JP2023145550A - Copolymer, curable polymer composition, cured product, and laminate - Google Patents

Abstract

To provide a curable polymer composition having excellent curability.SOLUTION: A copolymer comprises: a monomer (i) unit represented by formula (I) [R1 represents a hydrogen atom, a methyl group, or an ethyl group; R2 represents a C1-2 alkylene group or a C3-5 alkylene group; R3 and R4 each independently represent a C1-2 alkyl group or a C3-5 alkyl group; and R3 and R4 may be bonded to each other to form a ring]; and a monomer (y) unit having a radically polymerizable group and one or more selected from a C4-30 alkyl group, a fluorine atom, and a silicon atom and not having an active group which generates a radical upon irradiation with an active energy ray. In the copolymer, the content of an active group which generates a radical upon irradiation with an active energy ray is 0.5-2.5 mmol/g, and the content of the monomer (y) unit is 1-80 mass%.SELECTED DRAWING: None

Description

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

A hard coat layer is sometimes provided on the surface of an article such as a thermoplastic resin film typified by a polyethylene terephthalate (PET) film for the purpose of imparting functions such as hardness and matteness.
As a hard coat layer, a layer obtained by curing a curable composition containing a compound having a radically polymerizable group and a photopolymerization initiator by radical polymerization is generally known.
However, in this method, a polymerization termination reaction due to oxygen occurs at the contact interface between the coating film of the curable composition and oxygen, that is, at the coating film surface, resulting in a decrease in curability and a reduction in the cured product of the curable composition. Mechanical properties may become 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 following is described.

JP2003-292828A

The curable composition described in Patent Document 1 uses an oligomer-type ultraviolet polymerization initiator to form a cured product such as a hard coat layer with excellent mechanical properties, but does not necessarily satisfy the curability.
The present invention provides a polymer capable of improving curability, a curable polymer composition containing the polymer, a cured product of the curable polymer composition, and a laminate having a layer consisting of the cured product. The purpose is to provide.

The present invention has the following aspects.
[1] A unit based on the group (Ia) represented by the following formula (Ia) and a monomer (i) having a radically polymerizable group, and a group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom A copolymer having a unit based on a monomer (y) (excluding the monomer (i)) having one or more selected types.

[In the formula, R ² represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R ³ and R ⁴ each independently represent a linear or branched alkylene group having 1 to 5 carbon atoms. It represents an alkyl group, and R ³ and R ⁴ may be combined with each other to form a ring. ]
[2] The copolymer of [1], wherein the monomer (i) is a compound represented by the following formula (I).

[In the formula, R ¹ represents a hydrogen atom, a methyl group, or an ethyl group. R ² , R ³ and R ⁴ are the same as in formula (Ia) above. ]
[3] The copolymer of [1] or [2], wherein the content of the group (Ia) per 1 g of the copolymer is 0.1 to 3.5 mmol/g.
[4], further comprising a unit based on a monomer (x) (excluding the monomer (i) above) having an active group that generates radicals upon irradiation with active energy rays, any one of [1] to [3] Copolymer.
[5] The copolymer of [4], wherein the monomer (x) has one or more types selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group.
[6] The active group of the monomer (x) is a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (excluding the group (Ia)), an α-aminoketone group, an α-diketone group, an α-diketone group. The copolymer of [4] or [5], which is one or more selected from the group consisting of dialkyl acetal groups, anthraquinone groups, thioxanthone groups, and phosphine oxide groups.
[7] The total content of the group (Ia) and the active group of the monomer (x) per 1 g of the copolymer is 0.1 to 3.5 mmol/g, [4] to [6] ] any copolymer.
[8] A curable polymer composition comprising the copolymer (A) of any one of [1] to [7] and a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule.
[9] A cured product of the curable polymer composition of [8].
[10] A laminate comprising a base material layer and a layer made of the cured product of [9].

According to the present invention, a laminate including a polymer capable of improving curability, a curable polymer composition containing the polymer, a cured product of the curable polymer composition, and a layer consisting of the cured product I can donate my body.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate of the present 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.

Embodiments of the present invention will be described in detail below.
In the present invention, "(meth)acrylate" is a general term for acrylate or methacrylate. "(Meth)acrylic" is a general term for acrylic and methacrylic.
"~" indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.

<Curable polymer composition>
The curable polymer composition includes a copolymer (A) having an active group (hereinafter also simply referred to as an active group) that generates radicals when irradiated with active energy rays, and a copolymer (A) having two or more radically polymerizable groups per molecule. Contains a polyfunctional compound (B) having a group.
When the curable polymer composition is irradiated with active energy rays, radicals are generated from the active groups of the copolymer (A), and the radically polymerizable groups of the polyfunctional compound (B) react with each other using the generated radicals as a starting point. progresses, and the entire curable polymer composition is cured.
The curable polymer composition can further contain an organic solvent, if necessary.
The curable polymer composition can further contain other components than those mentioned above, if necessary.

<Copolymer (A)>
The copolymer (A) has a unit based on monomer (i), a unit based on monomer (y), and may further have a unit based on monomer (x).
[Monomer (i)]
Monomer (i) has a group (Ia) represented by the following formula (Ia) and a radically polymerizable group. It is a compound with Group (Ia) is an intramolecularly cleavable active group.
Monomer (i) is easily cleaved to generate radicals when irradiated with active energy rays, so it has high initiation efficiency and contributes to improving curability. Specifically, curing can be started quickly and the amount of light irradiation required to obtain a cured product with a desired hardness can be reduced. Further, if the amount of light irradiation is the same, the hardness of the cured product can be further increased and the scratch resistance can be further improved.

In formula (Ia), R ² is a linear or branched alkylene group having 1 to 5 carbon atoms. R ² is an ethylene group, a propane-1,3-diyl group, a butane-1,3- Diyl group and butane-1,4-diyl group are preferred, and ethylene group is more preferred.
R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be combined with each other to form a ring. The number of carbon atoms in the ring formed by R ³ and R ⁴ is preferably 5 to 8, more preferably 6.
The cyclic group formed by R ³ , R ⁴ or R ³ and R ⁴ is preferably a methyl group, an ethyl group, or a cyclohexyl group in terms of reactivity with compound (B) and ease of availability, and a methyl group is more preferable. Preferably, R ³ and R ⁴ are both methyl groups.

Examples of the radically polymerizable group of monomer (i) include functional groups containing radically polymerizable unsaturated bonds (carbon-carbon double bonds, etc.), and specific examples include (meth)acryloyl group and (meth)acrylamide group. , vinyl group, etc.
As the monomer (i), compounds represented by the following formula (I) are used in terms of ease of synthesis of monomer (i), ease of synthesis of copolymer (A), and curability of the cured product. is preferred. In formula (I), R ¹ represents a hydrogen atom, a methyl group or an ethyl group. Among these, a hydrogen atom or a methyl group is preferred, and a methyl group is particularly preferred. R ² , R ³ and R ⁴ are the same as in formula (Ia) above.

[Monomer (x)]
Monomer (x) is a compound (excluding monomer (i)) having an active group and a radically polymerizable group.
As used herein, the active group refers to an atomic group containing a structure that generates radicals upon irradiation with active energy rays (a structure that has photopolymerization initiating properties). As the structure having photopolymerization initiating properties, various known structures can be employed, such as hydrogen abstraction type, electron transfer type, and intramolecular cleavage type.
Specific examples of the active group include benzophenone group, acetophenone group, benzoin group, α-hydroxyketone group (excluding the group (Ia) above), α-aminoketone group, α-diketone group, α-diketone dialkyl acetal group, anthraquinone group. group, thioxanthone group, and phosphine oxide group.
Among these, a benzophenone group, an acetophenone group, or an α-hydroxyketone group is preferable because they are less susceptible to oxygen inhibition during curing and provide good surface curing properties when forming a cured layer.

