JP7099414B2 - Laminate - Google Patents

Description

The present invention relates to a laminate.

A method of expressing fine irregularities on the surface of a base material to impart matteness is known.
For example, in Patent Document 1, a paint containing a specific urethane acrylate, a reactive diluent, and a specific photoinitiator is applied onto a substrate, and then a cured resin is irradiated with ultraviolet rays in a specific low wavelength band. A method of generating fine wrinkles on the surface and further irradiating with ultraviolet rays in a specific high wavelength band to cure the inside of the resin is described.

Japanese Unexamined Patent Publication No. 9-53024

According to the method described in Patent Document 1, a laminated body in which an uneven layer made of a cured resin having an uneven surface is present on a substrate can be obtained, but the step of forming the uneven layer is complicated and manufacturable. Is inferior. In addition, the uneven layer alone may not be sufficient to support the functions required in various applications.
An object of the present invention is to provide a laminated body which is excellent in manufacturability of an uneven layer and can exhibit a plurality of functions including matting property.

The present invention has the following aspects.
[1] It has a base material layer and an uneven surface having unevenness provided on one surface of the base material layer.
The uneven layer is a cured product of a composition containing a polymer (X) having an active group that generates radicals by irradiation with active energy rays.
Further, the primer layer provided between the base material layer and the uneven layer, the surface functional layer provided on the surface of the uneven layer opposite to the base material layer side, and the base material layer. A laminate having one or more layers selected from the group consisting of back surface functional layers provided on the surface opposite to the uneven layer side.
[2] The active group is a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. The laminate of the above [1], which is one or more selected from the group consisting of.
[3] The laminated body of the above [1] or [2], wherein the surface functional layer is an antifouling layer, an antistatic layer, a refractive index adjusting layer, an infrared absorbing layer, an ultraviolet absorbing layer, or a color correction layer.
[4] The laminate according to any one of the above [1] to [3], wherein the back surface functional layer is an adhesive layer, an antistatic layer, a refractive index adjusting layer, or an anti-blocking layer.
[5] The laminate according to any one of the above [1] to [4], wherein the primer layer contains a resin.
[6] The laminate according to any one of [1] to [5] above, wherein the primer layer contains a compound derived from a cross-linking agent.
[7] The laminate according to any one of [1] to [6] above, wherein the polymer (X) has a unit based on the (meth) acrylic acid ester having the active group.
[8] The laminate of the above [7], wherein the polymer (X) further has a unit based on a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms.
[9] The laminate of [7] or [8], wherein the polymer (X) further has a unit based on a (meth) acrylic acid ester having a hydrogen donating functional group.
[10] The laminate according to any one of the above [1] to [9], wherein the content of the active group per 1 g of the uneven layer is 0.001 to 1 mmol / g.
[11] The laminate according to any one of the above [1] to [10], wherein the composition further contains a compound (Y) having a radically polymerizable group.

The laminate of the present invention is excellent in the manufacturability of the concavo-convex layer and can exhibit a plurality of functions including matte property.

It is a schematic sectional drawing which shows an example of the laminated body of this invention. It is a schematic sectional drawing which shows another example of the laminated body of this invention. It is a schematic sectional drawing which shows another example of the laminated body of this invention. It is a schematic sectional drawing which shows another example of the laminated body of this invention. It is a schematic sectional drawing which shows another example of the laminated body of this invention.

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 acid.
For the analysis of the components in each of the uneven layer, the primer layer, the front surface functional layer, and the back surface functional layer, for example, TOF-SIMS (time-of-flight secondary ion mass spectrometry), ESCA (X-ray photoelectric spectroscopy), fluorescent X It can be performed by line, IR (infrared spectroscopy), or the like.
"~" 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.
The dimensional ratios in FIGS. 1 to 5 are for convenience of explanation and are different from the actual ones.

[Laminate]
The laminate of the present invention (hereinafter, also referred to as “the present laminate”) has a base material layer and an uneven layer provided on one surface of the base material layer. The laminated body further includes 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 has 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.

FIG. 1 is a schematic cross-sectional view showing an example of the present laminated body.
The laminate 10 includes a base material layer 1, an uneven layer 2 provided on one surface 1a of the base material layer 1, a primer layer 3 provided between the base material layer 1 and the uneven layer 2, and a primer layer 3. Has.

FIG. 2 is a schematic cross-sectional view showing another example of the present laminated body.
The laminate 10 is provided on the base material layer 1, the uneven layer 2 provided on one surface 1a of the base material layer 1, and the surface opposite to the base material layer 1 side of the uneven layer 2. It has a surface functional layer 4.

FIG. 3 is a schematic cross-sectional view showing another example of the present laminated body.
The laminate 10 includes a base material layer 1, an uneven layer 2 provided on one surface 1a of the base material layer 1, a primer layer 3 provided between the base material layer 1 and the uneven layer 2, and a primer layer 3. It has a surface functional layer 4 provided on a surface of the uneven layer 2 opposite to the base material layer 1 side.

FIG. 4 is a schematic cross-sectional view showing another example of the present laminated body.
The laminate 10 includes a base material layer 1, an uneven layer 2 provided on one surface 1a of the base material layer 1, a primer layer 3 provided between the base material layer 1 and the uneven layer 2, and a primer layer 3. It has a back surface functional layer 5 provided on a surface 1b opposite to the uneven layer 2 side of the base material layer 1.

FIG. 5 is a schematic cross-sectional view showing another example of the present laminated body.
The laminate 10 includes a base material layer 1, an uneven layer 2 provided on one surface 1a of the base material layer 1, a primer layer 3 provided between the base material layer 1 and the uneven layer 2, and a primer layer 3. The front surface functional layer 4 provided on the surface of the base material layer 2 opposite to the base material layer 1 side, and the back surface functional layer provided on the surface 1b of the base material layer 1 opposite to the base material layer 2 side. 5 and.

The haze of the present laminate is not particularly limited as long as the matting property is exhibited, but is usually 0.5% or more, preferably 1% or more, more preferably 5% or more, still more preferably 10% or more. It is particularly preferably in the range of 20% or more, most preferably in the range of 30% or more, and the upper limit is, for example, 99%. When the haze is at least the above lower limit value, it is easy to improve the matte property.
The haze of the present laminate is 0 from the incident light due to forward scattering of the transmitted light incident from the outermost surface of the laminate on the side where the uneven layer exists with respect to the base material layer and passing through the present laminate. It is a percentage of transmitted light deviated by 0.044 rad (2.5 °) or more (ratio of diffuse transmittance to total light transmittance) and is measured according to JIS K 7136.

The 60 ° mirror 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 100 or less, more preferably 80 or less, still more preferably 50 or less in consideration of mattability. It is particularly preferably in the range of 30 or less, and most preferably in the range of 15 or less. There is no particular lower limit, but it is preferably 1 or more. When the 60 ° mirror surface gloss is not more than the above upper limit value, the matte property is likely to be good.
The 60 ° mirror gloss is measured according to JIS Z 8741. 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).

(Base 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.

As the resin base material, various resin films (sheets) can be used, for example, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, etc. Polyvinyl alcohol film, nylon film and the like can be mentioned.
When developing this laminate for display applications, polyester films, poly (meth) acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferable. Among these, polyester films, poly (meth) acrylate films, and polyolefin films are preferable for anti-glare applications, and polyester films are 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. Among them, 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.
The homopolyester is preferably obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. 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.
The ultimate viscosity of the polyester is preferably 0.5 to 1.0 dL / g, more preferably 0.55 to 0.75 dL / g. The ultimate viscosity is measured by the method described in Examples described later.

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.

As the poly (meth) acrylate constituting the poly (meth) acrylate film that can be used as the base material layer, any acrylic resin may be used as long as it has a unit based on the (meth) acrylate. 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 to have at least one selected from the group consisting of a unit based on meta) acrylate and a unit based on ethyl (meth) acrylate as a main component, and particularly to have a unit based on methyl (meth) acrylate as a main component. preferable.
It is also possible to impart properties such as flexibility by incorporating a unit based on (meth) acrylate other than the alkyl (meth) acrylate or a unit based on other monomers into 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, titanium oxide, acrylic resin, styrene resin, urea resin, and phenol. Examples thereof include organic particles such as a resin, an epoxy resin, and a benzoguanamine resin. 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 particularly preferable in that a small amount is likely to produce an effect.
The shape of the particles is not particularly limited, and any of spherical, lumpy, 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, problems due to a decrease in transparency of the base material layer are unlikely to occur.
The average particle size of the particles is a value of 50% integrated (mass basis) in the equivalent spherical distribution measured by the centrifugal sedimentation 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 there is a balance with the average particle size of the particles, but the total number of layers containing the particles in the base material layer It is preferably in the range of 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and further preferably in the range of 0.0005 to 1% by mass with respect to the mass. When the content of the particles is 5% by mass or less, problems such as falling off of the particles and deterioration of the transparency of the base material layer are unlikely to occur.

