JP2023108836A - Cured film and laminate, and methods for producing these - Google Patents

Abstract

To provide a method for producing a laminate, which forms a cured film having excellent matting property.SOLUTION: Provided are: a cured film having uneven structures on the surface, where the uneven structure includes, as defined by ISO 25178, Spd (density of peaks) of the film surface of 1000 [1/mm2] or more, Sdq (root mean square gradient) of 0.2 or more, and Sdr (developed interfacial area ratio) of 1% or more; a laminate including the cured film; and methods for producing these.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to cured films and laminates, and methods for producing these.

Building materials such as wallpaper and flooring, display materials, decorative films, electronic materials, etc.
In order to impart matte properties and the like, the surface of the base material may be provided with fine irregularities.
Patent Document 1 discloses, as a method of forming unevenness on the surface of a biaxially oriented thermoplastic resin film used in a magnetic recording medium, a method of decomposing the surface by irradiating the surface of the resin film with an excimer laser beam. .
In Patent Document 2, as a method for forming unevenness on the film surface, a wrinkle-shaped uneven structure is formed on the surface by utilizing the fact that phase separation occurs in the process of drying a coating film containing two or more compounds with different solubility. Disclosed is a method for obtaining a cured film having

JP-A-4-305430 JP 2021-24177 A

However, the method described in Patent Literature 1 can only form a concave-convex structure with a certain size, and a high matting effect and low glossiness cannot be obtained.
In the method described in Patent Document 2, a laminate is obtained in which a wrinkled uneven layer made of a resin cured product having unevenness due to phase separation is present on a substrate, but the wrinkled uneven structure of a certain size is obtained. However, a high matting effect and low glossiness cannot be obtained.

An object of the present invention is to provide a laminate having a cured film excellent in high mattness and low glossiness on a substrate, and a layer comprising the cured film, and a method for producing the same.

The present invention has the following aspects.
[1] A cured film having an uneven structure on the surface, wherein the uneven structure has a peak point density Spd of 1000 [1/mm ² ] or more on the coating surface defined by ISO 25178, a root mean square gradient Sdq of 0.2 or more, The developed interface area ratio Sdr is 1% or more, and the (meth)acrylate group is 1
A cured film characterized by having a compound containing one or more.
[2] The cured film according to [1], wherein the absolute value of the peak arithmetic mean curvature Spc defined by ISO25178 of the uneven structure is 100 [1/mm] or more.
[3] Scale of the uneven structure defined in ISO25178-2:2012
3. The cured film according to claim 2, which has an ea fractal complexity (Safc) of 2 or more.
[4] The compound containing one or more (meth)acrylate groups has a cyclic structure (meth)
The cured film according to any one of claims 1 to 3, which is one or more selected from the group consisting of acrylates, difunctional (meth)acrylates and trifunctional (meth)acrylates.
[5] Average length of roughness curve elements according to JIS B0601:2013 of the uneven structure
Rsm) is 1 μm or more, the cured film according to any one of claims 1 to 4.
[6] Claims 1 to 5, wherein the average value (θa) of the local inclination angles of the concave-convex structure is 2° or more.
The cured film according to any one of the above.
[7] The cured film according to any one of [1] to [6], which has a surface 60° gloss of 50 or less.
[8] The cured film according to any one of [1] to [7], which has a surface haze value of 10% or more.
[9] Claims 1 to 8, wherein the active energy ray-curable composition containing a polymer having an active group that generates radicals upon irradiation with an active energy ray is cured by irradiating it with vacuum ultraviolet light.
The method for producing a cured film according to any one of the above.
[10] A laminate comprising a substrate and a layer comprising the cured film according to any one of [1] to [8].
[11] An active energy ray-curable composition containing a polymer having an active group that generates radicals upon irradiation with an active energy ray is laminated on a substrate, and cured by irradiation with vacuum ultraviolet light. The method for producing the laminate according to 1.

The cured film of the present invention is excellent in high mattness and low glossiness.
According to the method for producing a cured film of the present invention, a cured film excellent in high matteness and low glossiness can be obtained.
The laminate of the present invention is excellent in high matting properties and low glossiness.
Laminates produced by the present invention are, for example, polarizing plates used in display members such as liquid crystal displays, optical members such as retardation plates and viewing angle expansion, electromagnetic wave shields used inside smartphones, tablets, etc. It can be used as a film coating member, a building material floor sheet coating member, and the like.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, "(meth)acrylate" is a generic term for acrylate or methacrylate. "(Meth)acryl" is a generic term for acryl and methacryl.
"~" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.

[Cured film]
The cured film of the present invention has an uneven structure (unsmooth structure) on its surface. As a result, the cured film has matte properties and low glossiness.

The thickness of the cured film (uneven layer) is preferably 0.1 to 100 μm, more preferably 0.2 to
50 μm, more preferably 0.3 to 30 μm, particularly preferably 0.5 to 10 μm. If the thickness of the cured product is within the above range, it is easy to achieve desired matte properties and low glossiness.
The thickness of the cured film indicates the maximum thickness of the uneven layer, and is determined by cross-sectional observation with an electron microscope.

The peak point density Spd of the uneven structure of the cured film indicates the number of peak points per unit area defined by ISO25178, preferably 1000 [1/mm ² ] or more, more preferably 300.
0 to 1,000,000 [1/mm ² ], more preferably 6000 to 500,000 [
1/mm ² ], particularly preferably in the range of 10,000 to 100,000 [1/mm ² ]. Within the above range, the surface has many sharp irregularities, and the desired mattness and low glossiness can be easily achieved.

The double mean square gradient Sdq of the uneven structure of the cured film indicates the average magnitude of the gradient calculated by the root mean square of the gradient at all points in a certain area defined by ISO 25178, preferably 0 0.1 or more, more preferably 0.2 to 100, still more preferably 0.5 to 10, and particularly preferably 0.7 to 3. Within the above range, the degree of undulation is increased, and the desired mattness and low glossiness can be easily achieved.

The expansion interface area ratio Sdr of the uneven structure of the cured film indicates the ratio of increase in the surface area of a certain region defined by ISO25178 to the area of the same region, preferably 0.1% or more, more preferably 1 to 100%. , more preferably 5 to 90%, particularly preferably 10 to 50%. Within the above range, the finely textured uneven surface is increased, and the desired mattness and low glossiness can be easily achieved.

The absolute value of the arithmetic mean curvature Spc of the peaks of the uneven structure of the cured film indicates the average curvature of the tip of the peaks defined by ISO25178, preferably 10 to 10,000 [1/mm].
, more preferably 50 to 7,000 [1/mm], more preferably 100 to 5,000
[1/mm], particularly preferably in the range of 500 to 3,000 [1/mm]. Within the above range, the surface has many sharp irregularities, and the desired mattness and low glossiness can be easily achieved.

Average length of roughness curve element (R
sm) is preferably 1 μm or more, more preferably 2 to 200 μm, even more preferably 3
~100 μm, particularly preferably 5-50 μm, most preferably 10-40 μm. Within the above range, the matting property is excellent, and in the case of low convex portions, the visibility is excellent when used for a display, etc., and the performance is well-balanced.

Scale area fractal complexity (
Safc) quantify the complexity of surface corrugations in a given area as defined in Fractal Methods of ISO 25178-2:2012, preferably from 1 to 10,000,
More preferably 3 to 1,000, still more preferably 5 to 500, particularly preferably 10 to 1
00 range. Within the above range, it is easy to achieve the desired matte properties and low glossiness.

The average value (θa) of the local inclination angle of the uneven structure of the cured film is preferably 2° or more, more preferably 4° or more, still more preferably 7° or more, particularly preferably 10° or more, and most preferably 15° or more. and the upper limit may be 90°. The higher the angle of inclination, the better the mattness.

The surface roughness (Sa) of the cured film is 0.1 μm or more, preferably 0.15 to 20 μm, more preferably 0.2 to 10 μm, still more preferably 0.3 to 5 μm, particularly preferably 0.4 to
It is in the range of 3 μm. Within the above range, the matting property is excellent, and in the case of low convex portions, the visibility is excellent when used for a display, etc., and the performance is well-balanced.

The cured film preferably has a 60° gloss (60° specular gloss) measured by the method described in Examples below, preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.
It is particularly preferably 15 or less, most preferably 10 or less, and the lower the better. When it is equal to or less than the above upper limit value, the matting property is excellent.
Similarly, the 20° gloss is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, particularly preferably 2 or less, and most preferably 1 or less, and the lower the better. When it is equal to or less than the above upper limit value, the matting property is excellent.

The cured film preferably has permeability. The total light transmittance measured by the method described in Examples below is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably 80% or more, and most preferably 90%. Within the above range, the higher the content, the better (the upper limit is 100%). It is excellent in permeability|transmittance in it being the said range.

The cured film preferably has a haze of 1% or more, more preferably 3% or more, still more preferably 5% or more, particularly preferably 10% or more, and most The range is preferably 20% or more, and the upper limit is, for example, 99%. When the haze is at least the above lower limit, it is easy to obtain good matte properties.
In particular, when used for antiglare in various displays, the content is preferably 40% or more, more preferably 50% or more, still more preferably 60% or more, particularly preferably 70% or more, and most preferably 80% or more. Yes, and the upper limit is, for example, 99%. Also, depending on the application, there are applications where the higher the value, the better. If it is at least the above lower limit, the antiglare property tends to be good.

