JP2021024926A - Hardened film, method for producing the same, and laminate - Google Patents

Abstract

To provide a hardened film that is excellent in matte and scratch resistance.SOLUTION: Provided is a hardened film having a structure in which protrusion streaks are formed in annular shape on the surface, and in which the protrusion streaks are constituted of wrinkle-shaped convexoconcave, and, in the plan view and in the width direction of the protrusion streak, the distance between the center of a protrusion and the center of a concavity adjacent to the protrusion in the convexoconcave is 0.5 to 20 μm and the arithmetical average height Sa of the surface is 0.01 to 5 μm.SELECTED DRAWING: Figure 1

Description

The present invention relates to a cured film, a method for producing the same, and a laminate.

On the surface of the base material, in order to impart matteness, light diffusivity, unevenness, etc. to building materials such as wallpaper, display members, decorative films, etc., and to improve visibility, design, etc. It may give fine irregularities.
Patent Document 1 describes hairline processing on a film for transfer foil when manufacturing decorative sheets for building materials, various parts of home appliances such as refrigerators and washing machines, various parts of OA products such as personal computers, and packaging containers by molding. , A method of providing a fine uneven shape by sandblasting, satin finish, or the like is disclosed.
Patent Document 2 discloses a method of dispersing acrylic particles in a resin binder as a method of forming surface irregularities of a light diffusion film used in a backlight unit of a liquid crystal display.

Japanese Unexamined Patent Publication No. 2004-231727 Japanese Unexamined Patent Publication No. 7-218705

However, the unevenness forming method described in Patent Document 1 cannot obtain sufficient matting property. Further, in the sandblasting process, the sand remaining in the film may cause a quality problem. Since the surface is still polished, it is difficult to impart antifouling properties.
In the method described in Patent Document 2, the acrylic particles may fall off during use, which may hinder the visibility of the display.
Further, it is difficult to achieve both matte property and scratch resistance by these conventional methods. For example, if the surface irregularities are increased in order to enhance the matte property, the scratch resistance tends to decrease.

An object of the present invention is to provide a cured film and a laminate having excellent matteness and scratch resistance, and a production method for obtaining a cured film having excellent matteness and scratch resistance.

The present invention has the following aspects.
[1] The surface has a structure in which ridges are formed in an annular shape, and the ridges are composed of wrinkled irregularities.
The distance between the center of the convex portion in the unevenness and the concave portion adjacent to the convex portion in the plan view and in the width direction of the convex portion is 0.5 to 20 μm.
A cured film having an arithmetic mean height Sa of the surface of 0.01 to 5 μm.
[2] The cured film of the above [1], wherein two or more of the structures are arranged adjacent to each other.
[3] The cured film according to [1] or [2], wherein the ratio of the area of the convex portion to the total area of the surface is 1 to 40% in a plan view.
[4] The cured film according to any one of [1] to [3], wherein the surface has a 60 ° mirror gloss of 60 or less.
[5] The cured film according to any one of [1] to [4] above, which is an antiglare film.
[6] It has a unit based on a monomer (x) having an active group that generates radicals by irradiation with active energy rays, and one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom. A copolymer (A) having a unit based on the monomer (y) and a unit based on the monomer (z) having a structure containing two or more aromatic rings that do not generate radicals by irradiation with active energy rays, and one molecule. The cured film according to any one of [1] to [5] above, which is a cured product of a curable composition containing a polyfunctional compound (B) having two or more radically polymerizable groups.
[7] It has a unit based on a monomer (x) having an active group that generates radicals by irradiation with active energy rays, and one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom and a silicon atom. A copolymer (A) having a unit based on the monomer (y) and a unit based on the monomer (z) having a structure containing two or more aromatic rings that do not generate radicals by irradiation with active energy rays, and one molecule. A method for producing a cured film, wherein a coating film of a curable composition containing a polyfunctional compound (B) having two or more radically polymerizable groups is formed, and the coating film is irradiated with active energy rays.
[8] A laminate having a base material layer and a layer made of the cured film according to any one of [1] to [6].
[9] The laminate of the above [8], wherein the 60 ° mirror glossiness of the outermost surface on the side where the layer made of the cured film exists with respect to the base material layer is 60 or less.
[10] The laminate of the above [8] or [9] having a haze of 20% or more.
[11] The laminate according to any one of [8] to [10], which is an antiglare film.
[12] Further, a primer layer provided between the base material layer and the layer made of the cured film, and a surface provided on the surface of the layer made of the cured film opposite to the base material layer side. [8] to [8] to [8] to [8] to [8], which have one or more layers selected from the group consisting of a functional layer and a back surface functional layer provided on a surface of the substrate layer opposite to the layer side of the cured film. 11] The laminate according to any one of.

The cured film of the present invention is excellent in matte property and scratch resistance.
According to the method for producing a cured film of the present invention, a cured film having excellent matte property and scratch resistance can be obtained.
The laminate of the present invention is excellent in matte property and scratch resistance.

The surface shape of the cured film obtained in Example 1 was detected by VertScan (registered trademark), and the convex portion was displayed in dark color and the concave portion was displayed in light color by binarization (scale: 236.87 μm × 177.60 μm). is there. The surface shape of the cured film obtained in Comparative Example 1 was detected by VertScan (registered trademark), and the convex portion was displayed in dark color and the concave portion was displayed in light color by binarization (scale: 236.87 μm × 177.60 μm). is there. It is a figure for demonstrating the measuring method of the distance between the center of the convex part in the concavo-convex and the concave part adjacent to a convex part.

Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, "(meth) acrylate" is a general term for acrylate or methacrylate. "(Meta) acrylic" is a general term for acrylic and methacrylic.
"~" Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

[Cured film]
The cured film of the present invention has a structure in which ridges are formed in an annular shape on the surface (hereinafter, also referred to as “annular structure”). In the example shown in FIG. 1, two or more annular structures are arranged adjacent to each other.

The ridges are composed of wrinkled irregularities. The wrinkled unevenness has a plurality of convex portions, for example, as shown in FIG. At least a part of the plurality of convex portions is formed along the circumferential direction of the annular structure, and is formed, for example, in an annular shape or a shape lacking a part of the ring. Further, a plurality of convex portions are arranged along the width direction of the ridges (the radial direction of the annular structure). Adjacent convex portions are connected to each other by concave portions located between the convex portions.

In the plan view and in the width direction of the ridge, the distance between the center of the convex portion in the unevenness and the concave portion adjacent to the convex portion is 0.5 to 20 μm, preferably 1 to 15 μm, and more preferably 2 to 10 μm. When the distance between the centers is equal to or more than the above lower limit value, the matte property is more excellent. When the distance between the centers is not more than the above lower limit value, the matte property and the scratch resistance are more excellent.

The method of measuring the distance between the centers will be described with reference to FIGS. 1 and 3. FIG. 3 is a plan view schematically showing a binarized ridge portion on the surface of the cured film. In FIG. 3, reference numeral 1 indicates a convex line, reference numeral 3 indicates a convex portion, and reference numeral 5 indicates a concave portion.
In the measurement of the center-to-center distance, first, the surface shape of a region of 236.87 μm × 177.60 μm randomly selected from the surface of the cured film is determined by the surface shape measurement system (“VertScan®” manufactured by Hitachi High-Tech Science Corporation. ) ”, And binarizing into two regions, convex and concave. Detailed measurement conditions and binarization procedure are as described in Examples described later. By binarization, FIG. As shown in FIG. 3, an image is obtained in which the convex portion 3 is displayed in dark color and the concave portion 5 is displayed in light color.
Then, as shown in FIG. 3, in the image obtained by binarization, at an arbitrary position of the convex portion 3 randomly selected, in the arrangement direction of the convex portion 3 and the concave portion 5 (the width direction of the convex portion 1). The distance D between the _{line L 3} passing through the center of the convex portion 3 _{and the line L 5} passing through the center of the concave portion 5 adjacent to the convex portion 3 is measured. The same measurement is performed at a total of 3 locations, and the average value is used as the center-to-center distance.

The height of the convex portion forming the ridge is higher than the maximum height of the region inside the annular structure.
The height of the convex portion constituting the convex strip is preferably 0.05 to 10 μm, more preferably 0.08 to 5 μm, based on the height of the valley bottom point of the concave portion adjacent to the convex portion. When the height of the convex portion constituting the convex strip is equal to or more than the above lower limit value, the matte property and the scratch resistance are more excellent. When the height of the convex portion forming the convex strip is equal to or less than the above upper limit value, the scratch resistance is more excellent.
The height of the ridges is measured by the surface shape measuring system described above.

The annular structure may have a substantially circular shape or a substantially polygonal shape in a plan view. Approximately circular shapes include circular shapes, elliptical shapes and their derivatives. The substantially polygonal shape includes a polygonal shape and a derivative shape thereof. The polygonal shape is, for example, a triangular shape to an octagonal shape.

