JP2021024931A - Curable polymer composition, cured product, and laminate - Google Patents

Abstract

To provide a curable polymer composition having excellent curability, a cured product of the curable polymer composition, and a laminate having a layer composed of the cured product.SOLUTION: A curable polymer composition has a copolymer (A) having a unit based on a monomer (x) having a first active group to generate a radical by irradiation with active energy rays and a unit based on a monomer (y) having at least one selected from the group consisting of an alkyl group with four or more carbon atoms, a fluorine atom, and a silicon atom, a polyfunctional compound (B) having two or more radical-polymerizable groups in one molecule, and a non-polymer (C) having a second active group to generate a radical by irradiation with active energy rays.SELECTED DRAWING: None

Description

The present invention relates to a curable polymer composition, a cured product of the curable polymer composition, and a laminate having a layer composed of the cured product.

A hard coat layer may be provided on the surface of an article such as a thermoplastic resin film represented by a polyethylene terephthalate (PET) film for the purpose of imparting functions such as hardness and slipperiness.
As the hard coat layer, a curable composition containing a compound having a radically polymerizable group and a photopolymerization initiator is generally known to be cured by radical polymerization.
However, in this method, the polymerization termination reaction due to oxygen occurs at the contact interface between the coating film of the curable composition and oxygen, that is, on the surface of the coating film, so that the curability is lowered or the cured product of the curable composition is cured. Mechanical properties may be insufficient.

Patent Document 1 describes an ultraviolet curable substance (A) having 5 to 7 functional groups, a urethane acrylate oligomer (B) having 2 to 3 functional groups, and an ultraviolet polymerization initiator (C) which is an oligomer (homopolymer). A curable composition for a hard coat containing the above is described.

Japanese Unexamined Patent Publication No. 2003-292828

The curable composition described in Patent Document 1 can form a cured product such as a hard coat layer having excellent mechanical properties by using an oligomer-type ultraviolet polymerization initiator, but it does not necessarily satisfy the curability.
An object of the present invention is to provide a curable polymer composition having excellent curability, a cured product of the curable polymer composition, and a laminate having a layer composed of the cured product.

The present invention has the following aspects.
[1] A unit selected from the group consisting of a unit based on a monomer (x) having a first active group that generates a radical by irradiation with an active energy ray, an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom 1 A copolymer (A) having a unit based on a monomer (y) having more than one species, a polyfunctional compound (B) having two or more radical polymerizable groups in one molecule, and radicals generated by irradiation with active energy rays. A curable polymer composition containing a non-polymer (C) having a second active radical.
[2] The curable polymer composition according to the above [1], wherein the content of the copolymer (A) is 0.1 to 50% by mass with respect to the non-volatile content of the curable polymer composition.
[3] The curable polymer composition according to the above [1] or [2], wherein the content of the first active group per 1 g of the copolymer (A) is 0.1 to 3.5 mmol / g. ..
[4] The first active group and the second active group independently form a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, and an α-. The curable polymer composition according to any one of the above [1] to [3], which is one or more selected from the group consisting of a diketone dialkylacetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group.
[5] Any of the above [1] to [4], wherein the content of the non-polymer (C) is 0.1 to 15% by mass with respect to the non-volatile content of the curable polymer composition. Curable polymer composition.
[6] The curable polymer composition according to any one of [1] to [5] above, wherein the mass ratio represented by the copolymer (A) / the non-polymer (C) is 0.1 to 10. Stuff.
[7] Any of the above [1] to [6], wherein the monomer (x) has one or more functional groups selected from the group consisting of a (meth) acryloyl group, a (meth) acrylamide group, and a vinyl group. The curable polymer composition.
[8] A cured product of the curable polymer composition according to any one of the above [1] to [7].
[9] The cured product of the above [8], wherein the copolymer (A) is unevenly distributed on the surface layer of the pre-cured product.
[10] The cured product of [8] or [9] above, wherein the haze is less than 10% and the 60 ° gloss is 130 or more.
[11] A laminate having a base material layer and a layer made of the cured product according to any one of [8] to [10].

According to the present invention, it is possible to provide a curable polymer composition having excellent curability, a cured product of the curable polymer composition, and a laminate having a layer composed of the cured product.

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

Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, "(meth) acrylate" is a general term for acrylate or methacrylate. "(Meta) acrylic" is a general term for acrylic and methacrylic.
"~" 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.

[Curable polymer composition]
The curable polymer composition comprises a unit based on a monomer (x) having a first active group that generates radicals by irradiation with active energy rays, an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom. A copolymer (A) having a unit based on a monomer (y) having one or more selected from the group, a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule, and an active energy ray. It contains a non-polymer (C) having a second active group that generates radicals upon irradiation.
When the curable polymer composition is irradiated with active energy rays, radicals are generated from the first active group of the copolymer (A) and the second active group of the non-polymer (C), respectively, and the generated radicals are generated. As a starting point, the reaction between the radically polymerizable groups of the polyfunctional compound (B) proceeds, and the entire curable polymer composition is cured.
The curable polymerization composition can further contain an organic solvent, if necessary.
The curable polymerization composition can further contain components other than the above, if necessary.

<Copolymer (A)>
The copolymer (A) is composed of a unit based on a monomer (x) having a first active group that generates radicals by irradiation with active energy rays, an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom. It has a unit based on the monomer (y) having one or more selected from the group.

[Monomer (x)]
The monomer (x) is a monomer having a first active group that generates radicals by irradiation with active energy rays.
Examples of the monomer (x) include a compound having a first active group and a radically polymerizable group.
The first active group may have a structure (structure having photopolymerization initiation property) that generates radicals by irradiation with active energy rays. As the structure having photopolymerization initiation property, various known structures can be adopted, and examples thereof include a hydrogen abstraction type, an electron transfer type, and an intramolecular cleavage type.
Specific examples of the first active group include a benzophenone group, an acetophenone group, a benzoin group, and an α-hydroxyketone group (for example, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methylpropanol. ), A group obtained by removing one hydrogen atom from the "hydroxyl group in 2-hydroxyethoxy"), α-aminoketone group, α-diketone group, α-diketone dialkylacetal group, anthraquinone group, thioxanthone group, phosphine oxide group, etc. Can be mentioned. Among these, a benzophenone group, an acetophenone group, and an α-hydroxyketone group are preferable because they are less susceptible to oxygen inhibition during curing and have good curability.
The α-hydroxyketone group may be one in which two groups other than the hydroxyl group bonded to the carbon atom adjacent to the ketone group form a ring.