[Method for producing cured film]
The method for producing a cured film of the present invention is a method of forming a coating film of the following curable composition and irradiating the coating film with an active energy ray.

(Curable composition)
The curable composition contains (meth)acrylate.

((meth)acrylate)
(Meth) acrylate to be blended in the curable composition is not particularly limited, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or more polyfunctional (meth) acrylate mixed one or more, cured It is possible to use those commercially available as flexible resin materials, or those to which other components are further added within the range not impairing the purpose of the present embodiment. Among these, monofunctional or bifunctional (meth)acrylates are preferable from the viewpoint of facilitating the formation of a steep concave-convex structure. Bifunctional (meth)acrylates are more preferred for applications that require scratch resistance. The use of polyfunctional (meth)acrylates is a preferable form in terms of improving scratch resistance and hardness, but depending on the compound used, it may be difficult to form an uneven structure, so the type of compound used and the mixing ratio should be carefully considered.

Examples of monofunctional (meth)acrylates include, but are not limited to, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)
Alkyl (meth)acrylates such as acrylates, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl ( hydroxyalkyl (meth) such as meth)acrylate
Alkoxyalkyl (meth)acrylates such as acrylates, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate Amino group-containing (meth) acrylate such as aromatic (meth) acrylate, diaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate
Ethylene oxide-modified (meth)acrylates such as acrylates, methoxyethylene glycol (meth)acrylates, phenoxypolyethylene glycol (meth)acrylates, phenylphenol ethylene oxide-modified (meth)acrylates, glycidyl (meth)acrylates
Acrylate, Tetrahydrofurfuryl (meth)acrylate, Cyclopentyl (meth)
Acrylate, 1-methylcyclopentyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate , 4-tert-butylcyclohexyl (meth)acrylate, 2-cyclohexylpropanyl (meth)acrylate, 4-acryloylmorpholine, benzyl (meth)acrylate, phenyl (meth)acrylate, phenylalkylene oxide-modified (meth)acrylate, nonylphenol ( meth) acrylate, nonylphenol alkylene oxide-modified (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl acrylate, biphenyl (meth) acrylate, biphenyl alkylene oxide-modified (meth) acrylate, isobornyl (
meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyl alkylene oxide-modified (meth)acrylate, dicyclopentenyl (meth)acrylate
dicyclopentenyl alkylene oxide-modified (meth) acrylate, adamantyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-ethyladamantyl (meth) acrylate, 2-isopropyladamantyl (meth) acrylate,
(3-ethyloxetan-3-yl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-oxo-1,3-dioxolan-4-yl) methyl (
meth) acrylate, mevalonic acid lactone (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, (3, 4-epoxycyclohexyl)methyl (meth)acrylate, (meth)acrylic acid and the like. Among these, (meth)acrylates with a cyclic structure are preferable in consideration of the ease of forming a steep uneven structure, and among these, (meth)acrylates having one or more benzene rings and condensed polycyclic hydrocarbons (Meth) acrylate, having a polycyclic structure such as a dicyclopentenyl structure (
More preferred are meth)acrylates and (meth)acrylates having a heterocyclic structure such as a morpholine structure. Particularly preferred are biphenylalkylene oxide-modified (meth)acrylate, dicyclopentenylalkylene oxide-modified (meth)acrylate, and 4-acryloylmorpholine.

The bifunctional (meth)acrylate is not particularly limited, but for example 1,4
-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate ) alkanediol di(meth)acrylate such as acrylate, bisphenol A ethylene oxide-modified di(meth)acrylate, bisphenol F ethylene oxide-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth) Acrylate, urethane di(meth)acrylate, epoxy di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol A alkylene oxide modified di(meth)acrylate, hydrogenated bisphenol A caprolactone modified di(meth)acrylate, water Hydrogenated bisphenol A glycidyl ether modified di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, hydrogenated bisphenol F caprolactone modified di(meth)acrylate, hydrogenated bisphenol F alkylene oxide modified di(meth)acrylate, hydrogenated bisphenol Hydrogenated bisphenol-modified di(meth)acrylate such as F glycidyl ether-modified di(meth)acrylate, bisphenol A di(meth)acrylate, bisphenol A alkylene oxide-modified di(meth)acrylate, bisphenol A caprolactone-modified di(meth)acrylate, Bisphenol A glycidyl ether-modified di(meth)acrylate, bisphenol F di(meth)acrylate, bisphenol F caprolactone-modified di(meth)acrylate, bisphenol F alkylene oxide-modified di(meth)acrylate, bisphenol F glycidyl ether-modified di(meth)acrylate Bisphenol-modified di (meth) acrylate, fluorene (meth) acrylate, fluorene alkylene oxide-modified di (meth) acrylate, isobornyl di (meth) acrylate, tricyclodecanediol di (meth) acrylate, tricyclodecanedimethanol di ( meth)acrylate, adamantyl di(meth)acrylate, dioxane glycol di(meth)acrylate, isosorbide di(meth)acrylate, isosorbide alkylene oxide-modified di(meth)acrylate, and the like.
Among these, considering the ease of forming an uneven structure, it is preferable that the alcohol residue has a structure without branches, and among these, alkyldiol di(meth)acrylate and alkylene oxide-modified di(meth)acrylate are more More preferred are alkyldiol di(meth)acrylates having 4 to 18 carbon atoms.

Trifunctional or higher polyfunctional (meth)acrylates are not particularly limited,
For example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified dipentaerythritol Hexa (meth) acrylate, ethylene oxide-modified (meth) acrylate such as ethylene oxide-modified pentaerythritol tetra (meth) acrylate, isocyanuric acid ethylene oxide-modified tri(
meth)acrylates, isocyanuric acid-modified tri(meth)acrylates such as ε-caprolactone-modified tris(acloxyethyl)isocyanurate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipenta urethane acrylates such as erythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer; Among these, the ethylene oxide-modified type and the trifunctional (meth)acrylate are preferable in consideration of the easiness of forming the concave-convex structure.

Active energy ray-curable compounds other than (meth)acrylates can also be used in the cured resin layer composition. Examples thereof include vinyl compounds such as styrene, vinyl halide and vinyl acetate, and diene compounds such as vinylidene halide, 1,3-butadiene, isoprene and chloroprene.

In the formation of the cured film, when using an active energy ray-curable compound, the content of the active energy ray-curable compound in the curable composition is preferably 5
~99.99% by mass, more preferably 30 to 99.9% by mass, more preferably 40 to 9
5% by weight, particularly preferably 50-90% by weight, most preferably 60-80% by weight. In the case of the above range, it becomes easy to form an uneven structure, and a cured film having excellent hardness can be formed.

(resin)
Various resins can be blended into the curable composition for the purpose of improving adhesion to the substrate. Various resins can be used as the resin, and examples thereof include conventionally known resins such as acrylic resins, polyester resins, polyurethane resins, and polyvinyl resins. Acrylic resin is preferable in terms of excellent affinity.

Considering the improvement of hardness, the above resin preferably has a vacuum ultraviolet curable functional group such as a carbon-carbon double bond. Examples of vacuum ultraviolet curable functional groups include (meth)acryloyl groups and vinyl ether compounds. Among these, a (meth)acryloyl group, particularly an acryloyl group, is preferred in view of ease of introduction and reactivity.

In addition, when a resin having a vacuum UV-curable functional group is blended, not only the properties directly related to the vacuum UV-curable functional group, such as an improvement in the hardness of the cured film, but also the irregularities tend to be reduced. That is, there is a tendency that the center-to-center distance (Rsm) between adjacent protrusions becomes smaller, and the surface roughness (Sa) also becomes smaller. In addition, haze may increase and gloss may decrease. These properties can exert a synergistic effect on the matte property, and it is preferable to incorporate the resin particularly when the laminate is used for applications such as displays where visibility is emphasized. In addition, the center-to-center distance (Rsm) and surface roughness (Sa) of the concave-convex structure of the cured film can be adjusted by appropriately selecting the compounding amount and type of the resin.

As a method for producing an acrylic resin having a vacuum ultraviolet curable functional group such as a carbon-carbon double bond, for example, a method for introducing the double bond includes adding a double bond and a carboxyl group to an acrylic resin having an epoxy group. A method of reacting a compound having a group (Method 1), a method of reacting a compound having a double bond and an epoxy group with an acrylic resin having a carboxyl group (Method 2), a double bond and a carboxyl group with an acrylic resin having a hydroxyl group. A method of reacting a compound having a (method 3), a method of reacting a compound having a double bond and a hydroxyl group with an acrylic resin having a carboxyl group (method 4), an acrylic resin having an isocyanate group and having a double bond and a hydroxyl group A method of reacting a compound (Method 5), a method of reacting an acrylic resin having a hydroxyl group with a compound having a double bond and an isocyanate group (Method 6), and the like. Also, the above methods may be used in combination. In the following,
A radically polymerizable monomer having a carbon-carbon double bond is sometimes referred to as a vinyl monomer.

Examples of the vinyl monomer having an epoxy group used for obtaining the acrylic resin having an epoxy group in Method 1 include glycidyl (meth)acrylate, 3,
4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like. Among these, glycidyl (meth)acrylate is preferred, and glycidyl methacrylate is particularly preferred, in consideration of good reactivity and ease of use of the material. These may use only 1 type, and may combine 2 or more types.

