JP2021165765A - Low refractive index member, transfer sheet, coating composition used for the same, and laminate using low refractive index member - Google Patents

Abstract

To provide a low refractive index member which has a thick low-refractive index layer, and yet offers good visibility by suppressing whitening and is capable of minimizing cracks and maintaining an anti-reflective property.SOLUTION: A low-refractive index member provided herein comprises a low-refractive index layer provided on a base material, the low-refractive index layer having a thickness in a range of 0.5-5.0 μm and containing hollow particles and a binder resin, where the hollow particles have an average particle diameter in a range of 60-140 nm. The low-refractive index member contains a cured product of a composition containing a silicone-based compound as the binder resin.SELECTED DRAWING: None

Description

The present invention relates to a low refraction member, a transfer sheet, a coating composition used for these, and a laminate using the low refraction member.

A low refraction member may be arranged on the surface of an image display device such as a liquid crystal display device or various articles such as a showcase in order to suppress reflection of external light.

The low-refractive index member is provided with a layer having a low refractive index (low-refractive index layer) on the surface to reduce the reflection on the surface of the low-refractive index layer itself, and further, the light reflected on the surface of the low-refractive index layer. It is designed to reduce the refractive index by interfering with the light reflected on the surface of the lower layer of the low refractive index layer.
Therefore, the thickness of the low refractive index layer of the low refractive index member is designed to be about 1/4 (around 100 nm) of the wavelength range of visible light (for example, Patent Document 1).

JP-A-2016-177186 (paragraph 0045)

Since the low refractive index layer is a thin film of about 100 nm as in Patent Document 1, even if the low refractive index layer is slightly damaged by scratching, the low refractive index layer partially disappears and the antireflection effect is partially exhibited. There is a problem of being lost. In particular, when hollow particles are used to lower the refractive index of the low refractive index layer, the scratch resistance of the low refractive index layer tends to decrease, so that the problem tends to become remarkable.

In order to solve the above problem, a means for forming the low refractive index layer by a dry process such as a sputtering method or a vacuum vapor deposition method can be considered. However, the dry process has a problem that the equipment becomes large and the cost rises significantly.
Further, in order to solve the above problem, a means for increasing the crosslink density of the low refractive index layer by using an ionizing radiation curable resin composition as the binder resin of the low refractive index layer formed by the wet method can be considered. However, when the cross-linking density of the low-refractive index layer is increased by using the ionizing radiation curable resin composition, the low-refractive index member may be curled, and further, due to the volume shrinkage of the low-refractive index layer at the time of cross-linking, The smoothness of the surface of the low refractive index layer may be lost, resulting in whitening due to surface diffusion.

In order to solve the above problems, the present inventors set the thickness of the low refractive index layer in the wavelength range of visible light so that the antireflection property can be maintained even if the low refractive index layer is slightly scraped by scratching. We considered making it much thicker than 1/4. However, if the thickness of the low refractive index layer is simply increased, the haze increases and the low refractive index layer becomes white and the visibility deteriorates, or it is low during the process of forming the low refractive index layer and when handling the low refractive index member. There were frequent cases where cracks occurred in the refractive index layer.
Therefore, the present inventors have further studied, and despite the thick film thickness of the low refractive index layer, whitening is suppressed, visibility is good, cracks are suppressed, and antireflection is maintained. We have completed a possible low-refractive index member.

The present invention provides the following [1] to [5].
[1] A low-refractive index member having a low-refractive index layer on a base material, the low-refractive index layer having a thickness of 0.5 to 5.0 μm and containing hollow particles and a binder resin. Hollow particles have an average particle diameter of 60 to 140 nm, and are low-refractive index members containing a cured product of a composition containing a silicone-based compound as the binder resin.
[2] A transfer sheet having a transfer layer on a base material, the base material side of the transfer layer is a low refractive index layer, and the low refractive index layer has a thickness of 0.5 to 5.0 μm. A transfer sheet containing hollow particles and a binder resin, the hollow particles having an average particle diameter of 60 to 140 nm, and containing a cured product of a composition containing a silicone-based compound as the binder resin.
[3] The coating composition for forming a low refractive index layer of a low refractive index member according to the above [1], which contains hollow particles having an average particle diameter of 60 to 140 nm and a silicone compound as a binder resin component.
[4] The coating composition for forming a low refractive index layer of the transfer sheet according to the above [2], which contains hollow particles having an average particle diameter of 60 to 140 nm and a silicone compound as a binder resin component.
[5] A laminated body having a vapor-deposited film on the low-refractive index layer of the low-refractive index member according to the above [1].

According to the present invention, there are provided a low refraction member, a transfer sheet, and a coating composition used for these, which can suppress whitening, have good visibility, and maintain antireflection even though the film thickness is thick. can do. Further, according to the present invention, it is possible to provide a laminated body using the low refraction member.

[Low refraction member]
The low-refractive index member of the present invention has a low-refractive index layer on a base material, and the low-refractive index layer has a thickness of 0.5 to 5.0 μm and contains hollow particles and a binder resin. The hollow particles have an average particle diameter of 60 to 140 nm, and the binder resin contains a cured product of a composition containing a silicone-based compound.

<Base material>
The base material serves as a support for forming the low refractive index layer.
The base material preferably has light transmittance, specifically, a base material having a total light transmittance of 50% or more, more preferably 80% or more, in accordance with JIS K7361-1: 1997. It is preferable, and more preferably 90% or more.

Examples of the base material include plastic and glass.
Glass is preferable to plastic because it is harder and tends to improve the scratch resistance of the low refractive index layer.

The plastic base material is a polyolefin resin such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, vinyl resin such as ethylene / vinyl alcohol copolymer, polyethylene terephthalate, and polyethylene. Polyester resins such as naphthalate and polybutylene terephthalate, acrylic resins such as methyl poly (meth) acrylate and ethyl poly (meth) acrylate, styrene resins such as polystyrene, polyamide resins such as nylon 6 or nylon 66. It can be formed from one or more of a cellulose-based resin such as triacetyl cellulose, a resin such as polycarbonate, and a polyimide-based resin.
Examples of the glass include non-alkali glass, nitrided glass, soda-lime glass, borosilicate glass, lead glass and the like.

The thickness of the base material is not particularly limited, but in the case of a plastic base material, it is preferably 10 to 500 μm, more preferably 20 to 400 μm, and further preferably 50 to 300 μm from the viewpoint of handleability. .. The plastic base material may be a plate-like material having a thickness of more than 500 μm.
Further, in the case of glass, from the viewpoint of handleability, strength and weight reduction, it is preferably 0.03 to 5.0 mm, more preferably 0.1 to 3.0 mm, and 0.3 to 2. It is more preferably 0 mm.

The base material is not limited to a flat plate shape, and may have a three-dimensional shape having a curved surface or the like. Further, the base material is not limited to colorless and may be colored.

<Low refractive index layer>
The low index of refraction layer is formed on at least one surface of the substrate. Further, the low refractive index layer is preferably located on the outermost surface on the side opposite to the base material of the low refractive index member.

