WO2023120634A1 - Laminated film and film laminate - Google Patents

Abstract

Provided is a laminated film comprising a cured resin layer on one surface of a substrate film (A), wherein: the cured resin layer has an uneven structure; the arithmetic mean height (Sa) of the surface of the cured resin layer is at least 500 nm; and, in a distribution curve obtained from a surface profile obtained from a surface observation of the cured resin layer by a white light interference microscope, where the horizontal axis is the protrusion height (X) and the vertical axis is the common logarithmic value log(Y) of the number (Y) of protrusions, the cured resin layer satisfies formula (1). (In the formula, log(Y)max represents the value where the common logarithm of the number of protrusions is at a maximum and Xmax represents the positive protrusion height when the common logarithm of the number of protrusions is at a maximum. Also, log(Y)85% represents the value where the common logarithm of the number of protrusions is 85% of the maximum value and X85% represents the positive protrusion height when the common logarithm of the number of protrusions is 85% of the maximum value.)

Description

Laminated films and film laminates

The present invention relates to laminated films and film laminates.

Conventionally, polyester films, especially polyethylene terephthalate films and polyethylene naphthalate films, have excellent mechanical properties, heat resistance, and chemical resistance. It is used for various purposes such as optical use such as display constituent members such as bull displays, bendable displays, and rollable displays, touch panels, anti-reflection, and anti-scattering of glass.

These polyester films, which are used in a wide range of applications, can be used to protect adhesive layers such as glass and steel plates that are mainly used outdoors in buildings, automobiles, trains, and airplanes.

When bonding a substrate film with an adhesive layer to an adherend such as glass or an automobile body, it is possible to visually check if air or moisture remains at the interface between the adhesive layer and the adherend after bonding. Poor appearance due to the generation of bubbles as small as several hundred microns, or reduction in adhesive force due to residual moisture may occur.

Therefore, as a countermeasure, water or an aqueous solution containing a surfactant is sprayed on the surface of the adhesive layer in advance, and a squeegee is used to remove water or debub. I was in a state of restraint.

Under such circumstances, for the purpose of forming fine grooves on the surface of the adhesive to allow the fluid to flow out at the adhesive interface, a fine embossed pattern composed of a large number of interconnecting linear protrusions was developed. A release liner having a surface has been proposed (Patent Document 1). In addition, as a pressure-sensitive adhesive sheet having excellent air release properties that can easily remove air pockets that may occur when it is attached to an adherend and also having good adhesiveness, a resin layer is formed on a substrate or a release material. A pressure-sensitive adhesive sheet has been proposed in which the surface of the resin layer on the side opposite to the base material or the release agent has adhesiveness and irregular shaped recesses are present on the surface (Patent Document 2). Furthermore, a paint film protective film for automobiles having a pressure-sensitive removable adhesive layer on the vehicle body surface side, a plastic film on the outside, and a surface center line average roughness (Ra) of 0.1 to 100 μm has been proposed. (Patent Document 3).

JP-A-2006-70273 WO2015/152352 JP-A-7-89468

Regarding the above-mentioned "wet sticking" method, skillful technique is required for the process of removing water or bubbles using a squeegee. With the expansion of the market for PPF (paint protection film) applications for wrapping applications and automobile paint protection, for example, when laminating a large area adhesive film of 1 m ² or more to an adherend, uniform It was becoming more and more difficult to laminate. In addition, it is also necessary to suppress air pockets that may occur during attachment to the adherend during attachment by water attachment.
In addition, the techniques disclosed in Patent Documents 1 to 3 are insufficient in terms of removing moisture or foam residue, or "air retention" generated during application to an adherend (air removal).
The present invention has been made in view of the above circumstances, and the problem to be solved is to provide a laminated film and a film laminate that are suitable for use in transferring uneven shapes to adherends.

As a result of intensive studies in view of the actual situation, the inventors found that the above problems can be easily solved by using a laminated film having a specific configuration, and have completed the present invention.

That is, the gist of the present invention provides the following [1] to [31].

[1] A cured resin layer is provided on one side of the base film (A), the cured resin layer has an uneven structure, the surface of the cured resin layer has an arithmetic mean height (Sa) of 500 nm or more, and is white. The horizontal axis is the projection height (X) and the vertical axis is the common logarithm value log(Y) of the number of projections (Y) obtained from the surface profile obtained by observing the surface of the cured resin layer with an interference microscope. A laminated film in which the cured resin layer satisfies the following formula (1) in the distribution curve.

[In the formula, log(Y)max indicates a value at which the common logarithm of the number of protrusions is maximized, and Xmax indicates a positive protrusion height when the common logarithm of the number of protrusions is maximized. log (Y) 85% indicates the value at which the common logarithm of the number of protrusions is 85% of the maximum value, and X85% is the positive protrusion height when the common logarithm of the number of protrusions is 85% of the maximum value. show. "Positive protrusion height" means, in the distribution curve, of the protrusions seen from the reference plane obtained from the height measured at each measurement point, the substrate film (A) side is a recess, and the recess is opposite. is defined as a convex portion, and means the projection height of the convex portion. ]
[2] The laminated film according to [1] above, wherein the cured resin layer satisfies the following formula (2) in the distribution curve.

[Wherein, Xmin indicates a positive protrusion height at which the number of protrusions is 0, log (Y) 85% indicates a value at which the common logarithm of the number of protrusions is 85% of the maximum value, and X85% is the protrusion A positive protrusion height is indicated when the common logarithm of the number is 85% of the maximum value. "Positive protrusion height" is as described above. ]
[3] The cured resin layer has a difference (Ah) between the height of positive projections and the height of negative projections when the number of projections is 85% of the maximum value in the distribution curve is 4 μm or more, and the number of projections The difference (Bh) between the height of the positive protrusion and the height of the negative protrusion when is 20% of the maximum value is 7 μm or more, and the following formula (3) is satisfied, and laminated to the above [1] or [2] the film.

In addition, "positive protrusion height" and "negative protrusion height" are obtained from heights measured at each measurement point when observed with a white light interference microscope (white light interferometer) in the distribution curve. Among the protrusions viewed from the reference surface, the base film (A) side is a recess, the opposite side of the recess is a protrusion, the protrusion height of the protrusion is a positive protrusion height, and the protrusion height of the recess is a positive protrusion height. Negative projection height.
[4] The laminated film according to any one of [1] to [3] above, wherein the cured resin layer is a cured product of a cured resin composition containing (meth)acrylate.
[5] A cured resin layer is provided on one side of the substrate film (A), the cured resin layer has an uneven structure, and the cured resin layer is a cured product of a cured resin composition containing (meth)acrylate. and the surface of the cured resin layer has an arithmetic mean height (Sa) of 500 nm or more.
[6] The laminated film according to [5] above, wherein the (meth)acrylate is a cured product of a curable resin composition containing a urethane-based (meth)acrylate and a trifunctional or higher (meth)acrylate.
[7] The laminated film according to [5] above, wherein the curable resin composition contains 50% by mass or less of a urethane-based (meth)acrylate and 25% by mass or more of a trifunctional or higher (meth)acrylate.
[8] The laminated film according to [6] or [7] above, wherein the curable resin composition contains two or more types of tri- or more functional (meth)acrylates.
[9] The laminated film according to any one of [1] to [8] above, wherein the cured resin layer further contains particles, and the particle content is 9% by mass or less.
[10] The laminated film as described in any one of [1] to [9] above, wherein the base film (A) is a polyester film.
[11] The laminated film according to any one of [1] to [10] above, wherein the base film (A) contains particles in a layer in contact with the cured resin layer.
[12] The laminated film according to [11] above, wherein the particles have an average particle diameter of 1 to 10 μm.
[13] The laminate according to any one of [1] to [12] above, wherein the arithmetic mean height (Sa) of the substrate film (A) on the side where the cured resin layer is formed is 5 nm or more. the film.
[14] The laminated film as described in any one of [1] to [13] above, wherein the base film (A) has a single-layer structure.
[15] The laminated film as described in any one of [1] to [13] above, wherein the base film (A) has a multi-layered structure consisting of at least two layers.
[16] The laminated film according to any one of [1] to [15] above, wherein the maximum peak height (Sp) of the surface of the cured resin layer is 10000 nm or more.
[17] The laminated film according to any one of [1] to [16] above, wherein the cured resin layer surface has a glossiness of 10% or less at 60 degrees.
[18] The laminated film as described in any one of [1] to [17] above, wherein the surface of the cured resin layer has a glossiness of 15% or less at 85 degrees.
[19] A method for producing the laminated film according to any one of [1] to [18] above, comprising the step of forming the cured resin layer by excimer lamp irradiation or ultraviolet (UV) irradiation. ,Production method.
[20] A release film comprising a cured resin layer of the laminated film according to any one of [1] to [18] above, and a release layer on the cured resin layer.
[21] The release film of [20] above, wherein the release layer contains at least one release agent selected from the group consisting of silicone compounds, melamine compounds, fluorine compounds, waxes and long-chain alkyl compounds. .
[22] A film laminate comprising the release film of [20] or [21] above and an adhesive layer on the release layer surface of the release film.
[23] A film laminate comprising the laminated film according to any one of [1] to [18] above and an adhesive layer on the surface of the cured resin layer of the laminated film.
[24] A transferred product obtained by transferring the unevenness of the surface of the cured resin layer of the laminated film according to any one of [1] to [18] above.
[25] A transfer product obtained by transferring the unevenness of the surface of the release layer of the release film of [20] or [21] above.
[26] The film laminate according to [22] or [23] above, wherein the adhesive layer is at least one selected from the group consisting of an acrylic adhesive layer, a urethane adhesive layer, and a silicone adhesive layer.
[27] The laminated film according to any one of [1] to [18] above, which is for protecting an adhesive layer.
[28] The release film according to the above [20] or [21], which is for protecting an adhesive layer.
[29] The laminated film according to any one of [1] to [18] and [27] above, which is used for automobile paint protection or wrapping film.
[30] The release film of any one of the above [20], [21] and [28], which is used for automobile paint protection or wrapping film.
[31] The film laminate according to [22] or [23] above, which is used for automobile paint protection or wrapping film.

ADVANTAGE OF THE INVENTION According to this invention, the laminated|multilayer film and film laminate which are suitable for the use which transfers uneven|corrugated shape to an adherend can be provided.
Specifically, a laminated film and a film laminate that are easy to cut into single sheets without water or bubble residue or air retention during lamination as much as possible when laminating to an adherend by water lamination or the like. can be provided, and its industrial value is high. It is particularly suitable for automobile coating or wrapping film.

2 is a bird's-eye view of the surface of the cured resin layer of the laminated film obtained in Example 1. FIG. 3 is a bird's-eye view of the surface of the cured resin layer of the laminated film obtained in Example 3. FIG. 3 is a bird's-eye view of the surface of the cured resin layer of the laminated film obtained in Comparative Example 1. FIG. 3 is a bird's-eye view of the surface of the cured resin layer of the laminated film obtained in Comparative Example 4. FIG. The figure which shows the state of a positive protrusion and a negative protrusion in a three-dimensional bird's-eye view. 4 is a distribution curve showing the relationship between the protrusion height and the number of protrusions of the laminated film obtained in Example 1. FIG. 4 is a distribution curve showing the relationship between the protrusion height and the number of protrusions of the laminated film obtained in Example 3. FIG. 4 is a distribution curve showing the relationship between the protrusion height and the number of protrusions of the laminated film obtained in Comparative Example 1. FIG. 4 is a distribution curve showing the relationship between the protrusion height and the number of protrusions of the laminated film obtained in Comparative Example 4. FIG.

The laminated film of the present invention comprises a cured resin layer having an uneven structure on one side of the base film (A). Each component will be described in detail below.

[Base film (A)]
A resin film is exemplified as the base film.
For example, polyethylene, polypropylene, cycloolefin polymer (COP), polyester, polystyrene, acrylic resin, polycarbonate, polyurethane, triacetylcellulose (TAC), polyvinyl chloride, polyethersulfone, polyamide, polyimide, polyamideimide, etc. A resin film formed into a shape can be mentioned. A mixture of these materials (polymer blend) or a composite of structural units (copolymer) may be used as long as they can be formed into a film.

Among the films exemplified above, polyester films are particularly preferable because of their superior physical properties such as heat resistance, flatness, optical properties, and strength. The substrate film (A), for example, a polyester film, may have a single-layer structure or a multilayer structure, and may have a 4-layer or more structure in addition to the 2-layer or 3-layer structure as long as the gist of the present invention is not exceeded. It may be multi-layered and is not particularly limited. It is preferable that the substrate film (A) has a multi-layered structure of at least two layers, and each layer has its own characteristic to achieve multi-functionality.

The polyester used for the polyester film can be obtained by polycondensing a dicarboxylic acid and a diol, and among them, those obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol are preferable. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like. Aliphatic glycols include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol and the like. Aliphatic glycols may be cycloaliphatic glycols such as 1,4-cyclohexanedimethanol.

Typical polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalene dicarboxylate (PEN), polybutylene terephthalate and the like. Such polyesters may be homopolymers that are not copolymerized. Alternatively, it may be a copolymer polyester in which 30 mol % or less of the dicarboxylic acid component is a dicarboxylic acid component other than the main component and/or 30 mol % or less of the diol component is a diol component other than the main component. . For example, polyethylene terephthalate has dicarboxylic acid units other than terephthalic acid in about 30 mol% or less of 100 mol% of dicarboxylic acid units, and ethylene glycol in about 30 mol% or less of 100 mol% of diol units. It may be a copolymer polyester having a diol unit other than the above.
The polyester may also be a mixture of homopolymer and copolyesters.

Although the intrinsic viscosity of the polyester is not particularly limited, it is preferably 0.45 to 1.0 dL/g, more preferably 0.5 to 0.9 dL/g, from the viewpoint of film-forming properties and productivity.

The polyester can be obtained by a conventionally known method, for example, by reacting a dicarboxylic acid and a diol to directly obtain a polyester with a low degree of polymerization, or by reacting a lower alkyl ester of a dicarboxylic acid and a diol with a conventionally known transesterification catalyst. , can be obtained by a method of performing a polymerization reaction in the presence of a polymerization catalyst.
As the polymerization catalyst, known catalysts such as antimony compounds, germanium compounds and titanium compounds may be used, but catalysts other than antimony compounds are preferably used. Alternatively, when an antimony compound is used, it is preferable to set the amount of the antimony compound to 100 ppm or less in terms of antimony element, since dullness of the film can be further reduced.

In addition, when a titanium compound is used as a catalyst, the amount of titanium used can be reduced due to the high activity of titanium, so the amount of metal remaining in the film is small. is preferable from the viewpoint of

In the laminated film of the present invention, the cured resin layer, which will be described later, needs to satisfy specific parameters for its surface roughness. Although the method of satisfying the specific parameters is not particularly limited, for example, inclusion of particles in the base film can be mentioned.
In the base film, the height of protrusions on the surface of the cured resin layer ( It is preferable to blend the particles so that X) and the number of projections (Y) satisfy formula (1) described later.
The type of particles to be blended is not particularly limited as long as the particles can impart the above properties. Examples include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, oxide Inorganic particles such as titanium, and organic particles such as (meth)acrylic resins, styrene resins, urea resins, phenol resins, epoxy resins, and benzoguanamine resins.
Furthermore, when the substrate film is a polyester film, precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester manufacturing process can be used.
Among these, silica particles, calcium carbonate particles, and (meth)acrylic resin particles are preferable because they are particularly effective even in small amounts.

The shape of the particles to be used is also not particularly limited, and any of spherical, massive, rod-like, flattened, etc. may be used. Its hardness, specific gravity, color and the like are not particularly limited. One type of these series of particles may be used alone, or two or more types may be used in combination as necessary.

The average particle diameter of the particles to be used is determined to remove water or bubbles, or, as will be described later, in an embodiment in which the laminated film of the present invention has an adhesive layer, to improve the effect of removing air during lamination with an adherend. Furthermore, it is preferably in the range of 1 to 10 μm, more preferably in the range of 1 to 8 μm, still more preferably in the range of 2 to 6 μm, and particularly preferably in the range of 2 to 5 μm.