Examples of the radically polymerizable group of the monomer (x) include functional groups containing radically polymerizable unsaturated bonds (carbon-carbon double bonds, etc.), and specific examples include (meth)acryloyl group and (meth)acrylamide group. , vinyl group, etc.
As the monomer (x), a (meth)acrylic ester having an active group is preferable from the viewpoint of ease of synthesis of the copolymer (A) and ease of adjusting the amount of introduced active group. For example, 4-methacryloyloxybenzophenone is preferred.

[Monomer (y)]
Monomer (y) is a compound (excluding monomer (i)) having 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, and a radically polymerizable group.
Monomer (y) is a monomer with low surface energy, and if copolymer (A) has a unit based on monomer (y), when a coating film of the curable polymer composition is formed, , the copolymer (A) tends to segregate on the surface side of the coating film. If the copolymer (A) having an active group is segregated on the surface side of the coating film, it is possible to suppress the polymerization termination reaction caused by oxygen on the coating film surface, and the curability is increased. Therefore, for example, curing can be performed with a low exposure amount. Furthermore, even thin films that tend to be susceptible to oxygen inhibition can be cured well.
Moreover, when the copolymer (A) segregates on the surface side of the coating film, the concentration of active groups on the coating film surface side increases. As a result, the curing speed when irradiated with active energy rays tends to be uneven between the surface side and the inside of the coating film.
For example, when the surface side of a coating film is cured first to form a cured film, and then the inside of the coating film is cured, the surface cured film buckles, resulting in wrinkle-like unevenness. As a result, a hardened layer (uneven layer) having an uneven surface is obtained. The curing time until the inside of the coating film is completely cured can be adjusted by the amount of radically polymerizable groups in the curable polymer composition, the type and amount of active groups, the irradiation amount of active energy rays, etc.
On the other hand, even if the copolymer (A) segregates on the surface side of the coating film, unevenness may not easily occur on the surface of the cured layer. For example, if the difference in curing speed between the surface side and the inside of the coating film is small and the cured film is not formed, or if the cured film has physical properties that make it difficult to buckle, the surface of the cured layer tends to be smooth. .

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

Examples of the monomer (r) include compounds having an alkyl group having 4 or more carbon atoms and a radically polymerizable group, and are easy to synthesize the compound and easy to adjust the amount of the alkyl group having 4 or more carbon atoms introduced. From this viewpoint, (meth)acrylic acid alkyl esters having an alkyl group having 4 or more carbon atoms are preferred.
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. ) 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, ) acrylate, adamantyl (meth)acrylate, etc.
Among these, it is preferable to include 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 in the alkyl group is within the above-mentioned preferred range, and considering ease of production, etc. - Ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are more preferred, and stearyl (meth)acrylate is particularly preferred.
These (meth)acrylic esters may be used alone or in combination of two or more.

Examples of the monomer (f) include compounds 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 explanation 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 improves the stain resistance of the cured product. If the copolymer (A) has units based on the monomer (f), when a coating film of the curable polymer composition is formed, the copolymer (A) will segregate on the surface side of the coating film. do. As a result, the curability increases and the concentration of units based on the monomer (f) on the surface side of the coating film increases, making it possible to efficiently impart antifouling properties to the surface of the cured product.

The monomer (f) preferably contains one or more 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 one or more selected from the group consisting of (meth)acrylic esters having a fluoroalkyl group and (meth)acrylic esters having a polydimethylsiloxane chain.

As the (meth)acrylic ester having a fluoroalkyl group, a (meth)acrylic ester having a perfluoroalkyl group is more preferable. The number of carbon atoms in the perfluoroalkyl group is preferably 4 or more.
Specific examples of (meth)acrylic esters having a polydimethylsiloxane chain include polydimethylsiloxanes having a molecular weight of 500 to 50,000 and substituted with a (meth)acryloyl group at one end. The molecular weight is preferably 1,000 to 30,000, more preferably 1,500 to 20,000.

[Monomer (h)]
The copolymer (A) may further contain 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-abstracting active group, curing is accelerated if the copolymer (A) contains units based on the monomer (h).
The hydrogen-donating functional group is preferably one or more selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, and an amide group. Among these, a hydroxyl group, an amino group, or an amide group are preferable from the viewpoint of promoting 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 explanation of the monomer (x).
From the viewpoint of ease of synthesis of the compound and ease of adjusting the amount of hydrogen-donating functional group introduced, (meth)acrylic acid ester having a hydrogen-donating functional group is preferable as the monomer (h).
Examples of the monomer (h) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl ( Hydroxyl group-containing monomers such as meth)acrylate, 10-hydroxydecyl(meth)acrylate, 12-hydroxylauryl(meth)acrylate, monobutylhydrokyl fumarate, 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, amino groups such as vinyl acetamide, or Examples include amide group-containing monomers. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and N,N-dimethyl have excellent curing accelerating effects when used in combination with active groups. Acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate are preferred, and 2-hydroxyethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate are more preferred. These compounds may be used alone or in combination of two or more.

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

It is preferable that the copolymer (A) has a plurality of active groups in the molecule.
The content of active groups per 1 g of the copolymer (A) is preferably 0.1 to 3.5 mmol/g, more preferably 0.5 to 2.5 mmol/g, even more preferably 0.8 to 2 It is in the range of .0 mmol/g. When the content of active groups is at least the lower limit of the above range, curability is better. In addition, the scratch resistance of the coating film is increased. When it is below the upper limit of the above range, the storage stability of the curable composition is excellent.
When the copolymer (A) has units based on monomer (i) and does not have units based on monomer (x), the content of active groups per 1 g of the copolymer (A) is: It is the content of group (Ia) per 1 g of copolymer (A).
When the copolymer (A) has a unit based on monomer (i) and a unit based on monomer (x), the content of active groups per 1 g of the copolymer (A) is ) is the total content of group (Ia) and active groups of monomer (x) per 1 g.

Monomer (i) contributes to improving the curability of the curable polymer composition. When the cured layer contains units based on monomer (x) in addition to units based on monomer (i), wrinkle-like irregularities are likely to be formed on the surface of the cured layer. By forming irregularities in the hardened layer, functions such as matte properties can be easily obtained.
The content of group (Ia) is preferably 10 mol% or more, more preferably 30 mol% or more, based on the total of group (Ia) and the active group of monomer (x). It may be 100 mol%. When it is at least the above lower limit, the effect of improving curability is excellent.
When the copolymer (A) has a unit based on monomer (i) and a unit based on monomer (x), the group (Ia) The content of is preferably 90 mol% or less, more preferably 70 mol% or less. If it is below the above upper limit, unevenness is likely to be formed on the surface of the cured layer.

The content of hydrogen-donating functional groups per 1 g of the copolymer (A) is preferably 0.1 to 3.5 mmol/g, more preferably 0.8 to 3.2 mmol/g, even 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, curability is better. When the content of the hydrogen-donating functional group is at most the upper limit of the above range, the copolymer (A) and the polyfunctional compound (B) will have excellent compatibility.

The ratio of units based on monomer (i) to the total mass of all units constituting the copolymer (A) is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass. % by weight, particularly preferably in the range from 30 to 60% by weight. When the proportion of units based on monomer (i) is at least the lower limit of the above range, curability is better. When the proportion of units based on monomer (i) is below the upper limit of the above range, the storage stability of the curable composition is excellent.
When the copolymer (A) has a unit based on monomer (i) and a unit based on monomer (x), the unit based on monomer (i) relative to the total mass of all units constituting the copolymer (A) The total proportion of units based on and monomer (x) is preferably in the range of 1 to 90% by weight, more preferably 10 to 80% by weight, even more preferably 20 to 70% by weight, particularly preferably 30 to 60% by weight. It is. When the total ratio is equal to or higher than the lower limit of the above range, the curability is more excellent. When the total ratio is below 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 units constituting the copolymer (A) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and even more preferably 8 to 50% by mass. It is in the range of % by mass. When the proportion of the units based on the monomer (y) is at least the lower limit of the above range, the curability is more excellent. When the proportion of units based on the monomer (y) is at most the upper limit of the above range, the copolymer (A) and the polyfunctional compound (B) will have excellent compatibility.