The size of the annular structure is preferably 1 to 300 μm, more preferably 10 to 200 μm, as a 10-point mean value of the maximum diameter of the inner region of the randomly selected annular structure. When the size of the annular structure is at least the above lower limit value, the scratch resistance is more excellent. When the size of the annular structure is not more than the above lower limit value, the matte property is more excellent.
The maximum diameter is measured by the surface shape measuring system described above.

The number of cyclic structures on the surface of the cured film may be one or two or more. From the viewpoint of matte property and scratch resistance, two or more are preferable.
When the number of cyclic structures on the surface of the cured film is two or more, the two or more annular structures may be arranged apart or adjacent to each other. From the viewpoint of matteness, it is preferable that they are arranged adjacent to each other.
The shape and arrangement of the two or more annular structures may be regular or irregular as shown in FIG. From the viewpoint of visibility of the display element and the handle layer arranged on the lower side, irregularity is preferable. Here, the term "irregular" in shape and arrangement means that the shapes and arrangements (arrangement direction, pitch, etc.) of two or more annular structures do not have a certain regularity and periodicity.

In a plan view, the number of annular structures per unit area of the surface of the cured film is preferably 50 to 2000 pieces / mm ² , and more preferably 200 to 1000 pieces / mm ² . When the number of cyclic structures is at least the above lower limit value, the matte property and the scratch resistance are more excellent. When the number of annular structures is not more than the above lower limit value, the scratch resistance is more excellent.

In a plan view, the ratio of the area of the convex portion to the total area of the surface of the cured film is preferably 1 to 40%, more preferably 5 to 35%, still more preferably 10 to 30%. When the ratio of the area of the convex portion is equal to or more than the above lower limit value, the matte property and the scratch resistance are more excellent. When the ratio of the area of the convex portion is equal to or less than the above upper limit value, the scratch resistance is more excellent.

A method of measuring the ratio of the area of the convex portion will be described with reference to FIG.
In measuring the ratio of the area of the convex portion, first, the surface shape of a region of 236.87 μm × 177.60 μm randomly selected from the surface of the cured film is determined by the surface shape measurement system (“VertScan” manufactured by Hitachi High-Tech Science Corporation). (Registered trademark) ”is measured and binarized into two areas, a convex portion and a concave portion. Detailed measurement conditions and binarization procedure are as described in Examples described later. By binarization, As shown in FIG. 1, an image is obtained in which the convex portion is displayed in dark color and the concave portion is displayed in light color.
Next, in the image obtained by binarization, the ratio of the total area of the convex portion (dark color portion) to the total area of the image is calculated.

The arithmetic mean height Sa of the surface of the cured film is 0.01 to 5 μm, preferably 0.05 to 4 μm, more preferably 0. It is l to 3 μm. When Sa is at least the lower limit of the above range, the matte property and the scratch resistance are excellent. When Sa is not more than the above upper limit value, the scratch resistance is excellent.
Sa is measured by the method described in Examples described later.

The 60 ° mirror gloss (60 ° gloss) of the surface of the cured product is preferably 60 or less, more preferably 50 or less, still more preferably 40 or less. When the 60 ° mirror glossiness is at least the above lower limit value, the matte property is more excellent.
The 60 ° mirror glossiness is measured by the method described in Examples described later.

The water contact angle on the surface of the cured film is preferably 65 to 130 °, more preferably 80 to 120 °, and even more preferably 85 to 115 °. If it is at least the lower limit of the above range, the antifouling property is more excellent, and if it is at least the upper limit value, the durability of the antifouling property is more excellent.
The water contact angle on the surface of the cured film is measured by the method described in Examples described later.

The cured film preferably has a pencil hardness measured by the method described in Examples described later, which is harder than F, and more preferably harder than 2H.

The thickness of the cured film is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm, and even more preferably 0.3 to 7 μm. When the thickness of the cured film is within the above range, it is easy to achieve the desired matting property.
The thickness of the cured film indicates the maximum thickness of the cured film and is determined by cross-sectional observation with an electron microscope.

An example of the cured film of the present invention is one composed of a cured product of the following curable composition.
A monomer (y) having a unit based on a monomer (x) having an active group that generates radicals by irradiation with active energy rays, and one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom and a silicon atom. ), And a copolymer (A) having a unit based on a monomer (z) having a structure containing two or more aromatic rings that does not generate radicals by irradiation with active energy rays, and two in one molecule. A curable composition containing the above-mentioned polyfunctional compound (B) having a radically polymerizable group.
The curable composition and the method for producing a cured film using the curable composition will be described in detail later.

The cured film of the present invention is suitable as an antiglare film because it has excellent matting properties.

[Manufacturing method of 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 active energy rays.

(Curable composition)
The curable composition includes a unit based on a monomer (x) having an active group (hereinafter, also simply referred to as “active group”) that generates radicals by irradiation with active energy rays, an alkyl group having 4 or more carbon atoms, and fluorine. A unit based on a monomer (y) having one or more selected from the group consisting of an atom and a silicon atom, and a monomer (z) having a structure containing two or more aromatic rings that do not generate radicals by irradiation with active energy rays. It contains a copolymer (A) having a unit based on it and a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule.

When the curable composition is irradiated with active energy rays, radicals are generated from the active groups of the copolymer (A), and the reaction between the radically polymerizable groups of the polyfunctional compound (B) proceeds from the generated radicals. The entire curable composition is cured.
When a coating film of a curable composition is formed and the coating film is irradiated with active energy rays, the surface side of the coating film is cured first to form a cured film. After that, when the inside of the coating film is cured, the cured coating film on the surface side buckles to form a cured film having wrinkle-like irregularities on the surface.
The curable composition can further contain a monofunctional compound, if desired.
The curable composition may further contain an organic solvent, if desired.
The curable composition may further contain a photopolymerization initiator, if desired.
The curable composition may further contain other components other than the above, if necessary.

<Copolymer (A)>
[Monomer (x)]
Examples of the monomer (x) include compounds having an active group and a radically polymerizable group.
The active group may have a structure that generates radicals by irradiation with active energy rays (a structure having photopolymerization initiation property). As the structure having photopolymerization initiation property, various known structures can be adopted, and examples thereof include a hydrogen abstraction type, an electron transfer type, and an intramolecular cleavage type.
Specific examples of the active group include a benzophenone group, an acetophenone group, a benzoin group, and an α-hydroxyketone group (for example, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methylpropanol "2". -A group obtained by removing one hydrogen atom from "hydroxyl group in hydroxyethoxy"), α-aminoketone group, α-diketone group, α-diketone dialkylacetal group, anthraquinone group, thioxanthone group, phosphine oxide group and the like. Among these, a benzophenone group, an acetophenone group, and an α-hydroxyketone group are preferable because they are less susceptible to oxygen inhibition during curing and have good surface curability when forming an uneven layer.

Examples of the radically polymerizable group of the monomer (x) include a functional group containing a radically polymerizable unsaturated bond (carbon-carbon double bond, etc.), and specific examples thereof include a (meth) acryloyl group and a vinyl group. Be done.
As the monomer having an active group, a (meth) acrylic acid ester having an active group is preferable from the viewpoint of easiness of synthesizing the copolymer (A) and easiness of adjusting the amount of the active group introduced.
Examples of the monomer having an active group include 4-methacryloyloxybenzophenone and 2- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy] ethyl methacrylate.

[Monomer (y)]
Examples of the monomer (y) include compounds having one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom and a silicon atom, and a radically polymerizable group. The radically polymerizable group is the same as above.

If the copolymer (A) has a unit based on the monomer (y), the copolymer (A) is likely to segregate on the surface side of the coating film when the coating film of the curable composition is formed. Become.
Since the copolymer (A) segregates on the surface side of the coating film, the concentration of active groups on the surface side of the coating film increases, and when irradiated with active energy rays, the surface side of the coating film is cured first. A cured film is formed, after which the inside of the coating is cured. When the inside of the coating film is cured, the cured film on the surface is buckled to develop wrinkle-like irregularities.
At this time, the shorter the curing time inside the coating film, the smaller the period of unevenness on the surface of the uneven layer, and the longer the curing time, the larger the period of unevenness on the surface of the uneven layer tends to be. The curing time can be adjusted by adjusting the amount of radically polymerizable groups in the curable composition, the amount of active groups (the amount of the copolymer (A) and the photopolymerization initiator), the amount of irradiation with active energy rays, and the like.
Further, if the copolymer (A) segregates on the surface side of the coating film, the curing reaction inside the coating film (base material layer side) is less susceptible to oxygen inhibition, and can be cured with a low exposure amount. Even a thin film that tends to be susceptible to oxygen inhibition can be cured well.
Further, if the monomer (y) has a fluorine atom or a silicon atom, at least one of water repellency and oil repellency can be imparted to the cured product, which contributes to the antifouling property of the cured product.