The first active group may be present at the end of the main chain of the copolymer (A), or may be present in a unit based on the monomer constituting the copolymer (A).
The copolymer (A) preferably has a plurality of first active groups in the molecule. As a result, the concentration of active groups near the surface of the coating film can be increased, and even if the irradiation amount of active energy rays is small, it can be sufficiently cured.

Examples of the radically polymerizable group of the monomer (x) include a functional group containing a radically polymerizable unsaturated bond (carbon-carbon double bond, etc.), and specific examples thereof include a (meth) acryloyl group and a (meth) acrylamide group. , Vinyl group and the like.
As the monomer (x), a (meth) acrylic acid ester having a first active group is preferable from the viewpoint of easy synthesis of the copolymer (A) and easy adjustment of the amount of active group introduced. ..
Examples of the monomer (x) include 4-methacryloyloxybenzophenone and 2- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy] ethyl methacrylate.

[Monomer (y)]
The monomer (y) is a monomer having at least one selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom.
The monomer (y) is a monomer having a small surface energy, and if the copolymer (A) has a unit based on the monomer (y), when the coating film of the curable polymer composition is formed, , The copolymer (A) is likely to segregate on the surface side of the coating film. If the copolymer (A) having the first active group segregates on the surface side of the coating film, the polymerization termination reaction due to oxygen on the coating film surface can be suppressed, and the curability is enhanced. Therefore, for example, it can be cured with a low exposure amount. In addition, even a thin film that tends to be susceptible to oxygen inhibition can be cured well.
Examples of the monomer (y) include a monomer (r) having an alkyl group having 4 or more carbon atoms, a monomer (f) having a fluorine atom or a silicon atom, and the like.

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

Examples of the monomer (r) include compounds having an alkyl group having 4 or more carbon atoms and a radically polymerizable group, and the ease of synthesizing the compound and the ease of adjusting the amount of the alkyl group having 4 or more carbon atoms introduced. From the above viewpoint, a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms is preferable.
Examples of the monomer (r) include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and isooctyl (meth). ) Acrylate, decyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) ) Acrylate, adamantyl (meth) acrylate and the like can be mentioned.
Among these, it is preferable to contain a (meth) acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms. The (meth) acrylic acid alkyl ester having a linear alkyl group having 4 or more carbon atoms is preferably one in which the number of carbon atoms of the alkyl group is in the above-mentioned preferable range, and in consideration of ease of production and the like, 2 -Ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate are more preferable, and stearyl (meth) acrylate is particularly preferable.
One of these (meth) acrylic acid esters may be used alone, or two or more thereof may be used in combination.

Examples of the monomer (f) include a compound having a fluorine atom or a silicon atom and a radically polymerizable group. The radically polymerizable group is the same as the radically polymerizable group exemplified above in the description of the monomer (x).
The monomer (f) is also a component that imparts at least one of water repellency and oil repellency to the cured product and enhances the antifouling property of the cured product. If the copolymer (A) has a unit based on the monomer (f), the copolymer (A) segregates on the surface side of the coating film when the coating film of the curable polymer composition is formed. To do. As a result, the curability is enhanced, and the concentration of the unit based on the monomer (f) on the surface side of the coating film is increased, so that the surface of the cured product can be efficiently imparted with antifouling property.

The monomer (f) preferably contains at least one selected from the group consisting of a compound having a fluoroalkyl group and a radically polymerizable group, and a compound having a polydimethylsiloxane chain and a radically polymerizable group.
It is more preferable that the monomer (f) contains at least one selected from the group consisting of a (meth) acrylic acid ester having a fluoroalkyl group and a (meth) acrylic acid ester having a polydimethylsiloxane chain.

As the (meth) acrylic acid ester having a fluoroalkyl group, a (meth) acrylic acid ester having a perfluoroalkyl group is more preferable. The perfluoroalkyl group preferably has 4 or more carbon atoms.
Specific examples of the (meth) acrylic acid ester having a polydimethylsiloxane chain include one-terminal (meth) acryloyl group-substituted polydimethylsiloxane having a molecular weight of 500 to 50,000. The molecular weight is preferably 1000 to 30000, more preferably 1500 to 20000.

[Monomer (h)]
The copolymer (A) may further have one or more units based on the monomer (h) having a hydrogen donating functional group, if necessary.
In particular, when the monomer (x) has a hydrogen abstraction type active group as the first active group, curing is promoted when the copolymer (A) contains a unit based on the monomer (h).
As the hydrogen donating functional group, one or more selected from the group consisting of a hydroxyl group, an amino group, a mercapto group and an amide group is preferable. Among these, a hydroxyl group, an amino group or an amide group is preferable from the viewpoint of accelerating the curing reaction particularly efficiently.

Examples of the monomer (h) include compounds having a hydrogen donating functional group and a radically polymerizable group. The radically polymerizable group is the same as the radically polymerizable group exemplified above in the description of the monomer (x).
From the viewpoint of ease of compound synthesis and ease of adjusting the amount of hydrogen-donating functional group introduced, the monomer (h) includes (meth) acrylic acid ester having a hydrogen-donating functional group and (meth) acrylamide. Kind is preferred.
Examples of the monomer (h) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (h). Hydroxyl-containing monomers such as meta) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, monobutylhydroquilfumarate, monobutylhydroxyitaconate; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, 2-[(butylamino) carbonyl] oxy ] Ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate ) Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, (meth) acryloylmorpholine, vinylacetamide and other amino groups or Examples thereof include amide group-containing monomers. Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N, N-dimethyl are excellent in the effect of promoting curing when used in combination with an active group. Acrylamide, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate are more preferable. One of these compounds may be used alone, or two or more of these compounds may be used in combination.

[Monomer (o)]
The copolymer (A) may further have a unit based on a monomer (monomer (o)) other than the above, if necessary. Examples of the monomer (o) include compounds having a radically polymerizable group and not having a first active group, an alkyl group having 4 or more carbon atoms, a fluorine atom, a silicon atom and a hydrogen donating functional group. .. The radically polymerizable group is the same as the radically polymerizable group exemplified above in the description of the monomer (x).
Examples of the monomer (o) include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid and salts thereof; methyl (meth) acrylate and ethyl (meth). (Meta) acrylates such as acrylate and propyl (meth) acrylate; Nitrogen-containing monomers such as (meth) acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene, vinyl propionate, vinyl acetate and the like. Examples thereof include vinyl esters; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and billidene chloride; and conjugated dienes such as butadiene.