The proportion of units based on the monomer (r) to the total mass of all units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 70% by mass, and even more preferably 5 to 60% by mass. %, particularly preferably in the range from 8 to 50% by weight. When the proportion of the units based on the monomer (r) is at least the lower limit of the above range, the curability is more excellent. When the proportion of units based on the monomer (r) is below the upper limit of the above range, the copolymer (A) and the polyfunctional compound (B) will have excellent compatibility.

The ratio of units based on monomer (f) to the total mass of all units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 70% by mass, and even more preferably 5 to 60% by mass. % range. When the proportion of the units based on the monomer (f) is at least the lower limit of the above range, the curability and antifouling properties will be better. When the proportion of units based on the monomer (f) is below the upper limit of the above range, the copolymer (A) and the polyfunctional compound (B) will have better compatibility.

The proportion of units based on the monomer (h) to the total mass of all units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 60% by mass, and even more preferably 3 to 50% by mass. %, particularly preferably in the range from 5 to 40% by weight. If the proportion of units based on the monomer (h) is within the above range, the curability will be 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, even 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 below the upper limit of the above range, the curable polymer composition has excellent coating properties.
The Mw of the copolymer (A) is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene. 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 still more preferably 25 to 100°C. When Tg is at least the lower limit of the above range, curability is better. When it is below the upper limit, the copolymer (A) and the polyfunctional compound (B) will have excellent compatibility.
The Tg of the copolymer (A) is determined by the Fox formula.

Copolymer (A) can be obtained, for example, by polymerizing monomer components including monomer (i) and monomer (y). The monomer component may further contain any one or more of monomer (x), monomer (h), and monomer (o) as necessary.
Polymerization is typically carried out in the presence of a polymerization initiator. During 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 which solution polymerization is preferred 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. Polyfunctional (meth)acrylates are preferred. The polyfunctional compound (B) may be used alone or in combination of two or more.

Examples of difunctional polyfunctional (meth)acrylates include, but are not limited to, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. (meth)acrylate, 1,9-nonanediol di(meth)acrylate, alkanediol di(meth)acrylate such as tricyclodecane dimethyloldi(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol F Examples 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.

Trifunctional or higher polyfunctional (meth)acrylates are not particularly limited, but include, for example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritol hexa(meth)acrylate. Isocyanuric acid modified tri(meth)acrylates such as erythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ε-caprolactone modified tris(acryloxyethyl)isocyanurate, Examples include urethane acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, dipentaerythritol hexa(meth)acrylate is preferred.

<Organic solvent>
The organic solvent is used as necessary for the purpose of improving workability when applying the curable polymer composition onto a substrate.
Organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether. , diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol, etc.; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone, etc. Amide solvents; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen solvents such as dichloromethane and chloroform; and the like. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferred since they tend to improve workability during coating.

<Photopolymerization initiator (C)>
The curable polymer composition may further contain one or more photopolymerization initiators (excluding copolymer (A)).
For example, there may be mentioned a photopolymerization initiator (C) which is a non-polymer having an active group that generates radicals when irradiated with active energy rays. The molecular weight of the photopolymerization initiator (C) is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4- Methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyl Dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, Phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2- Examples include morpholino-1-propanone, tribromophenyl sulfone, tribromomethyl phenyl sulfone, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

<Acrylic resin (P)>
The curable polymer composition further contains an acrylic resin (P ) may also contain one or more of the following.
The acrylic resin (P) is a polymer of polymerizable monomers including (meth)acrylic monomers.
Examples of the acrylic resin (P) include homopolymers or copolymers of (meth)acrylic monomers, copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers, etc. Can be mentioned.
In particular, the content of units based on (meth)acrylic monomers is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass with respect to the total mass of all units constituting the acrylic resin (P). The above copolymers or homopolymers of (meth)acrylic monomers are preferred. These can be obtained from commercial products (for example, DIANAL series manufactured by Mitsubishi Chemical Corporation).

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

The curable polymer composition may further contain particles having an average primary particle diameter of 0.01 μm or more and 10 μm or less in order to further improve the matting properties of the uneven layer.
The particles may be organic particles or inorganic particles, and two or more types may be used in combination. The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group.
The surface-modified particles can be obtained by, for example, reacting a silane coupling agent and inorganic particles at 25° C. to 120° C. for about 1 hour to 24 hours in the presence of an acid, a base, or a silane coupling reaction catalyst such as aluminum acetylacetonate. Obtained by method.

A monofunctional (meth)acrylate or (meth)acrylic acid having one radically polymerizable group per molecule is added to the curable polymer composition in order to adjust the viscosity and the curing speed by active energy rays. be able to.
The monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acrylate, and octyl (meth)acrylate. Acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cresol (meth)acrylate, di Cyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate ) 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)acrylate ) acrylate, etc.

<Content>
The curable polymer composition may contain polymerization accelerators such as thiol group-containing compounds, antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers, etc., to the extent that the effects of the present invention are not impaired. May contain

The content of copolymer (A) relative to the nonvolatile content of the curable polymer composition is preferably 0.5 to 50% by mass, more preferably 1 to 20% by mass, and even more preferably 1.5 to 5% by mass. is within the range of If it is at least the lower limit of the above range, the curability will be better. When it is below the upper limit, coating properties are excellent.
The nonvolatile content of the curable polymer composition is the total mass of components other than the organic solvent. The non-volatile content of a curable polymer composition can be measured by a conventionally known method. It is measured by the change in height.

The content of active groups derived from the copolymer (A) per 100 g of nonvolatile content of the curable polymer composition is preferably 0.1 to 20 mmol/100 g, more preferably 0.5 to 15 mmol/100 g, and The amount is preferably in the range of 1.0 to 12 mmol/100g, particularly preferably 1.5 to 10 mmol/100g. When the content of active groups is at least the lower limit of the above range, curability is better. When it is below the upper limit, the storage stability of the curable composition is excellent.

The ratio of the polyfunctional compound (B) to the nonvolatile content of the curable polymer composition is preferably 50 to 99.5% by mass, more preferably 70 to 99% by mass, and even more preferably 80 to 98.5% by mass. range. Within the above range, the curability is better.

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

When the curable polymer composition contains a photoinitiator (C), the ratio of the photoinitiator (C) to the nonvolatile content of the curable polymer composition is preferably 0.1 to 15% by mass, More preferably 0.5 to 10% by weight, still more preferably 1 to 6% by weight. Within the above range, curability is better.

<Cured product>
The cured product of the curable polymer composition is obtained by applying the curable polymer composition onto the surface of a substrate or article to form a coating film, drying as necessary, and then applying active energy rays to the coating film. It can be formed by irradiation.
The method of applying the curable polymer composition is not particularly limited. For example, the coating can be performed by a known method such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, or spray coating.

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

Examples of active energy rays include ultraviolet rays, α rays, β rays, γ rays, and the like. Among these, ultraviolet rays are preferred.
The irradiation amount of the active energy ray can be appropriately selected depending on the active energy ray to be irradiated.
When using ultraviolet rays, it is preferable to irradiate so that the cumulative amount of light is 100 mJ/cm ² or more and 3000 mJ/cm ² or less, more preferably 200 mJ/cm ² or more and 2000 mJ/cm ^{2 or} less. Further, the illumination intensity is preferably 50 mW/cm ² or more and 600 mW/cm ² or less, more preferably 75 mW/cm ² or more and 450 mW/cm ² or less, and even more preferably 100 mW/cm ² or more and 300 mW/cm ^{2 or} less. As a light source, use a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam using a scanning or curtain-type electron beam acceleration path, or a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a low-pressure mercury lamp. I can do it.