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 antioxidant, 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.

(Concave and convex layer)
In the uneven layer, the surface opposite to the base material layer side is an uneven surface (non-smooth surface) having unevenness. As a result, the laminated body has a matte property.
Examples of the shape of the unevenness include a wrinkle-like shape and a shape in which a plurality of granular convex portions are dispersedly arranged. The height and period of the unevenness of the uneven layer can be appropriately selected in consideration of desired matteness, haze, 60 ° mirror glossiness and the like.

The height of the unevenness is preferably in the range of 0.1 to 10 μm, more preferably 0.1 to 5 μm, still more preferably 0.2 to 3 μm, and particularly preferably 0.3 to 2 μm. When the thickness of the uneven layer is within the above range, it is easy to achieve the desired matte property.
The height of the uneven layer is determined by height analysis using a laser microscope, for example, as shown in Examples described later. The height of the uneven layer may be determined by another method, for example, by observing the cross section of an electron microscope.

The thickness of the uneven layer 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 5 μm. When the thickness of the uneven layer is within the above range, it is easy to achieve the desired matte property.
The thickness of the concavo-convex layer indicates the maximum thickness of the concavo-convex layer, and is determined by observing the cross section with an electron microscope.

The uneven layer is composed of a cured product of a composition (hereinafter, also referred to as “curable polymer composition”) containing a polymer (X) having an active group that generates radicals by irradiation with active energy rays. ..
For example, a coating film of a curable polymer composition is formed on one surface of a base material layer, the surface side of the coating film is cured first to form a cured film, and then the inside of the coating film is formed. By curing, the cured coating film on the surface buckles, and an uneven layer having wrinkle-like irregularities is formed. The method of forming the uneven layer will be described in detail later.

Radical polymerizable groups are present together with active groups in the curable polymer composition. When the curable polymer composition is irradiated with active energy rays, radicals are generated from the active groups of the polymer (X), and the reaction between the radically polymerizable groups proceeds from the generated radicals to proceed with the curable polymer composition. The whole thing hardens.
Examples of the radically polymerizable group include a functional group containing a radically polymerizable unsaturated bond (carbon-carbon double bond and the like), and specific examples thereof include a (meth) acryloyl group and a vinyl group.
The curable polymer composition may have a radically polymerizable group in the polymer (X), but preferably further contains a compound (Y) having a radically polymerizable group.
The curable polymer composition may further contain an organic solvent, if necessary.
The curable polymer composition may further contain components other than the above, if necessary.

<Polymer (X)>
The active group in the polymer (X) 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 extraction 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 "a hydroxyl group in hydroxyethoxy"), an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, an anthraquinone group, a thioxanthone group, a 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.

The active group may be present at the end of the main chain of the polymer (X), or may be present in a unit based on the monomer constituting the polymer (X).
The polymer (X) preferably has a plurality of active groups in the molecule. As a result, the concentration of the active group 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.

As the polymer (X), a polymer having a unit based on a monomer having an active group is preferable from the viewpoint of introducing a plurality of active groups into the molecule.
Examples of the monomer having an active group include compounds having an active group and a radically polymerizable group. Examples of the radically polymerizable group include the same as described above.
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 polymer (X) 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.

The polymer (X) preferably has a unit based on a monomer having an alkyl group having 4 or more carbon atoms in addition to a unit based on a monomer having an active group. If the polymer (X) has this unit, the polymer (X) tends to segregate on the surface side of the coating film when the coating film of the curable polymer composition is formed. If the polymer (X) 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, resulting in oxygen inhibition. Even a thin film that tends to be susceptible to susceptibility can be cured well.

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 polymer (X) 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, and further preferably in the range of 4 to 30, from the viewpoint of more effectively segregating the polymer (X) on the surface of the coating film. It is preferably in the range of 12-18.

Examples of the monomer having an alkyl group having 4 or more carbon atoms include a compound having an alkyl group having 4 or more carbon atoms and a radically polymerizable group, and the ease of synthesizing the compound and the amount of the alkyl group having 4 or more carbon atoms introduced. From the viewpoint of ease of adjustment, a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms is preferable.
Examples of the monomer having an alkyl group having 4 or more carbon atoms include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 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, dicyclopentanyl (meth) ) Acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and the like.
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.
One of these (meth) acrylic acid esters may be used alone, or two or more thereof may be used in combination.

The polymer (X) is added to a unit based on a monomer having an alkyl group having an alkyl group having 4 or more carbon atoms or carbon from the viewpoint of segregating the polymer (X) more effectively on the surface of the coating film. Instead of the unit based on the monomer having an alkyl group of several 4 or more, the unit may have a unit based on the monomer containing a fluorine atom.
As the monomer containing a fluorine atom, a (meth) acrylic acid ester containing a fluorine atom is preferable, and a (meth) acrylic acid ester having a perfluoroalkyl group is more preferable. The perfluoroalkyl group preferably has 4 or more carbon atoms.

The polymer (X) may further have a unit based on the monomer having a hydrogen donating functional group, if necessary. In particular, when a hydrogen abstraction type is included as the active group, it is preferable to include a unit based on a monomer having a hydrogen donating functional group. When the polymer (X) has this unit, the curable polymer 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 be promoted particularly efficiently and unevenness is 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 viewpoint of the above, (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-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-vinylcaprolactum, 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 thereof include an amino group- or amide group-containing monomer. Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (N, N-) are excellent in the effect of promoting curing 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 polymer (X) may further have a unit based on a monomer other than the above, if necessary. Examples of other monomers include compounds having a radically polymerizable group and having no active group, an alkyl group having 4 or more carbon atoms, a fluorine atom and a 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, citraconic acid and salts thereof; methyl (meth) acrylate, 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. Esters; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and billidene chloride; conjugated diene such as butadiene.

The content of the active group per 1 g of the polymer (X) is preferably 0.1 to 3.5 mmol / g, more preferably 0.3 to 3.0 mmol / g, still more preferably 0.5 to 2. It is in the range of 7 mmol / g, particularly preferably 1.0 to 2.5 mmol / g. When the content of the active group is within the above range, the curability is more excellent and the unevenness can be formed more effectively.

The ratio of the units based on the monomer having an active group to the total mass of all the units constituting the polymer (X) 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% by mass, particularly preferably 30 to 60% by mass. When the ratio of the unit based on the monomer having an active group is within the above range, unevenness can be formed more effectively.

The ratio of the units based on the monomer having an alkyl group having 4 or more carbon atoms to the total mass of all the units constituting the polymer (X) is preferably 80% by mass or less, more preferably 1 to 70% by mass, still more preferable. Is in the range of 5 to 60% by mass, particularly preferably 8 to 50% by mass. When the ratio of the unit based on the monomer having an alkyl group having 4 or more carbon atoms is within the above range, unevenness can be formed more effectively.

The ratio of the unit based on the monomer having a hydrogen donating functional group to the total mass of all the units constituting the polymer (X) is preferably 80% by mass or less, more preferably 1 to 60% by mass, still more preferably 3. It is in the range of about 50% by mass, particularly preferably 5 to 40% by mass. When the ratio of the unit based on the monomer having a hydrogen donating functional group is within the above range, the unevenness can be formed more effectively.

The weight average molecular weight (Mw) of the polymer (X) is preferably in the range of 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000. When Mw is within the above range, the coatability of the curable polymer composition and the ease of forming irregularities are improved.
Mw of the polymer (X) 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 polymer (X) is preferably in the range of −30 to 150 ° C., more preferably 0 to 120 ° C., and even more preferably 25 to 100 ° C. When Tg is within the above range, the ease of forming unevenness is improved.

The polymer (X) can be obtained, for example, by polymerizing a monomer component containing a monomer having an active group. The monomer component may further contain any one or more of a monomer having an alkyl group having 4 or more carbon atoms, a monomer containing a fluorine atom, a monomer having a hydrogen donating functional group, and other monomers, if necessary. good.
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.