The copolymer (A) preferably has a plurality of first active groups in the molecule.
The content of the first active group per gram of the copolymer (A) is preferably 0.1 to 3.5 mmol / g, more preferably 0.5 to 2.5 mmol / g, still more preferably 0. It is in the range of 8 to 2.0 mmol / g. When the content of the first active group is at least the lower limit of the above range, the curability is more excellent. In addition, the scratch resistance of the coating film is enhanced. When the content of the first active group is not more than the upper limit of the above range, the storage stability of the curable composition is excellent.

The content of the hydrogen donating functional group per gram of the copolymer (A) is preferably 0.1 to 3.5 mmol / g, more preferably 0.8 to 3.2 mmol / g, still more preferably 1. It is in the range of 0 to 3.0 mmol / g. When the content of the hydrogen donating functional group is at least the lower limit of the above range, the curability is more excellent. When the content of the hydrogen donating functional group is not more than the upper limit of the above range, the compatibility between the copolymer (A) and the polyfunctional compound (B) is excellent.

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

The ratio of the units based on the monomer (y) to the total mass of all the units constituting the copolymer (A) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and further preferably 8 to 50. It is in the range of mass%. When the ratio of the unit based on the monomer (y) is at least the lower limit of the above range, the curability is more excellent. When the ratio of the unit based on the monomer (y) is not more than the upper limit of the above range, the compatibility between the copolymer (A) and the polyfunctional compound (B) is excellent.

The ratio of the units based on the monomer (r) to the total mass of all the units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 70% by mass, and further preferably 5 to 60% by mass. %, Especially preferably in the range of 8 to 50% by mass. When the ratio of the unit based on the monomer (r) is at least the lower limit of the above range, the curability is more excellent. When the ratio of the unit based on the monomer (r) is not more than the upper limit of the above range, the compatibility between the copolymer (A) and the polyfunctional compound (B) is excellent.

The ratio of the units based on the monomer (f) to the total mass of all the units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 70% by mass, and further preferably 5 to 60% by mass. %, Especially preferably in the range of 8 to 50% by mass. When the ratio of the unit based on the monomer (f) is at least the lower limit of the above range, the curability is more excellent. In addition, the cured product has excellent antifouling properties. When the ratio of the unit based on the monomer (f) is not more than the upper limit of the above range, the compatibility between the copolymer (A) and the polyfunctional compound (B) is more excellent.

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

The weight average molecular weight (Mw) of the copolymer (A) is preferably in the range of 1,000 to 500,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 60,000. .. When Mw is at least the lower limit of the above range, the curability is more excellent. When Mw is not more than the upper limit of the above range, the coatability of the curable polymer composition is excellent.
The Mw of the copolymer (A) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC). Detailed measurement conditions are as described in Examples described later.

The glass transition temperature (Tg) of the copolymer (A) is preferably in the range of -30 to 180 ° C, more preferably 0 to 150 ° C, and even more preferably 25 to 100 ° C. When Tg is at least the lower limit of the above range, the curability is more excellent. When it is not more than the upper limit value, the compatibility between the copolymer (A) and the polyfunctional compound (B) is excellent.
The Tg of the copolymer (A) can be obtained by actual measurement using a differential scanning calorimeter (DSC) or the like or by the Fox formula.

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

<Polyfunctional compound (B)>
The polyfunctional compound (B) may be any compound having two or more radically polymerizable groups in one molecule, and various known compounds can be used.
As the polyfunctional compound (B), a polyfunctional (meth) acrylate is preferable.
The polyfunctional compound (B) may be used alone or in combination of two or more.

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

The trifunctional or higher polyfunctional (meth) acrylate is not particularly limited, but for example, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate. , Ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethyl propanetri (meth) acrylate, isocyanurate ethylene oxide-modified tri (meth) acrylate, ε-caprolactone-modified tris (acroxyethyl) isocyanurate Isocyanuric acid-modified tri (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer and the like. Be done. Among these, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferable.

<Non-polymer (C)>
The non-polymer (C) has a second active group that generates radicals when irradiated with active energy rays. The non-polymer (C) is a compound that is not a polymer and has a function of a polymerization initiator.
As described above, the copolymer (A) segregates on the surface side of the coating film, but the non-polymer (C) is dispersed in the coating film. Therefore, even if the copolymer (A) segregates on the surface of the coating film when irradiated with active energy rays, the curing rate is less likely to be uneven between the surface side and the inside of the coating film, and the surface side of the coating film side. As the curing progresses at, the curing also progresses inside. As a result, the surface of the coating film tends to be smooth.

The second active group is the same as the first active group exemplified above in the description of the copolymer (A).
The second active group may be of the same type as the first active group or may be of a different type.

Examples of the non-polymer (C) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-. Dimethyl-4-methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, pivaloine ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, p. -T-Butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4 -Phenyloxyacetophenone, phenylglycilate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl ] -2-morpholino-1-propanol, tribromophenylsulfone, tribromomethylphenylsulfone, 1- [4- (2-hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanol and the like. Among these, 1- [4- (2-hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanol is preferable. One of these non-polymers (C) may be used alone, or two or more thereof may be used in combination.

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

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

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

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

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

<Content>
The content of the copolymer (A) with respect to the non-volatile content of the curable polymer composition is preferably 0.1 to 50% by mass, more preferably 0.2 to 30% by mass, still more preferably 0.5 to 20%. It is in the range of% by mass, particularly preferably 0.8 to 8% by mass. When the content of the copolymer (A) is within the above range, the curability is more excellent.
The non-volatile content of the curable polymer composition is the total mass of the components other than the organic solvent. The non-volatile content of the curable polymer composition can be measured by a conventionally known method. For example, the weight when 1 g of the composition is spread and heated at 100 ° C. for 1 hour to volatilize the organic solvent. Measured by the change in solvent.

The content of the copolymer (A) with respect to 100 parts by mass of the polyfunctional compound (B) is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and further preferably 0.5 to 20 parts by mass. It is in the range of parts by mass, particularly preferably 1 to 10 parts by mass. When the content of the copolymer (A) is within the above range, the curability is more excellent.