The monomer (y) is a compound having an alkyl group having 4 or more carbon atoms and a radically polymerizable group, a compound having a fluoroalkyl group and a radically polymerizable group, and a compound having a polydimethylsiloxane chain and a radically polymerizable group. It is preferable to include one or more selected from the group consisting of.
The monomer (y) comprises a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms, a (meth) acrylic acid ester having a fluoroalkyl group, and a (meth) acrylic acid ester having a polydimethylsiloxane chain. It is more preferable to include one or more selected from the group. One of these (meth) acrylic acid esters may be used alone, or two or more thereof may be used in combination.

The alkyl group having 4 or more carbon atoms may be linear, branched or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the copolymer (A) on the surface of the coating film, the alkyl group is preferably linear.
The carbon number of the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, from the viewpoint of segregating the copolymer (A) on the surface of the coating film more effectively. More preferably, it is in the range of 12-18.

Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth). ) Acrylate, Octyl (meth) acrylate, Isooctyl (meth) acrylate, Decyl (meth) acrylate, Nonyl (meth) acrylate, Isononyl (meth) acrylate, Decyl (meth) acrylate, Isodecyl (meth) acrylate, Dodecyl (meth) acrylate , Myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, Examples thereof include dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.
Among these, it is preferable to contain a (meth) acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms. The (meth) acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms is preferably one in which the number of carbon atoms of the alkyl group is in the above-mentioned preferable range, and in consideration of ease of production and the like, 2 -Ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate are more preferable, and stearyl (meth) acrylate is particularly preferable.

The (meth) acrylic acid ester containing a fluoroalkyl group is more preferably a (meth) acrylic acid ester having a perfluoroalkyl group. The perfluoroalkyl group preferably has 4 or more carbon atoms.

Specific examples of the (meth) acrylic acid ester having a polydimethylsiloxane chain include one-terminal (meth) acryloyl group-substituted polydimethylsiloxane having a molecular weight of 500 to 50,000. The molecular weight is preferably 1000 to 30000, more preferably 1500 to 20000.

[Monomer (z)]
The monomer (z) is a compound having a structure containing two or more aromatic rings that do not generate radicals when irradiated with active energy rays (hereinafter, also referred to as “aromatic polycyclic structure”) and a radically polymerizable group. Can be mentioned. The aromatic polycyclic structure may be any as long as it does not correspond to an active group and contains two or more aromatic rings. For example, naphthalene, anthracene, phenanthrene, naphthalene, benzo [a] anthracene, benzo [a] phenanthrene. , Pyrene, benzo [c] phenanthrene, perylene, fluorene and the like fused ring structure, biphenyl structure, bisphenol structure and the like. The radically polymerizable group is the same as above.

If the copolymer (A) has a unit based on the monomer (z), the above-mentioned cyclic structure is likely to be formed when the coating film of the curable composition is irradiated with active energy rays and cured. ..
As described above, the copolymer (A) segregates on the surface of the coating film, so that the aromatic polycyclic structure exists on the surface side of the coating film. When the inside of the coating film is cured after the surface side of the coating film is cured, the buckling of the surface side (cured film) is partially suppressed by the Π-Π stacking interaction between the aromatic polycyclic structures. To. As a result, it is presumed that the portion where buckling is not suppressed becomes an annular structure, and the portion where buckling is suppressed becomes an inner region of the annular structure.

The monomer (z) is a (meth) acrylic acid having an aromatic polycyclic structure from the viewpoint of easy synthesis of the copolymer (A) and easy adjustment of the amount of the aromatic polycyclic structure introduced. Esters are preferred.
Examples of the (meth) acrylic acid ester having an aromatic polycyclic structure include ethylene oxide (EO) -modified -о-phenylphenol (meth) acrylate, biphenylmethyl (meth) acrylate, and 2-hydroxy-о-phenylphenolpropyl. Examples thereof include (meth) acrylate and naphthyl (meth) acrylate. The number of moles of EO added in the EO-modified -о-phenylphenol (meth) acrylate is, for example, 1 to 5.

[Monomer (h)]
The copolymer (A) may further have a unit based on the monomer (h) having a hydrogen donating functional group, if necessary.
In particular, when the monomer (x) has a hydrogen abstraction type active group, it is preferable to include a unit based on the monomer (h). When the copolymer (A) has this unit, the curable composition can be effectively cured from the surface of the coating film, and unevenness can be easily formed.
Examples of the hydrogen donating functional group include a hydroxyl group, an amino group, a mercapto group, an amide group and the like. Among these, a hydroxyl group, an amino group or an amide group is preferable from the viewpoint that the curing reaction can proceed particularly efficiently and unevenness can be easily formed.

Examples of the monomer having a hydrogen-donating functional group include a compound having a hydrogen-donating functional group and a radically polymerizable group, and the ease of synthesizing the compound and the ease of adjusting the amount of the hydrogen-donating functional group introduced. From the above viewpoint, (meth) acrylic acid esters and (meth) acrylamides having a hydrogen-donating functional group are preferable.
Examples of the monomer having a hydrogen donating functional group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8. Hydroxyl group-containing monomers such as −hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, monobutylhydroquilfumarate, monobutylhydroxyitaconate; N, N-dimethyl ( Meta) acrylamide, N, N-diethyl (meth) acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, 2-[(butylamino) ) Carbonyl] oxy] ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl Aminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, (meth) acryloylmorpholine, vinylacetamide, etc. Examples of the amino group- or amide group-containing monomer of the above. Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (N, N-) are excellent in curing accelerating effect when used in combination with an active group. Dimethylacrylamide, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate are preferable, and N, N-diethylaminoethyl (meth) acrylate is more preferable in that unevenness is easily increased. These compounds may be used alone or in combination of two or more.

The copolymer (A) may further have units based on other monomers other than the above, if necessary. Other monomers include, for example, an active group, an alkyl group having 4 or more carbon atoms, a fluorine atom, a silicon atom, and two or more aromatic rings that do not generate radicals when irradiated with active energy rays. Examples thereof include compounds having a structure containing and having no hydrogen donating functional group.
Other monomers 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 salts thereof; methyl (meth) acrylate and ethyl (meth) acrylate. , (Meta) acrylates such as propyl (meth) acrylate; Nitrogen-containing monomers such as (meth) acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, vinyl propionate, vinyl acetate and the like. Examples thereof include esters; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and billidene chloride; and conjugated dienes such as butadiene.

The active group may be present at the end of the main chain of the copolymer (A), or may be present in a unit based on the monomer constituting the copolymer (A).
The copolymer (A) preferably has a plurality of active groups in the molecule. As a result, the concentration of active groups near the surface of the coating film can be increased, and unevenness such as a wrinkle-like structure can be easily developed on the surface after curing.
The content of the active group per gram of the copolymer (A) is preferably 0.1 to 3.5 mmol / g, more preferably 0.5 to 2.5 mmol / g, still more preferably 0.8 to 2. It is in the range of 0.0 mmol / g. When the content of the active group is at least the lower limit of the above range, the cyclic structure can be formed more effectively. When it is not more than the upper limit value, the curability of the curable composition is more excellent.

The ratio of the units based on the monomer (x) to the total mass of all the units constituting the copolymer (A) is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and further preferably 20 to 70. It is in the range of mass%, particularly preferably 30 to 60 mass%. When the ratio of the unit based on the monomer (x) is at least the lower limit of the above range, the curability is more excellent and the unevenness can be formed more effectively. When it is not more than the upper limit value, the storage stability of the curable composition is more excellent.

The ratio of the units based on the monomer (y) to the total mass of all the units constituting the copolymer (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 15 to 50. It is in the range of mass%. When the ratio of the unit based on the monomer (y) is not more than the lower limit of the above range, the unevenness can be formed more effectively. When it is not more than the upper limit value, the compatibility between the copolymer (A) and the polyfunctional compound (B) is more excellent.

The ratio of the units based on the monomer (z) to the total mass of all the units constituting the copolymer (A) is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 60. It is in the range of mass%, particularly preferably 25 to 50 mass%. When the ratio of the units based on the monomer (z) is equal to or higher than the lower limit of the above range, the cyclic structure can be formed more effectively. When the ratio of the unit based on the monomer (z) is not more than the upper limit of the above range, the curability of the curable composition is more excellent.

The ratio of the units based on the monomer (h) to the total mass of all the units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 60% by mass, and further preferably 3 to 50% by mass. %, Especially preferably in the range of 5 to 40% by mass. When the ratio of the unit based on the monomer (h) is within the above range, unevenness can be formed more effectively.

The weight average molecular weight (Mw) of the copolymer (A) is preferably in the range of 1,000 to 500,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 60,000. .. When Mw is equal to or higher than the lower limit of the above range, the cyclic structure can be formed more effectively. If it is not more than the upper limit value, the workability at the time of manufacturing the cured film is good.
The Mw of the copolymer (A) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC). Detailed measurement conditions are as described in Examples described later.