In the low refractive index member of the present invention, the low refractive index layer needs to have a thickness of 0.5 to 5.0 μm. When the thickness of the low refractive index layer is less than 0.5 μm, even if the low refractive index layer is slightly damaged by scratching, the antireflection property of the scratched portion is lost, and visibility cannot be improved. Further, when the thickness of the low refractive index layer exceeds 5.0 μm, the absolute amount of hollow particles increases, so that the low refractive index layer is whitened due to internal diffusion, and visibility cannot be improved. , The low refractive index layer is cracked during the formation process (curing shrinkage) of the low refractive index layer and when the low refractive index member is handled.

Further, in the low refractive index member of the present invention, the low refractive index layer contains hollow particles and a binder resin, and the hollow particles are required to have an average particle diameter of 60 to 140 nm.
When the average particle size of the hollow particles is less than 60 nm, the proportion of air having a low refractive index decreases, so that the refractive index of the low refractive index layer cannot be sufficiently lowered, and the antireflection property is lowered. Further, when the average particle size of the hollow particles exceeds 140 nm, the diffusion of the hollow particles becomes strong, the low refractive index layer becomes white, and the visibility cannot be improved.

Further, the low-refractive index member of the present invention is required to contain a cured product of a composition containing a silicone-based compound as a binder resin for a low-refractive index layer.
When the binder resin does not contain a cured product of the composition containing a silicone compound, the refractive index of the low refractive index layer cannot be sufficiently lowered, and the antireflection property is lowered.

As described above, in the low refractive index member of the present invention, the thickness of the low refractive index layer is 0.5 to 5.0 μm, the average particle diameter of the hollow particles is 60 to 140 nm, and the binder resin is a silicone compound. By including the cured product of the composition containing the mixture, it is possible to suppress whitening, have good visibility, and maintain antireflection property even though the film thickness is thick.

<< Hollow particles >>
Hollow particles refer to particles having an outer shell layer, the inside of the particles surrounded by the outer shell layer is hollow, and the inside of the particles contains air.
The outer shell layer of the hollow particles may be an inorganic substance or an organic substance, and examples thereof include those made of metal, metal oxide, resin, silica and the like. Of these, hollow silica particles in which the outer shell layer is silica are preferable. By using the hollow silica particles as the hollow particles, the affinity between the binder resin containing the cured product of the composition containing the silicone compound and the outer shell of the hollow particles is increased, and the difference in refractive index is reduced. The internal haze can be easily lowered.
When the outer shell layer is silica, the silica may be in a crystalline, sol-like, or gel-like state.
The shape of the hollow particles may be a substantially spherical shape such as a true sphere, a spheroid shape, or a polyhedral shape that can be approximated to a sphere, a chain shape, a needle shape, a plate shape, a piece shape, a rod shape, a fibrous shape, or the like. Among them, it is preferably a true sphere and a substantially spherical shape, and more preferably a spheroid or a true sphere.

As described above, the hollow particles are required to have an average particle size of 60 to 140 nm. The average particle size of the hollow particles is preferably 65 to 120 nm, more preferably 67 to 110 nm, further preferably 70 to 100 nm, and even more preferably 70 to 90 nm.

The average particle size of the hollow particles can be calculated by the following operations (1) to (3).
(1) The cross section of the low refraction member is imaged by TEM or STEM. The acceleration voltage of TEM or STEM is preferably 10 kv to 30 kV, and the magnification is preferably 50,000 to 300,000 times.
(2) Arbitrary 10 particles are extracted from the observation image, and the particle size of each particle is calculated. The particle size is measured as the distance between two straight lines in a combination of the two straight lines so that the distance between the two straight lines is maximized when the cross section of the particle is sandwiched between two arbitrary parallel straight lines.
(3) The same operation is performed 5 times on the observation image on another screen of the same sample, and the value obtained from the number average of a total of 50 particles is defined as the average particle size.

The hollow particles are preferably surface-treated.
As the surface treatment of the hollow particles, a surface treatment using a silane coupling agent is more preferable, and among these, a surface treatment using a silane coupling agent having a (meth) acryloyl group or an epoxy group is preferable.
By surface-treating the hollow particles with a silane coupling agent, the affinity between the hollow particles and the binder resin is improved, the dispersion of the hollow particles becomes uniform, and the agglomeration of the hollow particles is less likely to occur. It is possible to easily suppress the decrease in transparency of the particles.

Examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltri. Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glysidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocia Nurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane , Trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like.

The content of the hollow particles is preferably 100 to 300 parts by mass, more preferably 150 to 250 parts by mass, and further preferably 180 to 220 parts by mass with respect to 100 parts by mass of the binder resin.
By setting the content of the hollow particles to 100 parts by mass or more, the refractive index of the low refractive index layer can be sufficiently lowered and the antireflection property can be easily improved. Further, by setting the content of the hollow particles to 300 parts by mass or less, it is possible to suppress whitening of the low refractive index layer due to an increase in internal diffusion while maintaining scratch resistance, and it is easy to suppress a decrease in visibility. can.

<< Binder resin >>
As described above, the low-refractive index member of the present invention needs to contain a cured product of a composition containing a silicone-based compound as a binder resin for a low-refractive index layer. The silicone-based compound is a compound having a siloxane bond (Si—O—Si) in the molecule.
The binder resin may contain a resin other than the cured product of the composition containing the silicone-based compound, but the ratio of the cured product of the composition containing the silicone-based compound to the total amount of the binder resin is 50% by mass or more. Is more preferable, 70% by mass or more is more preferable, 90% by mass or more is further preferable, and 100% by mass or more is further preferable.
The silicone-based compound can be cured by, for example, a cross-linking reaction of a reactive functional group described later, a dealcohol condensation reaction of an alkoxy group, a dehydration condensation of a silanol group, or the like.

The silicone-based compound is preferably one in which a substituted hydrocarbon group having a reactive functional group as a substituent is directly bonded to a silicon atom. Examples of the reactive functional group include an epoxy group, a mercapto group, a (meth) acrylic group, an amino group, a vinyl group and an isocyanate group.
Hereinafter, a silicone-based compound in which a substituted hydrocarbon group having a reactive functional group as a substituent is directly bonded to a silicon atom may be referred to as a “reactive functional group-containing silicone compound”.

When the hollow particles are surface-treated with a silane coupling agent, the internal haze is lowered by using a silicone compound containing a reactive functional group, and whitening is suppressed even though the film thickness of the low refractive index layer is thick. This makes it easier to improve visibility. The reason for this is that by using the reactive functional group-containing silicone compound, the side of the silicone compound having the reactive functional group (the side rich in the organic component) is the reactive functional of the silane coupling agent attached to the hollow particles. It is considered that the difference in refractive index is reduced by making it easier to face the group.
The reactive group of the reactive functional group-containing silicone compound is a cationically reactive reactive group having a small polymerization shrinkage from the viewpoint of suppressing the interfacial peeling between the hollow particles and the binder resin and suppressing the surface unevenness of the low refractive index layer. It is preferably present, and more preferably an epoxy group having excellent adhesion to glass or silica. Suppressing the surface irregularities of the low refractive index layer leads to suppression of whitening of the low refractive index layer and improvement of scratch resistance of the low refractive index, and also forms a vapor-deposited film evenly on the low refractive index layer. It is preferable because it can be facilitated.

