JP2022025625A - Cured film and laminate, and method for producing the same - Google Patents

Abstract

To provide a cured film and a laminate, excellent in delustering properties and scratch resistance; and to provide a method for producing the cured film and the laminate.SOLUTION: Provided is a cured film formed by irradiating an active energy ray-curable composition with active energy rays, and in the cured film, the active energy ray-curable composition includes a polymer (A) having an unsaturated double bond and polyfunctional (meth)acrylate (B) at a main chain or a side chain, and has a wrinkle-like uneven structure on a surface thereof. Provided is a method for producing the cured film, in which the active energy ray-curable composition including the polymer (A) having the unsaturated double bond at the main chain or the side chain or a cured product of the polymer (A) is irradiated with vacuum ultraviolet rays. Provided is a laminate having the cured film on a base material. Provided is a method for producing the laminate, in which the active energy ray-curable composition including the polymer (A) having the unsaturated double bond and the polyfunctional (meth)acrylate (B) at the main chain or the side chain is laminated on the base material, and is cured by irradiation with the vacuum ultraviolet rays.SELECTED DRAWING: None

Description

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

In order to impart matte properties to building materials such as wallpaper, display members, decorative films, etc., the surface of the base material may be provided with fine irregularities. Further, these members may be required to have antistatic properties.
Patent Document 1 discloses a method of irradiating the surface of a biaxially oriented thermoplastic resin film used for a magnetic recording medium with excimer laser light to form fine irregularities.
Patent Document 2 describes, as a method of forming irregularities on the film surface having a hard coat layer used for an antireflection film, by irradiating a film on which a hard coat layer containing a hard coat resin and inorganic fine particles is formed with excima light. , A method of decomposing a portion of the hardcourt resin on the surface layer is disclosed.

Japanese Unexamined Patent Publication No. 4-305430 Japanese Unexamined Patent Publication No. 2014-224920

However, the method described in Patent Document 1 can only obtain a specific uneven structure in which a sufficient matting effect cannot be obtained. Further, since unevenness is directly formed on the biaxially oriented thermoplastic resin film, it is difficult to apply it to a display application or the like which is used by imparting various surface properties such as scratch resistance and antistatic property.
In the method described in Patent Document 2, only the hard coat resin of the hard coat layer is decomposed to expose the inorganic fine particles to the surface, so that the particles are easily dropped off, which hinders visibility when used for a display or the like. It may come. Further, there is a problem that the surface uneven structure is limited by the shape and distribution of particles.
An object of the present invention is to provide a cured film and a laminated body having excellent matte property and scratch resistance, and a method for producing such a cured film and the laminated body.

The present invention has the following aspects.
[1] A cured film formed by irradiating an active energy ray-curable composition with active energy rays, wherein the active energy ray-curable composition is a polymer having an unsaturated double bond in the main chain or the side chain. A cured film containing (A) and polyfunctional (meth) acrylate (B) and having a wrinkle-like uneven structure on the surface.
[2] The cured film according to the above [1], wherein the polymer (A) is a (meth) acrylic acid ester copolymer (A1).
[3] The cured film according to the above [1] or [2], wherein the active energy ray-curable composition does not substantially contain particles.
[4] The average length (RSm) of the roughness curve element according to JIS B0601: 2013 in the uneven structure is 1 to 50 μm, and the arithmetic mean height (Sa) defined by ISO25178 is 0.1 to 5 μm. The cured film according to any one of the above [1] to [3].
[5] The cured film according to any one of [1] to [4] above, wherein the average value (θa) of the local inclination angles in the uneven structure is 2 ° or more.
[6] The cured film according to any one of [1] to [5] above, wherein the 60 ° gloss is 50 or less.
[7] The above-mentioned [1], wherein the active energy ray-curable composition containing the polymer (A) having an unsaturated double bond in the main chain or the side chain and the polyfunctional (meth) acrylate (B) is irradiated with vacuum ultraviolet rays. ] To [6]. The method for producing a cured film according to any one of [6].
[8] A laminate having the cured film according to any one of [1] to [6] above on a substrate.
[9] The laminate according to the above [8], wherein the base material is a film.
[10] An active energy ray-curable composition containing a polymer (A) having an unsaturated double bond in the main chain or a side chain and a polyfunctional (meth) acrylate (B) is laminated on a substrate, and vacuum ultraviolet rays are used. The method for producing a laminate according to the above [8] or [9], wherein the laminate is cured by irradiating with.

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

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

[Cured film]
The cured film of the present invention (hereinafter, simply referred to as "cured film") is formed by irradiating an active energy ray-curable composition with active energy rays, and has a wrinkle-like uneven structure (non-smooth structure) on the surface. It has. Since the cured film has a matte property, it is suitable as an antiglare film.
Since the active energy ray-curable composition contains a polymer (A) having an unsaturated double bond in the main chain or a side chain and a polyfunctional (meth) acrylate (B), the cured film contains the polymer (A). ) And the polyfunctional (meth) acrylate (B) are contained in a crosslinked state.

(Average length of roughness curve elements)
The average length of the roughness curve element in the uneven structure of the cured film is the average length of the roughness curve element according to JIS B0601: 2013 (RSm, hereinafter simply referred to as “RSm”). The evaluation length when calculating RSm was 236.87 μm. RSm is preferably in the range of 1 to 50 μm or more, more preferably 2 to 40 μm, still more preferably 3 to 35 μm, particularly preferably 4 to 30 μm, and most preferably 5 to 25 μm. Within the above range, the matte property is excellent, and the visibility when used for a display or the like is excellent.

(Arithmetic mean height)
The arithmetic mean height in the uneven structure of the cured film is the arithmetic mean height (Sa, hereinafter simply referred to as “Sa”) defined in ISO25178. The evaluation area for calculating Sa is 177.60 μm × 236.87 μm. Sa is preferably in the range of 0.1 to 5 μm or more, more preferably 0.2 to 3 μm, still more preferably 0.3 to 2 μm, and particularly preferably 0.3 to 1.5 μm. Within the above range, the matte property is excellent, and the visibility when used for a display or the like is excellent.

(Average value of inclination angle of uneven structure)
The average value (θa, hereinafter simply referred to as “θa”) of the local inclination angle in the uneven structure of the cured film can be measured by the method described in Examples described later. The evaluation length when calculating θa was 236.87 μm. θa is preferably in the range of preferably 2 ° or more, more preferably 4 ° or more, further preferably 7 ° or more, particularly preferably 10 ° or more, most preferably 15 ° or more, and the upper limit may be 90 °. The higher the tilt angle, the better the matte property.

(Thickness)
The thickness of the cured film (concave and convex layer) is preferably 0.1 to 100 μm, more preferably 0.2 to 20 μm, still more preferably 0.3 to 10 μm, and particularly preferably 0.3, from the viewpoint of improving the matte property. The range is ~ 7 μm. The thickness of the cured film indicates the maximum thickness of the uneven layer, and is determined by observing the cross section with an electron microscope.

(gross)
The 60 ° gloss (60 ° mirror gloss) of the surface of the cured film measured by the method described in Examples described later is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. Hereinafter, the range is most preferably 11 or less, and the lower the range, the more preferable. The smaller the 60 ° gloss value, the better the matte property.
Similarly, the 20 ° gloss is preferably in the range of 20 or less, more preferably 10 or less, further preferably 5 or less, particularly preferably 2 or less, and most preferably 1 or less, and the lower the value, the more preferable. The smaller the 20 ° gloss value, the better the matte property.

(Pencil hardness)
The pencil hardness of the cured film measured by the method described in Examples described later is preferably F or more, more preferably H or more, still more preferably 2H or more. Within the above range, it has excellent scratch resistance and is suitable for applications such as displays where visibility is important.

[Manufacturing method of cured film and laminate]
In the cured film of the present invention and the laminate of the present invention having the same (hereinafter, simply referred to as “laminate”), for example, a coating film of a curable composition is laminated on a substrate, and the surface side (hereinafter, the coating film) of the coating film is laminated. It can be manufactured by a method of forming a cured film on the surface of the base material by irradiating the surface of the base material with active energy rays (on the opposite side of the base material).
By irradiating the surface side of the coating film of the curable composition with active energy rays, the surface side of the coating film is cured first to form a cured film. After that, when the inside of the coating film is cured, the cured film on the surface side that has been cured first buckles, so that a cured film having a wrinkle-like uneven structure is formed on the surface.

(Curable composition)
The curable composition used for forming the cured film is a polymer (A) having an unsaturated double bond in the main chain or the side chain (hereinafter referred to as the polymer (A)) and a polyfunctional (meth) acrylate (B). including. The curable composition may further contain a monofunctional active energy ray-curable compound, a non-active energy ray-curable compound, an organic solvent, a photopolymerization initiator, and other components, if necessary. ..

(Polymer (A))
The polymer (A) is not particularly limited, and a conventionally known polymer having an unsaturated double bond can be used. Examples of such a polymer include a (meth) acrylic acid ester copolymer having an unsaturated double bond, a reactive urethane resin having an unsaturated double bond, and a reactive epoxy having an unsaturated double bond. Examples thereof include a resin, an allyl resin having an unsaturated double bond, and a polyester resin having an unsaturated double bond. Among these, the (meth) acrylic acid ester copolymer (A1) having an unsaturated double bond is preferable from the viewpoint of improving curability and scratch resistance.

The unsaturated double bond refers to a functional group having a carbon-carbon double bond. Examples thereof include (meth) acryloyl group, (meth) acrylamide group, vinyl group, allyl group, vinyl ether group and the like. The polymer having an unsaturated double bond may contain only one of the functional groups, or may contain two or more of them. Among these, the (meth) acryloyl group is preferable because the curability by the active energy ray is excellent, and the acryloyl group is particularly preferable.