The thickness of the cured layer is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm, even more preferably 0.3 to 5 μm. If the thickness of the cured product is within the above range, desired matte properties can be easily achieved.
The thickness of the hardened layer is determined by cross-sectional observation using an electron microscope.
When the hardened layer is an uneven layer having unevenness on the surface, the thickness of the hardened layer indicates the maximum thickness of the uneven layer.

The haze of the cured layer measured by the method described in the Examples below can be adjusted depending on the surface shape. When wrinkle-like unevenness is formed on the surface, the haze increases. If the surface is made smooth, the haze will be lower.
When the active groups derived from the copolymer (A) in the curable polymer composition contain both the group (Ia) and the active group of the monomer (x), the haze of the cured layer is preferably 0.2%. The content is more preferably 0.5% or more, further preferably 1.0% or more, particularly preferably 1.2% or more, and the upper limit is, for example, 99%. If the haze is equal to or higher than the above lower limit, properties such as matte properties and anti-blocking properties due to unevenness can be easily obtained.
When the active group derived from the copolymer (A) in the curable polymer composition is the group (Ia) only, the haze of the cured layer is preferably less than 10%, more preferably 0.1 to 5%. , more preferably in the range of 0.2 to 0.8%. When it is below the above upper limit, transparency will be better, and visibility will be better when used for various purposes.

<Laminated body>
The laminate of the present invention (hereinafter also referred to as "this laminate") has a base material layer and a layer made of a cured product of a curable polymer composition (hereinafter also referred to as "cured layer"). . The present laminate further includes a primer layer provided between the base layer and the cured layer, a surface functional layer provided on the surface of the cured layer opposite to the base layer, and the It is preferable to have one or more layers selected from the group consisting of a back functional layer provided on the surface of the base 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.

The surface of the cured layer of this laminate (the surface opposite to the base material side) may be smooth or may have irregularities.
1 to 5 are schematic cross-sectional views showing an example of the present laminate in which the cured layer is an uneven layer having an uneven surface. The dimensional ratios in FIGS. 1 to 5 are for convenience of explanation and are different from the actual ones.
The laminate 10 in the example of FIG. It has a primer layer 3.
The laminate 10 in the example of FIG. 2 includes a base material layer 1, a cured layer 2 provided on one surface 1a of the base material layer 1, and a surface of the cured layer 2 on the opposite side from the base material layer 1 side. It has a surface functional layer 4 provided thereon.
The laminate 10 in the example of FIG. It has a primer layer 3 and a surface functional layer 4 provided on the surface of the cured layer 2 opposite to the base material layer 1 side.
The laminate 10 in the example of FIG. It has a primer layer 3 and a back functional layer 5 provided on the surface 1b of the base material layer 1 on the opposite side to the cured layer 2 side.
The laminate 10 in the example of FIG. The primer layer 3, the surface functional layer 4 provided on the surface of the cured layer 2 opposite to the base layer 1 side, and the surface functional layer 4 provided on the surface 1b of the base material layer 1 opposite to the cured layer 2 side. It has a back functional layer 5.

<Base material layer>
As the base material layer, known materials can be used, such as resin base materials, metal base materials, and paper base materials. Among these, resin base materials are preferred from the viewpoint of processability.
The resin base material may have a single layer structure or a multilayer structure of two or more layers, and is not particularly limited. It is preferable that the resin base material has a multilayer structure of two or more layers, each layer having its own characteristics, and multifunctionality.

Various resin films (sheets) can be used as the resin base material, such as polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, Examples include polyvinyl alcohol film and nylon film.
When this laminate is used for display purposes, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for anti-glare applications, and polyester films are more preferred 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 preferred. Among these, a uniaxially stretched film stretched in a uniaxial direction or a biaxially stretched film stretched in a biaxial direction is preferred, and a biaxially stretched film is more preferred from the viewpoint of excellent balance of mechanical properties and flatness.

The polyester constituting the polyester film that can be used as the base layer may be a homopolyester or a copolyester.
As the homopolyester, one obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol is preferable. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalene dicarboxylic acid. Examples of aliphatic glycols include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Each of the aromatic dicarboxylic acids and aliphatic glycols may be used alone or in combination of two or more.
Examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol, and the like. The dicarboxylic acid component and the glycol component may be used alone or in combination of two or more.
Typical polyesters include polyethylene terephthalate and polyethylene naphthalate.

Among the polyester films mentioned above, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferable in consideration of mechanical strength and heat resistance, and are easy to manufacture and easy to handle for applications such as surface protection films. Considering this, 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 layer may be any poly(meth)acrylate having a unit based on (meth)acrylate, and various acrylic resins can be used. (Meth)acrylates include alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and more. Examples include alkyl (meth)acrylates having alkyl groups with a large number of carbon atoms.
Considering transparency, processability, and chemical resistance, poly(meth)acrylate preferably contains units based on alkyl(meth)acrylate having an alkyl group having 1 to 4 carbon atoms as a main component, and methyl( It is more preferable that the main component is at least one selected from the group consisting of units based on meth)acrylate and units based on ethyl (meth)acrylate, and it is particularly preferable that the main component is units based on methyl (meth)acrylate. preferable.
It is also possible to impart properties such as flexibility to the poly(meth)acrylate by incorporating units based on (meth)acrylates other than alkyl(meth)acrylates or units based on other monomers.
The proportion of units based on alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms relative to the total mass of 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 anti-blocking properties.
The type of particles can be appropriately selected depending on the purpose and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide, acrylic resin, styrene resin, urea resin, and phenol. Examples include organic particles such as resin, epoxy resin, and benzoguanamine resin. Furthermore, when the base material layer includes a polyester film, precipitated particles in which a part of a metal compound such as a catalyst is precipitated in the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are particularly preferred because they are effective even in small amounts.
The shape of the particles is not particularly limited, and may be spherical, lumpy, rod-like, flat, or the like. Further, there are no particular limitations on its hardness, specific gravity, color, etc.
Two or more types of these particles may be used in combination as necessary.

The average particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. If the average particle size is 10 μm or less, problems due to a decrease in transparency of the base layer are unlikely to occur.
The average particle diameter of the particles is a value of 50% of the integrated value (based on mass) in an equivalent spherical distribution measured by a centrifugal sedimentation type particle size distribution analyzer.

When the base material layer contains particles, the content of particles in the base material layer cannot be determined unconditionally because it also has to do with the average particle size of the particles, but the total content of the particles in the base material layer The amount is preferably 5% by mass or less, more preferably 0.0003 to 3% by mass, and even more preferably 0.0005 to 1% by mass. When the content of particles is 5% by mass or less, problems such as falling off of particles and reduction in transparency of the base layer are less likely to occur.

The base layer can contain additives other than the above-mentioned particles, if necessary. As additives, known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments can be used.

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

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

In one preferred embodiment, the primer layer is an adhesion-enhancing layer. If the adhesion between the base 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 laminate can be used for various purposes.
When the primer layer is an adhesion improving layer, the primer layer preferably contains one or both of a resin and a compound derived from a crosslinking agent from the viewpoint of improving the adhesion between the base 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 electrification and frictional electrification to the outermost surface of the laminate, particularly to the outermost surface on the side where the cured layer is present with respect to the base material layer.
In order to make the primer layer an antistatic layer, for example, an antistatic agent may be contained in the primer layer.

As the resin, conventionally known resins 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 these, polyester resins, acrylic resins, and urethane resins are preferred in consideration of adhesion performance and coating properties.
When the base layer is a resin film, the resin for the base layer is preferably the same type of resin as the resin for the resin film from the viewpoint of compatibility between the primer layer and the base layer. For example, when the base layer is a polyester film, the primer layer preferably contains a polyester resin. When the base layer is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

Examples of polyester resins include those whose main constituent components are polyhydric carboxylic acids and polyhydric hydroxy compounds.
Examples of polyhydric carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid. 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, Examples thereof include trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt, and ester-forming derivatives thereof.
Examples of polyhydric hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1 , 5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly Examples include tetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like.
One or more of these compounds may be selected as appropriate, and a polyester resin may be synthesized by a conventional polycondensation reaction.