The glass transition temperature (Tg) of the copolymer (A) is preferably in the range of -30 to 180 ° C, more preferably 0 to 150 ° C, and even more preferably 25 to 100 ° C. When Tg is at least the lower limit of the above range, the curability of the curable composition is more excellent. When it is not more than the upper limit value, the compatibility between the copolymer (A) and the polyfunctional compound (B) is more excellent.
The Tg of the copolymer (A) is calculated by the following formula (relationship formula of Tg (° C.) of the copolymer according to the Fox formula).
1 / (273 + Tg) = Σ { _Wi / (273 + Tg _i )}
_Wi : Mass fraction of _{monomer i Tg i} : Tg (° C.) of homopolymer of monomer i
The Tg of the homopolymer is a value using the numerical value described in "Polymer Handbook 4th Edition by John Wiley &Sons".

The copolymer (A) can be obtained, for example, by polymerizing a monomer component containing a monomer (x), a monomer (y), and a monomer (z). The monomer component may further contain any one or more of the monomer (h) and other monomers, if necessary.
The polymerization is typically carried out in the presence of a polymerization initiator. At the time of polymerization, a chain transfer agent may be used in combination, if necessary.
Examples of the polymerization method include known methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among them, solution polymerization is preferable because it is easy to operate and has high productivity.

<Polyfunctional compound (B)>
The polyfunctional compound (B) may be any compound having two or more radically polymerizable groups in one molecule, and various known compounds can be used. Polyfunctional (meth) acrylates are preferred. The polyfunctional compound (B) may be used alone or in combination of two or more.

The bifunctional polyfunctional (meth) acrylate is not particularly limited, but for example, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di. Alcandiol di (meth) acrylate such as (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, bisphenol F Examples thereof include bisphenol-modified di (meth) acrylate such as ethylene oxide-modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, urethane di (meth) acrylate, and epoxy di (meth) acrylate.

The trifunctional or higher polyfunctional (meth) acrylate is not particularly limited, and is, for example, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and penta. Isocyanuric acid-modified tri (meth) acrylates such as erythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, and ε-caprolactone-modified tris (acroxyethyl) isocyanurate, Examples thereof include urethane acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, dipentaerythritol hexa (meth) acrylate is preferable.

<Monofunctional compound>
The curable composition can contain a monofunctional compound having one radically polymerizable group in one molecule for adjusting the viscosity and the curing rate with active energy rays.
As the monofunctional compound, a monofunctional (meth) acrylate is preferable.
Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth) acrylate, and octyl (meth) acrylate. , 2-Ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cresol (meth) acrylate, dicyclo Penthenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, ethyldiethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, polyurethane mono (meth) acrylate, polyepoxy mono (meth) acrylate, polyester mono (meth) Examples include acrylate.

<Organic solvent>
The organic solvent is used as necessary for the purpose of improving workability when the curable composition is applied onto a surface of a substrate or the like.
Aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol and other ether solvents; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate and other ester solvents; dimethylformamide, diethylformamide, N-methylpyrrolidone and the like. Amid-based solvents; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and butanol; halogen-based solvents such as dichloromethane and chloroform; and the like. One of these organic solvents may be used alone, or two or more thereof may be used in combination. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferable because they can easily improve workability in coating.

<Photopolymerization initiator>
The curable composition may further contain one or more photopolymerization initiators (excluding the copolymer (A)) (hereinafter, also referred to as "photopolymerization initiator (C)").
For example, a photopolymerization initiator (C) which is a non-polymer having an active group that generates radicals by irradiation with active energy rays can be mentioned. The molecular weight of the photopolymerization initiator (C) 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, benzyl diphenyl 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-butyl Dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, Phenylglycioxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl] -2- Examples thereof include morpholino-1-propanone, tribromophenyl sulfone, and tribromomethylphenyl sulfone. These photopolymerization initiators may be used alone or in combination of two or more.

<Other ingredients>
The curable composition may further contain a leveling agent in order to improve the appearance of the cured product.
Examples of the leveling agent include an acrylic leveling agent, a silicone-based leveling agent, and a fluorine-based leveling agent. These leveling agents may be used alone or in combination of two or more.

The curable composition can further contain particles (D) having an average primary particle diameter of 0.01 μm or more and 10 μm or less in order to further improve the matting property of the uneven layer.
The particles (D) may be organic particles or inorganic particles, and two or more kinds may be used in combination. The inorganic particles may be particles whose surface is modified with a silane coupling agent having a reactive group such as a (meth) acryloyl group.
For the surface-modified particles, for example, the silane coupling agent and the inorganic particles are reacted at 25 ° C. to 120 ° C. for about 1 to 24 hours in the presence of a silane coupling reaction catalyst such as an acid, a base, or acetylacetone aluminum. Obtained by the method.

The curable composition contains a polymerization accelerator such as a thiol group-containing compound, an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, etc., as long as the effects of the present invention are not impaired. May be.

The content of the copolymer (A) in the curable composition is such that the content of the active group derived from the copolymer (A) per 100 g of the non-volatile content of the curable composition is 0.1 to 20 mmol / 100 g. The amount is more preferably 0.5 to 15 mmol / 100 g, further preferably 1 to 12 mmol / 100 g, and particularly preferably 1.5 to 10 mmol / 100 g. When the content of the active group is at least the lower limit of the above range, the curability is more excellent, the unevenness can be formed more effectively, and the matte property is more excellent. If it is less than the upper limit value, it becomes easy to form an annular uneven structure.

The ratio of the copolymer (A) to the non-volatile content of the curable composition is preferably in the range of 0.5 to 50% by mass, more preferably 1 to 20% by mass, and further preferably 1.5 to 5% by mass. is there. When it is at least the lower limit of the above range, the curability is more excellent. It also has better antifouling properties. If it is not more than the upper limit value, unevenness can be formed more effectively.
The non-volatile content of the curable composition is the total mass of the components other than the organic solvent. The non-volatile content of the curable composition can be measured by a conventionally known method, for example, the weight when 1 g of the composition is spread and heated at 100 ° C. for 1 hour to volatilize the organic solvent. Measured by change.

The ratio of the polyfunctional compound (B) to the non-volatile content of the curable composition is preferably in the range of 50 to 99.5% by mass, more preferably 70 to 99% by mass, and further preferably 80 to 98.5% by mass. is there. When it is at least the lower limit of the above range, the curability is more excellent. If it is not more than the upper limit value, unevenness can be formed more effectively.

The content of the organic solvent with respect to 100 parts by mass of the non-volatile content of the curable composition is preferably 10 to 1900 parts by mass, more preferably 40 to 400 parts by mass, from the viewpoint of improving operability in the coating operation.

The ratio of the photopolymerization initiator (C) to the non-volatile content of the curable composition is preferably less than 15% by mass, more preferably less than 10% by mass, further preferably less than 5% by mass, and may be 0% by mass. .. When it is at least the lower limit of the above range, the curability is more excellent. If it is not more than the upper limit value, unevenness having excellent matteness is likely to be formed.

When the curable composition contains the particles (D), the ratio of the particles (D) to the non-volatile content of the curable composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass. More preferably less than 1-10% by mass. If it is at least the lower limit of the above range, the scratch resistance is more excellent. If it is below the upper limit, the transparency is better.

(Formation of coating film)
The coating film of the curable composition can be formed, for example, by applying the curable composition on the surface of the substrate or the article and drying it if necessary.

The method of applying the curable composition is not particularly limited. For example, it can be applied by a known method such as a dip coating method, an air knife coating method, a curtain coating method, a spin coating method, a roller coating method, a bar coating method, a wire bar coating method, a gravure coating method, and a spray coating method.

When the curable composition contains an organic solvent, it is preferable to heat-dry it in advance before irradiating it with active energy rays. By heating and drying in advance, the organic solvent in the coating film can be effectively removed. When the copolymer (A) segregates on the surface side of the coating film, the concentration of the copolymer (A) on the surface side of the coating film is increased by removing the organic solvent, and the surface of the cured product is wrinkled. Unevenness is likely to appear.
The drying temperature for heat drying is preferably 30 ° C. or higher and 200 ° C. or lower, and more preferably 40 ° C. or higher and 150 ° C. or lower. The drying time is preferably 0.01 minutes or more and 30 minutes or less, and more preferably 0.1 minutes or more and 10 minutes or less.

(Irradiation of active energy rays)
Examples of the active energy ray include ultraviolet rays, α rays, β rays, γ rays and the like. Among them, ultraviolet rays are preferable.
The irradiation amount of the active energy ray can be appropriately selected according to the active energy ray to be irradiated.
When ultraviolet rays are used, it is preferable to irradiate to the integrated light quantity of irradiation is 100 mJ / cm ² or more 3000 mJ / cm ² or less, 200 mJ / cm ² or more 2000 mJ / cm ² or less being more preferred. As the illuminance is preferably 50 mW / cm ² or more 600 mW / cm ² or less, more preferably 75 mW / cm ² or more 450 mW / cm ² or less, 100 mW / cm ² or more 300 mW / cm ² or less is more preferred. As the light source, use a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or a scanning type, a high pressure mercury lamp such as an electron beam by a curtain type electron beam acceleration path, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, etc. Can be done.

