JP2022172161A - laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of exhibiting a plurality of functions including a lusterless property.

SOLUTION: A laminate 10 comprises: a substrate layer 1; an irregular layer 2 disposed on one surface of the substrate layer 1, and having irregularities due to phase separation; and at least one layer selected from the group consisting of a primer layer 3 disposed between the substrate layer 1 and the irregular layer 2, a surface functional layer 4 disposed on an opposite surface to the substrate layer 1 side of the irregular layer 2, and a rear face functional layer 5 disposed on an opposite surface to the irregular layer 2 side of the substrate layer 1. An anti-static layer is provided as the surface functional layer 4 or the primer layer 3, and a surface resistance value on the outermost surface at a side at which the irregular layer 2 exists, to the substrate layer 1 is 2×10¹⁰ Ω or less.

SELECTED DRAWING: Figure 5

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to laminates.

There is known a method of imparting a matte property to the surface of a base material by developing fine unevenness on the surface.
For example, Patent Documents 1 to 4 describe a method of obtaining a cured film having unevenness on the surface by utilizing phase separation in the process of drying a coating film containing two compounds having different solubility. .

Japanese Patent No. 4739720 Japanese Patent No. 4901914 Japanese Patent Application Laid-Open No. 2011-2820 JP 2018-72588 A

According to the methods described in Patent Documents 1 to 4, a laminate having an uneven layer made of a resin cured product having unevenness due to phase separation on a substrate is obtained. In some cases, the textured layer alone may not be sufficient to achieve this.

An object of the present invention is to provide a laminate capable of exhibiting multiple functions including matting properties.

The present invention has the following configurations.
[1] A substrate layer and an uneven layer having unevenness due to phase separation provided on one surface of the substrate layer, and further provided between the substrate layer and the uneven layer a primer layer provided on a surface of the uneven layer opposite to the substrate layer side, and a surface functional layer provided on the surface of the uneven layer opposite to the substrate layer side, and provided on the surface of the substrate layer opposite to the uneven layer side It has one or more layers selected from the group consisting of the back functional layer, has an antistatic layer as the surface functional layer or the primer layer, and is the most on the side where the uneven layer is present with respect to the base layer. A laminate whose surface has a surface resistance of 2×10 ¹⁰ Ω or less.
[2] The front 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, and the back functional layer is an adhesive layer, an antistatic layer, The laminate according to [1], which is a refractive index adjusting layer or an anti-blocking layer.
[3] The laminate according to [1] or [2], wherein the surface functional layer has a thickness of 0.001 to 3 μm, and the back functional layer has a thickness of 0.001 to 30 μm.
[4] The laminate according to any one of [1] to [3], wherein the outermost surface of the substrate layer on which the uneven layer is present has a haze of 0.5 to 99%.
[5] The laminate according to any one of [1] to [4], wherein the 60° specular gloss of the outermost surface of the substrate layer on the side where the uneven layer is present is 100 or less.
[6] Having an antistatic layer as the surface functional layer or the primer layer, and having a surface resistance value of 1×10 ¹³ Ω on the outermost surface of the substrate layer on the side where the uneven layer is present, [ 1] The laminate according to any one of [5].
[7] It has an antistatic layer as the back functional layer, and the outermost surface of the substrate layer on the side opposite to the uneven layer has a surface resistance value of 1×10 ¹³ Ω or less. The laminate according to any one of [1] to [6].
[8] The compound (X) in which the uneven layer contains at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group, and a compound (X) that does not contain the polar group. The laminate according to any one of [1] to [7], which is a cured product of a composition containing the compound (Y).
[9] The laminate according to [8], wherein the compound (X) has an SP value of 15.1 or more and the compound (Y) has an SP value of 15.0 or less.
[10] Described in [8] or [9], wherein (X):(Y) represents the mass ratio of the compound (X) and the compound (Y) in the uneven layer, and is 10:90 to 80:20. laminate.
[11] The laminate according to any one of [1] to [10], wherein the uneven layer has a thickness of 1 to 10 μm.
[12] The laminate according to any one of [1] to [11], wherein the substrate layer has a thickness of 2 to 350 μm.
[13] The laminate according to any one of [1] to [12], wherein the substrate layer is a substrate selected from polyester film, polyacrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetylcellulose film. body.
[14] The laminate according to any one of [1] to [13], wherein the primer layer contains a resin.
[15] The laminate according to any one of [1] to [14], wherein the primer layer contains a compound derived from a cross-linking agent.
[16] The laminate according to any one of [1] to [15], wherein the primer layer contains an antistatic agent.
[17] The laminate according to any one of [8] to [16], wherein the compound (X) is a polymer compound.
[18] The laminate according to any one of [8] to [17], wherein the compound (X) is at least one selected from (meth)acrylic polymers, polyvinyl alcohols and celluloses.
[19] The laminate according to [18], wherein the (meth)acrylic polymer is obtained by reacting an epoxy group with a carboxylic acid.
[20] The laminate according to any one of [8] to [19], wherein the compound (X) contains a carbon-carbon unsaturated bond.
[21] The laminate according to any one of [8] to [20], wherein the compound (Y) is a (meth)acrylic polymer.
[22] The laminate according to any one of [8] to [20], wherein the compound (Y) is (meth)acrylate.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has a matte property can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the laminated body of this invention. FIG. 4 is a schematic cross-sectional view showing another example of the laminate of the present invention; FIG. 4 is a schematic cross-sectional view showing another example of the laminate of the present invention; FIG. 4 is a schematic cross-sectional view showing another example of the laminate of the present invention; FIG. 4 is a schematic cross-sectional view showing another example of the laminate of the present invention;

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description content as long as it does not exceed the gist of the present invention. Arbitrary modifications can be made without departing from the gist of the invention.

In the present invention, "(meth)acrylate" is a generic term for acrylate or methacrylate. "(Meth)acryl" is a generic term for acryl and methacryl.
"~" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.
The laminate of the present invention will be described below with reference to FIGS. 1 to 5. FIG. 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 "this laminate") has a substrate layer and an uneven layer provided on one surface of the substrate layer. The laminate further comprises a primer layer provided between the substrate layer and the uneven layer, a surface functional layer provided on a surface of the uneven layer opposite to the substrate layer, and It has one or more layers selected from the group consisting of back functional layers provided on the surface of the substrate layer opposite to the irregular layer side.

FIG. 1 is a schematic cross-sectional view showing an example of this laminate.
The laminate 10 includes a substrate layer 1, an uneven layer 2 provided on one surface 1a of the substrate layer 1, a primer layer 3 provided between the substrate layer 1 and the uneven layer 2, have

FIG. 2 is a schematic cross-sectional view showing another example of the laminate.
The laminate 10 includes a substrate layer 1, an uneven layer 2 provided on one surface 1a of the substrate layer 1, and a surface of the uneven layer 2 opposite to the substrate layer 1 side. and a surface functional layer 4 .

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

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

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

The uneven layer 2 has unevenness due to phase separation. Specifically, the uneven layer 2 has unevenness 2C formed of concave portions 2A and convex portions 2B on the surface opposite to the base layer 1 side.

"base material layer"
The base layer 1 is made of a base film.
As the base film, for example, conventionally known films such as resin films, metal films, and paper can be used, but resin films are preferable from the viewpoint of workability.
The structure of the base film is not particularly limited, and may be a single layer structure or a multilayer structure of two or more layers. It is preferable that the base film has a multi-layered structure of two or more layers, and each layer has its own characteristic to achieve multi-functionality.

Examples of resin films include polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, triacetylcellulose films, polystyrene films, polyvinyl chloride films, polyvinyl alcohol films, and nylon films.
In particular, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetyl cellulose film are preferred for use in displays. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferably used. Furthermore, considering transparency, moldability, and versatility, a polyester film is more preferably used.

The polyester film may be an unstretched film (sheet) or a stretched film. Among these, stretched films uniaxially or biaxially stretched are preferred. Among them, a biaxially stretched film is preferred from the viewpoint of excellent balance of mechanical properties and flatness.

The polyester used for the polyester film that can be used as the base film may be homopolyester or copolyester.
When the base film is made of homopolyester, it is preferably obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol.
Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Aliphatic glycols include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and the like. Aromatic dicarboxylic acids and aliphatic glycols may be used alone or in combination of two or more.

Examples of the dicarboxylic acid component of the copolymer polyester include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid, and the like, and a glycol component. Examples include one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol, and the like.

Typical polyesters include polyethylene terephthalate, polyethylene naphthalate, and the like.
The intrinsic viscosity of polyester is preferably 0.5 to 1.0 dL/g, more preferably 0.55 to 0.75 dL/g. The intrinsic viscosity is measured by the method described in Examples below.

A more preferable form of the polyester film is a film formed from polyethylene terephthalate or polyethylene naphthalate, considering the mechanical strength and heat resistance, among the above. A film formed of polyethylene terephthalate is more preferable in consideration of the handleability of the film.

As the poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the base film, any one having units based on (meth)acrylate can be used, and various acrylic resins can be used. (Meth)acrylates include alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate; Examples thereof include alkyl (meth)acrylates having alkyl groups with a large number of carbon atoms. Among these, considering the transparency, workability, and chemical resistance, it is preferable that the main component is a unit based on an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, and based on methyl (meth)acrylate It is more preferably composed mainly of at least one selected from the group consisting of units and units based on ethyl (meth)acrylate, and preferably composed mainly of units based on methyl (meth)acrylate.

