JP2013008025A - Laminate for antireflection and manufacturing method thereof, and curable composition - Google Patents

Abstract

An object of the present invention is to provide a curable composition capable of forming a cured film having excellent antireflection properties and scratch resistance in a single coating step, an antireflection laminate having the cured film, and a method for producing the same.
An antireflection laminate according to the present invention comprises a cellulose resin substrate, a polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) for dissolving the cellulose resin, hollow A cured film of a curable composition comprising silica particles (B) and solid particles (C) having a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. The cellulose resin base material and the cured film are laminated in contact with each other, and the (B) particles and the (C) particles are unevenly distributed on the opposite side of the cellulose resin base material in the cured film. It is characterized by.
[Selection] Figure 1

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 antireflection 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 for producing an antireflection film is 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).

JP 2001-316604 A

  However, the conventional method has a problem that the uneven distribution of silica particles is unstable and sufficient antireflection properties cannot be obtained, and the scratch resistance of the cured film surface is not excellent.

  Therefore, some embodiments according to the present invention provide a curable composition that can form a cured film having excellent antireflection properties and scratch resistance in a single coating step by solving the above-described problems, or An antireflection laminate having a 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:
A cellulose resin substrate;
A polymerizable compound (A) containing 5% by mass to 75% by mass of a polymerizable component (A1) for dissolving the cellulose resin, hollow silica particles (B), a refractive index of 1.50 or less, and a transmission electron microscope A cured film of a curable composition comprising solid particles (C) having a measured number average particle diameter of 100 nm or more, and
The cellulose resin substrate and the cured film are laminated in contact with each other, and the (B) particles and the (C) particles are unevenly distributed on the opposite side of the cellulose resin substrate in the cured film. And Here, the component that dissolves the cellulose resin is a cellulose resin film having a thickness of 18 μm cut into a size of 18 cm × 1 cm, soaked in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film at 80 ° C. The component whose mass reduction | decrease rate of the film when dried with a vacuum dryer for 24 hours is 1% or more is said.

[Application Example 2]
One aspect of the antireflection laminate according to the present invention is:
A cellulose resin substrate;
2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ), Hollow silica particles (B) and a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. And a cured film of the curable composition containing the solid particles (C) in that,
The cellulose resin substrate and the cured film are laminated in contact with each other, and the particles (B) and (C) are unevenly distributed on the opposite side of the cellulose resin substrate in the cured film. And

  Here, “the particles are unevenly distributed on the side opposite to the cellulose resin substrate in the cured film” means that the density of the particles on the side opposite to the cellulose resin substrate in the cured film is the cellulose in the cured film. It means that it is higher than the density of the particles on the resin substrate side. The relative size of the density of the particles on the cellulose resin substrate side and the opposite side of the cellulose resin substrate in the cured film can be determined, for example, by observing the cross section of the antireflection laminate with an electron microscope. . The larger the density difference between the cellulose resin substrate side and the opposite side, the better. The (B) particles and (C) particles are present at high density on the side opposite to the cellulose resin substrate in the cured film, and the (B) particles and (C) are present on the cellulose resin substrate side in the cured film. It is particularly preferred that the particles are substantially absent.

[Application Example 3]
In the antireflection laminate of Application Example 1 or Application Example 2,
The said cured film can contain the cellulose resin which forms the said cellulose resin base material.

[Application Example 4]
In the antireflection laminate of any one of Application Examples 1 to 3,
The (C) particles may be at least one selected from solid silica particles and solid magnesium fluoride particles.

[Application Example 5]
In the antireflection laminate of any one of Application Examples 1 to 4,
The blending ratio of the (B) particles and the (C) particles can be in the range of (B) particles: (C) particles = 80: 20 to 99.9: 0.1 on a mass basis.

[Application Example 6]
One aspect of the method for producing an antireflection laminate according to the present invention is as follows.
A polymerizable compound (A) containing 5% by mass to 75% by mass of a polymerizable component (A1) for dissolving the cellulose resin, hollow silica particles (B), a refractive index of 1.50 or less, and a transmission electron microscope It includes a step of applying a curable composition containing solid particles (C) having a measured number average particle diameter of 100 nm or more to a cellulose resin substrate and then curing the composition. Here, the component that dissolves the cellulose resin is a cellulose resin film having a thickness of 18 μm cut into a size of 18 cm × 1 cm, soaked in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film at 80 ° C. The component whose mass reduction | decrease rate of the film when dried with a vacuum dryer for 24 hours is 1% or more is said.

[Application Example 7]
One aspect of the antireflection laminate according to the present invention is:
2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ), Hollow silica particles (B) and a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. After a curable composition comprising the solid particles (C) was applied to a cellulose resin substrate in that, characterized in that it comprises a step of curing.

[Application Example 8]
In the production method of the antireflection laminate of Application Example 6 or Application Example 7,
The (C) particles may be at least one selected from solid silica particles and solid magnesium fluoride particles.

[Application Example 9]
In the method for manufacturing an antireflection laminate according to any one of Application Example 6 to Application Example 8,
The blending ratio of the (B) particles and the (C) particles can be in the range of (B) particles: (C) particles = 80: 20 to 99.9: 0.1 on a mass basis.

[Application Example 10]
One aspect of the curable composition according to the present invention is:
A curable composition used for producing an antireflection laminate,
A polymerizable compound (A) containing 5% by mass to 75% by mass of a polymerizable component (A1) for dissolving the cellulose resin, hollow silica particles (B), a refractive index of 1.50 or less, and a transmission electron microscope It is characterized by containing solid particles (C) having a measured number average particle diameter of 100 nm or more. Here, the component that dissolves the cellulose resin is a cellulose resin film having a thickness of 18 μm cut into a size of 18 cm × 1 cm, soaked in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film at 80 ° C. The component whose mass reduction | decrease rate of the film when dried with a vacuum dryer for 24 hours is 1% or more is said.

[Application Example 11]
One aspect of the curable composition according to the present invention is:
A curable composition used for producing an antireflection laminate,
2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ), Hollow silica particles (B) and a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. Characterized by containing a solid particle (C) within that.