In the case of a single-layer film, the content of particles in the substrate film is preferably in the range of 0.1 to 10% by mass with respect to the total polyester constituting the film. When the content of the particles is 0.1% by mass or more, water is removed or bubbles are removed, or air is removed during lamination with an adherend in an embodiment in which the laminated film of the present invention includes an adhesive layer, as described later. A sufficient punching effect is obtained, and the productivity of the base film is ensured when the content is 10% by mass or less. From the above viewpoints, the content of the particles in the substrate film is more preferably 0.3 to 10% by mass, still more preferably 0.4 to 10% by mass, still more preferably 0.4 to 8% by mass, Especially preferably, it is in the range of 2 to 7% by mass.

Moreover, when the substrate film is a multilayer film, the surface layer may contain particles having a predetermined content and particle size. For example, when the base film is a polyester film, by using a polyester film having a polyester layer containing particles only on the surface layer, it is possible to form sufficient unevenness, and the addition of particles reduces productivity. can be avoided. In any case, the particles should be contained in the layer in contact with the cured resin layer.
That is, in the laminated film of the present invention, the base film removes water or bubbles from the surface layer on the side in contact with the cured resin layer, or as described later, in the aspect in which the laminated film of the present invention includes an adhesive layer, The content of the particles is preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass, from the viewpoint of the productivity of the base film while imparting a sufficient effect of air release during lamination with the adherend. is in the range of 0.3 to 10% by mass, more preferably 0.4 to 10% by mass, even more preferably 0.4 to 8% by mass, and particularly preferably 2 to 7% by mass.
The average particle size of the particles is the same as that of the single layer described above.

The method of adding particles to the substrate film is not particularly limited, and conventionally known methods can be employed. For example, when the base film is a polyester film, it can be added at any stage of polyester production, but preferably at the stage of esterification or after the completion of transesterification, the particles are added and polycondensed. The reaction may proceed.
Alternatively, a kneading extruder with a vent is used to blend a slurry of particles dispersed in ethylene glycol or water with a polyester raw material, or a kneading extruder is used to mix dried particles with a polyester raw material. It is carried out by a method such as blending.

In addition to the particles described above, the base film may optionally contain conventionally known antioxidants, heat stabilizers, lubricants, antistatic agents, fluorescent whitening agents, dyes, fillers (inorganic fillers or organic fillers). fillers), pigments and the like can be added. In addition, depending on the purpose such as ultraviolet protection film base material, use of glass to be protected, prevention of coating film deterioration of body such as steel plate, etc., an ultraviolet absorber, particularly a benzoxazinone-based ultraviolet absorber, etc. may be contained.

From the viewpoint of using the laminated film of the present invention as a release film, the thickness of the base film is preferably in the range of 20 to 350 μm, more preferably 20 to 250 μm, still more preferably 25 to 125 μm, particularly preferably It is in the range from 25 to 100 μm, particularly preferably from 25 to 60 μm.
In addition, when the base film has a multilayer structure, the total thickness shall be within the above range.

The polyester film can be made into a laminated structure using various conventionally known methods such as coextrusion. In this case, the thickness of the outermost layer is preferably 2 μm or more, more preferably 3 μm or more, and is preferably ⅛ or less of the total thickness, as the thickness of only one side. By setting it to the above range, as described above, it is possible to produce a polyester film having a polyester layer containing particles only on the surface layer, to enable sufficient unevenness formation, and to avoid a decrease in productivity due to particles. It becomes possible.

In the laminated film, the arithmetic mean height (Sa) of the surface of the substrate film on which the cured resin layer is formed is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 100 nm or more, particularly preferably 400 nm or more. It is preferably 600 nm or more. By setting the surface roughness of the polyester film in contact with the lower portion of the cured resin layer to the above numerical value or more, it becomes easier to obtain more suitable performance as the laminated film of the present invention.

Hereinafter, the manufacturing method when the base film (A) is a polyester film will be specifically described, but the present invention is not particularly limited to the following examples as long as the gist of the present invention is satisfied.
In general, undried or dried polyester chips are first supplied to a melt extruder and heated to a temperature above the melting point of the respective polymer to melt them by known techniques. The molten polymer is then extruded through a die and quench solidified on a rotating cooling drum to a temperature below the glass transition temperature to provide an unoriented sheet in a substantially amorphous state. In this case, in order to improve the flatness of the sheet, it is preferable to increase the adhesion between the sheet and the rotating cooling drum.

From the viewpoint of film strength, it is preferable to biaxially stretch the sheet obtained as described above to form a film. Specifically, the unstretched sheet is stretched in the longitudinal direction (machine direction) at 70 to 145° C., preferably 80 to 120° C., by a factor of 2.0 to 4.5, preferably 3.0. The film is stretched at a draw ratio of up to 4.0 times to obtain a uniaxially stretched film.
Then, it is stretched in the transverse direction (width direction), which is perpendicular to the machine direction (machine direction), at a draw ratio of 3.0 to 6.5 times, 3.5 to 6.0 times at 90 to 160 ° C. to obtain a biaxially stretched film.
Subsequently, heat treatment (heat setting) is preferably performed at 210 to 260° C. under tension or under relaxation within 30% for 10 to 600 seconds. A method of relaxing 1 to 10% in the longitudinal direction and/or the transverse direction in the highest temperature zone of the heat treatment and/or the cooling zone at the exit of the heat treatment is preferred.
The longitudinal direction (machine direction) of the film refers to the direction in which the film advances in the film manufacturing process, that is, the winding direction of the film roll. The lateral direction (width direction) refers to a direction parallel to the film surface and perpendicular to the longitudinal direction, that is, a direction parallel to the central axis of the film roll.

In particular, when it is used in applications where it is desired to keep the heat shrinkage small, the heat treatment temperature is preferably 215 to 250°C, more preferably 220 to 245°C, and even more preferably 230 to 245°C. By setting the heat treatment temperature within the above temperature range, the heat shrinkage rate can be suppressed as much as possible.

In particular, the laminated film of the present invention is suitable for protecting the adhesive layer used mainly for glass, steel plates, etc. used outdoors, such as for automobiles, signboards, solar power generation, road signs and road-related members such as sound insulation walls. be.

[Cured resin layer]
The laminated film of the present invention comprises a cured resin layer on one side of the substrate film (A).
The cured resin composition forming the cured resin layer preferably contains an active energy ray-curable compound.

By irradiating the curable resin composition with active energy rays, the surface side of the cured resin layer (the coating film when the cured resin layer is formed by coating) formed from the curable resin composition is first cured to form a cured film. is formed. After that, when the inside of the cured resin layer (coating film) is cured, the cured resin layer (cured coating film) on the surface side buckles to form a cured film having unevenness on the surface.
The cured resin layer composition can further contain an organic solvent, if necessary.
The cured resin layer composition may further contain components other than those described above, if necessary.

(Meth)acrylates are suitable as active energy ray-curable compounds. That is, in one aspect of the present invention, the cured resin layer is preferably a cured product of a cured resin composition containing (meth)acrylate.
In addition, in this specification, when the description of "(meth)acrylate" is used, it means one or both of "acrylate" and "methacrylate". Similarly, the description "(meth)acrylic acid" means one or both of "acrylic acid" and "methacrylic acid", and the description "(meth)acryloyl" refers to "acryloyl" and "methacryloyl". either or both.

(Meth) acrylate is not particularly limited, monofunctional (meth) acrylate, bifunctional (meth) acrylate, one of polyfunctional (meth) acrylate, or a mixture of two or more thereof, curable resin It is possible to use those commercially available as materials, or those to which other components are further added as long as the purpose of the present embodiment is not impaired.
Among these, monofunctional or bifunctional (meth)acrylates are preferable from the viewpoint of facilitating the formation of a steep concave-convex structure. Bifunctional (meth)acrylates are more preferred for applications that require scratch resistance. The use of polyfunctional (meth)acrylate is preferable in terms of improving scratch resistance and hardness, but depending on the compound used, it may be difficult to form an uneven structure. be careful.
For example, when a urethane-based (meth)acrylate is used as the polyfunctional (meth)acrylate, the amount of the urethane-based (meth)acrylate in 100% by mass of the (meth)acrylate resin contained in the cured resin layer is Although it varies depending on the resin composition of the resin layer, when it is preferably 50% by mass or less, more preferably 30% by mass or less, the surface of the cured resin layer is moderately easy to deform, and the desired uneven structure can be appropriately formed. can.
Furthermore, the amount of trifunctional or higher polyfunctional (meth)acrylates, excluding the urethane-based (meth)acrylate, is 50% by mass or less, more preferably 30% by mass or less, and particularly in the range of 25% by mass or more, In addition, by using together with 50% by mass or less of the urethane-based (meth)acrylate, it is possible to appropriately form a target concave-convex structure by causing a moderately hard region to exist on the surface of the cured resin layer. When two or more of the tri- or higher polyfunctional (meth)acrylates other than urethane-based (meth)acrylates are mixed, the amount of each polyfunctional (meth)acrylate should satisfy the above range.

Examples of bifunctional (meth)acrylates include, but are not limited to, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 , 9-nonanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, isobornyl di(meth)acrylate, tricyclodecanediol di(meth)acrylate, adamantyldiol di(meth)acrylate, etc. (Meth)acrylate, bisphenol A di(meth)acrylate, bisphenol A alkylene oxide-modified di(meth)acrylate such as bisphenol A ethylene oxide-modified di(meth)acrylate, bisphenol A caprolactone-modified di(meth)acrylate, bisphenol A glycidyl ether Modified di(meth)acrylate, bisphenol F di(meth)acrylate, bisphenol F caprolactone modified di(meth)acrylate, bisphenol F alkylene oxide modified di(meth)acrylate, bisphenol F Bisphenol-modified di(meth)acrylates such as glycidyl ether-modified di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol A alkylene oxide-modified di(meth)acrylate, hydrogenated bisphenol A caprolactone-modified di(meth) ) acrylate, hydrogenated bisphenol A glycidyl ether modified di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, hydrogenated bisphenol F caprolactone modified di(meth)acrylate, hydrogenated bisphenol F alkylene oxide modified di(meth)acrylate , Hydrogenated bisphenol F glycidyl ether-modified di(meth)acrylate and other hydrogenated bisphenol-modified di(meth)acrylates, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate and other polyalkylene glycol di(meth)acrylates , glycerin di(meth)acrylate, urethane di(meth)acrylate, epoxy di(meth)acrylate, fluorene di(meth)acrylate, fluorene alkylene oxide-modified di(meth)acrylate, dioxane glycol di(meth)acrylate, isosorbide di(meth)acrylate , isosorbide alkylene oxide-modified di(meth)acrylate, and the like.
Among these, a structure without branching is preferable in consideration of the ease of forming an uneven structure, and alkanediol di(meth)acrylate or glycerin di(meth)acrylate is more preferable, and has 4 to 18 carbon atoms. Alkanediol di(meth)acrylates are more preferred.

Monofunctional (meth)acrylates include, but are not limited to, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl (meth) ) acrylate, trimethylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 2-cyclohexylpropanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyladamantyl (meth)acrylate, 2-ethyladamantyl (meth)acrylates, alkyl (meth)acrylates such as 2-isopropyladamantyl (meth)acrylate, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, methoxy Alkoxyalkyl (meth)acrylates such as ethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (Meth) acrylates, aromatic group-containing (meth) acrylates such as phenoxyethyl (meth) acrylate, amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethylene glycol ( meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, ethylene oxide-modified (meth)acrylate such as phenylphenol ethylene oxide-modified (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenylalkylene oxide-modified ( meth)acrylate, nonylphenol (meth)acrylate, nonylphenol alkylene oxide-modified (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylbenzyl (meth)acrylate, biphenyl (meth)acrylate, biphenylalkylene oxide-modified (meth)acrylate, dicyclo pentenyl (meth)acrylate, dicyclopentanyl alkylene oxide-modified (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, dicyclopentenyloxyethyl (meth) Dicyclopentenyl alkylene oxide-modified (meth)acrylate such as acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl (meth) ) acrylate, mevalonate lactone (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, (3,4 -epoxycyclohexyl)methyl (meth)acrylate and the like. Among these, a ring structure is preferable in consideration of the ease of forming a steep concave-convex structure.

Trifunctional or higher polyfunctional (meth)acrylates are not particularly limited, but for example, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra( Ethylene oxide-modified poly(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, etc. meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate such as ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, pentaerythritol triacrylate hexa Examples include urethane acrylates such as methylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, condensate of isophorone diisocyanate and dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, the ethylene oxide-modified type and the trifunctional (meth)acrylate are preferable in consideration of ease of formation of the concave-convex structure. In one aspect of the present invention, the curable resin composition preferably contains two or more of the tri- or higher polyfunctional (meth)acrylates.

An active energy ray-curable compound other than (meth)acrylate can be used in the cured resin layer composition. Examples thereof include vinyl compounds such as styrene, vinyl halide and vinyl acetate, and diene compounds such as vinylidene halide, acrylamide, vinylamide, (meth)acrylonitrile, 1,3-butadiene, isoprene and chloroprene.

In the formation of the cured resin layer, when an active energy ray-curable compound is used, the content thereof in the cured resin composition is preferably 5% by mass or more, more preferably 30%, of the non-volatile content of the curable resin composition. % by mass or more, more preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more. There is no particular upper limit and it may be 100% by mass, preferably 99% by mass or less, more preferably 98% by mass or less. When the content of the active energy ray-curable compound in the curable resin composition is within the above range, it is possible to easily form an uneven structure and to form a cured film having excellent hardness and scratch resistance. An uneven structure can be obtained.

For the purpose of improving the adhesion between the cured resin layer and the base film (A), various resins can be further added to the cured resin composition. Various conventionally known resins can be used as the resin, and examples thereof include acrylic resins, polyester resins, polyurethane resins, and polyvinyl resins. Among these, acrylic resins are preferable in that they are particularly excellent in transparency, affinity with (meth)acrylate, and closeness in refractive index.

When unevenness transfer is performed on a cured resin layer, it is preferable to include a resin having an active energy ray-curable functional group such as a carbon-carbon double bond in consideration of improving scratch resistance and hardness. Active energy ray-curable functional groups include (meth)acryloyl groups and vinyl ether compounds. Among these, a (meth)acryloyl group, particularly an acryloyl group, is preferred in view of ease of introduction and reactivity.

In further studies, when the curable resin composition further contains a resin having an active energy ray-curable functional group, the active energy ray-curable functional group is directly involved in improving scratch resistance and hardness. It has been found that not only the properties can be improved, but also an appropriate concave-convex shape can be formed on the surface of the cured resin layer. That is, it was found that the center-to-center distance (Rsm) between adjacent protrusions in the unevenness becomes smaller, and the arithmetic mean height (Sa), which is one of the indices of the surface roughness of the uneven structure, also increases. . In addition, there were cases where the haze increased and cases where the gloss decreased. These properties can exert a synergistic effect on the matte property, and are important properties particularly in applications where visibility is important, such as display applications.

As a method for introducing a double bond into an acrylic resin having an active energy ray-curable functional group such as a carbon-carbon double bond, for example, a compound having a double bond and a carboxyl group is added to an acrylic resin having an epoxy group. A method of reacting (Method 1), a method of reacting a compound having a double bond and an epoxy group with an acrylic resin having a carboxyl group (Method 2), and a compound having a double bond and a carboxyl group reacted with an acrylic resin having a hydroxyl group. (Method 3), a method of reacting a compound having a double bond and a hydroxyl group with an acrylic resin having a carboxyl group (Method 4), a method of reacting a compound having a double bond and a hydroxyl group with an acrylic resin having an isocyanate group. (Method 5), a method of reacting an acrylic resin having a hydroxyl group with a compound having a double bond and an isocyanate group (Method 6), and the like. Also, these methods may be used in combination.
In the following description, radically polymerizable monomers having carbon-carbon double bonds are sometimes referred to as vinyl monomers.

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

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

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

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

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

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

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

Examples of compounds having double bonds and hydroxyl groups in method 4 include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. These may use only 1 type, and may combine 2 or more types.

Examples of the vinyl monomer having an isocyanate group used to obtain the acrylic resin having an isocyanate group in Method 5 include isocyanatoethyl (meth)acrylate.

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

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

In Method 6, the compound having a double bond and an isocyanate group includes, for example, isocyanatoethyl (meth)acrylate. These may use only 1 type, and may combine 2 or more types.