Poly(meth)acrylates may contain units based on (meth)acrylates other than alkyl(meth)acrylates or units based on other monomers to impart properties such as flexibility.
The ratio of units based on alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms to the total mass of poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

Particles can be blended into the base film for the purpose of imparting lubricity, preventing scratching in each step, and improving anti-blocking properties. When particles are blended, the type of particles to be blended is not particularly limited as long as they are particles capable of imparting lubricity. Specific examples include silica, calcium carbonate, magnesium carbonate, barium carbonate, and sulfuric acid. Examples include inorganic particles such as calcium, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin and benzoguanamine resin. Furthermore, when the substrate layer includes a polyester film, precipitated particles obtained by depositing a portion of a metal compound such as a catalyst during the polyester production process can also be used. Among these, silica particles and calcium carbonate particles are preferable because they are particularly effective even in small amounts.

The average particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, still more preferably 0.01 to 3 μm. If the average particle size exceeds 10 μm, there is a concern that the transparency of the film may be lowered.

In addition, the average particle diameter of particles refers to the value of 50% of the integrated (weight basis) in the equivalent spherical distribution measured using a centrifugal sedimentation particle size distribution analyzer.

When the substrate layer contains particles, the particle content in the substrate film cannot be generalized due to the balance with the average particle size of the particles, but the total mass of the layer containing the particles in the substrate layer. is preferably 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and even more preferably in the range of 0.0005 to 1% by mass. When the particle content exceeds 5% by mass, it is difficult for the particles to fall off and the transparency of the film to deteriorate.

The shape of the particles to be used is not particularly limited, and any of spherical, lumpy, rod-like, flattened and the like may be used. Moreover, there are no particular restrictions on its hardness, specific gravity, color, and the like. Two or more kinds of these particles may be used in combination, if necessary.

In addition to the particles described above, conventionally known ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments, and the like can be added to the base film, if necessary.

The thickness of the substrate film is not particularly limited as long as it can be formed into a film.

Examples of production of the base film will be specifically described, but the production is not limited to the following examples, and commonly known film-forming methods can be employed. In general, a resin is melted, formed into a sheet, and stretched for the purpose of increasing the strength, etc., to produce a film.

For example, when producing a biaxially oriented polyester film, first, a polyester raw material is melt-extruded from a die using an extruder, and the melted sheet is cooled and solidified by cooling rolls to obtain an unstretched sheet. In this case, it is preferable to increase the adhesion between the sheet and the rotary cooling drum in order to improve the flatness of the sheet, and the electrostatic application adhesion method or the liquid coating adhesion method is preferably employed.
Next, the obtained unstretched sheet is stretched in one direction by a roll or 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.
Next, the film is drawn in a direction perpendicular to the drawing direction of the first stage, preferably at a temperature of 70 to 170° C. and at a draw ratio of 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 under relaxation within 30% to obtain a biaxially oriented film. In the above stretching, a method of stretching in one direction in two or more stages can also be employed. In that case, it is preferable that the stretching ratios in the two directions finally fall within the ranges described above.

A simultaneous biaxial stretching method can also be employed for film production. For example, in the simultaneous biaxial stretching method in the case of a polyester film, the unstretched sheet is usually 70 to 120 ° C., preferably 80 to 110 ° C. The temperature is controlled at the same time in the machine direction and the width direction to stretch and orient. The method. The draw ratio is 4 to 50 times, preferably 7 to 35 times, more preferably 10 to 25 times in terms of area ratio. Subsequently, heat treatment is performed at a temperature of 180 to 270° C. under tension or under relaxation within 30% to obtain a stretched and oriented film. Conventionally known stretching methods such as a screw method, a pantograph method, a linear drive method, and the like can be used for the simultaneous biaxial stretching apparatus that employs the above-described stretching method.

"Uneven layer"
In the uneven layer 2 by phase separation, the composition of materials with different compatibility causes phase separation in the process of coating, drying and curing, thereby forming an uneven shape on the surface. Conventionally known materials can be used as the material that causes phase separation. In particular, a composition composed of materials having different polarities is preferable because it is easy to form by a method of coating a film. For example, a compound (X) containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group, and a compound (Y) containing no such polar group. A combination is mentioned. Moreover, in order to maintain the formed concave-convex shape and use it for various purposes, it is preferably a curable composition for a hard coat.

The compound (X) containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate group, and a thiol group is characterized by a hydrogen bond, which results in unevenness due to phase separation. Structures can be formed. Among these hydrogen-bonding groups, hydroxyl, amino, amido, and glycidyl groups are preferable because they easily form uneven structures due to phase separation. In particular, hydroxyl, amino, and amido groups are stable when materials are mixed. It is preferable from the viewpoint of the property and ease of forming irregularities. In addition, the compound may have not only one type of polar group, but also a plurality of types of polar groups. For example, a compound containing both a hydroxyl group and an amide group is preferable because it facilitates the formation of irregularities.

In addition, considering ease of forming unevenness due to phase separation, the compound (X) is preferably a high molecular weight compound rather than a low molecular weight compound. As the polymer compound, (meth)acrylic polymers, polyvinyl alcohols, and celluloses are preferable because they can introduce a larger number of polar groups, especially from the viewpoint that various functional groups can be introduced and performance can be easily controlled. In, a (meth)acrylic polymer is more preferred.

Furthermore, in order to increase the hardness of the uneven layer 2 due to phase separation, it is preferred that the compound (X) contains a carbon-carbon unsaturated bond. The hardness of the uneven layer 2 formed by phase separation can be adjusted by the content of carbon-carbon unsaturated bonds. The carbon-carbon unsaturated bond means a carbon-carbon double bond or a carbon-carbon triple bond, preferably a carbon-carbon double bond, and a carbon-carbon double bond (meta ) is more preferably an acryloyl group, and more preferably an acryloyl group in consideration of the reactivity of the carbon-carbon unsaturated bond.

In the (meth)acrylic polymer, the compound (X) containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group has those polar groups It can be prepared by copolymerization of the containing (meth)acrylate monomer and other (meth)acrylate monomers, or by copolymerizing (meth)acrylate containing an epoxy group with other (meth)acrylate monomers. A hydroxyl group can also be generated by reacting the epoxy group portion of the polymer obtained by polymerization with an acid, a base, or the like. In particular, the method of using glycidyl (meth)acrylate is useful because it is easy to control the amount of hydroxyl groups.

(Meth)acrylates containing an epoxy group include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl ( meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like. Among these, glycidyl (meth)acrylate is preferred, and glycidyl acrylate is particularly preferred, in consideration of good reactivity and ease of use of the material.

When a hydroxyl group is introduced using a (meth)acrylate containing an epoxy group, the proportion of the (meth)acrylate containing an epoxy group in the (meth)acrylate polymer is preferably 10% by mass or more, More preferably 30% by mass or more, still more preferably 50% by mass or more, particularly preferably 80% by mass or more, the upper limit is 100% by mass. By using it in the said range, it becomes easy to control the polarity of a polymer, and it becomes easy to form uneven|corrugated structure by phase separation.

Compounds used in (meth)acrylate polymers containing epoxy groups to form hydroxyl groups include acids and bases. Considering the stability of (meth)acrylate polymers, acids are preferred. Acids are preferred. Among the carboxylic acids, the use of (meth)acrylic acid makes it possible to introduce a double bond, which is a more preferable form. Among (meth)acrylic acids, acrylic acid is most suitable considering the reactivity of the epoxy group and carboxylic acid and the reactivity of the introduced double bond. It is also a preferred form to use a hydroxycarboxylic acid such as lactic acid in order to introduce more hydroxyl groups.
Additionally, it is possible to react more than one type of carboxylic acid with an epoxy group to form more than one type of structure.

The epoxy group to be reacted is generally 1% by mass or more, preferably 20% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, and the upper limit may be 100% by mass. . By reacting in this range, a hydroxyl group is generated, and a form that facilitates the formation of unevenness due to phase separation is obtained.

Examples of (meth)acrylamide-based monomers for containing an amide group in compound (X) include (meth)acryloylmorpholine, hydroxylmethyl (meth)acrylamide, hydroxylethyl (meth)acrylamide, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, ) acrylamide, N-isopropyl(meth)acrylamide and the like.
Acrylamide monomers are preferred to methacrylamide monomers in view of ease of introduction. Among the above, (meth)acryloylmorpholine is particularly preferred, and acryloylmorpholine is more preferred, in consideration of the stability and polarity of the polymer. These (meth)acrylamide-based monomers may be used singly or in combination of two or more.

Moreover, when using a (meth)acrylic polymer as the compound (X), various polymerizable (meth)acrylates can be used in addition to the above-described compound group. For example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, stearyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate ) acrylate, butoxyethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate and other alkyl (meth)acrylate monomers; perfluoro (meth)acrylate monomers having a fluoroalkyl group such as hexylethyl (meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate, 1H,1H,9H-hexadecafluorononyl (meth)acrylate; N, (Meth)acrylate monomers having an amino group such as N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate monomers having a hydroxyl group such as 1,6-hexanediol mono(meth)acrylate; vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide-modified hydroquinone divinyl ether, ethylene oxide-modified bisphenol A divinyl ether, Hydrocarbon-based monomers having a vinyl group such as pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, and ditrimethylolpropane polyvinyl ether can be used.