The reactive functional group-containing silicone compound preferably has a reactive functional group equivalent of 200 to 900 g / mol, more preferably 220 to 600 g / mol, and even more preferably 250 to 400 g / mol.
By setting the reactive functional group equivalent to 900 g / mol or less, the amount of the reactive functional group becomes sufficient, and the above effect (good visibility) can be easily obtained. Further, by setting the equivalent of the reactive functional groups to 200 g / mol or more, shrinkage due to self-crosslinking of the reactive functional groups is suppressed, and the interface between the hollow particles and the binder resin is peeled off and the surface of the low refractive index layer is made uneven. It can be easily suppressed.

The reactive functional group-containing silicone compound is one or more hydrolysates of an organosilicon compound represented by the following general formula (1), and one or more hydrophiles of an organosilicon compound represented by the following general formula (1). Degraded polycondensates, hydrolyzed polycondensates of one or more organosilicon compounds represented by the following general formula (1) and one or more organosilicon compounds represented by the following general formula (2), and the like. Be done. Among these, one or more hydrolyzed polycondensates of the organosilicon compound represented by the following general formula (1), one or more of the organosilicon compounds represented by the following general formula (1), and the following general formula ( The hydrolyzed polycondensate with one or more of the organosilicon compounds represented by 2) is preferable because it is difficult to volatilize even with heat during formation of the vapor-deposited film, and therefore it is easy to improve the adhesion to the vapor-deposited film. Hereinafter, in the present specification, one or more hydrolyzed polycondensates of organosilicon compounds may be referred to as “oligomeric silicone compounds”.

R _n −SiX _4-n (1)
[In equation (1), n is an integer of 1-3. Further, in the formula (1), R is a substituted hydrocarbon group having 1 to 10 carbon atoms having a reactive functional group as a substituent, and when n is 2 to 3, R is different even if they are the same as each other. You may. Further, in the formula (1), X is an alkoxy group having 1 to 4 carbon atoms, a silanol group, a halogen or hydrogen, and when n is 1 to 2, X may be the same as or different from each other. ]
R ² _n −SiX _4-n (2)
[In equation (2), n is an integer of 1-3. Further, in the formula (2), R ² is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms having no reactive functional group, and when n is 2 to 3, R ² is the same as each other. May be different. Further, in the formula (2), X is an alkoxy group having 1 to 4 carbon atoms, a silanol group, a halogen or hydrogen, and when n is 1 to 2, X may be the same as or different from each other. ]

Examples of the organosilicon compound represented by the general formula (1) include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, and γ-glycidoxymethyltrioxysilane. , Gamma-glycidoxyethyl trimethoxysilane,
γ-glycidoxyethyl triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltrioxysilane, γ- (meth) acrylooxyethyl Trimethoxysilane, γ- (meth) acrylooxyethyl triethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acrylo Oxypropyltriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and N-β (aminoethyl) γ -Aminopropyltrimethoxysilane and the like can be mentioned.
Examples of the organic silicon compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane. , Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, Butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxy Examples thereof include silane, perfluorooctylethyltrimethoxysilane and perfluorooctylethyltriethoxysilane.

Further, as the silicone compound, one or more hydrolyzed polycondensates of the organosilicon compound represented by the above general formula (2) are also preferable. One or more hydrolyzed polycondensates of the organic silicon compound represented by the above general formula (2) can suppress the unevenness of the surface of the low refractive index layer due to curing shrinkage, and further, at the time of forming a thin-film deposition film. It is preferable because it is difficult to volatilize even with the heat of the above, and it is easy to improve the adhesion with the vapor deposition film.

Further, the silicone compound preferably has an alkoxy group. Further, it is preferable that the alkoxy group is directly linked to a silicon atom.
By using a silicone compound having an alkoxy group, when the base material is glass, the adhesiveness between the base material and the low refractive index layer can be improved, and the scratch resistance can be further improved. .. Further, by using a silicone-based compound having an alkoxy group, the adhesiveness between the low refractive index layer and the vapor deposition film is good when the structure of the laminate described later (the structure having the vapor deposition film on the low refractive index layer) is adopted. Can be.

The amount of the alkoxy group in the silicone compound having an alkoxy group is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass.
By setting the amount of the alkoxy group to 5% by mass or more, it is possible to easily improve the adhesiveness with an inorganic substance (for example, glass as a base material or a vapor-deposited film formed on a low refractive index layer). By setting the amount of the alkoxy group to 60% by mass or less, the shrinkage of the low refractive index layer due to the dealcoholization reaction of the alkoxy group is suppressed, the interface between the hollow particles and the binder resin is peeled off, and the surface of the low refractive index layer is made uneven. Can be easily suppressed.

The composition containing the silicone-based compound may contain a curing catalyst, if necessary.
For example, when the reactive functional group of the reactive functional group-containing silicone compound is an epoxy group, one or more selected from amine-based catalysts, acidic catalysts and basic catalysts as the curing catalyst in the composition containing the silicone-based compound. Is preferably included.
Further, in order to promote the reaction between the alkoxy group of the silicone compound-based compound and an inorganic substance such as glass, the composition containing the silicone-based compound is one or more catalysts selected from acidic catalysts, basic catalysts and amine-based catalysts. Is preferably included.

<< Thickness >>
As described above, the low-refractive index member of the present invention requires the low-refractive index layer to have a thickness of 0.5 to 5.0 μm.
The thickness of the low refractive index layer is preferably 0.7 to 4.0 μm, more preferably 0.8 to 3.5 μm, and even more preferably 1.0 to 3.0 μm.
In the present specification, the thickness of the low refractive index layer can be calculated as an average value of measured values at 10 points. The variation in thickness is preferably within ± 15%, more preferably within ± 10%, further preferably within ± 7%, and within 5% with respect to the average thickness. Is even more preferable.
The thickness of the low refractive index layer can be measured by, for example, a microspectroscopy.

<< Refractive index >>
The refractive index of the low refractive index layer is preferably 1.30 or less, more preferably 1.27 or less. By setting the refractive index of the low refractive index layer to 1.30 or less, it is possible to suppress the increase in the reflectance of the surface of the low refractive index layer and facilitate the improvement of visibility. The lower limit of the refractive index of the low refractive index layer is about 1.10.
In the present specification, the refractive index refers to the refractive index at a wavelength of 589.3 nm.
The refractive index of the low refractive index layer can be calculated by, for example, a microspectroscopy.

The low refractive index layer may contain additives such as antistatic agents, antioxidants, surfactants, dispersants and UV absorbers.

The low-refractive index layer is, for example, a wet method in which a coating liquid for forming a low-refractive index layer containing each component constituting the low-refractive index layer is applied onto the base material, dried and cured, and a wet method is used on the base material. It can be formed by a transfer method or the like that transfers the formed low refractive index layer.

<Other layers>
The low-refractive index member of the present invention may have another layer between the base material and the low-refractive index layer.
Other layers include, for example, a hard coat layer for improving the scratch resistance of the low refractive index layer, an adhesive layer for improving the adhesiveness between the base material and the low refractive index layer, an antistatic layer, and the like. Can be mentioned.