The content of the polyfunctional compound (B) with respect to the non-volatile content of the curable polymer composition is preferably 10 to 99.8% by mass, more preferably 50 to 99.7% by mass, still more preferably 70 to 99% by mass. , Particularly preferably in the range of 80 to 98% by mass. When the content of the polyfunctional compound (B) is within the above range, the curability and scratch resistance are more likely to be improved.

The content of the non-polymer (C) with respect to the non-volatile content of the curable polymer composition is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.5 to 8%. It is in the range of mass%, particularly preferably 1 to 6 mass%. When the content of the non-polymer (C) is within the above range, the smoothness and curability will be better.

The content of the non-polymer (C) with respect to 100 parts by mass of the polyfunctional compound (B) is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 8 parts. It is in the range of parts by mass, particularly preferably 1 to 6 parts by mass. When the content of the non-polymer (C) is within the above range, the smoothness and curability will be better.

The mass ratio (A / C ratio) represented by the copolymer (A) / non-polymer (C) is preferably 0.1 to 10, more preferably 0.15 / 7, and even more preferably 0.2. It is in the range of ~ 5. When the A / C ratio is within the above range, the balance between curability and smoothness of the coating film is excellent.

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

[Cured product]
For the cured product of the curable polymer composition, the curable polymer composition is applied onto the surface of the base material or the article to form a coating film, and if necessary, dried, and then the coating film is exposed to active energy rays. It can be formed by irradiating.
The method for applying the curable polymer composition is not particularly limited. For example, a curable polymer composition by a known method such as a dip coating method, an air knife coating method, a curtain coating method, a spin coating method, a roller coating method, a bar coating method, a wire bar coating method, a gravure coating method, or a spray coating method. Can be applied.

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

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

The cured product of the curable polymer composition is a cured product in which the copolymer (A) is unevenly distributed on the surface layer.
The uneven distribution of the copolymer (A) on the surface layer of the cured product means TOF-SIMS (time-of-flight secondary ion mass spectrometry) and ESCA (X-ray photoelectron spectroscopy) by etching with argon or the like. Alternatively, it can be confirmed by staining with osmium, ruthenium or the like, or incineration treatment with plasma or the like, and cross-sectional observation with a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

When the cured product is measured by TOF-SIMS, for example, the detection intensity (I) of the secondary ion peak species derived from the copolymer (A) observed on the etching surface at a depth of 50 nm is determined by etching at a depth of 1 μm. If the value (detection intensity ratio: I / II) divided by the detection intensity (II) of the secondary ion peak species derived from the copolymer (A) observed on the surface exceeds 1.0, the cured product It can be said that the copolymer (A) is unevenly distributed near the surface layer.
When the thickness of the cured product is less than 1 μm, the detection intensity (I) of the secondary ion peak species derived from the copolymer (A) observed on the etching surface at a depth of 1/10 of the thickness is observed. ) And the value divided by the detection intensity (II) of the secondary ion peak species derived from the copolymer (A) observed on the etching surface at the depth of 9/10 of the thickness. it can.
The value of the detection intensity ratio: I / II is preferably 1.2 or more, more preferably 1.3 or more, still more preferably 1.5 or more. The I / II value indicates the distribution of the copolymer (A) in the cured product in the thickness direction, and the larger the I / II value, the more the copolymer (A) is on the surface layer of the cured product. It is unevenly distributed.

In addition, in the comparison of the detected intensity ratios, the influence of contamination may be considered, but for more accurate consideration, the outermost layer (non-etched surface) is also observed on the outermost layer (non-etched surface). The detection intensity (III) of the secondary ion peak species derived from the polymer (A) is the detection intensity (II) of the secondary ion peak species derived from the copolymer (A) observed on the etching surface at a depth of 1 μm. The value divided by) (detection intensity ratio: III / II) is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.3 or more, and particularly preferably 1.5 or more.
When the thickness of the cured product is less than 1 μm, the detection intensity (III) of the secondary ion peak species derived from the copolymer (A) observed on the outermost layer (the surface not etched) and the depth are the same. It can be evaluated by the value divided by the detection intensity (II) of the secondary ion peak species derived from the copolymer (A) observed on the etching surface at the portion of 9/10 of the thickness.

In similar ion species, both positive and negative ions are preferably more than 1.0, more preferably 1.2 or more, still more preferably 1.3 or more, and particularly preferably 1.5 or more.
Some compounds are easily ionized and some are not easily ionized, and it is preferable to confirm the detection intensity ratio with one that is easily ionized. Examples of those that are easily ionized include fluorine-based compounds, amino groups, and alkyl groups.

When the cured product is measured by ESCA, the same method as TOF-SIMS described above can be used. That is, it is possible to confirm whether or not the copolymer (A) is unevenly distributed on the surface layer by etching the surface and comparing the elements and chemical states found by the measurement near the surface layer and the deep layer.
When measuring the cured product by SEM or TEM, if the difference in electron density of the compounds used is small and cannot be observed without treatment, stain with osmium or ruthenium, or incinerate with plasma, etc. in combination. Can be done. When the cured product is cross-sectionally observed, it can be confirmed whether or not the density of the observed image is different from that of other locations at the surface side portion of the cured product having a film thickness of half or more.

The surface of the cured product is preferably a smooth surface.
The surface roughness of the cured product is preferably 20 nm or less, more preferably 10 nm or less, still more preferably 5 nm or less. The lower limit is not particularly limited, but is preferably 1 nm. When the surface roughness is not more than the above upper limit value, the transparency is good, and the visibility when used for various purposes is good.
The haze of the cured product is preferably in the range of less than 10%, more preferably 0.1 to 5%, still more preferably 0.1 to 2%. When the haze is less than the upper limit of the above range, the transparency is good, and the visibility when used for various purposes is good.
The 60 ° gloss (60 ° mirror gloss) of the cured product is preferably 130 or more, more preferably 140 or more, still more preferably 150 or more. When the 60 ° gloss is at least the above lower limit value, the transparency is good, and the visibility when used for various purposes is good.
For the surface roughness of the cured product, use the surface shape measurement system to measure the uneven shape of the surface of any region on the surface of the cured product by the optical interferometry, perform complementation and baseline correction, and read the data. Measured at.
The haze of the cured product and the 60 ° gloss are measured by the methods described in Examples described later, respectively.

The water contact angle of the cured product is preferably in the range of 75 ° or more, more preferably 80 to 120 °, and even more preferably 85 to 110 °. When the water contact angle is at least the lower limit of the above range, the water repellency and antifouling property are excellent.
The water contact angle of the cured product is measured by the method described in Examples described later.