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

In Method 1, the epoxy group-containing monomer in the epoxy group-containing acrylic resin is preferably 5% by weight or more, more preferably 10% by weight or more, of the total amount of monomers constituting the epoxy group-containing acrylic resin, More preferably, it is in the range of 15% by weight or more. The upper limit is not particularly limited, but is preferably 99.9% by weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less, particularly preferably 50% by weight or less, and most preferably 40% by weight or less. is in the range of
When the amount of the epoxy group-containing monomer in the epoxy group-containing acrylic resin is within the above range, not only the adhesion between the cured resin layer (cured resin film) and the substrate, the scratch resistance, and the hardness are improved, It tends to be possible to form an appropriate uneven shape, and it is possible to achieve a decrease in Rsm, an improvement in Sa, an increase in haze and a decrease in gloss in some cases.

Further, in Method 1, the compound having a double bond and a carboxyl group is preferably 10 to 150 mol% as a ratio of the double bond and the carboxyl group to the epoxy group of the acrylic resin having an epoxy group, and more It is preferably 30 to 130 mol %, more preferably 50 to 110 mol %. By using the compound having a double bond and a carboxyl group within the above range, the reaction can proceed just enough and the residue of the raw material can be reduced.

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

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

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

Examples of organic solvents used for radical polymerization include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA) and isobutanol; ethylene glycol dimethyl ether, propylene glycol monomethyl ether, and the like. ester solvents such as 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.

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

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

The amount of the chain transfer agent used is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, and 1.0 to 15 parts by mass with respect to a total of 100 parts by mass of the raw material vinyl monomer. More preferred.

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

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

The amount of double bonds in the acrylic resin is preferably 0.1 to 10 mmol/g, more preferably 0.2 to 7.0 mmol/g, even more preferably 0.5 to 5.0 mmol/g, particularly preferably 0.5 to 5.0 mmol/g. It ranges from 8 to 4.0 mmol/g, most preferably from 1.0 to 3.0 mmol/g.
When the amount of double bonds in the acrylic resin is within this range, adhesion between the cured resin layer and the substrate, scratch resistance, and hardness are improved, and the irregular shape tends to be controlled more precisely. A reduction in Rsm, an improvement in Sa, and in some cases an increase in haze and a reduction in gloss can be achieved. The amount of double bonds means the concentration of (meth)acryloyl groups in the acrylic resin, that is, the amount of (meth)acryloyl groups introduced.

The weight-average molecular weight (Mw) of the acrylic resin should be appropriately selected according to the application of the cured resin layer composition, and is usually 5,000 or more, preferably 7,000 or more, and more preferably 9,000 or more. and is usually 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 50,000 or less. Within the above range, it becomes easier to form surface unevenness. The weight average molecular weight (Mw) of the resin can be determined by gel permeation chromatography (GPC) as a converted value based on polystyrene standards. Specific measurement conditions are shown in Examples below.

When the curable resin composition contains the above resin other than the active energy ray-curable compound, the content thereof is preferably the non-volatile content of the curable resin composition from the viewpoint of the appearance and adhesion of the cured film. is in the range of 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. If the resin content is too high, there is a concern that the hardness of the cured film will be lowered.

In the laminated film of the present invention, the cured resin layer must satisfy specific parameters for its surface roughness. Although the method of satisfying the specific parameters is not particularly limited, for example, it is possible to include particles in the cured resin layer. By including particles in the cured resin layer, the matting property can be further improved.
Particles are not particularly limited, and conventionally known particles can be used. Specific examples include silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, inorganic particles such as titanium oxide, acrylic resin, styrene resin, urea. Examples include organic particles such as resins, phenol resins, epoxy resins, and benzoguanamine resins.
The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The organic particles are preferably of a crosslinked type, more preferably crosslinked acrylic resin particles or crosslinked styrene resin particles, in order to maintain their shape.
These particles may be used in combination of two or more.

The average primary particle size of the particles is preferably in the range of 0.01 to 30 µm, more preferably 0.05 to 10 µm, even more preferably 0.1 to 5 µm, and particularly preferably 0.5 to 3 µm. When the average primary particle size of the particles is within the above range, the improvement in mattness is excellent.

The content of the particles in the cured resin layer is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably The range is 20% by mass or less, most preferably 9% by mass or less. Although the lower limit is not particularly limited, it is preferably 0.1% by mass or more, more preferably 1% by mass or more.

(Photoinitiator)
When forming the cured resin layer using an active energy ray-curable compound, a photopolymerization initiator may be used. As for the molecular weight of the said photoinitiator, 1000 or less are preferable.
Specific examples of photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyldiphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'. -dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloyl ethyl ether, benzyldimethylketal, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro- 4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosuberone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio ) phenyl]-2-morpholino-1-propanone, 1-hydroxycyclohexyl-phenylketone, tribromophenylsulfone, tribromomethylphenylsulfone and the like.
These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator in the curable resin composition is preferably 20% by mass or less, more preferably 10% by mass, of the non-volatile components of the curable resin composition, from the viewpoint of promoting curability and hardness of the cured resin layer. Below, more preferably 8% by mass or less, particularly preferably 6% by mass or less.

(Polymers having active groups that generate radicals upon irradiation with active energy rays)
When forming the cured resin layer, a polymer having an active group that generates radicals upon irradiation with active energy rays (hereinafter referred to as polymer) may be used. An active group that generates radicals by irradiation with active energy rays (hereinafter referred to as an active group) is a group that has a structure that generates radicals by irradiation with active energy rays, in other words, a structure that has photopolymerization initiation properties. Structures having photopolymerization initiation properties include, for example, a hydrogen abstraction type, an electron transfer type, and an intramolecular cleavage type. In the present invention, radicals generated from active groups react with the polymer itself or active energy ray-curable compounds to form a crosslinked structure.
(active group)
Active groups include, for example, a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (for example, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone's "2- a group obtained by removing one hydrogen atom from the "hydroxyl group in hydroxyethoxy"), α-aminoketone group, α-diketone group, α-diketone dialkylacetal group, anthraquinone group, thioxanthone group and phosphine oxide group. Among these, a benzophenone group, an acetophenone group, and an α-hydroxyketone group are preferable because they are less susceptible to oxygen inhibition during curing and have good surface curability when forming an uneven layer.

The active group may exist at the end of the main chain of the polymer, or may exist in a constituent unit derived from a monomer constituting the polymer.
Polymers can increase the concentration of active groups near the surface of the coating film. It is preferable to have a plurality of active groups inside.

As the polymer having a plurality of active groups, a polymer having structural units derived from the monomer (a) having active groups is preferable.

(monomer (a))
Examples of the monomer (a) include compounds having an active group and a radically polymerizable group. Examples of radically polymerizable groups include functional groups containing radically polymerizable unsaturated bonds such as carbon-carbon double bonds.
As the monomer (a), a (meth)acrylic acid ester is preferable from the viewpoint of easiness of polymer synthesis and easiness of adjustment of the introduction amount of the active group. Examples of such (meth)acrylic acid esters include 4-methacryloyloxybenzophenone and 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate.

The ratio of structural units derived from the monomer (a) to the total mass of all units constituting the polymer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 15 to 70% by mass. %, particularly preferably in the range from 30 to 60% by weight. If this ratio is within the above range, the curability can be improved, and the concave-convex structure can be effectively formed.

(monomer (b))
The polymer preferably has structural units derived from the monomer (b) having a chain structure in addition to structural units derived from the monomer (a) having an active group. The monomer (b) includes a compound having at least one chain structure selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluoroalkyl group, and a polydimethylsiloxane chain, and a radically polymerizable group. . Radically polymerizable groups include functional groups containing radically polymerizable unsaturated bonds such as carbon-carbon double bonds.
As the monomer (b), a (meth)acrylic acid ester is preferable from the viewpoint of ease of polymer synthesis and ease of adjustment of the introduction amount of the chain structure. If the polymer has this unit, when a coating film of the curable composition is formed, the polymer tends to segregate on the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (on the substrate film side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured at low exposure doses and can cure well even thin coatings that tend to be susceptible to oxygen inhibition.

The alkyl group having 4 or more carbon atoms may be linear or branched, and may contain a monocyclic or polycyclic ring structure. From the viewpoint of more effectively segregating the polymer on the surface of the coating film, the alkyl group is preferably linear.
The number of carbon atoms in the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, still more preferably 8, from the viewpoint of more effectively segregating the polymer on the surface of the coating film. ~18 range.

Examples of the monomer having an alkyl group having 4 or more carbon atoms include compounds having an alkyl group having 4 or more carbon atoms and a radically polymerizable group. Examples of such compounds include (meth)acrylic acid alkyl esters, fumaric acid dialkyl esters, maleic acid dialkyl esters, and aliphatic olefins. A (meth)acrylic acid alkyl ester is preferable from the viewpoint of ease of synthesis and ease of adjustment of the amount of alkyl groups having 4 or more carbon atoms to be introduced.

Examples of such (meth)acrylic acid alkyl esters include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, ) acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate , cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentanyl (meth)acrylate ) acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate and the like.
Among these, it is preferable to include a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 4 or more carbon atoms. As the (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 4 or more carbon atoms, those in which the number of carbon atoms in the alkyl group is within the preferred range described above are preferable, and ease of production, etc. is also taken into consideration. Then, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate and stearyl (meth)acrylate are more preferable, and 2-ethylhexyl (meth)acrylate and stearyl (meth)acrylate are particularly preferable.
One of these (meth)acrylic acid alkyl esters may be used alone, or two or more thereof may be used in combination.

From the viewpoint of more effectively segregating the polymer on the surface of the coating film, the polymer contains, in addition to a structural unit derived from a monomer having an alkyl group having 4 or more carbon atoms, or an alkyl group having 4 or more carbon atoms. Instead of the structural unit derived from the monomer, it may have a structural unit derived from a monomer containing a fluoroalkyl group or a polydimethylsiloxane chain.

As the monomer containing a fluoroalkyl group, a (meth)acrylic acid ester containing a fluoroalkyl group is preferable, and a (meth)acrylic acid ester containing a perfluoroalkyl group is more preferable.
(Meth)acrylic acid esters having a perfluoroalkyl group include, for example, 2,2,2-trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 3F), 2,2,3,3-tetrafluoropropyl Acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 4F), 1H, 1H, 5H-octafluoropentyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 8F), 1H, 1H, 5H-octafluoropentyl methacrylate (Osaka Organic Chemical Industry Co., Ltd., Viscoat 8FM), 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate (Osaka Organic Chemical Industry Co., Ltd., Viscoat 13F), 1H, 1H, 2H, 2H-nonafluorohexyl acrylate (Unimatec Co., Ltd., CHEMINOX FAAC-4), 1H, 1H, 2H, 2H-nonafluorohexyl methacrylate (Unimatec Co., Ltd., CHEMINOX FAMAC-4), 1H, 1H, 2H, 2H-tridecafluorooctyl methacrylate (Unimatec Co., Ltd. Company, CHEMINOX FAMAC-6), 2-(perfluorohexyl)ethyl methacrylate (manufactured by Daikin Industries, Ltd., trade name: C6SFMA monomer), etc. are commercially available. The perfluoroalkyl group preferably has 3 or more carbon atoms.

The monomer containing a polydimethylsiloxane chain is preferably a (meth)acrylic acid ester containing a polydimethylsiloxane chain. Specific examples of (meth)acrylic acid esters having a polydimethylsiloxane chain include polydimethylsiloxane having a molecular weight of 500 to 50,000 and having a (meth)acryloyl group substituted on one end. The molecular weight is preferably 1,000 to 30,000, more preferably 1,500 to 20,000. (Meth) acrylic acid esters having a polydimethylsiloxane chain, for example, "FM-0711", "FM-0721", "FM-0725" (all manufactured by JNC Co., Ltd.) and "X-24-8201". , “X-22-174DX” and “X-22-2426” (both from Shin-Etsu Chemical Co., Ltd.) are commercially available.

The ratio of the monomer (b) to the total mass of all units constituting the polymer is preferably 80% by mass or less, more preferably 1 to 55% by mass, still more preferably 5 to 50% by mass, particularly preferably It is in the range of 8 to 40% by mass. If the ratio of the monomer (b) is within the above range, the curability can be improved and the uneven structure can be effectively formed.

(Monomer having a hydrogen-donating functional group)
The polymer may have structural units derived from a monomer having a hydrogen-donating functional group, if necessary. In particular, when a hydrogen-abstraction type active group is included, it is preferable to include a structural unit derived from a monomer having a hydrogen-donating functional group. If the polymer has this unit, the coating film of the curable composition is effectively cured from the surface, so that the curability is improved and the uneven structure is easily formed.
Hydrogen-donating functional groups include, for example, hydroxyl groups, amino groups, mercapto groups, and amide groups. Among these, a hydroxyl group, an amino group, or an amide group is preferable from the viewpoint that the curing reaction progresses particularly efficiently, the curability is improved, or an uneven structure is easily formed.

Examples of the monomer having a hydrogen-donating functional group include compounds having a hydrogen-donating functional group and a radically polymerizable group. From the viewpoint of ease of use, (meth)acrylic acid esters having a hydrogen-donating functional group are preferred.
Examples of monomers having a hydrogen-donating functional group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. , 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, monobutylhydroxyl fumarate, monobutylhydroxyitaconate and other hydroxyl group-containing monomers; N, N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, 2- [(Butylamino)carbonyl]oxy]ethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylate, N , N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine , vinylacetamide and other amino group- or amide group-containing monomers.
Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N,N-dimethyl are excellent in curing acceleration effect in combination with active groups. Acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate are preferable, and N,N-diethylaminoethyl (meth)acrylate is more preferable in that the uneven structure can be easily increased. . These compounds may be used alone or in combination of two or more.

(other monomers)
The polymer may further have constitutional units derived from monomers other than those described above, if necessary. Other monomers include compounds having a radically polymerizable group and not having an active group, an alkyl group having 4 or more carbon atoms, a fluorine atom, a silicon atom, or a hydrogen-donating functional group.
Other monomers include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, and salts thereof; methyl (meth) acrylate, ethyl (meth)acrylates such as (meth)acrylate and propyl (meth)acrylate; glycidyl (meth)acrylate, (meth)acryloyloxybenzophenone; nitrogen-containing monomers such as (meth)acrylonitrile; styrene, α-methylstyrene, divinyl styrene compounds such as benzene and vinyl toluene; vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

The ratio of structural units derived from a monomer having a hydrogen-donating functional group to the total mass of all units constituting the polymer is preferably 80% by mass or less, more preferably 1 to 40% by mass, and still more preferably 3. to 35% by weight, particularly preferably 5 to 34% by weight. If this ratio is within the above range, the curability can be improved, and the concave-convex structure can be effectively formed.

(Weight average molecular weight)
The weight average molecular weight (Mw) of the polymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 300,000, still more preferably 5,000 to 200,000, and particularly preferably 10,000 to 150,000. When the Mw is within the above range, the coating properties and curability of the curable composition tend to be further improved, and the easiness of forming the concave-convex structure tends to be further improved.
Mw of a polymer is a value converted to standard polystyrene measured by gel permeation chromatography (GPC). Detailed measurement conditions are as described in the examples below.

The content of active groups per gram of the polymer is preferably 0.1 to 3.5 mmol/g, more preferably 0.3 to 3.0 mmol/g, still more preferably 0.5 to 2.7 mmol/g. , particularly preferably in the range of 1.0 to 2.5 mmol/g. If the content of the active group is within the above range, the curability will be more excellent, and unevenness can be formed more effectively.

(Glass-transition temperature)
The glass transition temperature (Tg) of the polymer is preferably in the range of -30 to 150°C, more preferably 0 to 120°C, still more preferably 25 to 100°C. When the Tg of the polymer is within the above range, the curability tends to be further improved, and the easiness of forming the concave-convex structure tends to be further improved.

(Production of polymer)
A polymer can typically be produced by polymerizing raw material monomers in the presence of a polymerization initiator. If necessary, a chain transfer agent may be used in combination during the polymerization. The polymerization method includes, for example, solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among them, solution polymerization is preferable in terms of simple operation and high productivity.