<Optical characteristics>
Low refractive member of the present invention is preferably diffuse light reflectance R _SCE measured from the low refractive index layer side is in the range below.
_RSCE uses an integrating sphere to apply light to the sample surface from all directions, opens the light trap corresponding to the normal reflection direction, and measures the reflected light other than the reflected light passing through the light trap. It is the reflectance calculated from the measured value. The surface of the low refractive index layer is almost smooth, and the proportion of diffusely reflected light is smaller than that of specularly reflected light. _{Therefore, RSCE, which} is obtained by removing the positively reflected light from the total reflected light, is a parameter suitable for showing the diffuse reflected light which is a very small component and showing the amount of diffuse reflection inside the low refraction layer. I can say.
Measuring device of a typical _{R SCE} is, JIS Z8722: has a configuration conforming to the geometric-condition c 2009. More specifically, a typical _RSCE measuring device uses D65 as the light source of the integrating sphere spectrophotometer, the position of the receiver is +8 degrees with respect to the normal of the sample, and the position of the light trap is. It is -8 degrees to the normal of the sample and the viewing angle is 2 degrees or 10 degrees. As a measurement apparatus of R _SCE include the trade name CM-2600d manufactured by Konica Minolta Co., Ltd.. In this specification, the viewing angle is set to 2 degrees.

The diffuse ray reflectance _RSCE is preferably 1.5% or less, more preferably 1.0% or less, and further preferably 0.5% or less.
By _{setting the RSCE} to 1.5% or less, the amount of diffuse reflection inside the low refractive index layer can be reduced, and whitening can be suppressed. _The lower limit of _{R SCE} is about 0.01%.

When the low-refractive index member has light transmission as a whole, in order to eliminate the influence of the back reflection of the low-refractive index member, the surface of the low-refractive index member opposite to the surface having the low refractive index layer is black. create a sample obtained by laminating Chakuzaiso and back films, it is preferable to measure the R _SCE a low refractive index layer side of the sample. The same applies to the measurement of the visual reflectance Y value, which will be described later.
The black pressure-sensitive adhesive layer of the sample preferably has a total light transmittance of 1% or less. Further, the difference (Δn) between the refractive index of the surface of the low refractive index member opposite to the surface having the low refractive index layer (for example, the refractive index of the base material) and the refractive index of the binder resin of the black pressure-sensitive adhesive layer. Is preferably within 0.10.

In the present specification, _RSCE , haze, total light transmittance and visual reflectance Y value are average values of 10 measured values.

The low refraction member of the present invention preferably has a haze according to JIS K7136: 2000 of 1.0% or less, more preferably 0.5% or less, and further preferably 0.2% or less. preferable. By setting the haze to 1.0% or less, whitening of the low refractive index layer can be suppressed and visibility can be easily improved.

In the low refraction member of the present invention, the total light transmittance of JIS K7361-1: 1997 is preferably 50.0% or more, more preferably 80% or more, still more preferably 90% or more. ..

The low-refractive index member of the present invention preferably has a visual reflectance Y value of 3.0% or less, preferably 2.0% or less, measured at a light incident angle of 5 degrees from the side having the low refractive index layer. Is more preferable. In the present specification, the visual reflectance Y value refers to the visual reflectance Y value of the CIE 1931 standard color system. The visual reflectance Y value can be calculated using a spectrophotometer (for example, manufactured by Shimadzu Corporation, trade name "UV-3600plus").

[Transfer sheet]
The transfer sheet of the present invention has a transfer layer on a base material, the base material side of the transfer layer is a low refractive index layer, and the low refractive index layer has a thickness of 0.5 to 5. It is 0 μm and contains hollow particles and a binder resin. The hollow particles have an average particle diameter of 60 to 140 nm, and as the binder resin, the binder resin contains a cured product of a composition containing a silicone-based compound. It is a waste.

<Base material>
The base material of the transfer sheet is preferably a plastic film from the viewpoint of workability during manufacturing and transfer of the transfer sheet.
As the plastic film as the base material of the transfer sheet, the same plastic film as that exemplified as the base material of the low refraction member can be used. From the viewpoint of handleability, the thickness of the plastic film is preferably 10 to 500 μm, more preferably 20 to 400 μm, and even more preferably 50 to 300 μm.
The surface of the base material of the transfer sheet may be mold-released in order to facilitate the peeling of the transfer layer from the base material.

Ra, Rz and Rp are preferably in the following ranges on the surface of the base material on the side where the low refractive index layer is formed, in order to suppress surface irregularities of the low refractive index layer exposed on the surface of the transfer layer after transfer. Details of Ra, Rz and Rp (measurement method, etc.) will be described later.
Ra: 2.5 nm or less Rz: 25 nm or less Rp: 12 nm or less

Ra is more preferably 2.0 nm or less, further preferably 1.5 nm or less, and even more preferably 1.2 nm or less. The lower limit of Ra is about 0.3 nm.
Rz is more preferably 20 nm or less, further preferably 15 nm or less, and even more preferably 10 nm or less. The lower limit of Rz is about 3 nm.
Rp is more preferably 10 nm or less, further preferably 8 nm or less, and even more preferably 6 m or less. The lower limit of Rp is about 2 nm.

<Transfer layer>
The transfer layer has at least a low refractive index layer. Further, the base material side of the transfer layer shall be composed of a low refractive index layer.
The low refractive index layer constituting the transfer layer has a thickness of 0.5 to 5.0 μm and contains hollow particles and a binder resin, and the hollow particles have an average particle diameter of 60 to 140 nm and the binder resin. As a result, it contains a cured product of a composition containing a silicone-based compound.
Embodiments and suitable embodiments of the low refractive index layer constituting the transfer layer and the hollow particles and the binder resin contained in the low refractive index layer are the low refractive index layer of the low refractive index member of the present invention described above and the low refractive index. The same applies to the embodiments and preferred embodiments of the hollow particles and the binder resin contained in the index layer. However, the surface shape of the low refractive index layer of the low refractive index member of the present invention described above (the surface shape on the side opposite to the base material of the low refractive index layer) is the basis of the low refractive index layer in the transfer sheet of the present invention. It corresponds to the shape of the surface on the material side (the shape of the surface exposed after transfer).

The transfer layer may have another layer on the side opposite to the base material with respect to the low refractive index layer. Examples of other layers include a hard coat layer for improving the scratch resistance of the low refractive index layer, an adhesive layer for improving the adhesiveness between the adherend and the transfer layer, an antistatic layer, and the like. Be done. In particular, in order to improve the adhesiveness with the adherend, the transfer layer preferably has an adhesive layer on the surface opposite to the base material.
The transfer layer can have a laminated structure as shown in (1) to (3) below, for example. In the case of (3) below, the binder resin of the low refractive index layer may contain a resin having adhesiveness. In the following (1) to (3), the layer located on the left side means that the layer is closer to the base material, and "/" means the interface between the layers.
(1) Low refractive index layer / adhesive layer (2) Low refractive index layer / hard coat layer / adhesive layer (3) Low refractive index layer

As the adhesive layer of the transfer layer, it is preferable to use a heat-sensitive or pressure-sensitive resin suitable for the material of the adherend. For example, when the material of the adherend is an acrylic resin, it is preferable to use an acrylic resin. When the material of the adherend is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene resin, acrylic resin, polystyrene resin, polyamide resin, etc., which have an affinity for these resins, should be used. Is preferable. Further, when the material of the adherend is polypropylene resin, it is preferable to use chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and kumaron inden resin. Further, when the material of the adherend is glass, it is preferable to use an ethylene-vinyl acetate copolymer resin and a polyethylene-based resin. When the material of the adherend is glass, the adhesiveness with various adhesives can be improved by using glass surface-treated with a silane coupling agent.
Further, the adhesive layer may be a so-called transparent optical adhesive layer (OCA). As the transparent optical adhesive layer, an acrylic resin is used from the viewpoint of optical properties, light resistance, weather resistance, heat resistance and transparency.
The thickness of the adhesive layer is preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm.