The double bond equivalent of the polymer (A) is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, still more preferably 0.5 to 5.0 mmol / g, and particularly preferably. Is in the range of 0.8 to 4.5 mmol / g. By using it in this range, not only the adhesion of the cured film to the substrate, scratch resistance, and hardness tend to be improved, but also the wrinkle-like uneven shape tends to be made finer, and RSm and Sa are reduced. At the same time, a cured film having excellent matte property can be obtained. The double bond amount means the concentration of (meth) acryloyl group in the acrylic resin, that is, the amount of (meth) acryloyl group introduced.

The weight average molecular weight of the polymer (A) is preferably 800 to 120,000, more preferably 2000 to 80000, still more preferably 5000 to 60000, and particularly preferably 10000 to 50000. When the molecular weight of the polymer having an unsaturated double bond is in the above range, the scratch resistance of the cured film is improved and the curability is also good, which is preferable.

The glass transition temperature of the polymer (A) is preferably −20 to 180 ° C., more preferably 0 to 120 ° C., still more preferably 10 to 110 ° C., particularly preferably 20 to 100 ° C., and most preferably 30 to 90 ° C. .. When the glass transition temperature of the polymer having an unsaturated double bond is in the above range, the scratch resistance of the cured film is improved and the curability is also good, which is preferable.

Among the polymers (A), the molecular weight, double bond equivalent, and glass transition temperature of the polymer can be easily adjusted, the uneven shape can be controlled, and the antiglare property, scratch resistance, and curability can be improved. A (meth) acrylic acid ester copolymer (A1) having an unsaturated double bond (hereinafter referred to as a copolymer (A1)) is preferable.

(Copolymer (A1))
Examples of commercially available copolymers (A1) include Hitachi Chemical's trade names Hitaroid 7975, Hitaroid 7988, Hitaroid 7975D, and DIC's trade names Unidick V-6840 and Unidick V-6841. It can also be produced by homopolymerizing or copolymerizing a monomer such as Unidic WHV-649 or Unidic EKS-675 and then introducing a (meth) acryloyl group. The method for producing the (meth) acrylic acid ester copolymer having a (meth) acryloyl group will be described in detail later.

In the case of producing the copolymer (A1), as a method of introducing an unsaturated double bond, a method of reacting an acrylic resin having an epoxy group with an unsaturated double bond and a compound having a carboxyl group (method 1). , A method of reacting an acrylic resin having a carboxyl group with an unsaturated double bond and a compound having an epoxy group (method 2), and a method of reacting an acrylic resin having a hydroxyl group with an unsaturated double bond and a compound having a carboxyl group (method 2). Method 3), a method of reacting an acrylic resin having a carboxyl group with an unsaturated double bond and a compound having a hydroxyl group (method 4), and reacting an acrylic resin having an isocyanate group with a compound having an unsaturated double bond and a hydroxyl group. Examples thereof include a method (method 5), a method of reacting an acrylic resin having a hydroxyl group with a compound having an unsaturated double bond and an isocyanate group (method 6). Further, the above methods may be used in combination. In the following, a radically polymerizable monomer having an unsaturated double bond may be referred to as a monomer.

In the method 1, examples of the monomer having an epoxy group used for obtaining the (meth) acrylic acid ester copolymer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth). ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate can be mentioned. Among these, glycidyl (meth) acrylate is particularly preferable, and glycidyl methacrylate is particularly preferable, in consideration of good reactivity and ease of use of the material. Only one kind of these may be used, or two or more kinds may be combined.

Examples of the compound having an unsaturated double bond and a carboxyl group in Method 1 include (meth) acrylic acid, carboxyethyl (meth) acrylate, an adduct of glycerindi (meth) acrylate and succinic anhydride, and pentaerythritol tri. Examples thereof include additions of (meth) acrylate and succinic anhydride, and additions of pentaerythritol tri (meth) acrylate and succinic anhydride. Among these, additions of (meth) acrylic acid, pentaerythritol tri (meth) acrylate and succinic anhydride are preferable, (meth) acrylic acid is more preferable, and acrylic acid is even more preferable. As the compound having a double bond and a carboxyl group, only one kind may be used, or two or more kinds may be combined.

In the above method 2, examples of the monomer having a carboxyl group used for obtaining the (meth) acrylic acid ester copolymer having a carboxyl group include (meth) acrylic acid, carboxyethyl (meth) acrylate, and many. Examples include basic acid-modified (meth) acrylate. Among these, (meth) acrylic acid is preferable, and acrylic acid is more preferable. Only one kind of these may be used, or two or more kinds may be combined.

Examples of the compound having an unsaturated double bond and an epoxy group in the method 2 include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferable. Only one kind of these may be used, or two or more kinds may be combined.

In the above method 3, examples of the vinyl monomer having a hydroxyl group used for obtaining the (meth) acrylic acid ester copolymer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. , Hydroxypropyl (meth) acrylate. Only one kind of these may be used, or two or more kinds may be combined.

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

In the method 4, the same (meth) acrylic acid ester copolymer as in the method 2 can be used as the (meth) acrylic acid ester copolymer having a carboxyl group.

Examples of the compound having an unsaturated double bond and a hydroxyl group in the above method 4 include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxypropyl (meth) acrylate. Only one kind of these may be used, or two or more kinds may be combined.

Examples of the vinyl monomer having an isocyanate group used for obtaining the (meth) acrylic acid ester copolymer having an isocyanate group in the method 5 include isocyanate ethyl (meth) acrylate.

In the method 5, as the compound having an unsaturated double bond and a hydroxyl group, for example, the same compounds as those mentioned in the method 4 can be used.

In the method 6, as the (meth) acrylic acid ester copolymer having a hydroxyl group, the same compound as in the method 3 can be used.

Examples of the compound having an unsaturated double bond and an isocyanate group in the method 6 include isocyanate ethyl (meth) acrylate. Only one kind of these may be used, or two or more kinds may be combined.

Among the above methods, method 1 is preferable from the viewpoint of cost and productivity. In method 1, the unsaturated double bond is a ring opening between the epoxy group of the (meth) acrylic acid ester copolymer having an epoxy group and the carboxyl group in the unsaturated double bond and the compound having a carboxyl group. Introduced by an addition reaction.

In the above method 1, the compound having an unsaturated double bond and a carboxyl group is the ratio of the compound having an unsaturated double bond and a carboxyl group to the epoxy group in the (meth) acrylic acid ester copolymer having an epoxy group. It is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, still more preferably 50 to 110 mol%. By using it in the above range, it is preferable from the viewpoint that the reaction proceeds in just proportion and the residue of the raw material is reduced.
Further, it may be a copolymer of a (meth) acrylate or other monomer other than the above, such as the above-mentioned (meth) acrylic acid ester copolymer having an epoxy group. The polymerization reaction of these raw materials is usually radical polymerization, and can be polymerized under conventionally known conditions.

Examples of the monomer that can be used together as a raw material include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl. (Meta) 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) ) (Meta) acrylates such as acrylates; ethyl (meth) acrylamide, n-butyl (meth) acrylamide, i-butyl (meth) acrylamide, t-butyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- Acrylamides such as hydroxypropyl (meth) acrylamide and N, N-dihydroxyethyl (meth) acrylamide; styrene-based monomers such as styrene, p-chlorostyrene and p-bromostyrene can be mentioned. Only one kind of these may be used, or two or more kinds may be combined.

The (meth) acrylic acid ester copolymer can be produced by a radical polymerization reaction using the above-mentioned raw material monomer. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

Examples of the organic solvent 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 and propylene glycol monomethyl ether. Ether-based solvent; ester-based solvent such as ethyl acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate; aromatic hydrocarbon solvent such as toluene can be mentioned. These organic solvents may be used alone or in combination of two or more.

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

Further, in the case of radical polymerization, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the (meth) acrylic acid ester copolymer. Examples of the chain transfer agent include butane thiol, octane thiol, decane thiol, dodecane thiol, hexadecane thiol, octadecane thiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, and octyl 3-mercaptopropionate. , Mercaptopropionic acid 2-ethylhexyl ester, thioglycolate 2-ethylhexyl, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) ) Dietanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrythiol, dodecyl mercaptan, diphenylsulfoxide, dibenzyl sulfide, 2,3-Dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thioapple acid, mercaptoacetic acid, mercapto-amber acid, 2-mercaptoethanesulfonic acid, etc. Examples include thiol-based compounds. 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 weight, more preferably 0.5 to 20 parts by weight, and further preferably 1.0 to 15 parts by weight with respect to 100 parts by weight of the total vinyl monomer as a raw material. preferable.

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

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

The amount of the double bond in the (meth) acrylic acid ester copolymer is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, and further preferably 0.5 to 5.0 mmol / g. g, particularly preferably in the range of 0.8 to 4.5 mmol / g. By using it in this range, not only the adhesion of the cured film to the substrate, the scratch resistance, and the hardness tend to be improved, but also the wrinkle-like uneven shape tends to be made finer, and the RSm is lowered, and Sa A reduction, and in some cases an increase in haze and, in some cases, a reduction in gloss can be achieved. The double bond amount means the concentration of the (meth) acryloyl group in the (meth) acrylic acid ester copolymer, that is, the amount of the (meth) acryloyl group introduced.

(Copolymer (A2))
Examples of the polymer (A2) having an unsaturated double bond (hereinafter referred to as the polymer (A2)) other than the (meth) acrylic acid ester copolymer having an unsaturated double bond (A1) are unsaturated. Examples thereof include a reactive urethane resin having an unsaturated double bond, a reactive epoxy resin having an unsaturated double bond, an allyl resin having an unsaturated double bond, and a polyester resin having an unsaturated double bond.

