JP2011133842A - Laminate for antireflection, method for manufacturing the same, and curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition can which form a cured film superior in a low refractive index and scratch resistance in one coating process; or to provide a laminate for antireflection, which has the cured film, and method for manufacturing thereof. <P>SOLUTION: The laminate 100 for antireflection includes a polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphoric ester group, and a sulfo group, and particles 22 having a refractive index of 1.40 or less on a base material 10. The laminate has the cured film 20 of the curable composition in which the total of hydroxyl group concentration, carboxyl group concentration, phosphoric ester group concentration, and sulfo group concentration in the whole polymerizable compound of 1 g is 2.0-15 mmol/g. The particles 22 are unevenly distributed on a reverse face side to a face brought into contact with the base material 10 of the cured film 20. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antireflection laminate, a method for producing the same, and a curable composition.

  In recent years, liquid crystal display devices have been used as display devices for televisions, personal computers, and the like. In such a liquid crystal display device, it has been proposed to use an antireflection film containing a low refractive index layer in order to prevent reflection of external light and improve image quality.

  An antireflection film used in a conventional liquid crystal display device has low refractive index properties and scratch resistance by applying a multilayer coating of a low refractive index layer and a hard coat layer. The antireflection film having such a multilayer structure can reduce the reflectance in the low refractive index layer, but has a problem that the productivity and cost are inferior because of the multilayer structure. Furthermore, the antireflection film produced by laminating the low refractive index layer and the hard coat layer has a problem that peeling easily occurs at the interface between the low refractive index layer and the hard coat layer.

  In order to solve such problems, a method of manufacturing an antireflection film has been proposed in which silica particles are modified with fluorine silane, and the silica particles are unevenly distributed in the liquid by surface energy, and then a cured film is formed. (For example, refer to Patent Document 1).

Japanese Patent No. 3861562

  However, the method described in Patent Document 1 has a problem that not only the uneven distribution of silica particles is insufficient and low refractive index is not obtained, but also the scratch resistance on the surface of the cured film is not excellent.

  Therefore, some embodiments according to the present invention provide a curable composition that can form a cured film excellent in low refractive index and scratch resistance by a single coating step by solving the above-described problems, or An antireflection laminate having the cured film and a method for producing the same are provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the antireflection laminate according to the present invention is:
On the substrate
A matrix having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate group and a sulfo group, and particles having a refractive index of 1.40 or less, Having a cured film having a total of group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration of 2.0 mmol / g to 15 mmol / g,
The particles are unevenly distributed on the surface side opposite to the surface in contact with the substrate in the cured film.

  According to such an antireflection laminate, the surface in contact with the substrate has a layer in which particles having a refractive index of 1.40 or less are present at a high density on the surface opposite to the surface in contact with the substrate. Since it has a layer substantially free of particles of 1.40 or less on the side, it can have both scratch resistance and low refractive index.

[Application Example 2]
In the antireflection laminate of Application Example 1,
The hydroxyl group concentration in 1 g of the matrix may be 2.0 mmol / g to 15 mmol / g.

[Application Example 3]
One aspect of the antireflection laminate according to the present invention is:
On the substrate
A polymerizable compound comprising a polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate ester group and a sulfo group, and particles having a refractive index of 1.40 or less, and A cured film of a curable composition having a total of 2.0 mmol / g to 15 mmol / g of hydroxyl group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration in 1 g;
The particles are unevenly distributed on the surface side opposite to the surface in contact with the substrate in the cured film.

  According to such an antireflection laminate, the surface in contact with the substrate has a layer in which particles having a refractive index of 1.40 or less are present at a high density on the surface opposite to the surface in contact with the substrate. Since it has a layer substantially free of particles of 1.40 or less on the side, it can have both scratch resistance and low refractive index.

[Application Example 4]
In the antireflection laminate of Application Example 3,
The curable composition may have a hydroxyl group concentration of 2.0 mmol / g to 15 mmol / g in 1 g of all polymerizable compounds.

[Application Example 5]
In the antireflection laminate of any one of Application Examples 1 to 4,
The particles can be hollow silica particles.