Acrylic resin is a polymer of polymerizable monomers including (meth)acrylic monomers.
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 other polymers (eg, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Alternatively, it also includes a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or dispersion. Similarly, polymers (or mixtures of polymers in some cases) obtained by polymerizing polymerizable monomers in polyurethane solutions or dispersions are also included. Similarly, polymers obtained by polymerizing polymerizable monomers in solutions or dispersions of other polymers (in some cases, polymer mixtures) are also included.

The polymerizable monomer is not particularly limited, but typical examples include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid; salts; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate; methyl ( Alkyl (meth)acrylates such as meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; (meth)acrylamide; Nitrogen-containing monomers such as diacetone acrylamide, N-methylolacrylamide, (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; γ- Examples include silicon-containing monomers such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and polypylidene chloride; and conjugated dienes such as butadiene.

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

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

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

Examples of polyester polyols include those obtained by reacting a polyvalent carboxylic acid or its acid anhydride with a polyhydric alcohol, and those having a derivative unit of a lactone compound such as polycaprolactone.
Examples of polyhydric carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2 , 5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2 -hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyl dialkanolamine, lactone diol and the like.

As the polyol, in consideration of adhesion performance, polyester polyols and polycarbonate polyols are preferred, and polyester polyols are particularly preferred.

The polyisocyanates used to obtain the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and toridine diisocyanate; α, α, α', α'- Aliphatic diisocyanates with aromatic rings such as tetramethylxylylene diisocyanate; Aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane Examples include diisocyanates, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanate, and the like. These may be used alone or in combination of two or more.

The chain extender is not particularly limited as long as it has two or more active groups that react with isocyanate groups, and in general, chain extenders having two hydroxyl groups or amino groups can be mainly used. .
Examples of chain extenders having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. Examples include glycol compounds such as glycol.
Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine, and diphenylmethane diamine, ethylene diamine, propylene diamine, hexane diamine, and 2,2-dimethyl-1,3-propane diamine. , 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine Aliphatic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprobilitine cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3 Examples include alicyclic diamines such as -bisaminomethylcyclohexane.

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

Ionic groups introduced into the structure of the urethane resin include various groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, and quaternary ammonium bases, but carboxyl groups are preferred.
The carboxyl group is preferably in the form of a salt that is neutralized with a neutralizing agent such as ammonia, amine, alkali metals, and inorganic alkalis. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In a urethane resin having carboxyl groups neutralized with a neutralizing agent, the carboxyl groups from which the neutralizing agent has been removed in the drying process after coating can be used as crosslinking reaction points with a crosslinking agent. This not only provides excellent stability in the liquid state before coating, but also makes it possible to further improve the durability, solvent resistance, water resistance, blocking resistance, etc. of the resulting primer layer.

Various methods can be used to introduce carboxyl groups into the urethane resin at each stage of the polymerization reaction. For example, there is a method in which a resin having a carboxyl group is used as a copolymerization component during prepolymer synthesis, and a method in which a component having a carboxyl group is used as a component such as a polyol, polyisocyanate, or chain extender. Particularly preferred is a method in which a carboxyl group-containing diol is used and a desired amount of carboxyl groups is introduced depending on the amount of this component. For example, a carboxyl group-containing diol can be copolymerized with a polyol used in the synthesis of a urethane resin.
Examples of carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, and bis-(2-hydroxyethyl)butanoic acid, whose carboxyl groups are neutralized with a neutralizing agent. Examples include salts such as salts.

The primer layer preferably contains a compound derived from a crosslinking agent in order to make the primer layer stronger and improve performance such as adhesion.
As the crosslinking agent, known materials can be used, such as melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, aziridine compounds, and the like. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred, and from the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, and isocyanate compounds are preferred. and epoxy compounds are more preferred, and oxazoline compounds and isocyanate compounds are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. By using two or more types in combination, the adhesion and durability may be further improved.

A melamine compound is a compound that has a melamine skeleton in the compound, and includes, for example, an alkylolated melamine derivative, a compound that is partially or completely etherified by reacting an alkylolated melamine derivative with alcohol, and these compounds. Mixtures may be mentioned. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. The melamine compound may be a monomer, a dimer or more, or a mixture thereof. Furthermore, melamine co-condensed with urea or the like can also be used, and a catalyst can also be used to increase the reactivity of the melamine compound.
As the melamine compound, one having a hydroxyl group is preferable in consideration of reactivity with various compounds.

The isocyanate compound is a compound having an isocyanate or an isocyanate derivative structure typified by a blocked isocyanate.
Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; Aliphatic isocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), isopropylidene dicyclohexy diisocyanate, etc. Examples include alicyclic isocyanates. Also included are polymers and derivatives of these isocyanates, such as burettes, isocyanurates, uretdionates, and carbodiimide-modified products. These may be used alone or in combination of two or more. Among the above isocyanate compounds, aliphatic isocyanates or alicyclic isocyanates are more preferred than aromatic isocyanates from the viewpoint of avoiding yellowing due to ultraviolet rays.

Examples of blocked isocyanates include those obtained by blocking the isocyanate groups of the above-mentioned isocyanate compounds with a blocking agent. Examples of blocking agents include bisulfites, phenol compounds such as phenol, cresol, and ethylphenol, alcohol compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, dimethyl malonate, 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 include amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetate amide, and oxime compounds such as formaldehyde, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime. These may be used alone or in combination of two or more.
As the blocked isocyanate, an isocyanate blocked with an active methylene compound is preferable from the viewpoint that the primer layer is not easily destroyed.

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

An oxazoline compound is a compound having an oxazoline group in its molecule.
As the oxazoline compound, a polymer containing an oxazoline group is preferred. The oxazoline group-containing polymer can be obtained by polymerizing an addition-polymerizable oxazoline group-containing monomer alone or with other monomers.
Examples of addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is suitable because it is industrially easily available.
Other monomers are not particularly limited as long as they are copolymerizable with the addition-polymerizable oxazoline group-containing monomer, such as alkyl (meth)acrylate (alkyl groups include methyl, ethyl, n-propyl, (Meth)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 acids and their salts (sodium salts, potassium salts, ammonium salts, tertiary amine salts, etc.); Unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylamide, N-alkyl (meth) ) Acrylamide, N,N-dialkyl (meth)acrylamide, (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group) unsaturated amides 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 monomers; α,β-unsaturated aromatic monomers such as styrene, α-methylstyrene, and the like. These may be used alone or in combination of two or more.

The amount of oxazoline groups per 1 g of oxazoline compound is preferably in the range of 0.5 to 10 mmol/g, more preferably 1 to 9 mmol/g, even more preferably 3 to 8 mmol/g, particularly preferably 4 to 6 mmol/g. . If the amount of oxazoline groups is within the above range, the durability of the coating film will be improved and the adhesion will be easier to adjust.

An epoxy compound is a compound having an epoxy group in its molecule.
Examples of epoxy compounds include condensates of epichlorohydrin and compounds having a hydroxyl group or amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), polyepoxy compounds, diepoxy compounds, There are monoepoxy compounds, glycidylamine compounds, etc. 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. Examples include polyglycidyl ethers. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Examples 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.

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

Carbodiimide compounds can be synthesized by known techniques, and generally a diisocyanate condensation reaction is used. The diisocyanate is not particularly limited, and both aromatic and aliphatic diisocyanates can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene Examples include diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, and the like.

In order to improve the water solubility and water dispersibility of polycarbodiimide compounds, surfactants may be added to the extent that the effects of the present invention are not lost, or quaternary ammonium salts of polyalkylene oxides and dialkylamino alcohols may be added. Hydrophilic monomers such as hydroxyalkyl sulfonate and the like may be added.

A silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule.
Examples of the silane coupling compound include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Epoxy group-containing compounds such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyl group-containing compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane Styryl group-containing compounds such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxy (Meth)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-mercaptopropylmethyldiethoxysilane and other mercapto group-containing compounds.