The hard coat layer of the transfer layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, and from the viewpoint of improving scratch resistance, ionizing radiation It is more preferable to include a cured product of the curable resin composition.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as needed.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyl group and an allyl group, and an epoxy group and an oxetanyl group. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bond group is preferable, a compound having two or more ethylenically unsaturated bond groups is more preferable, and a compound having two or more ethylenically unsaturated bond groups is particularly preferable. Polyfunctional (meth) acrylate compounds are more preferred. As the polyfunctional (meth) acrylate compound, either a monomer or an oligomer can be used.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, an ultraviolet ray (UV) or an electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion-rays can also be used.
In the present specification, (meth) acrylate means acrylate or methacrylate, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acryloyl group means acryloyl group or methacryloyl group. means.

The thickness of the hard coat layer is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 1 to 30 μm. By setting the thickness of the hard coat layer within the above range, it is possible to improve scratch resistance and easily suppress the occurrence of cracks in the transfer layer during transfer. When high hardness such as glass substitute is required, the thickness of the hard coat layer is preferably 10 to 30 μm.

A release layer may be provided between the base material and the transfer layer in order to improve the peelability of the transfer layer. The release layer can be formed from a general-purpose release agent such as a silicone-based release agent or a fluorine-based release agent.

<< Surface shape of the low refractive index layer constituting the transfer layer on the substrate side >>
As described above, the substrate side of the transfer layer is composed of a low refractive index layer. The surface shape of the low refractive index layer on the base material side (the surface shape on the side opposite to the base material of the low refractive index layer) is the arithmetic mean roughness Ra, the maximum height Rz, and the maximum height Rp of the roughness curve. It is preferable that one or more selected from the following satisfies the following range, more preferably two or more satisfy the following range, and further preferably all three satisfy the following range.
A low refractive index layer is located on the surface of the laminate formed by transferring the transfer layer onto the adherend. Therefore, when Ra, Rz and Rp satisfy the following ranges, when the surface of the laminated body (the surface of the low refractive index layer) is rubbed with a nail or the like, the nail or the like gets caught in the unevenness and scratches occur. It can be suppressed and the scratch resistance can be easily improved. Further, when Ra, Rz and Rp satisfy the following ranges, when the surface of the laminated body (the surface of the low refractive index layer) is touched with a finger or the like, sebum or the like enters the unevenness and the refractive index changes. However, it is possible to suppress the decrease in antireflection property.
Ra: 2.5 nm or less Rz: 25 nm or less Rp: 12 nm or less

Ra is more preferably 2.0 nm or less, further preferably 1.5 nm or less, and even more preferably 1.2 nm or less. Ra is preferably 0.3 nm or more in order to prevent tiny scratches from being visually recognized.
Rz is more preferably 20 nm or less, further preferably 15 nm or less, and even more preferably 10 nm or less. The Rz is preferably 3 nm or more in order to prevent the appearance of very small scratches.
Rp is more preferably 10 nm or less, further preferably 8 nm or less, and even more preferably 6 m or less. The Rp is preferably 2 nm or more in order to prevent the appearance of very small scratches.

The definitions of Ra, Rz and Rp shall be in accordance with JIS B0601: 2001. Ra, Rz and Rp shall be calculated as follows using an atomic force microscope (trade name "WET-9100", manufactured by Shimadzu Corporation). Specifically, first, a plurality of flat circular metal plates are prepared, a carbon double-sided tape manufactured by Nissin EM Co., Ltd. is attached to each metal plate, and the metal plate and the adherend are attached via the tape. A measurement sample is prepared by bonding the transfer layer to the adherend side of the laminated body formed by transferring the transfer layer onto the body. The measurement sample is then left overnight in a desiccator to ensure adhesion of the metal plate, tape and the laminate. After leaving overnight, the measurement sample was fixed on the measuring table of an atomic force microscope (trade name "WET-9400", manufactured by Shimadzu Corporation) with a magnet, and in the tapping mode, the measurement area was 5 μm square, and the space between atoms. Observe the surface shape with a force microscope. Then, Ra, Rz, and Rp are calculated from the observed data using the surface analysis software built in the atomic force microscope. The vertical scale at the time of surface analysis is 20 nm. The atmosphere at the time of observation is 23 ° C. ± 5 ° C. and a humidity of 40 to 65%, and NCHR-20 manufactured by NanoWorld is used as the cantilever. In addition, when observing, 10 places are randomly selected from the places where there are no foreign substances or scratches on one sample, and the surface shapes of the 10 places are observed. Then, Ra, Rz, and Rp are calculated from all the obtained 10-point data using the surface analysis software built into the atomic force microscope, and the arithmetic mean values of the 10 points are calculated as Ra, Rz, and Rp of each sample. And.

Further, Ra, Rz, and Rp are used to define the surface shape of the low refractive index layer on the substrate side for the following reasons.
Ra is used to see the average height of peaks and valleys on the surface of the low index of refraction layer, and Rz is the maximum value of peak height and valley depth of the surface of the low index of refraction layer. It is used to see the sum of the maximum values, and Rp is used to see the maximum value of the peak height on the surface of the low index of refraction layer. Here, since Ra looks at the average value of the heights of the peaks and valleys existing on the surface of the low refractive index layer, although the rough surface shape of the low refractive index layer can be known, it is assumed that there are large peaks and valleys. Is also averaged, and its existence may be overlooked. Further, since Rp looks at the maximum value of the mountain height on the surface of the low refractive index layer, when two parameters of Ra and Rp are used, even if there is a large valley, its existence is overlooked. Furthermore, since Rz looks at the sum of the maximum value of the peak height and the maximum value of the valley depth on the surface of the low refractive index layer, when two parameters of Ra and Rz are used, it may be lost. It may not be possible to tell whether the mountains are high or the valleys are deep. Therefore, in order to more accurately determine whether or not the surface shape is uniform and flat, one parameter of Ra, two parameters of Ra and Rp, or two parameters of Ra and Rz are not sufficient, and Ra , Rz and Rp are required. Therefore, in the present invention, the surface shape of the low refractive index layer is defined by using three parameters of Ra, Rz and Rp.