[Application Example 6]
One aspect of the method for producing an antireflection laminate according to the present invention is as follows.
A polymerizable compound comprising a polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate ester group and a sulfo group, and particles having a refractive index of 1.40 or less, and The step of curing after applying a curable composition having a total of 2.0 mmol / g to 15 mmol / g of hydroxyl group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration in 1 g to a substrate. It is characterized by including.

  According to such a method for producing an antireflection laminate, once the curable composition satisfying the above conditions is applied to a substrate and cured, the refractive index is on the side opposite to the surface in contact with the substrate. A layer in which particles of 1.40 or less are present at high density can be formed, and a layer in which particles of 1.40 or less are not substantially present can be formed on the side in contact with the substrate. As a result, an antireflection laminate having both scratch resistance and low refractive index can be produced.

[Application Example 7]
In the manufacturing method of the antireflection laminate of Application Example 6,
The curable composition may have a hydroxyl group concentration of 2.0 mmol / g to 15 mmol / g in 1 g of all polymerizable compounds.

[Application Example 8]
In the production method of the antireflection laminate of Application Example 6 or Application Example 7,
The particles can be hollow silica particles.

[Application Example 9]
One aspect of the curable composition according to the present invention is:
A polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate group, and a sulfo group, and particles having a refractive index of 1.40 or less,
The total of the hydroxyl group concentration, carboxyl group concentration, phosphate ester group concentration and sulfo group concentration in 1 g of all polymerizable compounds is 2.0 mmol / g to 15 mmol / g.

[Application Example 10]
In the curable composition of Application Example 9,
The hydroxyl group concentration in 1 g of all polymerizable compounds can be 2.0 mmol / g to 15 mmol / g.

[Application Example 11]
In the curable composition of Application Example 9 or Application Example 10,
The particles can be hollow silica particles.

  According to the method for producing an antireflection laminate according to the present invention, a specific curable composition is once applied to a substrate and cured, so that the refractive index is on the surface opposite to the surface in contact with the substrate. Can form a layer in which particles having a particle size of 1.40 or less are present at a high density, and a layer substantially free of particles having a particle size of 1.40 or less can be formed on the side in contact with the substrate. As a result, an antireflection laminate having both scratch resistance and low refractive index can be produced.

It is sectional drawing which showed typically the laminated body for reflection concerning this Embodiment.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included.

1. Curable composition The curable composition which concerns on this Embodiment is (A) The polymeric compound which has 1 or more types of polar groups selected from a hydroxyl group, a carboxyl group, a phosphate ester group, and a sulfo group, B) particles having a refractive index of 1.40 or less. Hereinafter, each component of the curable composition which concerns on this Embodiment is demonstrated in detail. In the following description, the materials (A) to (D) may be abbreviated as components (A) to (D), respectively.

1.1. (A) Polymerizable compound The curable composition which concerns on this Embodiment has (A) polymeric compound. The polymerizable compound (A) according to the present embodiment is a compound having a polymerizable functional group, and is preferably a compound having a (meth) acryloyl group, a vinyl group, or an epoxy group. Furthermore, the polymerizable compound (A) includes (A1) a polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate ester group, and a sulfo group. The curable composition which concerns on this Embodiment should just contain the polymeric compound which has the said (A1) polar group, and the polymeric compound (henceforth (A2) component which does not have a polar group other than this) May be included). One of the functions of the polymerizable compound having a polar group (A1) is to increase the film formability of the curable composition by causing uneven distribution of the component (B) described later when forming a cured film. Is mentioned.

  The component (A1) is not particularly limited as long as it has one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate ester group and a sulfo group, but preferably (meth) acrylic esters. is there.

  Examples of the polymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol di ( Examples include meth) acrylate, hexahydrophthalic acid epoxy acrylate, glycerin epoxy acrylate, 2,3-dihydroxypropyl (meth) acrylate, and 2-hydroxyethyl vinyl ether.