Examples of the compound having a double bond and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerol di(meth)acrylate and succinic anhydride, pentaerythritol tri Adducts of (meth)acrylate and succinic anhydride, adducts of pentaerythritol tri(meth)acrylate and phthalic anhydride, and the like. Among these, (meth)acrylic acid and adducts of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. In addition, the compound which has a double bond and a carboxyl group may use only 1 type, and may combine 2 or more types.

Examples of the vinyl monomer having a carboxyl group used to obtain the acrylic resin having a carboxyl group in Method 2 include (meth)acrylic acid, carboxyethyl (meth)acrylate, polybasic acid-modified (meth)acrylate, and the like. is mentioned. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These may use only 1 type, and may combine 2 or more types.

In Method 2, examples of the compound having a double bond and an epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and the like. Among these, glycidyl (meth)acrylate is preferred. These may use only 1 type, and may combine 2 or more types.

Examples of the vinyl monomer having a hydroxyl group used for obtaining the acrylic resin having a hydroxyl group in Method 3 include 2-hydroxyethyl (meth)acrylate, 4
- hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate and the like. These may use only 1 type, and may combine 2 or more types.

In Method 3, the compound having a double bond and a carboxyl group may be the same compound as in Method 1.

In Method 4, the same acrylic resin as used in Method 2 can be used as the acrylic resin having a carboxyl group.

In Method 4, the compound having a double bond and a hydroxyl group includes, for example, 2
-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate and the like. These may use only 1 type, and may combine 2 or more types.

In Method 5, the vinyl monomer having an isocyanate group used for obtaining the acrylic resin having an isocyanate group includes, for example, isocyanatoethyl (meth)acrylate.

In Method 5, the compound having a double bond and a hydroxyl group may be, for example, the same compounds as those listed in Method 4 above.

In method 6, the same compound as in method 3 can be used as the acrylic resin having a hydroxyl group.

In method 6, the compound having a double bond and an isocyanate group is
Examples thereof include isocyanatoethyl (meth)acrylate. These may use only 1 type, and may combine 2 or more types.

Among the above methods, method 1 is preferable because the reaction can be easily controlled. In method 1, the double bond is introduced by ring-opening/addition reaction between the epoxy group of the acrylic resin having the epoxy group and the carboxyl group of the compound having the double bond and the carboxyl group.

In Method 1, the monomer having an epoxy group in the acrylic resin having an epoxy group is preferably 5
% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more. The upper limit is not particularly limited, but is preferably 99.9% by weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less, particularly preferably 50% by weight or less, and most preferably 40% by weight or less. is in the range. By using it in this range, there is a tendency not only to improve the adhesion to the substrate of the cured film, scratch resistance, and hardness, but also to make the uneven shape finer, lowering Rsm, lowering Sa, An increase in haze and a decrease in gloss can be achieved in some cases.

In Method 1, the compound having a double bond and a carboxyl group is preferably 10 to 150 mol% as a ratio of the compound having a double bond and a carboxyl group to the epoxy group in the acrylic resin having an epoxy group. and more preferably 30 to 13
0 mol %, more preferably 50 to 110 mol %. It is preferable to use it in this range from the viewpoint of allowing the reaction to proceed just enough and reducing the residue of the raw material.

Furthermore, the acrylic resin such as the acrylic resin having an epoxy group as described above may be obtained by copolymerizing (meth)acrylates other than those described above or other vinyl monomers.
The polymerization reaction of these raw materials is usually radical polymerization, and can be carried out under conventionally known conditions.

Monomers that can be used together as raw materials include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (
meth) acrylate, phenyl (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, octoxy ( poly)ethylene glycol (meth)acrylate, octoxy (poly)propylene glycol (meth)acrylate, octoxytetramethylene glycol (meth)acrylate, lauroxy (poly)ethylene glycol (meth)acrylate,
(Meth)acrylates such as stearoxy (poly)ethylene glycol (meth)acrylate; ethyl (meth)acrylamide, n-butyl (meth)acrylamide, i-butyl (
Acrylamides such as meth)acrylamide, t-butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-dihydroxyethyl (meth)acrylamide; styrene, p-chlorostyrene , p-bromostyrene and other styrenic monomers. These may use only 1 type, and may combine 2 or more types.

The acrylic resin can be produced by a radical polymerization reaction using the raw vinyl monomers described above. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

Examples of organic solvents used for radical polymerization include acetone and methyl ethyl ketone (M
EK) and other ketone solvents; ethanol, methanol, isopropyl alcohol (IPA)
, isobutanol and other alcohol solvents; ethylene glycol dimethyl ether, propylene glycol monomethyl ether and other ether solvents; ethyl acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate and other ester solvents; toluene and other aromatic carbonization A hydrogen solvent and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

Examples of radical polymerization initiators used for radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2'-azobisbutyronitrile, 2,2'-azobis( ,4-dimethylvaleronitrile), 2,2'-azobis (4-
azo compounds such as methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the raw material vinyl monomers.

Moreover, a chain transfer agent can be used for the purpose of controlling the weight-average molecular weight of the acrylic resin during the radical polymerization. Examples of chain transfer agents include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexylmercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, and octyl 3-mercaptopropionate. , 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy ) diethanethiol, ethanethiol, 4-methylbenzenethiol, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol,
Thiol compounds such as thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid.
These may be used alone or in combination of two or more.

The amount of the chain transfer agent used is 0.1 to 2 parts per 100 parts by weight of the raw material vinyl monomer.
5 parts by weight is preferred, 0.5 to 20 parts by weight is more preferred, and 1.0 to 15 parts by weight is even more preferred.

The reaction time for radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours.
The reaction temperature is preferably 40-120°C, more preferably 50-100°C.

In order to react a compound or the like having a double bond and a carboxyl group with an acrylic resin, a compound or the like having a double bond and a carboxyl group is added to the acrylic resin obtained as described above to obtain triphenylphosphine, In the presence of one or more catalysts such as tetrabutylammonium bromide, tetramethylammonium chloride, and triethylamine, the reaction is usually carried out at a temperature of 90 to 140°C, preferably 100 to 120°C, for approximately 3 to 9 hours. good. Here, the catalyst is used in a ratio of about 0.5 to 3 parts by weight with respect to a total of 100 parts by weight of the raw material (meth)acrylic acid ester polymer and the compound such as a compound having a double bond and a carboxyl group. It is preferable to use This reaction may be carried out continuously after the acrylic resin is produced by the polymerization reaction, or after the acrylic resin is once separated from the reaction system, a compound such as a compound having a double bond and a carboxyl group is added. may

The amount of double bonds in the acrylic resin is preferably 0.1 to 10 mmol/g, more preferably 0.2 to 7.0 mmol/g, even more preferably 0.5 to 5.0 mmol/g, particularly preferably 0.5 to 5.0 mmol/g. 8-4.0 mmol/g, most preferably 1.0-3.0 mmol/g
is in the range. By using it in this range, there is a tendency not only to improve the adhesion to the substrate of the cured film, scratch resistance, and hardness, but also to make the uneven shape finer, lowering Rsm, lowering Sa, An increase in haze and a decrease in gloss can be achieved in some cases. note that,
The amount of double bonds means the concentration of (meth)acryloyl groups in the acrylic resin, that is, the amount of (meth)acryloyl groups introduced.

The weight-average molecular weight (Mw) of the resin should be appropriately selected according to the application of the curable composition.
000 or more, usually 200,000 or less, preferably 100,000 or less,
It is more preferably 70,000 or less, still more preferably 50,000 or less. Within the above range, it becomes easier to form surface unevenness. The weight average molecular weight (Mw) of the resin can be determined by gel permeation chromatography (GPC) as a converted value based on polystyrene standards. Specific measurement conditions are shown in Examples below.

When a resin is blended in the curable composition, the content is preferably 80% by mass or less, more preferably 3 to 60% by mass, more preferably 5 to 50% by mass, based on the nonvolatile content.
Especially preferably, it is in the range of 8 to 40% by mass. In the case of the above range, there is a tendency that not only the adhesion of the cured film to the substrate, the scratch resistance, and the hardness can be improved, but also the uneven shape can be made finer.
A reduction in sm, a reduction in Sa, and in some cases an increase in haze and a reduction in gloss can be achieved.

Particles may be added to the curable composition in order to further improve the matting property of the cured film due to the uneven structure. Particles are not particularly limited, and conventionally known particles can be used. Specific examples include silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, inorganic particles such as titanium oxide, acrylic resin, styrene resin,
Organic particles such as urea resin, phenol resin, epoxy resin, benzoguanamine resin, and the like are included. The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The organic particles are preferably of a crosslinked type, more preferably crosslinked acrylic resin particles or crosslinked styrene resin particles, in order to maintain their shape. These particles may be used in combination of two or more.

The average primary particle diameter of the particles is preferably 0.01 to 30 μm, more preferably 0.01 to 30 μm.
05 to 10 μm, more preferably 0.1 to 5 μm, particularly preferably 0.5 to 3 μm. In the case of the said range, it is excellent in matting improvement.