(Polymer content)
The content of the polymer in the nonvolatile matter of the curable composition of the present invention is 0.5% by mass or more from the viewpoint of imparting an uneven structure to the surface of the cured product and improving the active energy ray curability25. 0% by mass or less is preferable, 0.7% by mass or more and 20.0% by mass or less is more preferable, 1.0% by mass or more and 15.0% by mass or less is even more preferable, and 2.0% by mass or more and 12.0% by mass The following is particularly preferable, and the most preferable range is 3.0% by mass or more and 12.0% by mass or less.
The non-volatile content of the curable composition is the total mass of components other than the solvent, such as an organic solvent. The proportion of non-volatile matter in the curable composition can be measured by a conventionally known method. It can be calculated from the change in weight.

From the viewpoint of improving the appearance of the cured resin layer, the cured resin composition may contain a leveling agent.
Examples of leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. These leveling agents may be used alone or in combination of two or more.

The content of the leveling agent in the cured resin composition is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on the nonvolatile content, from the viewpoint of improving the appearance of the cured film. is in the range of

A polymerization accelerator such as a compound containing a thiol group, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, and the like may be used in the cured resin layer as long as they do not impair the effects of the present invention.

(Organic solvent)
A cured resin layer can be formed, for example, by applying a cured resin composition onto a substrate film. At that time, an organic solvent may be used as necessary in order to improve the workability when applying the curable resin composition onto the base film.
Organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether. Ether solvents such as , diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetol; Ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; Dimethylformamide, diethylformamide, N-methylpyrrolidone, etc. amide solvents; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen solvents such as dichloromethane and chloroform; Among them, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferred because they tend to improve workability in coating.
These organic solvents may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of improving workability, the ratio of the organic solvent to 100 parts by mass of the nonvolatile matter in the cured resin layer composition is preferably 10 parts by mass or more and 1900 parts by mass or less, more preferably 40 parts by mass or more and 400 parts by mass or less.
The non-volatile content of the cured resin layer composition is the total mass of components other than the solvent, such as an organic solvent. The non-volatile content of the cured resin layer composition can be measured by a conventionally known method. measured by the change in

(Method for forming cured resin layer)
The cured resin layer can be formed by coating the cured resin layer composition on the substrate film to form a coating film, drying the coating film if necessary, and irradiating the coating film with an active energy ray.
The method of applying the cured resin layer composition is not particularly limited. For example, it can be applied by known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating.

When the cured resin layer composition contains an organic solvent, it is preferable to preliminarily heat and dry the composition before irradiating it with active energy rays. By drying by heating in advance, the solvent in the coating film can be effectively removed.
The drying temperature of heat drying is preferably 30° C. or higher and 200° C. or lower, more preferably 40° C. or higher and 150° C. or lower. The drying time is preferably 0.01 to 30 minutes, more preferably 0.1 to 10 minutes.

(Irradiation of active energy rays)
The active energy ray includes at least one selected from the group consisting of ultraviolet rays, vacuum ultraviolet rays, electron beams, and ionizing radiation from the viewpoint of effectively curing the surface of the coating film. The method for forming the cured resin layer in one aspect of the present invention preferably includes a step of forming the cured resin layer by excimer lamp irradiation or ultraviolet (UV) irradiation.

"Ultraviolet rays" refers to active energy rays whose radiation spectrum has a maximum value between 200 nm and 600 nm. For example, ultraviolet lamps include high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, LEDs, xenon flashes, and electrodeless lamps.

The cumulative amount of UV light to be irradiated is preferably 1 to 5000 mJ/cm ² , more preferably 50 to 3000 mJ/cm ² , still more preferably 100 to 1000 mJ/cm ² , and particularly preferably 200 to 700 mJ/cm ² . . Also, the illuminance is preferably in the range of 1 to 1000 mW/cm ² , more preferably 50 to 500 mW/cm ² and even more preferably 80 to 300 mW/cm ² .

The vacuum ultraviolet rays (ultraviolet rays having a wavelength of 200 nm or less) are most suitable for excimer light having a half width of 50 nm or less. mentioned. Among these, xenon excimer light is preferable in consideration of ease of use, effective unevenness formation, curability of the cured resin layer, and the like.

When vacuum ultraviolet rays are used, the integrated light quantity of irradiation is preferably 1 to 3000 mJ/cm ² , more preferably 3 to 1000 mJ/cm ² , still more preferably 5 to 500 mJ/cm ² , and particularly preferably 10 to 100 mJ/cm ² . is in the range. Also, the illuminance is preferably in the range of 1 to 500 mW/cm ² , more preferably 2 to 300 mW/cm ² , still more preferably 3 to 100 mW/cm ² .

As for the atmosphere when irradiating vacuum ultraviolet rays, it is preferable to use an environment with little oxygen, such as a nitrogen atmosphere. The oxygen concentration is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.

After the above vacuum ultraviolet irradiation, it is preferable to irradiate active energy rays other than vacuum ultraviolet rays in order to harden the cured resin layer to the depth. Examples of active energy rays other than vacuum ultraviolet rays include ultraviolet rays, electron beams, and the like, and among these, ultraviolet rays are more preferable in consideration of the curability of the cured film.

(Thickness of cured resin layer)
The thickness of the cured resin layer is preferably 1 to 100 μm, more preferably 2 to 80 μm, still more preferably 3 to 50 μm, particularly preferably 3 to 30 μm. If the thickness of the cured resin layer is within the above range, it is easy to achieve the desired mattness and to adjust the hardness.
Moreover, in one aspect of the present invention, there is provided a transfer product in which the concave-convex structure on the surface of the cured resin layer is transferred. At that time, the thickness of the transfer product obtained by transferring the concavo-convex pattern of the cured resin layer indicates the maximum thickness of the concavo-convex layer, and is obtained by cross-sectional observation with an electron microscope.

[Release layer]
The laminated film of the present invention may have a release layer on the cured resin layer.
Hereinafter, a mode in which the laminated film of the present invention is a release film having a release layer on the cured resin layer will be described.
The role of the release layer is not only to protect various objects to be protected and prevent contamination of the protective film, but also to improve the handleability of the laminated film of the present invention. For example, when the laminated film of the present invention is stacked in sheets or wound into a roll, the release layer has effects such as prevention of sticking to the adhesive layer on the back side of the laminated film and ease of peeling. In addition to the above, there are effects such as improving slipperiness to facilitate production of the laminated film, improving the handleability of the laminated film, and improving the workability of the adhesive layer to the laminated film. One aspect|mode of this invention WHEREIN: The said release film can be used suitably for adhesion layer protection.
The thickness of the release layer is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 0.001 to 5 μm, more preferably 0.01 to 3 μm, and still more preferably 0.1 to 2 μm. is. By setting the film thickness of the release layer within the above range, the appearance, water repellency, and releasability (prevention of sticking to the adhesive layer) can be improved.
In addition, in one embodiment of the present invention, there is also provided a transfer product obtained by transferring the unevenness of the surface of the release layer of the release film. At that time, the thickness of the transfer product obtained by transferring the unevenness to the surface of the release layer indicates the maximum thickness of the uneven layer, and is obtained by cross-sectional observation with an electron microscope.

<Release agent>
The release agent that forms the release layer is not particularly limited, and conventionally known release agents can be used. Examples thereof include at least one selected from the group consisting of long-chain alkyl group-containing compounds, melamine compounds, fluorine compounds, silicone compounds, and waxes.
Among these, long-chain alkyl compounds and fluorine compounds are preferred from the viewpoints of less staining in the sense of transfer to the side to be protected and excellent water repellency. Alternatively, a silicone compound is particularly preferable from the viewpoint of improving releasability from the adhesive layer.
These release agents may be used alone or in combination of multiple types.

(Long-chain alkyl group-containing compound)
A long-chain alkyl group-containing compound is a compound having a linear or branched alkyl group having usually 6 or more carbon atoms, preferably 8 or more carbon atoms, more preferably 12 or more carbon atoms. Although the upper limit of the number of carbon atoms is not particularly limited, it is 30, for example.
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, it is preferably a long-chain alkyl group-containing polymer compound. Moreover, from the viewpoint of obtaining releasability effectively, a polymer compound having a long-chain alkyl group in a side chain is more preferable.

A polymer compound having a long-chain alkyl group in its 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 releasability 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 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.

A polymer compound having a long-chain alkyl group in a side chain may be a polymer of a long-chain alkyl (meth)acrylate or a copolymer of a long-chain alkyl (meth)acrylate and another vinyl group-containing monomer. . Examples of 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.

(Fluorine compound)
The fluorine compound is not particularly limited as long as it contains a fluorine atom in the compound. Organic fluorine compounds are preferably used from the viewpoint of coating appearance by in-line coating, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene. be done. 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.

Examples of compounds having a perfluoroalkyl group include 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.
Among the above-described materials, polymers are preferred in consideration of heat resistance and stain resistance. The polymer may be a polymer of a single compound or a polymer of multiple compounds. From the viewpoint of releasability, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, it may be a polymer with a compound containing a long-chain alkyl compound as described later. Polymerization with vinyl chloride is also preferable from the viewpoint of adhesion to the substrate.

(silicone compound)
A silicone compound is a compound having a silicone structure in its molecule. Examples thereof include alkylsilicones such as dimethylsilicone and diethylsilicone, phenylsilicone having a phenyl group, and methylphenylsilicone. Silicone compounds having various functional groups in the silicone structure can also be used, for example, polyether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl and a silicone compound having a hydrocarbon group such as a group or various aromatic groups in the silicone structure. Silicones with vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms are also common, and it is also possible to use both together to use addition-type silicones (types resulting from the addition reaction of vinyl groups and hydrogen silane). It is possible.

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 stain resistance, it is preferable to use a curable silicone resin, and as the type of curable type, any type of curing reaction such as an addition type or an active energy ray curable type can be used. The curable silicone resin will be detailed later.

<Polyether group-containing silicone compound>
As the silicone compound, a polyether group-containing silicone compound is preferable from the viewpoints of little back surface transfer, good dispersibility in an aqueous solvent, and high suitability for in-line coating. The position of the polyether group in the silicone structure is not particularly limited, and the silicone may have a polyether group on its side chain or terminal, or may have a polyether group on its main chain. From the viewpoint of dispersibility in an aqueous solvent, it is preferable to have a polyether group at the side chain or terminal.

A conventionally known structure can be used as the polyether group.
From the viewpoint of dispersibility in an aqueous solvent, an aliphatic polyether group is preferable to an aromatic polyether group, and among the aliphatic polyether groups, an alkyl polyether group is preferable. From the viewpoint of synthesis due to steric hindrance, linear alkyl polyether groups are preferable to branched alkyl polyether groups, and polyether groups composed of linear alkyl having 8 or less carbon atoms are particularly preferable. Furthermore, when the solvent is water, a polyethylene glycol group or a polypropylene glycol group is preferred in consideration of dispersibility in water, and the polyethylene glycol group is particularly optimal.

The number of ether bonds in the polyether group is usually in the range of 1 to 30, preferably in the range of 2 to 20, more preferably in the range of 3 to 3, from the viewpoint of dispersibility in aqueous solvents and improvement in durability of the release layer. 15 ranges. If the ether bond is at least the above lower limit value, sufficient dispersibility can be ensured, and if it is at most the above upper limit value, durability and release performance are not adversely affected.

When a polyether group is present on the side chain or end of the silicone structure, the end of the polyether group is not particularly limited, and may be a hydroxyl group, an amino group, a thiol group, a hydrocarbon group such as an alkyl group or a phenyl group, or a carboxylic acid group. , a sulfonic acid group, an aldehyde group, an acetal group, and the like can be used. Among them, considering the dispersibility in water and the crosslinkability for improving the strength of the release layer, at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxylic acid group, and a sulfonic acid group is preferable, particularly , the hydroxyl group is most suitable.

The polyether group content in the polyether group-containing silicone compound is preferably in the range of 0.001 to 0.30, more preferably 0.01 to 0.01, in terms of molar ratio, with the siloxane bond of the silicone being 1. 20, more preferably 0.03 to 0.15, particularly preferably 0.05 to 0.12. By setting the content within this range, dispersibility in water, durability of the release layer, and good releasability can be maintained.

The molecular weight of the polyether group-containing silicone compound is preferably not too large in consideration of dispersibility in aqueous solvents, and is preferably somewhat large in consideration of the durability and release performance of the release layer. A balance between these two properties is required, and the number average molecular weight is preferably in the range of 1,000 to 100,000, more preferably in the range of 3,000 to 30,000, and still more preferably in the range of 5,000 to 10,000.

Considering the change over time of the release layer, the release performance, and the staining property in various processes, it is preferable that the low-molecular-weight component (500 or less in number average molecular weight) of the silicone compound is as small as possible. The proportion of the entire compound is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
In addition, when condensation-type silicone is used as a silicone compound, if vinyl groups (vinylsilane) and hydrogen groups (hydrogensilane) bonded to silicon remain unreacted in the release layer, various properties may change over time. becomes. Therefore, as the amount of functional groups in the silicone, the content of the unreacted functional groups is preferably 0.1 mol % or less, and more preferably not contained.

<Surfactant>
Since it is difficult to apply the polyether group-containing silicone alone, it is preferable to use it after dispersing it in water. Various conventionally known surfactants can be used for dispersing. Examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
Among these, when considering the dispersibility of the polyether group-containing silicone and the compatibility with polymers other than the polyether group-containing silicone that can be used to form the release layer, anionic surfactants and nonionic surfactants agents are preferred.
Fluorine compounds can be used instead of these surfactants.

Examples of anionic surfactants include sodium dodecylbenzenesulfonate, sodium alkylsulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylallyl ether sulfate, polyoxyalkylene Sulfonate salts such as alkenyl ether sulfate ammonium salts, sulfate ester salts, carboxylate salts such as sodium laurate and potassium oleate, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ethers Phosphate bases such as phosphate are included.
Among these, the sulfonate system is preferable from the viewpoint of good dispersibility.

Examples of nonionic surfactants include ether-type surfactants obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to compounds having hydroxyl groups such as higher alcohols and alkylphenols, polyhydric alcohols such as glycerin and sugars, and fatty acids. Examples include an ester type with an ester bond, an ester/ether type with an alkylene oxide added to a fatty acid or a polyhydric alcohol fatty acid ester, and an amide type with an amide bond between a hydrophobic group and a hydrophilic group.
Among these, the ether type is preferable in consideration of solubility in water and stability, and the ether type to which ethylene oxide is added is more preferable in consideration of handleability.

It depends on the molecular weight and structure of the polyether group-containing silicone compound used, as well as on the type of surfactant used, so it cannot be said unconditionally, but as a guideline, the amount of surfactant used is the polyether group-containing silicone With the compound as 1, the mass ratio is preferably in the range of 0.01 to 0.5, more preferably 0.05 to 0.4, and still more preferably 0.1 to 0.3.

<Curable silicone resin>
When using a silicone compound as a release agent that constitutes the release layer, a curable silicone resin can be used as described above. The curable silicone resin may be a resin containing a curable silicone resin as a main component, or a modified silicone obtained by graft polymerization of a curable silicone resin and an organic resin such as a urethane resin, an epoxy resin, or an alkyd resin. good. Moreover, when the adhesive layer is a silicone adhesive, it preferably contains a fluorosilicone resin or the like.

As the type of the curable silicone resin, any existing curing reaction type can be used, such as a heat curing type such as an addition type or a condensation type, or an electron beam curing type such as an ultraviolet curing type. A single curable silicone resin may be used alone, or a plurality of curable silicone resins may be used in combination.
Furthermore, there are no particular restrictions on the coating form of the curable silicone resin when forming the release layer, and it may be dissolved in an organic solvent, in the form of an aqueous emulsion, or in the form of no solvent. . A surfactant is preferably used in the water-based emulsion.
As for the surfactant, the same surfactant as used in the polyether group-containing silicone compound can be used. Among them, anionic surfactants and nonionic surfactants are preferred from the viewpoint of dispersibility of the curable silicone resin.