<Compound (Y)>
As the compound (Y), any compound having a radically polymerizable group may be used, and various known compounds can be used, for example, (meth) acrylate, other monomers copolymerizable with (meth) acrylate, and the like. Can be mentioned.
From the viewpoint of the strength of the uneven layer, the compound (Y) preferably contains a polyfunctional compound having a bifunctionality or higher (the number of radically polymerizable groups is 2 or more), and preferably contains a polyfunctional compound having a trifunctionality or higher. More preferred. As the polyfunctional compound, polyfunctional (meth) acrylate is preferable.
A polyfunctional compound and a monofunctional compound may be used in combination as the compound (Y) for the purpose of adjusting the curing rate, adjusting the viscosity for improving the coating appearance, and the like.

Examples of the monofunctional compound include monofunctional (meth) acrylate and (meth) acrylic acid. The monofunctional (meth) acrylate is not particularly limited, but is, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth). ) Alkyl (meth) acrylates such as acrylates, cyclohexyl (meth) acrylates and isobornyl (meth) acrylates, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates and hydroxybutyl (meth) acrylates. , Methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, alkoxyalkyl (meth) acrylate such as ethoxypropyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like. Amino group-containing (meth) acrylates such as aromatic (meth) acrylates, diaminoethyl (meth) acrylates, diethylaminoethyl (meth) acrylates, methoxyethylene glycol (meth) acrylates, phenoxypolyethylene grease (meth) acrylates, and phenylphenols. Examples thereof include ethylene oxide-modified (meth) acrylate such as ethylene oxide-modified (meth) acrylate, glycidyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

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) acrylates such as (meth) acrylates, 1,9-nonanediol di (meth) acrylates, tricyclodecanedimethylol di (meth) acrylates, bisphenol A ethylene oxide-modified di (meth) acrylates, 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.

<Organic solvent>
The organic solvent is used, if necessary, for the purpose of improving workability when the curable polymer composition is applied onto the substrate.
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. Of 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.

<Other ingredients>
The curable polymer composition has sufficient photocurability due to the polymer (X), but further contains various photopolymerization initiators (excluding the polymer (X)) for the purpose of promoting curability. Can be done.
The photopolymerization initiator is preferably a non-polymer having an active group and a molecular weight of 1000 or less, for example, 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, benzyldimethylketal, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglycilate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1 -Propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanol, tribromophenyl sulfone, tribromomethylphenyl sulfone and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

The curable polymer composition can further contain a leveling agent in order to improve the appearance of the cured product in the formation of the uneven layer.
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 polymer composition can further contain particles 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 may be organic particles or inorganic particles, and two or more kinds may be used in combination. The inorganic particles may be particles surface-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 polymer composition contains a polymerization accelerator such as a compound containing a thiol group, 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. It may be contained.

The content of the polymer (X) in the curable polymer composition is such that the content of the active group per 1 g of the uneven layer is 0.001 to 1 mmol / g, more preferably 0.006 to 0.6 mmol / g. , More preferably 0.003 to 0.3 mmol / g, and particularly preferably 0.01 to 0.2 mmol / g. When the content of the active group is within the above range, unevenness is likely to be formed.

The ratio of the polymer (X) to the total mass of the uneven layer is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 10% by mass, and particularly preferably. It is in the range of 0.8 to 8% by mass. When the ratio of the polymer (X) is within the above range, unevenness is likely to be formed.
The ratio of the polymer (X) to the total mass of the uneven layer can be adjusted by the ratio (mass%) of the polymer (X) to the non-volatile content of the curable polymer composition. The ratio of the polymer (X) to 100 parts by mass of the non-volatile content of the curable polymer composition is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, and further preferably 0.5 to 0.5. It is in the range of 10% by mass, particularly preferably 0.8 to 8% by mass.
The non-volatile content of the curable polymer composition is the total mass of the components other than the organic solvent. The non-volatile content of the curable polymer 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 the change in solvent.

The ratio of the compound (Y) to the non-volatile content of the curable polymer composition is preferably 10 to 99.9% by mass, more preferably 50 to 99.8% by mass, still more preferably 70 to 99.5% by mass. Particularly preferably, it is in the range of 80 to 99.2% by mass. When the ratio of the compound (Y) is within the above range, it becomes easy to form an uneven layer having desired matte property, scratch resistance and hardness.

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

When the curable polymer composition contains a photopolymerization initiator, the content of the photopolymerization initiator can be appropriately selected within a range that does not impair the effects of the present invention.
The ratio of the photopolymerization initiator to the non-volatile content of the curable polymer composition is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. , 0% by mass. When the ratio of the photopolymerization initiator is within the above range, the amount of radicals generated from the photopolymerization initiator is sufficiently small when the coating film of the curable polymer composition is cured, and unevenness is likely to occur.

(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 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 in which the 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, dodecandicarboxylic acid, glutaric acid, succinic acid, Examples thereof include trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt 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-Pentane Glycol, Neopentyl Glycol, 1,4-Cyclohexanedimethanol, p-Xylylene Glycol, Bisphenol A-ethylene Glycol Additive, Diethylene Glycol, Triethylene Glycol, Polyethylene Glycol, Polyethylene 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 the 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, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and the like. Salt: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroquilfumarate, monobutylhydroxyitaconate and other hydroxyl group-containing monomers; methyl ( Alkyl (meth) acrylates such as meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; (meth) acrylamide, Nitrogen-containing monomers such as diacetone acrylamide, N-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; conjugated diene such as butadiene can be mentioned.

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 a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, and an acrylic polyol. 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. Examples of 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, those having a derivative unit of a lactone compound such as polycaprolactone, and the like.
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-Dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2 -Hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamine, 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.

As the polyisocyanate used to obtain the urethane resin, aromatic diisocyanis such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, trizine diisocyanate; α, α, α', α'- An aliphatic diisocyanate having an aromatic ring such as tetramethylxamethylene diisocyanate; an aliphatic diisocyanate such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; Examples thereof include alicyclic diisocyanates such as diisocyanate and isopropyridene dicyclohexyldicyclohexyl diisocyanate. 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 generally, 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, 2,2-dimethyl-1,3-propanediamine. , 2-Methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonandiamine, 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 -Examples include alicyclic diamines such as bisaminomethylcyclohexane.

Urethane resins are typically used in the form of dispersions or solutions. The medium of the dispersion liquid or the 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 ionic 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, and 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. For 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 crosslinking reaction point by the crosslinking agent. This makes it possible to improve the stability of the obtained primer layer in the state of the liquid before coating, and further improve the durability, solvent resistance, water resistance, blocking resistance and the like of the obtained primer layer.

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, there are a method of using a resin having a carboxyl group as a copolymerization component at the time of prepolymer synthesis, 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 group 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.
Examples of the carboxyl group-containing diol include dimethylol propionic acid, dimethylol butanoic acid, bis- (2-hydroxyethyl) propionic acid, and bis- (2-hydroxyethyl) butanoic acid, and these 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. By using two or more types together, the adhesion and durability may be further improved and improved.

The melamine compound is a compound having a melamine skeleton in the compound, for example, an alkyrylated melamine derivative, a compound obtained by reacting an alkyrylated 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 in which urea or the like is co-condensed can be used, or a catalyst can be used to increase the reactivity of the melamine compound.
As the melamine compound, a compound having a hydroxyl group is preferable 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 diphenyldiisocyanate, phenylenedi isocyanate and naphthalenedi isocyanate; 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 isocyanate. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide-modified compounds of these isocyanates can also be 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 by 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 malonate and diethyl malonate. Methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and other active methylene compounds, butyl mercaptan, dodecyl mercaptan and other mercaptan compounds, ε-caprolactam, δ-valerolactam and other lactam compounds, diphenylaniline, aniline, Examples thereof include amine compounds such as ethyleneimine, acid amide compounds such as acetoanilide 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 the sense of improving the dispersibility and crosslinkability of the isocyanate-based 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 polymer containing an oxazoline group can be obtained by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of the additive-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 the addition-polymerizable oxazoline group-containing monomer, and is, for example, an alkyl (meth) acrylate (as the 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, (alkyl groups include 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 and the like. Halogen-containing α, β-unsaturated monomers; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene, etc. may be mentioned. These may be used alone or in combination of two or more.