Examples of the reactive epoxy resin having a (meth) acryloyl group include Hitachi Chemical's trade names Hitaroid 7851 and Hitaroid 7663, and Dicell Ornex's trade names EBECRYL645, EBECRYL648, EBECRYL860, EBECRYL1606, EBECRYL3606, EBECRYL360 , EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, DIC's trade name Unidic 5500, Unidic 5502, Nippon Kayaku's trade name KAYARAD R-115, R-130, R-388, EAM-2160, Examples thereof include trade names GENOMER2235, GENOMER2252, GENOMER2263, GENOMER2253, GENOMER2255, and GENOMER2259 manufactured by RAHN.

Examples of commercially available products in the case of a reactive urethane resin having a (meth) ultraviolet group include, for example, Hitachi Chemical's trade names Hitaroid 4861, Hitaroid 4863, Hitaroid 7902-1, Hitaroid 7909-1, and Hitaroid 7903-. 1, Hitaroid 7903-3, Hitaroid 7903-B, Hitaroid 7903-4, Hitaroid 7906D-3E, Tessrac 2300, Tesslac 2311, Tesslac 2304, Tesslac 2310, Tesslac 2328, Tesslac 2350, TA24-195H, Toagosei products name Aronix M-1100, M-1200, manufactured by Daicel Orunekusu Co., Ltd. under the trade name EBECRYL204, EBECRYL205, EBECRYL210, EBECRYL215, EBECRYL220, EBECRYL230, EBECRYL244, EBECRYL245, EBECRYL264, EBECRYL265, EBECRYL270, EBECRYL280 / 15IB, EBECRYL284, EBECRYL285, EBECRYL294 / 25HD, EBECRYL1259, EBECRYL1290, EBECRYL4491, EBECRYL4820, EBECRYL4858, EBECRYL5129, EBECRYL8210, EBECRYL8254, EBECRYL8301R, EBECRYL8307, EBECRYL8402, EBECRYL8405, EBECRYL8411, EBECRYL8413, EBECRYL8465, EBECRYL8800, EBECRYL8804, EBECRYL8807, EBECRYL9260, EBECRYL9270, EBECRYL8311, EBECRYL8701, EBECRYL9227EA, KRM8528, KRM8667, KRM8904, KRM8452, KRM8286, KRM7735, KRM8200, Mitsubishi Chemical Co., Ltd. trade names UV-3610ID80, UV-3640PE80, UV-3630ID80, UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA , UV-3300B, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6640B, trade names made by DIC Unidic V-4000BA, Unidic V-4221, Unidic RC29-124, Kyoeisha Chemical Co., Ltd. Product name AH made by the company -600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, KAYARAD UX-3204, UX-4101, UXT-6100, UX-6101, manufactured by Nippon Kayaku Co., Ltd. UX-7101, UX-8101, UX-0937, UXF-4002, DPHA-40H, UX-5000, UX-5005, brand name Art Resin UN-333, UN-350, UN-1255, UN manufactured by Negami Kogyo Co., Ltd. -2600, UN-2700, UN-5500, UN-5590, UN-5507, UN-6060PTN, UN-6200, UN-6202, UN-6300, UN-6301, UN-7600, UN-7700, UN-99000PEP , UN-9200A, RAHN trade names GENOMER4188 / EHA, GENOMER4215, GENOMER4217, GENOMER4230, GENOMER4267, GENOMER4269 / M22, GENOMER4205, GENOMER4256, GENOMER4256, GENOMER4256

Examples of the polyester resin having a (meth) acryloyl group include trade names Aronix M-6100, M-6200, M-6250, M-6500, M-7100, M-8100, M-9050, manufactured by Toagosei Co., Ltd. EBECRYL811, EBECRYL812, EBECRYL851, EBECRYL852, EBECRYL884, EBECRYL885, RAHN product names GENOMER3334, GENOMER3414, GENOMER3414, GENOMER34

Examples of the polymer having an unsaturated double bond that is not a (meth) acryloyl group include Dapp A, Dapp S, Dapp K, which are diallyl phthalate resins (DAP resins) manufactured by Osaka Soda Co., Ltd., and Radpar AD-32. Examples thereof include allyl resins such as AD-044. Examples of the unsaturated polyester resin having a vinyl group include Yupica 7017 and 7015 manufactured by Japan U-Pica Company, Rigolac M411 and M543 manufactured by Showa Denko Co., Ltd., and Sandoma P101 and P201 manufactured by DH Material Co., Ltd.

The content of the polymer (A) in the curable composition is preferably 5 to 70% by mass, more preferably 7 to 60% by mass, particularly preferably 10 to 55% by mass, and 20 to 20 to 50% by mass with respect to the non-volatile content. Most preferably 50% by mass. When the content of the polymer (A) is in this range, scratch resistance and curability are excellent.

The non-volatile component of the curable composition is the total mass of components other than the solvent such as an organic solvent. The non-volatile content of the curable composition can be measured by a conventionally known method, for example, the weight when 1 g of the composition is spread and heated at 100 ° C. for 1 hour to volatilize the organic solvent. Measured by change.

(Polyfunctional (meth) acrylate (B))
The polyfunctional (meth) acrylate (B) is a bifunctional or higher polyfunctional compound having a (meth) acryloyl group that is not a polymer. By containing the polyfunctional (meth) acrylate (B) in the curable composition, it is possible to facilitate the formation of a concavo-convex structure when irradiated with active energy rays.

Examples of the polyfunctional (meth) acrylate (B) include a compound obtained by condensing a polyhydric alcohol with a compound having a (meth) acryloyl group and a carboxyl group, and a polyhydric alcohol and a (meth) acryloyl group and an isocyanate group. A compound obtained by an addition reaction with a compound having a polyhydric isocyanate, a compound obtained by an addition reaction between a polyhydric isocyanate and a compound having a (meth) acryloyl group and a hydroxyl group, and a compound having an acryloyl group and a carboxyl group reacted with a polyvalent epoxy group compound. Examples thereof include the compounds obtained by the above-mentioned. These compounds may be simply referred to as polyfunctional (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates and the like. However, the polyfunctional (meth) acrylate (B) is not limited to the above-mentioned compound group.

The number of functional groups of the polyfunctional (meth) acrylate (B) is preferably 20 or less. From the viewpoint of facilitating the formation of a concavo-convex structure during irradiation with active energy rays, 15 functional or less is more preferable, 6 functional or less is further preferable, trifunctional or less is particularly preferable, and bifunctional is most preferable.

The viscosity of the polyfunctional (meth) acrylate (B) at 25 ° C. is preferably 1 to 7000 mPa · s, more preferably 2 to 2000 mPa · s, particularly preferably 3 to 1000 mPa · s, and most preferably 4 to 400 mPa · s. .. When the viscosity of the polyfunctional (meth) acrylate (B) is in this range, it is possible to easily form an uneven structure when irradiated with active energy rays.

The weight average molecular weight of the polyfunctional (meth) acrylate (B) is preferably 150 to 5000, more preferably 200 to 4000, particularly preferably 250 to 3000, and most preferably 300 to 2000. When the weight average molecular weight of the polyfunctional (meth) acrylate (B) is in this range, it is possible to easily form an uneven structure during irradiation with active energy rays.

Examples of the polyfunctional (meth) acrylate (B) include bifunctional (meth) acrylate and trifunctional or higher (meth) acrylate. Only one type of polyfunctional (meth) acrylate may be used, or two or more types may be used in combination.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. Alcandiol di (meth) acrylates such as di (meth) acrylates and tricyclodecanedimethylol di (meth) acrylates, bisphenols such as bisphenol A ethylene oxide-modified di (meth) acrylates and bisphenol F ethylene oxide-modified di (meth) acrylates. Examples include modified di (meth) acrylates.

Among these, considering the ease of forming a wrinkle-like uneven structure, a structure without branching is preferable, an alkyldiol di (meth) acrylate is more preferable, and an alkyldiol di (4 to 18 carbon atoms) having 4 to 18 carbon atoms is preferable. Meta) acrylate is more preferred.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include glycerintri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Ethylene oxides such as tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and ethylene oxide-modified pentaerythritol tetra (meth) acrylate. Isocyanuric acid-modified tri (meth) acrylates such as modified (meth) acrylates, isocyanuric acid ethylene oxide-modified tri (meth) acrylates, ε-caprolactone-modified tris (acroxyethyl) isocyanurate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymers. , Pentaerythritol Triacrylate Tolulinediisocyanate Urethane Prepolymer, Dipentaerythritol Pentaacrylate Hexamethylene Diisocyanate Urethane Prepolymer and the like. Among these, ethylene oxide-modified type and trifunctional (meth) acrylate are preferable in consideration of the ease of forming a wrinkled uneven structure. In particular, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate is more preferable in order to achieve both ease of forming a wrinkle-like uneven structure and scratch resistance and hardness.

The content of the polyfunctional acrylate (B) in the curable composition is preferably 95 to 30% by mass, more preferably 90 to 40% by mass, particularly preferably 85 to 45% by mass, and 80% by mass with respect to the non-volatile content. ~ 50% by mass is most preferable. When the content of the polyfunctional (meth) acrylate (B) is in this range, the antiglare property is excellent.