The type of curable silicone resin used in the present invention is not limited, but from the viewpoint of excellent release properties such as easy release properties, the use of curable silicone resins containing alkenyl groups is preferred in the present invention. Examples of curable silicone resins containing alkenyl groups include diorganopolysiloxanes represented by the following general formula (1).
R _(3-a) X _a SiO—(RXSiO) _m —(R ₂ SiO) _n —SiX _a R _(3-a) (1)

In general formula (1), R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is an alkenyl group-containing organic group. a is an integer of 0 to 3, preferably 1, and m is 0 or more, but when a=0, m is 2 or more. m and n are numbers satisfying 100≦m+n≦20000, respectively. Note that the above formula does not mean a block copolymer.
R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cycloalkyl groups such as cyclohexyl group, phenyl group, tolyl and aryl groups such as groups, and particularly preferred are a methyl group and a phenyl group.
X is an alkenyl group-containing organic group, preferably having 2 to 10 carbon atoms, specifically vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, cyclo A hexenylethyl group, a vinyloxypropyl group, and the like can be mentioned, and a vinyl group, a hexenyl group, and the like are particularly preferable.
A specific example of a curable silicone resin containing an alkenyl group is a dimethylsiloxane-methylhexenylsiloxane copolymer (96 mol% of dimethylsiloxane units, 4 mol% of methylhexenylsiloxane units) blocked with trimethylsiloxy groups at both ends of the molecular chain. dimethylvinylsiloxy group-blocked dimethylsiloxane/methylhexenylsiloxane copolymer at both chain ends (97 mol% of dimethylsiloxane units, 3 mol% of methylhexenylsiloxane units), dimethylsiloxane/methylhexenylsiloxane copolymer with dimethylhexenylsiloxy group-blocked at both molecular chain ends Polymers (95 mol % of dimethylsiloxane units, 5 mol % of methylhexenylsiloxane units) can be mentioned.
The number average molecular weight of the curable silicone resin is preferably 50,000 or more, more preferably 80,000 or more, even more preferably 100,000 or more, and particularly preferably 150,000 or more. On the other hand, the number average molecular weight is preferably 600,000 or less, more preferably 500,000 or less, and even more preferably 400,000 or less.

The release layer is preferably a layer obtained by curing a silicone resin composition containing the curable silicone resin and a curing agent for curing the curable silicone resin. Curing agents include polyorganosiloxanes containing SiH groups.
A polyorganosiloxane containing SiH groups can react with a curable silicone resin containing alkenyl groups to form a stronger silicone release layer. The SiH group-containing polyorganosiloxane is an organohydrogenpolysiloxane having at least two, preferably three or more silicon-bonded hydrogen atoms in one molecule, and is linear, branched, or cyclic. and the like can be used, and compounds represented by the following general formula (2) can be mentioned, but are not limited to these.
H _b R ¹ _(3-b) SiO—(HR ¹ SiO) _x —(R ¹ ₂ SiO) _y —SiR ¹ _(3-b) H _b (2)

In general formula (2), R ¹ is a monovalent hydrocarbon group containing no aliphatic unsaturated bond and having 1 to 6 carbon atoms. b is an integer of 0 to 3, and x and y are each integers.
Specific examples include methylhydrogenpolysiloxane with trimethylsiloxy group-blocked at both molecular chain ends, dimethylsiloxane-methylhydrogensiloxane copolymer with trimethylsiloxy group-blocked at both molecular chain ends, and methyl with dimethylhydrogensiloxy group-blocked at both molecular chain ends. Examples include hydrogen polysiloxane and dimethyl siloxane/methyl hydrogen siloxane copolymer with dimethylhydrogensiloxy groups blocked at both ends of the molecular chain.
In the silicone resin composition, the molar ratio of Si—H groups to alkenyl groups (Si—H groups/alkenyl groups) is preferably 0.1 to 2.0, more preferably 0.3 to 2.0. is more preferable, and 0.3 to 1.8 is even more preferable.

Specific examples of various types of commercially available silicone resins that can be used in the present invention include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, X-62-2461, X-62-1387, X-62-5039, X-62-5040, KNS-3051, X-62-1496, KNS320A, KNS316, X-62-1574A/B, X-62-7052, X-62-7028A/B, X-62-7619, X-62-7213, X-41-3035 as manufactured by Momentive Performance Materials , YSR -3022, TPR -6700, TPR -6720, TPR -6721, TPR6501, TPR6501, UV9300, UV9425, XS56 -A2775, XS56 -A2982, UV9430, TPR660, TPR660 4, TPR6605, Made by Toray Dow Ning Co., Ltd. as SRX357, SRX211, SD7220, SD7292, LTC750A, LTC760A, LTC303E, LTC856, LTC761, SP7259, BY24-468C, SP7248S, BY24-452, DKQ3-202, DKQ3-203, DKQ3- 204, DKQ3-205, DKQ3- 210, DEHESIVE 636, 919, 920, 921, 924, 929 among the DEHESIVE series manufactured by Asahi Kasei Wacker Silicone Co., Ltd. are exemplified.

The release layer preferably contains a platinum-based catalyst that promotes an addition-type reaction. Therefore, the silicone resin composition preferably further contains a platinum-based catalyst.
Examples of platinum-based catalysts include platinum-based compounds such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid and olefins, complexes of chloroplatinic acid and alkenylsiloxane, platinum black, platinum-supported silica, and platinum-supported Activated carbon can be exemplified.
The content of the platinum-based catalyst in the release layer is not particularly limited, but is, for example, in the range of 0.01 to 10.0% by mass, preferably 0.01 to 5.0% by mass.
When the content of the platinum-based catalyst in the release layer is 0.01% by mass or more, a sufficient peeling force is obtained, the curing reaction proceeds sufficiently, and problems such as surface deterioration do not occur. On the other hand, if the content of the platinum-based catalyst in the release layer is 10.0% by mass or less, in addition to being advantageous in terms of cost, the reactivity is enhanced and process problems such as the generation of gel foreign matter do not occur.

Addition-type silicone compounds are highly reactive, so in some cases, acetylene alcohol may be added as a non-reactive inhibitor. Examples of non-reactive inhibitors include organic compounds having a carbon-carbon triple bond and a hydroxyl group, preferably 3-methyl-1-butyn-3-ol and 3,5-dimethyl-1-hexyne. -3-ol and at least one compound selected from the group consisting of phenylbutynol.

In order to adjust the releasability of the release layer, various release control agents may be used in combination. In the case of making the release force heavy release, generally an organopolysiloxane resin, silica particles, a heavy release type silicone seed, etc. are added to the release layer in an appropriate content to obtain the desired release force. Adjustments can be made.
Specific examples of commercially available heavy release agents include KS-3800 and X-92-183 manufactured by Shin-Etsu Chemical Co., Ltd., and SDY7292, BY24-843 and BY24-4980 manufactured by Dow Corning Toray Co., Ltd. be done.
When the release force is to be lightened, various low-molecular-weight siloxane compounds are selected and the content in the release layer is appropriately adjusted so that the siloxane migration component exhibits release performance.
Examples of low-molecular-weight siloxane compounds include low-molecular-weight cyclic siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Examples of compounds other than the low-molecular-weight cyclic siloxane include a dimethylsiloxane oligomer having both molecular chain terminals blocked with trimethylsiloxy groups; and a dimethylsiloxane oligomer having both molecular chain terminals blocked with dimethylhydroxysiloxy groups. These low-molecular-weight siloxane compounds may be mixed and used as needed.
These low-molecular-weight siloxane compounds are usually contained in the silicone resin in an amount of 0.1 to 15.0% by mass, preferably 0.1 to 10.0% by mass, and more preferably 0.1 to 5% by mass as migration components. , the desired light release can be achieved. When the content of the low-molecular-weight siloxane compound is 0.1% by mass or more, the migration component is sufficient, and sufficient releasability is exhibited. On the other hand, when the content of the low-molecular-weight siloxane compound is 15.0% by mass or less, excessive precipitation of migrating components does not occur, and there is no problem of process contamination.

It is preferable to use an organosilicon compound represented by the following general formula (3) in combination with the release layer in order to improve the adhesion of the coating film to the laminated film of the present invention.
Si(X) _d (Y) _e (R ¹ ) _f (3)
[In the above formula, X is an organic group having at least one selected from the group consisting of an epoxy group, a mercapto group, a (meth)acryloyl group, an alkenyl group, a haloalkyl group and an amino group; R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydrolyzable group, and multiple Ys may be the same or different. , d is an integer of 1 or 2, e is an integer of 2 or 3, f is an integer of 0 or 1, and d+e+f=4. ]

As the organosilicon compound represented by the general formula (3), those having two hydrolyzable groups Y (D unit source) or three (T unit source) can be used.

In general formula (3), the monovalent hydrocarbon group R ¹ having 1 to 10 carbon atoms is particularly preferably a methyl group, an ethyl group or a propyl group.

In general formula (3), examples of the hydrolyzable group Y include the following. methoxy, ethoxy, butoxy, isopropenoxy, acetoxy, butanoxime, amino and the like. These hydrolyzable groups may be used alone or in combination of multiple types. Among them, a methoxy group or an ethoxy group is particularly preferable because it can impart good storage stability to the coating material and has suitable hydrolyzability.

Specific examples of the organosilicon compound contained in the release layer include vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl ) Ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 5-hexenyltrimethoxysilane, p-styryl Examples include trimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, and the like.

The content of the organosilicon compound in the release layer is preferably 0.5 to 5.0 parts by mass, preferably 0.5 to 2.0 parts by mass, with respect to 100 parts by mass of the curable silicone resin. is. When the content of the organosilicon compound is 0.5 parts by mass or more, the desired adhesion can be easily ensured. It is not too strong and can be easily peeled off when originally necessary.

(wax)
The release layer may contain wax as a release agent.
Wax is selected from natural waxes, synthetic waxes, and waxes blended with them.
Natural waxes include vegetable waxes, animal waxes, mineral waxes, and petroleum waxes. Plant waxes include candelilla wax, carnauba wax, rice wax, Japan wax, jojoba oil and the like. Animal waxes include beeswax, lanolin, whale wax and the like. Mineral waxes include montan wax, ozokerite, and ceresin. Petroleum wax includes paraffin wax, microcrystalline wax, petrolatum, and the like.
Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters, ketones and the like. Synthetic hydrocarbons include, for example, Fischer-Tropsch wax (also known as Sasol wax), polyethylene wax, and other low-molecular-weight polymers (specifically, polymers with a number-average molecular weight of 500 to 20,000). Examples include the following polymers: polypropylene, ethylene-acrylic acid copolymer, polyethylene glycol, polypropylene glycol, block or graft combination of polyethylene glycol and polypropylene glycol, and the like. Modified waxes include montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives and the like. The derivative here is a compound obtained by purification, oxidation, esterification, saponification, or a combination thereof. Hydrogenated waxes include hydrogenated castor oil and hydrogenated castor oil derivatives.

Among the waxes described above, synthetic waxes are preferable, polyethylene waxes are more preferable, and oxidized polyethylene waxes are even more preferable, from the viewpoint of stabilizing the properties.
The number average molecular weight of the synthetic wax is preferably in the range of 500 to 30,000, more preferably 1,000 to 15,000, and still more preferably 2,000 to 8,000 from the viewpoints of stability of properties such as blocking and handleability.

(melamine compound)
The release layer can also contain a melamine compound as a release agent.
Although the melamine compound is not particularly limited, melamine-based resins can be mentioned. Examples of the melamine resin include melamine formaldehyde resin, methylated melamine formaldehyde resin, butylated melamine formaldehyde resin, etherified melamine formaldehyde resin, epoxy-modified melamine formaldehyde resin, urea melamine resin, acrylic melamine resin and the like. In particular, alkyl melamine formaldehyde resins, especially butylated melamine formaldehyde resins, are preferred because of their excellent release performance.

<Crosslinking agent>
When forming the release layer, it is preferable to use various cross-linking agents in combination in order to strengthen the release layer and stabilize performance such as water repellency. In particular, it is preferable to use together with a polyether group-containing silicone compound.

Conventionally known materials can be used as the cross-linking agent. Examples thereof include melamine compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, aziridine compounds and the like. Among them, melamine compounds, epoxy compounds, isocyanate compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferable, and furthermore, melamine compounds are preferred from the viewpoint of being able to maintain moderate water repellency and to strengthen the release layer. , oxazoline compounds and isocyanate compounds are preferred, and melamine compounds are particularly preferred.
One kind of these crosslinking agents may be used, or two or more kinds thereof may be used in combination.

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. The melamine compound may be either a monomer, a dimer or higher polymer, or a mixture thereof. Considering the reactivity with various compounds, the melamine compound preferably contains a hydroxyl group.
Furthermore, 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 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 obtained by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like, and one of these can be used alone or two or more of them can be used in combination. be able to. Among them, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
Other monomers are not limited as long as they are copolymerizable with addition-polymerizable oxazoline group-containing monomers. For example, alkyl (meth) acrylate (as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group) ( meth)acrylic acid esters; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) Unsaturated carboxylic acids; unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylamide, N-alkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; styrene, α-methylstyrene, and α,β-unsaturated aromatic monomers, etc., and these monomers may be used alone or in combination of two or more.

The oxazoline group content 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 within the above range, it becomes easier to adjust the water repellency.

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, methylenebis(4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate, etc. and the like are exemplified. Polymers and derivatives of these isocyanates such as burettes, isocyanurates, uretdione compounds 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.

When used in the form of blocked isocyanate, examples of blocking agents include bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol. active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoylacetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; ε-caprolactam, δ-valerolactam, etc. lactam compounds, diphenylaniline, aniline, amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetic acid amide, oxime compounds such as formaldehyde, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime. can be done. These may be used alone or in combination of two or more. Among them, an isocyanate compound blocked with an active methylene compound is preferable from the viewpoint that it is particularly effective in reducing the migration of the adhesive layer to the adherend.

The isocyanate compound may be used alone, or may be used as a mixture or combination with various polymers. In order to improve 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.

Epoxy compounds are compounds having an epoxy group in the molecule, and examples thereof include condensates of epichlorohydrin with hydroxyl groups and amino groups such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A. , 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. Polyglycidyl ethers are mentioned. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether. glycidyl ether, polytetramethylene glycol diglycidyl ether; Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3- bis(N,N-diglycidylamino)cyclohexane and the like.

Among them, polyether-based epoxy compounds are preferable from the viewpoint of having good various properties. As for the amount of epoxy groups, a polyepoxy compound having a polyfunctionality of 3 or more is preferable to a bifunctional one.

A carbodiimide-based compound is a compound that has 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 release layer.

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

Furthermore, surfactants, polyalkylene oxides, quaternary ammonium salts of dialkylaminoalcohols, and hydroxyalkylsulfonic acids are added to improve the water solubility and water dispersibility of the polycarbodiimide compounds within the range that does not impair the effects of the present invention. Hydrophilic monomers such as salts may be added and used.

A silane coupling compound is an organosilicon compound that has 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 (epoxycyclohexyl)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, and mercapto group-containing compounds such as ethoxysilane.

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 release layer. .

In addition, since these cross-linking agents are designed to be reacted to improve the performance of the release layer during the drying process and film formation process, unreacted products of these cross-linking agents are included in the formed release layer. , a compound after the reaction, or a mixture thereof.

<Various polymers>
Various polymers such as polyester resins, acrylic resins, urethane resins, and vinyl resins can be used to form the release layer to improve coating appearance and transparency, and to control water repellency and slipperiness. be. Among various polymers, polyester resins, acrylic resins, urethane resins, and vinyl resins are preferable, and polyester resins and acrylic resins are more preferable, from the viewpoint of easy control of water repellency.

Polyester resins include those composed of, for example, the following polyvalent carboxylic acid and polyvalent hydroxy compound as main constituents. That is, polyvalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic 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, p-hydroxybenzoic acid, trimellitic acid monopotassium salt, ester-forming derivatives thereof, and the like can be used. , Polyvalent hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl- 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like can be used. 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 composed of polymerizable monomers including acrylic and methacrylic monomers (hereinafter, acrylic and methacrylic are sometimes collectively abbreviated as (meth)acrylic). These may be homopolymers, copolymers, or copolymers with polymerizable monomers other than acrylic and methacrylic monomers.

Also included are copolymers of the above polymers and other polymers (eg, polyester, polyurethane, etc.). Examples are block copolymers and 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 as the case may be) obtained by polymerizing polymerizable monomers in other polymer solutions or dispersions.