The amount of oxazoline groups per 1 g 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, triglycidyltris (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 type or aliphatic type can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, 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-based 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 dialkylaminoalcohol 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. Propyl 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) acryloxylpropyltrimethoxysilane, 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 thereof 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 polymer-type compound having an ammonium group, it is preferable that the ammonium group is 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 a precursor group of an ammonium 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 a polymer compound having an ammonium group. As the addition-polymerizable monomer containing an ammonium group or a precursor group of an ammonium group, one kind may be polymerized alone, two or more kinds may be copolymerized, or another 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 an alkyl group, a phenyl group, 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 chemically bonded to the two substituents 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 subjecting a diallylamine derivative to cyclization polymerization using a radical polymerization catalyst. A compound having a carbon-carbon unsaturated bond having a polymerizable carbon-carbon unsaturated bond with the diallylamine derivative may be used as a copolymerization component. The polymerization is carried out using a known polymerization initiator such as hydrogen peroxide, benzoyl peroxide, and tertiary butyl peroxide in a polar solvent (water, methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile, etc.). It can be carried out by a method, but it 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 500,000, more preferably 2000 to 350,000, and even more preferably 5000 to 200,000. 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 coatability 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 in the form of 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, polythiophene-based (polythiophene or polythiophene derivative) is preferable because it has both high transparency and high conductivity, is difficult to color, and easily develops 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 conductivity performance.
Conductive organic polymers are preferable in that they show high conductivity, have 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 may be a defoaming agent, a coatability 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. It is a 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 develop 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.

(Surface functional layer)
The surface functional layer is provided on the uneven layer to impart various functions.
Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, a low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, a color correction layer, and the like.
The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the uneven layer. The antistatic layer is provided 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. The refractive index adjusting layer is provided, for example, in order to improve the total light transmittance of the laminated body.

The antifouling layer contains an antifouling component.
As the antifouling component, known compounds such as a silicone compound, a fluorine compound, and a long-chain alkyl group-containing compound can be used. Of these, silicone compounds and fluorine compounds are preferable from the viewpoint of exhibiting stronger antifouling performance, and fluorine compounds and long-chain alkyl groups are contained from the viewpoint of being less likely to contaminate the partner with which the antifouling layer comes into contact. Compounds are preferred.

The silicone compound is a compound having a silicone structure in the molecule, and examples thereof include alkyl silicones (dimethyl silicone, diethyl silicone, etc.) and silicones having a phenyl group (phenyl silicone, methyl phenyl silicone, etc.).
The silicone compound may have various functional groups. Examples of the functional group include an ether group, a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, a halogen group such as fluorine, a perfluoroalkyl group, and a hydrocarbon group such as various alkyl groups and various aromatic groups. .. As another functional group, a silicone having a vinyl group or a hydrogen silicone in which a hydrogen atom is directly bonded to a silicon atom can be exemplified, and both can be used in combination as an addition type silicone (a type obtained by an addition reaction between a vinyl group and a hydrogen silane). It is also possible to use it. It is also possible to introduce a double bond such as an acryloyl group and react at the double bond portion.

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

A fluorine compound is a compound containing a fluorine atom in the compound. As the fluorine compound, an organic fluorine compound is preferably used, and examples thereof include a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing a fluorine atom, and an aromatic fluorine compound such as fluorobenzene. From the viewpoint of releasability, a perfluoroalkyl group-containing compound is preferable. As the fluorine compound, a compound containing a long-chain alkyl group as described later can also be used.

Examples of the perfluoroalkyl group-containing compound include perfluoroalkyl (meth) acrylate, perfluoroalkylmethyl (meth) acrylate, 2-perfluoroalkylethyl (meth) acrylate, and 3-perfluoroalkylpropyl (meth) acrylate. Perfluoroalkyl group-containing (meth) acrylates such as 3-perfluoroalkyl-1-methylpropyl (meth) acrylate, 3-perfluoroalkyl-2-propenyl (meth) acrylate and their polymers, perfluoroalkylmethylvinyl ether, Perfluoroalkyl group-containing vinyl ethers such as 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl ether and their polymers. Can be mentioned. Considering heat resistance and stain resistance, it is preferably a polymer. The polymer may be a polymer of a single compound or a polymer of a plurality of compounds. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later.
From the viewpoint of antifouling property, the perfluoroalkyl group preferably has 3 to 11 carbon atoms.

The long-chain alkyl group-containing compound is a compound having a linear or branched alkyl group (long-chain alkyl group) having a carbon number of usually 6 or more, preferably 8 or more, and more preferably 12 or more. Examples of the long-chain alkyl group include a hexyl group, an octyl group, a decyl group, a lauryl group, an octadecyl group, a behenyl group and the like.
Examples of the long-chain alkyl group-containing compound include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. Be done.
The long-chain alkyl group-containing compound is preferably a polymer compound in consideration of heat resistance and stain resistance. Further, from the viewpoint of effectively obtaining antifouling property, a polymer compound having a long-chain alkyl group in the side chain is more preferable.

The polymer compound having a long-chain alkyl group in the side chain can be obtained, for example, by reacting a polymer compound having a reactive group with a long-chain alkyl group-containing compound capable of reacting with the reactive group.
Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, an acid anhydride and the like. Examples of the polymer compound having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, and a reactive group-containing poly (meth) acrylic resin. Among these, polyvinyl alcohol is preferable in consideration of antifouling property and ease of handling.
Examples of the long-chain alkyl group-containing compound that can react with the above-mentioned reactive group include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate, hexyl chloride, and octyl. Examples thereof include long-chain alkyl group-containing acid chlorides such as chloride, isocyanate, lauryl chloride, octadecylloride, and behenyl chloride, long-chain alkyl group-containing amines, and long-chain alkyl group-containing alcohols. Among these, long-chain alkyl group-containing isocyanates are preferable, and octadecyl isocyanates are particularly preferable, in consideration of releasability and ease of handling.

The polymer compound having a long-chain alkyl group in the side chain can also be obtained as a polymer of a long-chain alkyl (meth) acrylate or a copolymer of a long-chain alkyl (meth) acrylate and another vinyl group-containing monomer. .. Examples of the long-chain alkyl (meth) acrylate include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate. Be done.

As necessary, the antifouling layer includes a resin, a compound derived from a cross-linking agent, an antistatic agent, an antifoaming agent, a coating property improving agent, a thickener, an ultraviolet absorber, an antioxidant, and foaming, in addition to an antifouling component. It may further contain agents, dyes, pigments and the like. The compounds derived from the resin and the cross-linking agent are as described above. The antifouling layer preferably has a crosslinked structure from the viewpoint of improving the strength and durability of the layer. Examples of the antifouling layer having a crosslinked structure include a layer of a cured product of a composition containing a compound having a plurality of radically polymerizable groups such as an acryloyl group or a crosslinking agent and an antifouling component.

The ratio of the antifouling component in 100% by mass of the surface functional layer cannot be unequivocally determined because it depends on the antifouling component used, but when the antifouling component is a silicone compound or a fluorine compound, it is usually 0.01. It is mass% or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. When the antifouling component is a long-chain alkyl group-containing compound, it is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit may be 100% by mass. do not have. When the ratio of the antifouling component is within the above range, the antifouling performance is more excellent.

The antistatic layer contains an antistatic agent. The antistatic agent is as described above.
The antistatic layer may be a resin, a compound derived from a cross-linking agent, a defoaming agent, a coatability improving agent, a thickener, an antifouling agent, an ultraviolet absorber, an antioxidant, and foaming, as required. It may further contain agents, dyes, pigments and the like. The compounds derived from the resin and the cross-linking agent are as described above.

The ratio of the antistatic agent in 100% by mass of the antistatic layer is not unconditional because it depends on the type of the antistatic agent, but is, for example, 0.1 to 100% by mass.

Examples of the refractive index adjusting layer include a high refractive index layer, a low refractive index layer, and a laminate thereof.
As a material constituting the high refractive index layer, a known high refractive index material can be used, for example, an aromatic structure-containing compound such as a benzene structure, a bisphenol A structure, a melamine structure, or a fluorene structure, and an aromatic structure-containing material. Condensed polycyclic aromatic compounds such as naphthalene, anthracene, phenanthrene, naphthalene, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, and perylene structures, which are considered to be high refractive index compounds among the compounds. Metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony tin oxide), ITO (indium tin oxide), titanium chelate, Examples thereof include metal-containing compounds such as metal chelate compounds such as zirconium chelate, compounds containing sulfur elements, and compounds containing halogen elements.

The metal oxide is preferably used in the state of particles because there is a concern that the adhesion may be deteriorated depending on the usage mode, and the average particle size thereof is preferably 100 nm or less, more preferably from the viewpoint of the appearance of coating. Is in the range of 50 nm or less, more preferably 25 nm or less.