When particles are blended in the curable composition, the content is preferably 50% by mass or less, more preferably 0.1 to 30% by mass, based on the non-volatile content, from the viewpoint of improving matting properties. , more preferably 0.5 to 20% by mass, and particularly preferably 1 to 15% by mass.

(Photoinitiator)
A photopolymerization initiator may be added to accelerate the curability of the curable composition. The molecular weight of the photopolymerization initiator is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyldiphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3′-dimethyl-4- methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone,
4,4′-bis(diethylamino)benzophenone, pivaloine ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4- Diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-( 4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(
methylthio)phenyl]-2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone and the like. These photopolymerization initiators may be used alone or in combination of two or more.

When a photopolymerization initiator is blended in the curable composition, the content thereof is preferably 20% by mass or less, more preferably 0.1 to 10% by mass, based on the nonvolatile content from the viewpoint of promoting curability. %
, more preferably 0.5 to 8% by mass, and particularly preferably 1 to 5% by mass.

(leveling agent)
A leveling agent can be added to the curable composition to improve the appearance of the cured film.
Examples of leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. These leveling agents may be used alone or in combination of two or more.

When blending a leveling agent in the curable composition, the content is preferably 10% by mass or less, more preferably 0.01 to 8, based on the nonvolatile content, from the viewpoint of improving the appearance of the cured film.
% by mass, more preferably in the range of 0.1 to 5% by mass.

(Various additives)
The curable composition may contain a polymerization accelerator such as a compound containing a thiol group, an antistatic agent, an antifouling agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, as long as the effects of the present invention are not impaired. Various additives such as agents may be blended.

(Organic solvent)
For the purpose of improving the workability of coating on a substrate, the curable composition may optionally contain an organic solvent.
Organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether;
Ether solvents such as isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate Ester solvents such as; dimethylformamide,
Amide solvents such as diethylformamide and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen solvents such as dichloromethane and chloroform; etc. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferred because they tend to improve workability in coating.

When an organic solvent is blended in the curable composition, the content is preferably 10 parts by mass or more and 1900 parts by mass or less with respect to 100 parts by mass of nonvolatile matter from the viewpoint of improving operability in coating operation, and 40 parts by mass. More preferably, the amount is 400 parts by mass or less.
The non-volatile content of the cured resin layer composition is the total mass of components other than the solvent, such as an organic solvent. The non-volatile content of the cured resin layer composition can be measured by a conventionally known method.
1 g of the composition is spread and heated at 100° C. for 1 hour to volatilize the organic solvent, and the change in weight is measured.

(Lamination of curable composition)
Examples of the method of laminating the curable composition on the substrate include a method of applying the curable composition to the surface of the substrate to form a coating film, and drying the film as necessary. The method of coating is not particularly limited, and for example, known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating can be used. method.

When the curable composition contains an organic solvent, it is preferably heated and dried in advance before being irradiated with vacuum ultraviolet rays. By drying by heating in advance, the solvent in the coating film can be effectively removed. The drying temperature of heat drying is preferably 30° C. or higher and 200° C. or lower, more preferably 40° C. or higher and 150° C. or lower. The drying time is preferably 0.01 minute or more and 30 minutes or less, and 0.1 minute or more and 1 minute or more.
0 minutes or less is more preferable.

(Irradiation of vacuum ultraviolet rays)
The curable composition laminated on the substrate is irradiated with vacuum ultraviolet rays to cure the composition to form a cured film, thereby forming a laminate in which the cured film is laminated on the substrate. Vacuum ultraviolet rays are ultraviolet rays with a wavelength of 200 nm or less, and excimer light with a half width of 50 nm or less is most suitable. Examples of excimer light include argon (126 nm), krypton (146 nm), xenon (172
nm), and argon/fluorine (193 nm). Among these, xenon excimer light is preferable in consideration of ease of handling, ability to form an effective concave-convex structure on the cured film, curability of the curable composition, and the like.

The integrated amount of vacuum ultraviolet rays to be irradiated is preferably 1 to 5000 mJ/cm ² , more preferably 3 to 3000 mJ/cm ² , still more preferably 5 to 1000 mJ/cm ² , and particularly preferably 10 to 500 mJ/cm ² . be. Also, the illuminance is preferably 1 to 10
00 mW/cm ² , more preferably 10 to 500 mW/cm ² , more preferably 50 to
It is in the range of 300 mW/cm ² .

In addition, it is preferable that the vacuum ultraviolet irradiation is performed in an oxygen-poor environment such as a nitrogen atmosphere. The oxygen concentration in the atmosphere is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.

After irradiating the vacuum ultraviolet rays, it is preferable to irradiate an active energy ray other than the vacuum ultraviolet rays in order to harden the cured film to the deep part. Examples of active energy rays include ultraviolet rays, electron rays, and the like, and among these, ultraviolet rays are more preferable in consideration of the curability of the cured film.
The cumulative amount of UV light to be irradiated is preferably 1 to 5000 mJ/cm ² , more preferably 50 to 3000 mJ/cm ² , still more preferably 100 to 2000 mJ/cm ² , and particularly preferably 200 to 1000 mJ/cm ² . . Also, the illuminance is preferably 1
It is in the range of up to 1000 mW/cm ² , more preferably 50-500 mW/cm ² , still more preferably 80-300 mW/cm ² .

[Method for manufacturing laminate]
In the present invention, a curable composition containing (meth)acrylate is laminated on a substrate, and vacuum ultraviolet rays are irradiated to cure the composition. By irradiating the coating film of the curable composition with vacuum ultraviolet rays, the surface side of the coating film is cured first to form a cured coating, and then when the inside of the coating film is cured, the cured coating film on the surface side is seated. By bending, a cured film having an uneven structure (unsmooth structure) on the surface is formed. Hereinafter, the laminate produced by the method of the present invention is simply referred to as "laminate".

(Base material)
A known substrate can be used, and examples thereof include resin substrates, metal substrates, and paper substrates. Among these, a resin substrate is preferable from the viewpoint of workability.
The resin base material may have a single layer structure or a multilayer structure of two or more layers, and is not particularly limited. It is preferable that the resin base material has a multi-layered structure of two or more layers and that each layer has its own characteristic to achieve multi-functionality.

Various resin films (sheets) can be used as the resin base material. A polyvinyl alcohol film, a nylon film, etc. are mentioned.
Polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred when the laminate is used for display applications. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for antiglare applications, and polyester films are more preferred in consideration of transparency, moldability, and versatility.
The polyester film may be a non-stretched film or a stretched film, preferably a stretched film. Among them, a uniaxially stretched film or a biaxially stretched film is preferable, and a biaxially stretched film is more preferable from the viewpoint of excellent balance of mechanical properties and flatness.

The polyester constituting the polyester film that can be used as the base material may be homopolyester or copolyester.
The homopolyester is preferably obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Aliphatic glycols include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and the like. Aromatic dicarboxylic acids and aliphatic glycols may be used alone or in combination of two or more.
Examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Glycol components include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like. Each of the dicarboxylic acid component and the glycol component may be used alone or in combination of two or more.
Representative polyesters include polyethylene terephthalate and polyethylene naphthalate.

As the polyester film, considering the mechanical strength and heat resistance, among the above, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferable, and are easy to manufacture and easy to handle as a surface protection film. Considering , a film formed from polyethylene terephthalate is more preferred.

As the poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as a base material, any one having units based on (meth)acrylate can be used, and various acrylic resins can be used. (Meth)acrylates include alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate; Alkyl (meth)acrylates having an alkyl group with a large number of carbon atoms are included.
Considering transparency, workability, and chemical resistance, poly(meth)acrylate has 1 to
It is preferable that the alkyl (meth) acrylate-based units of 4 are the main component, and at least one selected from the group consisting of methyl (meth) acrylate-based units and ethyl (meth) acrylate-based units is the main component. is more preferable, and it is particularly preferable to have units based on methyl (meth)acrylate as the main component.
Poly(meth)acrylates may contain units based on (meth)acrylates other than alkyl(meth)acrylates or units based on other monomers to impart properties such as flexibility.
The ratio of units based on alkyl (meth)acrylate having 1 to 4 carbon atoms to the total mass of poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

The base material can contain particles for the purpose of imparting lubricity, preventing scratching in each step, and improving anti-blocking properties.
The type of particles can be appropriately selected depending on the purpose, and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, acrylic resin, styrene resin, urea resin, and phenol. Examples include organic particles such as resins, epoxy resins, and benzoguanamine resins. Furthermore, when the substrate layer includes a polyester film, deposited particles obtained by depositing a part of a metal compound such as a catalyst in the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are preferable because they are particularly effective even in small amounts.
The shape of the particles is not particularly limited, and may be spherical, massive, rod-like, flat, or the like. Moreover, there are no particular restrictions on its hardness, specific gravity, color, and the like.
Two or more kinds of these particles may be used in combination, if necessary.

The average particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, still more preferably 0.01 to 3 μm. If the average particle size is 10 μm or less, problems due to a decrease in transparency of the base material layer are less likely to occur.
The average particle diameter of particles is the value of 50% of the cumulative (mass basis) in the equivalent spherical distribution measured by a centrifugal sedimentation particle size distribution analyzer.