The raw material to be used is not limited to one type, and two or more types may be used in combination to prepare a (meth)acrylic polymer, or two or more types may be used in combination to prepare a (meth)acrylic polymer. is preferred.

Polymerization conditions for producing a (meth)acrylic polymer are not particularly limited, and known methods can be appropriately selected. Usually, the reaction to obtain a (meth)acrylic polymer is a radical polymerization reaction, and by polymerizing raw material monomers at a desired polymerization temperature in an organic solvent in the presence of a radical polymerization initiator, a (meth)acrylic polymer can be obtained. You can get a union.

For example, the organic solvent includes ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as ethanol, methanol, isopropyl alcohol and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ethyl acetate. , propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene; These organic solvents may be used alone or in combination of two or more.

Radical polymerization initiators include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide, 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) , 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds. These radical polymerization initiators may be used alone or in combination of two or more.

The polymerization temperature is usually 20-150°C, preferably 50-100°C. The polymerization time is usually 1 to 72 hours, preferably 3 to 36 hours.

Moreover, the conditions for the reaction between the epoxy group and the carboxylic acid compound described above are not particularly limited, and a known method can be appropriately selected. The reaction may be carried out without a catalyst or in the presence of a catalyst. Examples of catalysts include tertiary amines such as triethylamine and benzyldimethylamine, ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide, triphenylphosphine, phosphines such as tributylphosphine; and phosphonium salts such as tetrabutylphosphonium bromide and tetrabutylphosphonium iodide. The amount of the catalyst used is usually 0.5% by mass or more, preferably 1.0% by mass or more, and usually 5.0% by mass or less, preferably 3.5% by mass, based on the weight of the polymer. It is below.

The reaction temperature for this reaction is usually 20 to 200°C, preferably 50 to 150°C. The reaction time is usually 1 to 72 hours, preferably 3 to 20 hours.

The weight-average molecular weight (Mw) of the (meth)acrylic polymer should be appropriately selected according to the application of the curable composition, and is usually 5000 or more, preferably 7000 or more, and more preferably is 9,000 or more, usually 100,000 or less, preferably 70,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less. Within the above range, it becomes easy to form irregularities due to phase separation on the surface after application. The weight average molecular weight (Mw) of the (meth)acrylic polymer can be determined by gel permeation chromatography (GPC) as a converted value based on polystyrene standards. Specific measurement conditions are shown in Examples below.

The (meth)acrylic polymer of the compound (X) has a (meth)acryloyl equivalent (amount of (meth)acryloyl groups introduced) of 1.0 to improve the scratch resistance of the uneven layer 2 due to phase separation to be formed. It is preferably 0 mmol/g or more, more preferably 2.0 mmol/g or more, and particularly preferably 2.5 mmol/g or more. From the viewpoint of preventing gelation, the (meth)acryloyl equivalent is preferably 10.0 mmol/g or less, more preferably 8.0 mmol/g or less, and 6.0 mmol/g or less. Especially preferred. The (meth)acryloyl equivalent is calculated based on the raw materials used, and the reaction between the epoxy group and the carboxylic acid such as (meth)acrylic acid is preferably selected so that the (meth)acryloyl equivalent falls within the above range.

As the compound (Y) containing no hydroxyl group, amino group, amido group, sulfonyl group, phosphate ester group or thiol group, conventionally known various compounds can be used. For example, (meth)acrylic polymers and various (meth)acrylic monomers can be used.

In the present invention, the "(meth)acrylic polymer" means a polymer synthesized from raw materials containing (meth)acrylic acid and/or (meth)acrylic acid derivative, and this polymer is further It is used in the sense of including modified polymers. Others are not particularly limited as long as it is a polymer using at least one raw material ((meth)acrylic monomer) of (meth)acrylic acid or (meth)acrylic acid derivative (e.g., (meth)acrylic monomer In addition, it may be a copolymer using a known polymerizable monomer such as a hydrocarbon-based monomer having a vinyl group.In addition, "(meth)acrylic acid derivative" means (meth)acrylic acid metal compounds having structures similar to (meth)acrylic acid, such as salts, (meth)acrylic acid esters, and (meth)acrylic acid amides).

The (meth)acrylic polymer is formed from a (meth)acrylic monomer containing no hydroxyl group, amino group, amide group, sulfonyl group, phosphate ester group, or thiol group or a monomer that undergoes a polymerization reaction therewith. things are mentioned.

As the (meth)acrylic monomer containing no hydroxyl group, amino group, amide group, sulfonyl group, phosphate ester group or thiol group, various conventionally known materials can be used. Although it may be a monofunctional compound, it is preferably a bifunctional or higher polyfunctional (meth)acrylate from the viewpoint of the strength of the uneven layer 2 formed, and more preferably a trifunctional or higher polyfunctional (meth)acrylate. In addition, since it is preferable that the polarity is low, those having few or no hydrogen bonding groups such as ethers such as ethylene oxide structures are preferable.

Examples of bifunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, (Meth)acrylates, alkanediol di(meth)acrylates such as tricyclodecanedimethylol di(meth)acrylate, bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylates, bisphenol F ethylene oxide-modified di(meth)acrylates di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di(meth)acrylate and the like.

Trifunctional or higher polyfunctional (meth)acrylates are not particularly limited, but for example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri (Meth)acrylates, trimethylolpropane tri(meth)acrylates, isocyanuric acid ethylene oxide-modified tri(meth)acrylates, isocyanuric acid-modified tri(meth)acrylates such as ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, pentaerythritol Urethane acrylates such as 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 particularly preferred.

The weight average molecular weight (Mw) of the (meth)acrylic monomer of compound (Y) is preferably 60 or more, more preferably 100 or more, still more preferably 200 or more, and preferably 8000 or less. , more preferably 6,000 or less, still more preferably 4,000 or less, and particularly preferably 2,000 or less. Within the above range, it is possible to obtain a coating liquid which exhibits phase separation during coating processes such as drying and UV irradiation and which is easy to handle while being uniformly compatible as a coating liquid.

Compound (X) and compound (Y) are compounds for phase separation. Therefore, from the viewpoint of the solubility parameter (SP value, Solubility Parameter), it is preferable that there is a large difference between the two.

The SP value of compound (X) is preferably 15.1 or more, more preferably 16.0 to 22.0, still more preferably 16.5 to 20.0, particularly preferably 17.0 to 19.5. Range. By using it in this range, it is possible to achieve both ease of forming an uneven structure by phase separation and coatability.

The SP value of compound (Y) is preferably 15.0 or less, more preferably 10.0 to 14.5, still more preferably 11.0 to 14.0, particularly preferably 12.0 to 13.5. Range. By using it in this range, it becomes easy to form an uneven structure due to phase separation from the compound (X).

Further, the difference in SP value between compound (X) and compound (Y) is preferably 0.5 or more, more preferably 1.0 to 9.0, even more preferably 2.0 to 8.0, particularly preferably It ranges from 3.0 to 7.0. If the difference is within this range, it becomes easier to form an uneven structure due to phase separation.

The mass ratio of the total amount of compound (X) to the total amount of compound (Y) is preferably 10:90 to 80:20, more preferably 12:88 to 60:40, particularly preferably 15:85 to 50:50, most preferably in the range 20:80 to 40:60. By setting the content in this range, it becomes easier to form an uneven structure due to phase separation.

Although the thickness of the uneven layer 2 is not particularly limited, it is preferably in the range of 1 to 10 μm, more preferably 1.5 to 8 μm, still more preferably 2.0 to 6 μm.
The thickness of the uneven layer is measured by cross-sectional observation with an electron microscope.

"primer layer"
Next, formation of the primer layer 3 that can be formed on the base film (base layer 1) will be described.
The primer layer 3 is a layer for the purpose of improving adhesion between the substrate layer 1 and the uneven layer 2 . If the adhesion between the substrate layer 1 and the uneven layer 2 is insufficient, the laminate may not be usable depending on the application. By having the primer layer 3, the adhesiveness between the base material layer 1 and the uneven layer 2 can be improved, and the laminate can be used for various purposes.

Other functions may be imparted to the primer layer 3 . Other functions include, for example, antistatic performance. If the primer layer 3 is an antistatic layer having antistatic performance, the outermost surface of the laminate, particularly the outermost surface on the side where the uneven layer 2 is present with respect to the base layer 1, dust due to peeling electrification or frictional electrification adhesion can be reduced. In order to impart antistatic performance to the primer layer 3 , for example, an antistatic agent may be incorporated into the primer layer 3 .

The primer layer 3 can be formed by a conventionally known method. Among them, it is preferable to form the primer layer 3 by coating in consideration of ease of formation of the primer layer 3 .
As a method by coating, it may be provided by in-line coating performed in the process of manufacturing the substrate film, or may be provided by offline coating in which the once-produced substrate film is coated outside the system. More preferably, it is formed by in-line coating.

Specifically, in-line coating is a method in which coating is performed at any stage from melt extrusion of the resin forming the base film to heat setting after stretching and winding up.
Usually, it is coated on an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, or a film after heat setting and before winding. Although it is not limited to the following, for example, in sequential biaxial stretching, a method in which a uniaxially stretched film stretched in the longitudinal direction (machine direction) is coated and then stretched in the transverse direction is excellent.
According to this method, the film formation and the formation of the primer layer 3 can be performed at the same time, which is advantageous in terms of manufacturing cost. In addition, since the film is stretched after coating, the thickness of the primer layer 3 can be changed by the stretching ratio. Also, thin film coating can be performed more easily than offline coating.