(Monofunctional (meth) acrylate)
Various monofunctional (meth) acrylates can also be added to the curable composition for the purpose of improving coatability and adhesion of the cured film to the substrate.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate. Alkyl (meth) acrylates such as isobornyl (meth) acrylates, hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylates, methoxyethyl (meth) acrylics, ethoxy Acrylic alkyl (meth) acrylates such as ethyl (meth) acrylates, methoxypropyl (meth) acrylates and ethoxypropyl (meth) acrylates, aromatic (meth) acrylates such as benzyl (meth) acrylates and phenoxyethyl (meth) acrylates, diaminos. Amino group-containing (meth) acrylates such as ethyl (meth) acrylates and diethylaminoethyl (meth) acrylates, methoxyethylene glycol (meth) acrylates, phenoxypolyethylene grease (meth) acrylates, phenylphenol ethylene oxide-modified (meth) acrylates, etc. Examples thereof include ethylene oxide-modified (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and (meth) acrylic acid.

The content of all active energy ray-curable compounds in the curable composition is preferably 5 to 99.99% by mass, more preferably 30 to 99.9% by mass, still more preferably, with respect to the non-volatile content. It is in the range of 40 to 95% by mass, particularly preferably 50 to 90% by mass, and most preferably 60 to 80% by mass. In the above range, a wrinkled uneven structure is likely to be formed, and a cured film having excellent hardness can be formed.

(resin)
It is also possible to add a resin having no unsaturated double bond to the curable composition for the purpose of improving the adhesion to the substrate. Various resins can be used as the resin, and examples thereof include conventionally known resins such as acrylic resin, polyester resin, polyurethane resin, and polyvinyl resin, and among these, transparency and (meth) acrylate are particularly present. Acrylic resin is preferable in terms of excellent affinity.

When the resin is blended in the curable composition, the content thereof is preferably 80% by mass or less, more preferably 3 to 60% by mass, still more preferably 5 to 50% by mass, and particularly preferably 5 to 50% by mass with respect to the non-volatile content. Is in the range of 10 to 40% by mass. In the above range, not only the adhesion of the cured film to the substrate, scratch resistance, and hardness tend to be improved, but also the wrinkle-like uneven structure tends to be made finer, resulting in a decrease in RSm, a decrease in Sa, and the like. In some cases, an increase in haze and a decrease in gloss can be achieved.

(particle)
It is also possible to add particles to the curable composition in order to further improve the matting property due to the wrinkle-like uneven structure of the cured film. The particles are not particularly limited, and conventionally known particles can be used. Specific examples include inorganic particles such as silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, acrylic resin, styrene resin, and urea. Examples thereof include organic particles such as a resin, a phenol resin, an epoxy resin, and a benzoguanamine resin. 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 a crosslinked type for maintaining the shape, and more preferably crosslinked acrylic resin particles and crosslinked styrene resin particles. Two or more kinds of these particles may be used in combination.

The average primary particle diameter of the particles is preferably in the range of 0.01 to 30 μm, more preferably 0.05 to 10 μm, still more preferably 0.1 to 5 μm, and particularly preferably 0.5 to 3 μm. In the range, it is excellent in improving the matte property.

When the particles are blended in the curable composition, the content thereof is preferably 30% by mass or less, more preferably 0.1 to 20% by mass, and further, with respect to the non-volatile content, from the viewpoint of improving the matting property. It is preferably in the range of 0.5 to 10% by mass, particularly preferably 1 to 8% by mass.
Since the curable composition can form an uneven structure on the surface of the cured film without blending particles, it also has a feature that the range of materials that can be used is wide. Therefore, it is possible to design a curable composition in a system that is substantially free of particles. In addition, "substantially" means that particles are not intentionally contained.

(Photopolymerization initiator)
A photopolymerization initiator may be added to promote the curability of the curable composition. The molecular weight of the photopolymerization initiator is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-. methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, pivaloyl in ethyl ether, benzyl dimethyl ketal, 1,1-dichloro acetophenone, p-t-butyl Dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, Phenylglycioxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanol, 2-methyl- [4- (methylthio) phenyl] -2- Examples thereof include morpholino-1-propanone, tribromophenyl sulfone, and tribromomethylphenyl sulfone. These photopolymerization initiators may be used alone or in combination of two or more.

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

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

When the leveling agent is blended in the curable composition, the content thereof is preferably 10% by mass or less, more preferably 0.01 to 8% by mass, based on the non-volatile content, from the viewpoint of improving the appearance of the cured film. , More preferably in the range of 0.1 to 5% by mass.

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

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

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

(Formation of coating film)
Examples of the method for forming a coating film of the curable composition include a method of applying the curable composition on the surface of a base material or an article to form a coating film and drying it if necessary. The method of coating is not particularly limited, but for example, known methods such as a dip coating method, an air knife coating method, a curtain coating method, a spin coating method, a roller coating method, a bar coating method, a wire bar coating method, a gravure coating method, and a spray coating method are known. Method can be mentioned.
When the curable composition contains an organic solvent, it is preferable to heat-dry it in advance before irradiating it with active energy rays. By heating and drying in advance, the solvent in the coating film can be effectively removed. The drying temperature for heat drying is preferably 30 ° C. or higher and 200 ° C. or lower, and more preferably 40 ° C. or higher and 150 ° C. or lower. The drying time is preferably 0.01 minutes or more and 30 minutes or less, and more preferably 0.1 minutes or more and 10 minutes or less.

(Irradiation of active energy rays)
The coating film of the curable composition formed on the surface of the base material or the article is irradiated with active energy rays to form a cured film, and a laminated body in which the cured film is laminated on the base material or the article is formed. As the active energy rays, those having high energy capable of effectively curing the surface of the coating film (those having a short wavelength) are preferable, and vacuum ultraviolet rays (ultraviolet rays having a wavelength of 200 nm or less) are more preferable. Among the vacuum ultraviolet rays, excimer light having a half width of 50 nm or less is the most suitable. Examples of the excimer light include argon excimer light (126 nm), krypton excimer light (146 nm), xenon excimer light (172 nm), and argon / fluorine excimer light (193 nm). Among these, xenon excimer light is preferable in consideration of ease of use, the formation of an effective uneven structure on the cured film, the curability of the curable composition, and the like.

When vacuum ultraviolet rays are used, the integrated amount of light to be irradiated 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 of. The illuminance is preferably in the range of 1 to 500 mW / cm ² , more preferably 2 to 300 mW / cm ² , and even more preferably 3 to 100 mW / cm ² .
Further, as the atmosphere at the time of vacuum ultraviolet irradiation, it is preferable to perform it in an environment with little oxygen such as a nitrogen atmosphere. The oxygen concentration in the atmosphere is preferably in the range of 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.

After irradiation with vacuum ultraviolet rays, it is preferable to irradiate with active energy rays other than vacuum ultraviolet rays in order to cure the cured film to a deep part. Examples of the active energy ray include ultraviolet rays and electron beams. Examples of ultraviolet rays include ultraviolet rays having a wavelength of 200 nm or more emitted from high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, UV-LED lamps, and the like. Examples of the electron beam include an electron beam irradiated from an EB irradiator or the like. As the active energy rays other than vacuum ultraviolet rays, ultraviolet rays are more preferable in consideration of the curability of the curable composition.

By the way, vacuum ultraviolet rays having a wavelength of 200 nm or less are significantly absorbed by oxygen. Therefore, the irradiation amount reaching the coating film depends on the oxygen concentration. For this reason, the curable resin composition used in the present invention is preferably one having good curability even when the intensity of excimer light is significantly reduced. Specifically, when only the high-pressure mercury lamp is irradiated without the excimer light irradiation, the integrated light amount until the stickiness of the coating film due to the touch of the finger disappears is preferably 1 to 3000 mJ / cm ² . It is more preferably ~ 2000 mJ / cm ² , more preferably 10 to 1000 mJ / cm ² , particularly preferably 15 to 400 mJ / cm ² , and most preferably 20 to 200 mJ / cm ² . .. By using a curable composition that can be cured within the above-mentioned range, the productivity of the cured film of the present invention can be improved.

[Laminate]
The laminate of the present invention has a layer made of a base material and a layer (concave and convex layer) made of a cured film of a curable composition. The laminate may further have a primer layer between the substrate and the cured film. Further, the back surface functional layer may be provided on the surface of the base material opposite to the cured film side. A surface functional layer may be provided on the surface of the cured film opposite to the base material as long as the effects of the present invention are not impaired.

(Base material)
As the base material, known ones can be used, and examples thereof include a resin base material, a metal base material, and a paper base material. Among these, a resin base material is preferable from the viewpoint of processability. The resin base material may have a single-layer structure or a multi-layer structure having two or more layers, and is not particularly limited. It is preferable that the resin base material has a multi-layer structure of two or more layers, and each layer has a characteristic to be multifunctional.
As the resin base material, various resin films (sheets) can be used, for example, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film. , Polyvinyl alcohol film, nylon film and the like.
When developing the laminate for display applications, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetyl cellulose film are preferable. Among these, polyester films, poly (meth) acrylate films, and polyolefin films are preferable for anti-glare applications, and polyester films are more preferable in consideration of transparency, moldability, and versatility.

The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferable. Among them, a uniaxially stretched film stretched in the uniaxial direction or a biaxially stretched film stretched in the biaxial direction is preferable, and a biaxially stretched film is more preferable from the viewpoint of excellent balance of mechanical properties and flatness.
The polyester constituting the polyester film that can be used as a base material may be a homopolyester or a copolymerized polyester.
The homopolyester is preferably obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Aromatic dicarboxylic acid and aliphatic glycol may be used alone or in combination of two or more.
Examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, and neopentyl glycol. The dicarboxylic acid component and the glycol component may be used alone or in combination of two or more.
Examples of typical polyesters include polyethylene terephthalate and polyethylene naphthalate.
As the polyester film, in consideration of mechanical strength and heat resistance, a film formed of polyethylene terephthalate or polyethylene naphthalate is more preferable, and ease of manufacture and handleability as a surface protective film or the like are more preferable. In consideration of the above, a film formed from polyethylene terephthalate is particularly preferable.