The cured product of the curable polymer composition is suitable as a hard coat layer.
When the cured product is a hard coat layer, the thickness of the cured product is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm, and even more preferably 0.3 to 5 μm. If the thickness of the cured product is within the above range, it can be made more excellent in curability and scratch resistance.
The thickness of the cured product indicates the maximum thickness of the cured product and is determined by cross-sectional observation with an electron microscope.
As for the hardness of the cured product, the pencil hardness measured by the method described in Examples described later is preferably harder than B, and more preferably harder than HB.
The cured product is preferably transparent. The total light transmittance of the cured product is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more. The upper limit is not particularly limited, but is preferably 99%. When the total light transmittance is at least the above lower limit value, the transparency becomes high, and the visibility when used for various purposes becomes good.
The total light transmittance of the cured product is measured by the method described in Examples described later.

[Laminate]
The laminate of the present invention (hereinafter, also referred to as “the present laminate”) has a base material layer and a layer composed of a cured product of the curable polymer composition (hereinafter, also referred to as “cured layer”). .. The laminate further comprises a primer layer provided between the base material layer and the cured layer, a surface functional layer provided on a surface of the cured layer opposite to the base material layer side, and the cured layer. It is preferable to have one or more layers selected from the group consisting of back surface functional layers provided on the surface of the base material layer opposite to the cured layer side.
This laminate is suitable as a hard coat film used, for example, as a protective film for articles.

1 to 5 are schematic cross-sectional views showing an example of this laminated body. The dimensional ratios in FIGS. 1 to 5 are for convenience of explanation and are different from the actual ones.
The laminate 10 of the example of FIG. 1 is provided between the substrate layer 1, the cured layer 2 provided on one surface 1a of the substrate layer 1, and the substrate layer 1 and the cured layer 2. It has a primer layer 3 and.
The laminate 10 of the example of FIG. 2 has a base material layer 1, a hardened layer 2 provided on one surface 1a of the base material layer 1, and a surface of the hardened layer 2 opposite to the base material layer 1 side. It has a surface functional layer 4 provided on the top.
The laminate 10 of the example of FIG. 3 is provided between the substrate layer 1, the cured layer 2 provided on one surface 1a of the substrate layer 1, and the substrate layer 1 and the cured layer 2. It has a primer layer 3 and a surface functional layer 4 provided on a surface of the cured layer 2 opposite to the base material layer 1 side.
The laminate 10 of the example of FIG. 4 is provided between the substrate layer 1, the cured layer 2 provided on one surface 1a of the substrate layer 1, and the substrate layer 1 and the cured layer 2. It has a primer layer 3 and a back surface functional layer 5 provided on a surface 1b opposite to the cured layer 2 side of the base material layer 1.
The laminate 10 of the example of FIG. 5 is provided between the substrate layer 1, the cured layer 2 provided on one surface 1a of the substrate layer 1, and the substrate layer 1 and the cured layer 2. The primer layer 3, the surface functional layer 4 provided on the surface of the cured layer 2 opposite to the substrate layer 1 side, and the surface 1b of the substrate layer 1 opposite to the cured layer 2 side. It has a back surface functional layer 5 and the like.

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

Various resin films (sheets) can be used as the resin base material, for example, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, etc. Examples thereof include a polyvinyl alcohol film and a nylon film.
When developing this laminate for display applications, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetyl cellulose film are preferable. Among these, polyester film, poly (meth) acrylate film, and polyolefin film are preferable for anti-glare use, and polyester film is more preferable in consideration of transparency, moldability, and versatility.
The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferable. Of these, a uniaxially stretched film stretched in the uniaxial direction or a biaxially stretched film stretched in the biaxial direction is preferable, and a biaxially stretched film is more preferable from the viewpoint of excellent balance of mechanical properties and flatness.

The polyester constituting the polyester film that can be used as the base material layer may be a homopolyester or a copolymerized polyester.
As the homopolyester, those obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol are preferable. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and the like. One type of each of the aromatic dicarboxylic acid and the aliphatic glycol may be used alone, or two or more types may be used in combination.
Examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like. One type of each of the dicarboxylic acid component and the glycol component may be used alone, or two or more types may be used in combination.
Examples of typical polyesters include polyethylene terephthalate and polyethylene naphthalate.

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

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

The base material layer can contain particles for the purpose of imparting slipperiness, preventing scratches in each step, and improving blocking resistance.
The type of particles can be appropriately selected according to the purpose and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, acrylic resin, styrene resin, urea resin, and phenol. Examples thereof include organic particles such as resins, epoxy resins, and benzoguanamine resins. Further, when the base material layer contains a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst in the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are preferable in that a small amount is particularly effective.
The shape of the particles is not particularly limited, and any of spherical, massive, rod-shaped, flat-shaped, and the like may be used. Further, the hardness, specific gravity, color and the like are not particularly limited.
Two or more kinds of these particles may be used in combination, if necessary.

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

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

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

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

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

In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the base material layer and the cured 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 layer and the cured layer is improved, and the laminated body can be used for various purposes.
When the primer layer is an adhesion improving layer, the primer layer preferably contains either one or both of a resin and a compound derived from a cross-linking agent from the viewpoint of improving the adhesion between the base material layer and the cured layer.

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

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

Examples of the polyester resin include those whose main constituents are a polyvalent carboxylic acid and a polyvalent hydroxy compound.
Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid. 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodiumsulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanediocarboxylic acid, glutaric acid, succinic acid, Examples thereof include trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, monopotassium trimellitic acid and ester-forming derivatives thereof.
Examples of the polyvalent hydroxy compound include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 2-methyl-1. , 5-Pentanediol, Neopentyl glycol, 1,4-Cyclohexanedimethanol, p-xylylene glycol, Bisphenol A-ethylene glycol adduct, Diethylene glycol, Triethylene glycol, Polyethylene glycol, Polypropylene glycol, Polytetramethylene glycol, Poly Examples thereof include tetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like.
One or more of each of these compounds may be appropriately selected, and a polyester resin may be synthesized by a conventional polycondensation reaction.

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

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

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

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

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

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

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

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

The chain extender is not particularly limited as long as it has two or more active groups that react with the isocyanate group, and in general, a chain extender having two hydroxyl groups or amino groups can be mainly used. ..
Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. Glycol compounds such as glycol can be mentioned.
Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine and 2,2-dimethyl-1,3-propanediamine. , 2-Methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine And other aliphatic diamines, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprovilitincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3 -Alicyclic diamines such as bisaminomethylcyclohexane and the like can be mentioned.