[Application Example 12]
In the curable composition of Application Example 10 or Application Example 11,
The (C) particles may be at least one selected from solid silica particles and solid magnesium fluoride particles.

[Application Example 13]
In the curable composition of any one of Application Example 10 to Application Example 12,
The blending ratio of the (B) particles and the (C) particles can be in the range of (B) particles: (C) particles = 80: 20 to 99.9: 0.1 on a mass basis.

  According to the antireflection laminate of the present invention, a layer in which (B) particles and (C) particles are present at high density on the surface of the cured film opposite to the surface in contact with the cellulose resin substrate. (Hereinafter also referred to as “low refractive index layer”), and the layer that is substantially free of (B) particles and (C) particles on the surface side in contact with the cellulose resin substrate (hereinafter also referred to as “hard coat layer”). Therefore, both antireflection properties and scratch resistance can be provided. Further, (C) the particles are present at a high density on the surface opposite to the surface in contact with the cellulose resin substrate, whereby the strut effect is exhibited and the scratch resistance is remarkably improved. Furthermore, unevenness | corrugation can also be formed in the outermost surface of a laminated body by selecting suitably the particle size of (C) particle | grains, and the film thickness of the low refractive index layer formed. As a result, it is possible to obtain an antireflection laminate that exhibits both the antireflection effect of the low refractive index layer and the antiglare effect of the unevenness on the outermost surface.

  According to the method for producing an antireflection laminate according to the present invention, the surface side opposite to the surface in contact with the cellulose resin is obtained by once applying and curing the curable composition on the cellulose resin as the base material. (B) particles and (C) particles are formed in a layer having a high density, and (B) particles and (C) particles are substantially not formed on the side in contact with the cellulose resin. it can. Thereby, it is possible to produce an antireflection laminate having both antireflection properties and scratch resistance.

It is sectional drawing which showed typically the laminated body for reflection which concerns on this Embodiment. 4 is a SEM photograph obtained by photographing the cured film surface of the antireflection laminate according to Example 4;

  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 according to the present embodiment includes (A) a polymerizable compound, (B) hollow silica particles, (C) a refractive index of 1.50 or less, and a transmission electron microscope. Solid particles having a measured number average particle diameter of 100 nm or more. Hereinafter, each component of the curable composition which concerns on this Embodiment is demonstrated in detail. In the present specification, the materials (A) to (E) may be abbreviated as the components (A) to (E), respectively.

1.1. (A) Polymerizable compound The polymerizable compound (A) used in the present embodiment is not particularly limited as long as it is a polymerizable compound, but a compound having an ethylenically unsaturated group is preferred. The polymerizable compound (A) is a polymerizable compound that dissolves the cellulose resin of the substrate (hereinafter also referred to as “(A1) component”), and a polymerizable compound other than the (A1) component (hereinafter referred to as “(A2) component”). It can also be classified as follows.

1.1.1. (A1) Component The curable composition concerning this Embodiment contains the polymeric compound which melt | dissolves the cellulose resin of (A1) base material. In the present invention, “dissolving the cellulose resin of the base material” means that the mass of the cellulose resin film of the base material having a thickness of 80 μm cut into a size of 18 cm × 1 cm is a ₀ (g), and this film is a room temperature environment. When the mass of the film after dipping in 6 g of the polymerizable compound for 2 hours and drying the taken-out film with a vacuum dryer at 80 ° C. for 24 hours is defined as a ₁ (g), ((a ₀ -a ₁ ) / A ₀ ) The mass reduction rate of the film represented by × 100 is 1% or more.

  When the curable composition according to the present embodiment contains the component (A1), it causes the uneven distribution of the component (B) and (C) particles, which will be described later, when forming a film, resulting in high hardness and reflection. It is possible to obtain an antireflection laminate having both the prevention property and the scratch resistance.

  The mechanism by which (B) particles and (C) particles are unevenly distributed is not clear, but in the present embodiment, for example, it is considered as follows. When the curable composition concerning this Embodiment is apply | coated on a cellulose resin base material, since (A1) component melt | dissolves a cellulose resin, it elutes in the curable composition with which the cellulose resin was apply | coated. Here, since the (B) particles and the (C) particles are inferior in affinity with the eluted cellulose resin, if the cellulose resin concentration in the curable composition is lower, that is, unevenly distributed on the interface opposite to the substrate. Guessed.

  On the other hand, in the curable composition containing only the resin that does not dissolve the cellulose resin of the base material, the cellulose resin does not elute into the curable composition, so the particles (B) and (C) as described above Does not occur. As a result, sufficient antireflection properties and scratch resistance cannot be imparted to the antireflection laminate.

  (A1) As the polymerizable compound that dissolves the cellulose resin of the substrate, a compound having one polymerizable group such as an ethylenically unsaturated group (hereinafter referred to as “monofunctional compound”) or the like as exemplified below. Examples thereof include compounds having two or more polymerizable groups such as ethylenically unsaturated groups (hereinafter referred to as “polyfunctional compounds”). Examples of the monofunctional compound as the component (A1) include polymerizable compounds having a mass reduction rate of 10% or more, such as 2-hydroxyethyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, N-vinylformamide, and the like. A polymerizable compound such as γ-butyrolactone acrylate and N-vinylcaprolactam having a mass reduction rate of 5% or more and less than 10%; a polymerizability such as hydroxypropyl (meth) acrylate having a mass reduction rate of 2% or more and less than 5%; Compounds and the like. Other examples include glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4-hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, and the like. Examples of the polyfunctional compound (A1) include ethylene glycol diacrylate and diethylene glycol diacrylate. These components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

1.1.2. (A2) Component The polymerizable compound other than the component (A1) which is the component (A2) is used for the purpose of improving the film-forming property of the curable composition and the hardness and scratch resistance of the cured film. Examples of the component (A2) include monofunctional compounds and polyfunctional compounds other than the component (A1). Among these, a polyfunctional compound is preferable in that a cured film having excellent hardness and scratch resistance can be formed by forming a crosslinked structure. As the polyfunctional compound as the component (A2), for example, a polyfunctional (meth) acrylic ester compound, a polyfunctional vinyl compound, a polyfunctional epoxy compound, or a polyfunctional alkoxymethylamine compound is preferable. ) An acrylic ester compound and a polyfunctional vinyl compound are more preferable. Multifunctional (meth) acrylic ester compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol Examples include diacrylate, tetraethylene glycol diacrylate, fluorinated adamantyl diacrylate, and 1,4-butanediol diacrylate. Examples of the polyfunctional vinyl compound include divinylbenzene. Polyfunctional epoxy compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglyceride. A glycidyl ether etc. are mentioned. Examples of the polyfunctional alkoxymethylamine compound include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like.