When the base material contains particles, the content of the particles in the base material layer cannot be generalized because there is a balance with the average particle size of the particles, but the total mass of the layer containing the particles in the base material layer preferably 5
% by mass or less, more preferably in the range of 0.0003 to 3% by mass, more preferably 0.00
05 to 1% by mass. If the content of the particles is 5% by mass or less, problems such as falling off of the particles and deterioration of the transparency of the substrate layer are less likely to occur.

The substrate may optionally contain additives other than the particles described above. Known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes and pigments can be used as additives.

The thickness of the base material is not particularly limited as long as it is within a film-forming range, but preferably 2
~350 μm, more preferably 5-250 μm, more preferably 10-100 μm.
A primer layer may be provided on the surface of the substrate on which the curable composition is laminated. When the substrate is a film or sheet, the surface opposite to the surface on which the curable composition is laminated may have a back functional layer.

A laminate produced by the method of the present invention (hereinafter also referred to as "this laminate") has a substrate layer and a cured film of a curable composition. The laminate may further have a primer layer between the substrate and the cured film. Further, the substrate may have a back functional layer on the surface opposite to the cured film side. A surface functional layer may be provided on the surface of the cured film opposite to the substrate side as long as it does not impair the effects of the present invention.

(primer layer)
The primer layer is provided to provide various functions such as improved adhesion between the substrate and the cured film. The primer layer may have a plurality of functions in one layer, or may be composed of a plurality of layers.

In one preferred embodiment, the primer layer is an adhesion improving layer. If the adhesiveness between the substrate layer and the cured film is insufficient, the laminate may not be usable depending on the application. By having the adhesion improving layer, the adhesion between the substrate layer and the cured film is improved, and the laminate can be used for various purposes. From the viewpoint of improving adhesion, the adhesion improving layer preferably contains either one or both of a compound derived from a resin and a cross-linking agent.

A conventionally known resin can be used as the resin contained in the primer layer. Specific examples of resins include polyester resins, acrylic resins, urethane resins, polyvinyl resins (
polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.). Among these resins, polyester resins, acrylic resins, and urethane resins are preferable in consideration of adhesion performance and coatability.
When the base material is a resin film, the resin contained in the primer layer is preferably the same type of resin as the resin film from the viewpoint of affinity with the base material. For example, when the substrate is a polyester film, the primer layer preferably contains a polyester resin. When the substrate layer is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

Examples of polyester resins include those composed mainly of polyvalent carboxylic acid and polyvalent hydroxy compound.
Polyvalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-
diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,
4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid , trimellitic anhydride, phthalic anhydride, trimellitic monopotassium salts and ester-forming derivatives thereof.
Examples of polyhydric hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1 ,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly Tetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like.
One or more of these compounds may be appropriately selected, and a polyester resin may be synthesized by a conventional polycondensation reaction.

An acrylic resin is a polymer of polymerizable monomers including (meth)acrylic monomers. Examples of acrylic resins include homopolymers and copolymers of (meth)acrylic monomers, copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers, and the like.
Acrylic resins may be copolymers of these polymers with other polymers (eg, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers, graft copolymers. Alternatively, a polymer obtained by polymerizing a polymerizable monomer in a polyester solution or dispersion (sometimes a mixture of polymers) is also included. Also included are polymers (optionally mixtures of polymers) obtained by polymerizing polymerizable monomers in a polyurethane solution or dispersion. Also included are polymers (possibly polymer mixtures) obtained by polymerizing polymerizable monomers in solutions or dispersions of other polymers.

The polymerizable monomer is not particularly limited, but particularly representative compounds include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and their salts of; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate; methyl ( Alkyl (meth)acrylates such as meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; (meth)acrylamide, Nitrogen-containing monomers such as diacetone acrylamide, N-methylolacrylamide and (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

A urethane resin is a polymer compound having urethane bonds in its molecule, and is typically synthesized by reacting a polyol with a polyisocyanate compound. A chain extender may be used when synthesizing the urethane resin. Polyols used to obtain urethane resins include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, and the like. These compounds may be used alone or in combination of two or more.

A polycarbonate polyol is obtained by a reaction (dealcoholization reaction) between a polyhydric alcohol and a carbonate compound. Polyhydric alcohols include ethylene glycol, 1,2
- propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1
,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-
hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane and the like. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like. Specific examples of polycarbonate polyols include poly(1,
6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate and the like.

Polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.

Polyester polyols include those obtained by reacting a polyhydric carboxylic acid or an acid anhydride thereof with a polyhydric alcohol, and those having a derivative unit of a lactone compound such as polycaprolactone.
Examples of polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid.
Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2 ,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2 -hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamine,
lactone diol and the like.

Polyester polyols and polycarbonate polyols are preferable as polyols, and polyester polyols are particularly preferable, in consideration of adhesion performance.

Polyisocyanate compounds used to obtain urethane resins include tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate,
Aromatic diisocyanates such as phenylene diisocyanate, naphthalene diisocyanate and tolidine diisocyanate; aliphatic diisocyanates having aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and isopropylidene dicyclohexyl diisocyanate. These may be used individually by 1 type, or may use 2 or more types together.

The chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Generally, chain extenders having two hydroxyl groups or two amino groups can be mainly used. .
Examples of chain extenders having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and esters such as neopentyl glycol hydroxypivalate. Glycol compounds such as glycol can be mentioned.
Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine. , 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-
1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,
Aliphatic diamines such as 10-decanediamine, 1-amino-3-aminomethyl-3,5,5
-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylitincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane and other alicyclic diamines.

Urethane resins are typically used in the form of dispersions or solutions. The medium for the dispersion or solution may be a solvent, but water is preferred.
Aqueous dispersions or aqueous solutions of urethane resin include a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the structure of the urethane resin, and a water-based type. In particular, a self-emulsifying type in which an ion group is introduced into the structure of a urethane resin to form an ionomer is preferable because it is excellent in the storage stability of the liquid and the water resistance and transparency of the resulting primer layer.

As the ionic group introduced into the structure of the urethane resin, various groups such as carboxyl group, sulfonic acid group, phosphoric acid group, phosphonic acid group, quaternary ammonium group and the like can be mentioned, but carboxyl group is preferred.
A carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amine, alkali metals or inorganic alkalis. Particularly preferred neutralizing agents are ammonia, trimethylamine and triethylamine. A urethane resin having carboxyl groups neutralized with a neutralizing agent can use the carboxyl groups removed from the neutralizing agent in the drying process after coating as crosslinking reaction sites with a crosslinking agent. As a result, the stability of the liquid state before coating is excellent, and the durability, solvent resistance, water resistance, blocking resistance, etc. of the resulting primer layer can be further improved.

As a method for introducing a carboxyl group into a urethane resin, various methods can be adopted in each stage of the polymerization reaction. For example, there is a method of using a resin having a carboxyl group as a copolymerization component when synthesizing a prepolymer, and a method of using a component having a carboxyl group as one component such as a polyol, a polyisocyanate compound, or a chain extender. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups depending on the charged amount of this component is preferred. For example, a carboxyl group-containing diol can be copolymerized with the diol used for synthesizing the urethane resin.
Carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)
Examples include butanoic acid and salts obtained by neutralizing their carboxyl groups with a neutralizing agent.

The primer layer preferably contains a compound derived from a cross-linking agent in order to strengthen the primer layer and improve performance such as adhesion.
As the cross-linking agent, known materials can be used, for example, melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, aziridine compounds and the like. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred. From the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, and isocyanate compounds are preferred. and epoxy compounds are more preferred, and melamine compounds, oxazoline compounds and isocyanate compounds are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. By using two or more kinds together, the adhesion and durability may be further improved and become favorable in some cases.

A melamine compound is a compound having a melamine skeleton in the compound.
Examples include alkylolated melamine derivatives, compounds obtained by reacting alkylolated melamine derivatives with alcohol to partially or completely etherify them, and mixtures thereof. Alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like. As a melamine compound,
It may be a monomer, or a dimer or higher polymer, or a mixture thereof. Further, melamine may be partially co-condensed with urea or the like, and a catalyst may be used to increase the reactivity of the melamine compound.
As the melamine compound, those having a hydroxyl group are preferable in consideration of reactivity with various compounds.

An isocyanate-based compound is a compound having an isocyanate derivative structure represented by an isocyanate compound or a blocked isocyanate compound.
Examples of isocyanate compounds include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate and naphthalene diisocyanate; aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate. An aliphatic isocyanate compound having
Aliphatic isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; group isocyanate compounds, and the like. Polymers and derivatives of these isocyanate compounds such as burettes, isocyanurates, uretdione compounds and carbodiimide modified products are also included. These may be used individually by 1 type, or may use 2 or more types together. Among the above isocyanate compounds, aliphatic isocyanate compounds or alicyclic isocyanate compounds are more preferable than aromatic isocyanate compounds from the viewpoint of avoiding yellowing due to ultraviolet rays.

Examples of blocked isocyanate compounds include those obtained by blocking the isocyanate groups of the above isocyanate compounds with a blocking agent. Examples of blocking agents include bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, dimethyl malonate, diethyl malonate, active methylene compounds such as methyl isobutanoylacetate, methyl acetoacetate, ethyl acetoacetate and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; lactam compounds such as ε-caprolactam and δ-valerolactam; Examples include amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetic acid amide, and oxime compounds such as formaldehyde, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime.
These may be used individually by 1 type, or may use 2 or more types together.
As the blocked isocyanate compound, an isocyanate compound blocked with an active methylene compound is preferred from the viewpoint that the primer layer is less likely to be destroyed.