The polymerizable monomer is not particularly limited, but 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. A urethane resin can usually be obtained by a reaction of a polyol and an isocyanate.
Polyols include polycarbonate polyols, polyester polyols, polyether polyols, polyolefin polyols, and acrylic polyols, and these compounds may be used singly 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 and the like.
Polycarbonate-based polyols obtained from these reactions include, for example, poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

Polyester polyols include polyvalent carboxylic 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.).

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

Polyisocyanate compounds used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and 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, dicyclohexyl Alicyclic diisocyanates such as methane diisocyanate and isopropylidene dicyclohexyl diisocyanate are exemplified. These may be used alone or in combination of multiple types.

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 and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- aliphatic diamines such as decanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1, and alicyclic diamines such as 3-bisaminomethylcyclohexane.

The urethane resin may use a solvent as a medium, but preferably uses water as a medium. For dispersing or dissolving the urethane resin in water, there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, a water-based type, and the like. In particular, a self-emulsifying type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferable because it is excellent in the storage stability of the liquid and the water resistance and transparency of the release layer obtained.

Examples of the ionic group to be introduced include 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 a urethane resin, various methods can be adopted in each stage of the polymerization reaction. For example, there is a method of using a resin having a carboxyl group as a copolymerization component when synthesizing a prepolymer, and a method of using a component having a carboxyl group as one component such as a polyol, 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, dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, etc. can be copolymerized with the diol used in the polymerization of the urethane resin. can be done. Moreover, the above carboxyl groups are preferably in the form of salts neutralized with ammonia, amines, alkali metals, inorganic alkalis or the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
Such a polyurethane resin can use the carboxyl groups removed from the neutralizing agent in the drying process after coating as cross-linking reaction points by other cross-linking agents. Therefore, the stability of the liquid before coating is excellent, and the durability, solvent resistance, water resistance, blocking resistance, etc. of the resulting release layer can be further improved.

<Antistatic agent>
It is also a preferred embodiment to incorporate an antistatic agent in the release layer to prevent defects due to adhesion of surrounding dust due to peel electrification or frictional electrification of the film as an antistatic release layer.
The antistatic agent contained in the release layer is not particularly limited, and conventionally known antistatic agents can be used. It is preferable to use a polymer type antistatic agent because it has good heat resistance and moist heat resistance.
Polymer-type antistatic agents include, for example, compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, and conductive polymers.

A compound having an ammonium group is a compound having an ammonium group in the molecule, and includes ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines. The compound having an ammonium group is preferably a polymer 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. preferable. For example, a polymer compound having an ammonium group obtained by polymerizing a monomer containing an addition-polymerizable ammonium group or a precursor of an ammonium group such as an amine is preferably used. The polymer may be obtained by polymerizing a monomer containing an addition-polymerizable ammonium group or an ammonium group precursor such as an amine alone, or a copolymer of a monomer containing these and other monomers. good too.

Among polymer compounds having an ammonium group, polymer compounds having a pyrrolidinium ring are also preferable in that they have excellent antistatic properties and heat stability.

The two substituents bonded to the nitrogen atom of the polymer compound having a pyrrolidinium ring are not particularly limited, but are each independently an alkyl group, a phenyl group or the like, and these alkyl groups and phenyl groups are represented below. It may be substituted with the groups shown. 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. Also, the two substituents attached to the nitrogen atom may be chemically bonded, for example, —(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=CH-, -CH ₂ OCH ₂ -, -(CH ₂ ) ₂ O (CH ₂ ) ₂ — and the like.

A polymer having a pyrrolidinium ring can be obtained 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, using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, or tertiary butyl peroxide. , can be carried out by a known method, but is not limited thereto.
In the present invention, a diallylamine derivative and a polymerizable compound having a carbon-carbon unsaturated bond may be used as copolymer components.

The polymer compound having an ammonium group is also preferably a polymer having a structure represented by the following general formula (4) from the viewpoint of being excellent in antistatic properties and heat and humidity resistance stability. It may be a single polymer, a copolymer, or a copolymer of a plurality of other components.

For example, in the above formula (4), R ¹ represents a hydrogen atom or a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ² represents -O-, -NH- or -S- , R ³ represents an alkylene group having 1 to 20 carbon atoms or another structure capable of forming the structure of general formula (4), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, A hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, a phenyl group or the like, or a hydrocarbon group to which a functional group such as a hydroxyalkyl group is provided, and X ^{1 -} represent various counter ions.

Among the above, in general formula (4), R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ is preferably an alkylene group having 1 to 6 carbon atoms, R ⁴ , R ⁵ and R ⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ , More preferably, one of R ⁵ and R ⁶ is a hydrogen atom and the other substituent is an alkyl group having 1 to 4 carbon atoms.

Examples of anions that serve as counter ions (counter ions) for the ammonium groups of the polymer compound having the above-mentioned ammonium groups include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

Although the number average molecular weight of the polymer compound having an ammonium group is not particularly limited, it is usually 1,000 to 500,000, preferably 2,000 to 350,000, and more preferably 5,000 to 200,000. When the molecular weight is 1,000 or more, the strength of the coating film becomes sufficient, and heat resistance stability is maintained. Further, when the molecular weight is 500,000 or less, the viscosity of the coating liquid is low, and the handleability and coating properties are good.

Examples of polyether compounds include polyethylene oxide, polyether ester amide, and acrylic resins having polyethylene glycol in side chains.

A compound having a sulfonic acid group is a compound containing sulfonic acid or sulfonate in the molecule. For example, compounds in which a large amount of sulfonic acid or sulfonate exists, such as polystyrene sulfonic acid, are preferably used. be done.

Examples of betaine compounds include quaternary ammonium salts. Examples include alkylcarbobetaines, alkylsulfobetaines, alkylamidohydroxysulfobetaines, alkylamidoamine-type betaines, and alkylimidazoline-type betaines. Among them, alkylsulfobetaine is preferred.

Examples of conductive polymers include polythiophene-based, polyaniline-based, polypyrrole-based, and polyacetylene-based polymers. Among them, a polythiophene system, for example, a combination of poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, is preferably used.
Conductive polymers are preferred over the other antistatic agents described above in that they have a lower resistance value. On the other hand, however, in applications where coloring and cost are concerns, it is necessary to devise measures such as reducing the amount used.

Further, within the scope of the present invention, the release layer may contain antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, and dyes, if necessary. , a pigment, etc. can also be used in combination.

<Proportion of release agent>
The proportion of the release agent in the release layer is not particularly limited, and the appropriate amount varies depending on the type of release agent. is not particularly limited, but is 100% by mass. Among them, the proportion of the release agent is preferably in the range of 25 to 99% by mass. Sufficient water repellency can be obtained when the proportion of the release agent is 3% by mass or more.

When a long-chain alkyl compound or fluorine compound is used as the release agent, the proportion in the release layer is preferably 5% by mass or more, more preferably 15 to 99% by mass, and still more preferably 20 to 95% by mass. % by weight, particularly preferably in the range from 25 to 90% by weight. When the content of the release agent is within the above range, water repellency and releasability from the adhesive layer are effective.
The proportion of the cross-linking agent in the release layer is preferably 95% by mass or less, more preferably 1 to 80% by mass, still more preferably 5 to 70% by mass, and particularly preferably 10 to 50% by mass. The cross-linking agent is preferably a melamine compound, an oxazoline compound, or an isocyanate compound, and is particularly preferably a melamine compound from the viewpoint of water repellency and release layer strength.

When an addition-type silicone compound is used as the release agent, the proportion in the release layer is preferably 5% by mass or more, more preferably 25% by mass or more, still more preferably 50% by mass or more, and particularly preferably It is in the range of 70% by mass or more. The upper limit of the preferred range is 99% by mass, and the more preferred upper limit is 90% by mass. When the content of the release agent is within the above range, water repellency and releasability from the adhesive layer are effective, and the appearance of the release layer is also good.

When a polyether group-containing silicone is used as the release agent, the proportion in the release layer is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 25% by mass or more, and particularly preferably is in the range of 40% by mass or more. The upper limit of the preferable range is 99% by mass, the more preferable upper limit is 80% by mass, and the more preferable upper limit is 70% by mass. When the content of the release agent is within the above range, water repellency and releasability from the adhesive layer are effective, and the appearance of the release layer is also good.
The proportion of the cross-linking agent is preferably 90 mass % or less, more preferably 10 to 70 mass %, still more preferably 20 to 40 mass %.

When wax is used as the release agent, the proportion in the release layer is preferably 5% by mass or more, more preferably 10 to 90% by mass, still more preferably 20 to 80% by mass, particularly preferably 25 to 80% by mass. It is in the range of 70% by mass. By using it in the above range, good water repellency can be obtained.
The proportion of the cross-linking agent is preferably 90 mass % or less, more preferably 10 to 70 mass %, still more preferably 20 to 50 mass %. As the cross-linking agent, a melamine compound is preferable from the viewpoint of water repellency and strength of the release layer.

<Proportion of antistatic agent>
When providing an antistatic release layer having antistatic performance as the release layer, the proportion of the antistatic agent varies depending on the type of antistatic agent, but is preferably in the range of 0.5% by mass or more, more preferably 3 to 90 mass %, more preferably 5 to 70 mass %, particularly preferably 8 to 60 mass %.

When an antistatic agent other than a conductive polymer is used as the antistatic agent, the proportion in the antistatic release layer is preferably 5% by mass or more, more preferably 10 to 90% by mass, and still more preferably 20 to 70%. % in the range by weight, particularly preferably in the range from 25 to 60% by weight.

When a conductive polymer is used as the antistatic agent, the proportion in the antistatic release layer is preferably 0.5% by mass or more, more preferably 3 to 70% by mass, more preferably 5 to 50% by mass, Particularly preferably, it is in the range of 8 to 30% by mass.

　Analysis of each component in the release layer can be performed, for example, by analysis such as TOF-SIMS, ESCA, fluorescent X-ray, and IR.

On the other hand, as an example of providing a release layer by offline coating, a case of using a curable silicone resin will be described.
As the type of curable silicone resin, as described above, any existing curing reaction type can be used, such as a heat curing type such as an addition type or a condensation type, or an electron beam curing type such as an ultraviolet curing type. may be used alone or in combination with multiple types of curable silicone resins. There are no particular restrictions on the form of application of the curable silicone resin when forming the release layer, and it may be dissolved in an organic solvent, an aqueous emulsion, or solvent-free.

Regarding the formation of the release layer, the series of compounds described above are used as a solution or dispersion in a solvent, and the liquid adjusted to a solid content concentration of about 0.1 to 80% by mass is coated on the film. is preferred.

<Method for forming release layer>
Methods for forming the release layer include, for example, methods such as coating, transfer, and lamination. Considering the ease of forming the release layer, it is preferably formed by coating.

The coating may be performed in-line, the film once manufactured may be coated outside the system, it may be performed off-line, or a combination of both may be used for coating.

Examples of coating methods 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, kiss coating, spray coating, Conventionally known coating methods such as calendar coating and extrusion coating can be used.

The drying and curing conditions for forming the release layer on the film are not particularly limited. In the case of the coating method, the drying temperature of the solvent such as water used in the coating solution is preferably 70 to 150°C, more preferably 80 to 130°C, and still 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.

If necessary, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used together. The surface of the laminated film forming the release layer may be previously subjected to surface treatment such as corona treatment or plasma treatment.

The laminated film of the present invention may have an adhesive layer on the release layer surface. The method of providing such an adhesive layer is not particularly limited. There is a method of coating in layers, and the like.

In the method of laminating from a releasable base material, it is necessary to pay attention to air bubbles and wrinkles when laminating, but it has the advantage that processes such as heat are not applied to the adhesive film, which is the final product. . In the direct coating method, when the adhesive layer is applied, heat is applied to the film for drying and curing, so it may be necessary to consider changes in the shrinkage rate of the film. It also has the advantage of uniformity. In general, it can be appropriately selected according to the configuration and purpose of the final product.

[Average surface roughness of cured resin layer surface (arithmetic mean height; Sa) and maximum peak height (Sp)]
The arithmetic mean height (Sa) of the cured resin layer surface of the laminated film of the present invention is required to be 500 nm or more. If the arithmetic mean height (Sa) is less than 500 nm, it is possible to remove water or bubbles when bonding to an adherend, or to bond with an adherend in an aspect in which the laminated film of the present invention has an adhesive layer. Insufficient air removal at time.
From the above viewpoints, it is more preferable that the arithmetic mean height (Sa) of the surface of the cured resin layer is 1000 nm or more. On the other hand, the arithmetic mean height (Sa) is preferably 2000 nm or less from the viewpoint of breakage and dropout of the uneven portion.
The maximum peak height (Sp) on the surface of the cured resin layer of the laminated film is preferably 10000 nm or more. If it is 10000 nm or more, the reproducibility of response shape transfer is sufficient when bonding to an adherend. From the above viewpoints, the maximum peak height (Sp) on the surface of the cured resin layer is preferably 11000 nm or more, more preferably 13000 nm or more. On the other hand, the thickness is preferably 20,000 nm or less from the viewpoint of damage and dropout of uneven portions.
Note that the arithmetic mean height (Sa, ISO 25178 surface properties) is a parameter obtained by expanding Ra (arithmetic mean height of lines) to a plane, and is the difference in height between points on the average plane of the surface. It is a numerical value representing the average of the absolute values. In addition, the maximum peak height (Sp, ISO 25178 surface properties) is the extension of the two-dimensional maximum peak height (Rp) to three dimensions, and is the maximum height from the surface where the height is 0 in the measurement area. be.

[Protrusion height (X) and number of protrusions (Y)]
In the laminated film of the present invention, the horizontal axis is the protrusion height (X), and the vertical axis is the number of protrusions ( In the distribution curve that is the common logarithm value log(Y) of Y), the cured resin layer needs to satisfy the following formula (1). The horizontal axis in the distribution curve was set as follows. That is, when observing with a white light interference microscope (white light interferometer), among the protrusions seen from the reference plane obtained from the height measured at each measurement point, the substrate film (A) side is a recess, and the recess is The projection height of the projection is defined as a positive projection height, and the projection height of the recess is defined as a negative projection height, and the horizontal axis is set.

[In the formula, log(Y)max indicates a value at which the common logarithm of the number of protrusions is maximized, and Xmax indicates a positive protrusion height when the common logarithm of the number of protrusions is maximized. log (Y) 85% indicates the value at which the common logarithm of the number of protrusions is 85% of the maximum value, and X85% is the positive protrusion height when the common logarithm of the number of protrusions is 85% of the maximum value. show. "Positive protrusion height" means, in the distribution curve, of the protrusions seen from the reference plane obtained from the height measured at each measurement point, the substrate film (A) side is a recess, and the recess is opposite. is defined as a convex portion, and means the projection height of the convex portion. ]
When the surface of the cured resin layer of the laminated film satisfies the following formula (1), it is possible to transfer a favorable irregular shape to the adherend when the laminated film is adhered to the adherend. For example, when it is laminated to the surface of the adhesive layer, it becomes easy to remove water or bubbles, or to remove air during lamination. A favorable low-gloss feeling can be obtained when the film is laminated with a resin layer.
The surface observation with a white light interference microscope is performed in a 237.65 μm×178.25 μm area of the laminated film according to ISO standard 25178.

From the above point of view, the value of the above formula (1) is preferably -0.25 or more, more preferably -0.19 or more. Regarding the upper limit, it is theoretically less than 0 and is not particularly limited other than that, but from the viewpoint of the difficulty of designing the laminated film and the manufacturing cost, it is preferably -0.05 or less, more preferably -0. 10 or less.

In the laminated film of the present invention, the surface of the cured resin layer needs to satisfy the above formula (1), and it is preferable that the distribution curve further satisfies the following formula (2). By satisfying the formula (2), it is possible to transfer a more favorable uneven shape to the adherend.

[In the formula, Xmin indicates a positive protrusion height at which the number of protrusions is 0, log (Y) 85% indicates a value at which the common logarithm of the number of protrusions is 85% of the maximum value, and X85% is the protrusion A positive protrusion height is indicated when the common logarithm of the number is 85% of the maximum value. "Positive protrusion height" is as described above. ]

From the viewpoint of transferring a good uneven shape to the adherend, the value of the above formula (2) is preferably -1.70 or more, more preferably -1.60 or more, still more preferably -1.50 or more, especially It is preferably -1.48 or more.