According to the in-line coating process described above, the thickness of the film does not change greatly depending on whether the primer layer 3 is formed, and the risk of scratches and foreign matter adhesion does not change greatly depending on whether the primer layer 3 is formed. This is a great advantage compared to off-line coating, which is a separate process.

Further, by providing the primer layer 3 by coating on the base film before stretching, the primer layer 3 can be stretched together with the base film, so that the formed primer layer 3 is suitable for the base film. It has adhesion.

Furthermore, in the production of biaxially stretched polyester film, the film can be restrained in the vertical and horizontal directions by holding the ends of the film with a clip or the like while stretching. A high temperature can be applied while maintaining flatness.
Therefore, since the heat treatment applied after the primer layer 3 is provided by coating can be made to a high temperature that cannot be achieved by other methods, the film-forming property of the primer layer 3 is improved, and a strong primer layer 3 is formed. can do. In particular, it is very effective for reacting a cross-linking agent.

Furthermore, in the case of a biaxially stretched polyester film, it was found that in-line coating improves adhesion and durability to the uneven layer due to phase separation. This makes it possible to heat-treat at a high temperature that cannot be obtained by off-line coating, and the heat-treatment makes the primer layer 3 itself stronger and more resistant to heat and mechanical action during the formation of the uneven layer 2 due to phase separation. This is thought to be due to

The material for forming the primer layer 3 preferably contains a resin from the viewpoint of improving adhesion to the uneven layer 2 . Conventionally known resins can be used as the resin. Specific examples of resins include polyester resins, acrylic resins, urethane resins, polyvinyl resins (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.). , acrylic resin and urethane resin are preferred. When the base film is a polyester film, a polyester resin is more preferable from the viewpoint of adhesion between the primer layer 3 and the base film. Moreover, when the base film is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

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

An acrylic resin is a polymer of polymerizable monomers including (meth)acrylic monomers.
Examples of acrylic resins include homopolymers and copolymers of (meth)acrylic monomers, copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers, and the like.

Acrylic resins may be copolymers of these polymers with other polymers (eg, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers, graft copolymers. Alternatively, a polymer obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion (sometimes a mixture of polymers) is also included. Also included are polymers obtained by polymerizing polymerizable monomers in polyurethane solutions and polyurethane dispersions (mixtures of polymers in some cases). Also included are polymers (polymer mixtures in some cases) obtained by polymerizing polymerizable monomers in other polymer solutions or dispersions in the same manner.

The polymerizable monomer is not particularly limited, but particularly representative compounds include various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid. and their salts; hydroxyl group-containing monomers; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc. (Meth)acrylic acid esters; various nitrogen-containing compounds such as (meth)acrylamide, diacetoneacrylamide, N-methylolacrylamide or (meth)acrylonitrile; styrene, α-methylstyrene, divinylbenzene, vinyltoluene various styrene derivatives; vinyl esters such as vinyl propionate and vinyl acetate; various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; monomers; various vinyl halides such as vinyl chloride and pyridene chloride; and various conjugated dienes such as butadiene.

A urethane resin is a polymer compound having a urethane bond in its molecule, and is typically synthesized by a reaction between a polyol and a polyisocyanate. Polyols include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.

Polycarbonate polyols are obtained from polyhydric alcohols and carbonate compounds by a dealcoholization reaction. Polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane diol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane and the like. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. Polycarbonate-based polyols obtained from these reactions include, for example, poly(1,6-hexylene) carbonate, poly(3- methyl-1,5-pentylene)carbonate and the like.

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

Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides. substances and polyhydric alcohols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2 ,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2 -hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamine, lactonediol, etc.), lactone compounds such as polycaprolactone Examples include those having a derivative unit.

Among the above polyols, polyester polyols and polycarbonate polyols are more preferably used in consideration of adhesion performance, and polyester polyols are particularly preferable.

Polyisocyanates used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, α, α, α', α'- Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate, aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane Alicyclic diisocyanates such as diisocyanate and isopropylidene dicyclohexyl diisocyanate are exemplified. These compounds may be used alone or in combination of two or more.

A chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with isocyanate groups. Alternatively, a chain extender having two amino groups can be mainly used.

Examples of chain extenders having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and esters such as neopentyl glycol hydroxypivalate. Glycols such as glycol can be mentioned. Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- aliphatic diamines such as decanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylitincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1 , and alicyclic diamines such as 3-bisaminomethylcyclohexane.

Urethane resins are typically used in the form of dispersions or solutions. The medium for the dispersion or solution may be a solvent, but water is preferred.
Aqueous dispersions or aqueous solutions of urethane resin include a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the structure of the urethane resin, and a water-based type. In particular, a self-emulsifying type in which an ionic group is introduced into the structure of a urethane resin to form an ionomer is excellent in the storage stability of the liquid and the water resistance and transparency of the resulting primer layer 3, and is therefore preferable.

The ionic group to be introduced includes various groups such as carboxyl group, sulfonic acid, phosphoric acid, phosphonic acid, and quaternary ammonium salt, but carboxyl group is preferred. As a method for introducing a carboxyl group into the urethane resin, various methods can be adopted in each stage of the polymerization reaction. For example, there is a method of using a resin having a carboxyl group as a copolymerization component when synthesizing a prepolymer, and a method of using a component having a carboxyl group as one component such as a polyol, polyisocyanate, or chain extender. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups depending on the charged amount of this component is preferred.

For example, copolymerization of dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, etc. with polyol used for polymerization of urethane resin. can be done. The carboxyl group is preferably neutralized with ammonia, amines, alkali metals, inorganic alkalis or the like to form a salt. Particularly preferred are ammonia, trimethylamine and triethylamine.
In such a urethane resin, the carboxyl groups removed from the neutralizing agent in the drying process after application can be used as cross-linking reaction sites by other cross-linking agents. As a result, the stability of the liquid state before coating is excellent, and the durability, solvent resistance, water resistance, blocking resistance, etc. of the resulting primer layer 3 can be further improved.

Moreover, in forming the primer layer 3, it is preferable to use a cross-linking agent together in order to make the primer layer 3 stronger and improve performance such as adhesion. As the cross-linking agent, conventionally known materials can be used, and examples thereof include melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, aziridine compounds, and the like. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred, and from the viewpoint of improving adhesion and durability, melamine compounds, oxazoline compounds, and isocyanate compounds are preferred. and epoxy compounds are more preferred, and oxazoline compounds and isocyanate compounds are particularly preferred. One type of these cross-linking agents may be used, but by using two or more types in combination, the adhesiveness and durability may be further improved and become favorable in some cases.

A melamine compound is a compound having a melamine skeleton in the compound. Mixtures can be used. As the alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used. Moreover, the melamine compound may be either a monomer or a polymer of dimers or higher, or a mixture thereof. Considering the reactivity with various compounds, the melamine compound preferably contains a hydroxyl group. Further, melamine may be partially co-condensed with urea or the like, and a catalyst may be used to increase the reactivity of the melamine compound.

An isocyanate-based compound is a compound having an isocyanate derivative structure represented by isocyanate or blocked isocyanate. Examples of isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate and naphthalene diisocyanate, and aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate. Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate, etc. and the like are exemplified. Polymers and derivatives of these isocyanates, such as buret products, isocyanurate products, uretdione products, and carbodiimide modified products, are also included. These may be used alone or in combination of multiple types. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.

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

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

An oxazoline compound is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer. Examples of addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., and a mixture of one or more of these can be used. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially. Other monomers are not limited as long as they are monomers copolymerizable with addition polymerizable oxazoline group-containing monomers. 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,N-dialkyl(meth)acrylamide, (as alkyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl 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 and vinylidene chloride , halogen-containing α,β-unsaturated monomers such as vinyl fluoride; α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene; Monomers can be used.

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, particularly preferably 4 to 6 mmol/g. . By using it in the above range, the durability of the coating film is improved and it becomes easy to adjust the adhesion.

An epoxy compound is a compound having an epoxy group in the molecule, for example, 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 polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds and the like. Examples of polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane. Examples of polyglycidyl ethers and diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. , polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, monoepoxy compounds such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, glycidylamine compounds such as N, N, N', N '-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino)cyclohexane and the like.

A carbodiimide-based compound is a compound having one or more carbodiimide or carbodiimide derivative structures in the molecule. A polycarbodiimide-based compound having two or more in the molecule is more preferable for better strength of the primer layer 3 .

A carbodiimide-based compound can be synthesized by a conventionally known technique, and generally a condensation reaction of diisocyanate is used. The diisocyanate is not particularly limited, and both aromatic and aliphatic can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and the like.

In order to improve the water-solubility and water-dispersibility of the polycarbodiimide-based compound, it is possible to add a surfactant, a polyalkylene oxide, a quaternary ammonium salt of a dialkylamino alcohol, a hydroxy Hydrophilic monomers such as alkylsulfonates may be added and used.

A silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule. For example, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4- epoxy group-containing compounds such as ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, etc. (Meth) acrylic group-containing compounds, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)- 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N -(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and other amino group-containing compounds, tris(trimethoxysilylpropyl) isocyanurate, isocyanurate group-containing compounds such as tris(triethoxysilylpropyl) isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, A mercapto group-containing compound such as ethoxysilane can be used.