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

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

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

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

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

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

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

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

The oxazoline compound is a compound having an oxazoline group in the molecule.
As the oxazoline compound, a polymer containing an oxazoline group is preferable. The oxazoline group-containing polymer is obtained by polymerization of the addition-polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of the addition-polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. One of these may be used alone, or two or more thereof may be used in combination. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition-polymerizable oxazoline group-containing monomer. For example, an alkyl (meth) acrylate (as an alkyl group, a methyl group, an ethyl group, an n-propyl group, etc. (Meta) acrylates such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl (meth) ) Acrylamide, N, N-dialkyl (meth) acrylamide, (the alkyl groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group. , Cyclohexyl group, etc.); Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; Vinyl chloride, vinylidene chloride, vinyl fluoride, etc. Halogen-containing α, β-unsaturated monomer; α, β-unsaturated aromatic monomer such as styrene, α-methylstyrene, etc. can be mentioned. One of these may be used alone, or two or more thereof may be used in combination.

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

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

The carbodiimide-based compound is a compound having one or more carbodiimide structure or carbodiimide derivative structure in the molecule.
As the carbodiimide-based compound, a polycarbodiimide-based compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable because of better primer layer strength and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The proportion of the compound derived from the cross-linking agent in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and further preferably 5 to 40% by mass. The range. When the ratio of the compound derived from the cross-linking agent is within the above range, the adhesion performance and the strength of the primer layer are more excellent.

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

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

<Surface functional layer>
The surface functional layer is provided on the hardened layer to impart various functions.
Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, a color correction layer, and the like.
The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured layer. The antistatic layer is provided to reduce adhesion of dust and the like due to peeling electrification and triboelectric charging to the outermost surface of the laminate, particularly the outermost surface on the side where the cured layer exists with respect to the base material layer. The refractive index adjusting layer is provided, for example, in order to improve the total light transmittance of the laminated body.

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

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

As the silicone compound, modified silicone such as acrylic 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. As the type of curing type, any curing reaction type such as a condensation type, an addition type, and an active energy ray curing type can be used.

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

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

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

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

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

In addition to antifouling components, the antifouling layer includes resins, cross-linking agent-derived compounds, antistatic agents, antifoaming agents, coatability improvers, thickeners, ultraviolet absorbers, antioxidants, and foaming agents. It may further contain agents, dyes, pigments and the like. The compounds derived from the resin and the cross-linking agent are as described above. The antifouling layer preferably has a crosslinked structure from the viewpoint of improving the strength and durability of the layer. Examples of the antifouling layer having a crosslinked structure include a layer of a cured product of a composition containing a compound having a plurality of radically polymerizable groups such as an acryloyl group or a crosslinking agent and an antifouling component.

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

The antistatic layer contains an antistatic agent. The antistatic agent is as described above.
In addition to antistatic agents, antistatic layers include resins, cross-linking agent-derived compounds, defoamers, coatability improvers, thickeners, antifouling agents, UV absorbers, antioxidants, and foaming agents, if necessary. It may further contain agents, dyes, pigments and the like. The compounds derived from the resin and the cross-linking agent are as described above.

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

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

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

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

The thickness of the surface functional layer is preferably 0.001 to 30 μm, more preferably 0.005 to 20 μm, still more preferably 0.01 to 10 μm, particularly preferably 0.02 to 5 μm, and most preferably 0.03 to 3 μm. Is in the range of. When the thickness of the surface functional layer is within the above range, the function of the surface functional layer is likely to be exhibited.
The surface functional layer can be formed by a known method.

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

As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, known ones can be used, and examples thereof include acrylic type, polyester type, urethane type, and rubber type. Among them, acrylic is preferable in consideration of versatility.
The antistatic layer and the refractive index adjusting layer are the same as the antistatic layer and the refractive index adjusting layer as the surface functional layer, respectively.

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

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

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

(2) Measurement of total light transmittance and haze A laminated body having a cured layer formed on a PET film was used as a measurement target. The total light transmittance and haze are JIS Z 8722 (geometric conditions for irradiation and light reception of transmitted objects), JIS K 7361-1 (test method for total light transmittance of plastic-transparent material) and JIS K 7136 (plastic-transparent). The value at a wavelength of 550 nm was measured using a haze meter “SH7000” manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with (How to obtain the haze of the material).
The haze of the laminated body is 0.044 rad (2.) of the transmitted light incident from the outermost surface on the side where the cured layer exists with respect to the base material layer and passing through the laminated body due to forward scattering. It is a percentage of transmitted light (ratio of diffuse transmittance to total light transmittance) deviated by 5 °) or more.

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

(4) Evaluation of curability ^{When ultraviolet rays were irradiated at an illuminance of 100 mW / cm 2} , the irradiation amount (integrated light amount) until the tack disappeared by touch was measured. Evaluation was made according to the following criteria.
A: It cures at an irradiation amount of 200 mJ / cm ^{2 or less.}
B: 200mJ / cm ² greater, cured with irradiation of less than 400 mJ / cm ^2.
C: 400mJ / cm ² or more, cured with irradiation of less than 600 mJ / cm ^2.
D: Curing with an irradiation amount of ^{600 mJ / cm 2 or more.}

(5) Measurement of 60 ° Gloss A laminate having a cured layer formed on a PET film was used as a measurement target. The 60 ° gloss (60 ° mirror gloss) was measured using a gloss meter "VG2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS Z 8741.

(6) Measurement of pencil hardness JIS K 5600-5-4 (General paint test method-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method)), pencil of hardened layer The hardness was measured. Evaluation was made according to the following criteria.
A: Pencil hardness is HB or higher.
B: Pencil hardness is B or less.

(7) Evaluation of Scratch Resistance A laminated body having a cured layer formed on a PET film was used as a measurement target. Under an atmosphere of 23 ° C and 55% RH, ^{a weight of 200 gf (per 4 cm 2 in} area) was placed on steel wool # 0000, and the surface of the hardened layer of the laminate was surfaced with a Gakushin Abrasion Tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) 15 The scratches were visually observed by rubbing back and forth. Evaluation was made according to the following criteria.
A: The number of scratches is 0.
B: The number of scratches is 1 or more and less than 50.
C: The number of scratches is 50 or more and less than 100.
D: The number of scratches is 100 or more.