[Laminate]
The laminate of the present invention (hereinafter, also referred to as “the present laminate”) has a base material layer and a layer composed of the cured film of the present invention (hereinafter, also referred to as “concavo-convex layer”).
The laminate further comprises a primer layer provided between the base material layer and the uneven layer, a surface functional layer provided on a surface of the uneven layer opposite to the base material layer side, and the above-mentioned. It may have one or more layers selected from the group consisting of back surface functional layers provided on the surface of the base material layer opposite to the uneven layer side.

The haze of the present laminate is usually 0.5% or more, preferably 1% or more, more preferably 5% or more, still more preferably 10% or more, particularly preferably 20% or more, and most preferably 30% or more. The upper limit is, for example, 99%. When the haze is at least the above lower limit value, the matte property is likely to be good.
Haze is measured by the method described in Examples described below.

The laminate preferably has transparency. The total light transmittance of this laminate is preferably in the range of 40 to 100%, more preferably 60 to 99%, and even more preferably 80 to 98%. If it is at least the lower limit of the above range, the transparency is excellent, and if it is at least the upper limit, the matte property is excellent.
The total light transmittance is measured by the method described in Examples described later.

The 60 ° mirror gloss (60 ° gloss) on the outermost surface of the laminated body on the side where the uneven layer exists with respect to the base material layer is preferably 60 or less, more preferably less than 50, and further preferably less than 20. is there. When it is not more than the above upper limit value, the matte property is excellent.
The 60 ° gloss is measured by the method described in Examples below.

(Base material layer)
As the base material layer, known ones can be used, and examples thereof include a resin base material, a metal base material, and a paper base material. Among these, a resin base material is preferable from the viewpoint of processability.
The resin base material may have a single-layer structure or a multi-layer structure having two or more layers, and is not particularly limited. It is preferable that the resin base material has a multi-layer structure of two or more layers, and each layer has a characteristic to be multifunctional.

Various resin films (sheets) can be used as the resin base material, for example, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, etc. Examples thereof include a polyvinyl alcohol film and a nylon film.
When developing this laminate for display applications, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetyl cellulose film are preferable. Among these, polyester film, poly (meth) acrylate film, and polyolefin film are preferable for anti-glare use, and polyester film is more preferable in consideration of transparency, moldability, and versatility.
The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferable. Of these, a uniaxially stretched film stretched in the uniaxial direction or a biaxially stretched film stretched in the biaxial direction 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 layer may be a homopolyester or a copolymerized polyester.
As the homopolyester, those obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol are preferable. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and the like. Aromatic dicarboxylic acid and aliphatic glycol 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. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like. The dicarboxylic acid component and the glycol component may be used alone or in combination of two or more.
Examples of typical polyesters include polyethylene terephthalate and polyethylene naphthalate.

As the polyester film, in consideration of mechanical strength and heat resistance, a film formed of polyethylene terephthalate or polyethylene naphthalate is more preferable, and ease of manufacture and handleability as a surface protective film or the like are more preferable. Considering the above, a film formed from polyethylene terephthalate is more preferable.

The poly (meth) acrylate constituting the poly (meth) acrylate film that can be used as the base material layer may be any one having a unit based on the (meth) acrylate, and various acrylic resins can be used. Examples of the (meth) acrylate 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. Examples thereof include alkyl (meth) acrylates having an alkyl group having a large number of carbon atoms.
Considering transparency, processability, and chemical resistance, the poly (meth) acrylate preferably contains a unit based on an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms as a main component, and methyl (meth) acrylate. It is more preferable that the main component is at least one selected from the group consisting of units based on meta) acrylate and units based on ethyl (meth) acrylate, and it is particularly preferable that the unit based on methyl (meth) acrylate is the main component. preferable.
It is also possible to impart properties such as flexibility by adding a unit based on (meth) acrylate other than the alkyl (meth) acrylate or a unit based on other monomers to the poly (meth) acrylate.
The ratio of the unit based on the alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms to the total mass of the poly (meth) acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

The base material layer can contain particles for the purpose of imparting slipperiness, preventing scratches in each step, and improving blocking resistance.
The type of particles can be appropriately selected according to 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 thereof include organic particles such as resins, epoxy resins, and benzoguanamine resins. Further, when the base material layer contains a polyester film, precipitated particles obtained by precipitating 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 in that a small amount is particularly effective.
The shape of the particles is not particularly limited, and any of spherical, massive, rod-shaped, flat-shaped, and the like may be used. Further, the hardness, specific gravity, color and the like are not particularly limited.
Two or more kinds of these particles may be used in combination, if necessary.

The average particle size of the particles is preferably in the range of 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. When the average particle size is 10 μm or less, the transparency of the base material layer is unlikely to decrease.
The average particle size of the particles is a value of 50% of the integration (number basis) in the equivalent spherical distribution measured by the dynamic light scattering type particle size distribution measuring device.

When the base material layer contains particles, the content of the particles in the base material layer cannot be unequivocally determined because it has a balance with the average particle size of the particles, but it is the total of the layers containing the particles in the base material layer. With respect to the mass, it is preferably 5% by mass or less, more preferably 0.0003 to 3% by mass, and further preferably 0.0005 to 1% by mass. When the content of the particles is 5% by mass or less, the particles are less likely to fall off or the transparency of the base material layer is lowered.

The base material layer can contain additives other than the above-mentioned particles, if necessary. As the additive, known additives such as an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a dye, and a pigment can be used.

The thickness of the base material layer is not particularly limited as long as it can form a film, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and further preferably 10 to 100 μm.

(Primer layer)
The primer layer is provided to impart various functions between the base material layer and the uneven layer.
Examples of the primer layer include an adhesion improving layer and an antistatic layer.
The primer layer may have a plurality of functions. For example, the adhesion improving layer may also serve as an antistatic layer.

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

In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, it is possible to reduce the adhesion of dust and the like due to peeling charging and triboelectric charging to the outermost surface of the laminated body, particularly the outermost surface on the side where the uneven layer exists with respect to the base material layer.
To make the primer layer an antistatic layer, for example, the primer layer may contain an antistatic agent.

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

Examples of the polyester resin include those whose main constituents are a polyvalent carboxylic acid and a polyvalent hydroxy compound.
Examples of the polyvalent carboxylic acid 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-sodiumsulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanediocarboxylic acid, glutaric acid, succinic acid, Examples thereof include trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, monopotassium trimellitic acid and ester-forming derivatives thereof.
Examples of the polyvalent hydroxy compound include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 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 Examples thereof include tetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like.
One or more of each of these compounds may be appropriately selected, and a polyester resin may be synthesized by a conventional polycondensation reaction.

The acrylic resin is a polymer of a polymerizable monomer containing a (meth) acrylic monomer.
Examples of the acrylic resin include homopolymers and copolymers of (meth) acrylic monomers, copolymers of (meth) acrylic monomers and polymerizable monomers other than (meth) acrylic monomers, and the like.
The acrylic resin may be a copolymer of these polymers and another polymer (for example, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Alternatively, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or dispersion is also included. Similarly, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a solution or dispersion of polyurethane is also included. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in a solution or dispersion of another polymer is also included.

The polymerizable monomer is not particularly limited, but typical compounds include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and the like. Salts: 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates, monobutylhydroquilfumalates, hydroxyl group-containing monomers such as monobutylhydroxyitaconate; methyl ( Alkyl (meth) acrylates such as meta) 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-methylol acrylamide and (meth) acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene, vinyl esters such as vinyl propionate and vinyl acetate; γ- Silicon-containing monomers such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and billidene chloride; and conjugated diene such as butadiene.

The urethane resin is a polymer compound having a urethane bond in the molecule, and is typically synthesized by a reaction between a polyol and a polyisocyanate. A chain extender may be used when synthesizing the urethane resin.
Examples of the polyol used to obtain the urethane resin include polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol and the like. These compounds may be used alone or in combination of two or more.

The polycarbonate polyol is obtained by a reaction (dealcohol 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, and 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-dimethylol heptane and the like. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like.
Specific examples of the polycarbonate polyol include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate and the like.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.

Examples of the polyester polyol include those obtained by reacting a polyvalent 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 the polyvalent carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid and the like.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, and 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-Diol-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, lactonediol and the like can be mentioned.

As the polyol, polyester polyol and polycarbonate polyol are preferable, and polyester polyol is particularly preferable, in consideration of adhesion performance.

Examples of the polyisocyanate used to obtain the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalene diisocyanate, and trizine diisocyanate; α, α, α', α'-. Aromatic diisocyanate having an aromatic ring such as tetramethylxylylene diisocyanate; aliphatic diisocyanate such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane Examples thereof include alicyclic diisocyanates such as diisocyanate and isopropyridene dicyclohexyldiisocyanate. These may be used alone or in combination of two or more.