The isocyanate-based compound may be used alone, or may be used as a mixture or combination with various polymers. From the viewpoint of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or combination with a polyester resin or a urethane resin.

An oxazoline compound is a compound having an oxazoline group in its molecule.
As the oxazoline compound, a polymer containing an oxazoline group is preferable. A polymer containing an oxazoline group can be obtained by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2
-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- 5-ethyl-2-oxazoline and the like. These may be used individually by 1 type, or may use 2 or more types together. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
Other monomers are not particularly limited as long as they are copolymerizable with addition-polymerizable oxazoline group-containing monomers. isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acids and salts thereof (sodium salts, potassium salts, ammonium salts, tertiary amine salts, etc.); Unsaturated nitriles such as acrylonitrile and methacrylonitrile; ) acrylamide, N,N-dialkyl (meth)acrylamide, (as alkyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group , cyclohexyl group, etc.); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. These may be used individually by 1 type, or may use 2 or more types together.

The amount of oxazoline groups per 1 g of the oxazoline compound is preferably 0.5 to 10 mmo
l/g, more preferably 1 to 9 mmol/g, still more preferably 3 to 8 mmol/g, particularly preferably 4 to 6 mmol/g. If the amount of oxazoline groups is within the above range, the durability of the coating film will be improved and the adhesion will be easily adjusted.

An epoxy compound is a compound having an epoxy group in its molecule.
Examples of epoxy compounds include epichlorohydrin and compounds having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin,
bisphenol A, etc.), polyepoxy compounds, diepoxy compounds,
There are monoepoxy compounds, glycidylamine compounds, and the like. As a polyepoxy compound,
Examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. .
Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1
, 6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,
Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether can be mentioned. Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-
Bis(N,N-diglycidylamino)cyclohexane may be mentioned.

A carbodiimide-based compound is a compound having one or more carbodiimide structures or carbodiimide derivative structures in the molecule.
As the carbodiimide-based compound, a polycarbodiimide-based compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable for better strength of the primer layer.

A carbodiimide-based compound can be synthesized by a known technique, and generally a condensation reaction of a diisocyanate compound is used. The diisocyanate compound is not particularly limited, and both aromatic and aliphatic compounds can be used. methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and the like.

In order to improve the water solubility and water dispersibility of the polycarbodiimide compound, a surfactant may be added, polyalkylene oxide,
Hydrophilic monomers such as quaternary ammonium salts of dialkylaminoalcohols and hydroxyalkylsulfonates may be added.

A silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule.
Silane coupling compounds include, for example, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4
- epoxy group-containing compounds such as ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; and styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane. , 3
-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3
- (meth)acryloyl group-containing compounds such as (meth)acryloxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyl Trimethoxysilane, N-2-(
aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-
3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl- 3-aminopropyltrimethoxysilane, N-
Amino group-containing compounds such as phenyl-3-aminopropyltriethoxysilane, tris(trimethoxysilylpropyl) isocyanurate, tris(triethoxysilylpropyl)
isocyanurate group-containing compounds such as isocyanurate; mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane; mentioned.

As the silane coupling compound, among the above compounds, from the viewpoint of the strength of the primer layer, epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, amino group-containing Silane coupling compounds are more preferred.

These cross-linking agents react during the drying process and the film-forming process to improve the performance of the primer layer. It can be inferred that unreacted products of the cross-linking agent, compounds after the reaction, or mixtures thereof are present as compounds derived from the cross-linking agent in the primer layer to be formed.

The primer layer may contain particles for blocking and improving slipperiness.
The primer layer may optionally contain antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, Additives such as pigments may be contained.

The ratio of the resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10 to
It is in the range of 99 mass %, more preferably 20 to 95 mass %, still more preferably 30 to 90 mass %. If the proportion of the resin is within the above range, the adhesion performance and the appearance of the primer layer are more excellent.

The ratio of the compound derived from the cross-linking agent in 100% by mass of the primer layer is, for example, 80% by mass or less,
Preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, still more preferably 5 to
It is in the range of 40% by mass. If the ratio of the compound derived from the cross-linking agent is within the above range, adhesion performance,
The strength of the primer layer is better.

The thickness of the primer layer depends on the material used for the primer layer and the performance to be developed, so it cannot be said unconditionally, but it is preferably 0.001 to 10 μm, more preferably 0.01 to 4
μm, more preferably in the range of 0.02 to 1 μm.
A primer layer can be formed by a well-known method.

(back functional layer)
The back surface functional layer is a layer provided for imparting various functions to the surface of the substrate opposite to the cured film side. Examples of the back functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, an antiblocking layer and the like. The back functional layer may have multiple functions in one layer,
It may be composed of multiple layers.
The adhesive layer is provided for bonding the laminate to various adherends. The antistatic layer is provided on the outermost surface of the laminate, particularly on the outermost surface of the substrate layer on the side opposite to the irregular layer side, in order to prevent the adhesion of surrounding dust due to separation electrification or frictional electrification, and the resulting defects. be provided. The refractive index adjusting layer is provided, for example, to improve the total light transmittance of the laminate. An anti-blocking layer is provided to reduce blocking of the laminate.

As the adhesive for forming the adhesive layer, a known one can be used, and acrylic, polyester, urethane, rubber and the like can be mentioned. Among them, the acrylic type is preferable in consideration of versatility.
The antistatic layer and the refractive index adjusting layer are the same as the antistatic layer and the refractive index adjusting layer as surface functional layers, respectively.

The thickness of the back functional layer depends on the material used for the back functional layer and the performance to be developed, so it cannot be said unconditionally, but it is, for example, 0.001 to 30 μm. When the back functional layer is an adhesive layer, the thickness is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back functional layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.0
1 to 5 μm.
A back surface functional layer can be formed by a well-known method. The back surface functional layer can be formed by coating the substrate with a solution or solvent dispersion of the series of compounds described above, adjusted to have a solid content concentration of about 0.1 to 80% by mass. preferable. The back functional layer may be formed after forming the cured film.

Examples of methods for forming the back functional layer include gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating,
Conventionally known coating methods such as kiss coating, spray coating, calendar coating, and extrusion coating can be used.

Drying and curing conditions for forming the back functional layer are not particularly limited. , preferably 80 to 130 ° C., more preferably 90 to 1
It is in the range of 20°C. As a guideline, the drying time is 3 to 200 seconds, preferably 5 to 1
20 seconds range. In addition, in order to improve the strength of the back functional layer, when it is carried out in the film manufacturing process, it is usually subjected to a heat treatment process at 150 to 270 ° C., preferably 170 to 230 ° C., more preferably 180 to 210 ° C. . The time for the heat treatment step is in the range of 3 to 200 seconds, preferably 5 to 120 seconds as a guideline.

(Surface functional layer)
Examples of surface functional layers include antifouling layers, antistatic layers, refractive index adjusting layers (antireflection layers, low-reflection layers, etc.), infrared absorption layers, ultraviolet absorption layers, color correction layers, and the like. The surface functional layer may have a plurality of functions in one layer, or may be composed of a plurality of layers.

The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured film. Conventionally known materials such as silicone compounds, fluorine compounds, long-chain alkyl group-containing compounds, and the like can be used as materials for the antifouling layer. Among these, silicone compounds and fluorine compounds are preferable for exhibiting stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferable from the viewpoint of not staining the other party with which the antifouling layer comes into contact.

The silicone compound is a compound having a silicone structure in the molecule, and examples thereof include alkylsilicones such as dimethylsilicone and diethylsilicone, and phenylsilicone and methylphenylsilicone having a phenyl group. Silicones having various functional groups can also be used, such as ether groups, hydroxyl groups,
Examples include hydrocarbon groups such as amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various aromatic groups. As other functional groups, silicones with vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms are also common, and both are used together to form addition-type silicones (those resulting from addition reactions between vinyl groups and hydrogen silane). It can also be used as A method of introducing a double bond such as an acryloyl group and reacting at the double bond is also preferred.

Modified silicones such as acrylic-grafted silicone, silicone-grafted acrylic, amino-modified silicone and perfluoroalkyl-modified silicone can also be used as the silicone compound. Considering heat resistance and contamination resistance, it is preferable to use a curable silicone resin, and any curing reaction type such as condensation type, addition type, active energy ray curing type can be used as the type of curing type.

A fluorine compound is a compound containing a fluorine atom in the compound. As the fluorine compound, organic fluorine compounds are preferably used, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene. A compound having a perfluoroalkyl group is preferable from the viewpoint of releasability. Furthermore, compounds containing long-chain alkyl compounds as described later can also be used as fluorine compounds.

A compound having a perfluoroalkyl group is, for example, perfluoroalkyl (meth)
Acrylates, perfluoroalkylmethyl (meth)acrylate, 2-perfluoroalkylethyl (meth)acrylate, 3-perfluoroalkylpropyl (meth)acrylate, 3-perfluoroalkyl-1-methylpropyl (meth)acrylate, 3- Perfluoroalkyl group-containing (meth)acrylates such as perfluoroalkyl-2-propenyl (meth)acrylates, polymers thereof, perfluoroalkylmethyl vinyl ethers,
Perfluoroalkyl group-containing vinyl ethers such as 2-perfluoroalkylethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl ether, polymers thereof, etc. are mentioned. Considering heat resistance and stain resistance, it is preferably a polymer. The polymer may be a single compound or a polymer of multiple compounds. From the viewpoint of antifouling properties, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later.