  The component (A2) is a monofunctional (meth) acrylic ester compound (for example, isobornyl acrylate, butyl acrylate, etc.), a monofunctional vinyl compound, a monofunctional epoxy compound, etc. to such an extent that the effects of the present invention are not impaired. May be included.

  The ratio of the polyfunctional compound contained in the component (A2) is preferably 50 to 100% by mass and 80 to 100% by mass when the total amount of the component (A2) is 100% by mass. More preferred is 100% by mass.

  In the curable composition which concerns on this Embodiment, 80-99 mass% is preferable when content of (A) component makes the sum total of the component except (E) solvent 100 mass%, 90- 98 mass% is more preferable. When the content of the component (A) is in the above range, a cured film having high hardness, antireflection properties and scratch resistance can be formed.

  The content of the component (A1) in the polymerizable compound (A) is 5% by mass to 75% by mass, preferably 10% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass. % Or less. In the present specification, “component (A)” refers to the sum of component (A1) and component (A2). By blending the component (A1) in the above range, not only can a cured film having high hardness and high scratch resistance be obtained, but also (B) particles on the opposite side of the cellulose resin substrate in the cured film (C) It becomes easy to make particles unevenly distributed.

1.2. (B) Hollow silica particle The curable composition which concerns on this Embodiment contains (B) hollow silica particle. Here, the “hollow particle” means a particle having one or more cavities having no opening to the outside. (B) Since the hollow silica particle has a cavity inside, it can have a lower refractive index than the solid silica particle. When the particles (B) are unevenly distributed, a function as an antireflection film can be imparted to the cured film. In addition, the uneven distribution of the (B) particles is expected to improve the hardness of the cured film and reduce the curl.

(B) The refractive index of particle | grains becomes like this. Preferably it is 1.40 or less, More preferably, it is 1.35 or less, Most preferably, it is 1.30 or less. (B) By making the refractive index of particle | grains 1.40 or less, the cured film excellent in antireflection property can be obtained. Further, the lower the refractive index of the particle (B), the lower the refractive index of air being 1.00, the more preferable, but since the strength of the hollow silica particles decreases as the refractive index decreases, the hardness of the cured film And scratch resistance also decreases. Therefore, the lower limit of the refractive index of the (B) particles 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, the “refractive index of particles” refers to JIS K7105 (ISO489), in which 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. The refractive index at Na-D line at 25 ° C. is measured in accordance with the calibration curve method, and the particle content is 100% by mass.

  The number average particle diameter of the (B) particles measured with a transmission electron microscope is preferably 1 to 100 nm, and more preferably 5 to 60 nm. The shape of the particles is not limited to a spherical shape, and may be an irregular shape. In addition, the number average particle diameter of (B) particles means the number average diameter obtained by measuring or calculating 1000 (B) particles with a transmission electron microscope. (B) By making the number average particle diameter of the particles within the above range, it becomes possible to achieve both transparency and scratch resistance of the cured film.

  (B) What was manufactured by the well-known method can be used for particle | grains. In addition, as a commercially available product of (B) particles, for example, “JX1008SIV” (manufactured by JGC Catalysts & Chemicals Co., Ltd.) (number average particle diameter 50 nm, refractive index 1.29, solid content 20% by mass obtained with a transmission electron microscope, Isopropyl alcohol solvent), “JX1009SIV” (number average particle diameter 50 nm, refractive index 1.29, solid content 20 mass%, methyl isobutyl ketone solvent determined with a transmission electron microscope) and the like.

1.3. (C) Solid particles The curable composition according to the present embodiment has (C) a solid particle having a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. Containing. When the (C) particles are present on the surface of the cured film, a low refractive index layer can be formed together with the particles (B) described above, and the function as an antireflection film can be imparted to the cured film. In addition, (C) particles are unevenly distributed on the surface of the cured film, so that an effect of improving the scratch resistance of the surface of the cured film is also expected. Here, the “solid particles” mean particles having no cavities or pores, and examples thereof include particles produced without using a core or porogen that is finally removed.

  (C) The refractive index of the particles is 1.50 or less, preferably 1.45 or less. The reason why the refractive index is set to 1.50 or less is that when particles having a refractive index exceeding 1.50 are added, it becomes difficult to obtain a cured film having excellent antireflection properties.

  The number average particle diameter of the (C) particles measured with a transmission electron microscope is 100 nm or more, preferably 300 nm or more, particularly preferably 300 nm or more and 500 nm or less. In addition, the number average particle diameter of (C) particles refers to the number average diameter obtained by measuring or calculating 1000 (C) particles with a transmission electron microscope. (C) In the low refractive index layer having (B) particles and (C) particles formed on the side opposite to the cellulose resin substrate in the cured film, when the number average particle diameter of the particles is within the above range, (C) The scratch resistance is remarkably improved because the particles exhibit the support effect. The shape of the particles is not limited to a spherical shape, and may be an irregular shape.