The chain extender is not particularly limited as long as it has two or more active groups that react with the isocyanate group, and in general, a chain extender having two hydroxyl groups or amino groups can be mainly used. ..
Examples of the chain extender 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 the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine and 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, 1,10-decanediamine And other aliphatic diamines, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprovilitincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3 -Alicyclic diamines such as bisaminomethylcyclohexane and the like can be mentioned.

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

Examples of the ionic group introduced into the structure of the urethane resin include various groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group and a quaternary ammonium base, but a carboxyl group is preferable.
The carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amines, alkali metals and inorganic alkalis. Particularly preferred neutralizers are ammonia, trimethylamine and triethylamine. In the urethane resin having a carboxyl group neutralized with a neutralizing agent, the carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a cross-linking reaction point by the cross-linking agent. As a result, the stability of the liquid before coating is excellent, and the durability, solvent resistance, water resistance, blocking resistance and the like of the obtained primer layer can be further improved.

As a method for introducing a carboxyl group into the urethane resin, various methods can be taken in each stage of the polymerization reaction. For example, at the time of prepolymer synthesis, there are a method of using a resin having a carboxyl group as a copolymerization component and a method of using a component having a carboxyl group as one component of a polyol, a polyisocyanate, a chain extender and the like. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups according to the amount of this component charged is preferable. For example, a carboxyl group-containing diol can be copolymerized with a polyol used for synthesizing a urethane resin.
Carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid, and their carboxyl groups are neutralized with a neutralizing agent. Examples include salt that has been neutralized.

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, and examples thereof include melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferable, and from the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, and isocyanate compounds are preferable. And epoxy compounds are more preferable, and oxazoline compounds and isocyanate compounds are particularly preferable. These cross-linking agents may be used alone or in combination of two or more. Adhesion and durability may be further improved and improved by using two or more types together.

A melamine compound is a compound having a melamine skeleton in the compound, for example, an alkylolated melamine derivative, a compound obtained by reacting an alkylolated melamine derivative with an alcohol to partially or completely etherify, and a compound thereof. Examples include mixtures. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like. The melamine compound may be either a monomer or a multimer of a dimer or more, or a mixture thereof may be used. Further, a melamine that is copolymerized with urea or the like can be used, or a catalyst can be used to increase the reactivity of the melamine compound.
The melamine compound preferably has a hydroxyl group in consideration of reactivity with various compounds.

The isocyanate-based compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate.
Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate and naphthalene diisocyanate; and aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate. Aliphatic isocyanates; aliphatic isocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), isopropyridene dicyclohexyldiisocyanate, etc. Examples thereof include alicyclic isocyanates. In addition, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimides of these isocyanates are also mentioned. These may be used alone or in combination of two or more. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates from the viewpoint of avoiding yellowing due to ultraviolet rays.

Examples of the blocked isocyanate include those in which the isocyanate group of the isocyanate-based compound is blocked with a blocking agent. Examples of the blocking agent include phenolic compounds such as heavy sulfites, phenol, cresol and ethylphenol, alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol, dimethyl malate and diethyl malonate. Active methylene compounds such as methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ε-caprolactam and δ-valerolactam, diphenylaniline, aniline, Examples thereof include amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetate amide, and oxime compounds such as formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime. These may be used alone or in combination of two or more.
As the blocked isocyanate, an isocyanate blocked by an active methylene compound is preferable from the viewpoint that the primer layer is not easily destroyed.

The isocyanate compound may be used alone, or may be used as a mixture or a bond with various polymers. In terms of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

The oxazoline compound is a compound having an oxazoline group in the molecule.
As the oxazoline compound, a polymer containing an oxazoline group is preferable. The oxazoline group-containing polymer is obtained by polymerization of the addition-polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of the addition-polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition-polymerizable oxazoline group-containing monomer. For example, an alkyl (meth) acrylate (as an alkyl group, a methyl group, an ethyl group, an n-propyl group, etc. (Meta) acrylates such as 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 acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl (meth) ) Acrylamide, N, N-dialkyl (meth) acrylamide, (the alkyl groups are 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; Vinyl chloride, vinylidene chloride, vinyl fluoride, etc. Halogen-containing α, β-unsaturated monomer; α, β-unsaturated aromatic monomer such as styrene, α-methylstyrene, etc. can be mentioned. These may be used alone or in combination of two or more.

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

The epoxy compound is a compound having an epoxy group in the molecule.
Examples of the epoxy compound include a condensate of epichlorohydrin and a compound having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), and examples thereof include polyepoxy compounds, diepoxy compounds, and the like. There are monoepoxy compounds, glycidylamine compounds and the like. Examples of the polyepoxy compound 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 can be mentioned. Examples of the diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol di. Examples thereof include glycidyl ether and polytetramethylene glycol diglycidyl ether. Examples of the monoepoxy compound include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of the glycidylamine compound include N, N, N', N'-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N-diglycidylamino) cyclohexane.

The carbodiimide-based compound is a compound having one or more carbodiimide structure or carbodiimide derivative structure 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 because of better primer layer strength and the like.

The carbodiimide-based compound can be synthesized by a known technique, and a condensation reaction of diisocyanate is generally used. The diisocyanate is not particularly limited, and any aromatic or aliphatic type can be used. Specifically, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, naphthalenediocyanate, hexamethylene. Examples thereof include diisocyanate, trimethylhexamethylene diisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate, dicyclohexyldiisocyanate, and dicyclohexylmethane diisocyanate.

In order to improve the water solubility and water dispersibility of the polycarbodiimide compound, a surfactant may be added as long as the effect of the present invention is not lost, or a quaternary ammonium salt of a polyalkylene oxide or a dialkylamino alcohol may be added. , Hydrophilic monomers such as hydroxyalkyl sulfonates may be added.

The silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzing group such as an alkoxy group in one molecule.
Examples of the silane coupling compound include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Epyl group-containing compounds such as 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane, vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane Such as styryl group-containing compounds, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy. (Meta) acryloyl group-containing compounds such as propylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethyldiethoxysilane, Amino group-containing compounds such as 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, Isocyanurate group-containing compounds such as tris (trimethoxysilylpropyl) isocyanurate and tris (triethoxysilylpropyl) isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane. , 3-Mercapto group-containing compounds such as mercaptopropylmethyldiethoxysilane and the like.

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

These cross-linking agents react in the drying process and the film forming process to improve the performance of the primer layer. It can be inferred that an unreacted product of the cross-linking agent, a compound after the reaction, or a mixture thereof is present as the compound derived from the cross-linking agent in the formed primer layer.

The antistatic agent contained in the primer layer is not particularly limited, and a known antistatic agent can be used. For example, a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, and betaine. Examples include compounds and conductive organic polymers.
As the antistatic agent, a polymer type antistatic agent is preferable because it has good heat resistance and moisture heat resistance.

The compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include an aliphatic amine, an alicyclic amine, and an ammonium compound of an aromatic amine.
The compound having an ammonium group is preferably a compound having a polymer type ammonium group.
In a compound having a polymer-type ammonium group, the ammonium group is preferably incorporated in the main chain or side chain of the polymer, not as a counter ion. As such a compound, for example, an addition polymerizable monomer having an ammonium group precursor group such as an ammonium group or an amine is polymerized, and if necessary, the precursor group of the ammonium group is converted into an ammonium group. Examples thereof include those obtained as polymer compounds having an ammonium group. As the addition-polymerizable monomer containing an ammonium group or a precursor group of an ammonium group, one type may be polymerized alone, two or more types may be copolymerized, or the other monomer may be copolymerized. You may.

As the compound having an ammonium group, a compound having a pyrrolidinium ring is also preferable in that it is excellent in antistatic property and heat stability.
The two substituents bonded to the nitrogen atom of the compound having a pyrrolidinium ring are independently alkyl groups, phenyl groups, etc., and even if these alkyl groups and phenyl groups are substituted with the groups shown below. Good. Substitutable groups are, for example, hydroxyl groups, amide groups, ester groups, alkoxy groups, phenoxy groups, naphthoxy groups, thioalkoxy, thiophenoxy groups, cycloalkyl groups, trialkylammonium alkyl groups, cyano groups and halogens. Further, the two substituents bonded to the nitrogen atom may be chemically bonded, and examples of the group in which the two substituents are chemically bonded include − (CH _{2 ) m} − (m =). 2 to 5 integers), -CH (CH ₃ ) CH (CH ₃ )-, -CH = CH-CH = CH-, -CH = CH-CH = N-, -CH = CH-N = C-, −CH ₂ OCH ₂ −, − (CH ₂ ) ₂ O (CH ₂ ) ₂ − and the like can be mentioned.

The compound having a pyrrolidinium ring is preferably a polymer having a pyrrolidinium ring.
The polymer having a pyrrolidinium ring can be obtained, for example, by cyclizing and polymerizing a diallylamine derivative using a radical polymerization catalyst. A compound having a carbon-carbon unsaturated bond polymerizable with the diallylamine derivative may be used as a copolymerization component. Polymerization is known in polar solvents (water, methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile, etc.) using polymerization initiators such as hydrogen peroxide, benzoyl peroxide, and tertiary butyl peroxide. It can be carried out by a method, but is not limited to this.