Among the above compounds, from the viewpoint of the strength of the primer layer, silane coupling compounds containing epoxy groups, silane coupling compounds containing double bonds such as vinyl groups and (meth)acrylic groups, and silane coupling compounds containing amino groups are recommended. More preferred are silane coupling compounds.

Note that these crosslinking agents react during the drying process and film forming process to improve the performance of the primer layer. It can be assumed that unreacted products of the crosslinking agent, compounds after the reaction, or a mixture thereof exist as compounds derived from the crosslinking agent in the formed primer layer.

The antistatic agent to be included in the primer layer is not particularly limited, and any known antistatic agent may be used, such as ammonium group-containing compounds, polyether compounds, sulfonic acid group-containing compounds, betaine, etc. Examples include compounds, conductive organic polymers, and the like.
As the antistatic agent, a polymer type antistatic agent is preferable because it has good heat resistance and moist heat resistance.

The compound having an ammonium group is a compound having an ammonium group in the molecule, and includes ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines.
The ammonium group-containing compound is preferably a polymer type ammonium group-containing compound.
In a polymer-type compound having an ammonium group, the ammonium group is preferably incorporated into the main chain or side chain of the polymer, rather than as a counter ion. Such compounds include, for example, polymerizing an addition-polymerizable monomer having an ammonium group or a precursor group of an ammonium group such as an amine, and converting the precursor group of an ammonium group to an ammonium group as necessary. Examples include polymer compounds having ammonium groups. Addition-polymerizable monomers containing ammonium groups or ammonium group precursor groups may be polymerized singly, two or more types may be copolymerized, or they may be copolymerized with other monomers. You can.

As a compound having an ammonium group, a compound having a pyrrolidinium ring is also preferable because it has excellent antistatic properties and heat resistance stability.
The two substituents bonded to the nitrogen atom of the compound having a pyrrolidinium ring are each independently an alkyl group, a phenyl group, etc., and even if these alkyl groups or phenyl groups are substituted with the groups shown below, good. Substitutable groups include, for example, a hydroxyl group, an amide group, an ester group, an alkoxy group, a phenoxy group, a naphthoxy group, a thioalkoxy group, a thiophenoxy group, a cycloalkyl group, a trialkylammonium alkyl group, a cyano group, and a halogen. Furthermore, the two substituents bonded to the nitrogen atom may be chemically bonded, and examples of groups in which the two substituents are chemically bonded include -(CH ₂ ) _m -(m= (integer from 2 to 5), -CH(CH ₃ )CH(CH ₃ )-, -CH=CH-CH=CH-, -CH=CH-CH=N-, -CH=CH-N=C-, -CH ₂ OCH ₂ -, -(CH ₂ ) ₂ O(CH ₂ ) ₂ - and the like.

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

Examples of the anion serving as a counter ion to the ammonium group of the above-mentioned ammonium group-containing compound include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

The number average molecular weight of the compound having an ammonium group is preferably 1,000 to 500,000, more preferably 2,000 to 350,000, and still more preferably 5,000 to 200,000. If the number average molecular weight is 1000 or more, the strength and heat resistance stability of the coating film will be better. 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 handling and coating properties are good.

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

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

As the conductive organic polymer, known materials can be used, and examples thereof include polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, polyphenylene sulfide-based, and the like. Among these, polythiophene-based materials (polythiophene or polythiophene derivatives) are preferred because they have both high transparency and high conductivity, are difficult to color, and are easy to exhibit performance through coating. Among the polythiophene compounds, compounds in which poly(3,4-ethylenedioxythiophene) is combined with polystyrene sulfonic acid are particularly preferred from the viewpoint of electrical conductivity.
Conductive organic polymers are preferable because they exhibit high conductivity, are less dependent on humidity, and can be expected to be used in a variety of applications.

The primer layer may contain particles for blocking and improving slipperiness.
The primer layer may contain an antifoaming agent, a coating improver, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, as necessary, within a range that does not impair the gist of the present invention. It may contain additives such as pigments.

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 even more preferably 30 to 90% by mass. If the proportion of the resin is within the above range, the adhesion performance and the appearance of the primer layer will be better.

The proportion of the compound derived from the crosslinking 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 even more preferably 5 to 40% by mass. range. If the proportion of the compound derived from the crosslinking agent is within the above range, the adhesion performance and the strength of the primer layer will be better.

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 fixed because it depends on the type of antistatic agent, but for example, it is 80% by mass or less. , preferably from 0.5 to 70% by weight, more preferably from 1 to 50% by weight. When the proportion of the antistatic agent is within the above range, it is easy to impart sufficient antistatic function to the primer layer, and even after forming a cured layer on the primer layer, it is easy to exhibit antistatic performance.

The thickness of the primer layer cannot be determined unconditionally because it depends on the material used for the primer layer and the performance to be developed, but it is preferably 0.001 to 10 μm, more preferably 0.01 to 4 μm, and still more preferably 0.001 to 10 μm. It is in the range of 0.02 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 provide various functions.
Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjustment layer (an antireflection layer, a low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, a color correction layer, and the like.
The antifouling layer is provided to improve antifouling performance by imparting water repellency and oil repellency to the hardened layer. The antistatic layer is provided to reduce the adhesion of dust and the like due to peel-off charging and frictional charging to the outermost surface of the laminate, particularly to the outermost surface on the side where the cured layer is present with respect to the base material layer. The refractive index adjustment layer is provided, for example, in order to improve the total light transmittance of the laminate.

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

The silicone compound is a compound having a silicone structure in its molecule, and includes, for example, alkyl silicones (dimethyl silicone, diethyl silicone, etc.) and silicones having a phenyl group (phenyl silicone, methylphenyl silicone, etc.).
The silicone compound may have various functional groups. Examples of functional groups include hydrocarbon groups such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various aromatic groups. . Examples of other functional groups include silicone having a vinyl group and hydrogen silicone in which a hydrogen atom is directly bonded to a silicon atom; both can be used together to form an addition type silicone (a type resulting from an addition reaction between a vinyl group and a hydrogen silane). It is also possible to use It is also possible to introduce a double bond such as an acryloyl group and react at the double bond.

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

A fluorine compound is a compound containing a fluorine atom in the compound. As the fluorine compound, organic fluorine compounds are suitably used, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene. From the viewpoint of mold releasability, perfluoroalkyl group-containing compounds are preferred. Compounds containing long-chain alkyl groups as described below can also be used as the fluorine compound.

Examples of perfluoroalkyl group-containing compounds include perfluoroalkyl (meth)acrylate, perfluoroalkylmethyl (meth)acrylate, 2-perfluoroalkylethyl (meth)acrylate, 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-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl ether, and polymers thereof, etc. can be mentioned. In consideration of heat resistance and stain resistance, polymers are preferred. The polymer may be a polymer of a single compound or a polymer of multiple compounds. Furthermore, it may be a polymer with a compound containing a long-chain alkyl compound as described later.
From the viewpoint of antifouling properties, the perfluoroalkyl group preferably has 3 to 11 carbon atoms.

A 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 hexyl group, octyl group, decyl group, lauryl group, octadecyl group, and behenyl group.
Examples of long-chain alkyl group-containing compounds 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. It will 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 properties, it is more preferable to use a polymer compound having a long-chain alkyl group in its side chain.

A polymer compound having a long-chain alkyl group in its 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 above-mentioned 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, reactive group-containing polyester resin, and reactive group-containing poly(meth)acrylic resin. Among these, polyvinyl alcohol is preferred in consideration of stain resistance and ease of handling.
Examples of long-chain alkyl group-containing compounds that can react with the above-mentioned reactive groups 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 isocyanate. Examples include long-chain alkyl group-containing acid chlorides such as chloride, decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride, long-chain alkyl group-containing amines, and long-chain alkyl group-containing alcohols. Among these, in consideration of mold releasability and ease of handling, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred.