Among the above compounds, epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, and amino group-containing silane coupling compounds are more preferable from the viewpoint of the strength of the primer layer 3. .

These cross-linking agents improve the performance of the primer layer 3 by reacting in the drying process and the film forming process. It can be assumed that unreacted products of these cross-linking agents, compounds after reaction, or mixtures thereof are present in the finished primer layer 3 .

The antistatic agent contained in the primer layer 3 is not particularly limited, and conventionally known antistatic agents can be used. It is preferably an inhibitor. Polymer-type antistatic agents include, for example, compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, and conductive organic polymers.

A compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines.
The compound having an ammonium group is preferably a polymer-type compound having an ammonium group, and the ammonium group is incorporated not as a counterion but in the main chain or side chain of the polymer. is preferred. Such compounds include, for example, an ammonium group or an addition-polymerizable monomer containing an ammonium group precursor such as an amine, which is polymerized, and if necessary, the ammonium group precursor group is converted to an ammonium group, A high molecular compound having an ammonium group can be mentioned. As the polymer, a monomer containing an addition-polymerizable ammonium group or an ammonium group precursor such as an amine may be polymerized alone, or a copolymer of a monomer containing these and other monomers may be used. may

As a compound having an ammonium group, a compound having a pyrrolidinium ring is also preferable from the viewpoint of excellent antistatic properties and heat resistance stability.
The two substituents bonded to the nitrogen atom of the pyrrolidinium ring-containing compound are each independently an alkyl group, a phenyl group, or the like, and even if these alkyl groups and phenyl groups are substituted with groups shown below, good. Substitutable groups are, for example, hydroxyl groups, amide groups, ester groups, alkoxy groups, phenoxy groups, naphthoxy groups, thioalkoxy groups, thiophenoxy groups, cycloalkyl groups, trialkylammoniumalkyl groups, cyano groups, halogens. In addition, the two substituents bonded to the nitrogen atom may be chemically bonded, and examples of the group in which the two substituents are chemically bonded include -(CH ₂ ) _m -(m= an integer of 2 to 5), -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.

The pyrrolidinium ring-containing compound is preferably a pyrrolidinium ring-containing polymer.
A polymer having a pyrrolidinium ring can be obtained, for example, by cyclopolymerizing a diallylamine derivative using a radical polymerization catalyst. Polymerization is carried out in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, or acetonitrile as a solvent with a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, or tertiary butyl peroxide. It can be implemented by any method, but is not limited to these. In the present invention, a diallylamine derivative and a compound having a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component.

Examples of the anion that serves as a counter ion for the ammonium group of the compound having an ammonium group include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

In addition, the compound having an ammonium group has a number average molecular weight (Mn) of 1,000 to 500,000, preferably 2,000 to 350,000, more preferably 5,000 to 200,000. If the molecular weight is less than 1,000, the strength of the coating film may be weak, or the heat resistance stability may be poor. On the other hand, when the molecular weight exceeds 500,000, the viscosity of the coating liquid increases, and the handleability and coating properties may deteriorate.

In the present invention, the number average molecular weight (Mn) of the compound having an ammonium group can be determined using GPC (gel permeation chromatography) as a converted value based on polystyrene standards.

Polyether compounds include, for example, polyethylene oxide, polyether ester amide, acrylic resins having polyethylene glycol in side chains, and the like.

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

As the conductive organic polymer, conventionally known materials can be used. Examples include polythiophene, polyaniline, polypyrrole, polyacetylene, polyphenylene sulfide, etc. Polythiophene derivative) is preferable because it has both high transparency and high conductivity, is difficult to be colored, and is easy to exhibit performance by coating. Among polythiophene-based materials, a compound obtained by combining poly(3,4-ethylenedioxythiophene) with polystyrenesulfonic acid is particularly preferable from the viewpoint of conductive performance. A conductive organic polymer is preferable in that it exhibits high conductivity, is less dependent on humidity, and can be expected to be used in various applications.

In addition, particles can be used together for the formation of the primer layer 3 to improve blocking and slipperiness.

In addition, as long as the gist of the present invention is not impaired, the formation of the primer layer 3 may optionally include antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, and foaming agents. It is also possible to use agents, dyes, pigments, etc. in combination.

The ratio of the resin in the primer layer 3 is usually 5% by mass or more, preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and still more preferably 30 to 90% by mass. By using it in the said range, it becomes easy to improve the appearance of the primer layer 3, and adhesiveness with the uneven|corrugated layer 2. FIG.

The proportion of the crosslinking agent in the primer layer 3 is generally 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and still more preferably 5 to 40% by mass. By using it in the above range, it becomes easy to improve the strength of the primer layer 3 and improve the adhesion between the uneven layer 2 and the primer layer 3 .

When imparting an antistatic function to the primer layer 3, it depends on the type of antistatic agent, so it is not general, but the proportion of the antistatic agent in the primer layer 3 is usually 80% by mass or less, preferably 0 .5 to 70% by weight, more preferably 1 to 50% by weight. By using it in the said range, it becomes easy to provide an antistatic function to the primer layer 3, and even after forming the uneven|corrugated layer 2 on the primer layer 3, it becomes easy to express antistatic performance.

The thickness of the primer layer 3 depends on the material used for the primer layer 3 and the performance to be developed, so it cannot be generalized, but it is usually 0.001 to 10 μm, preferably 0.01 to 4 μm, more preferably 0.01 to 4 μm. 02 to 1 μm.

Regarding the formation of the primer layer 3, the above-mentioned series of compounds are used as a solution or a dispersion in a solvent, and the base film is coated with a liquid adjusted to a solid content concentration of about 0.1 to 80% by mass. It is preferred to produce laminates. Especially when it is provided by in-line coating, it is more preferable to use an aqueous solution or a water dispersion. A small amount of an organic solvent may be contained in the coating liquid for the purpose of improving dispersibility in water and film-forming properties. In addition, only one type of organic solvent may be used, or two or more types may be used as appropriate.

Examples of methods for forming the primer layer 3 include gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, Conventionally known coating methods such as kiss coating, spray coating, calendar coating, and extrusion coating can be used.

The drying and curing conditions for forming the primer layer 3 on the base film are not particularly limited, but in the case of the coating method, the drying of the solvent such as water used in the coating liquid is as follows. The range is usually 50 to 150°C, preferably 80 to 130°C, more preferably 90 to 120°C. The drying time is in the range of 3 to 200 seconds, preferably 5 to 120 seconds, as a guideline. In addition, in order to improve the strength of the primer layer 3, when it is performed in the film manufacturing process, it is usually subjected to a heat treatment process at 150 to 270 ° C., preferably 170 to 230 ° C., more preferably 180 to 210 ° C. . The time for the heat treatment step is in the range of 3 to 200 seconds, preferably 5 to 120 seconds as a guideline.

Moreover, you may combine heat processing and active-energy-ray irradiation, such as ultraviolet irradiation, as needed. The substrate film constituting the laminate in the present invention may be previously subjected to surface treatment such as corona treatment or plasma treatment.

"Surface functional layer"
A surface functional layer 4 may be provided on the uneven layer 2 formed by phase separation to provide various functions. Examples of the surface functional layer 4 include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, 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 2 formed by phase separation. As the material used for the antifouling layer 2, conventionally known materials such as silicone compounds, fluorine compounds, long-chain alkyl group-containing compounds, and the like can be used. Among these, silicone compounds and fluorine compounds are preferred for exhibiting stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of not staining the other party with which the antifouling layer comes into contact.

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

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

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

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

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

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

The compound having an alkyl group capable of reacting with the reactive group includes, for example, hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, behenyl isocyanate and other long-chain alkyl group-containing isocyanates, hexyl chloride, and octyl chloride. , long-chain alkyl group-containing acid chlorides such as decyl chloride, lauryl chloride, octadecyl chloride 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 preferred, and octadecyl isocyanate is particularly preferred, in consideration of releasability and ease of handling.

Polymer compounds having long-chain alkyl groups in side chains can also be obtained by polymerizing long-chain alkyl (meth)acrylates or by copolymerizing long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. . Examples of long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate. be done.

The content of the antifouling material in the surface functional layer 4 for exhibiting the antifouling performance described above depends on the material used, so it cannot be generalized, but in the case of silicone compounds and fluorine compounds, it is usually 0.00. 01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. Further, when a long-chain alkyl group-containing compound is used, the content is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is 100% by mass. I don't mind. By using it in the above range, it is possible to have effective antifouling performance.

As the antistatic agent used when forming the antistatic layer as the surface functional layer 4, various antistatic agents used in the primer layer 3 described above can be used. Moreover, for example, a method of introducing a double bond such as an acryloyl group into a compound having an ammonium group and reacting at the double bond is also preferable.

Examples of refractive index adjusting layers include high refractive index layers, low refractive index layers, and laminates thereof.
As a material used for forming a refractive index adjustment layer as the surface functional layer 4, when aiming at increasing the refractive index, for example, aromatic-containing materials such as a benzene structure, a bisphenol A structure, a melamine structure, and a fluorene structure are used. Also, among aromatics, naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, condensed polyolefins such as perylene structures, which are considered high refractive index compounds. Metals such as cyclic aromatic compounds, zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony tin oxide), ITO (indium tin oxide) Examples thereof include oxides, metal-containing compounds such as metal chelate compounds such as titanium chelate and zirconium chelate, compounds containing sulfur elements, and compounds containing halogen elements.