The cured resin layer surface of the laminated film of the present invention must satisfy the above formula (1), and furthermore, the positive protrusion height and the negative protrusion height when the number of protrusions is 85% of the maximum value. the difference (Ah) is 4 μm or more, and the difference (Bh) between the positive projection height and the negative projection height when the number of projections is 20% of the maximum value is 7 μm or more, and the following (3) It is preferable to satisfy the formula

In addition, "positive protrusion height" and "negative protrusion height" are measured at each measurement point when observing with a white light interference microscope (white light interferometer) in the distribution curve, Of the protrusions seen from the reference plane obtained from the height measured at each measurement point, the substrate film (A) side is a concave portion, the opposite side of the concave portion is a convex portion, and the protrusion height of the convex portion is a positive value. The projection height and the projection height of the recess are defined as negative projection heights.

As shown in FIGS. 1 to 5, in the present invention, attention is paid to both the upper and lower uneven shapes with respect to the reference plane of the three-dimensional bird's-eye view obtained by observing the surface of the cured resin layer with a white interference microscope. Characteristic. Usually, only the upper (positive side) shape is considered with respect to the reference plane, but as shown in FIG. 5, in the present invention, the lower (minus side) shape is Also, by considering the surface state comprehensively, the uneven shape of the surface of the cured resin layer is optimized.
Furthermore, as a result of paying attention to the distribution of the protrusion height and the number of protrusions, it was found that the number of protrusions tended to decrease stepwise, particularly as the positive protrusion height from the reference plane increased. This point is also a point greatly different from conventional products, for example, a type in which particles are kneaded.

[Air release index]
The air release index of the surface of the cured resin layer is preferably 5000 seconds or less, more preferably 3000 seconds or less, even more preferably 2000 seconds or less, and particularly preferably 700 seconds or less.
Satisfying the above range indicates that the air is quickly released from the gaps, and that the shape allows the air to escape well.
In the present invention, the lower limit of the air release index is not particularly limited, but is, for example, 20 seconds or more, preferably 30 seconds or more. By making the lower limit of the air release index equal to or higher than the above lower limit, for example, it is possible to suppress powder falling of particles from the surface of the cured resin layer during the processing step.
The air release index can be measured by the method described in Examples.

[Glossiness of Cured Resin Layer Surface]
The surface of the cured resin layer of the laminated film of the present invention preferably has a glossiness of 10% or less at 60 degrees. When the glossiness at 60 degrees is equal to or less than the above upper limit, the matting property is excellent. The glossiness at 60 degrees is more preferably 9% or less, still more preferably 6% or less.
Further, the surface of the cured resin layer of the laminated film of the present invention preferably has a glossiness of 15% or less at 85 degrees. When the glossiness at 85 degrees is equal to or less than the above upper limit value, the matte property is more excellent. The glossiness at 85 degrees is more preferably 10% or less, still more preferably 9% or less.

<Adhesive layer>
In an aspect in which the laminated film of the present invention is a release film, the release film can be suitably used as a film for protecting the adhesive layer. The adhesive layer is preferably at least one selected from the group consisting of a silicone-based adhesive layer, an acrylic adhesive layer, and a urethane-based adhesive layer.

(Silicone adhesive layer)
The silicone-based adhesive layer can be formed using the silicone-based adhesive described below.
The silicone pressure-sensitive adhesive that constitutes the silicone-based pressure-sensitive adhesive layer may be any pressure-sensitive adhesive containing silicone as a main component resin.
Here, the “main component resin” means a resin having the largest content ratio (mass) among the resins constituting the pressure-sensitive adhesive. Although not particularly limited, for example, it is a resin that accounts for 50% by mass or more, particularly 70% by mass or more, and especially 80% by mass or more (including 100% by mass) of the resin constituting the adhesive.
Examples of silicone pressure-sensitive adhesives include addition reaction type, peroxide curing type and condensation reaction type silicone pressure-sensitive adhesives. Among them, the addition reaction type silicone pressure-sensitive adhesive is preferable from the viewpoint of being curable at low temperature in a short time. The addition-reactive silicone pressure-sensitive adhesive cures when the pressure-sensitive adhesive layer is formed on the support. When an addition-reactive silicone pressure-sensitive adhesive is used as the silicone pressure-sensitive adhesive, the silicone pressure-sensitive adhesive may contain a catalyst such as a platinum catalyst.
For example, the addition reaction type silicone pressure-sensitive adhesive is applied to a support after adding a catalyst such as a platinum catalyst to a silicone resin solution that has been diluted with a solvent such as toluene, and stirring the solution until uniform. , 100-130° C. for 1-5 minutes. In addition, if necessary, a cross-linking agent or an additive for controlling adhesive force may be added to the addition reaction type silicone pressure-sensitive adhesive. Alternatively, the base film may be subjected to a primer treatment before forming the adhesive layer.

Examples of commercially available silicone resins used for addition-reactive silicone pressure-sensitive adhesives include SD4580PSA, SD4584PSA, SD4585PSA, SD4587LPSA, SD4560PSA, SD4570PSA, SD4600FCPSA, SD4593PSA, DC7651ADHESIVE, DC7652ADHESIVE, LTC-755, LTC-310 ( Both Toray manufactured by Dow Corning), KR-3700, KR-3701, KR-3704, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, X-40- 3323, X-40-3306, X-40-3270-1 (all manufactured by Shin-Etsu Chemical Co., Ltd.), AS-PSA001, AS-PSA002, AS-PSA003, AS-PSA004, AS-PSA005, AS-PSA012, AS-PSA014, PSA-7465 (all manufactured by Arakawa Chemical Industries, Ltd.), TSR1512, TSR1516, TSR1521 (all manufactured by Momentive Performance Materials) and the like can be mentioned.

(Acrylic adhesive layer)
The acrylic pressure-sensitive adhesive layer can be formed using the acrylic pressure-sensitive adhesive described below.
The acrylic pressure-sensitive adhesive constituting the acrylic pressure-sensitive adhesive layer may be a pressure-sensitive adhesive containing a (meth)acrylic acid ester (co)polymer as a main component resin. The meaning of the "main component resin" is as described above.
In addition to the (meth)acrylic acid ester (co)polymer, the acrylic pressure-sensitive adhesive further contains a photopolymerization initiator, a cross-linking agent, a silane coupling agent, and other materials as necessary. It can be formed from a composition.
The acrylic pressure-sensitive adhesive layer can be formed from a conventionally known pressure-sensitive adhesive composition, and for example, the pressure-sensitive adhesive composition described in JP-A-2019-210446 may be used.

(Urethane adhesive layer)
The urethane-based adhesive layer can be formed using the urethane-based adhesive described below.
The urethane-based pressure-sensitive adhesive that constitutes the urethane-based pressure-sensitive adhesive layer may be any pressure-sensitive adhesive containing a urethane-based base polymer as a main component resin. The meaning of the "main component resin" is as described above.
A reaction product of a polyol and a polyisocyanate compound can be used as the urethane-based base polymer of the urethane-based pressure-sensitive adhesive.
Examples of the polyol component include polymer-type polyols such as polyester polyols, polyether polyols, polycarbonate polyols and caprolactone polyols. These polyol components may be used alone or in combination of two or more.
Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates. These polyisocyanate compounds may be used alone or in combination of two or more.

(Thickness of adhesive layer)
The thickness of the adhesive layer (after drying) is preferably 1 to 100 μm, more preferably 5 to 80 μm, even more preferably 10 to 60 μm, particularly preferably 20 to 50 μm.
When it is at least the above lower limit value, sufficient adhesive strength can be obtained, and when it is at most the above upper limit value, handling is easy.

(Total thickness of release film with adhesive layer)
In the present invention, the total thickness of the release film with an adhesive layer is preferably 500 μm or less, more preferably 40 μm or more and 350 μm or less, still more preferably 40 μm or more and 200 μm or less, still more preferably 50 μm or more and 150 μm or less, from the viewpoint of handleability. be.

[Film laminate]
One aspect of the present invention provides a film laminate having an adhesive layer on the release film surface. The film laminate basically has a configuration of substrate film/curable resin layer/releasing layer/adhesive layer. The base film, cured resin layer, release layer and adhesive layer are as described above.
Further, in another aspect of the present invention, there is provided a film laminate comprising the laminated film described above and an adhesive layer on the surface of the cured resin layer of the laminated film. The film laminate basically has a configuration of substrate film/curable resin layer/adhesive layer. The base film, cured resin layer and adhesive layer are as described above.

(Base film)
Examples of base films include polyethylene, polypropylene, cycloolefin polymer (COP), polyester, polystyrene, acrylic resin, polycarbonate, polyurethane, triacetylcellulose (TAC), polyvinyl chloride, polyethersulfone, polyamide, A resin film obtained by forming a polymer such as polyimide or polyamideimide into a film can be mentioned. A mixture of these materials (polymer blend) or a composite of structural units (copolymer) may be used as long as they can be formed into a film. Among them, as described above, the base film is preferably a polyester film.

The thickness of the base film is preferably 20-350 μm, more preferably 25-250 μm, still more preferably 25-125 μm, particularly preferably 25-100 μm, and most preferably 25-60 μm.

(Arithmetic mean height (Sa) of cured resin layer surface)
In the film laminate of the present invention, the surface roughness (arithmetic mean height; Sa) of the surface of the cured resin layer after peeling of the release film is required to be 500 nm or more.
When the arithmetic average height (Sa) is less than 500 nm, when the release film is peeled off from the film laminate of the present invention and the adhesive layer is attached to the adherend, moisture or bubbles remain, and during attachment There is a lot of air in the adhesive, which causes a poor appearance or a decrease in adhesive strength due to residual moisture. In the present invention, the surface roughness is 500 nm or more, so that when the release film is peeled from the film laminate of the present invention and the adhesive layer is adhered to the adherend, moisture or bubbles remain, and lamination Since the amount of air is small, it is possible to significantly suppress the appearance defects and the decrease in adhesive strength as described above.
From the above viewpoints, the arithmetic mean height (Sa) of the cured resin layer surface is preferably 800 nm or more, more preferably 1000 nm or more, and still more preferably 1100 nm or more.

Although the thickness of the cured resin layer is not particularly limited, it is preferably 1 to 100 μm, more preferably 2 to 80 μm, still more preferably 3 to 50 μm, and particularly preferably 3 to 30 μm. By satisfying the above range, good transfer properties and adhesion properties can be exhibited.

<Method for producing film laminate>
The method for producing the film laminate of the present invention is not particularly limited. can be manufactured. At that time, the uneven shape on the surface of the release film can be transferred to the surface of the adhesive layer and/or the base film (B).

<Application>
The laminated film, release film and film laminate of the present invention can be suitably used for various transfer applications by utilizing the uneven shape of the cured resin layer. For example, it is useful as a PPF (paint protection film) for the purpose of protecting automobile paint. Alternatively, it is also useful for protecting the adhesive layer. It is also useful as a wrapping film for wrapping printed adhesive films for automobiles, trucks, trains, airplanes, and the like. According to the laminated film and film laminate of the present invention, even when a large-area pressure-sensitive adhesive film as described above is attached to an adherend, workability is good, and the adherend can be easily and uniformly coated. It is possible to laminate to

Although the present invention will be described in more detail below with reference to examples, the present invention is not limited to the following examples as long as it does not exceed the gist thereof. Moreover, the measurement method and evaluation method used in the present invention are as follows.

(1) Method for measuring intrinsic viscosity of polyester 1 g of polyester from which incompatible components have been removed is precisely weighed, and 100 ml of a mixed solvent of phenol/tetrachloroethane = 50/50 (mass ratio) is added to dissolve. Measured in °C.

(2) Measurement method of average particle diameter (d ₅₀ : μm) Accumulation (mass basis) 50 in equivalent spherical distribution measured using a centrifugal sedimentation particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) % was taken as the average particle size.

(3) Method for measuring number-average molecular weight and weight-average molecular weight GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used for measurement under the following conditions.
Measurement conditions: TOSOH TSK-GEL GHXL-L, G4000HXL, G2000HXL
Solvent: Tetrahydrofuran (THF)
Column temperature: 40°C
Flow rate: 1.0 ml/min Detector: RI
Injection concentration: 0.2 w/v%
Injection volume: 0.1 ml
The number average molecular weight and weight average molecular weight were calculated in terms of polystyrene.

(4) Surface roughness of the polyester film, distribution curve of the surface of the cured resin layer, and number of projections measured for projection height White interferometer (Hitachi High-Tech Science Co., Ltd. "Vert Scan" (registered trademark) R5500) Laminated film (Sample) On the surface, the uneven shape of the surface in an area of 237.65 μm × 178.25 μm was measured by light interferometry, and the relationship between the protrusion height of each 0.06 µm and the number of protrusions at each protrusion height was diagrammed. , represented as a distribution curve. The common logarithms of the number of projections at projection heights of X1 μm and X2 μm were set to log(Y1) and log(Y2). The common logarithm log(Y)max of the maximum number of protrusions, the value log(Y) 85% that is 85% of the maximum value, and the value log(Y) 20% that is 20% of the maximum value were obtained. Among the protrusions seen from the reference plane obtained from the measurement, the base film (A) side is a concave portion, the opposite side of the concave portion is a convex portion, the protrusion height of the convex portion is the positive protrusion height, and the protrusion of the concave portion With the height as a negative protrusion height, the positive protrusion height Xmax corresponding to log (Y) max from the distribution curve, the positive protrusion height X85% corresponding to log (Y) 85%, and the maximum number of protrusions Difference between positive projection height and negative projection height when 85% of (Ah), difference between positive projection height and negative projection height when the number of projections is 20% of the maximum value (Bh) , the ratio of Ah to Bh (Bh/Ah), and the positive protrusion height Xmin at which the number of protrusions is zero.

(5) Glossiness (60 degrees, 85 degrees)
Using VG-2000 manufactured by Nippon Denshoku Industries, the 60-degree gloss and 85-degree gloss of the surface of the cured resin layer of the laminated film were measured.

(6) Air release index A laminated film (sample) was cut into a size of 70 mm square, and the laminated film and a polyester film with a hole of 5 mm in diameter in the center were placed so that the surface of the cured resin layer of the laminated film was the polyester film. They were laminated so as to be in contact with each other, and the air release index was measured.
The air release index was measured using a digibec smoothness tester (DB-2, manufactured by Toyo Seiki Co., Ltd.) under an atmosphere of 23° C. temperature and 50% RH humidity. At this time, the pressure of the pressure device is 100 kPa, the vacuum vessel is a small vacuum vessel with a volume of 380 ml, and the time for 1 mL of air to flow, that is, the time until the pressure in the vessel changes from 50.7 kPa to 48.0 kPa. (seconds) was measured, and the obtained number of seconds was taken as the air release index.
The smaller the value of this air escape index, the more quickly the air escapes from the gaps, indicating that the shape allows better air escape.

Examples and comparative examples are shown below. The polyester resins used in producing the polyester films used in the examples and comparative examples and the cured resin composition used in producing the laminated films are as follows. be.

<Polyester resin A>
Polyester resin made of polyethylene terephthalate (intrinsic viscosity: 0.85 dl/g)
<Polyester resin B>
Polyester resin composed of copolymerized polyethylene terephthalate containing 22 mol % of isophthalic acid (intrinsic viscosity: 0.70 dl/g, melting point: 198°C)
<Polyester resin C>
Polyester resin composition (intrinsic viscosity: 0.6 dl/g) in which spherical silica particles having an average particle size of 2.7 μm are blended in polyethylene terephthalate
<Polyester resin D>
Polyester resin composition (intrinsic viscosity: 0.6 dl/g) in which spherical silica particles having an average particle size of 4.1 μm are blended in polyethylene terephthalate
<Polyester resin E>
Polyester resin composition (intrinsic viscosity: 0.6 dl/g) in which alkyl methacrylate-styrene copolymer particles having an average particle diameter of 4 μm are blended in polyethylene terephthalate

<Cured resin composition>
Acrylates (A), Acrylates (B), Acrylates (C), Acrylates (D), Acrylates (E), Acrylates (F), Polymers (G1), Polymers (G2), Particles (H), Each material of the photopolymerization initiator (I) was mixed in the amounts shown in Tables 1 and 2 (parts by mass, converted to non-volatile content) (for components other than acrylates (A) to (F), the above acrylate resin is the amount for a total of 100 parts by mass). Next, a mixed solvent of propylene glycol monomethyl ether (hereinafter referred to as PGM) and methyl ethyl ketone (hereinafter referred to as MEK) (PGM:MEK (mass ratio) is 7:3) is added so that the solid content concentration becomes 30% by mass, and is uniformly mixed. to obtain a curable composition (coating liquid) used in each example and comparative example.