(C) Although it will not specifically limit as long as the particle | grains satisfy | fill the conditions mentioned above, Specifically, a solid silica particle, a solid inorganic fluoride particle, etc. are mentioned. As a solid silica particle, a well-known thing can be used, for example, commercial items, such as brand name "SC1050-KJA" and "SC2050-KD" by Admatechs Co., Ltd., can be used. Solid inorganic fluoride particles include aluminum fluoride particles (refractive index 1.38), calcium fluoride particles (refractive index 1.23-1.45), lithium fluoride particles (refractive index 1.30). And magnesium fluoride particles (refractive index: 1.38 to 1.40). Among these, magnesium fluoride particles are preferable because they are easily available. As a commercial item of a magnesium fluoride particle, Nissan Chemical Industries Ltd. brand name "MFS-10P" etc. are mentioned.

  Further, when it is desired to provide the antiglare performance by forming irregularities on the outermost surface of the laminate, it is also possible to use particles that are normally used in antiglare films as (C) particles. For example, polymers such as styrene polymers, acrylonitrile-styrene copolymers, polycarbonate polymers, acrylic (co) polymers, ethylene (co) polymers, epoxy (co) polymers, melamine resins, silicone resins, etc. Examples thereof include inorganic particles such as particles, silica, alumina, zirconium, titanium, zinc, magnesium, and talc. The addition amount and particle size of these particles are appropriately selected depending on the required surface roughness and antiglare performance, but usually those having an average particle size of 100 nm to 5 μm determined by the dynamic scattering method are used. Preferably it is 100 nm-3 micrometers. A narrow particle size distribution is preferred. The addition amount is usually 3 to 40 parts by mass, preferably 5 to 30 parts by mass, and particularly preferably 10 to 25 parts by mass with respect to 100 parts by mass of the monomer component.

  Similarly, when it is desired to impart antiglare performance to the antireflection laminate according to the present invention, the antireflection function and the antiglare function as a whole of the laminate are not impaired in consideration of the blending amount and the refractive index difference with other components. If it is within the range, particles having a refractive index exceeding 1.50 can be further blended separately from the particles (C). Furthermore, the refractive index of the particles to be blended is preferably 1.60 or less, and more preferably 1.55 or less. The preferable material, particle diameter, and blending amount are the same as those of the particles (C) used when imparting the antiglare performance described above.

  One or both of (B) particles and (C) particles used in the present embodiment may be those whose surfaces have been modified with a surface modifier. Examples of the surface modifier include compounds having a polymerizable unsaturated group and a hydrolyzable silyl group (hereinafter also referred to as “polymerizable surface modifier”). Examples of the polymerizable unsaturated group of the polymerizable surface modifier include a vinyl group, a (meth) acryloyl group, and an epoxy group.

  As the polymerizable surface 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.

  However, in this specification, the polymerizable compound refers to the polymerizable compound (A), and the particles (B) and (C) having a polymerizable group by modification with a polymerizable surface modifier, etc. It is not included in the polymerizable compound.

  As the surface modifier, a compound having a hydrolyzable silyl group containing fluorine (hereinafter also referred to as “fluorine-containing surface modifier”) may be used. 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. By using the fluorine-containing surface modifier, the (B) particles and (C) particles can be unevenly distributed efficiently. Commercially available products such as tridecafluorooctyltrimethoxysilane can be used as the fluorine-containing surface modifier used in the present embodiment.

  Moreover, the surface modifier which has an alkyl group, and the surface modifier which has a silicone chain can also be used similarly to a fluorine-containing surface modifier.

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

  In order to make (B) particles and (C) particles used in the present embodiment into modified particles, both (B) particles and (C) particles and a surface modifier are mixed and hydrolyzed. Can be combined. The ratio of the organic polymer component, that is, the hydrolyzate and condensate of hydrolyzable silane, in the obtained modified particles is usually a constant value of weight loss% when the dry powder is completely burned in air. For example, it can be determined by thermogravimetric analysis from room temperature to usually 800 ° C.

  The binding amount of the surface modifier to the modified particles is preferably 0.01 to 40% by mass, more preferably 0.1 to 40% by mass, with the modified (B) particles or (C) particles being 100% by mass. 30% by mass, particularly preferably 1 to 20% by mass. By making the amount of the surface modifying agent reacted with the (B) particles and (C) particles within the above range, not only can the dispersibility of the (B) particles and (C) particles in the composition be improved. Further, the effect of enhancing the transparency and scratch resistance of the obtained cured film can be expected.

  In the curable composition according to the present embodiment, the total content of (B) particles and (C) particles can be adjusted as appropriate according to the thickness of the cured film to be formed, but the total of components excluding the solvent When the content is 100% by mass, the content is preferably 0.1 to 10% by mass. Specifically, since the (B) particles and the (C) particles are the main components of the low refractive index layer, the thickness of the layer formed by uneven distribution of the (B) component and the (C) component is 50 to What is necessary is just to mix | blend so that it may become the range of 200 nm. The specific blending amount is, for example, preferably 0.4 to 1.2% by mass, more preferably 0 when the total thickness of the components excluding the solvent is 100% by mass when the thickness of the cured film is 10 μm. Within the range of 5 to 1% by mass. When the film 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 when the film thickness of the cured film is 3 μm, preferably 1 .2-4% by mass, more preferably 1.5-3% by mass. A layer (low refractive index layer) in which (B) particles and (C) particles exhibit high antireflection properties when the total content of (B) particles and (C) particles is less than the above range (low refractive index layer) May not be formed. On the other hand, when the total content of (B) particles and (C) particles exceeds the above range, a layer (low refractive index layer) in which (B) particles and (C) particles exhibiting antireflection properties exist at high density ) Becomes too large, and the reflectance reduction effect may not be exhibited.

  The blending ratio of the (B) particles and (C) particles is preferably (B) particles: (C) particles = 80: 20 to 99.9: 0.1 (mass ratio). When the ratio of (C) particles to the total of (B) particles and (C) particles is 20% or more, the film thickness of the low refractive index layer cannot be controlled and sufficient antireflection performance may not be obtained. (C) If the proportion of particles is less than 0.1%, scratch resistance may not be improved. For the above reasons, (B) particles: (C) particles = 85: 15 to 99.8: 0.2 are more preferable, and 90:10 to 99.7: 0.3 are particularly preferable.