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

The base material may contain particles for the purpose of imparting slipperiness, preventing scratches in each step, and improving blocking resistance.
The type of particles can be appropriately selected according to the purpose and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide, acrylic resin, styrene resin, urea resin, and phenol. Examples thereof include organic particles such as a resin, an epoxy resin, and a benzoguanamine resin. Further, when the base material layer contains a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst in the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are particularly preferable in that a small amount is likely to produce an effect.
The shape of the particles is not particularly limited, and any of spherical, lumpy, rod-shaped, flat-shaped, and the like may be used. Further, the hardness, specific gravity, color and the like are not particularly limited.
Two or more kinds of these particles may be used in combination, if necessary.
The average primary particle size of the particles is preferably in the range of 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. When the average primary particle size is 10 μm or less, problems due to a decrease in the transparency of the base material are unlikely to occur.
The average primary particle diameter of the particles is a value of 50% (mass basis) integrated in the equivalent spherical distribution measured by the centrifugal sedimentation type particle size distribution measuring device.
When the base material contains particles, the content cannot be unequivocally determined because there is a balance with the average primary particle size of the particles, but the total mass of the base material (when the base material is composed of a plurality of layers). It is preferably in the range of 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and further preferably in the range of 0.0005 to 1% by mass with respect to the total mass of the layer containing the particles). When the content of the particles is 5% by mass or less, problems such as falling off of the particles and deterioration of the transparency of the base material are unlikely to occur.

The base material may contain additives other than the above-mentioned particles, if necessary. As the additive, known additives such as an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a dye, and a pigment can be used.
When the base material is a film, the thickness thereof is not particularly limited as long as it can be formed into a film, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and further preferably 10 to 100 μm. be.

(Primer layer)
The primer layer is appropriately provided to impart various functions between the base material and the cured film (concave and convex layer). The primer layer may have a single function or a plurality of functions, or may be composed of a plurality of layers.
In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the base material and the uneven layer is insufficient, the laminate may not be usable depending on the application. By having the adhesion improving layer, the adhesion between the base material and the uneven layer is improved, and the laminated body can be used for various purposes. From the viewpoint of improving adhesion and the like, it is preferable that the adhesion improving layer contains either one or both of the resin and the compound derived from the cross-linking agent.
In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, it is possible to reduce the adhesion of dust and the like due to peeling charging and triboelectric charging to the outermost surface of the laminated body, particularly the outermost surface on the side where the uneven layer exists with respect to the base material.
To make the primer layer an antistatic layer, for example, the primer layer may contain an antistatic agent.

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

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

The acrylic resin is a polymer of a polymerizable monomer containing a (meth) acrylic monomer. Examples of the acrylic resin include homopolymers and copolymers of (meth) acrylic monomers, copolymers of (meth) acrylic monomers and polymerizable monomers other than (meth) acrylic monomers, and the like.
The acrylic resin may be a copolymer of these polymers and another polymer (for example, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Alternatively, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or dispersion is also included. Similarly, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a solution or dispersion of polyurethane is also included. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in a solution or dispersion of another polymer is also included.
The polymerizable monomer is not particularly limited, but typical compounds include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and the like. Salt: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroquilfumarate, monobutylhydroxyitaconate and other hydroxyl group-containing monomers; methyl ( Alkyl (meth) acrylates such as meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; (meth) acrylamide, Nitrogen-containing monomers such as diacetone acrylamide, N-methylol acrylamide and (meth) acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene, vinyl esters such as vinyl propionate and vinyl acetate; γ- Silicon-containing monomers such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and billidene chloride; conjugated diene such as butadiene can be mentioned.

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

The polycarbonate polyol is obtained by a reaction (dealcohol reaction) between a polyhydric alcohol and a carbonate compound. Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-. Pentandiol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Examples thereof include decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate and ethylene carbonate. Specific examples of the polycarbonate polyol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.

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

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

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

Examples of the polyisocyanate compound used to obtain a urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, and trizine diisocyanate; α, α, α', An aliphatic diisocyanate having an aromatic ring such as α'-tetramethylxylylene diisocyanate; an aliphatic diisocyanate such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate. , Dicyclohexylmethane diisocyanate, alicyclic diisocyanate such as isopropyridene dicyclohexyldiisocyanate and the like. These may be used alone or in combination of two or more.
The chain extender is not particularly limited as long as it has two or more active groups that react with the isocyanate group, and generally, a chain extender having two hydroxyl groups or amino groups can be mainly used. ..
Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. Glycol compounds such as glycol can be mentioned.
Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine, and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine. , 2-Methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine And other aliphatic diamines, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprovilitincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3 -Examples include alicyclic diamines such as bisaminomethylcyclohexane.

Urethane resins are typically used in the form of dispersions or solutions. As the medium of the dispersion liquid or the solution, a solvent may be used, but water is preferable.
Examples of the aqueous dispersion or aqueous solution of the urethane resin include a forced emulsification type using an emulsifier, a self-emulsifying type in which a hydrophilic group is introduced into the structure of the urethane resin, and a water-soluble type. In particular, the self-emulsifying type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferable because it is excellent in storage stability of the liquid and the water resistance and transparency of the obtained primer layer.
Examples of the ionic group introduced into the structure of the urethane resin include various groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group and a quaternary ammonium base, but a carboxyl group is preferable. ..
The carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amines, alkali metals and inorganic alkalis. Particularly preferred neutralizers are ammonia, trimethylamine and triethylamine. For the urethane resin having a carboxyl group neutralized with a neutralizing agent, the carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by the crosslinking agent. This makes it possible to improve the stability of the obtained primer layer in the state of the liquid before coating, and to improve the durability, solvent resistance, water resistance, blocking resistance and the like of the obtained primer layer.
As a method for introducing a carboxyl group into the urethane resin, various methods can be taken in each stage of the polymerization reaction. For example, a method of using a resin having a carboxyl group as a copolymerization component at the time of prepolymer synthesis, and a method of using a component having a carboxyl group as one component of a polyol, a polyisocyanate compound, a chain extender and the like can be mentioned. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl group according to the amount of this component charged is preferable. For example, a carboxyl group-containing diol can be copolymerized with a diol used for synthesizing a urethane resin.
Examples of the carboxyl group-containing diol include dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, and bis- (2-hydroxyethyl) butanoic acid, and these carboxyl groups are neutralizing agents. Examples include neutralized salt.

In order to make the primer layer stronger and improve the performance such as adhesion, it is preferable that the primer layer contains a compound derived from a cross-linking agent.
As the cross-linking agent, known materials can be used, and examples thereof include melamine compounds, isocyanate compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferable, and from the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, and isocyanate compounds are preferable. And epoxy compounds are more preferable, and melamine compounds, oxazoline compounds and isocyanate compounds are particularly preferable. These cross-linking agents may be used alone or in combination of two or more. Adhesion and durability may be further improved by using two or more types together.

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

The isocyanate-based compound is a compound having an isocyanate derivative structure typified by an isocyanate compound or a blocked isocyanate compound.
Examples of the isocyanate compound include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyldiisocyanate, phenylenedi isocyanate and naphthalene diisocyanate; aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate. Lipid isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexanediisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), isopropi. Examples thereof include alicyclic isocyanate compounds such as redendicyclohexyldiisocyanate. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide-modified compounds of these isocyanate compounds can also be mentioned. These may be used alone or in combination of two or more. Among the above isocyanate compounds, an aliphatic isocyanate compound or an alicyclic isocyanate compound is preferable to an aromatic isocyanate compound from the viewpoint of avoiding yellowing due to ultraviolet rays.
Examples of the blocked isocyanate compound include those in which the isocyanate group of the isocyanate compound is blocked with a blocking agent. Examples of the blocking agent include phenolic compounds such as heavy sulfites, phenol, cresol and ethylphenol, alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol, dimethyl malonate and diethyl malonate. , Methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and other active methylene compounds, butyl mercaptan, dodecyl mercaptan and other mercaptan compounds, ε-caprolactam, δ-valerolactam and other lactam compounds, diphenylaniline, aniline , Amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetate amide, and oxime compounds such as formaldehyde, acetaldoxime, acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime. These may be used alone or in combination of two or more.
As the blocked isocyanate compound, an isocyanate compound blocked with an active methylene compound is preferable from the viewpoint that the primer layer is not easily destroyed.
The isocyanate compound may be used alone, or may be used as a mixture or a bond with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

The oxazoline compound is a compound having an oxazoline group in the molecule. As the oxazoline compound, a polymer containing an oxazoline group is preferable. The polymer containing an oxazoline group can be obtained by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of the additive-polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2. -Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline can be mentioned. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline group-containing monomer, and is, for example, an alkyl (meth) acrylate (as the alkyl group, a methyl group, an ethyl group, or an n-propyl group). , Isobutyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group) and other (meth) acrylates; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, Unsaturated carboxylic acids such as styrene sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl ( Meta) acrylamide, N, N-dialkyl (meth) acrylamide, (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl Unsaturated amides such as groups (groups, cyclohexyl groups, etc.); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; vinyl chloride, vinylidene chloride and vinyl fluoride. Halogen-containing α, β-unsaturated monomers such as; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene, etc. may be mentioned. These may be used alone or in combination of two or more.
The amount of oxazoline groups per 1 g of the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, still more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. .. When the amount of the oxazoline group is within the above range, the durability of the coating film is improved and the adhesion can be easily adjusted.