As a material constituting the low refractive index layer, a known low refractive index material can be used, for example, an acrylic resin, a urethane resin, or a compound in which a fluorine atom is incorporated in the resin (for example, a fluorine resin, a main component). Resins such as (compounds containing a fluorine resin in the seed skeleton, compounds containing a perfluoroalkyl group in the side chain); hollow silica particles, magnesium fluoride, fluorine atom-containing inorganic compounds such as calcium fluoride, hollow particles and nanoporous thereof. Examples include inorganic materials such as particles.

The thickness of the surface functional layer is preferably smaller than the height of the unevenness on the surface of the uneven layer. If the thickness of the surface functional layer is smaller than the height of the unevenness, it is difficult to reduce the matting performance due to the unevenness even if the surface functional layer is provided.
The thickness of the surface functional layer cannot be unequivocally determined because it depends on the height of the unevenness on the surface of the uneven layer, but is preferably 0.001 to 1 μm, more preferably 0.005 to 0.7 μm, and further preferably 0.01. It is in the range of ~ 0.5 μm, particularly preferably 0.02 to 0.2 μm, and most preferably 0.03 to 0.08 μm. When the thickness of the surface functional layer is within the above range, it is easy to achieve both the expression of the function by the surface functional layer and the matte property due to the unevenness of the uneven layer.

(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, an anti-blocking layer, and the like.
The adhesive layer is provided to join the laminated body to various adherends. The antistatic layer is used to prevent the adhesion of surrounding dust and the like due to peeling and triboelectric charging to the outermost surface of the laminate, especially the outermost surface on the side opposite to the uneven layer side of the base material layer, and defects due to it. It will be 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 cannot be unequivocally determined because it depends on the material used for the back surface functional layer and the performance to be developed, 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.

(Preferable aspect)
A preferred embodiment of the present laminate is a laminate having a surface functional layer and a primer layer, as shown in FIG. 3 or FIG. 5, in which at least one of the surface functional layer and the primer layer is an antistatic layer.
The surface resistance value of the laminate of this embodiment on the outermost surface on the side where the uneven layer exists with respect to the base material layer is preferably 1 × 10 ¹³ Ω or less, more preferably 1 × 10 ¹² Ω or less, still more preferably. It is 5 × 10 ¹¹ Ω or less, more preferably 1 × 10 ¹¹ Ω or less, and particularly preferably 5 × 10 ¹⁰ Ω or less. When the surface resistance value is not more than the above upper limit value, it is easy to suppress the adhesion of dust and the like to the outermost surface.
The surface resistance value (also referred to as surface resistivity or sheet resistance) on the outermost surface can be adjusted by adjusting the amount of the antistatic agent contained in the antistatic layer.

Another preferred embodiment of the present laminate is a laminate having a back surface functional layer and the back surface functional layer being an antistatic layer, as shown in FIG. 4 or FIG.
The surface resistance value of the laminate of this embodiment on the outermost surface on the side opposite to the side where the uneven layer exists with respect to the base material layer is preferably 1 × 10 ¹³ Ω or less, more preferably 1 × 10 ¹² Ω or less. It is more preferably 5 × 10 ¹¹ Ω or less, further preferably 1 × 10 ¹¹ Ω or less, and particularly preferably 5 × 10 ¹⁰ Ω or less. When the surface resistance value is not more than the above upper limit value, it is easy to suppress the adhesion of dust and the like to the outermost surface.

[Manufacturing method of laminated body]
This laminated body can be manufactured, for example, by a manufacturing method having the following steps a and at least one of steps b to d.
Step a: A step of forming an uneven layer on one surface of a base material (base material layer).
Step b: A step of forming a primer layer on one surface of the base material before the step a.
Step c: A step of forming a surface functional layer on the uneven layer.
Step d: A step of forming a back surface functional layer on the other surface of the base material.
When step b is performed before step a, in step a, an uneven layer is formed on the primer layer.

The base material constitutes the base material layer. As the base material, those manufactured by a known manufacturing method may be used, or commercially available products may be used.
Hereinafter, the method for producing the resin film will be specifically described, but the method for producing the resin film is not limited to the following production methods, and a known film forming method can be adopted.
As a general method for producing a resin film, there is a method in which the resin is melted, made into a sheet, and if necessary, stretched for the purpose of increasing the strength or the like.
For example, in the case of producing a biaxially stretched polyester film, first, a polyester raw material is melt-extruded from a die using an extruder, and the melted sheet is cooled and solidified with a cooling roll to obtain an unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the molten sheet and the cooling roll, and the electrostatic application adhesion method and the liquid coating adhesion method are preferably adopted. Then, the obtained unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine. The stretching temperature is preferably 70 to 120 ° C., more preferably 80 to 110 ° C., and the stretching ratio is preferably 2.5 to 7 times, more preferably 3.0 to 6 times. Then, in the direction orthogonal to the stretching direction of the first stage, stretching is preferably performed at 70 to 170 ° C., preferably 2.5 to 7 times, more preferably 3.0 to 6 times. Subsequently, heat treatment is performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially stretched film.
In the above stretching, a method of performing one-way stretching in two or more steps can also be adopted. In that case, it is preferable to finally set the draw ratios in the two directions within the above ranges.

A simultaneous biaxial stretching method can also be adopted in the production of the resin film. For example, in the simultaneous biaxial stretching method in the case of a polyester film, the unstretched sheet is simultaneously stretched and oriented in the mechanical direction and the width direction in a state where the temperature is controlled at 70 to 120 ° C., preferably 80 to 110 ° C. It is a method, and the stretch ratio is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area ratio. Then, the heat treatment is subsequently performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a stretched film.
As for the simultaneous biaxial stretching device that adopts the above-mentioned stretching method, a conventionally known stretching method such as a screw method, a pantograph method, and a linear drive method can be adopted.

(Step a)
The uneven layer can be formed by applying the curable polymer composition on one surface of the substrate to form a coating film, drying the coating film as necessary, and then irradiating the coating film with active energy rays.

The method for applying the curable polymer composition is not particularly limited, and is 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. It can be applied by a known method such as a coat.

When the curable polymer 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, the concentration of the polymer (X) on the surface side of the coating film becomes high, and wrinkle-like irregularities appear on the surface of the cured product. It will be easier to do.
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.

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 so that the integrated light amount of irradiation is 100 mJ / cm ² or more and 3000 mJ / cm ² or less, and more preferably 200 mJ / cm ² or more and 2000 mJ / cm ² or less. The illuminance is preferably 50 mW / cm ² or more and 600 mW / cm ² or less, more preferably 75 mW / cm ² or more and 450 mW / cm ² or less, and further preferably 100 mW / cm ² or more and 300 mW / cm ² or less. As the light source, 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 using a curtain type electron beam acceleration path, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, etc. shall be used. Can be done.

In step a, the uneven layer having unevenness can be formed with good manufacturability.
The mechanism by which unevenness appears in step a is presumed as follows.
The polymer (X) is more likely to segregate on the surface side of the coating film than a general photopolymerization initiator (non-polymer having an active group). When the polymer (X) 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 and cured. A film is formed and then the inside of the coating is cured. As 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 cycle of the unevenness on the surface of the uneven layer, and the longer the curing time, the larger the cycle of the 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 polymer composition, the amount of active groups (the amount of the polymer (X) and the photopolymerization initiator), the amount of irradiation with active energy rays, and the like.

(Step b)
The primer layer can be formed by a known method. Considering the ease of forming the primer layer, it is preferable to form the primer layer by the coating method.
To form a primer layer by the coating method, for example, a coating liquid containing a component (resin, a cross-linking agent, an antistatic agent, etc.) for forming the primer layer and a medium (water, etc.) is applied on one surface of the substrate. It can be coated on the surface, dried, and cured if necessary.
One surface of the base material may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

The coating liquid may be a solution or a dispersion liquid.
The medium of the coating liquid may be an organic solvent or water. When water is used, a small amount of an organic solvent may be used in combination for the purpose of improving the dispersibility in water, improving the film-forming property, and the like. One type of organic solvent may be used alone, or two or more types may be used in combination.
The solid content concentration of the coating liquid is, for example, about 0.1 to 80% by mass.