1.4. (D) Polymerization initiator The curable composition according to the present embodiment may contain (D) a polymerization initiator. As such (D) polymerization initiator, for example, when it contains (meth) acrylic ester compound and / or vinyl compound as component (A), a compound that thermally generates active radical species (thermal polymerization initiator) And general-purpose products such as compounds (radiation (light) radical polymerization initiators) that generate active radical species upon irradiation with radiation (light). In addition, when an epoxy compound and / or an alkoxymethylamine compound is contained as the component (A), general-purpose products such as an acidic compound and a compound (radiation (light) acid generator) that generates an acid by radiation (light) irradiation are used. Can be mentioned. Among these, a radiation (photo) 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.

Commercially available products of radiation (photo) radical polymerization initiators include, for example, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur, manufactured by BASF Japan Ltd. 1116, 1173, Lucirin TPO, 8893; Ubekril P36 manufactured by UCB; Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B manufactured by Lamberti.

  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.

  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 (D) polymerization initiator used as necessary is preferably 0.01 when the total of the components excluding the solvent is 100% by mass. It is in the range of ˜15% by mass, more preferably 0.1˜8% by mass. By blending in the above range, a cured product having higher hardness and scratch resistance can be obtained. In addition, (D) a polymerization initiator can also use multiple types of compounds together.

1.5. (E) Solvent The curable composition according to the present embodiment adjusts the thickness of the coating film (hereinafter referred to as “curable composition layer”) and the viscosity of the curable composition when applied to the cellulose resin substrate. In order to do so, it can be diluted with (E) solvent. For example, when the curable composition according to the present embodiment is used as an antireflection film or a coating material, the viscosity at 25 ° C. is usually 0.1 to 50,000 mPa · sec, preferably 0.5 to 10 1,000 mPa · s.

(E) Examples of the solvent include alcohols such as methanol, ethanol, propanol, 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 (E) solvent used as needed is 50-10,000 when the sum total of the component except (E) solvent is 100 mass parts. It is preferably within the range of parts by mass. (E) Content of a solvent can be suitably determined in consideration of a coating film thickness, a viscosity of a curable composition, and the like.

  In addition, you may select the solvent which melt | dissolves a cellulose resin as a part or all of (E) solvent used as needed in the curable composition which concerns on this Embodiment. Here, the solvent for dissolving the cellulose resin means that an 80 μm-thick cellulose resin film cut into a size of 18 cm × 1 cm is immersed in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film is 24 ° C. at 24 ° C. A component whose mass reduction rate of the film is 1% or more when dried in a vacuum drier for a period of time and is not included in the component (A1). Specific examples include cyclohexanone, acetone, methyl ethyl ketone, acetylacetone, diacetone alcohol, and the like. (E) By using a part or all of the solvent as a solvent that dissolves the cellulose resin, the cellulose resin can be eluted more efficiently, and the adhesion between the cured film and the substrate can be further increased. C) The uneven distribution of particles can be further increased. (E) The proportion of the solvent used for dissolving the cellulose resin can be appropriately determined according to the amount of (E) solvent used, the type of component (A1), and the amount used.

1.6. 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. Among these, by using a compound containing a fluorine atom or a compound having a siloxane chain as a particle dispersant, the uneven distribution of (B) particles and (C) particles is promoted and the refractive index of the coating film is lowered. be able to.

1.7. Manufacturing method of curable composition The curable composition which concerns on this Embodiment is (A) polymeric compound, (B) hollow silica particle, (C) solid particle, and (D) polymerization initiator as needed. , (E) A solvent and other additives can be added and mixed 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.

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) (A) a polymerizable compound, (B) hollow silica particles, and (C) a refractive index of 1. And (A1) the cellulose resin of the base material that occupies the polymerizable compound (A1) and has a number average particle diameter of 100 nm or more as measured with a transmission electron microscope. A step of preparing a curable composition having a polymerizable compound content of dissolving 5% by mass to 75% by mass (hereinafter also referred to as “step (a)”), and (b) the curable composition. Is applied to the cellulose resin substrate and then dried and cured (hereinafter also referred to as “step (b)”).

  According to such a method for producing an antireflection laminate, the curable composition is once applied to a cellulose resin as a base material and cured, whereby (B) particles and ( C) A cured film in which particles are unevenly distributed can be formed. Thereby, an antireflection laminate having both antireflection properties and scratch resistance 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 the curable composition are as described above, detailed description thereof is omitted.

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

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

  After coating by the above method, volatile components such as a solvent are dried. Specifically, the said curable composition is apply | coated on a cellulose resin base material, and a volatile component is dried at 0-200 degreeC, Preferably it is 20-150 degreeC, More preferably, it is 20-120 degreeC. If the temperature exceeds 200 ° C., the cellulose resin substrate may be deformed, or the binder component that contributes to the curing of the curable composition layer may volatilize to lower the strength. Examples of the drying method include a hot air type, a drum type, an infrared type, an induction heating type, and the like, and are appropriately determined depending on the size and thickness of the substrate. When heating with the hot air method, if the wind speed is too fast, the uneven distribution of the particles (B) and (C) and the appearance of the coating film may be impaired, so the wind speed of the hot air may be 20 m / sec or less. Preferably, it is 5 m / sec.

  When the curable composition prepared in step (a) is applied on a cellulose resin substrate, the component (A1) contained in the curable composition interacts with the cellulose resin contained in the cellulose resin substrate. And a cellulose resin may mix in a curable composition layer, or (A1) component may osmose | permeate a cellulose resin. Whether or not the cellulose resin is mixed in the curable composition layer is determined by, for example, measuring the obtained cured film with a Raman spectrometer and observing a peak of a specific functional group of the cellulose resin. Can be determined.