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

The carbodiimide-based compound is a compound having one or more carbodiimide structure or carbodiimide derivative structure in the molecule. As the carbodiimide-based compound, a polycarbodiimide-based compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable from the viewpoint of the strength of the primer layer.
The carbodiimide-based compound can be synthesized by a known method, and a condensation reaction of a diisocyanate compound is generally used. The diisocyanate compound is not particularly limited, and any aromatic or aliphatic type can be used. For example, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, hexamethylene diisocyanate, etc. Examples thereof include trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyldiisocyanate, and dicyclohexylmethane diisocyanate.
In order to improve the water solubility and water dispersibility of the polycarbodiimide compound, a surfactant may be added as long as the effect of the present invention is not lost, or a quaternary ammonium salt of a polyalkylene oxide or a dialkylaminoalcohol may be added. , Hydrophilic monomers such as hydroxyalkyl sulfonates may be added.

The silane coupling compound is an organic silicon compound having an organic functional group and a hydrolyzing group such as an alkoxy group in one molecule. Examples of the silane coupling compound include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Propyl group-containing compounds such as 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane, vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane Such as styryl group-containing compounds, 3- (meth) acryloxylpropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy. (Meta) acryloyl group-containing compounds such as propylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, Amino group-containing compounds such as 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, Isocyanurate group-containing compounds such as tris (trimethoxysilylpropyl) isocyanurate and tris (triethoxysilylpropyl) isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane. , 3-Mercapto group-containing compounds such as mercaptopropylmethyldiethoxysilane.
Among the above compounds, the silane coupling compound contains an epoxy group-containing silane coupling compound, a double bond-containing silane coupling compound such as a vinyl group or a (meth) acrylic group, and an amino group from the viewpoint of the strength of the primer layer. Silane coupling compounds are preferred.

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

The antistatic agent contained in the primer layer is not particularly limited, and a known antistatic agent can be used. For example, a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, and betaine. Examples include compounds and conductive organic polymers.
The primer layer may contain particles for blocking and improving slipperiness.
The primer layer may be a defoaming agent, a coating property improving agent, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, as necessary, as long as the gist of the present invention is not impaired. It may contain an additive such as a pigment.

The proportion of the resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and further preferably 30 to 90% by mass. When the ratio of the resin is within the above range, the adhesion performance and the appearance of the primer layer are more excellent.
The proportion of the compound derived from the cross-linking agent in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and further preferably 5 to 40% by mass. It is a range. When the ratio of the compound derived from the cross-linking agent is within the above range, the adhesion performance and the strength of the primer layer are more excellent.
The thickness of the primer layer cannot be unconditionally determined because it depends on the material used for the primer layer and the performance to be expressed, but it is preferably 0.001 to 10 μm, more preferably 0.01 to 4 μm, and further preferably 0. It is in the range of 02 to 1 μm.
The primer layer can be formed by a known method.

(Surface functional layer)
The surface functional layer is a layer provided to impart various functions to the surface of the cured film (concave and convex layer) opposite to the base material layer. Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, and a color correction layer. The surface functional layer may have a single function or a plurality of functions, or may be composed of a plurality of layers.

The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured film. As the material used for the antifouling layer, conventionally known materials such as a silicone compound, a fluorine compound, and a long-chain alkyl group-containing compound can be used. Among these, a silicone compound or a fluorine compound is preferable for exhibiting stronger antifouling performance, and a fluorine compound or a long-chain alkyl group-containing compound is preferable from the viewpoint of not contaminating the partner with which the antifouling layer comes into contact.

Examples of the silicone compound are compounds having a silicone structure in the molecule, and examples thereof include alkyl silicones such as dimethyl silicone and diethyl silicone, and phenyl silicone and methyl phenyl silicone having a phenyl group. As the silicone, those having various functional groups can also be used, for example, an ether group, a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, a halogen group such as fluorine, a perfluoroalkyl group, various alkyl groups and various types. Examples thereof include a hydrocarbon group such as an aromatic group. As other functional groups, silicones having a vinyl group and hydrogen silicones in which a hydrogen atom is directly bonded to a silicon atom are also common, and both are used in combination to form an addition type (type by an addition reaction between a vinyl group and a hydrogensilane). It can also be used as. Further, a method of introducing a double bond such as an acryloyl group and reacting at the double bond portion is also preferable.
Further, as the silicone compound, modified silicone such as acrylic graft silicone, silicone graft acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone can also be used. Considering heat resistance and stain resistance, it is preferable to use a curable silicone resin, and any of the curable reaction types such as condensation type, addition type, and active energy ray curable type can be used as the curable type.

The fluorine compound is a compound containing a fluorine atom. As the fluorine compound, an organic fluorine compound is preferably used, and examples thereof include a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing a fluorine atom, and an aromatic fluorine compound such as fluorobenzene. From the viewpoint of releasability, a compound having a perfluoroalkyl group is preferable. Further, as the fluorine compound, a compound containing a long-chain alkyl compound as described later can also be used.
Examples of the compound having a perfluoroalkyl group include perfluoroalkyl (meth) acrylate, perfluoroalkylmethyl (meth) acrylate, 2-perfluoroalkylethyl (meth) acrylate, and 3-perfluoroalkylpropyl (meth) acrylate. , 3-Perfluoroalkyl-1-methylpropyl (meth) acrylate, 3-perfluoroalkyl-2-propenyl (meth) acrylate and other perfluoroalkyl group-containing (meth) acrylates and polymers thereof, perfluoroalkylmethylvinyl 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 their polymers. Can be mentioned. Considering heat resistance and stain resistance, it is preferably a polymer. The polymer may be a single compound alone or a polymer of a plurality of compounds. Further, from the viewpoint of antifouling property, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later.

The long-chain alkyl compound is a compound having a linear or branched alkyl group having a carbon atom number of usually 6 or more, preferably 8 or more, and more preferably 12 or more. Examples of the alkyl group include a hexyl group, an octyl group, a decyl group, a lauryl group, an octadecyl group, a behenyl group and the like. Examples of the compound 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, and long-chain alkyl group-containing quaternary ammonium salts. .. Considering heat resistance and stain resistance, a polymer compound is preferable. Further, from the viewpoint of effectively obtaining antifouling property, a polymer compound having a long-chain alkyl group in the side chain is more preferable.
The polymer compound having a long-chain alkyl group in the side chain can be obtained 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 group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group. Examples of the compound having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, and a reactive group-containing poly (meth) acrylic resin. Among these, polyvinyl alcohol is preferable in consideration of antifouling property and ease of handling.
Examples of the compound having an alkyl group capable of reacting with the above-mentioned reactive group include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate and behenyl isocyanate, hexyl chloride and octyl chloride. , Isocyanate, lauryl chloride, octadecyl chloride, behenyl chloride and the like, long-chain alkyl group-containing acid chlorides, long-chain alkyl group-containing amines, long-chain alkyl group-containing alcohols and the like. Among these, long-chain alkyl group-containing isocyanates are preferable, and octadecyl isocyanates are particularly preferable, in consideration of releasability and ease of handling.
Further, the polymer compound having a long-chain alkyl group in the side chain can also be obtained by a polymer of a long-chain alkyl (meth) acrylate or a copolymerization of the long-chain alkyl (meth) acrylate with another vinyl group-containing monomer. .. Examples of the long-chain alkyl (meth) acrylate include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate. ..

The content of the above-mentioned antifouling material for exhibiting the antifouling performance in the surface functional layer cannot be unequivocally determined because it depends on the material used, but in the case of a silicone compound or a fluorine compound, it is usually 0.01. It is in the range of mass% or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. When a long-chain alkyl group-containing compound is used, it is usually in the range of 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is 100% by mass. It doesn't matter. By using it in the above range, it can have effective antifouling performance.

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

Examples of the refractive index adjusting layer include a high refractive index layer, a low refractive index layer, and a laminate thereof.
Conventionally known materials can be used as the material of the refractive index adjusting layer for the purpose of increasing the refractive index, and for example, an aromatic-containing material such as a benzene structure, a bisphenol A structure, a melamine structure, and a fluorene structure can be used. Condensations such as naphthalene, anthracene, phenanthrene, naphthalene, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, and perylene structures, which are considered to be compounds having high refractive index among aromatic compounds. Metals such as cyclic aromatic compounds, zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimon oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimon tin oxide), ITO (indium tin oxide) Examples thereof include metal-containing compounds such as oxides and metal chelate compounds such as titanium chelate and zirconium chelate, compounds containing sulfur elements, and compounds containing halogen elements.
The metal oxide is preferably used in the state of particles because there is a concern that the adhesion may be deteriorated depending on the usage mode, and the average primary particle diameter thereof is preferably 100 nm or less from the viewpoint of coating appearance and the like. The range is preferably 50 nm or less, more preferably 25 nm or less.
As the material of the refractive index adjusting layer for the purpose of lowering the refractive index, conventionally known materials can be used, and examples thereof include acrylic resin and urethane resin having a low refractive index. Further, in particular, a compound in which a fluorine atom is incorporated in a resin, for example, a fluororesin, a compound containing a fluororesin in the main species skeleton, and a compound containing a perfluoroalkyl group in the side chain can be mentioned. Further, examples of the inorganic material include hollow silica particles, fluorine atom-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and hollow particles and nanoporous particles thereof.

The thickness of the surface functional layer is preferably 5 times or less, more preferably 2 times or less, the height from the concave portion to the convex portion of the concave-convex structure of the cured film. The smaller this magnification is, the less likely it is that the matting performance of the cured film will deteriorate. The thickness of the surface functional layer cannot be unequivocally determined because it depends on the height from the concave portion to the convex portion of the concave-convex structure of the cured film, but it is usually 0.001 to 3 μm, preferably 0.005 to 2 μm, and more preferably 0. The range is 01 to 1 μm, more preferably 0.02 to 0.5 μm, and particularly preferably 0.03 to 0.2 μm. By using it in the above range, it is possible to achieve both the expression of the function by the surface functional layer and the matte property of the cured film.
The surface functional layer can be formed by a known method.