  Examples of the polymerizable compound having a carboxyl group include acrylic acid, acrylic acid dimer, succinic acid-modified dipentaerythritol pentaacrylate, 2,2,2-triacryloyloxymethyl ethyl succinic acid, 10-methacryloyloxydecamethylenemalon. Acid, 4-methacryloylaminosalicylic acid, 4-methacryloyloxyethyloxycarbonylphthalic acid, 4-methacryloyloxyethyloxycarbonylphthalic anhydride, N-methylacryloyl-N ′, N′-dicarboxymethyl 1,4 -Diaminobenzene, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-vinylbenzoic acid, 3,4,3 ', 4'-biphenyltetracarboxylic anhydride and 2-hydroxyethyl methacrylate : 2 adduct, 1 of pyromellitic anhydride and 2-hydroxyethyl methacrylate: 2 adducts.

Examples of the polymerizable compound having a phosphate ester group include phosphoric acid triacrylate, 2-methacryloyloxyethyl phosphoric acid, 2-methacryloyloxyethyl phenyl phosphoric acid, 10-methacryloyloxydecamethylene phosphoric acid, 4-vinylbenzyl phosphor Acid, pentaacryloyldipentaerythritol phosphoric acid, and the like.
Examples of the polymerizable compound having a sulfo group include 2-acrylamido-2-methylpropanesulfonic acid.

  As the component (A1), among the components exemplified above, pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, succinic acid-modified dipentaerythritol pentaacrylate, 2,2,2-triacryloyloxymethyl It preferably contains ethyl succinic acid, phosphoric acid triacrylate, or the like.

  These (A1) polymerizable compounds having a polar group may be used singly or in combination of two or more, and as described above, they may be used in combination with (A2) a polymerizable compound having no polar group. .

  The polymerizable compound having no polar group is used for the purpose of improving the film-forming property of the curable composition. Examples of the polymerizable compound (A2) having no polar group include a polyfunctional (meth) acrylic ester compound, a polyfunctional vinyl compound, a polyfunctional epoxy compound, and an alkoxymethylamine compound. Acrylic ester compounds are preferred. (Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanate Nurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate Rate, and the like. Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and the like. As epoxy compounds, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, etc. Is mentioned. Examples of the alkoxymethylamine compound include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like.

  In the curable composition according to the present embodiment, the polar group concentration in 1 g of the total polymerizable compound is 2.0 mmol / total of hydroxyl group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration. It is necessary to be in the range of g to 15 mmol / g.

  When the polar group concentration in 1 g of the total polymerizable compound satisfies the above range, when the curable composition according to the present embodiment is applied on the substrate, the mutual relationship between the polar group of the component (A1) and the substrate Due to the action, the component (A1) shifts in the surface direction in contact with the substrate. It is considered that the component (B) described later is unevenly distributed on the surface opposite to the surface in contact with the substrate. By curing the curable composition in such a state, a cured film in which the component (B) is unevenly distributed can be formed on the surface opposite to the surface in contact with the substrate. Such a cured film has an excellent antireflection function because the component (B) is unevenly distributed on the surface of the cured film. When the polar group concentration in 1 g of all polymerizable compounds does not satisfy the above range, the component (B) cannot be unevenly distributed on the surface of the cured film, and the antireflection function of the cured film is impaired.

  Content of (A) component in the curable composition which concerns on this Embodiment is in the range of 60-99.5 mass% when the sum total of the component except a solvent is 100 mass%, and is 70-99. It is preferably in the range of mass%, more preferably in the range of 80 to 98 mass%. By blending component (A) in the above range, not only can a cured film having high hardness be obtained, but component (B) is unevenly distributed on the surface opposite to the surface in contact with the substrate. It becomes easy to make.

1.2. (B) Particles The curable composition according to the present embodiment contains (B) particles having a refractive index of 1.40 or less. When such particles are unevenly distributed on the surface of the cured film, a low refractive index layer can be formed, and the function as an antireflection film can be imparted to the cured film. In addition, since the particles are unevenly distributed on the surface of the cured film, the effects of improving the hardness of the surface of the cured film and reducing the curl are also expected.

  The particles are not particularly limited as long as the refractive index is 1.40 or less, and examples thereof include hollow silica particles and metal fluoride particles. Among these, hollow silica particles mainly composed of silica are preferable. Since the hollow silica particles have cavities inside, the refractive index can be further reduced as compared with the solid particles.