A polymer compound having a long-chain alkyl group in a 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 long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate. It will be done.

In addition to antifouling components, the antifouling layer may contain resins, compounds derived from crosslinking agents, antistatic agents, antifoaming agents, coatability improvers, thickeners, ultraviolet absorbers, antioxidants, and foaming agents, as necessary. It may further contain agents, dyes, pigments, etc. The compounds derived from the resin and the crosslinking 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 an antifouling component and a compound or crosslinking agent having a plurality of radically polymerizable groups such as acryloyl groups.

The proportion of the antifouling component in 100% by mass of the surface functional layer cannot be determined unconditionally as 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. The content is at least 0.1% by mass, more preferably at least 0.2% by mass, and the upper limit may be 100% by mass. When the antifouling component is a long-chain alkyl group-containing compound, it is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit may be 100% by mass. do not have. If the proportion of the antifouling component is within the above range, the antifouling performance will be better.

The antistatic layer contains an antistatic agent. The antistatic agent is as described above.
The antistatic layer may contain an antistatic agent, a resin, a compound derived from a crosslinking agent, an antifoaming agent, a coating improver, a thickener, an antifouling agent, an ultraviolet absorber, an antioxidant, and a foaming agent, as necessary. It may further contain agents, dyes, pigments, etc. The compounds derived from the resin and the crosslinking agent are as described above.

The proportion of the antistatic agent in 100% by mass of the antistatic layer depends on the type of antistatic agent, so it is not fixed, 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 the material constituting the high refractive index layer, known high refractive index materials can be used, such as aromatic structure-containing compounds such as benzene structure, bisphenol A structure, melamine structure, fluorene structure, etc. Condensed polycyclic aromatic compounds such as naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, perylene structure, which are considered to be high refractive index compounds among 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 include metal-containing compounds such as metal chelate compounds such as zirconium chelate, compounds containing sulfur elements, compounds containing halogen elements, and the like.

Metal oxides are preferably used in the form of particles, as there is a concern that adhesion may deteriorate depending on the form in which they are used, and the average particle size is preferably 100 nm or less, more preferably 100 nm or less, from the viewpoint of coating appearance, etc. is in the range of 50 nm or less, more preferably 25 nm or less.

As the material constituting the low refractive index layer, known low refractive index materials can be used, such as acrylic resins, urethane resins, compounds in which fluorine atoms are incorporated (for example, fluorine resins, Resins such as compounds containing fluororesin in the seed skeleton, compounds containing perfluoroalkyl groups in the side chain); inorganic compounds containing fluorine atoms such as hollow silica particles, magnesium fluoride, calcium fluoride, and 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, even more preferably 0.01 to 10 μm, particularly preferably 0.02 to 5 μm, and most preferably 0.03 to 3 μm. is within the range of If the thickness of the surface functional layer is within the above range, the function of the surface functional layer is likely to be expressed.
When the hardened layer is a layer that exhibits various functions due to its unevenness, the thickness of the surface functional layer is preferably smaller than the height of the unevenness on the surface of the uneven layer. If the thickness of the surface functional layer is smaller than the height of the irregularities, even if the surface functional layer is provided, functions such as matting properties and anti-blocking properties due to the irregularities will not be easily reduced.
The surface functional layer can be formed by a known method.

<Back functional layer>
The back functional layer is provided to impart various functions to the surface of the base material layer on the side opposite to the cured layer side.
Examples of the back functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an antiblocking layer.
The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is used to prevent the adhesion of surrounding dust, etc. due to peeling electrification and frictional electrification to the outermost surface of the laminate, especially the outermost surface of the base layer opposite to the cured layer side, and to prevent defects caused by this. provided. The refractive index adjustment layer is provided, for example, in order to improve the total light transmittance of the laminate. The anti-blocking layer is provided to reduce blocking of the laminate.

As the adhesive for forming the adhesive layer, known adhesives can be used, including acrylic, polyester, urethane, rubber, and the like. Among them, acrylic is preferred 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, respectively, as surface functional layers.

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

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
The measurement method and evaluation method used in the present invention are as follows.

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

(2) Total light transmittance/haze A laminate in which a cured layer was formed on a PET film was measured. Total light transmittance and haze are determined according to JIS Z8722Z (Geometric conditions for irradiation and light reception of transparent objects) and JIS K7361-1 (Test method for total light transmittance of plastics - transparent materials) and JIS K7136 (Plastics - Test method for total light transmittance of transparent materials). The value at a wavelength of 550 nm was measured using a haze meter "SH7000" manufactured by Nippon Denshoku Industries.
Note that the haze of the laminate is 0.044 rad (2. 5°) or more (ratio of diffuse transmittance to total light transmittance).

(3) Scratch resistance A laminate in which a cured layer was formed on a PET film was measured. In an atmosphere of 23°C and 55% RH, a weight of 200gf (per ^4cm2 area) was placed on steel wool #0000, and the surface of the hardened layer of the laminate was tested with a Gakushin abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 15 minutes. Scratches were visually observed by rubbing back and forth. Evaluation was made using 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.

(4) Leveling property The surface of the cured layer (10 cm x 10 cm) was visually observed to check the number of cracks and bump defects. Evaluation was made using the following criteria.
A: The total number of cracks and bump defects is less than 10.
B: The total number of cracks and bump defects is 10 or more.

(5) Curability When irradiated with ultraviolet rays at an illuminance of 100 mW/cm ² , the amount of irradiation (integrated light amount) until no tackiness was felt by finger touch was measured. Evaluation was made using the following criteria.
A: Cures with an irradiation dose of 100 mJ/cm ² or less.
B: Cures with an irradiation dose of more than 100 mJ/cm ² and less than 200 mJ/cm ² .
C: Cures with an irradiation dose of 200 mJ/cm ² or more and less than 300 mJ/cm ² .
D: Cures with an irradiation dose of 300 mJ/cm ² or more.

A copolymer was produced with the composition shown in Table 1. The raw materials in the table are as follows.
<Monomer (i)>
i-1: 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate obtained in Synthesis Example 1 below: In formula (I), R ¹ , R ³ , R ⁴ are A compound in which a methyl group and R ² are an ethylene group.
<Monomer (x)>
x-1: 4-methacryloyloxybenzophenone.
<Monomer (r)>
r-1: stearyl methacrylate.
r-2: 2-ethylhexyl methacrylate.
<Monomer (h)>
h-1: Diethylaminoethyl methacrylate.
<Other monomers (o)>
o-1: Methyl methacrylate.
<Chain transfer agent (t)>
t-1: n-dodecylmercaptan t-2: 3-mercaptopropyltrimethoxysilane <polymerization initiator (k)>
k-1: 2,2'-azobis(2,4-dimethylvaleronitrile)

(Synthesis Example 1: Synthesis of monomer (i-1))
Methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was distilled under reduced pressure, and a fraction with a purity of 99.8% or more was collected to obtain a distillate of methacrylic anhydride. Distillation under reduced pressure was carried out by gradually raising the temperature from room temperature to 90° C. under a pressure of 30 pa.
Separately, 22.4 g (0.1 mol) of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone (manufactured by Tokyo Chemical Industry Co., Ltd.) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 30.4 g (0.3 mol) of methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 500 mL of methylene chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.). 23.1 g (0.15 mol) of the above-mentioned distillate of methacrylic anhydride was added dropwise thereto at room temperature, and the mixture was stirred for 12 hours.
After washing the resulting reaction solution three 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 H-NMR analysis confirmed that the obtained compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate.
^1H NMR (300MHz, chloroform-d): δ8.06 (d, J = 9.0Hz, 2H), 6.96 (d, J = 9.0Hz, 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, 1.0Hz, 3H), 1.61 (s, 6H).