(8) Measurement of water contact angle The water contact angle (liquid volume 2 μL) of the cured layer was measured using a contact angle meter (“Drop Master 500” manufactured by Kyowa Interface Science Co., Ltd.).

(9) Measurement of I / II and III / II values By TOF-SIMS (time-of-flight secondary ion mass spectrometry), the cured layer is etched under the following conditions, and the cured layer I / II and III / The value of II was measured.
(TOF-SIMS measurement conditions)
-Device: Time-of-flight secondary ion mass spectrometer (manufactured by ULVAC PHI Co., Ltd., "TRIFT V") equipped with a gas cluster ion beam (GCIB),
· Primary ion: _Au ^{3 +} (trimer of gold ions),
・ Acceleration voltage: 30kV,
-Measurement range: 100 μm square.
(Etching conditions)
・ Gas used: Ar,
・ Acceleration voltage: 15kV (5nA),
・ Irradiation range: 500 μm square,
-Irradiation time: 30 seconds.

The detection intensity (I) of the secondary ion peak species derived from the copolymer (A) observed on the etching surface when the etching depth is 50 nm and the etching depth when the etching depth is 1 μm. The detection intensity (II) of the secondary ion peak species derived from the copolymer (A) observed on the etched surface was measured, and the detection intensity (I) was divided by the detection intensity (II) (detection intensity ratio). : I / II) was obtained and used as the value of I / II. When the detection intensity ratio exceeds 1.0 in the secondary ion peak species, it is determined that the copolymer (A) is unevenly distributed on the surface layer of the cured layer.
Similarly, the detection intensity (III) of the secondary ion peak species derived from the copolymer (A) observed on the outermost layer (the surface not etched) before etching the cured layer is measured in advance, and the detection intensity is measured. The value (detection intensity ratio: III / II) obtained by dividing (III) by the detection intensity (II) was determined.

A copolymer was produced with the compositions shown in Table 1. The monomers in the table are as follows.
<Monomer (x)>
x-1: 4-methacryloyloxybenzophenone.
x-2: 2- [4- (2-Hydroxy-2-methyl-1-oxopropyl) phenoxy] ethyl methacrylate obtained in Synthesis Example 1 below.
<Monomer (r)>
r-1: Stearyl methacrylate.
r-2: 2-ethylhexyl methacrylate.
<Monomer (h)>
h-1: 2-Hydroxyethyl methacrylate.
h-2: N, N-diethylaminoethyl methacrylate.
<Monomer (o)>
o-1: Methyl methacrylate.

(Synthesis Example 1: Synthesis of Monomer (x-2))
Methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was distilled under reduced pressure, and a fraction having a purity of 99.8% or more was recovered to obtain a distilled methacrylic anhydride. The vacuum distillation was carried out by a method of gradually raising the temperature from room temperature to 90 ° C. at a pressure of 30 pa.
Separately, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methylpropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.4 g (0.1 mol), and triethylamine (Tokyo Chemical Industry Co., Ltd.) 30.4 g (0.3 mol) manufactured by Methylene Chloride Tokyo Chemical Industry Co., Ltd.) was dissolved in 500 mL. 23.1 g (0.15 mol) of the distillate of the methacrylic anhydride was added dropwise thereto at room temperature, and the mixture was stirred for 12 hours.
The obtained reaction solution was washed 3 times with 500 mL of ion-exchanged water, the organic phase was concentrated, and the solvent was distilled off. The residue was purified by column chromatography (ethyl acetate / hexane = 10/90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%).
^{1 1} H-NMR analysis confirmed that the obtained compound was 2- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy] ethyl methacrylate.
^{1 1} H NMR (300 MHz, chloroform-d): δ8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0) .6Hz, 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1Hz, 2H), 4.29 (dd, J = 5.5, 4.1Hz, 3H), 1 .94 (dd, J = 1.6, 1.0 Hz, 3H), 1.61 (s, 6H).

(Production Example 1: Production of copolymer (A-1))
73 parts by mass of methyl isobutyl ketone (hereinafter referred to as MIBK) is placed in a flask equipped with a stirrer, a cooling tube and a thermometer, and then the inside of the flask is replaced with nitrogen to raise the temperature to 65 ° C. and the monomer (x). -1) 25 parts by mass of monomer (x-2), 10 parts by mass of monomer (r-1), 30 parts by mass of monomer (r-2), 10 parts by mass of monomer (h-2), polymerization initiator A mixed solution of 0.8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 78 parts by mass of MIBK was added dropwise over 2 hours. After another 2 hours, in order to increase the polymerization rate, a mixed solution of 0.5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 0.6 parts by mass of MIBK was added and held for 5 hours. Then, the reaction solution was cooled to 40 ° C. to obtain a MIBK solution (A-1) of the copolymer. Hereinafter, the solid content in the solution (A-1) is referred to as a copolymer (A-1).
The solid content (nonvolatile content) of the solution (A-1) is 40% by mass, the weight average molecular weight (Mw) of the copolymer (A-1) is 19,800, and the content of the first active group is 1. It was .77 mmol / g and the amount of hydrogen donating functional group was 1.38 mmol / g. Table 1 shows these results and the composition of the mixed solution.

(Production Example 2: Production of copolymer (A-2))
In Production Example 1, the composition of the mixed solution is 50 parts by mass of monomer (x-2), 20 parts by mass of monomer (r-1), 30 parts by mass of monomer (o-1), and 3 parts by mass of n-dodecyl mercaptan as a chain transfer agent. A solution of the copolymer MIBK under the same conditions as in Production Example 1 except that the part, 1 part by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as the polymerization initiator, and 78 parts by mass of MIBK were changed. (A-2) was obtained. Hereinafter, the solid content in the solution (A-2) is referred to as a copolymer (A-2).
The solid content (nonvolatile content) of the solution (A-2) is 40% by mass, the weight average molecular weight (Mw) of the copolymer (A-2) is 10070, and the content of the first active group is 1. It was .69 mmol / g and the amount of hydrogen donating functional group was 0.00 mmol / g. Table 1 shows these results and the composition of the mixed solution.