When the primer layer is formed by the coating method, the primer layer may be formed by in-line coating performed in the manufacturing process of the base material, or may be performed outside the manufacturing process of the base material (coating once manufactured on the base material outside the system). Although it may be formed by an offline coating, it is preferably formed by an in-line coating. In the case of in-line coating, the medium of the coating liquid is preferably water.

Specifically, the in-line coating is a method of coating at an arbitrary stage from melt-extruding the resin forming the base material, stretching the resin, heat-fixing the resin, and winding the resin. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat fixing, and a film after heat fixing and before winding. Although not limited to the following, for example, in sequential biaxial stretching, a method of coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) and then stretching in the lateral direction is particularly excellent.
According to such a method, since the base material can be manufactured and the primer layer can be formed at the same time, there is an advantage in manufacturing cost, and the thickness of the primer layer is changed depending on the draw ratio in order to perform stretching after coating. It is also possible to perform thin film coating more easily than offline coating.

Further, according to the above-mentioned in-line coating process, the thickness of the obtained film does not change significantly depending on the presence or absence of the formation of the primer layer, and the risk of scratches and foreign matter adhesion does not change significantly depending on the presence or absence of the formation of the primer layer. This is a great advantage over offline coating, which involves a separate coating process.
Further, by providing the primer layer on the base material layer before stretching, the primer layer can be stretched together with the base material layer, so that the formed primer layer has appropriate adhesion to the base material layer.

Further, in the production of a biaxially stretched polyester film, the film can be restrained in the vertical and horizontal directions by stretching while gripping the end of the film with a clip or the like, and in the heat fixing step, a flat surface without wrinkles or the like. High temperature can be applied while maintaining the sex.
Therefore, since the heat treatment applied after the primer layer is provided by coating can be at a high temperature which cannot be achieved by other methods, the film-forming property of the primer layer can be improved and a strong primer layer can be formed. can. In particular, it is very effective for reacting a cross-linking agent.

Furthermore, in the case of the biaxially stretched polyester film, it was found that the in-line coating also improves the adhesion and durability with the uneven layer. It is considered that this is because it is possible to heat-treat at a high temperature that cannot be obtained by offline coating, and the heat treatment makes the primer layer itself stronger and stronger against heat and mechanical action such as when forming an uneven layer. ..

Coating methods for forming the primer layer include gravure coat, reverse roll coat, die coat, air doctor coat, blade coat, rod coat, bar coat, curtain coat, knife coat, transfer roll coat, squeeze coat, impregnation coat, etc. Known coating methods such as kiss coat, spray coat, calendar coat, and extrusion coat can be used.

The drying and curing conditions for forming the primer layer are not particularly limited, but the drying of the medium such as water used for the coating liquid is usually 50 to 150 ° C., preferably 80 to 130 ° C. , More preferably in the range of 90 to 120 ° C. The drying time is, as a guide, in the range of 3 to 200 seconds, preferably 5 to 120 seconds.

In order to improve the strength of the primer layer, it is preferable to perform heat treatment as a drying treatment or after drying. The temperature of the heat treatment is, for example, in the range of 150 to 270 ° C, preferably 170 to 230 ° C, and more preferably 180 to 210 ° C. The heat treatment time is, for example, in the range of 3 to 200 seconds, preferably 5 to 120 seconds.
If necessary, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination.

(Step c)
The surface functional layer can be formed by a known method. Considering the ease of forming the surface functional layer, it is preferable to form the surface functional layer by a coating method.
The method for forming the surface functional layer by the coating method is the same as the method for forming the primer layer by the coating method, except that the components contained in the coating liquid are dependent on the surface functional layer to be formed.

(Step d)
The back surface functional layer can be formed by a known method. Considering the ease of forming the back surface functional layer, it is preferable to form the back surface functional layer by the coating method.
The method of forming the back surface functional layer by the coating method is the same as the method of forming the primer layer by the coating method, except that the components contained in the coating liquid are dependent on the back surface functional layer to be formed.
When the back surface functional layer is an adhesive layer, the back surface functional layer may be formed by adhering a film-like adhesive layer on the other surface of the base material.

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) Measurement of the ultimate viscosity of polyester For the ultimate viscosity of polyester, 1 g of polyester from which components incompatible with polyester have been removed is precisely weighed, and 100 mL of a mixed solvent of phenol / tetrachloroethane = 50/50 (mass ratio) is added. Was dissolved and measured at 30 ° C.

(2) Measurement of average particle size (d50: μm) 50% value of integration (mass basis) in equivalent spherical distribution measured using a centrifugal sedimentation type particle size distribution measuring device (SA-CP3 type manufactured by Shimadzu Corporation). Was taken as the average particle size.

(3) Measurement of weight average molecular weight (Mw) Equipment: "HLC-8120GPC" manufactured by Tosoh Corporation,
Column: "TSKgel Super H1000 + H2000 + H3000" manufactured by Tosoh Corporation,
Detector: Differential refractive index detector (RI detector / built-in),
Solvent: Tetrahydrofuran,
Temperature: 40 ° C,
Flow rate: 0.5 mL / min,
Injection volume: 10 μL,
Concentration: 0.2% by mass,
Calibration sample: monodisperse polystyrene,
Calibration method: Polystyrene conversion.

(4) Measurement of glass transition temperature (Tg) 5 mg of a sample is enclosed in an aluminum pan, and a differential scanning calorimeter (EXSTAR DSC6200 manufactured by Seiko Instruments Co., Ltd.) is used at a rate of 10 ° C. per minute under a nitrogen atmosphere. The temperature was raised and lowered from -100 ° C to 250 ° C, from 250 ° C to -100 ° C, and from -100 ° C to 250 ° C, and the turning point at the second temperature rise was defined as the glass transition temperature (Tg).

(5) Measurement of thickness of primer layer and functional layer (front surface functional layer, back surface functional layer) The surface of the primer layer or the functional layer was dyed with _RuO4 and embedded in an epoxy resin. Then, the section prepared by the ultramicrotomy method was stained with _RuO4 , and the cross section of the primer layer or the functional layer was measured using a transmission electron microscope (H-7650 manufactured by Hitachi High-Technologies Corporation, acceleration voltage 100 kV).

(6) Measurement of haze The haze of the laminated body was measured using a haze meter HM-150 manufactured by Murakami Color Technology Laboratory Co., Ltd. in accordance with JIS K 7136.

(7) Measurement of glossiness The 60 ° mirror surface glossiness (hereinafter, also simply referred to as “glossiness”) on the outermost surface of the laminated body on the side where the uneven layer exists with respect to the base material layer is described in JIS Z 8741. It was measured using a gloss meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd.

(8) Measurement of surface resistance value Using a high resistivity meter manufactured by Mitsubishi Chemical Analytech Co., Ltd .: High Resta MCP-HP450, the sample was conditioned for 30 minutes in a measurement atmosphere with an overvoltage of 100 V, 23 ° C, and 50% RH. Then, the surface resistivity value was measured.
When the surface resistance value is OVER, it means that the surface resistance value is too high to be measured by a high resistivity meter.
When the surface resistance value is UNDER, the surface resistance value is so low that it cannot be measured by a high resistivity meter. Therefore, the value measured by the following method was used as the surface resistance value.
Low resistivity meter manufactured by Mitsubishi Chemical Analytech Co., Ltd .: Loresta GP MCP-T610 with four-probe type ESP probe (probe interval: 5 mm, probe tip shape: cylinder with diameter 2 mm, probe push pressure: 240 g / piece , The RCF value was constant at 4.235), the sample was conditioned for 30 minutes in a measurement atmosphere at 23 ° C. and 50% RH, and then the surface resistivity value was measured.

(9) Evaluation of matte property A laminated body was installed in a room lit with a white linear fluorescent lamp, the distance between the fluorescent lamp and the laminated body was set to 2.5 m, and the base material layer of the laminated body was used. On the other hand, the mattness of the outermost surface on the side where the uneven layer exists (the state of reflection of the fluorescent lamp) was visually evaluated. In the evaluations A to C, it is a judgment that the matte property can be confirmed.
A: The reflected image of the fluorescent lamp is strongly blurred, and the outline of the fluorescent lamp cannot be confirmed.
B: The reflected image of the fluorescent lamp is blurred, but the outline is slightly confirmed.
C: The reflected image of the fluorescent lamp is a little blurry and the outline is confirmed, but it is observed in a wavy shape and appears in dark white.
D: The reflected image of the fluorescent lamp is clear and the outline is clearly confirmed, and it appears linear and white.