The curing conditions for the curable composition are not particularly limited. Specifically, the curable composition is applied on a cellulose resin substrate, preferably after drying volatile components at 0 to 200 ° C., and then subjected to curing treatment with radiation and / or heat for antireflection. A laminate can be formed. 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. 1 is a cross-sectional view schematically showing the antireflection laminate according to the present embodiment. 1 includes both (B) particles and (C) particles. As shown in FIG. 1, in the antireflection laminate 100 according to the present embodiment, a cured film 20 obtained by curing the above-described curable composition is formed on a cellulose resin substrate 10 that is a substrate. The density of the particles 22 on the side opposite to the cellulose resin substrate in the cured film 20 is higher than the density of the particles 22 on the cellulose resin substrate side in the cured film 20. That is, a region 26 (also referred to as “low refractive index layer 26”) in which the particles 22 exist at a relatively high density is formed on the opposite side of the cured film 20 from the cellulose resin substrate. A region 24 (also referred to as “hard coat layer 24”) in which the particles 22 are not substantially present is formed on the cellulose resin substrate side. The boundary between the region 24 and the region 26 is not necessarily clear, but the boundary is clear because most of the particles 22 in the cured film 20 gather in the region 26 and the region 24 does not substantially contain the particle 22. Preferably there is. Due to the uneven distribution of the particles 22 in the region 26, the refractive index of the region 26 becomes lower than the refractive index of the region 24. Thereby, the laminated body for antireflection excellent in antireflection property can be obtained. Further, when the region 24 contains a polyfunctional compound as the component (A1) or the component (A2), a cured film having a crosslinked structure is formed, so that an antireflection laminate having excellent hardness and scratch resistance is obtained. Can do.

  The antireflection laminate 100 may have another layer with a film thickness of 30 nm or less in contact with the side opposite to the cellulose resin substrate 10 in the region 26 as long as the antireflection performance is not affected. In addition, in this invention, a cured film means the film | membrane obtained by apply | coating and hardening the curable composition of the cured film 20, and there may be adjustment of a component in the process of application | coating and hardening.

  The reason why the particles 22 are unevenly distributed is not necessarily clear, but since the component (A1) dissolves the cellulose resin and the cellulose resin is eluted into the curable composition layer, the particles 22 having low affinity with the cellulose resin are present. It is presumed that the cellulose resin concentration in the curable composition layer is unevenly distributed on the low side (that is, the side opposite to the cellulose resin substrate in the curable composition layer). By curing the curable composition in such a state, the cured film 20 in which the particles 22 are unevenly distributed on the side opposite to the cellulose resin substrate in the cured film can be formed.

  On the other hand, in the curable composition containing only the polymerizable compound that does not dissolve the cellulose resin of the base material, since there is no interaction with the cellulose resin, (B) particles and (C) particles are unevenly distributed on the surface of the cured film. Cannot be performed, and the antireflection function of the cured film is impaired.

  Hereinafter, each layer of the antireflection laminate according to the present embodiment will be described.

2.2.1. Cellulose resin substrate The substrate used in the antireflection laminate according to the present embodiment is a cellulose resin substrate. By using a cellulose resin as a substrate, the component (A1) contained in the curable composition described above dissolves or swells the cellulose resin, whereby the low refractive index layer in which the particles 22 are present at a relatively high density. 26 can be formed. On the other hand, when a resin other than the cellulose resin is used as the base material, the above-described effects are not achieved. In the present embodiment, the cellulose resin base material may be a base material itself formed of a cellulose resin, or a base material having a cellulose resin layer on the surface of a base material such as polyethylene terephthalate or polycarbonate. . Here, examples of the cellulose resin that can be used as the substrate include triacetyl cellulose (TAC), diacetyl cellulose, and cellulose acetate butyrate.

  In addition, the antireflection laminate having a base material made of cellulose resin is used in a wide range of hard coats and / or reflections such as a protective film for a polarizer in a camera lens unit, a television (CRT) screen display unit, or a liquid crystal display device In the field of use of the anti-reflection 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 region that is formed on the cellulose resin substrate 10 side of the cured film 20 obtained by curing the above-described curable composition and in which the particles 22 are not substantially present.

  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 hardness may be insufficient. On the other hand, if the thickness exceeds 50 μm, it is difficult to form a homogeneous film or the curling of the laminate is increased. It may be difficult. When the hard coat layer is formed, the component (A1) dissolves the cellulose resin as described above. Therefore, the obtained hard coat layer 24 is a layer containing the cellulose resin in addition to the component (A).

2.2.3. Low Refractive Index Layer The low refractive index layer 26 is formed on the opposite side of the cellulose resin substrate 10 of the cured film 20 obtained by curing the curable composition described above, and the particles 22 are present at a relatively high density. It consists of areas to be.

  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. By setting the thickness of the low refractive index layer 26 within the above range, a sufficient antireflection effect can be obtained at wavelengths in the visible region.

  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. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

3.1. Example of production of surface-modified solid silica particles 3.1.1. Production of Particle Surface Modifier After adding dropwise over 22 hours at 50 ° C. with stirring 222 parts by mass of isophorone diisocyanate to a solution consisting of 221 parts by mass of mercaptopropyltrimethoxysilane and 1 part by mass of dibutyltin dilaurate in dry air. The mixture was heated and stirred at 70 ° C. for 3 hours. NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (consisting of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Of these, it is a hydroxyl group that is involved in the reaction. It is only pentaerythritol triacrylate.) After adding 549 parts by mass at 30 ° C. over 1 hour, the mixture is heated and stirred at 60 ° C. for 10 hours to obtain a particle modifier (Cb-1) containing a polymerizable unsaturated group. It was. As a result, 773 parts by mass of the particle modifier (Cb-1) was obtained, and 220 parts by mass of pentaerythritol tetraacrylate that was not involved in the reaction was mixed.

3.1.2. Production of surface-modified solid silica particles 8.4 parts of the particle modifier (Cb-1) obtained in the above-mentioned "Production of particle surface modifier", solid silica particles (manufactured by Nissan Chemical Industries, Ltd., trade name: IPA) -ST-ZL) isopropanol (IPA) sol (silica concentration 30%) 90.2 parts (solid content 27.1 parts), 0.1N sulfuric acid 0.03 parts and distilled water 0.1 parts, After stirring at 60 ° C. for 4 hours, 1.3 parts of orthoformate methyl ester was added, and further heated and stirred at the same temperature for 1 hour to obtain a cloudy dispersion of surface-modified solid silica particles (C-1). . 2 g of this particle dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, which was 36% by mass. The number average particle diameter measured using a transmission electron microscope was 100 nm.