In order to set Ra, Rz and Rp in the above range, it is preferable that the surface of the low refractive index layer on the substrate side has a region in which hollow particles are substantially not present. In other words, it is preferable that the surface of the low refractive index layer on the substrate side has a region in which substantially only the binder resin exists.
Since the hollow particles have a light specific gravity, the hollow particles and the binder resin component are applied onto the base material of the transfer sheet to form a low refractive index layer, so that the hollow particles emerge on the surface of the coating film. It is possible to easily form a region where hollow particles are sparse and the binder resin is dense on the surface of the low refractive index layer on the substrate side.
By having a region on the surface of the low refractive index layer on the substrate side where only the binder resin is substantially present, the surface unevenness of the laminate formed by transferring the transfer layer onto the adherend is reduced, and scratch resistance is reduced. In addition to being able to improve the property, it is also possible to improve the antifouling property because it is difficult for dirt to enter the unevenness.

The region in which only the binder is substantially present on the surface of the low refraction layer on the substrate side can be calculated by the following operations (I) to (III).
(I) The cross section of the transfer sheet is imaged by TEM or STEM. The acceleration voltage of TEM or STEM is preferably 10 kv to 30 kV, and the magnification is preferably 50,000 to 300,000 times.
(II) Arbitrary 10 particles close to the base material side are extracted from the observation image, and the linear distance from the point closest to the base material of each particle to the base material is calculated.
(III) Perform the same operation 5 times on the observation image on another screen of the same sample, and obtain the value obtained from the number average of a total of 50 pieces on the surface of the low refraction layer on the substrate side, substantially only the binder exists. Area to be used.

The region of substantially only the binder resin on the surface of the low refractive index layer on the substrate side is preferably 1 nm or more, more preferably 2 nm or more from the surface of the low refractive index layer. From the viewpoint of maintaining antireflection, the region is preferably 20 nm or less, and more preferably 15 nm or less.
It should be noted that the region in which only the binder resin is substantially present is the binder on the surface of the low refractive index layer on the substrate side at 500 nm in the width direction of the low refractive index layer in the photograph in which the vertical cross section of the transfer sheet is imaged by STEM. It refers to the region where only the resin exists.
Further, of the entire surface of the low refractive index layer on the substrate side, the region in which only the binder resin is substantially present is preferably 60% or more, more preferably 70% or more, and more preferably 80% or more. It is more preferably 90% or more, and even more preferably 90% or more.

<Subject>
The material of the adherend that transfers the transfer layer is not particularly limited, and examples thereof include various plastics, glass, ceramics, metal, and wood. Further, the thickness of the adherend is not particularly limited, and may be a thin one such as a micron level or a thick one such as a plate. Further, the shape of the adherend is not particularly limited, and may be a flat shape or a three-dimensional shape.

[Coating Composition A]
The coating composition A of the present invention contains hollow particles having an average particle diameter of 60 to 140 nm and a silicone-based compound as a binder resin component, and is a coating for forming a low refractive index layer of the low refractive index member of the present invention described above. It is a composition.

[Coating Composition B]
The coating composition B of the present invention contains hollow particles having an average particle diameter of 60 to 140 nm and a silicone-based compound as a binder resin component, and is a coating composition for forming a low refractive index layer of the transfer sheet of the present invention described above. It is a thing.

The embodiments and preferred embodiments of the hollow particles and the binder resin component contained in the coating compositions A and B are the above-described embodiments of the hollow particles and the binder resin component contained in the low refractive index layer of the low refractive index member of the present invention. And similar to preferred embodiments.

The coating compositions A and B preferably contain a solvent.
Solvents include, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), Aromatic hydrocarbons (toluene, xylene, etc.), carbon halides (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (butanol, cyclohexanol, etc.), cellosolves (butanol, cyclohexanol, etc.) Methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.) and the like can be exemplified, and a mixture thereof may be used.
The content of the solvent in the coating compositions A and B is preferably 60 to 95% by mass, more preferably 70 to 90% by mass, based on the total amount of the coating composition. By setting the solvent content to 60% by mass or more, it is possible to suppress the increase in viscosity of the coating composition and improve the workability at the time of coating, and by setting it to 95% by mass or less, drying unevenness is suppressed. It can be done easily.

Further, the coating compositions A and B may contain additives such as a surfactant, a dispersant, an antistatic agent, an antioxidant and an ultraviolet absorber.

The coating compositions A and B can be formed into a low refractive index layer by, for example, being applied onto a substrate, prebaked (dried), and further thermoset.
At the time of prebaking (drying), the temperature is preferably 60 to 150 ° C., more preferably 80 to 120 ° C., and the time is preferably 40 to 200 seconds, more preferably 50 to 150 seconds.
At the time of thermosetting, the temperature is preferably 150 to 260 ° C., more preferably 170 to 250 ° C., and the time is preferably 5 to 45 minutes, more preferably 15 to 35 minutes.
By setting the drying conditions and thermosetting conditions of the coating compositions A and B within the above ranges, rapid drying of the coating compositions A and B and / or rapid curing of the binder resin can be suppressed, and a low refractive index layer can be suppressed. It is possible to easily prevent the surface of the surface from becoming uneven.

[Laminate]
The laminate of the present invention has a vapor-deposited film on the low-refractive index layer of the low-refractive index member of the present invention described above.

The vapor deposition film is silicon (Si), boron (B), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium. Vacuum vapor deposition using inorganic substances such as (Ti), lead (Pb), zirconium (Zr), yttrium (Y), indium (In), antimony (Sb), these oxides, and one or more of these nitrides as raw materials. It can be formed by a physical vapor deposition (PVD) method such as sputtering, ion plating, or a chemical vapor deposition (CVD) method such as plasma chemical vapor deposition, thermochemical vapor deposition, or photochemical vapor deposition.
The thickness of the thin-film deposition film is usually about 5 to 500 nm.

The surface shape of the low refractive index layer located under the vapor-deposited film preferably has few irregularities. By reducing the unevenness of the surface shape of the low refractive index layer, it is possible to easily form the vapor-deposited film evenly and neatly. In order to reduce the unevenness of the surface shape of the low refractive index layer, it is preferable to use a component having less shrinkage as the binder resin of the low refractive index layer, or to form the low refractive index layer by transfer.

Further, the low refractive index layer located under the vapor-deposited film preferably contains a cured product of the composition containing a silicone-based compound having an alkoxy group as a cured product of the composition containing the silicone-based compound. With this configuration, it is possible to easily improve the adhesion between the low refractive index layer and the vapor-deposited film.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the embodiments described in the examples.

1. 1. Evaluation and Measurement The following measurements and evaluations were performed on the low refraction members obtained in Examples and Comparative Examples. The results are shown in Table 1. The sizes of the low refraction member and the sample used in the following measurements and evaluations are examples, and are not limited thereto. For example, in the measurement of scratch resistance of 1-1 below, a low refraction member of 10 cm square is used, but the size may be smaller than this.
The atmosphere at the time of each measurement and evaluation was a temperature of 23 ° C. ± 5 ° C. and a humidity of 40 to 65%. Further, before the start of each measurement and evaluation, the low refraction member (or a sample prepared from the low refraction member) was exposed to the atmosphere for 30 minutes or more.

1-1. Scratch resistance Using a 10 cm square low refractive index member, press # 0000 steel wool against the surface of the low refractive index layer, ^{rub it 10 times with a load of 50 g / cm 2} , and then place a black plate on the back surface of the sample. Then, the antireflection property was visually evaluated under the illumination of a fluorescent lamp. The one in which the antireflection property of the scratched portion and the non-abrased portion could not be distinguished was designated as "A", and the one in which the antireflection property of the scraped portion and the non-scraped portion could be distinguished was designated as "C".