  The refractive index of the particles is 1.40 or less, preferably 1.35 or less, more preferably 1.30 or less. The reason for setting the refractive index to 1.40 or less is that a cured film having excellent antireflection properties cannot be obtained even if particles having a refractive index exceeding 1.40 are added. The antireflection performance is preferably as low as possible with a refractive index of 1.00. However, when hollow particles are used, the strength of the cured film and scratch resistance are reduced because the strength of the particles decreases as the refractive index decreases. The nature is also reduced. Therefore, the lower limit of the refractive index is preferably 1.20.

  The “refractive index” in this specification refers to the refractive index of Na-D line (wavelength 589 nm) at 25 ° C. In the present specification, “refractive index of particles” means that a composition in which the content of particles in a solid content is 1% by mass, 10% by mass, and 20% by mass is formed in the same matrix, according to JIS K7105. The refractive index at the Na-D line at 25 ° C. is measured, and the particle content is 100% by mass calculated by the calibration curve method.

  The number average particle diameter of the particles measured with a transmission electron microscope is preferably 1 to 100 nm, more preferably 5 to 60 nm. The shape of the particles is not limited to a spherical shape, and may be an irregular shape.

  Examples of commercially available hollow silica particles include “JX1008SIV” manufactured by JGC Catalysts & Chemicals Co., Ltd. (number average particle diameter 50 nm, solid content 20% by mass, isopropyl alcohol solvent obtained with a transmission electron microscope), “JX1009SIV” ( And a number average particle diameter of 50 nm, a solid content of 20% by mass, and a methyl isobutyl ketone solvent) obtained with a transmission electron microscope.

  The hollow silica particles used in the present embodiment may be modified with a particle modifier. Examples of the particle modifier include compounds having a polymerizable unsaturated group and a hydrolyzable silyl group (hereinafter also referred to as “polymerizable particle modifier”). Examples of the polymerizable unsaturated group of the polymerizable particle modifier include a vinyl group and a (meth) acryloyl group. The hydrolyzable silyl group is a group that reacts with water to produce a silanol group (Si—OH). For example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups on silicon. A group, an alkoxyl group such as an n-butoxy group, an aryloxy group, an acetoxy group, an amino group, or a halogen atom is bonded.

  As the polymerizable particle modifier used in the present embodiment, a commercially available product such as methacryloyloxypropyltrimethoxysilane can be used, for example, a compound described in International Publication No. WO97 / 12942 is used. You can also.

  Further, as the particle modifier, a compound having a hydrolyzable silyl group containing fluorine (hereinafter, also referred to as “fluorine-containing particle modifier”) can be used. By using the fluorine-containing particle modifier, it is possible to efficiently distribute the hollow silica particles. Commercially available products such as tridecafluorooctyltrimethoxysilane can be used as the fluorine-containing particle modifier used in the present embodiment.

  Furthermore, a particle modifier having an alkyl group and a particle modifier having a silicone chain can be used in the same manner as the fluorine-containing particle modifier.

  The above various particle modifiers may be used alone or in combination of two or more.

  In order to modify the hollow silica particles used in the present embodiment, the hollow silica particles and the particle modifier may be mixed and hydrolyzed to bond them together. The ratio of the organic polymer component, that is, the hydrolyzate and condensate of hydrolyzable silane, in the obtained reactive hollow silica particles is usually the weight loss when the dry powder is completely burned in air. The constant value of can be determined, for example, by thermogravimetric analysis from room temperature to usually 800 ° C. in air.

  The binding amount of the particle modifier to the reactive hollow silica particles is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, based on 100% by mass of the modified hollow silica particles. Especially preferably, it is 1-20 mass%. By setting the amount of the particle modifier to react with the hollow silica particles in the above range, not only can the dispersibility of the hollow silica particles in the composition be improved, but also the transparency and scratch resistance of the resulting cured product can be improved. We can expect improvement effect.

  In the curable composition which concerns on this Embodiment, content of (B) component can be suitably adjusted according to the film thickness of the cured film to form. For example, when the thickness of the cured film is 10 μm, when the total of the components excluding the solvent is 100% by mass, preferably 0.4 to 1.2% by mass, more preferably 0.5 to 1% by mass. Within range. For example, when the thickness of the cured film is 7 μm, it is preferably 0.6 to 1.8% by mass, more preferably 0.7 to 1.5% by mass, and preferably when the thickness of the cured film is 3 μm. Is in the range of 1.2 to 4 mass%, more preferably 1.5 to 3 mass%. When the content of the component (B) is less than the above range, it may be impossible to form a layer (low refractive index layer) in which the component (B) that exhibits antireflection properties exists at a high density. On the other hand, if the content of the component (B) exceeds the above range, the thickness of the layer (low refractive index layer) in which the component (B) that exhibits antireflection properties is present at a high density becomes too large, and reflection occurs. The rate reduction effect may not appear.