(Production Example 3: Production of Copolymer (A-3))
In Production Example 1, the composition of the mixed solution is 40 parts by mass of the monomer (x-1), 10 parts by mass of the monomer (r-1), 15 parts by mass of the monomer (r-2), and 17.5 parts by mass of the monomer (h-1). Production example except that the parts were changed to 17.5 parts by mass of the monomer (h-2), 0.8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as the polymerization initiator, and 78 parts by mass of MIBK. The copolymer MIBK was obtained as a solution (A-3) under the same conditions as in 1. Hereinafter, the solid content in the solution (A-3) is referred to as a copolymer (A-3).
The solid content (nonvolatile content) of the solution (A-3) was 40% by mass. The weight average molecular weight (Mw) of the copolymer (A-3) is 5730, the content of the first active group is 1.48 mmol / g, and the amount of hydrogen donating functional group is 2.26 mmol / g. Met. Table 1 shows these results and the composition of the mixed solution.

(Examples 1 to 3 and Comparative Examples 1 to 2: Production of coating liquid (curable polymer composition))
Each material shown in Table 2 was mixed so as to have the ratio (parts by mass) shown in Table 2 in terms of non-volatile content. Then, a mixed solvent (PGM: MEK (mass ratio) of 7: 3) of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) was added so that the solid content concentration was 40% by mass, and the mixture was uniform. A coating liquid (curable polymer composition) was obtained by stirring until The materials in the table are as follows.
A-1: MIBK solution of the copolymer (A-1) obtained in Production Example 1.
A-2: MIBK solution of the copolymer (A-2) obtained in Production Example 2.
A-3: MIBK solution of the copolymer (A-3) obtained in Production Example 3.
B-1: Caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., "Kayarad DPCA-20").
C-1: 1- [4- (2-Hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanone (manufactured by IGM Resins, "Omnirad 2959").

The obtained coating liquid was applied to a PET film having a thickness of 50 μm (manufactured by Mitsubishi Chemical Corporation, “T602E50”) with a bar coater No. 8, and dried with a hot air dryer heated to 70 ° C. for 60 seconds to remove the solvent. After volatilization, a cured layer (cured product) having a thickness of 3 μm was formed by irradiating ultraviolet rays with an ^{integrated light amount of 250 mJ / cm 2} and an illuminance of 100 mW / cm ^{2 in} an air atmosphere with a high-pressure mercury lamp. As a result, a laminated body in which a layer made of a cured product was laminated on a base material layer made of PET film was obtained.
For the irradiation of ultraviolet rays, a UV conveyor of an eye graphics high-power UV device (model: US5-X1802-X1202) was used. The integrated light amount is a value when the integrated light amount having a wavelength of 300 to 390 nm is measured with an illuminometer manufactured by Iwasaki Electric Co., Ltd. (eye ultraviolet integrated illuminance meter "UVPF-A1", "PD-365").
The items shown in Table 2 were measured or evaluated for the obtained laminate by the above method. The results are shown in Table 2.

In addition, the values of I / II and III / II of the cured layer of the laminate obtained in Example 2 were measured by the above method.
When the etching depth when the cured layer of the laminate obtained in Example 2 was irradiated with GCIB for 1800 seconds was measured with a laser microscope, the film thickness was reduced to a depth of 3.1 μm. In this case, the etching depth is 50 nm by the GCIB irradiation for 30 seconds, and the etching depth is 1 μm by the GCIB irradiation for 600 seconds. Therefore, the detection intensity (I) of the secondary ion peak species derived from the copolymer (A) observed on the etching surface when the irradiation time of GCIB is 30 seconds, and the intensity (I) observed on the etching surface when the irradiation time is 600 seconds. The detection intensities (II) of the secondary ion peak species derived from the copolymer (A) were measured, and the detection intensity ratio (I / II) was determined. The results are shown in Table 3.
Similarly, the secondary ion peak derived from the copolymer (A) observed on the outermost layer (non-etched surface) of the cured layer before the cured layer is irradiated with GCIB, that is, when the irradiation time of GCIB is 0 seconds. The detection intensity (III) of the species was measured in advance, and the detection intensity ratio (III / II) was determined. The results are shown in Table 3.

As shown in the results of Table 2, the curable polymer compositions obtained in Examples 1 to 3 containing the copolymer (A), the polyfunctional compound (B) and the non-polymer (C) were cured. It was excellent in sex. Further, the cured product of these curable polymer compositions was excellent in transparency, smoothness, leveling property, hardness, and scratch resistance.
As shown in the results of Table 3, the cured layers of the laminate obtained in Example 2 all had a detection intensity ratio (I / II) of more than 1.0, and the surface layer of the cured layer was a copolymer ( A) was unevenly distributed.

On the other hand, the curable polymer compositions obtained in Comparative Examples 1 and 2 containing no copolymer (A) were inferior in curability. Moreover, the cured product of these curable polymer compositions was inferior in leveling property. In particular, the cured product of the curable polymer composition obtained in Comparative Example 2 was also inferior in scratch resistance.

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

Claims (11)

A unit based on a monomer (x) having a first active group that generates a radical by irradiation with an active energy ray, and one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom. A copolymer (A) having a unit based on the monomer (y) having, a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule, and a second radical generated by irradiation with active energy rays. A curable polymer composition containing a non-polymer (C) having an active radical of. The curable polymer composition according to claim 1, wherein the content of the copolymer (A) is 0.1 to 50% by mass with respect to the non-volatile content of the curable polymer composition. The curable polymer composition according to claim 1 or 2, wherein the content of the first active group per 1 g of the copolymer (A) is 0.1 to 3.5 mmol / g. The first active group and the second active group independently form a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, and an α-diketone dialkylacetal. The curable polymer composition according to any one of claims 1 to 3, which is one or more selected from the group consisting of a group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. The curability according to any one of claims 1 to 4, wherein the content of the non-polymer (C) is 0.1 to 15% by mass with respect to the non-volatile content of the curable polymer composition. Polymer composition. The curable polymer composition according to any one of claims 1 to 5, wherein the mass ratio represented by the copolymer (A) / the non-polymer (C) is 0.1 to 10. The invention according to any one of claims 1 to 6, wherein the monomer (x) has one or more functional groups selected from the group consisting of a (meth) acryloyl group, a (meth) acrylamide group, and a vinyl group. Curable polymer composition. A cured product of the curable polymer composition according to any one of claims 1 to 7. The cured product according to claim 8, wherein the copolymer (A) is unevenly distributed on the surface layer of the cured product. The cured product according to claim 8 or 9, wherein the haze is less than 10% and the 60 ° gloss is 130 or more. A laminate having a base material layer and a layer made of the cured product according to any one of claims 8 to 10.

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