Since there is a concern that the metal oxide may deteriorate the adhesion depending on the form of use, it is preferable to use it in the form of particles, and the average particle size thereof is preferably 100 nm or less, more preferably 100 nm or less, from the viewpoint of coating appearance. is in the range of 50 nm or less, more preferably 25 nm or less.

As the material used for forming the refractive index adjustment layer as the surface functional layer 4, conventionally known materials can be used for the purpose of lowering the refractive index. For example, acrylic resins and urethane resins are generally used. This is possible because of the low refractive index. In addition, compounds in which a fluorine atom is incorporated in a resin, such as a fluororesin, a compound containing a fluororesin in the main species skeleton, and a compound containing a perfluoroalkyl group in a side chain are also included. Examples of inorganic materials include hollow silica particles, fluorine atom-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and hollow particles and nanoporous particles thereof.

The thickness of the surface functional layer 4 is preferably smaller than the height of the unevenness formed by the uneven layer 2 due to phase separation. This is because if the height is equal to or greater than the height of the unevenness, the matting performance due to the unevenness is reduced. The thickness of the surface functional layer 4 depends on the height of the unevenness and cannot be generalized, but is usually 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, further preferably 0.01 to 1 μm. 02 to 0.5 μm, particularly preferably 0.03 to 0.2 μm.
By using it in the above range, it is possible to achieve both the expression of the function of the surface functional layer 4 and the matting property due to the unevenness of the uneven layer 2 due to phase separation.

Regarding the formation of the surface functional layer 4 and the back functional layer 5, which will be described later, the series of compounds described above is used as a solution or dispersion in a solvent, and the base material is a liquid adjusted to have a solid content concentration of about 0.1 to 80% by mass. It is preferred to produce the laminate in the manner of coating on a film. Especially when it is provided by in-line coating, it is more preferable to use an aqueous solution or a water dispersion. A small amount of an organic solvent may be contained in the coating liquid for the purpose of improving dispersibility in water and film-forming properties. In addition, only one type of organic solvent may be used, or two or more types may be used as appropriate.

Methods for forming the surface functional layer 4 and the back functional layer 5 include, for example, gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, Conventionally known coating methods such as squeeze coating, impregnation coating, kiss coating, spray coating, calendar coating and extrusion coating can be used.

Drying and curing conditions for forming the surface functional layer 4 and the back functional layer 5 on the substrate film are not particularly limited, but in the case of the coating method, the water used in the coating liquid may be used. The temperature for drying the solvent is generally 50 to 150°C, preferably 80 to 130°C, more preferably 90 to 120°C. The drying time is in the range of 3 to 200 seconds, preferably 5 to 120 seconds, as a guideline. In addition, in order to improve the strength of the surface functional layer 4 and the back functional layer 5, when performing in the film manufacturing process, heat treatment is usually performed at 150 to 270 ° C., preferably 170 to 230 ° C., more preferably 180 to 210 ° C. It is a process. The time for the heat treatment step is in the range of 3 to 200 seconds, preferably 5 to 120 seconds as a guideline.

"Back functional layer"
A back functional layer 5 may be provided on the opposite side of the uneven layer 2 formed by phase separation to provide various functions. As the back functional layer 5, for example, an adhesive layer for adhering to various adherends, an antistatic layer for preventing defects due to adhesion of surrounding dust due to film separation electrification or frictional electrification, etc. A pressure-sensitive adhesive layer for bonding to the base material of the film, a refractive index adjusting layer for improving the total light transmittance, an anti-blocking layer for reducing blocking of the film, and the like.

Antistatic agents such as those described above can be used to form the antistatic layer, and conventionally known adhesives can be used to form the adhesive layer. Among them, the acrylic type is preferable in consideration of versatility, and the refractive index adjustment layer can use the above-described high refractive index material or low refractive index material.

The thickness of the back functional layer 5 depends on the material used for the back functional layer and the performance to be developed, so it cannot be said unconditionally, but it is, for example, 0.001 to 30 μm. When the back functional layer 5 is an adhesive layer, the thickness is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back functional layer 5 is an antistatic layer, the thickness is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm.

Analysis of components in the primer layer 3, the uneven layer 2 due to phase separation, the surface functional layer 4, and the back functional layer 5 can be performed, for example, by Time-of-Flight Secondary Ion Mass Spectrometry, Analysis can be performed by TOF-SIMS), X-ray photoelectron spectroscopy (Electron Spectroscopy for Chemical Analysis, ESCA), fluorescent X-rays, infrared spectroscopy (IR), and the like.

The haze on the outermost surface of the laminate 10 on the side where the uneven layer 2 is present with respect to the base material layer 1 is not particularly limited as long as the matting property is expressed, but is preferably 0.5 to 99%, and 1 to 1 80% is more preferred, and 2-50% is even more preferred. By using it in the above range, it is easy to obtain good matte properties.
The haze at the outermost surface of the laminate 10 on the side where the uneven layer 2 exists with respect to the base material layer 1 means that the haze is incident from the outermost surface on the side where the uneven layer 2 exists with respect to the base material layer 1 . Percentage of transmitted light that deviates from the incident light by 0.044 rad (2.5°) or more (ratio of diffuse transmittance to total light transmittance) due to forward scattering, among the transmitted light that passes through the JIS K 7136 Measured in compliance.

The 60° specular gloss (60° gloss) of the outermost surface of the laminate 10 on the side where the uneven layer 2 is present with respect to the base material layer 1 is preferably 100 or less, more preferably 80 in consideration of the matting property. Below, more preferably 70 or less. Although there is no particular lower limit, it is preferably 1 or more. By using it in the above range, it is easy to obtain good matte properties.
The 60° specular glossiness is measured according to JIS Z8741. The principle of specular glossiness measurement is to measure the specularly reflected light flux φs from the sample surface with respect to a specified incident angle θ (60° for 60° specular glossiness).

When an antistatic layer is provided as the surface functional layer 4 or the primer layer 3, the antistatic performance is preferably the surface resistance value at the outermost surface of the laminate 10 on the side where the uneven layer 2 is present with respect to the base layer 1. is 1×10 ¹³ Ω or less, more preferably 1×10 ¹² Ω or less, still more preferably 5×10 ¹¹ Ω or less, still more preferably 1×10 ¹¹ Ω or less, and particularly preferably 5×10 ¹⁰ Ω or less. If the thickness is within the above range, adhesion of dust or the like to the outermost surface can be easily suppressed.
The surface resistance value (also referred to as surface resistivity or sheet resistance) of the outermost surface can be adjusted by adjusting the amount of the antistatic agent contained in the antistatic layer.

When an antistatic layer is provided as the back functional layer 5, the antistatic performance is such that the surface resistance value of the outermost surface on the side opposite to the side on which the uneven layer 2 is present with respect to the base material layer 1 is preferably 1 × 10. It is ¹³ Ω or less, more preferably 1×10 ¹² Ω or less, still more preferably 5×10 ¹¹ Ω or less, still more preferably 1×10 ¹¹ Ω or less, and particularly preferably 5×10 ¹⁰ Ω or less. If the surface resistance value is equal to or less than the upper limit value, adhesion of dust or the like to the outermost surface can be easily suppressed.

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

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

(2) Average particle size (d50: μm)
Shimadzu Corp., centrifugal sedimentation type particle size distribution analyzer SA-CP3 model was used to measure the equivalent spherical distribution, and the value of 50% of the integration (weight basis) was taken as the average particle size.

(3) SP value measurement method The SP value was measured by the following method.
Weigh 0.5 g of sample into a 100 ml beaker and add 10 ml of acetone to dissolve the sample. While stirring with a magnetic stirrer, hexane is added dropwise, and the dropwise amount (vh) of hexane at the point where turbidity occurs in the solution (turbidity point) is determined. Next, the drop amount (vd) of deionized water at the turbid point when deionized water is used instead of hexane is determined. From vh and vd, the SP value is obtained from the reference: SUH, CLARKE, J.P. P. S. A-1, 5, 1671-1681 (1967). If the solubility parameter cannot be determined by the above method because the sample does not dissolve in acetone, the method proposed by Fedors et al. Specifically, it is obtained by referring to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pp. 147-154)".

(4) Method for measuring 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

(5) Method for Measuring Viscosity Measured using an E-type viscometer TV-20 manufactured by Toki Sangyo Co., Ltd. at a solid content of 30% by mass and a temperature of 25°C.

(6) Method for measuring acrylic acid consumption rate 0.5 g of the reaction solution is placed in an Erlenmeyer flask and diluted to 10 g with a propylene glycol monomethyl ether solution. To this solution was added 0.1 g of an ethanol solution of phenolphthalein (10%) as an indicator, and a 0.1N ethanolic potassium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added until the solution turned red. ) was added dropwise. The amount of unreacted acrylic acid was quantified from the dropping amount.

(7) Thickness of Primer Layer, Front Functional Layer, and Back Functional Layer The surfaces of the primer layer, front functional layer, and back functional layer were dyed with RuO ₄ and embedded in epoxy resin. After that, the section prepared by the ultrathin section method was stained with RuO ₄ and the cross section of the primer layer or functional layer was measured using a transmission electron microscope (H-7650 manufactured by Hitachi High-Technologies Corporation, acceleration voltage 100 kV).

(8) Method for measuring haze Haze was measured according to JIS K 7136 using a haze meter HM-150 manufactured by Murakami Color Research Laboratory.