Examples of the anion that becomes the counter ion (counter ion) of the ammonium group of the above-mentioned compound having an ammonium group include ions such as halogen ion, sulfonate, phosphate, nitrate, alkyl sulfonate, and carboxylate.

The number average molecular weight of the compound having an ammonium group is preferably 1000 to 500000, more preferably 2000 to 350,000, and even more preferably 5000 to 20000. When the number average molecular weight is 1000 or more, the strength and heat resistance stability of the coating film are more excellent. When the number average molecular weight is 500,000 or less, the viscosity of the coating liquid for forming the primer layer is low, and the handleability and coating property are good.

Examples of the polyether compound include polyethylene oxide, a polyether ester amide, and an acrylic resin having polyethylene glycol in the side chain.

In a compound having a sulfonic acid group, the sulfonic acid group may be neutralized with a neutralizing agent to form a salt. As the compound having a sulfonic acid group, a compound having a plurality of sulfonic acid groups in the molecule, such as polystyrene sulfonic acid and a salt thereof, is preferable.

As the conductive organic polymer, known materials can be used, and examples thereof include polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, and polyphenylene sulfide-based. Among these, a polythiophene type (polythiophene or polythiophene derivative) is preferable because it has both high transparency and high conductivity, is difficult to color, and easily exhibits performance by coating. Among the polythiophenes, a compound obtained by combining poly (3,4-ethylenedioxythiophene) with polystyrene sulfonic acid is particularly preferable from the viewpoint of conductive performance.
The conductive organic polymer is preferable in that it exhibits high conductivity, has little humidity dependence, and can be expected to be used in various applications.

The primer layer may contain particles for blocking and improving slipperiness.
The primer layer is a defoaming agent, a coating property improving agent, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, as necessary, as long as the gist of the present invention is not impaired. It may contain an additive such as a pigment.

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

The proportion 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, and further preferably 5 to 40% by mass. The range. When the ratio of the compound derived from the cross-linking agent is within the above range, the adhesion performance and the strength of the primer layer are more excellent.

When the primer layer is an antistatic layer containing an antistatic agent, the proportion of the antistatic agent in 100% by mass of the primer layer is not unconditional because it depends on the type of the antistatic agent, but is, for example, 80% by mass or less. It is preferably in the range of 0.5 to 70% by mass, more preferably 1 to 50% by mass. When the ratio of the antistatic agent is within the above range, it is easy to impart a sufficient antistatic function to the primer layer, and it is easy to exhibit the antistatic performance even after the uneven layer is formed on the primer layer.

The thickness of the primer layer cannot be unconditionally determined because it depends on the material used for the primer layer and the performance to be expressed, but it is preferably 0.001 to 10 μm, more preferably 0.01 to 4 μm, and further preferably 0. It is in the range of 02 to 1 μm.
The primer layer can be formed by a known method.

(Back function layer)
The back surface functional layer is provided to impart various functions to the surface of the base material layer opposite to the uneven layer side.
Examples of the back surface functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an anti-blocking layer.
The adhesive layer is provided to join the laminated body to various adherends. The antistatic layer is used to prevent adhesion of surrounding dust due to peeling electrification or triboelectric charging to the outermost surface of the laminate, particularly the outermost surface of the base material layer opposite to the uneven layer side, and defects caused by the adhesion. Provided. The refractive index adjusting layer is provided, for example, in order to improve the total light transmittance of the laminated body. The anti-blocking layer is provided to reduce blocking of the laminate.

As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, known ones can be used, and examples thereof include acrylic type, polyester type, urethane type, and rubber type. Among them, acrylic 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 the surface functional layer, respectively.

The thickness of the back surface functional layer depends on the material used for the back surface functional layer and the performance to be developed, and therefore cannot be unconditionally determined, but is, for example, 0.001 to 30 μm. When the back surface functional layer is an adhesive layer, it is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back surface functional layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm.
The back surface functional layer can be formed by a known method.

This laminate is suitable as an antiglare film because it has excellent matte properties.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
The measurement method and evaluation method used in the present invention are as follows.

(1) Weight average molecular weight (Mw)
The weight average molecular weight of the copolymer was measured by GPC under the following conditions.
Equipment: Waters "e2695",
Column: "TSKgel Super H3000 + H4000 + H6000" manufactured by Tosoh Corporation,
Detector: Differential refractive index detector (RI detector / built-in),
Solvent: tetrahydrofuran,
Temperature: 40 ° C,
Flow velocity: 0.5 mL / min,
Injection volume: 10 μL,
Concentration: 0.2% by mass,
Calibration sample: monodisperse polystyrene,
Calibration method: Polystyrene conversion.

(2) Total light transmittance / haze A laminated body having an uneven layer formed on a PET film was used as a measurement target. The total light transmittance and haze are JIS Z8722Z (geometric conditions for irradiation and light reception of transmitted objects) and JIS K7361-1 (test method for total light transmittance of plastic-transparent material) JIS K7136 (length of plastic-transparent material). The value at a wavelength of 550 nm was measured using a haze meter “SH7000” manufactured by Nippon Denshoku Kogyo Co., Ltd.
The haze of the laminated body is 0.044 rad (2.) of the transmitted light incident from the outermost surface on the side where the uneven layer exists with respect to the base material layer and passing through the laminated body due to forward scattering. It is a percentage of transmitted light (ratio of diffuse transmittance to total light transmittance) deviated by 5 °) or more.

(3) Leveling property The surface (10 cm × 10 cm) of the uneven layer was visually observed to check the number of repellents and bump defects. Evaluation was made according to the following criteria.
A: The total number of repellent and lump defects is less than 10.
B: The total number of repellent and lump defects is 10 or more.

(4) Curability In each example, the irradiation conditions (curing conditions) when irradiating ultraviolet rays were adjusted so that ^{the irradiation amount per irradiation was 100 mJ / cm 2} (illuminance was 100 mW / J / cm ^2). The irradiation amount (integrated light amount) until the tack disappeared by touch was measured.
A: Curing is performed with an irradiation amount of more than 200 mJ / cm ² and 400 mJ / cm ^{2 or less.}
B: cures many 600 mJ / cm ² less dose than 400 mJ / cm ^2.
C: Curing with an irradiation amount of more than ^{600 mJ / cm 2.}

(5) A laminate in which an uneven layer was formed on a 60 ° gloss PET film was used as a measurement target. The 60 ° gloss (60 ° mirror gloss) was measured using a gloss meter "VG2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS Z 8741. The lower the 60 ° gloss value, the better the matte property.
The principle of measuring the specular gloss is to measure the specular reflected luminous flux φs from the sample surface with respect to the specified incident angle θ (60 ° in the case of 60 ° mirror gloss).

(6) Pencil hardness JIS K5600-5-4 General paint test method-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method), the pencil hardness of the uneven layer was measured.

(7) Scratch resistance Under an atmosphere of 23 ° C and 55% RH, ^{a weight of 200 gf (per area 4 cm 2} ) is placed on steel wool # 0000, and the surface of the uneven layer is surfaced with a Gakushin wear tester (manufactured by Toyo Seiki). The scratches were visually observed by rubbing back and forth. Evaluation was made according to the following criteria.
A: There are 1 or more and less than 50 scratches.
B: There are 50 or more and less than 100 scratches.
C: More than 100 scratches are made.

(8) Water contact angle (water repellency and stain resistance)
The water contact angle (liquid volume 2 μL) of the uneven layer was measured using a contact angle meter (“Drop Master 500” manufactured by Kyowa Interface Science Co., Ltd.). The larger the value of the water contact angle, the better the evaluation of water repellency (stain resistance).

(9) Surface shape of the concavo-convex layer (arithmetic mean height Sa, area ratio of convex portion, presence / absence of annular structure, distance between convex portion in convex strip forming annular structure and concave portion adjacent to convex portion, convex strut Height of convex parts, size of annular structure (10-point average value of maximum diameter of inner region of annular structure), number of annular structures per unit area in plan view)
Using a surface shape measurement system (Hitachi High-Tech Science Co., Ltd. "VertScan" (registered trademark) VS1330), the uneven shape of the surface in the region of 236.87 μm × 177.60 μm is measured by optical interferometry on the surface of the uneven layer. Then, the arithmetic mean height Sa, the area ratio of the convex portion, the distance between the convex portion in the convex portion of the annular structure and the center of the concave portion adjacent to the convex portion, and the convex portion constituting the convex portion are performed by complementing and correcting the baseline. The height, the size of the annular structure (10-point mean value of the maximum diameter of the inner region of the annular structure), and the number of annular structures per unit area in a plan view were calculated. The magnification of the objective lens at the time of measurement was set to 20 times.
The area ratio of the convex portion was analyzed by binarizing the region into two regions, a concave portion and a convex portion, by image analysis. In the analysis, the bearing function of the surface shape measurement system is used, and in the load curve obtained from the roughness curve of the surface of the uneven layer, both the peak side height threshold value and the valley side height threshold value are set to 0.1 μm and binary values are obtained. It was obtained by calculating the area of the protruding mountain portion (dark colored portion in FIGS. 1 and 2). The analysis conditions of the load curve are as follows.
<Load curve analysis>
・ Number of histogram divisions: 100
-Type of load curve: Bearing curve-Height threshold specification: 100 nm
・ Valley side threshold specification: 100 nm

A copolymer was produced with the compositions shown in Table 1. The monomers in the table are as follows.
<Monomer (x)>
x-1: 4-methacryloyloxybenzophenone.
<Monomer (y)>
y-1: Stearyl methacrylate.
y-2: 2-ethylhexyl methacrylate.
<Monomer (z)>
z-1: EO-modified -о-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10T).
<Monomer (h)>
h-1: 2-Hydroxyethyl methacrylate.
h-2: Diethylaminoethyl methacrylate.
<Polymerization initiator (k)>
k-1: Azobis (2,4-dimethylvaleronitrile).