(10) Evaluation of Adhesion between Base Material Layer and Concavo-convex Layer The concavo-convex layer, or the concavo-convex layer and the surface functional layer provided on the concavo-convex layer, are cross-cut 11 × 11 at 1 mm intervals. A square of × 10 was created, and a 24 mm wide tape (Cellotape (registered trademark) CT-24 manufactured by Nichiban Co., Ltd.) was attached on the squares, and the cells were rapidly peeled off at a peeling angle of 180 degrees. After that, the peeled surface was observed, and the case where the peeled area was less than 5% was designated as A, the case where the peeled area was 5% or more and less than 30% was designated as B, the case where the peeled area was 30% or more and less than 50% was designated as C, and the case where the peeled area was 50% or more was designated as D. ..

(11) Evaluation of pen writeability (antifouling property) The outermost surface of the laminated body on the side where the uneven layer exists with respect to the base material layer was written with oil-based black magic McKee finely manufactured by Zebra Co., Ltd. After that, the outermost surface was visually observed, and the case where the ink was repelled was designated as A, and the case where the ink was not repelled was designated as B. It should be noted that repelling the ink is evaluated as having excellent antifouling property.

(12) Evaluation of Adhesiveness When the evaluation surfaces (the outermost surface of the laminated body on the side opposite to the side where the uneven layer exists with respect to the base material layer) are bonded to each other, the case where they are bonded by adhesive force is A. The case where it does not stick is defined as B.

(13) Evaluation of Concavo-convex Height of Concavo-convex Layer Using a laser microscope (OLS-3500 manufactured by Olympus), the objective lens is 100 times larger, and the most concavo-convex layer on the side where the concavo-convex layer exists with respect to the base material layer. After observing a 120 μm × 90 μm region on the surface, correcting the inclination of the X-axis and Y-axis, and correcting the isolation point removal, the height difference between the peaks and valleys on the outermost surface was measured by step measurement analysis. ..
Five mountains are randomly selected from multiple mountains existing in the observation area, and for each mountain, the position of the top of the mountain and the lowest position (valley) between the mountain and the adjacent mountain. The height difference from (position) was obtained, and the average value obtained by averaging the height differences at five locations was taken as the height of the unevenness.

The polyester used as the base material (polyester film) in Examples and Comparative Examples is as follows.

<Polyester (A)>
A polyethylene terephthalate homopolymer having an ultimate viscosity of 0.63 dL / g, obtained by using magnesium acetate tetrahydrate and tetrabutyl titanate as a polymerization catalyst.

<Polyester (B)>
A polyethylene terephthalate homopolymer having an ultimate viscosity of 0.64 dL / g, obtained by using magnesium acetate tetrahydrate, orthophosphoric acid and germanium dioxide as a polymerization catalyst.

<Polyester (C)>
A formulation in which silica particles with an average particle diameter of 2 μm are blended with a dL / g polyethylene terephthalate homopolymer having an ultimate viscosity of 0.63 (silica particle content: 0.3% by mass with respect to the mass of the polyethylene terephthalate homopolymer). ).

(Production Example 1: Production of (A-1))
Methyl isobutyl ketone (hereinafter referred to as MIBK) (78 parts by mass) is placed in a flask equipped with a stirrer, a cooling tube and a thermometer, and then the inside of the flask is replaced with nitrogen and the temperature is raised to 65 ° C. 4-. Methacryloyloxybenzophenone (40 parts by mass), stearyl methacrylate (10 parts by mass), ethylhexyl methacrylate (30 parts by mass), hydroxyethyl methacrylate (10 parts by mass), diethylaminoethyl methacrylate (10 parts by mass), azobis (2,4-dimethyl) A mixed solution of valeronitrile (0.8 parts by mass) and MIBK (78 parts by mass) was added dropwise over 2 hours. After another 2 hours, in order to increase the polymerization rate, a mixed solution of azobis (2,4-dimethylvaleronitrile) (0.5 parts by mass) and MIBK (0.6 parts by mass) was added and held for 5 hours. Then, the reaction solution was cooled to 40 ° C. to obtain a MIBK solution (A-1) of a polymer having an active group.
The solid content (nonvolatile content) of (A-1) is 40% by mass, the weight average molecular weight (Mw) of the polymer in (A-1) is 17200, the glass transition temperature is 48 ° C., and the content of active groups. Was 1.5 mmol / g.

(Manufacturing Example 2: Manufacture of (A-2))
The composition ratio of the mixed solution was 4-methacryloyloxybenzophenone (50 parts by mass), stearyl methacrylate (20 parts by mass), methyl methacrylate (30 parts by mass), azobis (2,4-dimethylvaleronitrile) (1.0 part by mass). ) Was obtained under the same conditions as in Production Example 1 to obtain a MIBK solution (A-2) of a polymer having an active group. The solid content (nonvolatile content) of (A-2) is 40% by mass, the weight average molecular weight (Mw) of the polymer in (A-2) is 10700, the glass transition temperature is 95 ° C., and the content of active groups. Was 1.8 mmol / g.

(Manufacturing Example 3: Manufacture of (C-1))
One-ended methacryloyl group-substituted polydimethylsiloxane having a number average molecular weight of 5000 (“Cyraplane FM0721” manufactured by JNC Co., Ltd., silicone-containing (meth) acrylate compound) (20) in a reactor equipped with a stirrer, a reflux cooling tube and a thermometer. (Mass part), glycidyl methacrylate (60 parts by mass), methyl methacrylate (10 parts by mass), stearyl methacrylate (10 parts by mass), MIBK (151 parts by mass) were charged, and after the start of stirring, the inside of the system was replaced with nitrogen to 55 ° C. The temperature was raised, and 2,2'-azobis (2,4-dimethylvaleronitrile) (1.2 parts by mass) and 1-dodecanethiol (0.9 parts by mass) were added thereto, and then the temperature inside the system was 65 ° C. After heating to 3 hours and stirring for 3 hours, 2,2'-azobis (2,4-dimethylvaleronitrile) (0.6 parts by mass) was further added, and the mixture was stirred at 65 ° C. for 3 hours. The temperature inside the system was raised to 100 ° C., and after stirring for 30 minutes, 163 parts by mass of MIBK was added, and the temperature inside the system was raised to 100 ° C. again. To this, p-methoxyphenol (0.5 parts by mass) and triphenylphosphine (2.6 parts by mass) are added, acrylic acid (31 parts by mass) is added, the temperature is raised to 110 ° C., and the mixture is stirred for 6 hours. did. After cooling, 4.8 parts by mass of MIBK was added to obtain a MIBK solution (C-1) of a silicone-based copolymer having a number average molecular weight of 6500. The non-volatile content of (C-1) was 30% by mass, and the number average molecular weight of the silicone-based copolymer in (C-1) was 6500.

(Preparation Example 1: Preparation of organic solvent-based coating liquid)
Each material shown in Table 1 is mixed so as to have the ratio (mass%) shown in Table 1 in terms of non-volatile content, and the coating liquid for the uneven layer (S1 to S3) and the coating liquid for the functional layer (F1, F2) was prepared. Each material in Table 1 is as follows.
(A-1): Polymer having an active group obtained in Production Example 1 (4-methacryloyloxybenzophenone / stearyl methacrylate / ethylhexyl methacrylate / hydroxyethyl methacrylate / diethylaminoethyl methacrylate = 40/10/30/10/10 ( MIBK solution of copolymer) of mass ratio).
(A-2): MIBK solution of the polymer having an active group (copolymer of 4-methacryloyloxybenzophenone / stearylmethacrylate / methylmethacrylate = 50/20/30 (mass ratio)) obtained in Production Example 2.
(B-1): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. KAYARAD (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.
(B-2): Pentaerythritol triacrylate. Viscoat V # 300 manufactured by Osaka Organic Chemical Industry Co., Ltd.
(C-1): A MIBK solution of a silicone-based copolymer (silicone compound) obtained in Production Example 3.
(C-2): Fluorine compound. SHIN-ETSU SUBELYN (registered trademark) KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd.
(D-1): Photopolymerization initiator. IGM Resins B. V. Omnirad 184, 1-hydroxycyclohexylphenyl ketone manufactured by Omnirad 184.
(D-2): Photopolymerization initiator. Benzophenone.