(9) Glossiness measurement method The glossiness (gloss) on the outermost surface of the laminate on the side where the uneven layer is present with respect to the base material layer is in accordance with JIS Z 8741, using a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. Measured as 60° specular gloss (60° gloss) using VG2000.

(10) Method for measuring surface resistance value Mitsubishi Chemical Analytech Co., Ltd., using a high resistivity meter: Hiresta MCP-HP450, applied overvoltage 100 V, 23 ° C., 50% RH measurement atmosphere humidity conditioning the sample for 30 minutes. The post-surface resistivity was measured.
A surface resistance value of OVER indicates that the surface resistance value is too high to be measured.
Moreover, when the surface resistance value was UNDER, it was measured by the following method.
Mitsubishi Chemical Analytech Co., Ltd., low resistivity meter: Loresta GP MCP-T610, four-probe ESP probe (probe spacing: 5 mm, probe tip shape: cylindrical with a diameter of 2 mm, probe pressing force: 240 g / piece , the RCF value was kept constant at 4.235), and the surface resistivity of the sample was measured after conditioning the humidity for 30 minutes in a measurement atmosphere of 23° C. and 50% RH.
The resistance value on the surface side (surface resistance value) and the resistance value on the back surface side (back surface resistance value) of the laminate were measured.

(11) Evaluation method for matte property The laminate was installed in a room lit by a white linear fluorescent lamp, and the distance between the fluorescent lamp and the laminate was set to 2.5 m. was evaluated for matting (reflection of fluorescent light). In the evaluations A to C, the matting property can be confirmed.
A: The reflected image of the fluorescent lamp is strongly blurred, and the outline of the fluorescent lamp cannot be confirmed.
B: The reflected image of the fluorescent lamp is blurred, but the outline can be slightly confirmed.
C: The reflected image of the fluorescent light is slightly blurred, and although the outline can be confirmed, it is observed as a wavy shape and appears dark white.
D: The reflected image of the fluorescent lamp is clear and the outline can be clearly confirmed, and the image is linear and appears white.

(12) Evaluation method of adhesion between base material layer and uneven layer 11 × 11 cross-cuts are performed on an area of 10 mm × 10 mm of the uneven layer or the surface functional layer provided thereon, and 24 mm on it. A wide tape (Nichiban Co., Ltd. Cellotape (registered trademark) CT-24) is attached and the peeled surface is observed after rapidly peeling off at a peeling angle of 180 degrees. If the peeling area is less than 5%, A, 5 % or more and less than 30%, C if 30% or more and less than 80%, and D if 80% or more.

(13) Evaluation method of pen writability (antifouling property) Oil-based black marker manufactured by Zebra Co., Ltd. A when repelling ink after writing on the uneven layer or surface functional layer with Mackie fine, but not repelled by the above oil-based marker , Water-Based Yellow Keikote 80 WA-SC-91 manufactured by Tombow Co., Ltd., the case where the ink was repelled was B, and the case where none of the above pens repelled was C.
It should be noted that repelling results in an evaluation of excellent antifouling properties.

(14) Evaluation Method of Adhesiveness When the evaluation surfaces (adhesive layer surfaces) were attached to each other, A was assigned to the case where they were attached by the adhesive strength, and B was assigned to the case where they were not attached.

Polyesters used in Examples and Comparative Examples are as follows.
<Polyester (A)>
A polyethylene terephthalate homopolymer having an intrinsic viscosity of 0.63 dl/g, obtained using magnesium acetate tetrahydrate and tetrabutyl titanate as polymerization catalysts.

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

<Polyester (C)>
A polyethylene terephthalate homopolymer containing 0.3% by mass of silica particles having an average particle size of 2 μm.

Examples of organic solvent-developable compounds that constitute the uneven layer and the functional layer (surface functional layer, back functional layer) are as follows.
(Compound example)
- A polymer containing a hydroxyl group and an unsaturated double bond: (A-1)
Propylene glycol monomethyl ether (157 parts by weight), glycidyl methacrylate (98 parts by weight), methyl methacrylate (1.0 parts by weight), ethyl acrylate (1.0 parts by weight) were placed in a flask equipped with a thermometer, stirrer and reflux condenser. ), mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2′-azobis(2,4-dimethylvaleronitrile) (1.0 parts by mass), γ-trimethoxysilylpropanethiol (Shin-Etsu Chemical Co., Ltd. 1.9 parts by mass of KBM-803 manufactured by Co., Ltd. was added and reacted at 65° C. for 3 hours.
After that, 2,2′-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, then propylene glycol monomethyl ether (138 parts by mass) and p-methoxyphenol ( 0.45 parts by mass) was added and heated to 100°C.
Next, acrylic acid (51 parts by mass) and triphenylphosphine (3.1 parts by mass) are added and reacted at 110° C. for 6 hours to obtain an unsaturated double bond amount (acryloyl equivalent (acryloyl group Amount introduced)) 4.6 mmol/g of (meth)acryloyl copolymer (A-1) was obtained.
The obtained (meth)acryloyl copolymer (A-1) had an SP value of 17.4 and a consumption rate of acrylic acid of 94%. This solution (solid content: 30% by mass) had a viscosity of 100 mPa·s at 25° C. and a weight average molecular weight (Mw) of 17,700.

- A polymer containing an amide group and an unsaturated double bond: (A-2)
Propylene glycol monomethyl ether (360 parts by mass) was added to a 2000 ml separable flask equipped with a thermometer, stirrer and reflux condenser. On the other hand, glycidyl methacrylate (180 parts by mass), acryloylmorpholine (180 parts by mass), propylene glycol monomethyl ether (180 parts by mass), 2,2′-azobis(2,4-dimethylvaleronitrile) (1 .8 parts by mass) was added to prepare a monomer solution.
After that, the stirrer of the separable flask was started, and then nitrogen gas was introduced into the separable flask and graduated cylinder at a flow rate of 300 ml/min for about 1 hour.
Next, the separable flask was immersed in an oil bath and heated to an internal temperature of 65°C. Then, the monomer solution prepared in the graduated cylinder was pumped into the separable flask and added dropwise over 2 hours to carry out radical polymerization. After the dropwise addition was completed, stirring was continued for 2 hours at an internal temperature of 65°C, and then 2,2'-azobis(2,4-dimethylvaleronitrile) (0.9 parts by mass) was further added and reacted for 3 hours. , propylene glycol monomethyl ether (259 parts by mass) and p-methoxyphenol (1.6 parts by mass) were added and heated to 100°C.
Next, acrylic acid (93 parts by mass) and triphenylphosphine (6.8 parts by mass) are added and reacted at 110° C. for 6 hours to give an unsaturated double bond having an amide group and an unsaturated double bond. A (meth)acryloyl copolymer (A-2) having a double bond content (acryloyl equivalent (amount of acryloyl groups introduced)) of 2.8 mmol/g was obtained.
The obtained (meth)acryloyl copolymer (A-2) had an SP value of 19.1 and a consumption rate of acrylic acid of 93%. This solution (solid content: 30% by mass) had a viscosity of 1,050 mPa·s and a weight average molecular weight (Mw) of 22,500 at 25°C.

・(Meth)acrylate: (B-1)
Dipentaerythritol hexaacrylate (SP value: 12.1)/(meth)acrylate: (B-2)
Urethane acrylate U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd. (SP value: 13.3)
・(Meth)acrylate: (B-3)
Pentaerythritol triacrylate succinic acid monoester

・Acrylic resin: (C)
Mitsubishi Chemical Corporation BR-80 (acrylic copolymer) (SP value: 13.4)

- Silicone compound: (D-1)
A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with a one-end methacryloyl group-substituted polydimethylsiloxane having a number average molecular weight (Mn) of 5000 (manufactured by JNC Co., Ltd. "Silaplane FM0721", a silicone-containing (meth)acrylate compound. ) (20 parts by mass), glycidyl methacrylate (60 parts by mass), methyl methacrylate (10 parts by mass), stearyl methacrylate (10 parts by mass), and methyl isobutyl ketone (MIBK) (151 parts by mass) were charged, and after stirring was started, the system was was replaced with nitrogen, the temperature was raised to 55° C., and 2,2′-azobis(2,4-dimethylvaleronitrile) (1.2 parts by mass) and 1-dodecanethiol (0.9 parts by mass) were added. After that, the inside of the system was heated to 65°C and stirred for 3 hours. Stirred for an hour. After heating the inside of the system to 100° C. and stirring for 30 minutes, 163 parts by mass of MIBK was added, and the inside of the system was heated to 100° C. again. After adding p-methoxyphenol (0.5 parts by mass) and triphenylphosphine (2.6 parts by mass) thereto, acrylic acid (31 parts by mass) was added, the temperature was raised to 110 ° C. and stirred for 6 hours. did. After cooling, 4.8 parts by mass of MIBK was added to obtain a MIBK solution of copolymer (D-1) having a number average molecular weight (Mn) of 6,500.

- Fluorine compound: (D-2)
Shin-Etsu Subelyn (registered trademark) KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd.

- Quaternary ammonium compound: (E)
A reactor equipped with a stirrer, a reflux condenser, and a thermometer was charged with N,N-dimethylaminoethyl methacrylate quaternary (66 parts by mass), N,N-dimethylaminoethyl methacrylate (20 parts by mass), 2- Ethylhexyl methacrylate (30 parts by mass), azobisisobutyronitrile (1 part by mass), isopropyl alcohol (200 parts by mass) and methyl ethyl ketone (100 parts by mass) were charged. The mixture was heated and reacted for 8 hours to obtain a solution of copolymer (E).