1-2. A low refraction member having a crack of 10 cm square was used, a black plate was placed on the back surface of the low refraction member, and it was visually evaluated whether or not a crack was generated in the low refractive index layer under the illumination of a fluorescent lamp. Those in which no cracks could be confirmed were designated as "A", and those in which fine cracks could be confirmed were designated as "C".

1-3. The refractive index of the low refractive index layer was calculated using a microspectroscopy film thickness meter (manufactured by Otsuka Electronics Co., Ltd., trade name "OPTM-A1") using a low refractive index member having a refractive index of 10 cm square. Those having a refractive index of 1.30 or less have good antireflection properties and are at a passing level.

1-4. Thickness of low refractive index layer Using a low refractive index member of 10 cm square, the thickness (μm) of the low refractive index layer was calculated by a microspectroscopy (manufactured by Otsuka Electronics Co., Ltd., trade name “OPTM-A1”). After confirming that there were no defects, the thickness at 10 points was measured, and the average value at 10 points was taken as the thickness of the low refractive index layer of each Example and Comparative Example.

1-5. Adhesiveness Using a 10 cm square low refractive index member, the adhesive strength between the base material (glass) and the low refractive index layer was evaluated by an adhesiveness test by the cross-cut method of JIS K5600-5-6: 1999. The classification numbers of adhesive strength are shown in Table 1. The classification numbers are the following 6 types from 0 to 5.
<Category number>
0: The edges of the cut are perfectly smooth and there is no peeling in the eyes of any grid.
1: Small peeling of the coating film at the intersection of the cuts. The cross-cut portion is clearly not affected by more than 5%.
2: The coating film is peeled off along the edge of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5% but not more than 15%.
3: The coating film is partially or wholly peeled off along the edges of the cut, and / or various parts of the eye are partially or wholly peeled off. The cross-cut area is clearly affected by more than 15% but not more than 35%.
4: The coating film is partially or wholly peeled off along the edge of the cut, and / or some eyes are partially or wholly peeled off. The cross-cut portion is clearly not affected by more than 65%.
5: Any degree of peeling that cannot be classified even in classification 4.

1-6. Haze The haze (%) of the low refraction member was measured according to JIS K7136: 2000. The light incident surface was on the base material side. Using a 10 cm square low refraction member, 10 places were randomly selected from the places where there were no scratches or defects in the sample, and the arithmetic mean value of the 10 places was taken as the haze (%) of the low refraction member of each example and comparative example. ..

1-7. Total light transmittance The total light transmittance (%) of the low refraction member was measured according to JIS K7361-1: 1997. The light incident surface was on the base material side. Using a 10 cm square low refraction member, randomly select 10 places from the parts without scratches or defects of the sample, and calculate the arithmetic mean value of 10 places as the total light transmittance (%) of the low refraction member of each example and comparative example. ).

1-8. Diffuse light reflectance R _SCE
The release film of the brand name "Clear Mierre" manufactured by Tomagawa Seisakusho was peeled off, and the exposed black adhesive layer was attached to the glass substrate side surface of the 10 cm square low refraction member of Examples and Comparative Examples. A sample was prepared in which a black adhesive layer (total light transmittance of 1% or less) and a plastic film were laminated on the surface of the glass substrate side.
Integrating sphere spectrophotometer (Konica Minolta Co., Ltd., trade name: CM-2600d) used, measured from the surface of the low refractive index layer side of the sample, diffuse light reflectance of the sample _(R SCE) (%) bottom. Ten places were randomly selected from the places where there were no scratches or defects in the sample, and the arithmetic mean value of the ten places was taken as the diffused light reflectance R _SCE (%) of the low refraction member of each Example and Comparative Example.
The light source of the integrating sphere spectrophotometer is D65, the position of the receiver is +8 degrees with respect to the normal of the sample, the position of the light trap is -8 degrees with respect to the normal of the sample, and the viewing angle is. It was twice.

2. Fabrication of low refraction member [Example 1]
A spin coater (MS-B150 (Mikasa)) is coated with a coating liquid for forming a low refractive index layer according to the following formulation on a 10 cm square, 0.7 mm thick glass substrate (non-alkali glass manufactured by Corning Inc., trade name "EAGLE XG"). It was coated with (manufactured by Co., Ltd.) and prebaked (dried) at 100 ° C. for 120 seconds to obtain a coating film. The coating film was heated at 200 ° C. for 20 minutes in an oven to cure the composition containing a silicone-based compound. A low refractive index layer having a thickness of 1.0 μm was formed to obtain a low refractive index member of Example 1. The glass substrate was measured and measured in accordance with JIS K7136: 2000. It was 1%, and the diffused light reflectance ( _RSCE ) was 0.04%.
<Coating liquid for forming a low refractive index layer>
-Hollow particles: 20 parts by mass (hollow silica particles having an average particle diameter of 75 nm formed by surface treatment with a silane coupling agent having a methacryloyl group)
Binder resin component: 10 parts by mass (substituted hydrocarbon group having an epoxy group as a substituent, oligomer-type silicone compound in which an alkoxy group is directly linked to a silicon atom, epoxy equivalent: 350 g / mol, alkoxy group amount: 42 Mass%, product number "X-41-1059A" manufactured by Shin-Etsu Chemical Industry Co., Ltd., 100% active ingredient)
-Surfactant: 0.21 parts by mass (trade name "F-554" manufactured by DIC Corporation, 100% active ingredient)
-Propylene glycol monomethyl ether acetate: 120 parts

[Example 2]
A low-refractive index member of Example 2 was obtained in the same manner as in Example 1 except that the thickness of the low-refractive index layer was changed to 3.0 μm.

[Example 3]
A low-refractive index member of Example 3 was obtained in the same manner as in Example 1 except that the content of hollow particles in the coating liquid for forming a low refractive index layer was changed to 10 parts by mass.

[Example 4]
The low particles of Example 4 are the same as in Example 1 except that the hollow particles of the coating liquid for forming a low refractive index layer are changed to hollow silica particles having an average particle diameter of 60 nm, which are surface-treated with a silane coupling agent. A refracting member was obtained.

[Example 5]
The low particles of Example 5 are the same as in Example 1 except that the hollow particles of the coating liquid for forming a low refractive index layer are changed to hollow silica particles having an average particle diameter of 100 nm, which are surface-treated with a silane coupling agent. A refracting member was obtained.

[Comparative Example 1]
A low-refractive index member of Comparative Example 1 was obtained in the same manner as in Example 1 except that the thickness of the low-refractive index layer was changed to 0.2 μm.

[Comparative Example 2]
A low-refractive index member of Comparative Example 2 was obtained in the same manner as in Example 1 except that the thickness of the low-refractive index layer was changed to 5.5 μm.

[Comparative Example 3]
Similar to Example 1, low in Comparative Example 3 except that the hollow particles of the coating liquid for forming a low refractive index layer were changed to hollow silica particles having an average particle diameter of 50 nm, which were surface-treated with a silane coupling agent. A refracting member was obtained.