・Acrylate (A): Dicyclopentenyloxyethyl acrylate (Funkryl FA-512AS manufactured by Showa Denko Materials)

・Acrylate (B): ethoxylated dipentaerythritol polyacrylate (A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd.)

Acrylate (C): a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Viscoat #300 manufactured by Osaka Organic Chemical Industry Co., Ltd.)

・Acrylate (D): a mixture of a condensate of isophorone diisocyanate and dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Mitsubishi Chemical Corporation, Shikou UV1700B)

・Acrylate (E): hyperbranched hexafunctional acrylate (CN2303 manufactured by Satomer)

・Acrylate (F): a mixture of glycerin diacrylate and glycerin triacrylate (Aronix M-930 manufactured by Toagosei Co., Ltd.)

(Synthesis Example 1: Synthesis of monomer (i-1))
Methacrylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was distilled under reduced pressure, and fractions with a purity of 99.8% or more were collected to obtain a distillate of methacrylic anhydride. The vacuum distillation was carried out by gradually raising the temperature from room temperature to 90° C. at a pressure of 30 pa.
Separately, 22.4 g (0.1 mol) of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (manufactured by Tokyo Chemical Industry Co., Ltd.), and triethylamine (Tokyo Kasei Kogyo Co., Ltd.) 30.4 g (0.3 mol) was dissolved in 500 mL of methylene chloride (Tokyo Kasei Kogyo Co., Ltd.). 23.1 g (0.15 mol) of the distillate of methacrylic anhydride was added dropwise thereto at room temperature and stirred for 12 hours.
After washing the resulting reaction solution with 500 mL of ion-exchanged water three times, the organic phase was concentrated and the solvent was distilled off. The residue was purified by column chromatography (ethyl acetate/hexane=10/90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%).
¹ H-NMR analysis confirmed that the obtained compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate.
1H NMR (300 MHz, chloroform-d: δ8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0.6 Hz , 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1 Hz, 2H), 4.29 (dd, J = 5.5, 4.1 Hz, 3H), 1.94 (dd, J=1.6, 1.0 Hz, 3H), 1.61 (s, 6H).

[Polymer having an active group that generates radicals upon exposure to active energy rays]
・Polymer (G1)
Into a flask equipped with a stirrer, condenser and thermometer, 75.0 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) was put and stirred. Then, the inside of the flask was replaced with nitrogen, and the temperature was raised to 65° C. 40.0 parts of 4-methacryloyloxybenzophenone (manufactured by Shinryo Corporation), 10.0 parts of stearyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: acrylic ester S). part, N,N-diethylaminoethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester DE) 10.0 parts, 2-ethylhexyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester EH) 30.0 parts, 2 -Hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester HO) 30.0 parts, 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, trade name: V- 65) A mixed solution of 0.8 parts and 75.9 parts of MIBK was added dropwise over 2 hours. After 2 hours, 0.5 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) and 1.0 parts of MIBK were added to increase the polymerization rate. was added and held for 5 hours. Thereafter, the reaction solution was cooled to 40° C. to polymerize a polymer (G1) having an active group capable of generating radicals upon irradiation with active energy rays. G1 had a non-volatile content of 40% and a weight average molecular weight (Mw) of 16,700.

・Polymer (G2)
In a flask equipped with a stirrer, condenser and thermometer, 89.2 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PMA), 36.1 parts of the monomer (i-1) obtained in Synthesis Example 1, 2 - (Perfluorohexyl) ethyl methacrylate (manufactured by Daikin Industries, trade name: C6SFMA monomer) 31.5 parts, 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester HO) 7.0 parts, glycidyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester G) 4.9 parts, 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, trade name: V-65)0. Add 4 parts and stir. Then, the inside of the flask was replaced with nitrogen and the temperature was raised to 90° C., 15.5 parts of the monomer (i-1) obtained in Synthesis Example 1, 2-(perfluorohexyl)ethyl methacrylate (manufactured by Daikin Industries, Ltd., product name: C6SFMA monomer) 13.5 parts, 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Co., trade name: Acryester HO) 3.0 parts, glycidyl methacrylate (manufactured by Mitsubishi Chemical Co., trade name: Acryester G)2. A mixed solution of 1 part and 57.1 parts of PMA was added dropwise over 4 hours. After 2 hours, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) and 6.0 parts of PMA were added to increase the polymerization rate. was added and held for 5 hours. Thereafter, the reaction solution was cooled to 40° C., 84.5 parts of PMA was added, and the mixture was stirred to polymerize a polymer (G2) having an active group capable of generating radicals upon exposure to active energy rays. G2 had a non-volatile content of 30% and a weight average molecular weight (Mw) of 110,900.

・ Particles (H): Crosslinked acrylic particles with an average particle size of 1.8 μm (MX-180TA manufactured by Soken Chemical Co., Ltd.)

· Photoinitiator (I): Omnirad 184 (manufactured by IGM Resins B.V.)

Example 1
The above-mentioned polyester resin A and the above-mentioned polyester resin C in such an amount that the amount of particles added is 0.4% by mass, respectively, were supplied to a vented twin-screw extruder. They were each melted at 285° C., co-extruded from a die, and cooled and solidified on a cooling roll whose surface temperature was set to 22° C. using an electrostatic contact adhesion method to obtain an unstretched sheet. Next, using the roll peripheral speed difference, the film is stretched 3.3 times in the longitudinal direction at a temperature of 85 ° C., guided to a tenter, stretched 4.0 times in the transverse direction at 140 ° C., and the main crystal The heat treatment was carried out at a heating zone temperature of 235°C. Thereafter, the film was relaxed by 10% in the transverse direction to obtain a biaxially stretched polyester film A having a thickness of 50 μm. The surface roughness of the obtained polyester film A was 0.012 μm.
Further, a curable resin composition having the composition shown in Table 1 was applied to a thickness (after drying) of 5 g/m ² and dried at 70°C for 60 seconds. Next, excimer light (half width 14 nm) by xenon (wavelength 172 nm) was applied with an integrated light quantity of 15 mJ/cm ² and an illuminance of 5 mW/cm ² (xenon excimer 172 nm light irradiation machine manufactured by Ushio Inc., lamp unit type: SUS05 (lamp house type: H0011, lighting power supply type: B0005), nitrogen flow (oxygen concentration 1% or less)), the dried coating was irradiated. Furthermore, ultraviolet rays were irradiated in the atmosphere with a high-pressure mercury lamp at an integrated light amount of 400 mJ/cm ² and an illuminance of 200 mW/cm ² (UV conveyor of a high-output UV device (model: US5-X1802-X1202) manufactured by Eyegraphics). A laminate having a cured resin layer having an uneven structure with a thickness (after drying) of 5 μm on the substrate film was obtained.

Examples 2 to 6 and Comparative Examples 1 to 4
Change the polyester film composition to the composition shown in Tables 1 and 2, change the cured resin composition to the composition shown in Tables 1 and 2, omit the excimer light irradiation step, and change the film thickness to 4 μm. A laminated film was obtained in the same manner as in Example 1 except for the above.

Comparative example 5
A laminate film was obtained by reproducing Example 2 of JP-A-2020-82657.
Properties of these films are shown in Tables 3 and 4 below.

From the results of Examples 1 to 5, since the laminated film of the present invention has a moderately roughened surface roughness, the uneven shape of the surface of the cured resin layer is transferred to the surface of the other adherend. Suitable for use. It was also found that the conventional kneading type matte film has a feature of having an uneven shape that is difficult to reproduce.

1 and 2 show bird's-eye views of the surfaces of the cured resin layers of the laminated films obtained in Examples 1 and 3, respectively. From these figures, the surface roughness of the cured resin layer of the laminated film of the present invention is visually recognized, and it is clear that the film surfaces of Comparative Examples 1 and 4 (see FIGS. 3 and 4) are different.
6 and 7 show the cured resin layer surfaces of the laminated films obtained in Examples 1 and 3, and FIGS. 8 and 9 show the cured resin layer surfaces of the laminated films obtained in Comparative Examples 1 and 4. , respectively, distribution curves obtained from surface profiles obtained from surface observation with a white light interference microscope. From FIGS. 6 to 9, it is clear that the shapes of the distribution curves are significantly different between the examples and the comparative examples.
For example, Example 3 and Comparative Example 2 differ in the configuration of the cured resin composition.
In Example 3, the blending ratio of acrylate with a small number of functional groups is small, and the cured resin layer has moderate hardness while also having moderate flexibility, so that the cured resin layer surface easily follows deformation and unevenness is formed. The feature is that it is devised so that it can be done easily. On the other hand, in Comparative Example 2, since the blending ratio of the acrylate containing the urethane acrylate is large, the cured resin layer is too soft, and there is no opportunity to form the convex portions, and it is presumed that it is difficult to form the desired unevenness.

Although the details of the mechanism of unevenness formation are unknown, it can be inferred as follows.
For example, in the reaction process of curing the curable resin composition, hard components (e.g., polyfunctional acrylate containing trifunctional or more) are first cured to form a film, and soft components (e.g., urethane acrylate) are formed later. , is deformed by the presence of the hard component, and is pushed upward to form a convex portion. Alternatively, a soft component (e.g., urethane acrylate) cures first, and then a hard component (e.g., polyfunctional acrylate containing tri- or more functional groups) rides on the soft component, resulting in the formation of protrusions. .
From the above, it is considered that the intended concave-convex structure can be appropriately formed by imparting an appropriate degree of hardness to the cured resin layer.

The laminated film of the present invention is suitable for use in transferring uneven shapes (for example, for automobile paint protection, wrapping film, etc.).

Claims (31)

1. A cured resin layer is provided on one side of the substrate film (A), the cured resin layer has an uneven structure, and the arithmetic mean height (Sa) of the surface of the cured resin layer is 500 nm or more,
   Obtained from the surface profile obtained from the surface observation of the cured resin layer with a white light interference microscope, the horizontal axis is the protrusion height (X), and the vertical axis is the common logarithm of the number of protrusions (Y) log(Y). A laminated film in which the cured resin layer satisfies the following formula (1) in a certain distribution curve.
   

   

   
   [In the formula, log(Y)max indicates a value at which the common logarithm of the number of protrusions is maximized, and Xmax indicates a positive protrusion height when the common logarithm of the number of protrusions is maximized. log (Y) 85% indicates the value at which the common logarithm of the number of protrusions is 85% of the maximum value, and X85% is the positive protrusion height when the common logarithm of the number of protrusions is 85% of the maximum value. show. "Positive protrusion height" means, in the distribution curve, of the protrusions seen from the reference plane obtained from the height measured at each measurement point, the substrate film (A) side is a recess, and the recess is opposite. is defined as a convex portion, and means the projection height of the convex portion. ]
2. The laminated film according to claim 1, wherein the cured resin layer satisfies the following formula (2) in the distribution curve.
   

   

   
   [Wherein, Xmin indicates a positive protrusion height at which the number of protrusions is 0, log (Y) 85% indicates a value at which the common logarithm of the number of protrusions is 85% of the maximum value, and X85% is the protrusion A positive protrusion height is indicated when the common logarithm of the number is 85% of the maximum value. "Positive protrusion height" is as described above. ]
3. In the cured resin layer, the difference (Ah) between the positive protrusion height and the negative protrusion height when the number of protrusions is 85% of the maximum value in the distribution curve is 4 μm or more, and the number of protrusions is the maximum value. 3. The laminated film according to claim 1, wherein the difference (Bh) between the height of the positive projection and the height of the negative projection when the height is 20% of 7 μm or more and satisfies the following formula (3).
   

   

   
   In addition, "positive protrusion height" and "negative protrusion height" are obtained from heights measured at each measurement point when observed with a white light interference microscope (white light interferometer) in the distribution curve. Among the protrusions viewed from the reference surface, the base film (A) side is a recess, the opposite side of the recess is a protrusion, the protrusion height of the protrusion is a positive protrusion height, and the protrusion height of the recess is a positive protrusion height. Negative projection height.
4. The laminated film according to any one of claims 1 to 3, wherein the cured resin layer is a cured product of a cured resin composition containing (meth)acrylate.
5. A cured resin layer is provided on one side of the base film (A),
   The cured resin layer has an uneven structure,
   The cured resin layer is a cured product of a cured resin composition containing (meth)acrylate, and the surface of the cured resin layer has an arithmetic mean height (Sa) of 500 nm or more.
   laminated film.
6. The laminated film according to claim 5, wherein the (meth)acrylate is a cured product of a cured resin composition containing a urethane-based (meth)acrylate and a trifunctional or higher (meth)acrylate.
7. The laminated film according to claim 5, wherein the cured resin composition contains 50% by mass or less of urethane-based (meth)acrylate and 25% by mass or more of trifunctional or higher (meth)acrylate.
8. The laminated film according to claim 6 or 7, wherein the curable resin composition contains two or more types of (meth)acrylates having tri- or higher functionality.
9. The laminated film according to any one of claims 1 to 8, wherein the cured resin layer further contains particles, and the particle content is 9% by mass or less.
10. The laminated film according to any one of claims 1 to 9, wherein the base film (A) is a polyester film.
11. The laminated film according to any one of claims 1 to 10, wherein the base film (A) contains particles in a layer in contact with the cured resin layer.
12. The laminated film according to claim 11, wherein the particles have an average particle size of 1 to 10 µm.
13. The laminated film according to any one of claims 1 to 12, wherein the arithmetic mean height (Sa) of the base film (A) on the side where the cured resin layer is formed is 5 nm or more.
14. The laminated film according to any one of claims 1 to 13, wherein the base film (A) has a single layer structure.
15. The laminated film according to any one of claims 1 to 13, wherein the base film (A) has a multilayer structure consisting of at least two layers.
16. The laminated film according to any one of claims 1 to 15, wherein the maximum peak height (Sp) on the surface of the cured resin layer is 10000 nm or more.
17. The laminated film according to any one of claims 1 to 16, wherein the cured resin layer surface has a glossiness of 10% or less at 60 degrees.
18. The laminated film according to any one of claims 1 to 17, wherein the cured resin layer surface has a glossiness of 15% or less at 85 degrees.
19. A method for producing the laminated film according to any one of claims 1 to 18, comprising a step of forming the cured resin layer by excimer lamp irradiation or ultraviolet (UV) irradiation.
20. A release film comprising the cured resin layer of the laminated film according to any one of claims 1 to 18, and a release layer on the cured resin layer.
21. The release film according to claim 20, wherein the release layer contains at least one release agent selected from the group consisting of silicone compounds, melamine compounds, fluorine compounds, waxes and long-chain alkyl compounds.
22. A film laminate comprising the release film according to claim 20 or 21 and an adhesive layer on the release layer surface of the release film.
23. A film laminate comprising the laminated film according to any one of claims 1 to 18 and an adhesive layer on the surface of the cured resin layer of the laminated film.
24. A transferred product obtained by transferring the unevenness of the surface of the cured resin layer of the laminated film according to any one of claims 1 to 18.
25. A transfer product obtained by transferring the unevenness of the surface of the release layer of the release film according to claim 20 or 21.
26. The film laminate according to claim 22 or 23, wherein the adhesive layer is at least one selected from the group consisting of an acrylic adhesive layer, a urethane adhesive layer and a silicone adhesive layer.
27. The laminated film according to any one of claims 1 to 18, which is for protecting the adhesive layer.
28. The release film according to claim 20 or 21, which is for protecting the adhesive layer.
29. The laminated film according to any one of claims 1 to 18 and 27, which is used for automobile paint protection or wrapping film.
30. The release film according to any one of Claims 20, 21 and 28, which is used for automobile paint protection or wrapping film.
31. The film laminate according to claim 22 or 23, which is used for automobile paint protection or wrapping film.

Images