A long-chain alkyl group-containing compound is a compound having a linear or branched alkyl group usually having 6 or more carbon atoms, preferably 8 or more carbon atoms, more preferably 12 or more carbon atoms. Examples of alkyl groups include hexyl group, octyl group, decyl group, lauryl group, octadecyl group,
behenyl group and the like. Examples of compounds having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, long-chain alkyl group-containing quaternary ammonium salts, and the like. . Considering heat resistance and stain resistance, a polymer compound is preferable. Further, from the viewpoint of effectively obtaining antifouling properties, it is more preferable to use a polymer compound having a long-chain alkyl group in its side chain.

A polymer compound having a long-chain alkyl group in a side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive groups include hydroxyl groups, amino groups, carboxyl groups, acid anhydrides, and the like.
Examples of compounds having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resins, and reactive group-containing poly(meth)acrylic resins. Among these, polyvinyl alcohol is preferable in consideration of antifouling properties and ease of handling.

The compound having an alkyl group capable of reacting with the reactive group includes, for example, hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate,
Long-chain alkyl group-containing isocyanates such as octadecyl isocyanate and behenyl isocyanate, long-chain alkyl group-containing acid chlorides such as hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride and behenyl chloride, long-chain alkyl group-containing amines, long chains Examples thereof include alkyl group-containing alcohols. Among these, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred, in consideration of releasability and ease of handling.

Polymer compounds having long-chain alkyl groups in side chains can also be obtained by polymerizing long-chain alkyl (meth)acrylates or by copolymerizing long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. . Long-chain alkyl (meth)acrylates include, for example, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate,
Lauryl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)
acrylates and the like.

The content of the antifouling material for exhibiting the antifouling performance described above in the surface functional layer depends on the material used, so it cannot be generalized.
. 01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. Further, when a long-chain alkyl group-containing compound is used, the content is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is 100% by mass. I don't mind. By using it in the above range, it is possible to have effective antifouling performance.

Various conventionally known antistatic agents can be used as the antistatic agent used when forming the antistatic layer as the surface functional layer. Moreover, for example, a method of introducing a double bond such as an acryloyl group into a compound having an ammonium group and reacting at the double bond is also preferable.

Examples of refractive index adjusting layers include high refractive index layers, low refractive index layers, and laminates thereof.
As a material used for forming a refractive index adjustment layer as a surface functional layer, for the purpose of increasing the refractive index, for example, an aromatic-containing compound such as a benzene structure, a bisphenol A structure, a melamine structure, or a fluorene structure , and condensed polycyclic structures such as naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, and perylene structures, which are considered high refractive index compounds among aromatics. formula aromatic compound, zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony
Tin oxide), metal oxides such as ITO (indium tin oxide), metal-containing compounds such as metal chelate compounds such as titanium chelate and zirconium chelate, compounds containing sulfur elements, compounds containing halogen elements, etc. is mentioned.

Since there is a concern that the adhesion of the metal oxide may decrease depending on the form of use, it is preferable to use it in the form of particles.
nm or less, more preferably 50 nm or less, and still more preferably 25 nm or less.

As a material used for forming a refractive index adjustment layer as a surface functional layer, conventionally known materials can be used when aiming to lower the refractive index. For example, acrylic resins and urethane resins are generally used. is possible because of its low refractive index. Further, compounds in which a fluorine atom is incorporated in a resin, for example, a fluororesin, a compound containing a fluororesin in the main species skeleton, and a compound containing a perfluoroalkyl group in a side chain are also included. In addition, as an inorganic material,
Examples thereof include hollow silica particles, fluorine atom-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and hollow particles and nanoporous particles thereof.

The thickness of the surface functional layer is preferably 5 times or less the height from the recesses to the protrusions of the uneven structure of the cured film. This is because when the height is five times or more of the height of the unevenness, the matting performance due to the unevenness is reduced. The thickness of the surface functional layer depends on the height of the unevenness, so it cannot be said unconditionally, but it is usually 0.00.
The range is 1 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, still more preferably 0.02 to 0.5 μm, particularly preferably 0.03 to 0.2 μm.
By using it in the above range, it is possible to achieve both the expression of the function by the surface functional layer and the matting property by the unevenness of the uneven layer.
A surface functional layer can be formed by a known method.

The surface functional layer contains the series of compounds described above as a solution or solvent dispersion, and has a solid concentration of 0.
. It is preferable to form the cured film in such a manner that the liquid adjusted to be about 1 to 80% by mass is coated on the cured film.

Examples of methods for forming the surface functional layer include gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating,
Conventionally known coating methods such as kiss coating, spray coating, calendar coating, and extrusion coating can be used.

Drying and curing conditions for forming the surface functional layer are not particularly limited. , preferably 80 to 130 ° C., more preferably 90 to 1
It is in the range of 20°C. As a guideline, the drying time is 3 to 200 seconds, preferably 5 to 1
20 seconds range. In addition, in order to improve the strength of the surface functional layer, when it is carried out in the film manufacturing process, it is usually subjected to a heat treatment process at 150 to 270 ° C., preferably 170 to 230 ° C., more preferably 180 to 210 ° C. . The time for the heat treatment step is in the range of 3 to 200 seconds, preferably 5 to 120 seconds as a guideline.

[EXAMPLES] Hereafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following Examples, unless the gist is exceeded.
The measurement methods and evaluation methods used in the present invention are as follows.

(1) Intrinsic viscosity of polyester Accurately weigh 1 g of polyester from which components incompatible with polyester have been removed, add 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (mass ratio) and dissolve, 30 ° C.
measured in

(2) Average particle size (d50: μm)
The value of 50% integration (weight basis) in the equivalent spherical distribution measured using a centrifugal sedimentation particle size distribution analyzer Model SA-CP3 manufactured by Shimadzu Corporation was taken as the average particle size.

(3) Weight average molecular weight (Mw) of acrylic polymer
The weight average molecular weight (Mw) of the acrylic polymer was determined by gel permeation chromatography (GPC
) Measured using “HLC-8120” (manufactured by Tosoh Corporation). As a column, TSKge
l G5000HXL*GMHXL-L (manufactured by Tosoh Corporation) was used. In addition, as standard polystyrene, F288/F80/F40/F10/F4/F1/A5000/A1000
/A500 (manufactured by Tosoh Corporation) and styrene were used to create a calibration curve.
The measurement was carried out using a solution 10 of the polymer dissolved in tetrahydrofuran to a concentration of 0.4%.
0 μl was used and the column oven temperature was 40°C. The weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

(4) Concavo-convex peak point density Spd, double mean square root gradient Sdq, developed interface area ratio Sdr, peak arithmetic mean curvature Spc, center-to-center distance between adjacent convex portions (Rsm), surface roughness (Sa )
, tilt angle and Scale area fractal complexity (Saf
c)
Surface shape measurement system ("Scanning white interference microscope VS1" manufactured by Hitachi High-Tech Science Co., Ltd.
330), for an area of 703.12 μm × 937.42 μm on the surface of the cured film,
Surface topography was measured by optical interferometry, imputed and baseline corrected, and data read. The magnification of the objective lens during measurement was set to 20 times.

(5) Total Light Transmittance/Haze A laminate obtained by forming a cured film on a base material was measured. Total light transmittance and haze are JI
S Z8722Z (geometric conditions for irradiation and light reception of transparent objects) and JIS K7361-1 (
Plastics - Test method for total light transmittance of transparent materials) In accordance with JIS K7136 (Plastics - How to obtain haze of transparent materials), a haze meter "SH700" manufactured by Nippon Denshoku Industries Co., Ltd.
0” was used for the measurement.

(6) 20° and 60° Gloss A laminate obtained by forming a cured film on a base material was measured. 20° and 60° gloss (20
° and 60° specular glossiness) were measured according to JIS Z 8741 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. The lower the gloss value, the better the mattness.

(7) Method for evaluating matting properties The laminate was placed in a room lit by a white linear fluorescent lamp, and the distance between the fluorescent lamp and the laminate was 2.
The length was set to 5 m, and the matting property (reflection of a fluorescent lamp) on the uneven layer side was evaluated by visual observation. In the evaluations A to C, the matting property can be confirmed.
A: The reflected image of the fluorescent lamp is strongly blurred, and the outline of the fluorescent lamp cannot be confirmed.
B: The reflected image of the fluorescent lamp is blurred, but the outline can be slightly confirmed.
C: The reflected image of the fluorescent light is slightly blurred, and although the outline can be confirmed, it is observed as a wavy shape and appears dark white.
D: The reflected image of the fluorescent lamp is clear and the outline can be clearly confirmed, and the image is linear and appears white.

Compounds used in Examples and Comparative Examples are as follows.
(Base material)
・Polyester: (S1)
A polyethylene terephthalate homopolymer having an intrinsic viscosity of 0.63 dl/g, obtained using magnesium acetate tetrahydrate and tetrabutyl titanate as polymerization catalysts.