(Back function layer)
The back surface functional layer is a layer provided to impart various functions to the surface of the base material layer opposite to the cured film (concave and convex layer). Examples of the back surface functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an anti-blocking layer. The back surface functional layer may have a single function or a plurality of functions, or may be composed of a plurality of layers.

The adhesive layer is provided to join the laminated body to various adherends. The antistatic layer is provided to prevent the adhesion of dust and the like due to peeling and triboelectric charging on the outermost surface of the laminated body, particularly the outermost surface on the side opposite to the uneven layer side of the base material layer, and defects due to the adhesion. The refractive index adjusting layer is provided, for example, in order to improve the total light transmittance of the laminated body. The anti-blocking layer is provided to reduce blocking of the laminate.
Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer include known pressure-sensitive adhesives such as acrylic, polyester, urethane, and rubber. Among them, an acrylic pressure-sensitive adhesive is preferable in consideration of versatility.
The components forming the antistatic layer and the refractive index adjusting layer are the same as those described in the surface functional layer.

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

(Formation of front surface functional layer and back surface functional layer)
The front surface functional layer and the back surface functional layer are, for example, coated on a predetermined surface with a liquid prepared by using the above-mentioned series of components as a solution or a dispersion of a solvent and having a solid content concentration of about 0.1 to 80% by mass as a guide. It can be formed by drying and curing.
Examples of coating methods include gravure coat, reverse roll coat, die coat, air doctor coat, blade coat, rod coat, bar coat, curtain coat, knife coat, transfer roll coat, squeeze coat, impregnation coat, kiss coat, and spray coat. , Conventionally known coating methods such as a calendar coat and an extruded coat can be mentioned.
The drying and curing conditions for forming the front surface functional layer and the back surface functional layer are not particularly limited, but the drying of the solvent such as water used in the coating liquid is usually 50 to 150 ° C., preferably 50 to 150 ° C. It is in the range of 80 to 130 ° C., more preferably 90 to 120 ° C. As a guideline for the drying time, it is in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Further, in order to improve the strength of the front surface functional layer and the back surface functional layer, it is preferable to perform heat treatment in the range of usually 150 to 270 ° C., preferably 170 to 230 ° C., and more preferably 180 to 210 ° C. after drying. As a guideline for the heat treatment time, it is in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Such heat treatment is suitable when the laminate is a film.

(Total light transmittance)
The laminate is preferably transparent. The total light transmittance measured by the method described in Examples described later is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably 80% or more, and most preferably 90%. The above range is preferable, and the higher the range, the more preferable (the upper limit is 100%).

(Haze)
The haze of the laminate measured by the method described in Examples described later is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, particularly preferably 10% or more, and most preferably. Is in the range of 20% or more, and the upper limit is, for example, 99%. The higher the haze, the better the matteness tends to be.
Further, particularly when used for anti-glare of various displays, it is preferably in the range of 40% or more, more preferably 50% or more, further preferably 60% or more, particularly preferably 70% or more, and most preferably 80% or more. Yes, the upper limit is, for example, 99%. Also, depending on the application, the higher the value, the more preferable the application.

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

(1) Extreme viscosity of polyester 1 g of polyester from which components incompatible with polyester have been removed is precisely weighed, 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) is added and dissolved, and the measurement is carried out at 30 ° C. did.

(2) Average primary particle diameter (d50: μm)
The value of 50% integrated (weight basis) in the equivalent spherical distribution measured using the centrifugal sedimentation type particle size distribution measuring device SA-CP3 manufactured by Shimadzu Corporation was taken as the average primary particle size.

(3) Weight average molecular weight (Mw) of acrylic polymer
The weight average molecular weight (Mw) of the acrylic polymer was measured using gel permeation chromatography (GPC) "HLC-8120" (manufactured by Tosoh Corporation). As the column, TSKgel G5000HXL * GMHXL-L (manufactured by Tosoh Corporation) was used. Further, as standard polystyrene, a calibration curve was prepared using F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (manufactured by Tosoh Corporation) and styrene. The measurement was carried out at a column oven temperature of 40 ° C. using 100 μl of a solution in which the polymer was dissolved in tetrahydrofuran so as to have a concentration of 0.4%. The weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

(4) RSm, Sa and tilt angle (θa)
Using a surface shape measurement system (Hitachi High-Tech Science, Inc. scanning white interference microscope "VS1330"), the surface shape of the surface of the cured film of 177.60 μm × 236.87 μm was measured by the optical interferometry method, and the data was obtained. An analysis was performed. The evaluation length used for calculating RSm and θa is 236.87 μm. The magnification of the objective lens at the time of measurement was set to 20 times for measurement. In this evaluation, the presence or absence of wrinkled uneven structure was also confirmed.
The processing conditions used for data analysis are as follows.
Surface correction: 4th order interpolation: Complete interpolation Filter: Medium 3 × 3 pixels Boundary processing: Symmetrical expansion to interpolate edges Trimming: None

(5) Total light transmittance / haze A laminated body having a cured film formed on a substrate was used as a measurement target. The total light transmittance and haze are JIS Z8722: 2009 (geometric conditions for irradiation and light reception of transmitted objects) and JIS K7361-1: 1997 (test method for total light transmittance of plastic-transparent material) JIS K7136: 2000 (plastic). -Measurement was performed using a haze meter "SH7000" manufactured by Japanese Industrial Standards Co., Ltd. in accordance with (How to obtain the haze of a transparent material).

(6) 20 ° and 60 ° gloss / matte property A laminated body having a cured film formed on a substrate was used as a measurement target. 20 ° and 60 ° gloss (20 ° and 60 ° mirror gloss) were measured using a gloss meter "VG2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS Z 8741-1997. The lower the gloss value, the better the matte property.

(7) Curability After applying and drying the curable composition by the method described in Examples and Comparative Examples, the illuminance is 100 mW / cm ² (high-power UV device manufactured by Eye Graphics Co., Ltd.) using only a high-pressure mercury lamp in an air atmosphere. When irradiated with ultraviolet rays of (model: US5-X1802-X1202) UV conveyor, the integrated light amount (mJ / cm ² ) until the stickiness of the coating film surface by the touch was eliminated was evaluated. The smaller the integrated amount of light until the stickiness disappears, the better the curability and the higher the productivity of the cured film. In addition, even if there is a problem that the irradiation amount of vacuum ultraviolet rays is attenuated by oxygen, the coating equipment is less likely to be contaminated. The evaluation criteria for curability are as follows.
A: 200mJ / cm ² or less integrated light amount eliminates stickiness B: 200mJ / cm ² or more to 400mJ / cm ² or less integrated light amount eliminates stickiness C: 400mJ / cm ² or more to 1000mJ / cm ² or less Eliminates stickiness with integrated light intensity D: Eliminates stickiness with integrated light intensity of more than 1000 mJ / cm ² to 3000 mJ / cm ² or less E: Eliminates stickiness with integrated light intensity greater than 3000 mJ / cm ²

(8) Pencil hardness JIS K5600-5-4: 1999 General paint test method-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method) was used to measure the pencil hardness of the cured film.

(9) Matte property A laminated body is installed in a room lit by a white, linear fluorescent lamp, and the distance between the fluorescent lamp and the laminated body is set to 2.5 m, and the matteness on the uneven layer side is visually observed. The sex (reflection of the fluorescent lamp) was evaluated according to the following evaluation criteria A to D. In the evaluations A to C, it is a judgment that the matte property can be confirmed.
A: The reflected image of the fluorescent lamp is strongly blurred, and the outline of the fluorescent lamp cannot be confirmed.
B: The reflected image of the fluorescent lamp is blurred, but the outline can be slightly confirmed.
C: The reflected image of the fluorescent lamp is a little blurry, and the outline can be confirmed, but it is observed in a wavy shape and appears dark white.
D: The reflected image of the fluorescent lamp is clear and the outline can be clearly confirmed, and it appears linear and white.

The materials used in the examples and comparative examples are as follows.
(Base material)
Polyester (S1): A polyethylene terephthalate homopolymer having an ultimate viscosity of 0.63 dl / g, which is obtained by using magnesium acetate tetrahydrate and tetrabutyl titanate as a polymerization catalyst.
Polyester (S2): A polyethylene terephthalate homopolymer having an ultimate viscosity of 0.64 dl / g, which is obtained by using magnesium acetate tetrahydrate, orthophosphoric acid and germanium dioxide as a polymerization catalyst.
Polyester (S3): A polyethylene terephthalate homopolymer containing 0.3% by mass of silica particles having an average primary particle diameter of 2 μm.

(Production of Polymer (A1-1) with Unsaturated Double Bond)
A polymer (A1-1) having an unsaturated double bond was produced by the following method.
Propyl glycol monomethyl ether (190 parts by mass), glycidyl methacrylate (98.0 parts by mass), methyl methacrylate (1.0 parts by mass), ethyl acrylate (1.0 parts by mass) in a flask equipped with a thermometer, a stirrer and a reflux cooling tube. 3 parts by mass), 3-mercaptopropyltrimethoxysilane (1.9 parts by mass) and 2,2'-azobis (2,4-dimethylvaleronitrile) (1.0 part by mass) at 65 ° C. for 3 hours. It was reacted. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, and then propylene glycol monomethyl ether (98 parts by mass) and p-methoxyphenol (by mass) were added. 0.5 part by mass) was added and heated to 100 ° C. Next, acrylic acid (50.0 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110 ° C. for 6 hours to obtain a double bond amount (acryloyl radical concentration (acryloyl radical)). A polymer (A1-1) having an unsaturated double bond having a radically polymerizable double bond in a side chain having a weight average molecular weight of 19700 and 4.50 mmol / g was obtained.