(Production Example 1: Production of copolymer (A-1))
70 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) was placed in a flask equipped with a stirrer, a condenser, and a thermometer.Then, the inside of the flask was replaced with nitrogen, the temperature was raised to 65°C, and the monomer (i-1 ) 50 parts by mass, 20 parts by mass of monomer (r-1), 30 parts by mass of monomer (o-1), 3 parts by mass of chain transfer agent (t-1), 1 part by mass of polymerization initiator (k-1), and A mixed solution of 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 polymerization initiator (k-1) and 0.6 parts by mass of MIBK was added and maintained for 5 hours. Thereafter, the reaction solution was cooled to 40° C. to obtain a copolymer MIBK solution (A-1). Hereinafter, the solid content in solution (A-1) will be referred to as copolymer (A-1).
The solid content (nonvolatile content) of solution (A-1) was 40% by mass. Table 1 shows the weight average molecular weight (Mw) of the copolymer (A-1) and the content of active groups per 1 g of the copolymer (A-1).

(Production Example 2: Production of copolymer (A-2))
In Production Example 1, the composition of the mixed solution was 25 parts by mass of monomer (i-1), 25 parts by mass of monomer (x-1), 10 parts by mass of monomer (r-1), 30 parts by mass of monomer (r-2), A copolymer MIBK solution (A -2) was obtained. Hereinafter, the solid content in solution (A-2) will be referred to as copolymer (A-2). The solid content (nonvolatile content) of solution (A-2) was 40% by mass. Table 1 shows the weight average molecular weight (Mw) of the copolymer (A-2) and the content of active groups per 1 g of the copolymer (A-2).

(Production Example 3: Production of copolymer (H-1))
In Production Example 1, 50 parts by mass of monomer (i-1) was changed to 50 parts by mass of monomer (x-1), and 3 parts by mass of chain transfer agent (t-1) was changed to 3 parts by mass of chain transfer agent (t-2). A MIBK solution (H-1) of the copolymer was obtained under the same conditions as in Production Example 1 except that the amount was changed. Hereinafter, the solid content in solution (H-1) will be referred to as copolymer (H-1). The solid content (nonvolatile content) of solution (H-1) was 40% by mass. Table 1 shows the weight average molecular weight (Mw) of the copolymer (H-1) and the content of active groups per 1 g of the copolymer (H-1).

(Examples 1 and 2, Reference Example 1, Comparative Example 1: Production of coating liquid (curable polymer composition))
The materials shown in Table 2 were mixed in the proportions (parts by mass) shown in Table 2 in terms of nonvolatile content. Then, a mixed solvent of propylene glycol monomethyl ether (hereinafter referred to as PGM) and methyl ethyl ketone (hereinafter referred to as MEK) (PGM:MEK (mass ratio) of 7:3) was added so that the solid content concentration was 40% by mass. A coating liquid (curable polymer composition) was obtained by stirring until the mixture was mixed.
Table 2 shows the content of active groups per 100 g of nonvolatile matter in the coating solution.

The materials in Table 2 are as follows.
A-1: MIBK solution of copolymer (A-1) obtained in Production Example 1.
A-2: MIBK solution of copolymer (A-2) obtained in Production Example 2.
H-1: MIBK solution of copolymer (H-1) obtained in Production Example 3.
B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.).
B-2: Pentaerythritol triacrylate (“Viscoat V#300” manufactured by Osaka Organic Chemical Industry Co., Ltd.).
P-1: Acrylic resin (Dyanal BR-80 manufactured by Mitsubishi Chemical Corporation).
C-1: Benzophenone.

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

As shown in the results in Table 2, the curable polymer compositions of Examples 1 and 2 containing copolymers (A-1) or (A-2) having units based on monomer (i) were A cured layer with excellent curability and scratch resistance compared to Example 1 and Comparative Example 1 was obtained.
In particular, the cured layer of Example 1 using copolymer (A-1) having units based on monomer (i) as copolymer (A) had a substantially smooth surface and a haze of 0.4. %Met.
In addition, in Example 2 in which copolymer (A-2) having units based on monomer (i) and units based on monomer (x) was used as copolymer (A), wrinkle-like unevenness was observed on the surface. The haze was 1.4%.

1... Base material layer 2... Cured layer 3... Primer layer 4... Surface functional layer 5... Back functional layer 10... Laminate

Claims (11)

A unit based on monomer (i) which is a compound represented by the following formula (I), and one or more selected from the group consisting of an alkyl group having 4 to 30 carbon atoms, a fluorine atom, and a silicon atom, and a radically polymerizable A copolymer having units based on a monomer (y) having a group and having no active group that generates radicals upon irradiation with active energy rays,
The content of active groups that generate radicals upon irradiation with active energy rays is 0.5 to 2.5 mmol/g per 1 g of the copolymer,
A copolymer, wherein the units based on the monomer (y) account for 1 to 80% by mass based on the total mass of all units of the copolymer.

[In the formula, R ¹ represents a hydrogen atom, a methyl group or an ethyl group, R ² represents an alkylene group having 1 to 2 carbon atoms or a linear or branched alkylene group having 3 to 5 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group having 1 to 2 carbon atoms or a linear or branched alkyl group having 3 to 5 carbon atoms, and R ³ and R ⁴ combine with each other to form a ring. You may. ] The monomer (y) is a (meth)acrylic acid alkyl ester having an alkyl group having 4 to 30 carbon atoms, and a radically polymerizable group selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group. The copolymer according to claim 1, which is one or more selected from the group consisting of compounds having a fluorine atom or a silicon atom. The method according to claim 1 or 2, further comprising one or more units selected from the group consisting of a unit based on the following monomer (x), a unit based on the following monomer (h), and a unit based on the following monomer (o). Copolymer.
Monomer (x): A monomer having an active group that generates radicals upon irradiation with active energy rays and a radically polymerizable group (excluding the monomer (i) above).
Monomer (h): has a hydrogen-donating functional group selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, and an amide group, and a radically polymerizable group, and is capable of releasing radicals by irradiation with active energy rays. Monomers (excluding the above monomer (y)) that do not have active groups generated.
Monomer (o): A monomer that has a radically polymerizable group and does not have an active group that generates radicals when irradiated with active energy rays (excluding the monomer (y) and the monomer (h)). It has a unit based on the monomer (x), and the radically polymerizable group of the monomer (x) is one or more types selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group. The copolymer according to claim 3. It has a unit based on the monomer (x), and the active group of the monomer (x) is a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (a group (Ia) represented by the following formula (Ia)) according to claim 3 or 4, which is one or more selected from the group consisting of α-aminoketone group, α-diketone group, α-diketone dialkyl acetal group, anthraquinone group, thioxanthone group, and phosphine oxide group. Copolymer.

[In the formula, R ² represents an alkylene group having 1 to 2 carbon atoms or a linear or branched alkylene group having 3 to 5 carbon atoms, and R ³ and R ⁴ each independently represent an alkylene group having 1 to 2 carbon atoms. represents an alkyl group or a linear or branched alkyl group having 3 to 5 carbon atoms, and R ³ and R ⁴ may be bonded to each other to form a ring. ] It has a unit based on the monomer (h), and the radically polymerizable group of the monomer (h) is one or more selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group. The copolymer according to any one of claims 3 to 5. The monomer (o) has a unit based on the monomer (o), and the monomer (o) is acrylic acid, acrylate, methacrylic acid, methacrylate, crotonic acid, crotonate, itaconic acid, itaconate, fumaric acid, Fumarate, maleic acid, maleate, citraconic acid, citraconic acid salt, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylonitrile, styrene, α-methylstyrene, divinylbenzene , vinyl toluene, vinyl propionate, vinyl acetate, phosphorus-containing vinyl compounds, vinyl chloride, polypyridine chloride, and butadiene. Polymer. A curable polymer composition comprising the copolymer (A) according to any one of claims 1 to 7 and a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule. A cured product of the curable polymer composition according to claim 8. The cured product according to claim 9, wherein the copolymer (A) is unevenly distributed on the surface of the cured product. A laminate comprising a base material layer and a layer made of the cured product according to claim 9 or 10.

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