1.3. (C) Polymerization initiator The curable composition according to the present embodiment may contain (C) a polymerization initiator. As such (C) polymerization initiator, for example, when it contains (meth) acrylic ester compound and / or vinyl compound as component (A), it is a compound (thermal radical polymerization) that generates active radical species thermally. Initiators) and general-purpose products such as compounds (radiation (light) radical polymerization initiators) that generate active radical species upon irradiation with radiation (light). Among these, a radiation (light) radical polymerization initiator is preferable.

  The radiation (photo) radical polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxy Benzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

  Examples of commercially available radiation (photo) radical polymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur, manufactured by Ciba Japan Co., Ltd. 1116, 1173, BASF's Lucillin TPO, 8893UCB's Uvekrill P36, Lamberti's Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, and the like.

  The thermal radical polymerization initiator is not particularly limited as long as it is decomposed by heating to generate radicals to initiate polymerization, and examples thereof include peroxides and azo compounds. Specific examples include: Examples include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile.

  In addition, as the polymerization initiator (C), when an epoxy compound and / or an alkoxymethylamine compound is contained as the component (A), an acidic compound and a compound that generates an acid by radiation (light) irradiation (radiation (light And general-purpose products such as acid generators).

  As the radiation (photo) acid generator, compounds such as triarylsulfonium salts and diaryliodonium salts can be used. Examples of commercially available radiation (light) acid generators include CPI-100P and 101A manufactured by San Apro.

  In the curable composition according to the present embodiment, the content of the (C) polymerization initiator used as necessary is preferably 0.01 when the total of the components excluding the solvent is 100% by mass. -20 mass%, More preferably, it exists in the range of 0.1-10 mass%. If it is less than 0.01% by mass, the hardness of the cured product may be insufficient, and if it exceeds 20% by mass, the hardness of the coating film may be impaired.

1.4. (D) Solvent The curable composition according to the present embodiment can be used after being diluted with (D) a solvent in order to adjust the thickness of the coating film. For example, the viscosity when the curable composition according to the present embodiment is used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., preferably 0.5 to 10, 000 mPa · sec / 25 ° C.

  (D) Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N -Amides such as methylpyrrolidone.

  In the curable composition which concerns on this Embodiment, content of (D) solvent used as needed is 50-10,000 when the sum total of the component except (D) solvent is 100 mass parts. It is preferably within the range of parts by mass. The content of the solvent can be appropriately determined in consideration of the coating film thickness, the viscosity of the curable composition, and the like.

1.5. Other Additives The curable composition according to the present embodiment includes, as necessary, a particle dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, an antiaging agent, and a thermal polymerization inhibitor. , Colorants, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like. In addition, by using a compound containing a fluorine atom and / or a compound having a siloxane chain as the exemplified particle dispersant, it is possible to promote uneven distribution of the hollow silica particles and to lower the refractive index of the coating film. it can.

1.6. Manufacturing method of curable composition The curable composition which concerns on this Embodiment is (A) polymeric compound, (B) particle | grains, (C) polymerization initiator, (D) solvent, and other addition as needed It can be prepared by adding each agent and mixing at room temperature or under heating conditions. Specifically, it can prepare using mixers, such as a mixer, a kneader, a ball mill, and a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition temperature of the thermal polymerization initiator added if necessary.

2. 2. Antireflection laminate and production method thereof 2.1. Manufacturing method of antireflection laminate The manufacturing method of the antireflection laminate according to the present embodiment includes (a) one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate group, and a sulfo group And a total of hydroxyl group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration in 1 g of all polymerizable compounds. A step of preparing a curable composition satisfying a relationship of 2.0 mmol / g to 15 mmol / g (hereinafter, also referred to as “step (a)”), and (b) applying the curable composition to a substrate. And a step of curing (hereinafter, also referred to as “step (b)”).