(Production of Polymer (A1-2) with Unsaturated Double Bond)
A polymer (A1-2) having an unsaturated double bond was produced by the following method.
In a flask equipped with a thermometer, a stirrer and a reflux condenser, propylene glycol monomethyl ether (190 parts by mass), glycidyl methacrylate (66 parts by mass), methyl methacrylate (33 parts by mass), ethyl acrylate (1.0 part by mass), And 2,2'-azobis (2,4-dimethylvaleronitrile) (0.8 parts by mass) were added, and the mixture was reacted at 65 ° C. for 3 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) (0.4 parts by mass) was further added and reacted for 3 hours, and then propylene glycol monomethyl ether (58 parts by mass) and p-methoxyphenol (by mass) were added. 0.5 part by mass) was added and heated to 100 ° C. Next, acrylic acid (30.4 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110 ° C. for 6 hours to obtain a double bond amount (acryloyl radical concentration (acryloyl radical)). A polymer (A1-2) having an unsaturated double bond having a radically polymerizable double bond on the side chain having a weight average molecular weight of 37600 and 3.45 mmol / g was obtained.

(Production of Polymer (A1-3) with Unsaturated Double Bond)
A polymer (A1-3) having an unsaturated double bond was produced by the following method.
In a flask equipped with a thermometer, a stirrer and a reflux condenser, propylene glycol monomethyl ether (190 parts by mass), glycidyl methacrylate (20 parts by mass), methyl methacrylate (79 parts by mass), ethyl acrylate (1.0 part by mass), And 2,2'-azobis (2,4-dimethylvaleronitrile) (0.6 parts by mass) were added, and the mixture was reacted at 65 ° C. for 3 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) (0.3 parts by mass) was further added and reacted for 3 hours, and then propylene glycol monomethyl ether (20 parts by mass) and p-methoxyphenol (20 parts by mass) were added. 0.5 part by mass) was added and heated to 100 ° C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110 ° C. for 6 hours to obtain a double bond amount (acryloyl radical concentration (introduction of acryloyl radicals). Amount)) A polymer (A1-3) having an unsaturated double bond having a radically polymerizable double bond in a side chain having a weight average molecular weight of 42700 at 1.27 mmol / g was obtained.

(Curable composition)
Each of the materials shown below was mixed in an amount (part by mass, converted to non-volatile content) shown in Table 1. Then, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM: MEK (mass ratio) 7: 3) was added so that the solid content concentration was 30% by mass, and the mixture was uniform. The curable composition (coating liquid) used in each Example and Comparative Example was obtained by stirring until.
Polymer (A1-1): Polymer having an unsaturated double bond produced by the above method (A1-1).
Polymer (A1-2): Polymer having an unsaturated double bond produced by the above method (A1-2).
Polymer (A1-3): Polymer having an unsaturated double bond produced by the above method (A1-3).
Polymer with unsaturated double bond (A2-1): modified epoxy acrylate (EBECRYL 3708 manufactured by Dycel Ornex)
(Meta) acrylate (B-1): 6-hexanediol diacrylate (bifunctional)
-(Meta) acrylate (B-2): Urethane acrylate (Shikou UV-1700B manufactured by Mitsubishi Chemical Corporation)
-Particle (C): Cross-linked acrylic particles with an average particle diameter of 1.8 μm (MX-180TA manufactured by Soken Chemical Co., Ltd.)
Photopolymerization Initiator (E): IGM Resins B.I. V. Omnirad 184 manufactured by the company

(Composition for forming a primer layer)
The polyester resin (P1), urethane resin (P2), melamine compound (P3), and particles (P4) shown below are polyester resin (P1) / urethane resin (P2) / melamine compound (P3) / particles (P4) (solid). (Mass ratio) = 60/25/10/5 to obtain a composition for forming a primer layer.
-Polyester resin (P1): An aqueous dispersion of a polyester resin having the following composition Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodiumsulfoisophthalic acid // (diol component) ethylene glycol / 1,4- Butanediol / diethylene glycol = 56/40/4 // 70/20/10 (mol%)
-Urethane resin (P2): Water dispersion of polyester urethane resin having the following composition Isophorone diisocyanate: Terephthalic acid: Isophthalic acid: Ethylene glycol: Diethylene glycol: Dimethylol propanoic acid = 12: 19: 18: 21: 25: 5 ( mol%)
-Melamine compound (P3): Hexamethoxymethylol melamine-Particles: (P4): Silica particles with an average primary particle diameter of 0.07 μm

(Polyester film base material)
A raw material obtained by mixing polyester (S1), (S2), and (S3) at a ratio of 91% by mass, 3% by mass, and 6% by mass, respectively, is used as a raw material for the outermost layer (surface layer), and polyester (S1) and (S2) are used. Raw materials mixed at a ratio of 97% by mass and 3% by mass, respectively, were used as raw materials for the intermediate layer, and each was supplied to two extruders, melted at 285 ° C., and then placed on a cooling roll set at 40 ° C. An unstretched sheet was obtained by co-extruding and cooling and solidifying in a layer structure of two types and three layers (surface layer / intermediate layer / surface layer = discharge amount of 1: 8: 1).
Next, after stretching 3.1 times in the vertical direction at a film temperature of 85 ° C. using the difference in roll peripheral speed, a composition for forming a primer layer was applied to one side of this vertically stretched film, and the film was guided to a tenter at 95 ° C. After drying for 10 seconds in the lateral direction, it was stretched 4.2 times at 120 ° C., heat-treated at 230 ° C. for 10 seconds, then relaxed by 2% in the lateral direction, and a primer layer having a thickness of 0.1 μm was placed on one side. A polyester film substrate having a thickness (after drying) of 50 μm was obtained.

[Examples 1 to 7]
The coating liquid shown in Table 1 was applied onto the primer layer of the polyester film with a bar coater, and dried at 70 ° C. for 1 minute. Next, the obtained coating film was irradiated with excimer light (half-value width 14 nm) using xenone (wavelength 172 nm) with an irradiation amount of 15 mJ / cm ² and an illuminance of 5 mW / cm ² (xenon excimer 172 nm light irradiator manufactured by Ushio Denki Co., Ltd., lamp unit model: Irradiate with SUS05 (lamp house model: H0011, lighting power supply model: B0005), nitrogen flow (oxygen concentration 1% or less)), and in an air atmosphere with a high-pressure mercury lamp, the integrated light amount is 400 mJ / cm ² , and the illuminance is 200 mW / cm ² . (UV conveyor of high-power UV device (model: US5-X1802-X1202) manufactured by Eye Graphics Co., Ltd.) is irradiated with ultraviolet rays to form a cured film having a wrinkle-like uneven structure with a thickness (after drying) of 5 μm and laminated. I got a body. Separately from this, the coating liquid shown in Table 1 was applied, and the curability of the sample dried at 70 ° C. for 1 minute was evaluated.
The obtained laminate had good scratch resistance (pencil hardness) and matte property. Table 2 shows all the evaluation results.

[Comparative Examples 1 to 4]
The coating was produced in the same manner as in Examples except that the coating composition was changed to the coating composition shown in Table 1, to obtain a laminate having a cured film. Table 2 shows all the evaluation results of the obtained laminated body.

[Comparative Example 5]
In Example 6, instead of excimer light, an integrated light amount of 250 mJ / cm ² and an illuminance of 100 mW / cm ² with a high-pressure mercury lamp in an air atmosphere (high-power UV device manufactured by Eye Graphics Co., Ltd. (model: US5-X1802-X1202)). A laminate having a cured film was obtained by producing in the same manner as in Example 6 except that the ultraviolet rays were irradiated on the UV conveyor. When the obtained laminated body was evaluated, as shown in Table 2, the uneven structure was not formed and it was not matte.

Claims (10)

A cured film formed by irradiating an active energy ray-curable composition with active energy rays, wherein the active energy ray-curable composition is a polymer (A) having an unsaturated double bond in the main chain or side chain. And a cured film containing polyfunctional (meth) acrylate (B) and having a wrinkle-like uneven structure on the surface. The cured film according to claim 1, wherein the polymer (A) is a (meth) acrylic acid ester copolymer (A1). The cured film according to claim 1 or 2, wherein the active energy ray-curable composition contains substantially no particles. Claimed that the average length (RSm) of the roughness curve elements according to JIS B0601: 2013 in the uneven structure is 1 to 50 μm, and the arithmetic mean height (Sa) defined by ISO25178 is 0.1 to 5 μm. Item 3. The cured film according to any one of Items 1 to 3. The cured film according to any one of claims 1 to 4, wherein the average value (θa) of the local inclination angles in the uneven structure is 2 ° or more. The cured film according to any one of claims 1 to 5, wherein the 60 ° gloss is 50 or less. The active energy ray-curable composition containing the polymer (A) having an unsaturated double bond in the main chain or the side chain and the polyfunctional (meth) acrylate (B) is irradiated with vacuum ultraviolet rays, according to claims 1 to 6. The method for producing a cured film according to any one of the following items. A laminate having the cured film according to any one of claims 1 to 6 on a substrate. The laminate according to claim 8, wherein the base material is a film. An active energy ray-curable composition containing a polymer (A) having an unsaturated double bond in the main chain or a side chain and a polyfunctional (meth) acrylate (B) is laminated on a substrate, and irradiated with vacuum ultraviolet rays. The method for producing a laminate according to claim 8 or 9, wherein the laminate is cured.