(Preparation Example 2: Preparation of water-based coating liquid)
Each material shown in Table 2 is mixed so as to have the ratio (mass%) shown in Table 2 in terms of non-volatile content to prepare a coating liquid (P1 to P4, F3 to F5) for a primer layer or a functional layer. did. Each material in Table 2 is as follows.
(IA): An aqueous dispersion of a polyester resin having the following monomer composition i.
Monomer composition i: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56/40/4 // 70/20 / 10 (mol%).
(IB): An aqueous dispersion of an acrylic resin having the following monomer composition ii.
Monomer composition ii: ethyl acrylate / normal butyl methacrylate / acrylic acid = 25/73/2 (% by mass).
(IC): Polyvinyl alcohol having a saponification degree of 88 mol% and a polymerization degree of 500.
(IIA): Hexamethoxymethylol melamine, which is a melamine compound.
(IIB): An acrylic polymer having an oxazoline group and a polyalkylene oxide chain, which is an oxazoline compound (oxazoline group amount = 4.5 mmol / g, Epocross manufactured by Nippon Shokubai Co., Ltd.).
(IIC): Polyglycerol polyglycidyl ether, which is a polyfunctional polyepoxy compound.
(III): Silica particles having an average particle size of 0.07 μm.
(IVA): A polymer having a pyrrolidinium ring in the main chain (compound having an ammonium group) having the following monomer composition iii. Number average molecular weight 30,000.
Monomer composition iii: diallyldimethylammonium chloride / dimethylacrylamide / N-methylolacrylamide = 90/5/5 (mol%).
(IVB): A conductive organic polymer compound in which poly (3,4-ethylenedioxythiophene) is combined with polystyrene sulfonic acid.
(V): An aqueous dispersion of an acrylic resin (glass transition point: −50 ° C.) having the following monomer composition iv.
Monomer composition iv: 2-ethylhexyl acrylate / methyl methacrylate / methacrylic acid = 85/12/3 (% by mass).

(Example 1)
A raw material obtained by mixing polyesters (A), (B) and (C) at a ratio of 91% by mass, 3% by mass and 6% by mass is used as a raw material for the outermost layer (surface layer), and polyesters (A) and (B) are used. Raw materials mixed at a ratio of 97% by mass and 3% by mass, respectively, were used as raw materials for the intermediate layer, and each was supplied to two extruders, melted at 285 ° C., and then placed on a cooling roll set at 40 ° C. An unstretched sheet was obtained by co-extruding and cooling and solidifying in a layer structure of two types and three layers (surface layer / intermediate layer / surface layer = discharge amount of 1: 8: 1).
Next, after stretching 3.1 times in the vertical direction at a film temperature of 85 ° C. using the difference in roll peripheral speed, the coating liquid P1 was applied to one side of the vertically stretched film, guided to a tenter, and at 95 ° C. for 10 seconds. After drying, the film was stretched 4.2 times at 120 ° C. in the lateral direction, heat-treated at 230 ° C. for 10 seconds, and then relaxed by 2% in the lateral direction. As a result, a polyester film having a thickness of 50 μm provided with a primer layer having a thickness (after drying) of 0.10 μm on one side was obtained.

The coating liquid S1 is applied onto the primer layer of the obtained polyester film, dried at 70 ° C. for 1 minute, and irradiated with ultraviolet rays with an integrated light amount of 600 mJ / cm ² and an illuminance of 100 mW / cm ² with a high-pressure mercury lamp to obtain a thickness. A 3 μm uneven layer was formed (after drying).

Next, the coating liquid F1 is applied onto the uneven layer, dried at 80 ° C. for 1 minute, and irradiated with ultraviolet rays at an integrated light intensity of 250 mJ / cm ² with a high-pressure mercury lamp to obtain a surface having a thickness (after drying) of 0.5 μm. A functional layer was formed.

As a result, a laminated body in which the polyester film, the primer layer, the uneven layer, and the surface functional layer were laminated in this order was obtained. The characteristics of the obtained laminate are shown in Table 4.
As shown in Table 4, the obtained laminate had matte and antifouling properties on the surface side.

(Examples 2 to 10)
In Example 1, the type of the coating liquid forming each of the primer layer, the uneven layer, and the surface functional layer and the thickness of the formed layer are changed to those shown in Table 3, or the primer layer or the surface functional layer is not provided. Obtained a laminated body in the same manner as in Example 1. The characteristics of the obtained laminate are shown in Table 4.

(Example 11)
In Example 1, after obtaining an unstretched sheet, the unstretched sheet is stretched 3.1 times in the vertical direction at a film temperature of 85 ° C. using the difference in roll peripheral speed, and then the coating liquid P4 is applied to both sides of the vertically stretched film. A polyester film was obtained in the same manner except for the above. Then, an uneven layer was formed in the same manner as in Example 1 to obtain a laminated body. The characteristics of the obtained laminate are shown in Table 4.
As shown in Table 4, the obtained laminate had a matte property on the front surface side and an antistatic property on the back surface side.

(Example 12)
In Example 11, the type of the coating liquid forming the primer layer and the thickness of the formed layer are changed to those shown in Table 3, and a surface functional layer is formed on the uneven layer in the same manner as in Examples 4 to 5. A laminated body was obtained in the same manner as in Example 11. The characteristics of the obtained laminate are shown in Table 4.

(Example 13)
The coating liquid F5 was applied to the side of the laminate obtained in Example 4 opposite to the uneven layer side, and dried to form a back surface functional layer having adhesive properties. The characteristics of the obtained laminate are shown in Table 4.

(Example 14)
An uneven layer and a surface functional layer were sequentially formed on one side of a polyacrylate (polymethylmethacrylate) film (Acriprene HBS 50 μm manufactured by Mitsubishi Chemical Corporation) in the same manner as in Example 1 to obtain a laminated body. The characteristics of the obtained laminate are shown in Table 4.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1 except that the primer layer and the surface functional layer were not provided in Example 1. The characteristics of the obtained laminate are shown in Table 4.
As shown in Table 4, the obtained laminate was inferior in adhesion between the base material layer and the uneven layer. Further, it has no function (antifouling property, antistatic property, etc.) other than the matte property which is the function of the uneven layer.

(Comparative Example 2)
A laminated body was obtained in the same manner as in Example 1 except that the primer layer, the uneven layer and the surface functional layer were not provided in Example 1. The characteristics of this laminated body are shown in Table 4.
As shown in Table 4, the obtained laminate had no matte property.

(Comparative Example 3)
In Comparative Example 1, a laminated body was obtained in the same manner as in Comparative Example 1 except that the type of the coating liquid forming the uneven layer was changed to that shown in Table 3.
As shown in Table 4, the obtained laminate had no matte property.

1 ... Base material layer 2 ... Concavo-convex layer 3 ... Primer layer 4 ... Front surface functional layer 5 ... Back surface functional layer 10 ... Laminated body

Claims (10)

It has a base material layer and an uneven layer having irregularities provided on one surface of the base material layer.
The uneven layer is a cured product of a composition containing a polymer (X) having an active group that generates radicals by irradiation with active energy rays, and the polymer (X) is further an alkyl having 4 or more carbon atoms. Units based on radical (meth) acrylic acid alkyl esters,
Further, the primer layer provided between the base material layer and the uneven layer, the surface functional layer provided on the surface of the uneven layer opposite to the base material layer side, and the base material layer. A laminate having one or more layers selected from the group consisting of back surface functional layers provided on the surface opposite to the uneven layer side. The group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, anthraquinone group, a thioxanthone group, and a phosphine oxide group. The laminate according to claim 1, which is one or more selected from the above. The laminate according to claim 1 or 2, wherein the surface functional layer is an antifouling layer, an antistatic layer, a refractive index adjusting layer, an infrared absorbing layer, an ultraviolet absorbing layer, or a color correction layer. The laminate according to any one of claims 1 to 3, wherein the back surface functional layer is an adhesive layer, an antistatic layer, a refractive index adjusting layer, or an anti-blocking layer. The laminate according to any one of claims 1 to 4, wherein the primer layer contains a resin. The laminate according to any one of claims 1 to 5, wherein the primer layer contains a compound derived from a cross-linking agent. The laminate according to any one of claims 1 to 6, wherein the polymer (X) has a unit based on the (meth) acrylic acid ester having the active group. The laminate according to any one of claims 1 to 7, wherein the polymer (X) further has a unit based on a (meth) acrylic acid ester having a hydrogen-donating functional group. The laminate according to any one of claims 1 to 8 , wherein the content of the active group per 1 g of the uneven layer is 0.001 to 1 mmol / g. The laminate according to any one of claims 1 to 9 , wherein the composition further contains a compound (Y) having a radically polymerizable group.

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