  According to such a method for producing an antireflection laminate, once the curable composition satisfying the above conditions is applied to a substrate and cured, the refractive index is on the side opposite to the surface in contact with the substrate. A layer in which particles of 1.40 or less are present at high density can be formed, and a layer in which particles of 1.40 or less are not substantially present can be formed on the side in contact with the substrate. As a result, an antireflection laminate having both scratch resistance and low refractive index can be produced. Hereinafter, it demonstrates for every process.

2.1.1. Step (a)
Step (a) is a step of preparing the curable composition described above. Since the structure and manufacturing method of such a curable composition are as described above, detailed description thereof will be omitted.

2.1.2. Step (b)
Step (b) is a step in which the curable composition prepared in step (a) is applied to a substrate and then cured.

  The method for applying the curable composition prepared in step (a) to the substrate is not particularly limited. For example, bar coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip Known methods such as coating, die coating, dip coating, offset printing, flexographic printing, and screen printing can be used.

The curing conditions of the curable composition are not particularly limited, but the curable composition described above is applied to various substrates, for example, a triacetyl cellulose resin substrate, a polyethylene terephthalate substrate, and the like, and cured. be able to. Specifically, after applying the curable composition and preferably drying the volatile component at 0 to 200 ° C., the antireflection laminate is formed by performing a curing treatment with radiation and / or heat. Can do. A preferable condition for curing with heat is 20 to 150 ° C., and is performed in a range of 10 seconds to 24 hours. When curing with radiation, it is preferable to use ultraviolet rays or electron beams. Irradiation light amount of the ultraviolet rays is preferably 0.01 to 10 J / cm ^2, more preferably 0.1~2J / cm ^2. Moreover, the irradiation conditions of an electron beam are a pressurization voltage of 10-300 kV, an electron density of 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount of 1-10 Mrad.

2.2. Anti-reflection laminate The anti-reflection laminate according to the present embodiment is produced by the above-described anti-reflection laminate production method. FIG. 1 is a cross-sectional view schematically showing the antireflection laminate according to the present embodiment. As shown in FIG. 1, in the antireflection laminate 100 according to the present embodiment, a cured film 20 obtained by curing the curable composition described above is formed on a base material 10, and the cured film 20 Among them, a hard coat layer 24 substantially free of particles 22 is formed on the surface side in contact with the substrate 10, and the particles 22 exist in high density on the surface side opposite to the surface in contact with the substrate 10. A low refractive index layer 26 is formed. Of the cured film 20, the part other than the particles (hereinafter also referred to as “matrix”) is obtained by curing other than the component (B) of the curable composition, and the hydroxyl group concentration, carboxyl group in the matrix 1g. The total of the concentration, phosphate group concentration and sulfo group concentration is preferably 2.0 mmol / g to 15 mmol / g. Hereinafter, each layer of the antireflection laminate according to the present embodiment will be described.

2.2.1. Although the kind of base material 10 used for the laminated body for antireflection which concerns on this Embodiment is not specifically limited, For example, triacetyl cellulose resin, polyethylene terephthalate resin, polycarbonate resin, polyester resin, acrylic type Resin, glass, etc. are mentioned. Among these, a substrate made of a triacetyl cellulose resin or a polyethylene terephthalate resin is preferable. By setting it as the laminated body for reflection prevention containing these base materials, it becomes easy to attract the (A) component contained in the curable composition mentioned above to a base material. In particular, when the base material is a triacetyl cellulose resin and 2-hydroxyethyl (meth) acrylate is contained as the component (A), such an effect is remarkably exhibited. Thereby, the low refractive index layer 26 in which the particles 22 are present at a high density can be formed on the surface opposite to the surface in contact with the substrate.

  In addition, by forming an antireflection laminate including these base materials, a wide range of hard coat and / or antireflection such as a color filter in a camera lens unit, a television (CRT) screen display unit, or a liquid crystal display device. In the field of use of the film, excellent scratch resistance and antireflection effect can be obtained.

2.2.2. Hard Coat Layer The hard coat layer 24 is composed of a layer in which the particles 22 are not substantially present in the cured film 20 having a two-layer structure obtained by curing the curable composition described above.