(Production Example 1: Production of copolymer (A-1))
73 parts of methylisobutylketone (hereinafter referred to as MIBK) was placed in a flask equipped with a stirrer, a cooling tube and a thermometer, and then the inside of the flask was replaced with nitrogen and the temperature was raised to 65 ° C. for the monomer (x-1). 40 parts by mass, 10 parts by mass of monomer (y-1), 30 parts by mass of monomer (y-2), 10 parts by mass of monomer (h-1), 10 parts by mass of monomer (h-2), polymerization initiator (k-) 1) A mixed solution of 0.8 parts by mass and 78 parts by mass of MIBK was added dropwise over 2 hours. After another 2 hours, in order to increase the polymerization rate, a mixed solution of 0.5 parts by mass of the polymerization initiator (k-1) and 0.6 parts by mass of MIBK was added and held for 5 hours. Then, the reaction solution was cooled to 40 ° C. to obtain a MIBK solution (A-1) of the copolymer. Hereinafter, the solid content in the solution (A-1) is referred to as a copolymer (A-1).
The solid content (nonvolatile content) of the solution (A-1) was 40%. Table 1 shows the weight average molecular weight (Mw) of the copolymer (A-1), the glass transition temperature, and the content of active groups per gram of the copolymer (H-1).

(Production Example 2: Production of copolymer (A-2))
73 parts of MIBK was placed in a flask equipped with a stirrer, a cooling tube and a thermometer, and then the inside of the flask was replaced with nitrogen and the temperature was raised to 65 ° C., 40 parts by mass of monomer (x-1) and monomer (y-1). ) 10 parts by mass, monomer (z-1) 30 parts by mass, monomer (h-1) 10 parts by mass, monomer (h-2) 10 parts by mass, polymerization initiator (k-1) 0.8 parts by mass, MIBK78 The mixed solution of parts by mass was added dropwise over 2 hours. After another 2 hours, in order to increase the polymerization rate, a mixed solution of 0.5 parts by mass of the polymerization initiator (k-1) and 0.6 parts by mass of MIBK was added and held for 5 hours. Then, the reaction solution was cooled to 40 ° C. to obtain a MIBK solution (A-2) of the copolymer. Hereinafter, the solid content in the solution (A-2) is referred to as a copolymer (A-2).
The solid content (nonvolatile content) of the solution (A-2) was 40%. Table 1 shows the weight average molecular weight (Mw) of the copolymer (A-2), the glass transition temperature, and the content of active groups per gram of the copolymer (H-1).

(Example 1, Comparative Examples 1 and 2)
Each material shown in Table 2 was mixed so as to have the ratio (parts by mass) shown in Table 2 in terms of non-volatile content. Then, a mixed solvent (PGM: MEK (mass ratio) of 7: 3) of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) was added so that the solid content concentration was 40% by mass, and the mixture was uniformly added. A coating liquid (curable composition) was obtained by stirring until
The materials in Table 2 are as follows.
A-1: MIBK solution of the copolymer (A-1) obtained in Production Example 1.
A-2: MIBK solution of the copolymer (A-2) obtained in Production Example 2.
B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.).
B-2: Pentaerythritol triacrylate (“Viscoat V # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.).
C-1: Benzophenone.
Table 2 shows the content of the active group with respect to 100 g of the solid content of the curable polymer composition in the coating liquid.

The obtained coating liquid was applied to a PET film having a thickness of 50 μm (“T602E50” manufactured by Mitsubishi Chemical Co., Ltd.) with a bar coater No. 8 and dried with a hot air dryer heated to 70 ° C. for 60 seconds to volatilize the solvent. In an air atmosphere, ultraviolet rays were irradiated with a high-pressure mercury lamp at an integrated light amount of 250 mJ / cm ² and an illuminance of 100 mW / cm ² to form an uneven layer (cured film) having a thickness of 2.5 μm. As a result, a laminate in which an uneven layer was laminated on a base material layer made of a PET film was obtained.
For the irradiation of ultraviolet rays, a UV conveyor of an eye graphics high-power UV device (model: US5-X1802-X1202) was used. The integrated light amount is a value when the integrated light amount having a wavelength of 300 to 390 nm is measured with an illuminometer manufactured by Iwasaki Electric Co., Ltd. (eye ultraviolet integrated illuminance meter "UVPF-A1", "PD-365").
The items shown in Table 2 were measured or evaluated for the obtained laminate by the above method. The results are shown in Table 2. Further, FIGS. 1 and 2 show binarized images of the surface shape of the uneven layer in each of Example 1 and Comparative Example 1.

As shown in FIG. 1, the uneven layer of Example 1 had an annular structure. As shown in Table 2, this uneven layer was excellent in matte property and scratch resistance, and also had good antifouling property. In addition, the coating liquid was also excellent in leveling property and curability.
On the other hand, in the uneven layer of Comparative Example 1 in which the polymer (A-1) was used instead of the polymer (A-2), wrinkle-like unevenness was evenly formed on the entire surface as shown in FIG. , Did not have an annular structure. As shown in Table 2, this uneven layer was inferior in scratch resistance. In addition, the curability of the coating liquid was also inferior.
As shown in Table 2, the uneven layer of Comparative Example 1 in which a general photopolymerization initiator (non-polymer having an active group) (C-1) was used instead of the polymer (A-2) was transparent. Was almost the same as that of Example 1, but the surface was almost smooth, no matte property was obtained, and scratch resistance and antifouling property were also inferior. In addition, the coating liquid was also inferior in leveling property, curability, and antifouling property.

1 ... Convex 3 ... Convex 5 ... Concave

Claims (12)

It has a structure in which ridges are formed in a ring shape on the surface, and the ridges are composed of wrinkled irregularities.
The distance between the center of the convex portion in the unevenness and the concave portion adjacent to the convex portion in the plan view and in the width direction of the convex portion is 0.5 to 20 μm.
A cured film having an arithmetic mean height Sa of the surface of 0.01 to 5 μm. The cured film according to claim 1, wherein two or more of the structures are arranged adjacent to each other. The cured film according to claim 1 or 2, wherein the ratio of the area of the convex portion to the total area of the surface is 1 to 40% in a plan view. The cured film according to any one of claims 1 to 3, wherein the surface has a 60 ° mirror gloss of 60 or less. The cured film according to any one of claims 1 to 4, which is an antiglare film. A monomer (y) having a unit based on a monomer (x) having an active group that generates radicals by irradiation with active energy rays, and one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom. ), And a copolymer (A) having a unit based on a monomer (z) having a structure containing two or more aromatic rings that does not generate radicals by irradiation with active energy rays, and two in one molecule. The cured film according to any one of claims 1 to 5, which is a cured product of a curable composition containing the above-mentioned polyfunctional compound (B) having a radically polymerizable group. A monomer (y) having a unit based on a monomer (x) having an active group that generates radicals by irradiation with active energy rays, and one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom. ), And a copolymer (A) having a unit based on a monomer (z) having a structure containing two or more aromatic rings that do not generate radicals by irradiation with active energy rays, and two in one molecule. A method for producing a cured film, wherein a coating film of a curable composition containing the above-mentioned polyfunctional compound (B) having a radical polymerizable group is formed, and the coating film is irradiated with active energy rays. A laminate having a base material layer and a layer made of the cured film according to any one of claims 1 to 6. The laminate according to claim 8, wherein the 60 ° mirror surface gloss on the outermost surface on the side where the layer made of the cured film exists with respect to the base material layer is 60 or less. The laminate according to claim 8 or 9, wherein the haze is 20% or more. The laminate according to any one of claims 8 to 10, which is an antiglare film. Further, a primer layer provided between the base material layer and the layer made of the cured film, and a surface functional layer provided on a surface of the layer made of the cured film opposite to the base material layer side. Any one of claims 8 to 11, further comprising one or more layers selected from the group consisting of the back surface functional layer provided on the surface of the base material layer opposite to the layer side of the cured film. The laminate according to the item.

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