3.2. Production Example of Curable Composition In a container shielded from ultraviolet rays, hollow silica particles (trade name “JX-1009SIV”, refractive index 1.29, methyl isobutyl ketone sol, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 4.5 parts by mass (0.9 parts by mass as a solid content), 0.3 parts by mass (0.1 parts by mass as a solid content) of surface-modified solid silica particles (C-1) produced in the above production example, 2-hydroxyethyl acrylate ( Product name "Light Ester HOA", manufactured by Kyoeisha Chemical Co., Ltd.) 26 parts by mass, pentaerythritol triacrylate (trade name "PET-30", manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass, 2-methyl-1 [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure (registered trademark) 907”, manufactured by BASF Japan Ltd.), 3 parts by mass, Silap Lane FM0725 (manufactured by Chisso Corporation) 0.1 parts by mass, and further, an appropriate amount of methyl isobutyl ketone was added and stirred at room temperature for 2 hours to obtain a uniform curable composition. 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.

3.3. Example 1 (Preparation of antireflection laminate)
The curable composition obtained in the above “3.2. Production of curable composition” was applied onto a triacetyl cellulose film using a bar coater so that the entire cured film thickness was about 7 μm, and 80 ° C. And dried for 2 minutes, and then cured using a high-pressure mercury lamp (300 mJ / cm ² ) under a nitrogen flow to obtain an antireflection laminate.

3.4. Examples 2-8, Comparative Examples 1-10
An antireflection laminate was obtained in the same manner as in Example 1 except that a curable composition containing the components shown in Tables 2 to 4 in the compositions shown in Tables 2 to 4 was used. In addition, in Table 2-Table 4, each component used as (C) particle | grains is as follows.
PIS-ZLST (INT-12A modified solid silica particles produced in “3.1. Example of production of surface-modified solid silica particles” above, number average particle diameter 100 nm)
SC1050-KJA (trade name, manufactured by Admatechs Co., Ltd., number average particle size 300 nm)
SC2050-KD (trade name, manufactured by Admatechs Co., Ltd., number average particle diameter 500 nm)

3.5. Evaluation test 3.5.1. (A) Solubility of polymerizable compound in triacetyl cellulose First, the solubility of (A) polymerizable compound described in Tables 2 to 4 in triacetyl cellulose was evaluated. The mass of an 80 μm-thick triacetyl cellulose film (trade name “TDY-80UL”, manufactured by FUJIFILM Corporation) cut to a size of 18 cm × 1 cm is a ₀ (g), and this film is 6 g at 25 ° C. When the mass of the film after dipping in a polymerizable compound for 2 hours and drying the taken-out film in a vacuum dryer at 80 ° C. for 24 hours is a ₁ (g), ((a ₀ −a ₁ ) / a ₀ ) The mass reduction rate of the film represented by x100 was measured. When the mass reduction rate is 1% or more, it is determined that the polymerizable compound dissolves triacetyl cellulose. When the mass reduction rate is less than 1%, the polymerizable compound does not dissolve triacetyl cellulose. It was judged. The results are shown in Table 1.

  Next, the following items of the antireflection laminates obtained in Examples and Comparative Examples were evaluated. The result is combined with Table 2-Table 4, and is shown. In addition, unless otherwise indicated below, a numerical value represents a mass part.

3.5.2. Reflectivity The cellulose resin substrate surface of the obtained antireflection laminate was coated with a black spray, and a spectral reflectance measurement device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, 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 4 together. If the reflectance is less than 3%, it can be determined that the reflectance is low.

3.5.3. Pencil Hardness The obtained antireflection laminate was fixed on a glass substrate and evaluated according to “JIS K5600-5-4” (ISO / DIS 15184). The result is combined with Table 2-Table 4, and is shown.

3.5.4. Scratch resistance (steel wool resistance test)
The obtained anti-reflection laminate was 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.). The surface was repeatedly rubbed 10 times under a load 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. Moreover, the scratch resistance of the antireflection laminate obtained by changing the load to 300 g or 400 g was evaluated. The result is combined with Table 2-Table 4, and is shown.
A: The cured film is not damaged.
B: Hardened film peeling or scratches are hardly observed, or slight thin scratches are observed on the cured film.
C: A streak is recognized on the entire surface of the cured film.
D: Peeling occurs in part of the cured film.
E: Peeling occurs on the entire surface of the cured film.

3.5.5. Confirmation of uneven distribution of particles When the cross section of the antireflection laminate according to Example 4 was observed with a transmission electron microscope (TEM), the plurality of particles were on the surface of the cured film, that is, on the side opposite to the cellulose resin substrate. It was confirmed that it was unevenly distributed on the surface and hardly existed on the cellulose resin substrate side. Furthermore, the photograph when the surface of a cured film is observed with a scanning electron microscope (SEM) is shown in FIG. As shown in the photograph of FIG. 2, on the surface of the cured film of the antireflection laminate according to Example 4, (B) fine irregularities formed by the uneven distribution of particles, and further protruding to the surface (C) Particles were confirmed.

3.6. Evaluation Results From the results in Table 2, in Examples 1 to 8, it was found that the reflectance was less than 3% and excellent antireflection properties were obtained. In view of the performance manifestation mechanism of the antireflection laminate, the low reflectivity is such that the particles (B), which are hollow particles, are unevenly distributed on the surface of the cured film, that is, on the surface opposite to the cellulose substrate, resulting in low refraction. This supports the formation of the rate layer. Moreover, it turned out that it is excellent also in abrasion resistance from the result of steel wool resistance. This confirms that the solid particles (C) are unevenly distributed on the surface of the cured film and exhibit the strut effect.