  Although the thickness of the hard-coat layer 24 is not specifically limited, Preferably it is 1-50 micrometers, More preferably, it is 1-10 micrometers. If the thickness of the hard coat layer 24 is less than 1 μm, the adhesion to the substrate 10 may not be improved. On the other hand, if it exceeds 50 μm, it may be difficult to form a homogeneous film. Because there is.

2.2.3. Low Refractive Index Layer The low refractive index layer 26 is composed of a layer in which particles 22 are present at a high density in the cured film 20 having a two-layer structure obtained by curing the curable composition described above.

  The thickness of the low refractive index layer 26 is not particularly limited, but is preferably 50 to 200 nm, more preferably 60 to 150 nm, and particularly preferably 80 to 120 nm. This is because if the thickness of the low refractive index layer 26 is less than 50 nm, a sufficient antireflection effect may not be obtained, whereas if it exceeds 200 nm, the antireflection effect may be reduced.

  The refractive index difference between the hard coat layer 24 and the low-refractive index layer 26 in the antireflection laminate 100 according to the present embodiment is preferably set to a value of 0.05 or more. This is because if the difference in refractive index between the hard coat layer 24 and the low refractive index layer 26 is less than 0.05, a synergistic effect in these antireflection films cannot be obtained, and the antireflection effect is lowered. Because there is a case to do.

3. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

3.1. Example 1
3.1.1. Production of curable composition In a container shielded from ultraviolet rays, hollow silica particles (trade name “JX-1009SIV”, 20 mass% methyl isobutyl ketone sol, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 5 mass parts (1 mass as solid content) Part), glycerin epoxy acrylate (trade name “Denacol DA314”, manufactured by Nagase ChemteX Corporation), 96 parts by mass, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one ( Trade name “Irgacure (registered trademark) 907”, manufactured by Ciba Japan Co., Ltd. 3 parts by mass, Silaplane FM0725 (manufactured by Chisso Corporation) 0.1 part by mass, and methyl isobutyl ketone (abbreviation of “MIBK” in the table) A suitable solution was obtained by adding a suitable amount of the solution and stirring at room temperature for 2 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 30 minutes, weighed, and the solid content was determined to be 50% by mass.

3.1.2. Preparation of Cured Film Sample The solution obtained in “3.1.1. Production of curable composition” was placed on a triacetyl cellulose (TAC) film (trade name “TDY-80UL”, manufactured by Fuji Film Co., Ltd.). It applied so that the whole cured film thickness might be set to about 7 micrometers using the bar coater, and it hardened | cured using the high pressure mercury lamp (300mJ / cm < ² >) under nitrogen flow after drying for 2 minutes at 80 degreeC. In addition, application | coating was performed so that a coating film might be formed in the inner surface of the film wound by roll shape.

3.2. Examples 2-13, Comparative Examples 1-4
A curable composition was produced in the same manner as in Example 1 except that the components shown in Tables 2 to 3 were blended in the compositions shown in Tables 2 to 3, and a cured film sample was obtained. Table 1 summarizes the types of polymerizable compounds, trade names, types of polar groups, and polar group concentrations.

  The particle “B-1” used in Example 13 was synthesized as follows. Hollow silica particles (trade name “JX-1009SIV”, methyl isobutyl ketone sol, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 90.9 parts by mass (solid content concentration: 20 parts by mass), tridecafluorooctyltrimethoxysilane (GE Toshiba Silicone) Co., Ltd.) 1 part by mass, 0.1 part by mass of isopropanol and 0.05 part by mass of ion-exchanged water were stirred at 80 ° C. for 3 hours, and then 0.7 part by mass of methyl orthoformate was added. A colorless transparent particle dispersion B-1 was obtained by heating and stirring at the same temperature for 1 hour. After weighing 2 g of B-1 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 22.5% by mass.

3.3. Evaluation test The characteristics of the curable compositions and cured films obtained in Examples and Comparative Examples were evaluated for the following items. The results are also shown in Tables 2 to 3.

3.3.1. Reflectance The back surface of the obtained cured film was painted with black spray, and a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, manufactured by Hitachi, Ltd.) was used. The reflectance in the wavelength range of 340 to 700 nm was measured from the substrate side and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and the reflectance of light at a wavelength of 550 nm is expressed. 2 to Table 3 together. If the reflectance is less than 3.0%, it can be determined that the reflectance is low.

