curable binder, a solvent, and an initiator.   The coating composition according to claim 1, wherein the polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of inorganic fine particles has a polydialkylsiloxane group in the side chain. The coating composition according to claim 1 or 2, wherein the polymer having a unit having a polydialkylsiloxane group and a unit having a reactive group for modifying the surface of inorganic fine particles has a structure represented by the following general formula [I]. .

(In the formula, R 1 and R 2 represent a hydrogen atom or an alkyl group. L 2 represents a divalent linking group having 10 or less carbon atoms, n 2 represents 0 or 1, and R 11 to R 15 each independently represent 1 to 1 carbon atoms. 5 represents an alkyl group or an aryl group, q is an integer of 10 to 500, L represents a divalent linking group having 10 or less carbon atoms, m represents 0 or 1, and A represents a hydroxyl group or a hydrolysis. Represents a possible group, y represents a number 0 <y <100.)   The first inorganic fine particles are surface-modified with a polymer having a unit having the polydialkylsiloxane group and a unit having a reactive group for modifying the surface of the inorganic fine particles, and an organosilicon compound having a polymerizable functional group. The coating composition according to claim 1, which is a fine particle.   The coating composition according to claim 1, wherein the first inorganic fine particles are silica particles.   The coating composition according to claim 1, wherein the curable binder is a fluorine-containing curable compound.   Furthermore, 2nd inorganic fine particle is contained, The coating composition in any one of Claims 1-6 characterized by the above-mentioned.   The coating composition according to claim 7, wherein the second inorganic fine particles are fine particles of titanium oxide or zirconium oxide.   The manufacturing method of the laminated body which forms the multilayer structure of 2 or more layers by the process of apply | coating the coating composition in any one of Claims 1-8 on a base material, the process of drying, and the process of hardening.   The laminated body which has a particle | grain containing layer produced using the manufacturing method of Claim 9.   The laminate according to claim 10, wherein the laminate has an antireflection function.