  On the other hand, from the results of Table 3, in Comparative Examples 1 to 3 not containing the component (A1), the scratch resistance is excellent, but the reflectance exceeds 3% and the antireflection property is inferior. There was found. Further, from the results of Table 4, in Comparative Examples 4 to 10 not containing (C) particles, the reflectivity was less than 3% and excellent in antireflection properties, but the low refractive index layer of (C) particles was excellent. It was found that the strut effect was not exhibited and the scratch resistance was poor.

Furthermore, in the cured film of Examples 1-8 and the comparative example 1, the cross section was sliced and the Raman spectroscopic measurement (The JEOL Co., Ltd. make, type | form "JRS-SYSTEM2000" was used) of the hard-coat layer was performed. As a result, a peak at 1740 cm ⁻¹ derived from the carbonyl group of triacetylcellulose was detected from the hard coat layers of Examples 1 to 8, but derived from triacetyl cellulose from the hard coat layer of Comparative Example 1. No peak was detected. That is, it was shown that the triacetyl cellulose of the base material was mixed in the hard coat layers of Examples 1 to 8.

  In all of Examples 1 to 8 and Comparative Examples 4 to 10, the density of (B) particles and (C) particles on the side opposite to the cellulose resin substrate in the cured film is the cellulose resin substrate in the cured film. It was higher than the density of the (B) particles and (C) particles on the side, and the (B) particles and (C) particles were substantially absent on the cellulose resin substrate side in the cured film. On the other hand, in Comparative Examples 1-3, the density of (B) particles and (C) particles was almost uniform in the cured film.

  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 ... Cellulose resin base material, 20 ... Cured film, 22 ... Particle, 24 ... Area | region where particle | grains do not exist substantially (hard-coat layer), 26 ... Area | region where particle | grain exists by relatively high density (low refractive index layer) ), 100 ... Laminated body for antireflection

Claims (13)

A cellulose resin substrate;
A polymerizable compound (A) containing 5% by mass to 75% by mass of a polymerizable component (A1) for dissolving the cellulose resin, hollow silica particles (B), a refractive index of 1.50 or less, and a transmission electron microscope A cured film of a curable composition comprising solid particles (C) having a measured number average particle diameter of 100 nm or more, and
The cellulose resin substrate and the cured film are laminated in contact with each other, and the (B) particles and the (C) particles are unevenly distributed on the opposite side of the cellulose resin substrate in the cured film. Laminate for use (Herein, the component that dissolves the cellulose resin means that an 80 μm-thick cellulose resin film cut into a size of 18 cm × 1 cm is immersed in 6 g of the component for 2 hours at 25 ° C. A component whose mass reduction rate of the film is 1% or more when dried in a vacuum dryer at 80 ° C. for 24 hours. A cellulose resin substrate;
2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ), Hollow silica particles (B) and a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. And a cured film of the curable composition containing the solid particles (C) in that,
The cellulose resin base material and the cured film are laminated in contact with each other, and the (B) particles and the (C) particles are unevenly distributed on the opposite side of the cellulose resin base material in the cured film. Laminated body. In claim 1 or claim 2,
The laminated body for antireflection in which the said cured film contains the cellulose resin which forms the said cellulose resin base material. 4. The antireflection laminate according to claim 1, wherein the (C) particles are at least one selected from solid silica particles and solid magnesium fluoride particles. 5. In any one of Claims 1 thru | or 4,
The blending ratio of the (B) particles and the (C) particles is an antireflection laminate in which (B) particles: (C) particles = 80: 20 to 99.9: 0.1 on a mass basis.   A polymerizable compound (A) containing 5% by mass to 75% by mass of a polymerizable component (A1) for dissolving the cellulose resin, hollow silica particles (B), a refractive index of 1.50 or less, and a transmission electron microscope A method for producing an antireflection laminate comprising a step of applying a curable composition containing solid particles (C) having a measured number average particle diameter of 100 nm or more to a cellulose resin substrate and then curing the composition. (Herein, the component that dissolves the cellulose resin is a cellulose resin film having a thickness of 18 μm cut to a size of 18 cm × 1 cm, immersed in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film at 80 ° C.) This refers to a component having a film mass reduction rate of 1% or more when dried in a vacuum dryer for 24 hours.   2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ), Hollow silica particles (B) and a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. Real After the particles a curable composition comprising the (C) was applied to a cellulose resin substrate, comprising the step of curing, the manufacturing method of the antireflection stack in that. In claim 6 or claim 7,
The method for producing an antireflection laminate, wherein the particle (C) is at least one selected from solid silica particles and solid magnesium fluoride particles. In any one of Claims 6 thru | or 8,
Production of the antireflection laminate in which the blending ratio of the (B) particles and (C) particles is in the range of (B) particles: (C) particles = 80: 20 to 99.9: 0.1 on a mass basis. Method.   A polymerizable compound (A) containing 5% by mass to 75% by mass of a polymerizable component (A1) for dissolving the cellulose resin, hollow silica particles (B), a refractive index of 1.50 or less, and a transmission electron microscope A curable composition used for producing an antireflection laminate comprising solid particles (C) having a measured number average particle diameter of 100 nm or more (here, a component for dissolving a cellulose resin) A film obtained by immersing a cellulose resin film having a thickness of 80 μm cut into a size of 18 cm × 1 cm in 6 g of the component at 25 ° C. for 2 hours, and drying the taken-out film at 80 ° C. for 24 hours in a vacuum dryer The mass reduction rate of 1% or more.   2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ), Hollow silica particles (B) and a refractive index of 1.50 or less and a number average particle diameter measured by a transmission electron microscope of 100 nm or more. Comprising the solid particles (C) in that, the curable composition used to manufacture the antireflection stack. In claim 10 or claim 11,
The (C) particles are at least one selected from solid silica particles and solid magnesium fluoride particles. In any one of claims 10 to 12,
The blend ratio of the (B) particles and (C) particles is (B) particles: (C) particles = 80: 20 to 99.9: 0.1 on a mass basis to produce an antireflection laminate. A curable composition used to make.