3.3.2. Scratch resistance (steel wool resistance test)
The obtained cured film is attached with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded. Scratching was repeated 10 times under the condition of 200 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The evaluation criteria are as follows.
AA: No damage occurs on the cured film.
A: Peeling of the cured film and occurrence of scratches are hardly observed, or slight thin scratches are observed on the cured film.
B: A streak is recognized on the entire surface of the cured film.
C: Separation of the cured film occurs.

3.3.3. Pencil hardness Based on "JIS K5600-5-4", the obtained cured film was fixed on a glass substrate and evaluated.

3.4. Evaluation results From the results of Table 2, in the cured films obtained by curing the curable compositions of Examples 1 to 13 in which the polar group concentration in the total polymerizable compound satisfies the above conditions, the reflectance is less than 3%. It was found to have antireflection properties. Moreover, it turned out that it is excellent also in abrasion resistance from the result of steel wool resistance.

  On the other hand, from the results of Table 3, in the cured film obtained by curing the curable compositions of Comparative Examples 1 to 4 in which the polar group concentration in the total polymerizable compound does not satisfy the above conditions, the scratch resistance is improved. Was excellent, but the reflectivity exceeded 3%, indicating that the reflectivity was inferior.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 10 ... Base material, 20 ... Cured film, 22 ... Particle | grains, 24 ... Hard-coat layer, 26 ... Low refractive index layer, 100 ... Laminated body for reflection prevention

Claims (12)

On the substrate
A matrix having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate group and a sulfo group, and particles having a refractive index of 1.40 or less, Having a cured film having a total of group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration of 2.0 mmol / g to 15 mmol / g,
The laminate for antireflection, in which the particles are unevenly distributed on the surface side opposite to the surface in contact with the substrate in the cured film. In claim 1,
The laminated body for antireflection whose hydroxyl group density | concentration in the said matrix 1g is 2.0 mmol / g-15 mmol / g. On the substrate
A polymerizable compound comprising a polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate ester group and a sulfo group, and particles having a refractive index of 1.40 or less, and A cured film of a curable composition having a total of 2.0 mmol / g to 15 mmol / g of hydroxyl group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration in 1 g;
The laminate for antireflection, in which the particles are unevenly distributed on the surface side opposite to the surface in contact with the substrate in the cured film. In claim 3,
The said curable composition is a laminated body for antireflection whose hydroxyl group density | concentration in 1 g of all the polymeric compounds is 2.0 mmol / g-15 mmol / g. In any one of Claims 1 thru | or 4,
The laminate is an antireflection laminate, wherein the particles are hollow silica particles.   A polymerizable compound comprising a polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate ester group and a sulfo group, and particles having a refractive index of 1.40 or less, and The step of curing after applying a curable composition having a total of 2.0 mmol / g to 15 mmol / g of hydroxyl group concentration, carboxyl group concentration, phosphate group concentration and sulfo group concentration in 1 g to a substrate. A method for producing an antireflection laminate. In claim 6,
The said curable composition is a manufacturing method of the laminated body for antireflection whose hydroxyl group density | concentration in 1 g of all the polymeric compounds is 2.0 mmol / g-15 mmol / g. In claim 6 or claim 7,
The method for producing an antireflection laminate, wherein the particles are hollow silica particles. A polymerizable compound having one or more polar groups selected from a hydroxyl group, a carboxyl group, a phosphate group, and a sulfo group, and particles having a refractive index of 1.40 or less,
The curable composition whose sum total of the hydroxyl group density | concentration in 1 g of all polymeric compounds, a carboxyl group density | concentration, a phosphate ester group density | concentration, and a sulfo group density | concentration is 2.0 mmol / g-15 mmol / g. In claim 9,
The curable composition whose hydroxyl group density | concentration in 1 g of all the polymeric compounds is 2.0 mmol / g-15 mmol / g. In claim 9 or claim 10,
A curable composition containing 2-hydroxyethyl (meth) acrylate as the polymerizable compound. In any one of claims 9 to 11,
The curable composition, wherein the particles are hollow silica particles.

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