[Comparative Example 4]
Similar to Example 1, low in Comparative Example 4 except that the hollow particles of the coating liquid for forming a low refractive index layer were changed to hollow silica particles having an average particle diameter of 150 nm, which were surface-treated with a silane coupling agent. A refracting member was obtained.

[Comparative Example 5]
Comparison was performed in the same manner as in Example 1 except that the binder resin component of the coating liquid for forming a low refractive index layer was changed to a non-silicone epoxy resin (product number "EHPE3150" manufactured by Daicel, 100% solid content). The low refractive index member of Example 5 was obtained.

[Comparative Example 6]
The hollow particles of the coating liquid for forming a low refractive index layer are changed to hollow silica particles having an average particle diameter of 50 nm formed by surface treatment with a silane coupling agent, and the content of the hollow particles of the coating liquid for forming a low refractive index layer is further changed. The low-refractive index member of Comparative Example 6 was obtained in the same manner as in Example 1 except that the amount was changed to 40 parts by mass.

As apparent from the results in Table 1, the low refractive member of Example 1-5, despite the thickness of the low refractive index layer is thick, haze and R _SCE is small, whitening is suppressed good visibility It can be confirmed that. Further, it can be confirmed that the low-refractive index members of Examples 1 to 5 can suppress cracks because the thickness of the low-refractive index layer is not too thick. Further, it can be confirmed that the low-refractive index members of Examples 1 to 5 have a refractive index of 1.30 or less in the low-refractive index layer, suppress surface reflection, and have antireflection property. Further, it can be confirmed that the low refraction members of Examples 1 to 5 cannot distinguish the antireflection property between the scratched portion and the non-abrased portion, and are excellent in the antireflection performance after rubbing.

3. 3. Preparation of Transfer Sheet [Example 6]
As a release sheet, an A4 size polyimide film having a thickness of 50 μm was prepared. A low refractive index layer having a thickness of 1.0 μm was formed on one surface of the polyimide film in the same manner as in Example 1.
Next, on the low refractive index layer, the following coating liquid for hard coating is applied, dried, and irradiated with ultraviolet rays (irradiation amount 50 mJ / cm ² ) so that the thickness after drying becomes 5 μm to form a hard coat layer. bottom. Next, the following coating liquid for an anchor coat layer was applied onto the hard coat layer so that the thickness after drying was 2 μm, and dried to form an anchor coat layer. Next, the following coating liquid for an adhesive layer is applied and dried on the anchor coat layer so that the thickness after drying is 2 μm to form a heat-sensitive adhesive layer, and the transfer of Example 6 is performed. I got a sheet.

<Coating liquid for hard coat layer>
-Composition containing UV curable acrylic acrylate, silica particles and photopolymerization initiator (manufactured by DNP Fine Chemical Co., Ltd., trade name: KYK coating agent (82L)): 100 parts by mass-Hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Product name: Coronate 2203): 2 parts by mass-Diluting solvent (methyl ethyl ketone, methyl isobutyl ketone): Appropriate amount

<Coating liquid for anchor coat layer>
-Acrylic polyol (manufactured by Taisei Fine Chemical Co., Ltd., trade name: Acryt 6RH084T): 100 parts by mass-Hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate 2203): 10 parts by mass-Diluting solvent (methyl ethyl ketone, toluene) : Appropriate amount

<Coating liquid for adhesive layer>
-Vinyl chloride vinyl acetate copolymer (trade name "ST-PA varnish", manufactured by DNP Fine Chemical Co., Ltd., solid content 30%): 100 parts by mass-Diluting solvent (methyl ethyl ketone, toluene): Appropriate amount

4. Transfer of resin layer to adherend A transparent acrylic plate (manufactured by Kuraray Co., Ltd., trade name "Paragrass P001 Clear") having a size of 10 cm square and a thickness of 2.0 mm was prepared as the adherend.
The transfer sheet of Example 6 is cut into a size of about 15 cm square so that the heat-sensitive adhesive layer side faces the adherend side on the adherend so that the entire surface of the transparent acrylic plate is covered. After arranging and fixing one piece of the transfer sheet on the roll transfer start side with tape, the roll temperature is 220 to 240 ° C. using a roll type hot stamping machine (manufactured by Navitas, trade name "RH-300"). The adherend and the transfer layer were brought into close contact with each other under the condition of a roll speed of 20 mm / s. Next, the release sheet (polyimide film) was peeled off to form a transfer layer on the adherend.
Next, ultraviolet irradiation (irradiation amount 800 mJ / cm ² ) was performed to accelerate the curing of the hard coat layer, and a low refraction member was obtained.

In the low-refractive-index member obtained by using the transfer sheet of Example 6, whitening was suppressed and visibility was good despite the thick film thickness of the low-refractive index layer. Further, in the low-refractive index member obtained by using the transfer sheet of Example 6, cracks could be suppressed because the thickness of the low-refractive index layer was not too thick. Further, the low-refraction member obtained by using the transfer sheet of Example 6 was a member having suppressed surface reflection and sufficient antireflection property. Further, the low-refractive-index member obtained by using the transfer sheet of Example 6 has a scratched portion even though it has a soft adhesive layer between the adherend (transparent acrylic plate) and the low-refractive index layer. The scratch resistance was so excellent that the antireflection property could not be distinguished from the non-scratched part.

Claims (10)

A low-refractive index member having a low-refractive index layer on a base material, the low-refractive index layer having a thickness of 0.5 to 5.0 μm and containing hollow particles and a binder resin. A low-refractive index member having an average particle size of 60 to 140 nm and containing a cured product of a composition containing a silicone-based compound as the binder resin. The low refraction member according to claim 1, wherein the hollow particles are contained in an amount of 100 to 300 parts by mass with respect to 100 parts by mass of the binder resin. The low-refractive-index member according to claim 1 or 2, wherein the silicone-based compound is formed by directly linking a substituted hydrocarbon group having a reactive functional group as a substituent to a silicon atom. The diffusion light reflectance R _SCE measured from the low refractive index layer side of the low refractive member is not more than 1.5%, the low refractive member according to any one of claims 1 to 3. The low refraction member according to any one of claims 1 to 4, wherein the haze according to JIS K7136: 2000 is 1.0% or less. The low-refractive index member according to any one of claims 1 to 5, wherein the low refractive index layer has a refractive index of 1.30 or less. A transfer sheet having a transfer layer on a base material, the base material side of the transfer layer is a low refractive index layer, and the low refractive index layer has a thickness of 0.5 to 5.0 μm and , A transfer sheet containing hollow particles and a binder resin, the hollow particles having an average particle diameter of 60 to 140 nm, and containing a cured product of a composition containing a silicone-based compound as the binder resin. The coating composition for forming a low refractive index layer of the low refractive index member according to any one of claims 1 to 6, which contains hollow particles having an average particle diameter of 60 to 140 nm and a silicone compound as a binder resin component. thing. The coating composition for forming a low refractive index layer of a transfer sheet according to claim 7, which contains hollow particles having an average particle diameter of 60 to 140 nm and a silicone compound as a binder resin component. A laminated body having a vapor-deposited film on the low-refractive index layer of the low-refractive index member according to any one of claims 1 to 6.