・Polyester: (S2)
A polyethylene terephthalate homopolymer having an intrinsic viscosity of 0.64 dl/g, obtained using magnesium acetate tetrahydrate, orthophosphoric acid and germanium dioxide as polymerization catalysts.

・Polyester: (S3)
A polyethylene terephthalate homopolymer containing 0.3% by mass of silica particles having an average particle size of 2 μm in S1.

(Curable composition)
The following (meth) acrylates (A-1), (meth) acrylates (A-2), (meth) acrylates (A-3), (meth) acrylates (A-4), (meth) acrylates (A- 5), (meth)acrylate (A-6), (meth)acrylate (A-7), (meth)acrylate (A-8), (meth)acrylate (A-9), acrylic resin (B),
Particles (C-1), particles (C-2), and photopolymerization initiator (D) were mixed in the amounts shown in Table 1 (parts by mass, converted to non-volatile content). Then, methyl ethyl ketone (hereinafter referred to as MEK) was added so that the solid content concentration was 50% by mass, and the mixture was stirred until uniform to obtain a curable composition (coating liquid) used in each example and comparative example. .

・(Meth)acrylate (A-1): dicyclopentenyloxyethyl acrylate (monofunctional acrylate)

・(Meth)acrylate (A-2): 4-acryloylmorpholine (monofunctional acrylate)

・(Meth)acrylate (A-3): 2-ethylhexyl acrylate (monofunctional acrylate)

・ (Meth) acrylate (A-4): EO-modified bisphenol A dimethacrylate (bifunctional methacrylate: New Frontier BPEM-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

・(Meth)acrylate (A-5): 1,6-hexanediol diacrylate (bifunctional acrylate)

・(Meth)acrylate (A-6): trimethylolpropane trimethacrylate (trifunctional methacrylate)

・ (Meth) acrylate (A-7): dipentaerythritol hexaacrylate (hexafunctional acrylate)

・ (Meth) acrylate (A-8): urethane acrylate (Shiko UV-3700B manufactured by Mitsubishi Chemical Corporation)

・ (Meth) acrylate (A-9): urethane acrylate (Shiko UV-3000B manufactured by Mitsubishi Chemical Corporation)

・(Meth)acrylate (A-10): urethane acrylate (Shiko UV-3310B manufactured by Mitsubishi Chemical Corporation)

・Acrylic resin (B) having a vacuum UV-curable functional group
Propylene glycol monomethyl ether (157 parts by weight), glycidyl methacrylate (98 parts by weight), methyl methacrylate (1.0 parts by weight), ethyl acrylate (1.0 parts by weight) were placed in a flask equipped with a thermometer, stirrer and reflux condenser. ), mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2′-azobis(2,4-dimethylvaleronitrile) (1.0 parts by mass), γ-trimethoxysilylpropanethiol (Shin-Etsu Chemical Co., Ltd. 1.9 parts by mass of KBM-803 manufactured by Co., Ltd. was added and reacted at 65° C. for 3 hours.
After that, 2,2′-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, then propylene glycol monomethyl ether (138 parts by mass) and p-methoxyphenol ( 0.45 parts by mass) was added and heated to 100°C.
Next, acrylic acid (51 parts by mass) and triphenylphosphine (3.1 parts by mass) are added and reacted at 110° C. for 6 hours to obtain an unsaturated double bond amount (acryloyl equivalent (acryloyl group Introduced amount)) 4.6 mmol/g of an acrylic resin (C2) having radically polymerizable double bonds in side chains was obtained. The weight average molecular weight (Mw) was 17,700.

・ Particles (C-1): crosslinked acrylic particles with an average particle size of 1.8 μm (MX-1 manufactured by Soken Chemical Co., Ltd.)
80TA)

・ Particles (C-2): Silicone particles with an average particle size of 2 μm (KMP-605 manufactured by Shin-Etsu Chemical Co., Ltd.
)

- Photopolymerization initiator (D): IGM Resins B.I. V. Company Omnirad 184

(Composition for forming primer layer)
Polyester resin (P1), urethane resin (P2), melamine compound (P3) shown below
), the particles (P4) are mixed at a ratio of polyester resin (P1)/urethane resin (P2)/melamine compound (P3)/particles (P4) (solid content mass ratio) = 60/25/10/5 to form a primer layer. A composition for
Polyester resin (P1): Aqueous dispersion of polyester resin having the following composition Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4- Butanediol/diethylene glycol = 56/40/4//70/20/10 (mol%)
・ Urethane resin (P2): isophorone diisocyanate: terephthalic acid: isophthalic acid:
Ethylene glycol: diethylene glycol: dimethylolpropanoic acid = 12:19:1
An aqueous dispersion of a polyester-based urethane resin formed from 8:21:25:5 (mol %).
・ Melamine compound (P3): hexamethoxymethylol melamine ・ Particles (P4): silica particles with an average particle size of 0.07 μm

(Polyester film substrate)
Polyesters (S1), (S2), and (S3) were mixed at a ratio of 91% by mass, 3% by mass, and 6% by mass, respectively, as a raw material for the outermost layer (surface layer), and polyesters (S1) and (S2)
are mixed at a ratio of 97% by mass and 3% by mass, respectively, as a raw material for the intermediate layer. , 2
An unstretched sheet was obtained by co-extrusion in a layer structure of seed 3 layers (surface layer/intermediate layer/surface layer = 1:8:1 discharge amount) and solidification by cooling.
Next, after stretching 3.1 times in the longitudinal direction at a film temperature of 85 ° C. using the roll peripheral speed difference,
A composition for forming a primer layer is applied to one side of this longitudinally stretched film, guided to a tenter, and 9
After drying at 5°C for 10 seconds, it was stretched 4.2 times in the transverse direction at 120°C, heat-treated at 230°C for 10 seconds, relaxed 2% in the transverse direction, and had a thickness (after drying) of 0.000. A 50 μm thick polyester film base having a 1 μm primer layer was obtained.

[Examples 1 to 8]
A coating solution shown in Table 1 was applied onto the primer layer of the polyester film substrate and dried at 70° C. for 1 minute. Next, excimer light (half width 14n
m) at an irradiation amount of 200 mJ/cm ² and an illuminance of 11 mW/cm ² (Ushio Inc. xenon excimer 172 nm light irradiation machine SVS3, lamp unit model: UEM343W-172ST
(Lamp house model: H2112, lighting power supply model: B0314), nitrogen flow (oxygen concentration 0.01% or less)) to irradiate the dried coating film. Furthermore, in an air atmosphere, a high-pressure mercury lamp was used with an integrated light amount of 300 mJ/cm ² and an illuminance of 150 mW/cm ² (high-power UV
Irradiate ultraviolet rays with the device (model: US5-X1802-X1202) UV conveyor),
A laminate having a cured film having an uneven structure with a thickness (after curing) of 5 μm on the substrate was obtained.

The resulting laminate had good matte properties. Table 2 shows the properties of this laminate.

[Comparative Examples 1, 2, 3]
A laminate having a cured film was obtained in the same manner as in Example 1, except that the coating composition of Example 1 was changed to that shown in Table 1. As shown in Table 2 below, the obtained laminate did not have a large concave-convex structure and exhibited low matting properties.

[Comparative Example 4]
In Example 1, production was carried out in the same manner as in Example 1 except that the composition of the coating agent was changed to that shown in Table 1, but the surface was not cured and a cured film could not be obtained. Therefore, as shown in Table 2 below, all items could not be evaluated.

Claims (11)

A cured film having an uneven structure on the surface, wherein the uneven structure has a peak point density Spd of 1000 [1/mm ² ] or more on the coating surface defined by ISO 25178 and a root mean square gradient Sdq
A cured film comprising a compound having a spread interface area ratio Sdr of 1% or more and containing one or more (meth)acrylate groups of 0.2 or more. The absolute value of the arithmetic mean curvature Spc of the peak defined by ISO25178 of the uneven structure is 1
00 [1/mm] or more, the cured film according to claim 1. Scale area fractal defined by ISO25178 of the uneven structure
3. The cured film according to claim 2, wherein the complexity (Safc) is 2 or more. The compound containing one or more (meth)acrylate groups is one or more selected from the group consisting of cyclic (meth)acrylates, bifunctional (meth)acrylates and trifunctional (meth)acrylates. The cured film according to any one of 1 to 3. Average length (Rsm
) is 1 μm or more, the cured film according to any one of claims 1 to 4. The cured film according to any one of claims 1 to 5, wherein the average value (θa) of the local inclination angles of the uneven structure is 2° or more. 7. The cured film according to any one of claims 1 to 6, which has a surface 60° gloss of 50 or less. The cured film according to any one of claims 1 to 7, which has a surface haze value of 10% or more. 9. The composition according to any one of claims 1 to 8, wherein the active energy ray-curable composition containing a polymer having an active group that generates radicals upon irradiation with an active energy ray is cured by irradiation with vacuum ultraviolet light. A method for producing a cured film of A laminate comprising a substrate and a layer comprising the cured film according to any one of claims 1 to 8. 11. The method according to claim 10, wherein an active energy ray-curable composition containing a polymer having an active group that generates radicals upon irradiation with an active energy ray is laminated on a substrate and cured by irradiation with vacuum ultraviolet light. A method for manufacturing a laminate.