- Photopolymerization initiator: (F-1)
IGM Resins B.I. V. Company Omnirad 127 Photopolymerization initiator: (F-2)
IGM Resins B.I. V. Company Omnirad 184

Examples of water-based spreading compounds that constitute the primer layer and the functional layer (surface functional layer, back functional layer) are as follows.
(Compound example)

・Polyester resin: (IA)
Aqueous dispersion of polyester resin having the following composition Monomer composition: (acid component) terephthalic acid/isophthalic acid/5-sodium sulfoisophthalic acid // (diol component) ethylene glycol/1,4-butanediol/diethylene glycol = 56/ 40/4//70/20/10 (mol%)

・Acrylic resin: (IB)
Aqueous dispersion of acrylic resin having the following composition Ethyl acrylate/N-butyl methacrylate/Acrylic acid = 25/73/2 (mass%)

・Polyvinyl alcohol: (IC)
Polyvinyl alcohol with a degree of saponification of 88 mol% and a degree of polymerization of 500

· Melamine compound: (IIA) hexamethoxymethylol melamine · oxazoline compound: (IIB)
Acrylic polymer having an oxazoline group and a polyalkylene oxide chain Epocross (oxazoline group weight = 4.5 mmol/g, manufactured by Nippon Shokubai Co., Ltd.) Epoxy compound: (IIC) polyglycerol polyglycidyl ether, which is a polyfunctional polyepoxy compound

Particles: (III) silica particles with an average particle size of 0.07 μm

- Antistatic agent (compound having an ammonium group): (IVA)
A polymer having a pyrrolidinium ring in the main chain and having the following composition: diallyldimethylammonium chloride/dimethylacrylamide/N-methylolacrylamide = 90/5/5 (mol%), number average molecular weight (Mn) 30,000

· Antistatic agent (conductive organic polymer compound): (IVB)
Conductive organic polymer compound composed of poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid

・Acrylic resin: (V)
Aqueous dispersion of acrylic resin having the following composition: 2-ethylhexyl acrylate/methyl methacrylate/methacrylic acid = 85/12/3 (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, respectively, 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, are used as raw materials for the intermediate layer, and each is supplied to two extruders. An unstretched sheet was obtained by co-extrusion in a layer structure of two kinds and three layers (discharge amount of surface layer/intermediate layer/surface layer=1:8:1) and solidification by cooling.
Next, after stretching 3.1 times in the longitudinal direction at a film temperature of 85 ° C. using the roll peripheral speed difference, coating liquid P1 shown in Table 2 below is applied to one side of this longitudinally stretched film, and guided to a tenter. After drying at 95° C. for 10 seconds, the film was stretched 4.2 times in the transverse direction at 120° C., heat-treated at 230° C. for 10 seconds, relaxed 2% in the transverse direction, and had a thickness (after drying) of 0.5. A 50 μm thick polyester film with a 1 μm primer layer was obtained.

Coating solution S1 shown in Table 1 below was applied to the primer layer of the obtained polyester film, dried at 70° C. for 1 minute, and exposed to light of 250 mJ/cm ² from a high-pressure mercury lamp on the coating film composed of coating solution S1. Irradiation caused the components of the coating to phase separate to form a textured layer with a thickness (after drying) of 5 μm.

Next, a coating solution F1 shown in Table 1 below was applied onto the uneven layer, dried at 80° C. for 1 minute, and a coating film made of the coating solution F1 was irradiated with light of 250 mJ/cm ² from a high-pressure mercury lamp. A functional layer having a thickness (after drying) of 0.5 μm was formed.

The resulting laminate gave good results in matting and antifouling tests based on pen writability.
The properties of this laminate are shown in Table 3 below.

[Examples 2 to 13]
A laminate was obtained in the same manner as in Example 1, except that the composition of the coating agent in Example 1 was changed to that shown in Tables 1 and 2. The properties of the obtained laminate are shown in Table 3 below.

[Example 14]
In Example 1, after obtaining an unstretched sheet, it was stretched 3.1 times in the longitudinal direction at a film temperature of 85 ° C. using a roll peripheral speed difference, and then on both sides of this longitudinally stretched film, A polyester film was obtained in the same manner except that the coating liquid P4 was applied. After that, in the same manner as in Example 1, an uneven layer was formed. The resulting laminate exhibited antistatic performance functions on the back side. The properties of this laminated film are shown in Table 3 below.

[Example 15]
A laminate was obtained in the same manner as in Example 14, except that the composition of the coating agent in Example 14 was changed to that shown in Tables 1 and 2. The properties of the obtained laminate are shown in Table 3 below.

[Example 16]
Coating solution F8 shown in Table 2 was applied to the back surface of the polyester film opposite to the uneven layer of the laminate obtained in Example 2 and dried to form a functional layer having adhesive properties. The properties of this laminate are shown in Table 3 below.

[Examples 17 and 18]
A coating liquid shown in Tables 1 and 2 below was formed in the same manner as in Example 1 on Acryprene HBS 50 μm manufactured by Mitsubishi Chemical Corporation. The properties of this laminate are shown in Table 3 below.

[Comparative Examples 1 and 2]
A laminate was obtained in the same manner as in Example 1, except that the primer layer and the functional layer were not provided in Example 1, and the uneven layer provided by phase separation was provided. When the resulting laminate was evaluated, as shown in Table 3 below, it had no adhesion to the substrate layer, antifouling properties, or antistatic properties, and no function other than that of the uneven layer was observed.

[Comparative Example 3]
A film was obtained in the same manner as in Example 1, except that the primer layer, uneven layer and functional layer were not provided. As shown in Table 3 below, the resulting film did not exhibit any matte properties.

REFERENCE SIGNS LIST 1 base material layer 2 uneven layer 3 primer layer 4 surface functional layer 5 back functional layer 10 laminate

Claims (22)

having a substrate layer and an uneven layer having unevenness due to phase separation provided on one surface of the substrate layer;
Furthermore, a primer layer provided between the substrate layer and the uneven layer, a surface functional layer provided on the surface of the uneven layer opposite to the substrate layer side, and Having one or more layers selected from the group consisting of a back functional layer provided on the surface opposite to the uneven layer side, having an antistatic layer as the surface functional layer or the primer layer, A laminate having a surface resistance value of 2×10 ¹⁰ Ω or less on the outermost surface of the substrate layer on the side where the uneven layer is present. 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 correcting layer, and the back functional layer is an adhesive layer, an antistatic layer, or a refractive index adjusting layer. A laminate according to claim 1, which is a layer or an anti-blocking layer. 3. The laminate according to claim 1, wherein the surface functional layer has a thickness of 0.001 to 3 μm, and the back functional layer has a thickness of 0.001 to 30 μm. 4. The laminate according to any one of claims 1 to 3, wherein the haze of the outermost surface of the substrate layer on the side where the uneven layer is present is 0.5 to 99%. 5. The laminate according to any one of claims 1 to 4, wherein the outermost surface of the substrate layer on which the uneven layer exists has a 60° specular gloss of 100 or less. Claims 1 to 1, wherein an antistatic layer is provided as the surface functional layer or the primer layer, and the surface resistance value of the outermost surface on the side of the substrate layer on which the uneven layer is present is 1 × 10 ¹³ Ω. 6. The laminate according to any one of 5. 2. The back surface functional layer has an antistatic layer, and the surface resistance of the outermost surface of the substrate layer on the side opposite to the uneven layer is 1×10 ¹³ Ω or less. 7. The laminate according to any one of items 1 to 6. The uneven layer contains a compound (X) containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate group, and a thiol group, and a compound (Y ), which is a cured product of a composition containing the laminate according to any one of claims 1 to 7. 9. The laminate according to claim 8, wherein the compound (X) has an SP value of 15.1 or more, and the compound (Y) has an SP value of 15.0 or less. 10. The laminate according to claim 8, wherein (X):(Y), which represents the mass ratio of the compound (X) and the compound (Y) in the uneven layer, is 10:90 to 80:20. The laminate according to any one of claims 1 to 10, wherein the uneven layer has a thickness of 1 to 10 µm. The laminate according to any one of claims 1 to 11, wherein the base layer has a thickness of 2 to 350 µm. The laminate according to any one of claims 1 to 12, wherein the substrate layer is a substrate selected from polyester film, polyacrylate film, polyolefin film, polycarbonate film, polyimide film and triacetylcellulose film. The laminate according to any one of claims 1 to 13, wherein the primer layer contains a resin. The laminate according to any one of claims 1 to 14, wherein the primer layer contains a compound derived from a cross-linking agent. The laminate according to any one of claims 1 to 15, wherein the primer layer contains an antistatic agent. The laminate according to any one of claims 8 to 16, wherein the compound (X) is a polymer compound. The laminate according to any one of claims 8 to 17, wherein the compound (X) is at least one selected from (meth)acrylic polymers, polyvinyl alcohols and celluloses. 19. The laminate according to claim 18, wherein the (meth)acrylic polymer is obtained by reacting an epoxy group with a carboxylic acid. The laminate according to any one of claims 8 to 19, wherein the compound (X) contains a carbon-carbon unsaturated bond. The laminate according to any one of claims 8 to 20, wherein the compound (Y) is a (meth)acrylic polymer. The laminate according to any one of claims 8 to 20, wherein the compound (Y) is a (meth)acrylate.

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